EP0604491A1 - Substituted 3-phenyluracils as herbicides - Google Patents

Substituted 3-phenyluracils as herbicides

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Publication number
EP0604491A1
EP0604491A1 EP92919190A EP92919190A EP0604491A1 EP 0604491 A1 EP0604491 A1 EP 0604491A1 EP 92919190 A EP92919190 A EP 92919190A EP 92919190 A EP92919190 A EP 92919190A EP 0604491 A1 EP0604491 A1 EP 0604491A1
Authority
EP
European Patent Office
Prior art keywords
alkyl
alkoxy
och
alkenyl
cyano
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Application number
EP92919190A
Other languages
German (de)
French (fr)
Inventor
Ralf Klintz
Peter Schaefer
Gerhard Hamprecht
Elisabeth Heistracher
Hans-Josef Wolf
Karl-Otto Westphalen
Matthias Gerber
Uwe Kardorff
Helmut Walter
Klaus Grossmann
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BASF SE
Original Assignee
BASF SE
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Application filed by BASF SE filed Critical BASF SE
Publication of EP0604491A1 publication Critical patent/EP0604491A1/en
Withdrawn legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D239/00—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings
    • C07D239/02—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings
    • C07D239/24—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members
    • C07D239/28—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, directly attached to ring carbon atoms
    • C07D239/46—Two or more oxygen, sulphur or nitrogen atoms
    • C07D239/52—Two oxygen atoms
    • C07D239/54—Two oxygen atoms as doubly bound oxygen atoms or as unsubstituted hydroxy radicals
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/48—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
    • A01N43/54—1,3-Diazines; Hydrogenated 1,3-diazines
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C265/00—Derivatives of isocyanic acid
    • C07C265/12—Derivatives of isocyanic acid having isocyanate groups bound to carbon atoms of six-membered aromatic rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C271/00—Derivatives of carbamic acids, i.e. compounds containing any of the groups, the nitrogen atom not being part of nitro or nitroso groups
    • C07C271/04—Carbamic acid halides
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C271/00—Derivatives of carbamic acids, i.e. compounds containing any of the groups, the nitrogen atom not being part of nitro or nitroso groups
    • C07C271/06—Esters of carbamic acids
    • C07C271/08—Esters of carbamic acids having oxygen atoms of carbamate groups bound to acyclic carbon atoms
    • C07C271/10—Esters of carbamic acids having oxygen atoms of carbamate groups bound to acyclic carbon atoms with the nitrogen atoms of the carbamate groups bound to hydrogen atoms or to acyclic carbon atoms
    • C07C271/22—Esters of carbamic acids having oxygen atoms of carbamate groups bound to acyclic carbon atoms with the nitrogen atoms of the carbamate groups bound to hydrogen atoms or to acyclic carbon atoms to carbon atoms of hydrocarbon radicals substituted by carboxyl groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C275/00—Derivatives of urea, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups
    • C07C275/28—Derivatives of urea, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups having nitrogen atoms of urea groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton
    • C07C275/32—Derivatives of urea, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups having nitrogen atoms of urea groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton being further substituted by singly-bound oxygen atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C275/00—Derivatives of urea, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups
    • C07C275/28—Derivatives of urea, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups having nitrogen atoms of urea groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton
    • C07C275/38—Derivatives of urea, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups having nitrogen atoms of urea groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton being further substituted by doubly-bound oxygen atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C275/00—Derivatives of urea, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups
    • C07C275/28—Derivatives of urea, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups having nitrogen atoms of urea groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton
    • C07C275/40—Derivatives of urea, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups having nitrogen atoms of urea groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton being further substituted by nitrogen atoms not being part of nitro or nitroso groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C275/00—Derivatives of urea, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups
    • C07C275/28—Derivatives of urea, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups having nitrogen atoms of urea groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton
    • C07C275/42—Derivatives of urea, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups having nitrogen atoms of urea groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton being further substituted by carboxyl groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D317/00—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms
    • C07D317/08—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3
    • C07D317/10—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 not condensed with other rings
    • C07D317/14—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 not condensed with other rings with substituted hydrocarbon radicals attached to ring carbon atoms
    • C07D317/28—Radicals substituted by nitrogen atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D405/00—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom
    • C07D405/02—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings
    • C07D405/04—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings directly linked by a ring-member-to-ring-member bond

Definitions

  • the present invention relates to new substituted 3-phenylurazils of the general formula I.
  • X 3 , X 4 oxygen or sulfur; X 5 oxygen, sulfur or a residue -NR 14 , with
  • R 14 is hydrogen, hydroxyl, C 1 -C 6 alkyl, C 3 -C 6 alkenyl, C 3 -C 6 alkynyl, C 3 -C 7 cycloalkyl,
  • C 1 -C 6 haloalkyl C 1 -C 6 alkoxy-C 1 -C 6 alkyl, C 1 -C 6 alkoxy, C 3 -C 6 alkenyloxy, C 3 -C 6 alkynyloxy, C 5 -C 7 cycloalkoxy, C 5 -C 7 cycloalkenyloxy,
  • C 1 -C 6 -alkyl can be replaced and the phenyl ring can in each case carry one to three of the following substituents: cyano, nitro, halogen, C 1 -C 6 -alkyl, C 2 -C 6 - Alkenyl, C 1 -C 6 haloalkyl, C 1 -C 6 alkoxy and C 1 -C 6 alkoxycarbonyl, heterocyclyl, heterocyclyl-C 1 -C 6 alkoxy, heterocyclyl- C 3 -C 6 -alkenyloxy, heterocyclyl- C 3 -C 6 alkynyloxy, where in each case one or two methylene groups of the carbon chains by -O-, -S- or
  • heterocyclyl ring can be three to seven members, saturated, unsaturated or aromatic and one to four heteroatoms selected from a group of one or two oxygen or
  • R 6 , R 7 C 1 -C 6 alkyl, C 1 -C 6 haloalkyl, C 3 -C 6 alkenyl,
  • R 6 and R 7 together form a saturated or unsaturated, two- to four-membered carbon chain which can carry an oxo substituent, it being possible for one link in this chain to be replaced by an oxygen, sulfur or nitrogen atom which is not adjacent to the variables X 3 and X 4 , and wherein the chain can carry one to three of the following radicals: cyano, nitro, amino, halogen, C 1 -C 6 alkyl, C 2 -C 6 alkenyl, C 1 -C 6 alkoxy, C 2 -C 6 Alkenyloxy, C 2 -C 6 alkynyloxy, C 1 -C 6 haloalkyl,
  • Cyano-C 1 -C 6 -alkyl hydroxy-C 1 -C 6 -alkyl, C 1 -C 6 -alkoxy- C 1 -C 6 -alkyl, C 3 -C 6 -alkenyloxy-C 1 -C 6 - alkyl, C 3 -C 6 alkynyloxy-C 1 -C 6 alkyl, C 3 -C 7 cycloalkyl,
  • C 1 -C 6 alkyl-substituted nitrogen atoms may be replaced and this ring one or two of the following
  • R 8 is hydrogen, cyano, C 1 -C 6 alkyl, C 2 -C 6 alkenyl, C 2 -C 6 alkynyl, C 1 -C 6 haloalkyl, C 3 -C 7 cycloalkyl, C 1 -C 6 -
  • R 9 , R 12 are hydrogen, cyano, halogen, C 1 -C 6 alkyl, C 1 -C 6 alkoxy,
  • R 10 is hydrogen, OR 17 , SR 17 , C 1 -C 6 alkyl, which can also carry one or two C 1 -C 6 alkoxy substituents, C 3 -C 6 alkenyl, C 3 -C 6 alkynyl, C 1 -C 6 haloalkyl, C 3 -C 7 cycloalkyl, C 1 -C 6 alkylthio-C 1 -C 6 alkyl, C 1 -C 6 alkyliminooxy, -N (R 15 ) R 16 or phenyl, which can carry one to three of the following substituents: cyano, nitro, halogen, C 1 -C 6 alkyl, C 2 -C 6 alkenyl, C 1 -C 6 haloalkyl, C 1 -C 6 alkoxy or C 1 -C 6 alkoxycarbonyl;
  • R 17 is hydrogen, C 1 -C 6 alkyl, C 3 -C 6 alkenyl, C 3 -C 6 alkynyl, C 3 -C 7 cycloalkyl, C 1 -C 6 haloalkyl, C 3 -C 6 - Haloalkenyl, cyano-C 1 -C 6 alkyl, C 1 -C 6 alkoxy-C 1 -C 6 alkyl, C 1 -C 6 alkylthio- C 1 -C 6 alkyl or C 1 -C 6 - Alkyl-oximino-C 1 -C 6 alkyl, C 1 -C 6 alkylcarbonyl, C 1 -C 6 alkoxycarbonyl,
  • R 11 is hydrogen, cyano, halogen, C 1 -C 6 alkyl, C 3 -C 6 alkenyl, C 3 -C 6 alkynyl, C 1 -C 6 alkoxy-C 1 -C 6 alkyl, C 1 -C 6 -alkylcarbonyl, C 1 -C 6 -alkoxycarbonyl, -NR 18 R 19 , where R 18 and R 19 have the meanings of R 15 and R 16 , or phenyl, which is one to three of the can carry the following substituents: cyano, nitro, halogen, C 1 -C 6 alkyl, C 1 -C 6 haloalkyl,
  • R 13 is hydrogen, cyano, C 1 -C 6 alkyl or C 1 -C 6 alkoxycarbonyl; or R 9 and R 10 together form a two- to five-membered group
  • Carbon chain one carbon atom of this chain by oxygen, sulfur or optionally C 1 -C 6 alkyl
  • Phenyl which can carry one to three of the following radicals: cyano, nitro, halogen, C 1 -C 6 alkyl, C 2 -C 6 alkenyl, C 1 -C 6 haloalkyl, C 1 -C 6 alkoxy and C 1 -C 6 alkoxycarbonyl; R 5
  • R 22 and R 23 represent one of the meanings of R 15 and R 16 , phenyl, which is one to three of the can carry the following radicals: cyano, nitro, halogen, C 1 -C 6 alkyl, C 2 -C 6 alkenyl, C 1 -C 6 haloalkyl, C 1 -C 6 alkoxy and C 1 -C 6 alkoxycarbonyl , or
  • R 4 and R 5 together form a saturated or unsaturated 3 or 4-membered carbon chain, which can contain one to three of the following heteroatoms: 1 or 2 oxygen atoms, 1 or 2 sulfur atoms and 1 to 3 nitrogen atoms, the chain still one to three of the following radicals can carry: cyano, nitro, amino, halogen, C 1 -C 6 alkyl, C 2 -C 6 alkenyl, C 1 -C 6 alkoxy, C 1 -C 6 alkylthio and C 1 -C 6 -alkoxycarbonyl; with the proviso that R 4 cannot simultaneously be the trifluoromethyl group R 5 if W is a group
  • R 10 is C 1 -C 6 alkoxy or C 3 -C 7 cycloalkoxy, and with the proviso that R 4 and R 5 are not simultaneously hydrogen if W is CH ( R 8 ) -CH (R 9 ) -CO-R 10 and R 9 do not represent halogen, and the salts and enol ethers of those compounds I in which R 3 is hydrogen.
  • the invention relates to herbicidally active 3-phenylurazils of the general formulas Ia and Ib
  • R 3 ' represents a C 1 -C 6 alkyl group, a C 3 -C 6 alkenyl group or a C 3 -C 6 alkynyl group.
  • the invention further relates to herbicidal, pesticidal and plant growth-regulating agents which contain these compounds as active substances.
  • R a is hydrogen or halogen
  • R b is C 1 -C 12 alkyl or cycloalkyl
  • R c is C 1 -C 12 alkyl or C 3 -C 12 alkenyl
  • R d for hydrogen, alkyl, hydroxymethyl or haloalkyl
  • R e for haloalkyl
  • R f for hydrogen, alkyl, haloalkyl, hydroxymethyl, halogen or nitro
  • X 1 for oxygen or
  • R g represents hydrogen, alkyl, alkoxy or alkoxyalkyl and R h represents hydrogen, alkyl, cycloalkyl, haloalkyl, phenyl or benzyl and R i represents halogen, nitro or cyano.
  • CH 482 402 teaches weed control agents, which as active ingredients include substituted urazile and thiourazile
  • aryl optionally substituted by fluorine, chlorine, bromine, hydroxyl, alkoxy, cyano, alkylthio, alkyl or nitro, R k dialkylphosphoryl, alkyl, alkenyl, cyano, hydrogen, against subst. Alkyl, against subst. Carbamyl, opp. Subst. Thiocarbamyl, against subst. Mercapto or acyl, R 1 alkyl, alkoxy, hydrogen, chlorine or bromine and R m alkylthio, alkoxy, alkylthioalkyl, alkenyl, cyano, thiocyano, nitro, halogen,
  • Alkyl or R 1 and R m together represent a tri, tetra or pentamethylene chain.
  • WO-A 87/07 602 includes compounds of the formula IV
  • Halogen and R s include a cyano, subst. Alkylcarbonyl, carbonyl or alkoxycarbonyl-alkyl group and R o signify hydrogen, alkyl, alkylcarbonyl, alkenyl and alkynyl.
  • herbicidal compositions which contain these substances and have a good herbicidal action. They are tolerated and therefore selective in broadleaved crops and in monocotyledonous plants, which are not among the Gramineae.
  • the compounds I, Ia and Ib according to the invention are furthermore suitable as defoliating or desiccating agents in, for example, cotton, potatoes, rapeseed, sunflower, soybeans or field beans. Some compounds I are also useful for controlling pests, especially insects.
  • the meanings given above for the substituents R 1 to R 17 are collective terms for an individual list of the individual group members. All alkyl, alkenyl, alkynyl, haloalkyl and haloalkoxy parts can be straight-chain or branched. The haloalkyl and haloalkoxy radicals can carry the same or different halogen atoms.
  • halogen fluorine, chlorine, bromine and iodine, preferably fluorine and chlorine
  • C 1 -C 6 alkyl methyl, ethyl, n-propyl, 1-methylethyl,
  • n-butyl 1-methyl-propyl, 2-methylpropyl, 1,1-dimethylethyl, n-pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 2,2-dimethylpropyl, 1-ethylpropyl, 1, 1-dimethylpropyl,
  • Trichloromethyl fluoromethyl, difluoromethyl, trifluoromethyl, chlorofluoromethyl, dichlorofluoromethyl, chlorodifluoromethyl, 1-fluoroethyl, 2-fluoroethyl, 2,2-difluoroethyl,
  • n-propoxymethyl 1,2-methylethoxy) methyl, n-butoxymethyl, (1-methylpropoxy) methyl, (2-methylpropoxy) methyl, (1,1-dimethylethoxy) methyl, methoxyethyl, ethoxyethyl, n-propoxyethyl, (1-methylethoxy ) ethyl, n-butoxyethyl, (1-methylpropoxy) ethyl, (2-methylpropoxy) ethyl, (1,1-dimethylethoxy) ethyl, 3- (methoxy) propyl, 2- (methoxy) propyl and 2- (ethoxy) - Propyl, preferably C 1 -C 4 alkoxy-C 1 -C 2 alkyl such as methoxymethyl, ethoxymethyl, 2-methoxyethyl and 2-ethoxyethyl; C 1 -C 6 alkylamino: methylamino, ethyla
  • C 1 -C 6 alkylcarbonyl methylcarbonyl, ethylcarbonyl, propylcarbonyl, 1-methylethylcarbonyl, butylcarbonyl, 1-methylpropylcarbonyl, 2-methylpropylcarbonyl, 1,1-dimethylethylcarbonyl, pentylcarbonyl, 1-methylbutylcarbonyl, 2-methylbutylcarbonyl, 3-methylbutylcarbonyl, 1,1-dimethylpropylcarbonyl, 1,2-dimethylpropylcarbonyl, 2,2-dimethylpropylcarbonyl, 1-ethylpropylcarbonyl, hexylcarbonyl, 1-methylpentylcarbonyl, 2-methylpentylcarbonyl, 3-methylpentylcarbonyl, 4-methylpentylcarbonyl, 1.1 -Dimethylbutylcarbonyl, 1,2-dimethylbutylcarbonyl, 1,3-di
  • 2-ethylbutylcarbamoyloxy 1,1,2-trimethylpropylcarbamoyloxy, 1,2,2-trimethylpropylcarbamoyloxy, 1-ethyl-1-methylpropylcarbamoyloxy and 1-ethyl-2-methylpropylcarbamoyloxy, preferably C 1 -C 4 alkylcarbamoyloxy, in particular
  • N- (1-methylpropyl) -N- (2-methylpropyl) aminoethoxy N- (1,1-dimethylethyl) -N- (1-methylpropyl) aminoethoxy, N- (1,1-dimethylethyl) -N- (2-methylpropyl) aminoethoxy.
  • the substituted phenylurazils I can be in the form of their agriculturally useful salts or enol ethers, provided that R 3 is hydrogen.
  • Suitable salts which can be used in agriculture are in general the salts of bases which do not impair the herbicidal action of I.
  • Particularly suitable basic salts are those of the alkali metals, preferably the sodium and potassium salts, those of the alkaline earth metals, preferably calcium, magnesium and barium salts and those of the transition metals, preferably manganese, copper, zinc and iron salts and the ammonium salts, the one to three C 1 -C 4 alkyl, hydroxy-C 1 -C 4 alkyl substituents and / or one
  • the variables preferably have the following meaning:
  • R 1 particularly preferably denotes a radical from the group 1.01-1.07,
  • R 2 is a radical from the group 2.01-2.05
  • R 3 is a radical from the group 3.01-3.97,
  • R 3 ' is a radical from group 3' .01 - 3 '. 17,
  • R 4 is a residue from group 4.01-4.72
  • R 5 is a residue from the group 5.001 - 5.105
  • R 4 and R 5 together form a residue from the group 45.01 - 45.54 and
  • W one of the following radicals W1-W7: W1 -C (R 8 ) (X 3 R 6 ) (R 4 R 7 )
  • W4 -CR 8 CR 9 -CH 2 -CO-R 10 ,
  • W6 -CR 8 CR 9 -CH 2 -CHR 13 -CO-R 10 ;
  • W7 -CR 8 CR 9 -CN; where X 3 and X 4 are independently O or S,
  • R 6 and R 7 independently of one another are a radical from group 6.01-6.19,
  • R 6 and R 7 together a radical from the group 67.01-67.63, R 8 a radical from the group 8.01-8.22,
  • R 9 and R 12 are a residue from group 9.01 - 9.23, R 10 is a residue from the group 10.01 - 10.144,
  • R 11 is a residue from group 11.01 - 11.25,
  • R 13 is a residue from the group 13.01 - 13.08,
  • R 14 is a radical from the group 14.001-14.162, and all these radicals can be combined with one another as desired.
  • w in the above formulas I-1 to I-24 each has one of the following meanings: -CHO, -COCH 3 , -COC 2 H 5 , -CO-nC 3 H 7 , -CO-iC 3 H 7 , -CO-nC 4 H 9 ,
  • -CH NCH 2 C ⁇ C-CH 3
  • -CH N-cyclopropyl
  • -CH N-cyclobutyl
  • -CH N-cyclopentyl
  • -CH N-cyclohexyl
  • -CH N-cycloheptyl
  • -CH N-2-CH 3 -C 6 H 4
  • -CH N-3-CH 3 -C 6 H 4
  • -CH N-4-CH 3 -C 6 H 4
  • -CH N-2-OCH 3 -C 6 H 4
  • -CH N-3-OCH 3 -C 6 H 4
  • -CH N-4-OCH 3 -C 6 H 4
  • -CH N-4-NO 2 -C 6 H 4
  • -CH N-4-CN-C 6 H 4
  • -CH N-2, 4- (Cl, Cl) -C 6 H 4
  • - CH N-2,4- (CH 3 , CH 3 ) -C 6 H 4
  • -CH N-CH 2 OCH 3
  • -CH N-CH 2 OC 2 H 5 ,
  • -CH N-OC (O) CH 3
  • -CH N-OC (O) C 2 H 5
  • -CH NO-CH 2 -CN
  • -CH NO- (CH 2 ) 3 -C 6 H 5
  • -CH NO- (CH 2 ) 4 -C 6 H 5
  • -CH NO- (CH 2 ) 3 C ⁇ C-4-FC 6 H 4
  • -CH 2 N-OCHOCH 3
  • -CH N-OC 2 H 4 OCH 3
  • -CH N-OCH 2 OC 2 H 5 ,
  • -CH N-OCH (CH 3 ) OCH 3
  • -CH N-OCH (CH 3 ) COOCH 3
  • -CH N-OCH (CH 3 ) COO-nC 4 H 9
  • -CH N-NH 2
  • -CH N-NHCH 3
  • -CH N-NHC 2 H 5
  • -CH N-NH- nC 3 H 7
  • -CH N-NH-iC 3 H 7
  • -CH N-NH-nC 4 H 9 ,
  • -CH N-NH-iC 4 H 9
  • -CH N-NH-SC 4 H 9
  • -CH N-NH-tert.-C 4 H 9
  • -CH N-NH-cyclopropyl
  • -CH N-NH-cyclobutyl
  • -CH N-NH-cyclopentyl
  • -CH N-NH-cyclohexyl
  • -CH N-NH-cycloheptyl
  • -CH NN ( CH 3 ) 2
  • -CH N-NHCH 2 -C ⁇ CH
  • -CH NN (CH 3 ) -CH 2 -C ⁇ CH
  • -CH N-NHCH 2 CF 3
  • -CH N-NH-CO-CH 3
  • -CH N-NH-CO-CH 2 H 5
  • -CH N-NH-COOCH 3
  • -CH N-NH-COOC 2 H 5
  • -CH N-NH-COO-tert.-C 4 H 9
  • -CH N-pyrrolidin-1-yl
  • -CH N-piperidin-1-yl
  • -CH N-morpholin-4-yl
  • -CH N-NH-C 6 H 5
  • -CH N-NH- (4-Cl-C 6 H 4 )
  • -CH CH-CO-OCH 3
  • -CH CH-CO-OC 2 H 5
  • -CH CH-CO-OnC 3 H 7
  • -CH CH-CO-OiC 3 H 7
  • -CH CH-CO-OnC 4 H 9
  • -CH CH-CO-O-tert.-C 4 H 9
  • -CH CH-CO-O- cyclopropyl
  • -CH CH-CO-O-cyclobutyl
  • -CH CH-CO-O-cyclopentyl
  • -CH CH-CO-O-cyclohexyl
  • -CH CH-CO-O-cycloheptyl
  • -CH C (CH 3 ) -COOH
  • -CH C (CH 3 ) -CO-OCH 3
  • -CH C (CH 3 ) -CO-OC 2 H 5
  • -CH C (CH 3 ) -CO-OnC 3 H 7 ,
  • -CH C (CH 3 ) -CO-O-tert-C 4 H 9
  • -CH C (CH 3 ) -CO-O-cyclopropyl
  • -CH C (CH 3 ) -CO-O-cyclobutyl
  • -CH C (CH 3 ) -CO-O-cyclopentyl
  • -CH C (CH 3 ) -CO-O-cyclohexyl
  • -CH C (CH 3 ) -CO-O-cycloheptyl
  • -CH C (C 2 H 5 ) -CO-O-cyclopropyl
  • -CH C (C 2 H 5 ) -CO-O-cyclobutyl
  • -CH C (C 2 H 5 ) -CO-O-cyclopentyl
  • -CH C (C 2 H 5 ) -CO-O-cyclohexyl
  • -CH C (C 2 H 5 ) -CO-O-cycl ⁇ heptyl
  • -CH C (Cl) -COOH
  • -CH C ( Cl) -CO-OCH 3
  • -CH C (Cl) -CO-OC 2 H 5
  • -CH C (Cl) -CO-OnC 3 H 7
  • -CH C (Cl) -CO-OiC 3 H 7
  • -CH C (Cl) -CO-OnC 4 H 9
  • -CH C (Cl) -CO-O-tert.-C 4
  • -CH C (Cl) -CO-O-cycloheptyl
  • -CH C (Br) -COOH
  • -CH C (Br) -CO-OCH 3
  • -CH C (Br) -CO-OC 2 H 5
  • -CH C (Br) -CO-OnC 3 H 7
  • -CH C (Br) -CO-OiC 3 H 7
  • -CH C (Br) -CO-OnC 4 H 9
  • -CH C (Br) -CO-O-tert.-C 4 H 9 ,
  • -CH C (CN) -CO-O-cyclopropyl
  • -CH C (CN) -CO-O-cyclobutyl
  • -CH C (CN) -CO-O-cyclopentyl
  • -CH C (CN) -CO-O-cyclohexyl
  • -CH C (CN) -CO-O-cycloheptyl
  • -CH CH-CO-OCH 2 -OCH 3
  • -CH CH-CO-OCH 2 -OC 2 H 5
  • -CH CH-CO-OCH 2 -OnC 3 H 5
  • -CH CH-CO-OCH 2 -OiC 3 H 5
  • -CH CH-CO-OCH (CH 3 ) -OCH 3
  • -CH CH-CO-OCH (CH 3 ) -OC 2 H 5
  • -CH CH-CO-O-CH 2 CH 2 -OCH 3
  • -CH CH-CO-O-CH 2 CH 2 -OC 2 H 5
  • -CH C (CH 3 ) -CO-OCH 2 -OCH 3
  • -CH C (CH 3 ) -CO-OCH 2 -OC 2 H 5
  • -CH C (CH 3 ) -CO-OCH 2 -OnC 3 H 5
  • -CH C (CH 3 ) -CO-OCH 2 -OiC 3 H 5
  • -CH C (CH 3 ) -CO-OCH (CH 3 ) -OCH 3
  • -CH C (CH 3 ) -CO-OCH (CH 3 ) -OC 2 H 5
  • -CH C (CH 3 ) -CO-O-CH 2 CH 2 -OCH 3
  • -CH C (CH 3 ) -CO-O-CH 2 CH 2 -OC 2 H 5
  • -CH C (C 2 H 5 ) -CO-OCH 2 -OCH 3
  • -CH C (C 2 H 5 ) -CO-OCH 2 -OiC 3 H 5
  • -CH C (C 2 H 5 ) -CO-OCH (CH 3 ) -OCH 3
  • -CH C (C 2 H 5 ) -CO-OCH (CH 3 ) -OC 2 H 5
  • -CH C (C 2 H 5 ) -CO-O-CH 2 CH 2 -OCH 3
  • -CH C (C 2 H 5 ) -CO-O-CH 2 CH 2 -OC 2 H 5
  • -CH C (Cl) -CO-OCH 2 -OCH 3
  • -CH C (Cl) -CO-OCH 2 -OiC 3 H 5
  • -CH C (Cl) -CO-OCH (CH 3 ) -OCH 3
  • -CH C (Cl) -CO-OCH (CH 3 ) -OC 2 H 5
  • -CH C (Cl) -CO-O-CH 2 CH 2 -OCH 3
  • -CH C (Cl) -CO-O-CH 2 CH 2 -OC 2 H 5
  • -CH C (Br) -CO-OCH 2 -OCH 3
  • -CH C (Br) -CO-OCH 2 -OiC 3 H 5
  • -CH C (Br) -CO-OCH (CH 3 ) -OCH 3
  • -CH C (Br) -CO-OCH (CH 3 ) -OC 2 H 5
  • -CH C (Br) -CO-O-CH 2 CH 2 -OCH 3 ,
  • -CH C (Br) -CO-O-CH 2 CH 2 -OC 2 H 5
  • -CH C (CN) -CO-OCH 2 -OCH 3
  • -CH C (CN) -CO-OCH 2 -OiC 3 H 5
  • -CH C (CN) -CO-OCH (CH 3 ) -OCH 3
  • -CH C (CN) -CO-OCH (CH 3 ) -OC 2 H 5
  • -CH C (CN) -CO-O-CH 2 CH 2 -OCH 3
  • -CH CH-CO-OCH 2 -CCl 3
  • -CH CH-CO-OCH 2 -oxiranyl
  • -CH CH-CO-O (CH 2 ) 3 -Br
  • -CH CH-CO-OCH 2 -CN
  • -CH CH-CO-O (CH 2 ) 2 -CN
  • -CH C (CH 3 ) -CO-OCH 2 -CF 3
  • -CH C ( CH 3 ) -CO-OCH 2 -CCl 3
  • -CH C (CH 3 ) -CO-OCH 2 -oxiranyl
  • -CH C (C 2 H 5 ) -CO-OCH 2 -CCl 3
  • -CH C (C 2 H 5 ) -CO-OCH 2 -oxiranyl
  • -CH C (C 2 H 5 ) -CO-OCH 2 -C ⁇ CH
  • -CH C (C 2 H 5 ) -CO-OCH 2 -CN
  • -CH C (C 2 H 5 ) -CO-O (CH 2 ) 2 -CN
  • -CH C (Cl) -CO-OCH 2 -CF 3
  • -CH C (Cl) -CO-OCH 2 -CCl 3
  • -CH C (Cl) -CO-OCH 2 -oxiranyl
  • -CH C (Cl) -CO-OCH 2 -C ⁇ CH
  • -CH C (Cl) -CO-OCH 2 -CN
  • -CH C (Br) -CO-OCH 2 -CCl 3
  • -CH C (Br) -CO-OCH 2 -oxiranyl
  • -CH C (Br) -CO-OCH 2 -C ⁇ CH
  • -CH C (Br) -CO-OCH 2 -CN
  • -CH C (CN) -CO-OCH 2 -CCl 3
  • -CH C (CN) -CO-OCH 2 -oxiranyl
  • -CH C (CN) -CO-OCH 2 -C ⁇ CH
  • -CH C (CN) -CO-OCH 2 -CN
  • -CH CH-CO-nC 3 H 7
  • -CH CH-CO-iC 3 H 7
  • -CH CH-CO-nC 4 H 9
  • -CH CH-CO-tert.-C 4 H 9
  • -CH CH-CO-CH 2 Cl
  • -CH CH-CO-CH 2 Br
  • -CH CH-CO-CHCl 2
  • -CH CH-CO-CH 2 -OCH 3
  • -CH CH-CO-CH (OCH 3 ) 2
  • -CH CH-CO-CH 2 -SCH 3
  • -CH C (CH 3 ) -CO-CH 3
  • -CH C (CH 3 ) -CO-C 2 H 5
  • -CH C (C 2 H 5 ) -CO-tert.-C 4 H 9
  • -CH C (C 2 H 5 ) -CO-CH 2 Cl
  • -CH C (C 2 H 5 ) -CO-CH 2 Br
  • -CH C (C 2 H 5 ) -CO-CHCl 2
  • -CH C (C 2 H 5 ) -CO-CH 2 -OCH 3
  • -CH C (C 2 H 5 ) -CO-CH (OCH 3 ) 2
  • -CH C (C 2 H 5 ) -CO-CH 2 -SCH 3
  • -CH C (Cl) -CO-CH 3
  • -CH C (Cl) -CO-C 2 H 5
  • -CH C (Cl) -CO-nC 3 H 7
  • -CH C (Cl) -CO-iC 3 H 7
  • -CH C (Cl) -CO-nC 4 H 9
  • -CH C (Cl) - CO-tert-C 4 H 9
  • -CH C (Cl) -CO-CH 2 Cl
  • -CH C (Cl) -CO-CH 2 Br
  • -CH C (Cl) -CO-CHCl 2
  • -CH C (Cl) -CO-CH 2 -OCH 3
  • -CH CH-CO-N (CH 3 ) 2
  • -CH CH-CO-NH-C 2 H 5
  • -CH CH-CO-N (C 2 H 5 ) 2
  • -CH CH-CO-NH-nC 3 H 7
  • -CH CH-CO-NH-iC 3 H 7
  • -CH CH-CO-NH-tert-C 4 H 9
  • -CH CH-CO-NH-cyclopropyl
  • -CH CH-CO-NH-cyclobutyl
  • -CH CH-CO-NH-cyclopentyl
  • -CH CH-CO-NH-cyclohexyl
  • -CH CH-CO-NH-cycloheptyl
  • -CH CH-CO-NH-cyclooctyl
  • -CH CH-CO-pyrrolidin-1-yl
  • -CH CH-CO-piperidin-1-yl
  • -CH CH-CO-morpholin-4-yl
  • -CH CH-CO-NH-CH 2 C ⁇ CH
  • -CH CH-CO-N (CH 3 ) -CH 2 C ⁇ CH
  • -CH CH-CO-NH- (CH 2 ) 2 Cl
  • -CH CH-CO-NH-C 6 H 5
  • -CH C (CH 3 ) -CO-NH 2
  • -CH C (CH 3 ) -CO-NHCH 3
  • -CH C (CH 3 ) -CO-NH-cyclopropyl
  • -CH C (CH 3 ) -CO-NH-cyclobutyl
  • -CH C (CH 3 ) -CO-NH-cyclopentyl
  • -CH C (CH 3 ) -CO-NH-cyclohexyl
  • -CH C (CH 3 ) -CO-NH-cycloheptyl
  • -CH C (CH 3 ) -CO-NH-cyclooctyl
  • -CH C (CH 3 ) -CO-pyrrolidin-1-yl
  • -CH C (CH 3 ) -CO-piperidin-1-yl
  • -CH C (CH 3 ) -CO-morpholin-4-yl
  • -CH C (CH 3 ) -CO-NH-CH 2 C ⁇ CH
  • -CH C (C 2 H 5 ) -CO-NH 2
  • -CH C (C 2 H 5 ) -CO-NHCH 3
  • -CH C (C 2 H 5 ) -CO-N (CH 3 ) 2
  • -CH C (C 2 H 5 ) -CO-NH-C 2 H 5
  • -CH C (C 2 H 5 ) -CO-N (C 2 H 5 ) 2
  • -CH C (C 2 H 5 ) -CO-NH-nC 3 H 7
  • -CH C (C 2 H 5 ) -CO-NH-iC 3 H 7
  • -CH C (Cl) -CO-NH-cyclopropyl
  • -CH C (Cl) -CO-NH-cyclobutyl
  • -CH C (Cl) -CO-pyrrolidin-l-yl
  • -CH C (Cl) -CO-pi peridin-1-yl
  • -CH C (Cl) -C0-morpholin-4-yl
  • -CH C (Cl) -CO-NH-CH 2 C ⁇ CH
  • -CH C (Br) -CO-pyrrolidin-1-yl
  • -CH C (Br) -CO-piperidin-l-yl
  • -CH C (Br) -C0-morphol in-4-y 1
  • -CH C (Br) -CO-NH-CH 2 C ⁇ CH
  • -CH C (CN) -CO-NH-cyclopropyl
  • -CH C (CN) -CO-NH-cyclobutyl
  • -CH C (CN) -CO-NH-cyclopentyl
  • -CH C (CN) -CO-NH-cyclohexyl
  • -CH C (CN) -CO-NH-cycloheptyl
  • -CH C (CN) -CO-NH-cyclooctyl
  • -CH C (CN) -CO-pyrrolidin-1-yl
  • -CH C (CN) -CO-pi peridin-1-yl
  • -CH C (CN) -CO-morpholin-4-yl
  • -CH CH-CO-SnC 4 H 9
  • -CH CH-CO-S-tert.-C 4 H 9
  • -CH C (CH 3 ) -CO-SCH 3
  • -CH C (CH 3 ) -CO-SC 2 H 5
  • -CH C (CH 3 ) -CO-SnC 3 H 7 ,
  • -CH C (CH 3 ) -CO-S-tert.-C 4 H 9
  • -CH C (C 2 H 5 ) -CO-SCH 3
  • -CH C (C 2 H 5 ) -CO-S-tert-C 4 H 9
  • -CH C (Cl) -CO-SCH 3
  • -CH C (Br) -CO-SCH 3
  • -CH C (Br) -CO-SC 2 H 5
  • -CH C (Br) -CO-SnC 3 H 7
  • -CH C (Br) -CO-SiC 3 H 7
  • -CH C (Br) -CO-SnC 4 H 9 ,
  • -CH C (Br) -CO-S-tert.-C 4 H 9
  • -CH C (CN) -CO-SCH 3
  • -CH C (CN) -CO-SC 2 H 5
  • -CH C (CN) -CO-SnC 3 H 7
  • -CH C (CN) -CO-SiC 3 H 7 ,
  • -CH C (CO-nC 3 H 7 ) -CO-OnC 3 H 7
  • -CH C (CF 3 ) -CO-OCH 3
  • -CH C (CF 3 ) -CO-O-tert.-C 4 H 9
  • -CH C (COOCH 3 ) 2
  • -CH C (COOC 2 H 5 ) 2
  • -CH C (COOCH 3 ) -CO-OC 2 H 5
  • -CH C (COO-nC 3 H 7 ) -CO-OCH 3
  • -CH C (COO-nC 3 H 7 ) -CO-OC 2 H 5
  • -CH C (COO-nC 3 H 7 ) 2
  • -CH CH- (CH 2 ) 2 -CO-OCH 3
  • -CH CH- (CH 2 ) 2-CO-OC 2 H 5
  • -CH CH-CH 2 -CH (COOCH 3 ) 2
  • -CH CH-CH 2 -CH (COOC 2 H 5 ) 2
  • -CH CH-CH 2 -CH (CN) -CO-OCH 3
  • -CH CH-CH 2 -CH (CN) -CO-OC 2 H 5
  • -CH CH-CH 2 -CH (CH 3 ) -CO-OCH 3
  • -CH CH-CH 2 -CH (CH 3 ) -CO-OC 2 H 5
  • -CH CH- (CH 2 ) 2 -CO-NH 2
  • -CH CH- (CH 2 ) 2 -CO-NH-CH 3
  • -CH CH-CH 2 -COOH
  • -CH CH-CH 2 -CO-OCH 3
  • -CH CH-CH 2 -CO-OC 2 H 5
  • -CH C (COOCH 3 ) -CH 2 -CO-OCH 3
  • -CH C (COOCH 3 ) -CH 2 -CO-OC 2 H 5
  • -CH CH-CH 2 -CO-NH 2
  • -CH CH-CH 2 -CO-NH-CH 3
  • -CH CH-CH 2 -CO-N (CH 3 ) 2
  • -CH (OCH 3 ) 2 , -CH (SCH 3 ) 2
  • -C (CH 3 ) N-CH 2 C ⁇ CH
  • -C (CH 3 ) N-CH 2 C ⁇ C-CH 3
  • -C (CH 3 ) N-cyclopropyl
  • -C (CH 3 ) N-cyclobutyl
  • -C (CH 3 ) N-cyclopentyl
  • -C (CH 3 ) N-cyclohexyl
  • -C (CH 3 ) N-cycloheptyl
  • -C (CH 3 ) N-CH 2 -OCH 3
  • -C (CH 3 ) N-CH 2 -OC 2 H 5
  • -C (CH 3 ) N-CH 2 CH 2 -OCH 3
  • - C (CH 3 ) N-CH 2 CH 2 -OC 2 H 5
  • -C (CH 3 ) N-OH
  • -C (CH 3 ) N-OCH 3
  • -C (CH 3 ) N-OC 2 H 5
  • -C (CH 3 ) NOnC 3 H 7
  • -C (CH 3 ) NOiC 3 H 7
  • -C (CH 3 ) N-OCH 2 CH 2 -Cl
  • -C (CH 3 ) N-OCH 2 CH 2 -F
  • -C (CH 3 ) N-OCH 2 -CF 3
  • -C (CH 3 ) NO-CO-CH 3
  • -C (CH 3 ) NO-CO-C 2 H 5
  • -C (CH 3 ) N-OCH 2 -CN
  • -C (CH 3 ) N-OCH (CH 3 ) -CO-OnC 4 H 9
  • -C (CH 3 ) N-NH 2
  • -C (CH 3 ) N-NH-CH 3
  • -C (CH 3 ) N-NH-C 2 H 5
  • -C (CH 3 ) N-NH-nC 3 H 7
  • -C (CH 3 ) N-NH-iC 3 H 7
  • -C (CH 3 ) N-NH-nC 4 H 9
  • -C (CH 3 ) N-NH-iC 4 H 9
  • -C (CH 3 ) N-NH-SC 4 H 9
  • -C (CH 3 ) N-NH-tert.-C 4 H 9
  • -C (CH 3 ) N-NH-cyclopropyl
  • -C (CH 3 ) N-NH-cyclobutyl
  • -C (CH 3 ) N-NH- cyclopropyl
  • -C (CH 3 ) N-NH-CO-CH 3
  • -C (CH 3 ) N-NH-CO-C 2 H 5
  • -C (CH 3 ) N-NH-CO-OCH 3
  • -C (CH 3 ) N-NH-CO-OC 2 H 5
  • -C (CH 3 ) N-NH-CO-O-tert.-C 4 H 9
  • -C (CH 3 ) N- pyrrolidin-1-yl
  • -C (CH 3 ) N-piperidin-1-yl
  • -C (CH 3 ) N-morpholin-4-yl
  • -C (CH 3 ) N-NH-C 6 H 5
  • -C (CH 3 ) N-NH- (4-Cl-C 6 H 4 ),
  • -C (CH 3 ) CH-CO-O-cyclobutyl
  • -C (CH 3 ) CH-CO-O-cyclopentyl
  • -C (CH 3 ) CH-CO-O-cyclohexyl
  • -C (CH 3 ) CH-CO-O-cycloheptyl
  • -C (CH 3 ) C (CH 3 ) -CO-O-tert.-C 4 H 9
  • -C (CH 3 ) C (CH 3 ) -CO-O-cyclopropyl
  • -C (CH 3 ) C (CH 3 ) -CO-O-cyclobutyl
  • -C (CH 3 ) C (CH 3 ) -CO-O-cyclopentyl
  • -C (CH 3 ) C (CH 3 ) -CO-O-cyclohexyl
  • -C (CH 3 ) C (CH 3 ) -CO-O-cycloheptyl
  • -C (CH 3 ) C (C 2 H 5 ) -COOH
  • -C (CH 3 ) C (C 2 H 5 ) -CO-OCH 3
  • -C (CH 3 ) C (C 2 H 5 ) -CO-O-tert.-C 4 H 9
  • -C (CH 3 ) C (C 2 H 5 ) -CO-O-cyclopropyl
  • -C (CH 3 ) C (C 2 H 5 ) -CO-O-cyclobutyl
  • -C (CH 3 ) C (C 2 H 5 ) -CO-O- cyclopentyl
  • -C (CH 3 ) C (C 2 H 5 ) -CO-0-cyclohexyl
  • -C (CH 3 ) C (Br) -C0-0-nC 4 Hg
  • -C (CH 3 ) C (BrJ-CO-0-tert.-C 4 Hg
  • -C (CH 3 ) C (CN) -CO-O-cyclopropyl
  • -C (CH 3 ) C (CN) -CO-O-cyclobutyl-
  • -C (CH 3 ) C (CN) -CO -0-cyclopentyl
  • -C (CH 3 ) C (CN) -CO-0-cyclohexyl
  • -C (CH 3 ) C (CN) -CO-O-cycloheptyl
  • -C (CH 3 ) CH- CO-OCH 2 -OCH 3 ,
  • -C (CH 3 ) CH-CO-OCH 2 -0C 2 H 5
  • -C (CH 3 ) CH-CO-OCH 2 -0-nC 3 H 7
  • -C (CH 3 ) CH-C0-0CH (CH 3 ) -OC 2 H 5
  • -C (CH 3 ) CH-CO-OCH 2 CH 2 -0CH 3
  • -C (CH 3 ) C (C1) -CO-OCH (CH 3 ) -OC 2 H 5
  • -C (CH 3 ) C (ClJ-CO-OCH 2 CH 2 -OCH 3
  • -C (CH 3 ) C (CIJ-CO-OCH 2 CH 2 -OC 2 H 5
  • -C (CH 3 ) C (Br) -CO-OCH 2 -OCH 3
  • -C (CH 3 ) C (BrJ- CO-OCH 2 -OC 2 H 5
  • -C (CH 3 ) C (Br) -CO-OCH 2 -O-Ii-C 3 H 7
  • -C (CH 3 ) C (Br) -CO- OiC 3 H 7
  • -C (CH 3 ) C (Br) -CO-OCH (CH 3 ) -OCH 3 ,
  • -C (CH 3 ) C ⁇ Br) -CO-OCH 2 -CCI 3
  • -C (CH 3 ) C (Br) -CO-OCH 2 -oxirany1
  • -C (CH 3 ) C (Br) -CO-O- (CH 2 ) 3 -Br
  • -C (CH 3 ) C (Br) -CO-OCH 2 -C ⁇ CH
  • -C (CH 3 ) C (Br) -CO-OCH 2 -CN
  • -C (CH 3 ) C (CN) -CO-OCH 2 -CCl 3
  • -C (CH 3 ) C (CN) -CO-OCH 2 -oxiranyl
  • -C (CH 3 ) C (CN) -CO-O- (CH 2 ) 3 -Br
  • -C (CH 3 ) C (CN) -CO-OCH 2 -CN,
  • -C (CH 3 ) CH-CO-C 2 H 5
  • -C (CH 3 ) CH-CO-nC 3 H 7
  • -C (CH 3 ) CH-CO-IC 3 H 7
  • -C (CH 3 ) CH-CO-nC 4 Hg
  • -C (CH 3 ) CH-CO-tert.-C 4 Hg
  • -C (CH 3 ) CH-CO-CH 2 Cl
  • -C (CH 3 ) CH-CO-CH 2 Br
  • -C (CH 3 ) CH-CO-CHCl 2
  • -C (CH 3 ) CH-CO-CH 2 -OCH 3
  • -C (CH 3 ) CH-CO-CH (OCH 3 ) 2 ,
  • -C (CH 3 ) C (CH 3 ) -CO-CH 2 -SCH 3
  • -C (CH 3 ) C (C 2 H 5 ) -CO-CH 3
  • -C (CH 3 ) C (C 2 Hs) -CO-C 2 H 5
  • -C (CH 3 ) C (C 2 H 5 ) -CO-nC 3 H 7 ,
  • -C (CH 3 ) C (CN) -CO-CH 2 -OCH 3
  • -C (CH 3 ) C (CN J -CO-CH (OCH 3 J 2 ,
  • -C (CH 3 ) C (Br) -CO-C 6 H 5
  • -C (CH 3 ) C (CN) -CO-C 6 H 5
  • -C (CH 3 ) CH-CO-NH 2
  • -C (CH 3 ) CH-CO-NHCH 3
  • -C (CH 3 ) CH-CO-N (CH 3 ) 2 ,
  • -C (CH 3 ) CH-CO-NH-C 2 H 5
  • -C (CH 3 ) CH-CO-N (C 2 H 5 ) 2
  • -C (CH 3 ) C (CH 3 ) -CO-NH-C 2 H 5
  • -C (CH 3 ) C (CH 3 ) -CO-N (C 2 H 5 ) 2
  • -C (CH 3 ) C (CH 3 ) -CO-NH-nC 3 H 7
  • -C (CH 3 ) C (CH 3 ) -CO-NH-iC 3 H 7 ,
  • -C (CH 3 ) C (CH 3 ) -CO-NH-tert-C 4 H 9
  • -C (CH 3 ) C (CH 3 ) -CO-NH-cyclopropyl
  • -C (CH 3 ) C (CH 3 ) -CO-NH-cyclobutyl
  • -C (CH 3 ) C (CH 3 ) -CO-NH-cyclopentyl
  • -C (CH 3 ) C (CH 3 ) -CO-NH-cyclohexyl
  • -C (CH 3 ) C (CH 3 ) -CO-NH-cycloheptyl
  • -C (CH 3 ) C (CH 3 ) -CO-NH-cyclooctyl
  • -C (CH 3 ) C (CH 3 ) -CO-pyrrolidin-1-yl
  • -C (CH 3 ) C (CH 3 ) -CO-piperidin-1-yl
  • -C (CH 3 ) C (CH 3 ) -CO-NH-CH 2 C ⁇ CH
  • -C (CH 3 ) C (CH 3 ) -CO-N (CH 3 ) -CH 2 C ⁇ CH
  • -C (CH 3 ) C (CH 3 ) -CO-NH- (CH 2 ) 2 Cl
  • -C (CH 3 ) C (CH 3 ) -CO-NH-C 6 H 5
  • -C (CH 3 ) C (C 2 H 5 ) -CO-NH 2
  • -C (CH 3 ) C (C 2 H 5 ) -CO-NH-nC 3 H 7
  • -C (CH 3 ) C (C 2 H 5 ) -CO-NH-iC 3 H 7
  • -C (CH 3 ) C (C 2 H 5 ) -CO-NH-tert-C 4 H 9
  • -C (CH 3 ) C (C 2 H 5 ) -CO-NH-cyclopropyl
  • -C (CH 3 ) C (C 2 H 5 ) -CO-NH-cyclobutyl
  • -C (CH 3 ) C (C 2 H5) -CO-piperidin-1-yl
  • -C (CH 3 ) C (C 2 H 5 ) -CO-morpholin-4-yl
  • -C (CH 3 ) C (Cl) -CO-NH-iC 3 H 7
  • -C (CH 3 ) C (Cl) -CO-NH-tert.-C 4 H 9
  • -C (CH 3 ) C (Cl) -CO-NH-cyclopropyl
  • -C (CH 3 ) C (Cl) -CO-NH-cyclobutyl
  • -C (CH 3 ) C (Cl) -CO-NH-cyclopentyl
  • - C (CH 3 ) C (Cl) -CO-NH-cyclohexyl
  • -C (CH 3 ) C (Cl) -CO-NH-cycloheptyl
  • -C (CH 3 ) C (Cl) -CO-NH -cyclooctyl
  • -C (CH 3 ) C (Cl) -CO-pyrrolidin-1-yl
  • -C (CH 3 ) C
  • -C (CH 3 ) C (Cl) -CO-NH-CH 2 C ⁇ CH
  • -C (CH 3 ) C (Cl) -CO-NH- (CH 2 ) 2 Cl
  • -C ( CH 3 ) C (Cl) -CO-NH-C 6 H 5
  • -C (CH 3 ) C (Br) -CO-NH 2
  • -C (CH 3 ) C (CN) -CO-NH-C 2 H 5
  • -C (CH 3 ) C (CN) -CO-N (C 2 H 5 ) 2
  • -C (CH 3 ) C (CN) -CO-NH-tert-C 4 H 9
  • -C (CH 3 ) C (CN) -CO-NH-cyclopropyl
  • -C (CH 3 ) C (CN) -CO-NH-cyclobutyl
  • -C (CH 3 ) C (CN) -CO-NH-cyclopentyl
  • -C (CH 3 ) C (CN) -CO-NH-cyclohexyl
  • -C (CH 3 ) C (CN) -CO-NH-cycloheptyl
  • -C (CH 3 ) C (CN) -CO-NH-cyclooctyl
  • -C (CH 3 ) C (CN) -CO-pyrrolidin-1- yl
  • -C (CH 3 ) C (CN) -CO-piperidin-1-yl
  • -C (CH 3 ) C (CN) -CO-morpholin-4-
  • -C (CH 3 ) C (COOCH 3 ) -CO-OC 2 H 5
  • -C (CH 3 ) C (COO-nC 3 H 7 ) -CO-OCH 3
  • -C (CH 3 ) C (COO-nC 3 H 7 ) -CO-OC 2 H 5
  • -C (CH 3 ) C (COO-nC 3 H 7 ) 2 ,
  • -C (CH 3 ) CH- (CH 2 ) 2 -COOH
  • -C (CH 3 ) CH-CH 2 -CH (CN) -CO-OCH 3
  • -C (CH 3 ) CH-CH 2 -CH (CN) -CO-OC 2 H 5
  • -C (CH 3 ) CH-CH 2 -CH (CH 3 ) -CO-OCH 3
  • -C (CH 3 ) CH-CH 2 -CH (CH 3 ) -CO-OC 2 H 5
  • -C (CH 3 ) CH- (CH 2 ) 2 -CO-NH 2
  • -C (CH 3 ) CH- (CH 2 ) 2 -CO-NH-CH 3
  • -C (CH 3 ) CH-CH 2 -CO-OC 2 H 5
  • -C (CH 3 ) C (COOCH 3 ) -CH 2 -CO-OCH 3 ,
  • -C (CH 3 ) CH-CH 2 -CO-NH-CH 3
  • -C (CH 3 ) CH-CH 2 -CO-N (CH 3 ) 2 .
  • X 1 and X 2 are oxygen, R 1 is halogen, R 2 is hydrogen or fluorine, R 3 is C 1 -C 6 -alkyl, partially or completely halogenated C 1 -C 2 -alkyl, R4 is C 1 -C 6 alkyl, partially or fully halogenated C 1 -C 2 alkyl; R 5 is hydrogen or R 4 and R 5 together represent a tetramethylene chain.
  • the substituted 3-phenylurazils are available in various ways, preferably one of the following
  • L 1 means low molecular weight alkyl, preferably C 1 -C 4 alkyl, or phenyl.
  • Suitable solvents or diluents are inert aprotic organic solvents, for example aliphatic or cyclic ethers such as 1,2-dimethoxyethane, tetrahydrofuran and dioxane, aromatic hydrocarbons such as benzene, toluene and xylenes, and inert polar organic solvents such as dimethylformamide or dimethyl sulfoxide, or else Water, where the polar solvents can optionally also be used as a mixture with a non-polar hydrocarbon such as n-hexane.
  • aprotic organic solvents for example aliphatic or cyclic ethers such as 1,2-dimethoxyethane, tetrahydrofuran and dioxane, aromatic hydrocarbons such as benzene, toluene and xylenes, and inert polar organic solvents such as dimethylformamide or dimethyl sulfoxide, or else Water, where the polar solvents
  • Suitable bases are preferably alkali metal alcoholates, especially sodium alcoholates such as sodium methoxide and sodium ethanolate, alkali metal hydroxides, especially sodium hydroxide and potassium hydroxide, alkali metal carbonates, especially sodium carbonate and potassium carbonate, and alkali metal hydrides, especially sodium hydride.
  • the solvent is particularly preferably an aliphatic or cyclic ether such as tetrahydrofuran and dimethylformamide and dimethyl sulfoxide.
  • the amount of base is preferably between the 0.5 and 2 molar amount, based on the amount of II or III.
  • reaction temperature between (-78) ° C and the boiling point of the reaction mixture is recommended, in particular between (-60) and 60 ° C.
  • (M ⁇ one equivalent of a metal ion, in particular an alkali metal ion such as sodium) before, for example in the case of the abovementioned preferred bases containing alkali metal in the form of the corresponding alkali metal salt.
  • the salt can be isolated and purified in a manner known per se, for example by recrystallization.
  • Products I in which R 3 is hydrogen are obtained by acidifying the reaction mixture obtained after the cyclization, for example with hydrochloric acid. b) alkylation or acylation of a substituted
  • the alkylation normally takes place with the halide, preferably the chloride or bromide, or the sulfate of an alkane, alkene, alkyne, cycloalkane, cyanoalkane, haloalkane, phenylalkane or alkoxyalkane.
  • the halide preferably the chloride or bromide, or the sulfate of an alkane, alkene, alkyne, cycloalkane, cyanoalkane, haloalkane, phenylalkane or alkoxyalkane.
  • Suitable acylating agents are e.g. Formic acid, alkane carboxylic acid or alkoxy carboxylic acid halides into consideration, the chlorides and bromides being preferred in each case.
  • the alkylation is conveniently carried out in the presence of an inert organic solvent and a base, for example in a protic solvent such as lower alcohols, preferably ethanol, optionally in a mixture with water, or in an aprotic solvent such as aliphatic or cyclic ethers, preferably 1,2-dimethoxyethane, Tetrahydrofuran and dioxane, aliphatic ketones, preferably acetone, amides, preferably dimethylformamide, or sulfoxides, preferably dimethyl sulfoxide.
  • Suitable bases are, for example, alcoholates such as sodium methoxide, sodium ethoxide and potassium tert-butoxide,
  • Hydroxides such as sodium hydroxide, potassium hydroxide and calcium hydroxide, carbonates such as sodium and potassium carbonate, and
  • Alkali metal hydroxides such as sodium hydride.
  • the cyclization product present as a salt is alkylated without prior isolation from the reaction mixture, in which case excess base, for example sodium hydride, a sodium alcoholate or sodium carbonate, still originating from the cyclization of the compound II or III , may be present. However, this base does not interfere; if desired, a further amount of the diluent which was also used for the cyclization of the compound II or III can also be added.
  • excess base for example sodium hydride, a sodium alcoholate or sodium carbonate
  • acylation with a halide can be carried out in an analogous manner, in which case it is particularly preferred in one
  • reaction temperature is generally between 0 ° C and about 100 ° C, preferably between 0 and 40 ° C.
  • the salts of those compounds I in which R 3 is hydrogen can also be obtained in a manner known per se from the products of the present method d).
  • the aqueous solution of an inorganic or organic base is mixed with the substituted 3-phenylurazil I, in which R 3 is hydrogen. Salt formation normally takes place at 20-25 ° C with sufficient speed.
  • the salt of 3-phenylurazil can then be isolated, for example by precipitation with a suitable inert solvent or by evaporation of the solvent.
  • Hal means halogen, preferably chlorine or bromine.
  • the reaction is advantageously carried out in the presence of an aprotic, polar solvent, for example an alkyl nitrile such as acetonitrile, propionitrile and butyronitrile, an alkyl urea such as N, N, N ', N'-tetramethyl urea, a dialkyl amide such as dimethylformamide, a dialkyl sulfoxide such as dimethyl sulfoxide or in N- Methyl-2-pyrrolidone, 1,2-dimethyl-imidazolidin-2-one, 1,2-dimethyl-3,4,5,6-tetrahydro-2 (1H) -pyrimidinone or hexamethylphosphoric triamide.
  • an alkyl nitrile such as acetonitrile, propionitrile and butyronitrile
  • an alkyl urea such as N, N, N ', N'-tetramethyl urea
  • Metal cyanides in particular a transition metal cyanide such as copper (I) cyanide, at elevated temperatures, preferably between 150 and 250 ° C.
  • Hal means chlorine or bromine
  • Me ⁇ means an equivalent of a metal ion, especially a transition metal ion, an alkali metal ion such as sodium and
  • the amount of base is not critical; normally 0.5 to 2 times the molar amount, based on the amount of IVa or IVb, is sufficient.
  • the reactions of IVa with HX 1 -R 3 ' and of IVb with HX 2 -R 3' can be carried out either without solvent in an excess of R 3 ' -OH or R 3' -SH or in a suitable inert organic solvent, for example in an aromatic such as toluene and xylene, in an ether such as diethyl ether, tetrahydrofuran and 1,2-dimethoxyethane, or in a halogenated hydrocarbon such as dichloromethane and chlorobenzene.
  • the acetalization is generally carried out in an inert aprotic organic solvent, for example in an aliphatic or cyclic ether such as diethyl ether, 1,2-dimethoxyethane, tetrahydrofuran and dioxane, in an aromatic hydrocarbon such as benzene, toluene, o-, m-, p-xylene and Mesitylene, or in a chlorinated hydrocarbon such as methylene chloride, chloroform and chlorobenzene, unless it is carried out without solvent in an excess of HX 3 R 6 , HX 4 R 7 or HX 3 (R 6 R 7 ) X 4 -H.
  • an inert aprotic organic solvent for example in an aliphatic or cyclic ether such as diethyl ether, 1,2-dimethoxyethane, tetrahydrofuran and dioxane, in an aromatic hydrocarbon such as benzene, toluene,
  • Resulting water of reaction can be removed from the reaction mixture as usual, e.g. by means of water separation.
  • the acetalization is preferably carried out in the presence of an organic acid such as p-toluenesulfonic acid and / or a Lewis acid such as tin tetrachloride, tin II chloride, iron III chloride, tellurium tetrachloride and boron trifluoroetherate or a suitable catalyst such as montmorillonite K 10, the
  • an organic acid such as p-toluenesulfonic acid and / or a Lewis acid such as tin tetrachloride, tin II chloride, iron III chloride, tellurium tetrachloride and boron trifluoroetherate or a suitable catalyst such as montmorillonite K 10
  • the amount of acid is usually between 0.5 and 100 mol%, based on the amount of starting material to be acetalized.
  • the proportions are not critical. For a complete reaction, all reactants are used in an approximately stoichiometric ratio, but an excess of HX 3 R 6 and HX 4 R 7 or HX 3 (R 6 R 7 ) X 4 -H is preferably used. if the reactants HX 3 R 6 and HX 4 R 7 or H-X3 (R 6 R 7 ) X 4 -H are used simultaneously as diluents, they are present in a large excess.
  • a temperature between (-78) and 180 ° C, preferably between (-40) and 150 ° C.
  • R 6 and R 7 do not form a common radical and X 3 R 6 and X 4 R 7 are not the same, they can, if desired, be purified and separated by methods known per se, such as crystallization and chromatography.
  • compounds of the formula I, where W is a group -C (R 8 ) (X 3 R 6 ) (X 4 R 7 ), in which R 6 and R 7 do not have a common one Form the rest and X 3 R 6 and X 4 R 7 are not the same can also be prepared by other methods known from the literature (see, for example, Tetrahedron Lett. 32, 467-470 (1991) and the literature cited therein).
  • acetalization via the detour of acetalization to the dialkylacetal, preferably dimethylacetal, and subsequent transacetalization in the presence of a suitable catalyst.
  • a suitable catalyst preferably dimethylacetal
  • the solvents, catalysts and other reaction conditions used for the umacetalization correspond to those already listed above for the acetalization.
  • suitable reactive derivatives are acetals and orthoesters.
  • the acetal can be used without the addition of acid, in the presence of an acid, eg a mineral acid such as hydrochloric acid and sulfuric acid, an organic carboxylic acid such as formic acid, acetic acid, oxalic acid and trifluoroacetic acid, in the presence of an acidic ion exchanger such as Amberlite ® (trademark of the company. "Aldrich”) IR120 or IRC84, or in the presence of a transition metal salt such as mercury (II) oxide, copper (I) oxide and iron (III) chloride.
  • an acid eg a mineral acid such as hydrochloric acid and sulfuric acid
  • an organic carboxylic acid such as formic acid, acetic acid, oxalic acid and trifluoroacetic acid
  • an acidic ion exchanger such as Amberlite ® (trademark of the company. "Aldrich”) IR120 or IRC84
  • a transition metal salt such as mercury (II) oxide, copper (I) oxide
  • solvents or diluents examples include aromatics such as benzene, toluene and o-, m-, p-xylene, aliphatic or cyclic ethers such as 1,2-dimethoxyethane, diethyl ether, tetrahydrofuran and dioxane, alcohols such as methanol, ethanol and isopropanol, polar organic solvents such as dimethylformamide, dimethyl sulfoxide and acetonitrile, ketones such as acetone and butanone, or water.
  • aromatics such as benzene, toluene and o-, m-, p-xylene
  • aliphatic or cyclic ethers such as 1,2-dimethoxyethane, diethyl ether, tetrahydrofuran and dioxane
  • alcohols such as methanol, ethanol and isopropanol
  • polar organic solvents such as dimethylform
  • the starting materials I where W is a group —C (R 8 ) (X 3 R 6 ) (X 4 R 7 ), and H 2 X 5 are used in at least a stoichiometric ratio, but there is also an excess H 2 X 5 , up to about 200 mol%, possible.
  • the amount of acid, ion exchanger or transition metal salt is not critical. In general, an amount of up to about 300 mol%, based on the amount of H 2 X 5 , is sufficient. In general, the reaction temperature is between (-78) and 180 ° C, preferably between 0 ° C and the boiling point of the respective diluent.
  • R 3 P C (R 9 ) -CH 2 -CO-R 10 Vb,
  • R 3 P c (R 9 ) -CH 2 -CH (R 13 ) -CO-R 10 Vd;
  • Phosphonium salts VI R 3 P ⁇ -CH (R 9 ) -CO-R 10 Hal ⁇ VIa,
  • Phosphonates VII (RO) 2 PO-CH (R 9 ) -CO-R 10 Vlla,
  • Those phosphorylides Vb and Vd, phosphonium salts VIb and VId and phosphonates Vllb and Vlld in which R 10 is hydrogen, alkyl or cycloalkyl are not very suitable.
  • the radicals R on the phosphorus may be the same or different and represent, for example, branched or unbranched C 1 -C 8 -alkyl groups, C 5 - or C 6 -cycloalkyl groups and in particular phenyl, the further (for the reaction inert substituents, for example C 1 -C 4 alkyl such as methyl, ethyl and tert-butyl, C 1 -C 4 alkoxy such as methoxy or halogen such as fluorine, chlorine and bromine) can carry.
  • triphenylphosphine used for the preparation of the phosphoryl ide v and phosphonium salts VI is particularly inexpensive and, moreover, the very inert and easily separable, solid triphenylphosphine oxide is formed in the reactions.
  • Suitable for the preparation of the phosphonates VII are, for example, those in Houben-Weyl, Methods of Organic Chemistry, Volume E2, 1982, pp. 345ff. described methods.
  • Inert organic solvents for example aromatics such as toluene and o-, m-, p-xylene, ethers such as 1,2-dimethoxyethane, diethyl ether, tetrahydrofuran and dioxane, polar organic solvents such as dimethylformamide and dimethyl sulfoxide, or alcohols such as methanol, ethanol are used as solvents and isopropanol.
  • aromatics such as toluene and o-, m-, p-xylene
  • ethers such as 1,2-dimethoxyethane, diethyl ether, tetrahydrofuran and dioxane
  • polar organic solvents such as dimethylformamide and dimethyl sulfoxide
  • alcohols such as methanol, ethanol are used as solvents and isopropanol.
  • reaction temperature is between (-40) and 150 ° C.
  • the compounds of the formulas V, VI and VII are known or can be prepared in a known manner (see, for example, Houben-Weyl, Methods of Org. Chemistry, Vol E1, p. 636ff, Georg Thieme Verlag, Stuttgart 1982, Chem. Ber. 95, 3993 (1962) or Houben-Weyl, Methods of Org. Chemistry, Vol. E2, p. 345 ff, Georg Thieme Verlag, Stuttgart 1982).
  • -CR 8 CR 11 -CH 2 -CO-R 12
  • -CR 8 CRH-CH 2 -CHR 15 -CO-R 12
  • R 9 or R 11 are hydrogen, cyano, alkoxycarbonyl or alkylcarbonyl, both the Knoevenagel condensation and the Perkin condensation are suitable
  • the reaction is usually carried out in an inert organic solvent or diluent, e.g. in an aromatic such as toluene and xylene, in a chlorinated hydrocarbon such as dichloromethane, chloroform and chlorobenzene, in an ether such as diethyl ether, 1,2-dimethoxy ether and tetrahydrofuran, in an alcohol such as methanol and ethanol, or in a mixture of the solvents mentioned.
  • an inert organic solvent or diluent e.g. in an aromatic such as toluene and xylene, in a chlorinated hydrocarbon such as dichloromethane, chloroform and chlorobenzene, in an ether such as diethyl ether, 1,2-dimethoxy ether and tetrahydrofuran, in an alcohol such as methanol and ethanol, or in a mixture of the solvents mentioned.
  • amines H 2 NR 14 are present as salts, for example as hydrochlorides or oxalates, the addition of a base such as preferably sodium carbonate, potassium carbonate, sodium hydrogen carbonate, triethylamine and pyridine is recommended for their release.
  • a base such as preferably sodium carbonate, potassium carbonate, sodium hydrogen carbonate, triethylamine and pyridine is recommended for their release.
  • the water of reaction formed can optionally be removed from the reaction mixture by distillation or with the aid of a water separator.
  • the cleavage is carried out without solvent or in an inert solvent or diluent with water or a reactive derivative of water.
  • the reaction can be carried out hydrolytically or under oxidative conditions, a reaction temperature between (-78) and 180 ° C., preferably between 0 ° C. and the boiling point of the diluent being recommended.
  • solvents or diluents are aromatics such as benzene, toluene and o-, m-, p-xylene, chlorinated hydrocarbons such as dichloromethane, chloroform and chlorobenzene, ethers such as dialkyl ether, 1,2-dimethoxyethane, tetrahydrofuran and dioxane, alcohols such as methanol and Ethanol, ketones such as acetone, esters of organic acids such as ethyl acetate or water, and mixtures of the solvents mentioned.
  • aromatics such as benzene, toluene and o-, m-, p-xylene
  • chlorinated hydrocarbons such as dichloromethane, chloroform and chlorobenzene
  • ethers such as dialkyl ether, 1,2-dimethoxyethane, tetrahydrofuran and dioxane
  • alcohols such as methanol and Ethano
  • oxidizing agents such as lead tetraacetate, sodium hypochlorite and hydrogen peroxide are particularly suitable.
  • the reaction can additionally be carried out in the presence of a catalyst such as copper (II) sulfate, titanium tetrachloride and boron trifluoroetherate.
  • a catalyst such as copper (II) sulfate, titanium tetrachloride and boron trifluoroetherate.
  • the amounts of acid, oxidizing agent and catalyst can be varied within a wide range. Normally, both the amount of acid and catalyst are between 5 and 200 mol%, and the amount of oxidizing agent is between 25 and 400 mol%, based on the amount of the compound to be oxidized, but they can also be used in a substantial excess.
  • k implementation of a substituted 3-phenylurazil I, wherein
  • X 2 means oxygen with a sulfurization reagent
  • the reaction is usually carried out in an inert solvent, for example in an aromatic hydrocarbon such as toluene and o-, m-, p-xylene, in an ether such as diethyl ether, 1,2-dimethoxyethane and tetrahydrofuran, or in an organic amine such as pyridine .
  • an aromatic hydrocarbon such as toluene and o-, m-, p-xylene
  • an ether such as diethyl ether, 1,2-dimethoxyethane and tetrahydrofuran
  • organic amine such as pyridine
  • Phosphorus (V) sulfide and 2,4-bis (4-methoxyphenyl) -1,3,2,4-dithiadiphosphetane-2,4-dithione are particularly suitable as the sulfurization reagent.
  • the amount of sulfurization reagent is not critical; normally 1 to 5 times the molar amount, based on the 3-phenylurazil to be sulfurized.
  • reaction temperature is between 20 and 200 ° C, preferably between 40 ° C and the boiling point of the
  • the halogenation is usually carried out in an inert organic solvent or diluent.
  • an inert organic solvent or diluent for example, aliphatic carboxylic acid such as acetic acid, or chlorinated aliphatic hydrocarbons such as methylene chloride, chloroform and carbon tetrachloride are suitable.
  • Low-boiling aliphatic carboxylic acids such as acetic acid are particularly preferred for iodination.
  • Elemental chlorine or bromine and sulfuryl chloride or sulfuryl bromide are particularly suitable for chlorination and bromination, a reaction temperature between 0 and 60 ° C., preferably between 10 and 30 ° C., being recommended.
  • the chlorination and bromination can take place in the presence of an acid-binding agent, sodium acetate and tertiary amines such as triethylamine, dimethylaniline and pyridine being particularly preferred.
  • an acid-binding agent sodium acetate and tertiary amines such as triethylamine, dimethylaniline and pyridine being particularly preferred.
  • Elemental iodine is particularly preferred as the iodination agent, in which case the reaction temperature is between about 0 and 110 ° C., preferably between 10 and 30 ° C.
  • the iodination is particularly advantageously carried out in the presence of a mineral acid such as fuming nitric acid.
  • a mineral acid such as fuming nitric acid.
  • the amount of halogenating agent is not critical; normally equimolar amounts of halogenating agent or an excess of up to about 200 mol%, based on the starting material to be halogenated, are used. Excess iodine can be removed, for example, after the reaction using saturated aqueous sodium bisulfite solution. m) reduction of a substituted 3-phenylurazil I, where
  • W means the cyano group
  • the reaction is conveniently carried out in an inert organic solvent, e.g. an aromatic such as toluene and o-, m-, p-xylene, an aliphatic or cyclic ether such as diethyl ether, tert-butyl methyl ether, tetrahydrofuran and dioxane, a chlorinated hydrocarbon such as methylene chloride, chloroform and chlorobenzene, or in an organic carboxylic acid such as formic acid.
  • an inert organic solvent e.g. an aromatic such as toluene and o-, m-, p-xylene, an aliphatic or cyclic ether such as diethyl ether, tert-butyl methyl ether, tetrahydrofuran and dioxane, a chlorinated hydrocarbon such as methylene chloride, chloroform and chlorobenzene, or in an organic carboxylic acid such as formic acid.
  • Suitable reducing agents are, for example, hydrogen or metal salts such as tin (II) chloride, metal hydrides such as diisobutyl aluminum hydride, diisopropyl aluminum hydride, lithium trisethoxy aluminum hydride and lithium bisethoxy aluminum hydride or triethylsilane.
  • metal salts such as tin (II) chloride
  • metal hydrides such as diisobutyl aluminum hydride, diisopropyl aluminum hydride, lithium trisethoxy aluminum hydride and lithium bisethoxy aluminum hydride or triethylsilane.
  • diisobutylaluminum hydride formic acid or hydrogen is preferred.
  • the reduction can be carried out in the presence of a catalyst such as triethyloxonium tetrafluoroborate or Raney nickel.
  • a catalyst such as triethyloxonium tetrafluoroborate or Raney nickel.
  • a reducing agent is used in formic acid without a diluent, this can also be present in a large excess.
  • the most advantageous reaction temperature depends on the particular reducing agent, but is generally between (-78) and 150 ° C. n) Phosgenation or thiophosgenation of an enaminamide of the formula VIII
  • the process can be carried out in an inert organic solvent with the aid of a suitable phosgenating or thiophosgenating agent, e.g. Phosgene, thiophosgene, trichloromethyl chloroformate or 1,1'-carbonyldiimidazole optionally in
  • a suitable phosgenating or thiophosgenating agent e.g. Phosgene, thiophosgene, trichloromethyl chloroformate or 1,1'-carbonyldiimidazole optionally in
  • Presence of a base e.g. an organic nitrogen base, e.g. Triethylamine, pyridine or 2, 6-lutidine, at temperatures between -20 and 130 ° C, preferably between 0 ° and the reflux temperature of the solvent used.
  • a base e.g. an organic nitrogen base, e.g. Triethylamine, pyridine or 2, 6-lutidine
  • aromatics such as toluene and o-, m-, p-xylene
  • halogenated hydrocarbons such as methylene chloride, chloroform, 1,2-dichloroethane and chlorobenzene
  • aliphatic or cyclic ethers such as 1,2-dimethoxyethane, tetrahydrofuran and dioxane
  • esters such as
  • the amount of phosgenating or thiophosgenating agent is not critical and is usually between 0.9 and
  • the enamine esters II can be prepared by methods known per se, e.g. one of the following:
  • Suitable solvents or diluents are, in particular, water solvents which are azeotropically miscible with water, for example aromatics such as benzene, toluene and o-, m-, p-xylene, halogenated hydrocarbons such as methylene chloride, chloroform, carbon tetrachloride and chlorobenzene, aliphatic and cyclic ethers such as 1,2 -Dimethoxyethane, tetrahydrofuran and dioxane, or cyclohexane, but also alcohols such as methanol and ethanol, into consideration.
  • aromatics such as benzene, toluene and o-, m-, p-xylene
  • halogenated hydrocarbons such as methylene chloride, chloroform, carbon tetrachloride and chlorobenzene
  • aliphatic and cyclic ethers such as 1,2 -Dimethoxye
  • Suitable acidic catalysts are preferably strong mineral acids such as sulfuric acid and hydrochloric acid, phosphorus-containing acids such as orthophosphoric acid and polyphosphoric acid, organic acids such as p-toluenesulfonic acid and acidic cation exchangers such as "Amberlyst 15" (Fluka).
  • Suitable basic catalysts are, for example, metal hydrides such as sodium hydride and particularly preferably metal alcoholates such as sodium methoxide and ethanolate.
  • metal hydrides such as sodium hydride and particularly preferably metal alcoholates such as sodium methoxide and ethanolate.
  • the ⁇ -ketoester XI and the phenylurea XII are expediently used in a stoichiometric ratio or one works with a slight excess of one or the other component up to about 10 mol%.
  • reaction is carried out at a temperature between 60 and 120 ° C., for the rapid removal of water formed, preferably at the boiling point of the reaction mixture.
  • L 3 represents C 1 -C 4 alkyl or phenyl.
  • This reaction can be carried out, for example, in an inert, water-miscible, organic solvent, for example an aliphatic or cyclic ether such as diethyl ether, 1,2-dimethoxyethane, tetrahydrofuran and dioxane, or a lower alcohol, in particular ethanol, the reaction temperature normally being between 50 and 150 ° C, preferably at the boiling point of the reaction mixture.
  • an inert, water-miscible, organic solvent for example an aliphatic or cyclic ether such as diethyl ether, 1,2-dimethoxyethane, tetrahydrofuran and dioxane, or a lower alcohol, in particular ethanol, the reaction temperature normally being between 50 and 150 ° C, preferably at the boiling point of the reaction mixture.
  • reaction can also be carried out in an aromatic diluent such as benzene, toluene and o-, m-, p-xylene, in which case either the addition of an acidic catalyst such as hydrochloric acid and p-toluenesulfonic acid or a base, for example an alkali metal alcoholate such as Sodium methoxide and sodium ethanolate, is recommended.
  • an acidic catalyst such as hydrochloric acid and p-toluenesulfonic acid or a base
  • an alkali metal alcoholate such as Sodium methoxide and sodium ethanolate
  • reaction is conveniently carried out in the presence of an essentially anhydrous, aprotic, organic solvent or diluent, for example an aliphatic or cyclic ether such as diethyl ether, 1,2-dimethoxyethane, tetrahydrofuran and dioxane, an aliphatic or aromatic hydrocarbon such as n-hexane, benzene, Toluene and o-, m-, p-xylene, a halogenated, aliphatic hydrocarbon such as methylene chloride, chloroform, carbon tetrachloride, 1,2-dichloroethane and chlorobenzene, an aprotic, polar solvent such as dimethylformamide, hexamethylphosphoric acid triamide and dimethyl sulfoxide, or a mixture of the above
  • an aliphatic or cyclic ether such as diethyl ether, 1,2-dimethoxyethane, tetrahydrofuran
  • a metal hydride base such as sodium and potassium hydride, an alkali metal or alkaline earth metal alcoholate such as sodium methoxide, sodium ethanolate and potassium tert-butoxide, or an organic tertiary base such as triethylamine and pyridine, the organic base simultaneously serving as a solvent can.
  • a metal hydride base such as sodium and potassium hydride
  • an alkali metal or alkaline earth metal alcoholate such as sodium methoxide, sodium ethanolate and potassium tert-butoxide
  • an organic tertiary base such as triethylamine and pyridine
  • the starting materials are expediently used in a stoichiometric ratio or one works with a slight excess of one or the other component up to about 20 mol%. If one works without solvent in the presence of an organic base, this is present in a large excess.
  • the reaction temperature is preferably in the range between (-80) and 50 ° C, particularly preferably between (-60) and 30 ° C.
  • the II obtained is converted directly (ie in situ) according to process variant a) into the corresponding compound I using excess base.
  • Any by-products e.g. C-alkylation products at
  • L 1 and L 4 represent C 1 -C 4 alkyl or phenyl.
  • This reaction is conveniently carried out in an aprotic, polar solvent or diluent such as dimethylformamide, 2-butanone, dimethyl sulfoxide and acetonitrile, advantageously in the presence of a base, for example an alkali metal or alkaline earth metal alcoholate, in particular a sodium alkanolate such as sodium methoxide, an alkali metal carbonate or alkaline earth metal , in particular sodium carbonate, or an alkali metal hydride such as lithium and sodium hydride.
  • a base for example an alkali metal or alkaline earth metal alcoholate, in particular a sodium alkanolate such as sodium methoxide, an alkali metal carbonate or alkaline earth metal , in particular sodium carbonate, or an alkali metal hydride such as lithium and sodium hydride.
  • the reaction temperature is generally between 80 and 180 ° C, preferably at the boiling point of the reaction mixture.
  • the information for method q) applies.
  • a sodium alcoholate is used as the base and the alcohol formed in the course of the reaction is distilled off continuously.
  • the enamine esters of the formula II prepared in this way can be cyclized to a salt of the substituted 3-phenylurazils I without isolation from the reaction mixture according to process variant a).
  • This reaction is advantageously carried out in the presence of an essentially anhydrous, aprotic, organic solvent or diluent, if desired in the presence of a metal hydride base such as sodium and potassium hydride or an organic tertiary base such as triethylamine and pyridine, where the organic base can also serve as a solvent.
  • a metal hydride base such as sodium and potassium hydride or an organic tertiary base such as triethylamine and pyridine, where the organic base can also serve as a solvent.
  • the reaction temperature is generally between (-80) and 150 ° C, preferably between (-60) ° C and the particular boiling point of the solvent.
  • reaction is conveniently carried out in the presence of an im
  • anhydrous, aprotic organic solvents and diluents for example an aliphatic or cyclic ether such as diethyl ether, 1,2-dimethoxyethane,
  • Tetrahydrofuran and dioxane an aliphatic or aromatic hydrocarbon such as n-hexane, benzene, toluene and o-, m-, p-xylene, a halogenated aliphatic hydrocarbon such as methylene chloride, chloroform, carbon tetrachloride,
  • 1,2-dichloroethane and chlorobenzene an aprotic, polar solvent such as dimethylformamide, hexamethylphosphoric triamide and dimethyl sulfoxide, or a mixture of the solvents mentioned.
  • a metal hydride base such as sodium and potassium hydride, an alkali metal or
  • Alkaline earth metal alcoholates such as sodium methoxide
  • organic tertiary base such as triethylamine and pyridine
  • the organic base can simultaneously serve as a solvent.
  • the starting materials are expediently used in a stoichiometric ratio or one works with a slight excess of one or the other component up to about 20 mol%. You work without
  • the reaction temperature is preferably in the range between (-80) and 150 ° C, particularly preferably between (-30) and the reflux temperature of the solvent used.
  • the enamine carboxylates of formula III are also new and can be used as herbicides. They can be prepared by processes known per se, for example from an aniline derivative of the formula XVI according to the following reaction scheme:
  • R 4 ' and R 5' are hydrogen or
  • reaction equations 1 and 2 are preferably carried out in an anhydrous, inert aprotic solvent, for example in a halogenated hydrocarbon such as methylene chloride, chloroform, carbon tetrachloride and chlorobenzene, an aromatic hydrocarbon such as benzene, toluene and o-, m-, p-xylene, or one aliphatic or cyclic ethers such as diethyl ether, dibutyl ether, 1,2-dimethoxyethane,
  • a halogenated hydrocarbon such as methylene chloride, chloroform, carbon tetrachloride and chlorobenzene
  • an aromatic hydrocarbon such as benzene, toluene and o-, m-, p-xylene
  • one aliphatic or cyclic ethers such as diethyl ether, dibutyl ether, 1,2-dimethoxyethane,
  • a basic catalyst e.g. 4-pyrrolidinopyridine, 4-dimethylamino-pyridine, 1,2-diazabicyclo [2,2,2] octane, 1,5-diazabicyclo [4,3,0] non-5-ene, 1,8-diazabicyclo [5, 4.0] undec-7-ene or diethylamine. Since the reaction is exothermic, a reaction temperature between (-10) and 50 ° C, preferably between 10 and 30 ° C is generally sufficient.
  • reaction according to reaction equation (G13) is an aminolysis, which is usually either without a solvent [cf. e.g. J. Soc. Dyes Col. 42, 81 (1926), Ber. 64, 970 (1931); Org. Synth., Coll. Vol. IV, 80 (1963) and JACS 70, 2402 (1948)] or in an inert anhydrous solvent or diluent, in particular in an aprotic solvent, for example in an optionally halogenated aromatic such as toluene, o-, m-, p- Xylene and chlorobenzene. It is recommended to work in the presence of a basic catalyst, eg a higher boiling amine [see for example Helv. Chim. Acta 11, 779 (1928) and US 2,416,738] or pyridine.
  • a basic catalyst eg a higher boiling amine [see for example Helv. Chim. Acta 11, 779 (1928) and US 2,416,738] or pyridine.
  • the reaction temperature is preferably between about 20 and 160 ° C.
  • the starting materials are expediently used in a stoichiometric ratio or one works with a slight excess of one or the other component up to about 10 mol%. If one works in the presence of a basic catalyst, an amount between 0.5 and 200 mol%, based on the amount of a starting material, is generally sufficient.
  • Suitable solvents or diluents are, in particular, water which is azeotropically miscible with water, for example aromatics such as benzene, toluene and o-, m-, p-xylene or halogenated hydrocarbons such as carbon tetrachloride and chlorobenzene.
  • Suitable catalysts are in particular strong mineral acids such as sulfuric acid, organic acids such as p-toluenesulfonic acid, phosphorus-containing acids such as orthophosphoric acid and polyphosphoric acid or acidic cation exchangers such as "Amberlyst 15" (Fluka).
  • reaction temperature is between about 70 and 150 ° C; however, to rapidly remove the water of reaction formed, it is expedient to work at the boiling point of the solvent.
  • the pyrimidone derivatives IVa and IVb, from which method d) starts can by halogenation, preferably chlorination and bromination, of 3-phenylurazilene I, in which R 3 is hydrogen, without solvent or in the presence of an inert solvent or diluent be preserved.
  • aprotic organic liquids for example aliphatic or aromatic hydrocarbons such as n-hexane, benzene, toluene and o-, m-, p-xylene, halogenated aliphatic hydrocarbons such as methylene chloride, chloroform and 1,2-dichloroethane, halogenated come as solvents or diluents aromatic hydrocarbons such as chlorobenzene, or tertiary amines such as N, N-dimethylaniline.
  • Particularly suitable halogenating agents are thionyl chloride, phosphorus pentachloride, phosphorus oxychloride, phosphorus pentabromide or phosphoryl bromide.
  • a mixture of phosphorus pentachloride and phosphorus oxychloride or of phosphorus pentabromide and phosphoryl bromide can also be particularly advantageous.
  • halogenating agent is not critical; For a complete reaction, at least equimolar amounts of halogenating agent and starting material to be halogenated are required. However, a 1- to 8-fold molar excess of halogenating agent can also be advantageous.
  • reaction temperatures are generally between 0 ° C and the reflux temperature of the reaction mixture, preferably between 20 and 120 ° C. x) C-acylation of an enamine of formula XXIV with an isocyanate or isothiocyanate of formula XII 4
  • reaction is conveniently carried out in the presence of an im
  • anhydrous, aprotic organic solvents and diluents for example an aliphatic or cyclic ether such as diethyl ether, 1,2-dimethoxyethane,
  • Tetrahydrofuran and dioxane an aliphatic or aromatic hydrocarbon such as n-hexane, benzene, toluene and o-, m-, p-xylene, a halogenated aliphatic hydrocarbon such as methylene chloride, chloroform, carbon tetrachloride,
  • 1,2-dichloroethane and chlorobenzene 1,2-dichloroethane and chlorobenzene, an aprotic, polar solvent such as dimethylformamide, hexamethylphosphoric triamide and dimethyl sulfoxide, or a mixture of the solvents mentioned.
  • an aprotic, polar solvent such as dimethylformamide, hexamethylphosphoric triamide and dimethyl sulfoxide, or a mixture of the solvents mentioned.
  • organic tertiary base such as triethylamine and pyridine
  • the organic base can simultaneously serve as a solvent
  • the starting materials are expediently used in a stoichiometric ratio or one works with a slight excess of one or the other component up to about 20 mol%. You work without
  • the reaction temperature is preferably in the range between (-80) and 150 ° C, particularly preferably between (-30) and the reflux temperature of the solvent used.
  • the process can be carried out in an inert, essentially anhydrous solvent or diluent or without a solvent, the compounds XIX preferably being reacted with phosgene or trichloromethyl chloroformate.
  • Suitable solvents or diluents are, in particular, aprotic, organic solvents, for example aromatics such as toluene and o-, m-, p-xylene, halogenated hydrocarbons such as methylene chloride, chloroform, 1,2-dichloroethane and chlorobenzene, aliphatic or cyclic ethers such as 1,2 -Dimethoxyethane, tetrahydrofuran and dioxane, or esters such as ethyl acetate, and mixtures of these solvents.
  • aromatics such as toluene and o-, m-, p-xylene
  • halogenated hydrocarbons such as methylene chloride, chloroform, 1,2-dichloroethane and chlorobenzene
  • aliphatic or cyclic ethers such as 1,2 -Dimethoxyethane, tetrahydrofuran and dioxane, or
  • the carbamic acid chlorides XVII are normally obtained, while a further increase in temperature up to the boiling point of the reaction mixture, on the other hand, predominantly leads to the formation of the phenyl isocyanates XIV which, with ammonia or a reactive derivative of ammonia the phenylurea derivatives XII can be implemented.
  • M ⁇ stands for the equivalent of a metal ion, in particular for an alkali metal ion such as sodium and potassium.
  • the reaction takes place in an inert solvent or diluent, for example in an aromatic hydrocarbon such as toluene and o-, m-, p-xylene, in an aliphatic or cyclic ether such as tetrahydrofuran and dioxane, in a lower alcohol such as methanol and ethanol Water or in a mixture of the solvents mentioned.
  • an aromatic hydrocarbon such as toluene and o-, m-, p-xylene
  • an aliphatic or cyclic ether such as tetrahydrofuran and dioxane
  • a lower alcohol such as methanol and ethanol Water or in a mixture of the solvents mentioned.
  • the amount of cyanate is not critical; For a complete reaction, at least equimolar amounts of aniline derivative XIX and cyanate are required, but an excess of cyanate, up to about 100 mol%, can also be advantageous.
  • the reaction temperature is generally between 0 ° C and the reflux temperature of the reaction mixture.
  • L 4 represents C 1 -C 4 alkyl or phenyl
  • L 5 stands for halogen, preferably chlorine or bromine, for C 1 -C 4 alkoxy or phenoxy.
  • Suitable solvents or diluents are aromatic hydrocarbons such as toluene and o-, m-, p-xylene, halogenated hydrocarbons such as methylene chloride, chloroform, 1,2-dichloroethane and chlorobenzene, aliphatic or cyclic
  • Ethers such as 1,2-dimethoxyethane, tetrahydrofuran and dioxane, esters such as ethyl acetate, alcohols such as methanol and ethanol, or water or two-phase mixtures of an organic solvent and water.
  • the reaction advantageously takes place in the presence of a base, e.g. an alkali metal hydroxide, carbonate or alcoholate such as sodium hydroxide, sodium carbonate, sodium methoxide and sodium ethanolate or a tertiary amine such as pyridine and triethylamine.
  • a base e.g. an alkali metal hydroxide, carbonate or alcoholate such as sodium hydroxide, sodium carbonate, sodium methoxide and sodium ethanolate or a tertiary amine such as pyridine and triethylamine.
  • a catalyst e.g. a Lewis acid such as antimony trichloride can be added.
  • the starting compounds and the base are expediently used in a stoichiometric ratio, but one or the other component can also be present in an excess, up to about 100 mol%.
  • the amount of catalyst is 1 to 50 mol%, preferably 2 to 30 mol%, based on the amount of used
  • reaction temperature is between (-40) ° C and the boiling point of the reaction mixture.
  • reaction mixtures are generally worked up by methods known per se, for example by removing the solvent, distributing the residue in a mixture of water and a suitable organic solvent and isolating the product of the organic phase.
  • the substituted 3-phenylurazils I, Ia and Ib can be used in the. Production arise as mixtures of isomers, however
  • optically active isomers can be synthesized, for example, from corresponding optically active starting materials.
  • the compounds of the formulas I, Ia and Ib can be prepared in the ways described above. However, it is also possible in individual cases to prepare certain compounds I advantageously from other compounds I by ester hydrolysis, amidation, esterification, transesterification, etherification, ether cleavage, olefination, reduction, oxidation or ring closure reaction at the positions of the radicals R 4 , R 5 and W. .
  • the substituted 3-phenylurazils I, Ia and Ib are suitable, both as isomer mixtures and in the form of the pure isomers, as herbicides. They are generally compatible and therefore selective in broadleaved crops and in monocotyledonous plants.
  • the substituted phenylurazils Ia and Ib or agents containing them can be used in a large number of crop plants for eliminating undesired plants, the following crops being mentioned as examples:
  • Coffea arabica Coffea canephora, coffee
  • Gossypium hirsutum Gossypium arboreum, cotton
  • Nicotiana tabacum N. rustica
  • the substituted 3-phenylurazils I, Ia and Ib are also suitable for the desiccation and defoliation of plants.
  • dessicants they are particularly suitable for drying out the aerial parts of crops such as potatoes, rapeseed, sunflower and soybeans. This enables fully mechanized harvesting of these important crops.
  • ease of harvesting which is made possible by the temporally concentrated decrease or decrease in the adhesive strength on the tree in the case of citrus fruits, olives or other types and varieties of pome, stone and nuts.
  • the same mechanism that is, the promotion of the formation of separating tissue between the fruit or leaf and shoot part of the plant is also essential for a well controllable defoliation of useful plants such as cotton.
  • the shortening of the time interval in which the individual cotton plants ripen leads to an increased
  • substituted 3-phenylurazils of the formulas I, Ia and Ib can also be used as growth regulators or for controlling pests from the class of the insects, arachnids and nematodes. They can be used to control pests in crop protection as well as in the hygiene, storage protection and veterinary sectors.
  • the harmful insects include from the order of the
  • Butterflies for example Agrotis ypsilon, Agrotis segetum, Alabama argillacea, Anticarsia gemmatalis, Argyresthia conjugella, Autographa gamma, Bupalus piniarius, Cacoecia murinana, Capua reticulana, Cheimatobia brumata,
  • Choristoneura fumiferana Choristoneura occidentalis, Cirphis unipuncta, Cydia pomonella, Dendrolimus pini, Diaphania
  • Sparganothis pilleriana Spodoptera frugiperda, Spodoptera littoralis, Spodoptera litura, Thaumatopoea pityocampa, Tortrix viridana, Trichoplusia ni, Zeiraphera canadensis.
  • Leptinotarsa decemlineata Limonius californicus, Lissorhoptrus oryzophilus, Melanotus communis, Meligethes aeneus, Melolontha hippocastani, Melolontha melolontha, Onlema oryzae,
  • Diptera From the order of the two-winged species (Diptera), for example, Aedes aegypti, Aedes vexans, Anastrepha ludens, Anopheles maculipennis, Ceratitis capitata, Chrysomya bezziana, Chrysomya hominivorax, Chrysomya macellaria, Contarinia sorghicola, Cordylobia
  • Liriomyza sativae Liriomyza trifolii, Lucilia caprina, Lucilia cuprina, Lucilia sericata, Lycoria pectoralis, Mayetiola destructor, Musca domestica, Muscina stabulans, Oestrus ovis, Oscinella frit, Pegomya hysocyami, Phorbia antiqua, Phorbia brassagaroletata, Phorbia brassagarolata, Phorbia brassagarolatais , Tabanus bovinus, Tipula oleracea, Tipula paludosa.
  • Thrips for example Frankliniella fusca, Frankliniella occidentalis, Frankliniella tritici, Scirtothrips citri, Thrips oryzae, Thrips palmi, Thrips tabaci.
  • From the order of the hymenoptera for example Athalia rosae, Atta cephalotes, Atta sexdens, Atta texana, Hoplocampa minuta, Hoplocampa testudinea, Monomorium pharaonis, Solenopsis geminata, Solenopsis invicta.
  • suckers for example Acyrthosiphon onobrychis, Adelges laricis, Aphidula nasturtii; Aphis fabae, Aphis pomi, Aphis sambuci, Brachycaudus cardui, Brevicoryne brassicae, Cerosipha gossypii, Dreyfusia
  • Dysaulacorthum pseudosolani Empoasca fabae, Macrosiphum avenae, Macrosiphum euphorbiae, Macrosiphon rosae, Megoura viciae, Metopolophium dirhodum, Myzodes persicae, Myzus cerasi,
  • Nilaparvata lugens Pemphigus bursarius, Perkinsiella
  • Acarina such as Amblyomma americanum, Amblyomma variegatum, Argas persicus, Boophilus annulatus, Boophilus decoloratus, Boophilus microplus, Brevipalpus phoenicis, Bryobia praetiosa, Dermacentor silvarum, Eotetranychus carpini, Eriophyes sheldoni, Hyinomminsusodes, Hyinomminsus, Ialobinus megnini, Paratetranychus pilosus, Permanyssus gallinae, Phyllocaptrata oleivora, Polyphagotarsonemus latus, Psoroptes ovis, Rhipicephalus appendiculatus, Rhipicephalus evertsi, Saccoptes scabiei, Tetranychus cinnabarinus, Tetranychuschus tetranychus kus
  • Carina such as Amblyomma american
  • root gall nematodes e.g. Meloidogyne hapla, Meloidogyne incognita
  • Dispersions emulsions, oil dispersions, pastes, dusts, spreading agents, granules by spraying, atomizing, dusting, scattering or pouring can be used.
  • the application forms depend entirely on the purposes; in any case, they should ensure the finest possible distribution of the active compounds according to the invention.
  • the formulations are prepared in a known manner, for example by stretching the active ingredient with solvents and / or carriers, if desired using emulsifiers and dispersants, and in the case of water as a diluent, other organic solvents can also be used as auxiliary solvents.
  • mineral oil fractions of medium to high boiling point such as kerosene and diesel oil, furthermore coal tar oils and oils of vegetable or animal origin, solvents such as aromatics (e.g. toluene, xylene), chlorinated aromatics (e.g. chlorobenzenes), paraffins (e.g. Petroleum fractions), alcohols (e.g. methanol, ethanol, butanol, cyclohexanol), ketones (e.g. cyclohexanone, isophorone), amines (e.g.
  • Carriers such as natural stone powder (e.g. kaolins, clays, talc, chalk) and synthetic stone powder (e.g. highly disperse silica, silicates); Emulsifiers such as nonionic and anionic emulsifiers (e.g. polyoxyethylene fatty alcohol ethers, alkyl sulfonates and aryl sulfonates) and dispersants such as lignin sulfite liquors and methyl cellulose.
  • Carriers such as natural stone powder (e.g. kaolins, clays, talc, chalk) and synthetic stone powder (e.g. highly disperse silica, silicates); Emulsifiers such as nonionic and anionic emulsifiers (e.g. polyoxyethylene fatty alcohol ethers, alkyl sulfonates and aryl sulfonates) and dispersants such as lignin sulfite liquors and methyl cellulose.
  • Aqueous use forms can be prepared from emulsion concentrates, dispersions, pastes, wettable powders or water-dispersible granules by adding water.
  • emulsion concentrates, dispersions, pastes, wettable powders or water-dispersible granules by adding water.
  • Substrates as such or dissolved in an oil or solvent can be homogenized in water by means of wetting agents, adhesives, dispersants or emulsifiers.
  • wetting agents adhesives, dispersants or emulsifiers.
  • concentrates consisting of active substance, wetting agent, adhesive, dispersant or emulsifier and possibly solvent or oil can also be prepared which are suitable for dilution with water.
  • alkali, alkaline earth, ammonium salts of aromatic sulfonic acids e.g. Lignin-,
  • Granules e.g. Coated, impregnated and homogeneous granules can be produced by binding the active ingredients to solid carriers.
  • Solid carriers are mineral earths such as silica gel, silicas, silica gels, silicates, talc, kaolin, limestone, lime, chalk, bolus, loess, clay, dolomite, diatomaceous earth, calcium and magnesium sulfate, magnesium oxide, ground plastics, fertilizers such as ammonium sulfate, ammonium phosphate, Ammonium nitrate, ureas and herbal products, such as
  • concentrations of the active ingredients I, Ia and Ib in the ready-to-use preparations can be varied within a wide range, for example between 0.0001 and 95% by weight. Concentrations between 0.01 and 95% by weight, preferably between 0.5 and 90% by weight, of active ingredient are recommended for use as herbicides or for regulating plant growth. For use as
  • Insecticides are formulations with 0.0001 to 10% by weight, preferably 0.01 to 1% by weight, of active ingredient.
  • the active ingredients are used in a purity of 90% to 100%, preferably 95% to 100% (according to the NMR spectrum).
  • the mixture of this dispersion with 100,000 parts by weight of water contains 0.02% by weight of the active ingredient.
  • Plant growth regulators can be done pre-emergence or post-emergence.
  • the plants are usually sprayed or dusted with the active compounds or the seeds of the test plants are treated with the active compounds. If the active ingredients are less compatible with certain crop plants, application techniques can be used in which the herbicidal compositions are sprayed with the aid of sprayers in such a way that the leaves of the sensitive crop plants are not hit wherever possible, while the active ingredients are applied to the leaves of unwanted plants growing below them or the uncovered floor area (post-directed, lay-by).
  • the application rates of active ingredient are 0.001 to 5.0, preferably 0.01 to 2 kg / ha of active substance (as), depending on the control target, season, target plants and growth stage.
  • the substituted 3-phenylurazils I, Ia and Ib can be mixed with numerous representatives of other herbicidal or growth-regulating active compound groups and applied together.
  • diazines, 4H-3,1-benzoxazine derivatives, benzothiadiazinones, 2,6-dinitroanilines, N-phenyl carbamates, thiol carbamates, halocarboxylic acids, triazines, amides, ureas, diphenyl ethers, triazinones, uraciles, benzofuran derivatives, cyclohexane-1,3 come as mixing partners -dione derivatives which carry, for example, a carboxy or carbimino group in the 2-position, quinolinecarboxylic acid derivatives, imidazolinones, sulfonamides,
  • the substituted 3-phenylurazils I, Ia and Ib can also be used together with other crop protection agents such as herbicides,
  • Growth regulators pesticides, fungicides and bactericides are applied. These agents can be added to the agents according to the invention in a weight ratio of 1: 100 to 100: 1, if desired also only immediately before use (tank mix). Also of interest is the miscibility with mineral salt solutions, which are used to remedy nutritional and trace element deficiencies. Non-phytotoxic oils and oil concentrates can also be added. Manufacturing examples
  • n-butanolate solution in n-butanol (prepared from 0.3 g of 80% sodium hydride and 50 ml of n-butanol) and stirred for 5 hours at room temperature. Then was at 0-5 ° C with 10 percent. Hydrochloric acid neutralized and the solution obtained at 0-5 ° C in 100 ml of water stirred. The aqueous phase was extracted with 100 ml of toluene, the combined organic phases were washed three times with 50 ml of water each time, dried over sodium sulfate and concentrated. The oil obtained was chromatographed on silica gel (dichloromethane), and the oil obtained was stirred with petroleum ether. The solid obtained was filtered off using
  • Washed and dried petroleum ether Washed and dried petroleum ether.
  • 1,2-dichloroethane was stirred at room temperature for 16 h. 0.2 g of sodium hydrogen carbonate was added, the mixture was stirred well and filtered off. The precipitate was washed with dichloromethane, the combined organic filtrates over sodium sulfate
  • Washed petroleum ether and dried in vacuo Washed petroleum ether and dried in vacuo.

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Abstract

L'invention concerne des 3-phényluraciles substitués de formule (I) dans laquelle X1 à X4 représentent O ou S; W représente -CH=O éventuellement substitué, -CH=S, -CH=NH, -CH(X3R6)(X4R7), (a), (b), (c), (d) ou bien (e); R6 et R7 représentent alkyle C1-C6, alcényle C3-C6, alkinyle C3-C6, alcoxy C1-C6-alkyle C1-C6 ou bien représentent ensemble une chaîne de carbone; R10 représente H, OH, SH, un groupe éther, un groupe thioéther, alkyle C1-C6 éventuellement substitué, alcényle C3-C6, alkinyle C3-C6, cycloalkyle C3-C7, amino éventuellement substitué ou phényle éventuellement substitué; R1 représente halogène, CN, NO2 ou bien CF3; R2 représente H ou halogène; R3 représente H, alkyle C1-C6, alcényle C3-C6, alkinyle C3-C6, cycloalkyle C3-C8, cycloalkylcarbonyle C3-C8, cyanoalkyle C1-C6, haloalkyle C1-C6, alcoxy C1-C6-alkyle C1-C6, CHO, alcanoyle C1-C6, alcoxycarbonyle C1-C6, haloalkylcarbonyle C1-C6, amino éventuellement substitué, phényle éventuellement substitué ou phényl-alkyle C1-C6; R4 et R5 représentent H, CN, halogène, alkyle C1-C6 éventuellement substitué, alcényle C2-C6, alkinyle C2-C6, cycloalkyle C3-C7 ou phényle éventuellement substitué; R5 représente également NO2, CHO, alkylcarbonyle C1-C6, haloalkylcarbonyle C1-C6, alcoxycarbonyle C1-C6, ou amino éventuellement substitué, ou bien R4 + R5 représentent une chaîne de carbone éventuellement substituée; sauf si R4 représente CF3 et simultanément R5 représente H lorsque W = -CH=CH-CO-R10, R10 représentant alcoxy C1-C6 ou bien cycloalcoxy C3-C7; l'invention concerne également les sels et les énoléthers des 3-phényluracyles de formule (I) dans laquelle R3 représente H. Ces 3-phényluracyles sont utilisés comme agents de dessication/de défoliation de plantes, comme insecticides ou herbicides.The invention relates to substituted 3-phenyluracils of formula (I) wherein X1 to X4 represent O or S; W represents -CH = O optionally substituted, -CH = S, -CH = NH, -CH (X3R6) (X4R7), (a), (b), (c), (d) or else (e); R6 and R7 represent C1-C6 alkyl, C3-C6 alkenyl, C3-C6 alkinyl, C1-C6 alkoxy-C1-C6 alkyl or else together represent a carbon chain; R10 represents H, OH, SH, an ether group, a thioether, optionally substituted C1-C6 alkyl, C3-C6 alkenyl, C3-C6 alkinyl, C3-C7 cycloalkyl, optionally substituted amino or optionally substituted phenyl; R1 represents halogen, CN, NO2 or else CF3; R2 represents H or halogen; R3 represents H, C1-C6 alkyl, C3-C6 alkenyl, C3-C6 alkinyl, C3-C8 cycloalkyl, C3-C8 cycloalkylcarbonyl, C1-C6 cyanoalkyl, C1-C6 haloalkyl, C1-C6 alkoxy-C1-C6 alkyl, CHO , C1-C6 alkanoyl, C1-C6 alkoxycarbonyl, C1-C6 haloalkylcarbonyl, optionally substituted amino, optionally substituted phenyl or phenyl-C1-C6 alkyl; R4 and R5 represent H, CN, halogen, optionally substituted C1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkinyl, C3-C7 cycloalkyl or optionally substituted phenyl; R5 also represents NO2, CHO, C1-C6 alkylcarbonyl, C1-C6 haloalkylcarbonyl, C1-C6 alkoxycarbonyl, or optionally substituted amino, or else R4 + R5 represent an optionally substituted carbon chain; unless R4 represents CF3 and simultaneously R5 represents H when W = -CH = CH-CO-R10, R10 representing C1-C6 alkoxy or alternatively C3-C7 cycloalkoxy; the invention also relates to the salts and the enolethers of 3-phenyluracyls of formula (I) in which R3 represents H. These 3-phenyluracyls are used as desiccating / defoliating agents for plants, as insecticides or herbicides.

Description

SUBSTITUIERTE-3-PHENYLURAZILE ALS HERBIZIDE  SUBSTITUTED-3-PHENYLURAZILES AS HERBICIDES
Beschreibung description
Die vorliegende Erfindung betrifft neue substituierte 3-Phenylurazile der allgemeinen Formel I The present invention relates to new substituted 3-phenylurazils of the general formula I.
in der die Variablen folgende Bedeutung haben: X1, X2 in which the variables have the following meaning: X 1 , X 2
Sauerstoff oder Schwefel;  Oxygen or sulfur;
W W
-C(R8)=X5, -C(R8)(X3R6)(X4R7), -C(R8)=C(R9)-CN, -C (R 8 ) = X 5 , -C (R 8 ) (X 3 R 6 ) (X 4 R 7 ), -C (R 8 ) = C (R 9 ) -CN,
-C(R8)=C(R9)-CO-R10, -CH(R8)-CH(R9)-CO-R10, -C (R 8 ) = C (R 9 ) -CO-R 10 , -CH (R 8 ) -CH (R 9 ) -CO-R 10 ,
-C(R8)=C(R9)-CH2-CO-R10, -C (R8)=C (R9 ) -C (R11 )=C (R12)-CO-R10 oder -C(R8)=C(R9)-CH2-CH(R13)-CO-R10 mit -C (R 8 ) = C (R 9 ) -CH 2 -CO-R 10 , -C (R 8 ) = C (R 9 ) -C (R 11 ) = C (R 12 ) -CO-R 10 or -C (R 8 ) = C (R 9 ) -CH 2 -CH (R 13 ) -CO-R 10 with
X3, X4 Sauerstoff oder Schwefel; X5 Sauerstoff, Schwefel oder ein Rest -NR14, mit X 3 , X 4 oxygen or sulfur; X 5 oxygen, sulfur or a residue -NR 14 , with
R14 Wasserstoff, Hydroxyl, C1-C6-Alkyl, C3-C6-Alkenyl, C3-C6-Alkinyl, C3-C7-Cycloalkyl, R 14 is hydrogen, hydroxyl, C 1 -C 6 alkyl, C 3 -C 6 alkenyl, C 3 -C 6 alkynyl, C 3 -C 7 cycloalkyl,
C1-C6-Halogenalkyl, C1-C6-Alkoxy-C1-C6-alkyl, C1-C6-Alkoxy, C3-C6-Alkenyloxy, C3-C6-Alkinyloxy, C5-C7-Cycloalkoxy, C5-C7-Cycloalkenyloxy, C 1 -C 6 haloalkyl, C 1 -C 6 alkoxy-C 1 -C 6 alkyl, C 1 -C 6 alkoxy, C 3 -C 6 alkenyloxy, C 3 -C 6 alkynyloxy, C 5 -C 7 cycloalkoxy, C 5 -C 7 cycloalkenyloxy,
C1-C6-Halogenalkoxy, C3-C6-Halogenalkenyloxy, Hydroxy-C1-C6-alkoxy, Cyano-C1-C6-alkoxy, C 1 -C 6 haloalkoxy, C 3 -C 6 haloalkenyloxy, hydroxy-C 1 -C 6 alkoxy, cyano-C 1 -C 6 alkoxy,
C3-C7-Cycloalkyl-C1-C6-alkoxy, C 3 -C 7 cycloalkyl-C 1 -C 6 alkoxy,
C1-C6-Alkoxy-C1-C6-alkoxy, C1-C6-Alkoxy- C3-C6-alkenyloxy, C1-C6-Alkylcarbonyloxy, C 1 -C 6 alkoxy-C 1 -C 6 alkoxy, C 1 -C 6 alkoxy- C 3 -C 6 alkenyloxy, C 1 -C 6 alkylcarbonyloxy,
C1-C6-Halogenalkylcarbonyloxy, C1-C6-Alkylcarbamoyloxy, C1-C6-Halogen- alkylcarbamoyloxy, C1-C6-Alkoxycarbonyl- C2-C6-alkoxy, C1-C6-AlkyIthio-C1-C6-alkoxy, Di-(C1-C6-alkyl)-amino-C1-C6-alkoxy, Phenyl, das einen bis drei der folgenden Substituenten tragen kann: Cyano, Nitro, Halogen, C1-C6-Alkyl, C 1 -C 6 haloalkylcarbonyloxy, C 1 -C 6 alkylcarbamoyloxy, C 1 -C 6 haloalkylcarbamoyloxy, C 1 -C 6 alkoxycarbonyl- C 2 -C 6 alkoxy, C 1 -C 6 alkyIthio-C 1 -C 6 alkoxy, Di- (C 1 -C 6 -alkyl) -amino-C 1 -C 6 -alkoxy, phenyl, which can carry one to three of the following substituents: cyano, nitro, halogen, C 1 -C 6 -alkyl,
C2-C6-Alkenyl, C1-C6-Halogenalkyl, C1-C6-Alkoxy und C1-C6-Alkoxycarbonyl, Phenyl-C1-C6-alkoxy, Phenyl-C3-C6-alkenyloxy oder Phenyl-C3-C6-alkinyloxy, wobei jeweils eine oder zwei Methylengruppen der Kohlenstoffketten durch -O-, -S- oder C 2 -C 6 alkenyl, C 1 -C 6 haloalkyl, C 1 -C 6 alkoxy and C 1 -C 6 alkoxycarbonyl, phenyl-C 1 -C 6 alkoxy, phenyl-C 3 -C 6 - alkenyloxy or phenyl-C 3 -C 6 -alkynyloxy, in each case one or two methylene groups of the carbon chains by -O-, -S- or
-N(C1-C6-Alkyl)- ersetzt sei n können und wobei der Phenylring jeweils einen bis drei der folgenden Substituenten tragen kann: Cyano, Nitro, Halogen, C1-C6-Alkyl, C2-C6-Alkenyl, C1-C6-Halogenalkyl, C1-C6-Alkoxy und C1-C6-Alkoxycarbonyl, Heterocyclyl, Heterocyclyl-C1-C6-alkoxy, Heterocyclyl- C3-C6-alkenyloxy, Heterocyclyl-C3-C6-alkinyloxy, wobei jeweils eine oder zwei Methylengruppen der Kohlenstoffketten durch -O-, -S- oder -N (C 1 -C 6 -alkyl) - can be replaced and the phenyl ring can in each case carry one to three of the following substituents: cyano, nitro, halogen, C 1 -C 6 -alkyl, C 2 -C 6 - Alkenyl, C 1 -C 6 haloalkyl, C 1 -C 6 alkoxy and C 1 -C 6 alkoxycarbonyl, heterocyclyl, heterocyclyl-C 1 -C 6 alkoxy, heterocyclyl- C 3 -C 6 -alkenyloxy, heterocyclyl- C 3 -C 6 alkynyloxy, where in each case one or two methylene groups of the carbon chains by -O-, -S- or
-N(C1-C6-Alkyl)- ersetzt sein können und wobei der Heterocyclylring drei- bis siebengliedrig, gesättigt, ungesättigt oder aromatisch sein kann und ein bis vier Heteroatome ausgewählt aus einer Gruppe von ein oder zwei Sauerstoff- oder -N (C 1 -C 6 alkyl) - can be replaced and wherein the heterocyclyl ring can be three to seven members, saturated, unsaturated or aromatic and one to four heteroatoms selected from a group of one or two oxygen or
Schwefel- und bis zu vier Stickstoffatomen enthalten kann und darüber hinaus ein bis drei der folgenden Substituenten tragen kann: Cyano, Nitro, Halogen, C1-C6-Alkyl, C2-C6-Alkenyl, Can contain sulfur and up to four nitrogen atoms and can also carry one to three of the following substituents: cyano, nitro, halogen, C 1 -C 6 alkyl, C 2 -C 6 alkenyl,
C1-C6-Halogenalkyl, C1-C6-Alkoxy oder C 1 -C 6 haloalkyl, C 1 -C 6 alkoxy or
C1-C6-Alkoxycarbonyl, C 1 -C 6 alkoxycarbonyl,
oder -N(R15)R16, wobei or -N (R 15 ) R 16 , where
R15, R16 R 15 , R 16
Wasserstoff, C1-C6-Alkyl, C3-C6-Alkenyl, Hydrogen, C 1 -C 6 alkyl, C 3 -C 6 alkenyl,
C3-C6-Alkinyl, C3-C6-Cycloalkyl, C1-C6-Halogenalkyl, C1-C6-Alkoxy-C1-C6-alkyl, C1-C6-Alkylcarbonyl, C1-C6-Alkoxycarbonyl, C1-C6-Alkoxycarbonyl-C1-C6-alkyl, C1-C6-Alkoxycarbonyl-C2-C6-alkenyl, wobei die Alkenylkette zusätzlich ein bis drei der folgenden Reste tragen kann: Halogen und Cyano oder Phenyl, das einen bis drei der folgenden Substituenten tragen kann: C 3 -C 6 alkynyl, C 3 -C 6 cycloalkyl, C 1 -C 6 haloalkyl, C 1 -C 6 alkoxy-C 1 -C 6 alkyl, C 1 -C 6 alkylcarbonyl, C 1 -C 6 -alkoxycarbonyl, C 1 -C 6 -alkoxycarbonyl-C 1 -C 6 -alkyl, C 1 -C 6 -alkoxycarbonyl-C 2 -C 6 -alkenyl, where the alkenyl chain can additionally carry one to three of the following radicals : Halogen and cyano or phenyl, the one to can carry three of the following substituents:
Cyano, Nitro, Halogen, C1-C6-Alkyl, C1-C6-Halogenalkyl, C3-C6-Alkenyl, C1-C6-Alkoxy und Cyano, nitro, halogen, C 1 -C 6 alkyl, C 1 -C 6 haloalkyl, C 3 -C 6 alkenyl, C 1 -C 6 alkoxy and
C1-C6-Alkoxycarbonyl, oder C 1 -C 6 alkoxycarbonyl, or
R15 und R 16 zusammen mit dem gemeinsamen R 15 and R 16 together with the common
Stickstoffatom einen gesättigten oder ungesättigten 4-7-gliedrigen Heterocyclus, wobei ein Ringglied durch -O-, -S-, -N=, -NH- oder  Nitrogen atom is a saturated or unsaturated 4-7-membered heterocycle, with a ring member by -O-, -S-, -N =, -NH- or
-N(C1-C6-Alkyl)- ersetzt sein kann, bedeuten; -N (C 1 -C 6 alkyl) - can be replaced;
R6, R7 C1-C6-Alkyl, C1-C6-Halogenalkyl, C3-C6-Alkenyl, R 6 , R 7 C 1 -C 6 alkyl, C 1 -C 6 haloalkyl, C 3 -C 6 alkenyl,
C3-C6-Alkinyl, C1-C6-Alkoxy-C1-C6-alkyl oder C 3 -C 6 alkynyl, C 1 -C 6 alkoxy-C 1 -C 6 alkyl or
R6 und R7 zusammen eine gesättigte oder ungesättigte, zwei- bis viergliedrige Kohlenstoffkette, die einen Oxosubstituenten tragen kann, wobei ein Glied dieser Kette durch ein den Variablen X3 und X4 nicht benachbartes Sauerstoff-, Schwefel- oder Stickstoffatom ersetzt sein kann, und wobei die Kette ein bis drei der folgenden Reste tragen kann: Cyano, Nitro, Amino, Halogen, C1-C6-Alkyl, C2-C6-Alkenyl, C1-C6-Alkoxy, C2-C6-Alkenyloxy, C2-C6-Alkinyloxy, C1-C6-Halogenalkyl,R 6 and R 7 together form a saturated or unsaturated, two- to four-membered carbon chain which can carry an oxo substituent, it being possible for one link in this chain to be replaced by an oxygen, sulfur or nitrogen atom which is not adjacent to the variables X 3 and X 4 , and wherein the chain can carry one to three of the following radicals: cyano, nitro, amino, halogen, C 1 -C 6 alkyl, C 2 -C 6 alkenyl, C 1 -C 6 alkoxy, C 2 -C 6 Alkenyloxy, C 2 -C 6 alkynyloxy, C 1 -C 6 haloalkyl,
Cyano-C1-C6-alkyl, Hydroxy-C1-C6-alkyl, C1-C6-Alkoxy- C1-C6-alkyl, C3-C6-Alkenyloxy-C1-C6-alkyl, C3-C6-Alkinyloxy-C1-C6-alkyl, C3-C7-Cycloalkyl, Cyano-C 1 -C 6 -alkyl, hydroxy-C 1 -C 6 -alkyl, C 1 -C 6 -alkoxy- C 1 -C 6 -alkyl, C 3 -C 6 -alkenyloxy-C 1 -C 6 - alkyl, C 3 -C 6 alkynyloxy-C 1 -C 6 alkyl, C 3 -C 7 cycloalkyl,
C3-C7-Cycloalkoxy, Carboxy, C1-C6-Alkoxycarbonyl, C1-C6-Alkyl-carbonyloxy-C1-C6-alkyl und Phenyl das einen bis drei der folgenden Reste tragen kann: Halogen, Cyano, Nitro, Amino, C1-C6-Alkyl, C 3 -C 7 cycloalkoxy, carboxy, C 1 -C 6 alkoxycarbonyl, C 1 -C 6 alkylcarbonyloxy-C 1 -C 6 alkyl and phenyl which can carry one to three of the following radicals: halogen, cyano , Nitro, amino, C 1 -C 6 alkyl,
C1-C6-Halogenalkyl, C1-C6-Alkoxy und C1-C6-Alkoxycarbonyl und wobei die Kette außerdem durch einen ankondensierten oder spiroverknüpften drei bis siebengliedrigen Ring substituiert sein kann, wobei ein bis zwei Kohlenstoffatome dieses Rings durch Sauerstoff-, Schwefel- und gegebenenfalls C 1 -C 6 haloalkyl, C 1 -C 6 alkoxy and C 1 -C 6 alkoxycarbonyl and wherein the chain can also be substituted by a fused or spiro-linked three to seven-membered ring, one or two carbon atoms of this ring by oxygen -, sulfur and possibly
C1-C6-Alkylsubstituierte Stickstoffatome ersetzt sein dürfen und dieser Ring ein bis zwei der folgendenC 1 -C 6 alkyl-substituted nitrogen atoms may be replaced and this ring one or two of the following
Substituenten tragen kann: Cyano, C1-C6-Alkyl, C2-C6-Alkenyl, C1-C6-Alkoxy, C1-C6-Cyanoalkyl, Can carry substituents: cyano, C 1 -C 6 alkyl, C 2 -C 6 alkenyl, C 1 -C 6 alkoxy, C 1 -C 6 cyanoalkyl,
C1-C6-Halogenalkyl und C1-C6-Alkoxycarbonyl; R8 Wasserstoff, Cyano, C1-C6-Alkyl, C2-C6-Alkenyl, C2-C6- Alkinyl, C1-C6-Halogenalkyl, C3-C7-Cycloalkyl, C1-C6-C 1 -C 6 haloalkyl and C 1 -C 6 alkoxycarbonyl; R 8 is hydrogen, cyano, C 1 -C 6 alkyl, C 2 -C 6 alkenyl, C 2 -C 6 alkynyl, C 1 -C 6 haloalkyl, C 3 -C 7 cycloalkyl, C 1 -C 6 -
Alkoxy-C1-C6-alkyl oder C1-C6-Alkoxycarbonyl; R9, R12 Wasserstoff, Cyano, Halogen, C1-C6-Alkyl, C1-C6-Alkoxy, Alkoxy-C 1 -C 6 alkyl or C 1 -C 6 alkoxycarbonyl; R 9 , R 12 are hydrogen, cyano, halogen, C 1 -C 6 alkyl, C 1 -C 6 alkoxy,
Halogen-C1-C6-alkyl, C1-C6-Alkylcarbonyl oder C1-C6- Alkoxycarbonyl; Halogen-C 1 -C 6 alkyl, C 1 -C 6 alkylcarbonyl or C 1 -C 6 alkoxycarbonyl;
R10 Wasserstoff, O-R17, S-R17, C1-C6-Alkyl, das noch einen oder zwei C1-C6-Alkoxysubstituenten tragen kann, C3-C6- Alkenyl, C3-C6-Alkinyl, C1-C6-Halogenalkyl, C3-C7- Cycloalkyl, C1-C6-Alkylthio-C1-C6-alkyl, C1-C6-Alkyliminooxy, -N(R15)R16 oder Phenyl, welches einen bis drei der folgenden Substituenten tragen kann: Cyano, Nitro, Halogen, C1-C6-Alkyl, C2-C6-Alkenyl, C1-C6- Halogenalkyl, C1-C6-Alkoxy oder C1-C6-Alkoxycarbonyl; R 10 is hydrogen, OR 17 , SR 17 , C 1 -C 6 alkyl, which can also carry one or two C 1 -C 6 alkoxy substituents, C 3 -C 6 alkenyl, C 3 -C 6 alkynyl, C 1 -C 6 haloalkyl, C 3 -C 7 cycloalkyl, C 1 -C 6 alkylthio-C 1 -C 6 alkyl, C 1 -C 6 alkyliminooxy, -N (R 15 ) R 16 or phenyl, which can carry one to three of the following substituents: cyano, nitro, halogen, C 1 -C 6 alkyl, C 2 -C 6 alkenyl, C 1 -C 6 haloalkyl, C 1 -C 6 alkoxy or C 1 -C 6 alkoxycarbonyl;
R17 Wasserstoff, C1-C6-Alkyl, C3-C6-Alkenyl, C3-C6-Alkinyl, C3-C7-Cycloalkyl, C1-C6-Halogenalkyl, C3-C6-Halogenalkenyl, Cyano-C1-C6-alkyl, C1-C6-Alkoxy-C1-C6-alkyl, C1-C6-Alkylthio- C1-C6-alkyl oder C1-C6-Alkyl-oximino-C1-C6-alkyl, C1-C6-Alkylcarbonyl, C1-C6-Alkoxycarbonyl, R 17 is hydrogen, C 1 -C 6 alkyl, C 3 -C 6 alkenyl, C 3 -C 6 alkynyl, C 3 -C 7 cycloalkyl, C 1 -C 6 haloalkyl, C 3 -C 6 - Haloalkenyl, cyano-C 1 -C 6 alkyl, C 1 -C 6 alkoxy-C 1 -C 6 alkyl, C 1 -C 6 alkylthio- C 1 -C 6 alkyl or C 1 -C 6 - Alkyl-oximino-C 1 -C 6 alkyl, C 1 -C 6 alkylcarbonyl, C 1 -C 6 alkoxycarbonyl,
C1-C6-Alkylcarbonyl-C1-C6-alkyl, C1-C6-Alkoxycarbonyl-C1-C6-alkyl, Phenyl oder Phenyl-C1-C6- alkyl, wobei die Phenylreste jeweils einen bis drei der folgenden Substituenten tragen können: Cyano, Nitro, Halogen, C1-C6-Alkyl, C1-C6-Halogenalkyl, C3-C6-Alkenyl, C1-C6-Alkoxy und C1-C6-Alkoxycarbonyl; C 1 -C 6 -alkylcarbonyl-C 1 -C 6 -alkyl, C 1 -C 6 -alkoxycarbonyl-C 1 -C 6 -alkyl, phenyl or phenyl-C 1 -C 6 - alkyl, the phenyl radicals in each case one to can carry three of the following substituents: cyano, nitro, halogen, C 1 -C 6 alkyl, C 1 -C 6 haloalkyl, C 3 -C 6 alkenyl, C 1 -C 6 alkoxy and C 1 -C 6 -Alkoxycarbonyl;
R11 Wasserstoff, Cyano, Halogen, C1-C6-Alkyl, C3-C6- Alkenyl, C3-C6-Alkinyl, C1-C6-Alkoxy-C1-C6-alkyl, C1-C6-Alkylcarbonyl, C1-C6-Alkoxycarbonyl, -NR18R19, wobei R18 und R19 die Bedeutungen von R15 und R16 haben, oder Phenyl, das noch einen bis drei der folgenden Substituenten tragen kann: Cyano, Nitro, Halogen, C1-C6-Alkyl, C1-C6-Halogenalkyl, R 11 is hydrogen, cyano, halogen, C 1 -C 6 alkyl, C 3 -C 6 alkenyl, C 3 -C 6 alkynyl, C 1 -C 6 alkoxy-C 1 -C 6 alkyl, C 1 -C 6 -alkylcarbonyl, C 1 -C 6 -alkoxycarbonyl, -NR 18 R 19 , where R 18 and R 19 have the meanings of R 15 and R 16 , or phenyl, which is one to three of the can carry the following substituents: cyano, nitro, halogen, C 1 -C 6 alkyl, C 1 -C 6 haloalkyl,
C3-C6-Alkenyl, C1-C6-Alkoxy und C1-C6-Alkoxycarbonyl; R13 Wasserstoff, Cyano, C1-C6-Alkyl oder C1-C6-Alkoxycarbonyl; oder R9 und R10 zusammen eine zwei- bis fünfgliedrige C 3 -C 6 alkenyl, C 1 -C 6 alkoxy and C 1 -C 6 alkoxycarbonyl; R 13 is hydrogen, cyano, C 1 -C 6 alkyl or C 1 -C 6 alkoxycarbonyl; or R 9 and R 10 together form a two- to five-membered group
Kohlenstoffkette, wobei ein Kohlenstoffatom dieser Kette durch Sauerstoff, Schwefel oder gegebenenfalls C1-C6-Alkyl Carbon chain, one carbon atom of this chain by oxygen, sulfur or optionally C 1 -C 6 alkyl
substituiertes Stickstoff ersetzt sein kann, substituted nitrogen can be replaced
R1 R 1
Halogen, Cyano, Nitro oder Trifluormethyl;  Halogen, cyano, nitro or trifluoromethyl;
R2 R 2
Wasserstoff oder Halogen;  Hydrogen or halogen;
R3 R 3
Wasserstoff, Nitro, C1-C6-Alkyl, C3-C6-Alkenyl, C3-C6-Alkinyl, C3-C8-Cycloalkyl, C3-C8-Cycloalkylcarbonyl, Cyano-C1-C6alkyl, C1-C6-Halogenalkyl, C1-C6-Alkoxy-C1-C6-alkyl, Formyl, C1-C6- Alkanoyl, C1-C6-Alkoxycarbonyl, C1-C6-Halogenalkylcarbonyl, C1-C6-Alkylcarbonyl-C1-C6-alkyl, C1-C6-Alkoxycarbonyl-C1-C6-alkyl eine Gruppe -N(R20)R21, wobei R20 und R21 für eine der Hydrogen, nitro, C 1 -C 6 alkyl, C 3 -C 6 alkenyl, C 3 -C 6 alkynyl, C 3 -C 8 cycloalkyl, C 3 -C 8 cycloalkylcarbonyl, cyano-C 1 -C 6 alkyl, C 1 -C 6 haloalkyl, C 1 -C 6 alkoxy-C 1 -C 6 alkyl, formyl, C 1 -C 6 alkanoyl, C 1 -C 6 alkoxycarbonyl, C 1 -C 6 -Halogenalkylcarbonyl, C 1 -C 6 -alkylcarbonyl-C 1 -C 6 -alkyl, C 1 -C 6 -alkoxycarbonyl-C 1 -C 6 -alkyl a group -N (R 20 ) R 21 , where R 20 and R 21 for one of the
Bedeutungen von R15 und R16 stehen, Meanings of R 15 and R 16 ,
Phenyl oder Phenyl-C1-C6-alkyl, wobei der Phenylring jeweils einen bis drei der folgenden Reste tragen kann: Cyano, Nitro, Halogen, C1-C6-Alkyl, C2-C6-Alkenyl, C1-C6-Halogenalkyl, Phenyl or phenyl-C 1 -C 6 -alkyl, where the phenyl ring can each carry one to three of the following radicals: cyano, nitro, halogen, C 1 -C 6 -alkyl, C 2 -C 6 -alkenyl, C 1 - C 6 haloalkyl,
C1-C6-Alkoxy und C1-C6-Alkoxycarbonyl; C 1 -C 6 alkoxy and C 1 -C 6 alkoxycarbonyl;
R4 R 4
Wasserstoff, Cyano, Nitro, Halogen, C1-C6-Alkyl, C2-C6-Alkenyl, C2-C6-Alkinyl, C3-C8-Cycloalkyl, C1-C6-Halogenalkyl, C1-C6- Hydroxyalkyl, Cyano-C1-C6-alkyl, C1-C6-Alkoxy, C1-C6-Alkylthio, C1-C6-Alkoxy-C1-C6-alkyl, C1-C6-Alkylthio-C1-C6-alkyl oder Hydrogen, cyano, nitro, halogen, C 1 -C 6 alkyl, C 2 -C 6 alkenyl, C 2 -C 6 alkynyl, C 3 -C 8 cycloalkyl, C 1 -C 6 haloalkyl, C 1 -C 6 - hydroxyalkyl, cyano-C 1 -C 6 alkyl, C 1 -C 6 alkoxy, C 1 -C 6 alkylthio, C 1 -C 6 alkoxy-C 1 -C 6 alkyl, C 1 -C 6 alkylthio-C 1 -C 6 alkyl or
Phenyl, welches einen bis drei der folgenden Reste tragen kann: Cyano, Nitro, Halogen, C1-C6-Alkyl, C2-C6-Alkenyl, C1-C6- Halogenalkyl, C1-C6-Alkoxy und C1-C6-Alkoxycarbonyl; R5 Phenyl which can carry one to three of the following radicals: cyano, nitro, halogen, C 1 -C 6 alkyl, C 2 -C 6 alkenyl, C 1 -C 6 haloalkyl, C 1 -C 6 alkoxy and C 1 -C 6 alkoxycarbonyl; R 5
Wasserstoff, Cyano, Nitro, Halogen, C1-C6-Alkyl, C2-C6-Alkenyl, C2-C6-Alkinyl, C3-C7-Cycloalkyl, C1-C6-Halogenalkyl, Hydrogen, cyano, nitro, halogen, C 1 -C 6 alkyl, C 2 -C 6 alkenyl, C 2 -C 6 alkynyl, C 3 -C 7 cycloalkyl, C 1 -C 6 haloalkyl,
C1-C6-Hydroxyalkyl, Cyano-C1-C6-alkyl, C1-C5-Alkoxy-C1-C6-alkyl, C1-C6-Alkylthio-C1-C6-alkyl, Formyl, C1-C6-Alkylcarbonyl, C1-C6-Halogenalkylcarbonyl, C1-C6-Alkoxycarbonyl, C 1 -C 6 hydroxyalkyl, cyano-C 1 -C 6 alkyl, C 1 -C 5 alkoxy-C 1 -C 6 alkyl, C 1 -C 6 alkylthio-C 1 -C 6 alkyl, Formyl, C 1 -C 6 alkylcarbonyl, C 1 -C 6 haloalkylcarbonyl, C 1 -C 6 alkoxycarbonyl,
C1-C6-Alkoxycarbonyl-C2-C6-alkenyl, -N(R22)R23, wobei R22 und R23 für eine der Bedeutungen von R15 und R16 stehen, Phenyl, welches einen bis drei der folgenden Reste tragen kann: Cyano, Nitro, Halogen, C1-C6-Alkyl, C2-C6-Alkenyl, C1-C6-Halogenalkyl, C1-C6-Alkoxy und C1-C6-Alkoxycarbonyl, oder C 1 -C 6 alkoxycarbonyl-C 2 -C 6 alkenyl, -N (R 22 ) R 23, where R 22 and R 23 represent one of the meanings of R 15 and R 16 , phenyl, which is one to three of the can carry the following radicals: cyano, nitro, halogen, C 1 -C 6 alkyl, C 2 -C 6 alkenyl, C 1 -C 6 haloalkyl, C 1 -C 6 alkoxy and C 1 -C 6 alkoxycarbonyl , or
R4 und R5 zusammen eine gesättigte oder ungesättigte 3- oder 4- gliedrige Kohlenstoffkette, welche ein bis drei der folgenden Heteroatome enthalten kann: 1 oder 2 Sauerstoffatomen, 1 oder 2 Schwefelatomen und 1 bis 3 Stickstoffatomen, wobei die Kette noch ein bis drei der folgenden Reste tragen kann: Cyano, Nitro, Amino, Halogen, C1-C6-Alkyl, C2-C6-Alkenyl, C1-C6-Alkoxy, C1-C6- Alkylthio und C1-C6-Alkoxycarbonyl; mit der Maßgabe, daß nicht gleichzeitig R4 die Trifluormethyl- gruppe R5 Wasserstoff sein können, wenn W eine Gruppe R 4 and R 5 together form a saturated or unsaturated 3 or 4-membered carbon chain, which can contain one to three of the following heteroatoms: 1 or 2 oxygen atoms, 1 or 2 sulfur atoms and 1 to 3 nitrogen atoms, the chain still one to three of the following radicals can carry: cyano, nitro, amino, halogen, C 1 -C 6 alkyl, C 2 -C 6 alkenyl, C 1 -C 6 alkoxy, C 1 -C 6 alkylthio and C 1 -C 6 -alkoxycarbonyl; with the proviso that R 4 cannot simultaneously be the trifluoromethyl group R 5 if W is a group
-CH=CH-CO-R10 mit R10 C1-C6-Alkoxy oder C3-C7-Cycloalkoxy bedeutet, und mit der Maßgabe, daß R4 und R5 nicht gleichzeitig Wasserstoff bedeuten, wenn W für CH(R8)-CH(R9)-CO-R10 und R9 nicht für Halogen stehen, sowie die Salze und Enolether derjenigen Verbindungen I, bei denen R3 Wasserstoff bedeutet. -CH = CH-CO-R 10 with R 10 is C 1 -C 6 alkoxy or C 3 -C 7 cycloalkoxy, and with the proviso that R 4 and R 5 are not simultaneously hydrogen if W is CH ( R 8 ) -CH (R 9 ) -CO-R 10 and R 9 do not represent halogen, and the salts and enol ethers of those compounds I in which R 3 is hydrogen.
Außerdem betrifft die Erfindung herbizid wirksame 3-Phenylurazile der allgemeinen Formeln Ia und Ib In addition, the invention relates to herbicidally active 3-phenylurazils of the general formulas Ia and Ib
in denen R3' eine C1-C6-Alkylgruppe, eine C3-C6-Alkenylgruppe oder eine C3-C6-Alkinylgruppe bedeutet. in which R 3 'represents a C 1 -C 6 alkyl group, a C 3 -C 6 alkenyl group or a C 3 -C 6 alkynyl group.
Des weiteren betrifft die Erfindung herbizide, pestizide und das Wachstum der Pflanzen regulierende Mittel, welche diese Verbindungen als wirksame Substanzen enthalten. The invention further relates to herbicidal, pesticidal and plant growth-regulating agents which contain these compounds as active substances.
Aus der US 4,979,982 sind herbizid wirksame 3-Phenylurazile der Formel I' bekannt No. 4,979,982 herbicidally active 3-phenylurazils of the formula I 'are known
wobei Ra Wasserstoff oder Halogen, Rb C1-C12-Alkyl oder Cycloalkyl und Rc C1-C12-Alkyl oder C3-C12-Alkenyl bedeuten. where R a is hydrogen or halogen, R b is C 1 -C 12 alkyl or cycloalkyl and R c is C 1 -C 12 alkyl or C 3 -C 12 alkenyl.
Ferner werden in der EP-A 408 382 u.a. Strukturen der Formel I" Furthermore, EP-A 408 382 et al. Structures of Formula I "
wobei Rd für Wasserstoff, Alkyl, Hydroxymethyl oder Halogenalkyl, Re für Halogenalkyl, Rf für Wasserstoff, Alkyl, Halogenalkyl, Hydroxymethyl, Halogen oder Nitro, X1 für Sauerstoff oder where R d for hydrogen, alkyl, hydroxymethyl or haloalkyl, R e for haloalkyl, R f for hydrogen, alkyl, haloalkyl, hydroxymethyl, halogen or nitro, X 1 for oxygen or
Schwefel, Rg für Wasserstoff, Alkyl, Alkoxy oder Alkoxyalkyl und Rh für Wasserstoff, Alkyl, Cycloalkyl, Halogenalkyl, Phenyl oder Benzyl und Ri für Halogen, Nitro oder Cyano stehen, beschrieben. Sulfur, R g represents hydrogen, alkyl, alkoxy or alkoxyalkyl and R h represents hydrogen, alkyl, cycloalkyl, haloalkyl, phenyl or benzyl and R i represents halogen, nitro or cyano.
Außerdem lehrt die CH 482 402 Unkrautbekämpfungsmittel, die als Wirkstoffe u.a. substituierte Urazile und Thiourazile der In addition, CH 482 402 teaches weed control agents, which as active ingredients include substituted urazile and thiourazile
Formel I"' I'"Formula I "' I '"
enthalten, wobei Aryl einen gegebenenfalls durch Fluor, Chlor, Brom, Hydroxyl, Alkoxy, Cyano, Alkylthio, Alkyl oder Nitro substituierten Arylrest, Rk Dialkylphosphoryl, Alkyl, Alkenyl, Cyano, Wasserstoff, geg. subst. Alkyl, geg. subst. Carbamyl, geg. subst. Thiocarbamyl, geg. subst. Mercapto oder Acyl, Rl Alkyl, Alkoxy, Wasserstoff, Chlor oder Brom und Rm Alkylthio, Alkoxy, Alkylthioalkyl, Alkenyl, Cyano, Thiocyano, Nitro, Halogen, contain, wherein aryl optionally substituted by fluorine, chlorine, bromine, hydroxyl, alkoxy, cyano, alkylthio, alkyl or nitro, R k dialkylphosphoryl, alkyl, alkenyl, cyano, hydrogen, against subst. Alkyl, against subst. Carbamyl, opp. Subst. Thiocarbamyl, against subst. Mercapto or acyl, R 1 alkyl, alkoxy, hydrogen, chlorine or bromine and R m alkylthio, alkoxy, alkylthioalkyl, alkenyl, cyano, thiocyano, nitro, halogen,
Wasserstoff oder geg. subst. Alkyl oder Rl und Rm zusammen eine Tri-, Tetra- oder Pentamethylenkette, bedeuten. Hydrogen or against subst. Alkyl or R 1 and R m together represent a tri, tetra or pentamethylene chain.
Außerdem sind der WO-A 87/07 602 u.a. Verbindungen der Formel Iιv In addition, WO-A 87/07 602 includes compounds of the formula IV
IV IV
zu entnehmen, wobei Rp und Rq Alkyl, Alkenyl, Alkinyl oder can be seen, wherein R p and R q alkyl, alkenyl, alkynyl or
Halogen und Rs u.a. eine Cyano-, subst. Alkylcarbonyl-, Carbonyl- oder Alkoxycarbonyl-alkylgruppe bedeuten und Ro Wasserstoff, Alkyl, Alkylcarbonyl, Alkenyl und Alkinyl bedeuten. Halogen and R s include a cyano, subst. Alkylcarbonyl, carbonyl or alkoxycarbonyl-alkyl group and R o signify hydrogen, alkyl, alkylcarbonyl, alkenyl and alkynyl.
Andere 3-Arylurazile vom Typ der Verbindungen I sind beispielsweise den folgenden Druckschriften zu entnehmen: EP-A 195 346, EP-A 260 621, EP-A 438 209, WO 88/10254, WO 89/02891 und Other 3-aryluraciles of the type of compounds I can be found, for example, in the following publications: EP-A 195 346, EP-A 260 621, EP-A 438 209, WO 88/10254, WO 89/02891 and
WO 89/03825, EP-A 473 551, WO 91/00278, WO 90/15057, WO 89/03825, EP-A 473 551, WO 91/00278, WO 90/15057,
EP-A 255047, EP-A 438 209, EP-A 408382, EP-A 476697, EP-A 255047, EP-A 438 209, EP-A 408382, EP-A 476697,
EP-A 420 194, US-A 4981 508, WO 91/07393, US-A 3 981 715, EP-A 420 194, US-A 4981 508, WO 91/07393, US-A 3 981 715,
DE-A 37 12782. DE-A 37 12782.
Die Selektivität dieser bekannten Herbizide bezüglich der Schadpflanzen vermag jedoch nur bedingt zu befriedigen, so daß der Erfindung neue herbizid wirksame Verbindungen als Aufgabe zugrunde lagen, mit denen sich (bei guter Verträglichkeit für die Nutzpflanzen) die Schadpflanzen besser als bisher gezielt bekämpfen lassen. Demgemäß wurden die eingangs definierten substituierten 3-Phenyl- urazile I, Ia und Ib gefunden. However, the selectivity of these known herbicides with regard to the harmful plants can only be satisfied to a limited extent, so that the invention was based on new herbicidally active compounds as a task with which (with good tolerance for the useful plants) the harmful plants can be controlled better than before. Accordingly, the substituted 3-phenylurazils I, Ia and Ib defined at the outset were found.
Auβerdem wurden herbizide Mittel gefunden, die diese Substanzen enthalten und eine gute herbizide Wirkung besitzen. Sie sind verträglich und somit selektiv in breitblättrigen Kulturen sowie in monokotylen Gewächsen, welche nicht zu den Gramineen zählen. In addition, herbicidal compositions have been found which contain these substances and have a good herbicidal action. They are tolerated and therefore selective in broadleaved crops and in monocotyledonous plants, which are not among the Gramineae.
Die erfindungsgemäβen Verbindungen I, Ia und Ib eignen sich des weiteren als Defoliations- bzw. Desiccationsmittel in z.B. Baumwolle, Kartoffel, Raps, Sonnenblume, Sojabohne oder Ackerbohnen. Einige Verbindungen I sind ferner brauchbar zur Bekämpfung von Schädlingen, insbesondere Insekten. Die vorstehend für die Substituenten R1 bis R17 genannten Bedeutungen stellen Sammelbegriffe für eine individuelle Aufzählungen der einzelnen Gruppenmitglieder dar. Sämtliche Alkyl-, Alkenyl-, Alkinyl-, Halogenalkyl- und Halogenalkoxyteile können geradkettig oder verzweigt sein. Die Halogenalkyl- und Halogenalkoxyrest können gleiche oder verschiedene Halogenatome tragen. The compounds I, Ia and Ib according to the invention are furthermore suitable as defoliating or desiccating agents in, for example, cotton, potatoes, rapeseed, sunflower, soybeans or field beans. Some compounds I are also useful for controlling pests, especially insects. The meanings given above for the substituents R 1 to R 17 are collective terms for an individual list of the individual group members. All alkyl, alkenyl, alkynyl, haloalkyl and haloalkoxy parts can be straight-chain or branched. The haloalkyl and haloalkoxy radicals can carry the same or different halogen atoms.
Im einzelnen bedeuten beispielsweise: - Halogen: Fluor, Chlor, Brom und Jod, vorzugsweise Fluor und Chlor; - C1-C6-Alkyl: Methyl, Ethyl, n-Propyl, 1-Methylethyl, Specifically, for example: halogen: fluorine, chlorine, bromine and iodine, preferably fluorine and chlorine; C 1 -C 6 alkyl: methyl, ethyl, n-propyl, 1-methylethyl,
n-Butyl, 1-Methyl-propyl, 2-Methylpropyl, 1,1-Dimethylethyl, n-Pentyl, 1-Methylbutyl, 2-Methylbutyl, 3-Methylbutyl, 2,2-Di-methylpropyl, 1-Ethylpropyl, 1,1-Dimethylpropyl, n-butyl, 1-methyl-propyl, 2-methylpropyl, 1,1-dimethylethyl, n-pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 2,2-dimethylpropyl, 1-ethylpropyl, 1, 1-dimethylpropyl,
1,2-Dimethylpropyl, n-Hexyl, 1-Methylpentyl, 2-Methylpentyl, 3-Methylpentyl, 4-Methylpentyl, 1,1-Dimethylbutyl, 1,2-Dimethylbutyl, 1,3-Dimethylbutyl, 2,2-Dimethylbutyl, 2,3-Dimethylbutyl, 3,3-Dimethylbutyl, 1-Ethylbutyl, 2-Ethylbutyl, 1,1,2-Trimethylpropyl, 1,2,2-Trimethylpropyl, 1-Ethyl-1- methylpropyl und 1-Ethyl-2-methylpropyl, vorzugsweise 1,2-dimethylpropyl, n-hexyl, 1-methylpentyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 1,1-dimethylbutyl, 1,2-dimethylbutyl, 1,3-dimethylbutyl, 2,2-dimethylbutyl, 2,3-dimethylbutyl, 3,3-dimethylbutyl, 1-ethylbutyl, 2-ethylbutyl, 1,1,2-trimethylpropyl, 1,2,2-trimethylpropyl, 1-ethyl-1-methylpropyl and 1-ethyl-2- methylpropyl, preferably
Methyl, Ethyl, Isopropyl, n-Butyl und tert.-Butyl; - C2-C6-Alkenyl: Vinyl und C3-C6-Alkenyl wie Prop-1-en-1-yl, Prop-2-en-1-yl, 1-Methylethenyl, n-Buten-1-yl, n-Buten-2-yl, n-Buten-3-yl, 1-Methyl-prop-1-en-1-yl, 2-Methyl-prop-1- en-1-yl, 1-Methyl-prop-2-en-1-yl, 2-Methyl-prop-2-en-1-yl, n-Penten-1-yl, n-Penten-2-yl, n-Penten-3-yl, n-Penten-4-yl, 1-Methyl-but-1-en-1-yl, 2-Methyl-but-1-en-1-yl, 3-Methyl- but-1-en-1-yl, 1-Methyl-but-2-en-1-yl, 2-Methyl-but-2- en-1-yl, 3-Methyl-but-2-en-1-yl, 1-Methyl-but-3-en-1-yl, 2-Methyl-but-3-en-1-yl, 3-Methyl-but-3-en-1-yl, 1,1-Dimethyl-prop-2-en-1-yl, 1,2-Dimethyl-prop-1-en-1-yl, Methyl, ethyl, isopropyl, n-butyl and tert-butyl; - C 2 -C 6 alkenyl: vinyl and C 3 -C 6 alkenyl such as prop-1-en-1-yl, prop-2-en-1-yl, 1-methylethenyl, n-buten-1-yl , n-buten-2-yl, n-buten-3-yl, 1-methyl-prop-1-en-1-yl, 2-methyl-prop-1-en-1-yl, 1-methyl-prop -2-en-1-yl, 2-methyl-prop-2-en-1-yl, n-penten-1-yl, n-penten-2-yl, n-penten-3-yl, n-pentene -4-yl, 1-methyl-but-1-en-1-yl, 2-methyl-but-1-en-1-yl, 3-methyl-but-1-en-1-yl, 1-methyl -but-2-en-1-yl, 2-methyl-but-2-en-1-yl, 3-methyl-but-2-en-1-yl, 1-methyl-but-3-en-1 -yl, 2-methyl-but-3-en-1-yl, 3-methyl-but-3-en-1-yl, 1,1-dimethyl-prop-2-en-1-yl, 1,2 -Dimethyl-prop-1-en-1-yl,
1,2-Dimethyl-prop-2-en-1-yl, 1-Ethyl-prop-1-en-2-yl,  1,2-dimethyl-prop-2-en-1-yl, 1-ethyl-prop-1-en-2-yl,
1-Ethyl-prop-2-en-1-yl, n-Hex-1-en-1-yl, n-Hex-2-en-1-yl, n-Hex-3-en-1-yl, n-Hex-4-en-1-yl, n-Hex-5-en-1-yl, 1-Methyl- pent-1-en-1-yl, 2-Methyl-pent-1-en-1-yl, 3-Methyl-pent-1- en-1-yl, 4-Methyl-pent-1-en-1-yl, 1-Methyl-pent-2-en-1-yl, 2-Methyl-pent-2-en-1-yl, 3-Methyl-pent-2-en-1-yl, 4-Methyl- pent-2-en-1-yl, 1-Methyl-pent-3-en-1-yl, 2-Methyl-pent-3- en-1-yl, 3-Methyl-pent-3-en-1-yl, 4-Methyl-pent-3-en-1-yl, 1-Methyl-pent-4-en-1-yl, 2-Methyl-pent-4-en-1-yl, 3-Methyl- pent-4-en-1-yl, 4-Methyl-pent-4-en-1-yl, 1,1-Dimethyl-but-2- en-1-yl, 1,1-Dimethyl-but-3-en-1-yl, 1,2-Dimethyl-but-1- en-1-yl, 1,2-Dimethyl-but-2-en-1-yl, 1,2-Dimethyl-but-3- en-1-yl, 1,3-Dimethyl-but-1-en-1-yl, 1,3-Dimethyl-but-2- en-1-yl, 1,3-Dimethyl-but-3-en-1-yl, 2,2-Dimethyl-but-3- en-1-yl, 2,3-Dimethyl-but-1-en-1-yl, 2,3-Dimethyl-but-2- en-1-yl, 2,3-Dimethyl-but-3-en-1-yl, 3,3-Dimethyl-but-1- en-1-yl, 3,3-Dimethyl-but-2-en-1-yl, 1-Ethyl-but-1-en-1-yl, 1-Ethyl-but-2-en-1-yl, 1-Ethyl-but-3-en-1-yl, 2-Ethyl- but-1-en-1-yl, 2-Ethyl-but-2-en-1-yl, 2-Ethyl-but-3-en-1-yl, 1,1,2-Trimethylprop-2-en-1-yl, 1-Ethyl-1-methyl-prop-2- en-1-yl, 1-Ethyl-2-methyl-prop-1-en-1-yl und 1-Ethyl-2- methyl-prop-2-en-1-yl, vorzugsweise Vinyl, Prop-2-en-1-yl und But-2-en-2-yl; - C2-C6-Alkinyl: Ethinyl und C3-C6-Alkinyl wie Prop-1-in-1-yl, Prop-2-in-3-yl, n-But-1-in-1-yl, n-But-1-in-4-yl, n-But-2- in-1-yl, n-Pent-1-in-1-yl, n-Pent-1-in-3-yl, n-Pent-1-in-4- yl, n-Pentin-5-yl, Pent-2-in-1-yl, Pent-2-in-4-yl, Pent-2- in-5-yl, 3-Methyl-but-1-in-1-yl, 3-Methyl-but-1-in-3-yl, 3-Methyl-but-1-in-4-yl, n-Hex-1-in-1-yl, n-Hex-1-in-3-yl, n-Hex-1-in-4-yl, n-Hex-1-in-5-yl, n-Hex-1-in-6-yl, n-Hex-2- in-1-yl, n-Hex-2-in-4-yl, n-Hex-2-in-5-yl, n-Hex-2-in-6-yl, n-Hex-3-in-1-yl, n-Hex-3-in-2-yl, 3-Methyl-pent-1-in-1-yl, 3-Methyl-pent-1-in-3-yl, 3-Methyl-pent-1-in-4-yl, 3-Methyl- pent-1-in-5-yl, 4-Methyl-pent-1-in-1-yl, 4-Methyl-pent-2-in- 4-yl und 4-Methyl-pent-2-in-5-yl, vorzugsweise Prop-2-inyl; - C3-C8-Cycloalkyl: Cyclopropyl, Cyclobutyl, Cyclopentyl, 1-ethyl-prop-2-en-1-yl, n-hex-1-en-1-yl, n-hex-2-en-1-yl, n-hex-3-en-1-yl, n-hex-4-en-1-yl, n-hex-5-en-1-yl, 1-methyl-pent-1-en-1-yl, 2-methyl-pent-1-en-1- yl, 3-methyl-pent-1-en-1-yl, 4-methyl-pent-1-en-1-yl, 1-methyl-pent-2-en-1-yl, 2-methyl-pent 2-en-1-yl, 3-methyl-pent-2-en-1-yl, 4-methyl-pent-2-en-1-yl, 1-methyl-pent-3-en-1-yl, 2-methyl-pent-3-en-1-yl, 3-methyl-pent-3-en-1-yl, 4-methyl-pent-3-en-1-yl, 1-methyl-pent-4- en-1-yl, 2-methyl-pent-4-en-1-yl, 3-methyl-pent-4-en-1-yl, 4-methyl-pent-4-en-1-yl, 1, 1-dimethyl-but-2-en-1-yl, 1,1-dimethyl-but-3-en-1-yl, 1,2-dimethyl-but-1-en-1-yl, 1,2- Dimethyl-but-2-en-1-yl, 1,2-dimethyl-but-3-en-1-yl, 1,3-dimethyl-but-1-en-1-yl, 1,3-dimethyl but-2-en-1-yl, 1,3-dimethyl-but-3-en-1-yl, 2,2-dimethyl-but-3-en-1-yl, 2,3-dimethyl-but- 1-en-1-yl, 2,3-dimethyl-but-2-en-1-yl, 2,3-dimethyl-but-3-en-1-yl, 3,3-dimethyl-but-1- en-1-yl, 3,3-dimethyl-but-2-en-1-yl, 1-ethyl-but-1-en-1-yl, 1-ethyl-but-2-en-1-yl, 1-ethyl-but-3-en-1-yl, 2-ethyl-but-1-en- 1-yl, 2-ethyl-but-2-en-1-yl, 2-ethyl-but-3-en-1-yl, 1,1,2-trimethylprop-2-en-1-yl, 1- Ethyl-1-methyl-prop-2-en-1-yl, 1-ethyl-2-methyl-prop-1-en-1-yl and 1-ethyl-2-methyl-prop-2-en-1- yl, preferably vinyl, prop-2-en-1-yl and but-2-en-2-yl; - C 2 -C 6 alkynyl: ethynyl and C 3 -C 6 alkynyl such as prop-1-in-1-yl, prop-2-in-3-yl, n-but-1-in-1-yl , n-but-1-in-4-yl, n-but-2-in-1-yl, n-pent-1-in-1-yl, n-pent-1-in-3-yl, n Pent-1-in-4-yl, n-pentyn-5-yl, pent-2-in-1-yl, pent-2-in-4-yl, pent-2-in-5-yl, 3 -Methyl-but-1-in-1-yl, 3-methyl-but-1-in-3-yl, 3-methyl-but-1-in-4-yl, n-hex-1-in-1 -yl, n-Hex-1-in-3-yl, n-Hex-1-in-4-yl, n-Hex-1-in-5-yl, n-Hex-1-in-6-yl , n-hex-2- in-1-yl, n-hex-2-in-4-yl, n-hex-2-in-5-yl, n-hex-2-in-6-yl, n-hex-3-in- 1-yl, n-hex-3-in-2-yl, 3-methyl-pent-1-in-1-yl, 3-methyl-pent-1-in-3-yl, 3-methyl-pent- 1-in-4-yl, 3-methyl-pent-1-in-5-yl, 4-methyl-pent-1-in-1-yl, 4-methyl-pent-2-in-4-yl and 4-methyl-pent-2-yn-5-yl, preferably prop-2-ynyl; C 3 -C 8 cycloalkyl: cyclopropyl, cyclobutyl, cyclopentyl,
Cyclohexyl, Cycloheptyl und Cyclooctyl, vorzugsweise Cyclopropyl, Cylopentyl und Cyclohexyl; - C1-C6-Halogenalkyl: Chlormethyl, Dichlormethyl, Cyclohexyl, cycloheptyl and cyclooctyl, preferably cyclopropyl, cyclopentyl and cyclohexyl; C 1 -C 6 haloalkyl: chloromethyl, dichloromethyl,
Trichlormethyl, Fluormethyl, Difluormethyl, Trifluormethyl, Chlorfluormethyl, Dichlorfluormethyl, Chlordifluormethyl, 1-Fluorethyl, 2-Fluorethyl, 2,2-Difluorethyl,  Trichloromethyl, fluoromethyl, difluoromethyl, trifluoromethyl, chlorofluoromethyl, dichlorofluoromethyl, chlorodifluoromethyl, 1-fluoroethyl, 2-fluoroethyl, 2,2-difluoroethyl,
2,2,2-Trifluorethyl, 2-Chlor-2-fluorethyl,  2,2,2-trifluoroethyl, 2-chloro-2-fluoroethyl,
2-Chlor-2,2-difluorethyl, 2,2-Dichlor-2-fluorethyl, 2,2,2- Trichlorethyl, Pentafluorethyl und 3-Chlorpropyl, vorzugsweise Trifluormethyl; - Hydroxy-(C1-C6)-alkyl: Hydroxymethyl, 1-Hydroxyeth-1-yl,2-chloro-2,2-difluoroethyl, 2,2-dichloro-2-fluoroethyl, 2,2,2-trichloroethyl, pentafluoroethyl and 3-chloropropyl, preferably trifluoromethyl; Hydroxy (C 1 -C 6 ) alkyl: hydroxymethyl, 1-hydroxyeth-1-yl,
2-Hydroxyeth-1-yl, 1-Hydroxy-prop-1-yl, 2-Hydroxy-prop-1-yl, 3-Hydroxy-prop-1-yl, l-Hydroxy-prop-2-yl, 2-Hydroxy-prop- 2-yl, 1-Hydroxy-but-1-yl, 2-Hydroxy-but-1-yl, 3-Hydroxy- but-1-yl, 4-Hydroxy-but-1-yl, l-Hydroxy-but-2-yl, 2-Hydroxy- but-2-yl, l-Hydroxy-but-3-yl, 2-Hydroxy-but-3-yl, 1-Hydroxy- 2-methyl-prop-3-yl, 2-Hydroxy-2-methyl-prop-3-y 1, 3-Hydroxy- 2-methyl-prop-3-yl und 2-Hydroxymethyl-prop-2-yl, vorzugsweise Hydroxymethyl; - Cyano-(C1-C6)-alkyl: Cyanomethyl, 1-Cyanoeth-1-yl, 2-Cyanoeth-1-yl, 1-Cyano-prόp-1-yl, 2-Cyano-prop-1-yl, 3-Cyanoprop-1-yl, 1-Cyano-prop-2-yl, 2-Cyano-prop-2-yl, 1-Cyanobut-1-yl, 2-Cyano-but-1-yl, 3-Cyano-but-1-yl, 4-Cyano-but-1- yl, 1-Cyano-but-2-yl, 2-Cyano-but-2-yl, 1-Cyano-but-3-yl, 2-Cyano-but-3-yl, 1-Cyano-2-methyl-prop-3-yl, 2-Cyano-2- methyl-prop-3-yl, 3-Cyano-2-methyl-prop-3-yl, und 2-Cyanomethyl-prop-2-yl, vorzugsweise Cyanomethyl; - Amino-(C1-C6)-alkyl: Aminomethyl, 1-Aminoethyl, 2-Aminoethyl, 1-Aminoprop-1-yl, 2-Aminoprop-1-yl, 3-Aminoprop-1-yl, 1-Aminobut-1-yl, 2-Aminobut-1-yl, 3-Aminobut-1-yl, 4-Aminobut-1-yl, 1-Aminobut-2-yl, 2-Aminobut-2-yl, 3-Aminobut-2-yl, 3-Aminobut-2-yl, 4-Aminobut-2-yl, 1-(Aminomethyl)-eth-1-yl, 1-(Aminomethyl)-1-(methyl)-eth-1-yl, und 1-(Aminomethyl)- prop-1-yl, vorzugsweise Aminomethyl; - Phenyl-C1-C6-alkyl: Benzyl, 1-Phenylethyl, 2-Phenylethyl, 1-Phenylprop-1-yl, 2-Phenylprop-1-yl, 3-Phenylprop-1-yl, 1-Phenylbut-1-yl, 2-Phenylbut-1-yl, 3-Phenylbut-1-yl, 2-hydroxyeth-1-yl, 1-hydroxy-prop-1-yl, 2-hydroxy-prop-1-yl, 3-hydroxy-prop-1-yl, l-hydroxy-prop-2-yl, 2- Hydroxy-prop-2-yl, 1-hydroxy-but-1-yl, 2-hydroxy-but-1-yl, 3-hydroxy-but-1-yl, 4-hydroxy-but-1-yl, l- Hydroxy-but-2-yl, 2-hydroxy-but-2-yl, l-hydroxy-but-3-yl, 2-hydroxy-but-3-yl, 1-hydroxy-2-methyl-prop-3- yl, 2-hydroxy-2-methyl-prop-3-y 1, 3-hydroxy-2-methyl-prop-3-yl and 2-hydroxymethyl-prop-2-yl, preferably hydroxymethyl; - Cyano- (C 1 -C 6 ) alkyl: cyanomethyl, 1-cyanoeth-1-yl, 2-cyanoeth-1-yl, 1-cyano-prόp-1-yl, 2-cyano-prop-1-yl , 3-cyanoprop-1-yl, 1-cyano-prop-2-yl, 2-cyano-prop-2-yl, 1-cyanobut-1-yl, 2-cyano-but-1-yl, 3-cyano -but-1-yl, 4-cyano-but-1-yl, 1-cyano-but-2-yl, 2-cyano-but-2-yl, 1-cyano-but-3-yl, 2-cyano -but-3-yl, 1-cyano-2-methyl-prop-3-yl, 2-cyano-2-methyl-prop-3-yl, 3-cyano-2-methyl-prop-3-yl, and 2-cyanomethyl-prop-2-yl, preferably cyanomethyl; - Amino- (C 1 -C 6 ) alkyl: aminomethyl, 1-aminoethyl, 2-aminoethyl, 1-aminoprop-1-yl, 2-aminoprop-1-yl, 3-aminoprop-1-yl, 1-aminobut -1-yl, 2-aminobut-1-yl, 3-aminobut-1-yl, 4-aminobut-1-yl, 1-aminobut-2-yl, 2-aminobut-2-yl, 3-aminobut-2 -yl, 3-aminobut-2-yl, 4-aminobut-2-yl, 1- (aminomethyl) -eth-1-yl, 1- (aminomethyl) -1- (methyl) -eth-1-yl, and 1- (aminomethyl) prop-1-yl, preferably aminomethyl; - Phenyl-C 1 -C 6 -alkyl: benzyl, 1-phenylethyl, 2-phenylethyl, 1-phenylprop-1-yl, 2-phenylprop-1-yl, 3-phenylprop-1-yl, 1-phenylbut-1 -yl, 2-phenylbut-1-yl, 3-phenylbut-1-yl,
4-Phenylbut-1-yl, 1-Phenylbut-2-yl, 2-Phenylbut-2-yl,  4-phenylbut-1-yl, 1-phenylbut-2-yl, 2-phenylbut-2-yl,
3-Phenylbut-2-yl, 3-Phenylbut-2-yl, 4-Phenylbut-2-yl,  3-phenylbut-2-yl, 3-phenylbut-2-yl, 4-phenylbut-2-yl,
1-(Phenylmethyl)-eth-1-yl, 1-(Phenylmethyl)-1-(methyl)- eth-1-yl, und 1-(Phenylmethyl)-prop-1-yl, vorzugsweise Benzyl; - C1-C6-Alkoxy: Methoxy, Ethoxy, n-Propoxy, 1-Methylethoxy, n-Butoxy, 1-Methyl-propoxy, 2-Methylpropoxy, 1,1-Dimethylethoxy, n-Pentoxy, 1-Methylbutoxy, 2-Methylbutoxy, 3-Methylbutoxy, 1, 1-Dimethylpropoxy, 1,2-Dimethylpropoxy, 2,2-Dimethylpropόxy, 1-Ethylpropoxy, n-Hexoxy, 1-Methylpentoxy, 2-Methylpentoxy, 3-Methylpentoxy, 4-Methylpentoxy, 1,1-Dimethylbutoxy, 1,2-Dimethylbutoxy, 1,3-Dimethylbutoxy, 2,2- Dimethylbutoxy, 2, 3-Dimethylbutoxy, 3,3-Dimethylbutoxy,1- (phenylmethyl) -eth-1-yl, 1- (phenylmethyl) -1- (methyl) -eth-1-yl, and 1- (phenylmethyl) prop-1-yl, preferably benzyl; - C 1 -C 6 alkoxy: methoxy, ethoxy, n-propoxy, 1-methylethoxy, n-butoxy, 1-methyl-propoxy, 2-methylpropoxy, 1,1-dimethylethoxy, n-pentoxy, 1-methylbutoxy, 2 -Methylbutoxy, 3-methylbutoxy, 1, 1-dimethylpropoxy, 1,2-dimethylpropoxy, 2,2-dimethylpropόxy, 1-ethylpropoxy, n-hexoxy, 1-methylpentoxy, 2-methylpentoxy, 3-methylpentoxy, 4-methylpentoxy, 1 , 1-dimethylbutoxy, 1,2-dimethylbutoxy, 1,3-dimethylbutoxy, 2,2-dimethylbutoxy, 2, 3-dimethylbutoxy, 3,3-dimethylbutoxy,
1-Ethylbutoxy, 2-Ethylbutoxy, 1,1,2-Trimethylpropoxy, 1,2,2- Trimethylpropoxy, 1-Ethyl-1-methylpropoxy und 1-Ethyl-2- methylpropoxy, vorzugsweise C1-C4-Alkoxy wie Methoxy und Ethoxy; - C1-C6-Halogenalkoxy: 2-Fluorethyloxy, 2,2-Difluorethyloxy, 2,2,2-Trifluorethyloxy, 2-Chlor-2-fluorethyloxy, 1-ethylbutoxy, 2-ethylbutoxy, 1,1,2-trimethylpropoxy, 1,2,2-trimethylpropoxy, 1-ethyl-1-methylpropoxy and 1-ethyl-2-methylpropoxy, preferably C 1 -C 4 alkoxy such as methoxy and ethoxy; C 1 -C 6 haloalkoxy: 2-fluoroethyloxy, 2,2-difluoroethyloxy, 2,2,2-trifluoroethyloxy, 2-chloro-2-fluoroethyloxy,
2-Chlor-2,2-difluorethyloxy, 2,2-Dichlor-2-fluorethyloxy, 2,2,2-Trichiorethyloxy und 3-Brom-prop-1-yloxy; - C1-C6-Alkylthio: Methylthio, Ethylthio, n-Propylthio, 2-chloro-2,2-difluoroethyloxy, 2,2-dichloro-2-fluoroethyloxy, 2,2,2-trichiorethyloxy and 3-bromo-prop-1-yloxy; C 1 -C 6 alkylthio: methylthio, ethylthio, n-propylthio,
1-Methylethylthio, n-Butylthio, 1-Methyl-propylthio,  1-methylethylthio, n-butylthio, 1-methyl-propylthio,
2-Methylpropylthio, 1,1-Dimethylethylthio, n-Pentylthio, 1-Methylbutylthio, 2-Methylbutylthio, 3-Methylbutylthio, 1,1-Dimethylpropylthio, 1,2-Dimethylpropylthio, 2,2-Dimethylpropylthio, 1-Ethylpropylthio, n-Hexylthio, 1-Methyl pentylthio, 2-Methylpentylthio, 3-Methylpentylthio, 2-methylpropylthio, 1,1-dimethylethylthio, n-pentylthio, 1-methylbutylthio, 2-methylbutylthio, 3-methylbutylthio, 1,1-dimethylpropylthio, 1,2-dimethylpropylthio, 2,2-dimethylpropylthio, 1-ethylpropylthio, n- Hexylthio, 1-methyl pentylthio, 2-methylpentylthio, 3-methylpentylthio,
4-Methylpentylthio, 1,1-Dimethylbuty lthio, 1,2-Dimethylbutylthio, 1,3-Dimethylbutylthio, 2,2-Dimethylbutylthio, 2,3-Dimethylbutylthio, 3,3-Dimethylbutylthio, 1-Ethylbutylth i o, 2-Ethyl butyl th i o, 1,1,2-Tr i methyl propy l th i o, 1,2,2- 4-methylpentylthio, 1,1-dimethylbutylthio, 1,2-dimethylbutylthio, 1,3-dimethylbutylthio, 2,2-dimethylbutylthio, 2,3-dimethylbutylthio, 3,3-dimethylbutylthio, 1-ethylbutylthio, 2-ethylbutyl th io, 1,1,2-Tr i methyl propy l th io, 1,2,2-
Trimethylpropylthio, 1-Ethyl-1-methy lpropylthio und 1-Ethyl- 2-methylpropylthio, vorzugsweise Cχ-C4~Alkylthio wie Methylthio und Ethylthio; - C1-C6-Alkoxy-C1-C6-alkyl: Methoxymethyl, Ethoxymethyl, Trimethylpropylthio, 1-ethyl-1-methylpropylthio and 1-ethyl-2-methylpropylthio, preferably Cχ-C4 ~ alkylthio such as methylthio and ethylthio; C 1 -C 6 alkoxy-C 1 -C 6 alkyl: methoxymethyl, ethoxymethyl,
n-Propoxymethyl, (1-Methylethoxy)methyl, n-Butoxymethyl, (1-Methylpropoxy)methyl, (2-Methylpropoxy)methyl, (1,1-Dimethylethoxy)methyl, Methoxyethyl, Ethoxyethyl, n-Propoxyethyl, (1-Methylethoxy)ethyl, n-Butoxyethyl, (1-Methylpropoxy)ethyl, (2-Methylpropoxy)ethyl, (1,1-Dimethylethoxy)- ethyl, 3-(Methoxy)propyl, 2-(Methoxy)propyl und 2-(Ethoxy)- propyl, vorzugsweise C1-C4-Alkoxy-C1-C2-alkyl wie Methoxymethyl, Ethoxymethyl, 2-Methoxyethyl und 2-Ethoxyethyl; - C1-C6-Alkylamino: Methylamino, Ethylamino, n-Propylamino, 1-Methylethylamino, n-Butylamino, 1-Methylpropylamino, 2-Methylpropylamino, 1,1-Dimethylethylamino, n-Pentylamino, 1-Methylbutylamino, 2-Methylbutylamino, 3-Methylbutylamino, 2,2-Dimethylpropylamino, 1-Ethylpropylamino, n-Hexylamino, 1,1-Dimethylpropylamino, 1,2-Dimethylpropylamino, 1-Methylpentylamino, 2-Methylpentylamino, 3-Methylpentylamino, 4-Methylpentylamino, 1,1-Dimethylbutylamino, 1, 2-Dimethylbutylamino, 1,3-Dimethylbutylamino, 2,2-Dimethylbutylamino, 2,3-Dimethylbutylamino, 3,3-Dimethylbutylamino, 1-Ethylbutylamino, 2-Ethylbutylamino, 1,1,2-Trimethylpropylamino, 1,2,2-Trimethylpropylamino, 1-Ethyl-1-methylpropylamino und 1-Ethyl-2-methylpropylamino, vorzugsweise C1-C4-Alkylamino wie Methylamino und Ethylamino; - Di-(C1-C6)-alkylamino: N,N-Dimethylamino, N,N-Diethylamino, N,N-Dipropylamino, N,N-Di-(1-methylethyl)amino, N,N-Dibutylamino, N,N-Di-(1-methylpropyl)amino, N,N-Di-(2-methylpropyl)amino, N,N-Di-(1,1-dimethylethyl)amino, N-Ethyl-N- methylamino, N-Methyl-N-propylamino, N-Methyl-N-(1-methylethyl)amino, N-Butyl-N-methylamino, N-Methyl-N-(1-methylpropyl)amino, N-Methyl-N-(2-methylpropyl)amino, N-(1,1-Di methylethyl)-N-methylamino, N-Ethyl-N-propylamino, N-Ethyl- N-(1-methyl-ethyl)amino, N-Butyl-N-ethylamino, N-Ethyl-N- (1-methyl-propyl) amino, N-Ethyl-N-(2-methylpropyl)amino, N-Ethyl-N-(1,1-dimethylethyl) amino, N-(1-Methylethyl)-N- propylamino, N-Butyl-N-propylamino, N-(1-Methylpropyl)-N- propylamino, N-(2-Methylpropyl)-N-propylamino, N-(1,1-Dimethylethyl)-N-propylamino, N-Butyl-N-(1-methyl-ethyl)amino, N-(1-Methylethyl)-N-(1-methylpropyl)amino, N-(1-Methylethy l)-N-(2-methylpropyl)amino, N-(1,1-Dimethylethyl)-N-(1- methylethyl) amino, N-Butyl-N-(l-methylpropyl)amino, N-Butyl- N-(2-methylpropyl) amino, N-Butyl-N-(1,1-dimethylethyl)amino, N-(1-Methylpropyl)-N-(2-methylpropyl)amino, N-(1,1-Dimethyl- ethyl)-N-(1-methylpropyl)amino und N-(1,1-Dimethylethyl)-N- (2-methylpropyl)amino, vorzugsweise Dimethyl amino und n-propoxymethyl, (1-methylethoxy) methyl, n-butoxymethyl, (1-methylpropoxy) methyl, (2-methylpropoxy) methyl, (1,1-dimethylethoxy) methyl, methoxyethyl, ethoxyethyl, n-propoxyethyl, (1-methylethoxy ) ethyl, n-butoxyethyl, (1-methylpropoxy) ethyl, (2-methylpropoxy) ethyl, (1,1-dimethylethoxy) ethyl, 3- (methoxy) propyl, 2- (methoxy) propyl and 2- (ethoxy) - Propyl, preferably C 1 -C 4 alkoxy-C 1 -C 2 alkyl such as methoxymethyl, ethoxymethyl, 2-methoxyethyl and 2-ethoxyethyl; C 1 -C 6 alkylamino: methylamino, ethylamino, n-propylamino, 1-methylethylamino, n-butylamino, 1-methylpropylamino, 2-methylpropylamino, 1,1-dimethylethylamino, n-pentylamino, 1-methylbutylamino, 2-methylbutylamino , 3-methylbutylamino, 2,2-dimethylpropylamino, 1-ethylpropylamino, n-hexylamino, 1,1-dimethylpropylamino, 1,2-dimethylpropylamino, 1-methylpentylamino, 2-methylpentylamino, 3-methylpentylamino, 4-methylpentylamino, 1.1 -Dimethylbutylamino, 1, 2-dimethylbutylamino, 1,3-dimethylbutylamino, 2,2-dimethylbutylamino, 2,3-dimethylbutylamino, 3,3-dimethylbutylamino, 1-ethylbutylamino, 2-ethylbutylamino, 1,1,2-trimethylpropylamino, 1 , 2,2-trimethylpropylamino, 1-ethyl-1-methylpropylamino and 1-ethyl-2-methylpropylamino, preferably C 1 -C 4 alkylamino such as methylamino and ethylamino; Di- (C 1 -C 6 ) alkylamino: N, N-dimethylamino, N, N-diethylamino, N, N-dipropylamino, N, N-di- (1-methylethyl) amino, N, N-dibutylamino, N, N-di- (1-methylpropyl) amino, N, N-di- (2-methylpropyl) amino, N, N-di- (1,1-dimethylethyl) amino, N-ethyl-N-methylamino, N -Methyl-N-propylamino, N-methyl-N- (1-methylethyl) amino, N-butyl-N-methylamino, N-methyl-N- (1-methylpropyl) amino, N-methyl-N- (2- methylpropyl) amino, N- (1,1-di methylethyl) -N-methylamino, N-ethyl-N-propylamino, N-ethyl-N- (1-methyl-ethyl) amino, N-butyl-N-ethylamino, N-ethyl-N- (1-methyl-propyl ) amino, N-ethyl-N- (2-methylpropyl) amino, N-ethyl-N- (1,1-dimethylethyl) amino, N- (1-methylethyl) -N-propylamino, N-butyl-N-propylamino , N- (1-methylpropyl) -N-propylamino, N- (2-methylpropyl) -N-propylamino, N- (1,1-dimethylethyl) -N-propylamino, N-butyl-N- (1-methyl- ethyl) amino, N- (1-methylethyl) -N- (1-methylpropyl) amino, N- (1-methylethyl) -N- (2-methylpropyl) amino, N- (1,1-dimethylethyl) -N - (1-methylethyl) amino, N-butyl-N- (l-methylpropyl) amino, N-butyl-N- (2-methylpropyl) amino, N-butyl-N- (1,1-dimethylethyl) amino, N - (1-Methylpropyl) -N- (2-methylpropyl) amino, N- (1,1-dimethylethyl) -N- (1-methylpropyl) amino and N- (1,1-dimethylethyl) -N- ( 2-methylpropyl) amino, preferably dimethyl amino and
Diethylamino; - C1-C6-Alkylcarbonyl : Methylcarbonyl, Ethylcarbonyl, Propylcarbonyl, 1-Methylethyl-carbonyl, Butylcarbonyl, 1-Methylpropylcarbonyl, 2-Methylpropy lcarbonyl, 1,1-Dimethylethylcarbonyl, Pentylcarbonyl, 1-Methylbuty lcarbonyl, 2-Methylbuty lcarbonyl, 3-Methylbutylcarbonyl, 1,1-Dimethylpropylcarbonyl, 1,2-Dimethy lpropylcarbonyl, 2,2-Dimethy lpropylcarbonyl, 1-Ethylpropylcarbonyl, Hexylcarbonyl, 1-Methylpentylcarbonyl, 2-Methylpenty lcarbonyl, 3-Methylpentylcarbonyl, 4-Methylpentylcarbonyl, 1,1-Dimethylbutylcarbonyl, 1,2-Dimethylbuty lcarbonyl, 1,3-Dimethylbutylcarbonyl, 2,2- Dimethylbutylcarbonyl, 2,3-Dimethylbutylcarbonyl, 3,3-Dimethylbutylcarbonyl, 1-Ethylbuty lcarbonyl, 2-Ethylbutylcarbonyl, 1,1,2-Trimethylpropylcarbonyl, 1,2,2-Trimethylpropylcarbonyl, 1-Ethyl-1-methylpropylcarbonyl und 1-Ethyl2-methy lpropylcarbonyl, vorzugsweise C1-C4-Alkylcarbonyl wie Methylcarbonyl und Ethylcarbonyl; - C1-C6-Alkylcarbonyloxy : Methylcarbonyloxy, Ethylcarbonyloxy, n-Propy lcarbonyloxy, 1-Methylethylcarbonyloxy, n-Butylcarbonyloxy, 1-Methylpropylcarbonyloxy, 2-Methylpropylcarbonyloxy, 1,1-Dimethylethylcarbonyloxy, n-Pentylcarbonyloxy, 1-Methy lbuty lcarbonyloxy, 2-Methy lbuty lcarbonyloxy, Diethylamino; C 1 -C 6 alkylcarbonyl: methylcarbonyl, ethylcarbonyl, propylcarbonyl, 1-methylethylcarbonyl, butylcarbonyl, 1-methylpropylcarbonyl, 2-methylpropylcarbonyl, 1,1-dimethylethylcarbonyl, pentylcarbonyl, 1-methylbutylcarbonyl, 2-methylbutylcarbonyl, 3-methylbutylcarbonyl, 1,1-dimethylpropylcarbonyl, 1,2-dimethylpropylcarbonyl, 2,2-dimethylpropylcarbonyl, 1-ethylpropylcarbonyl, hexylcarbonyl, 1-methylpentylcarbonyl, 2-methylpentylcarbonyl, 3-methylpentylcarbonyl, 4-methylpentylcarbonyl, 1.1 -Dimethylbutylcarbonyl, 1,2-dimethylbutylcarbonyl, 1,3-dimethylbutylcarbonyl, 2,2-dimethylbutylcarbonyl, 2,3-dimethylbutylcarbonyl, 3,3-dimethylbutylcarbonyl, 1-ethylbutylcarbonyl, 2-ethylbutylcarbonyl, 1,1,2-trimethylpropylcarbonyl , 1,2,2-trimethylpropylcarbonyl, 1-ethyl-1-methylpropylcarbonyl and 1-ethyl2-methylpropylcarbonyl, preferably C 1 -C 4 alkylcarbonyl such as methylcarbonyl and ethylcarbonyl; C 1 -C 6 alkylcarbonyloxy: methylcarbonyloxy, ethylcarbonyloxy, n-propylcarbonyloxy, 1-methylethylcarbonyloxy, n-butylcarbonyloxy, 1-methylpropylcarbonyloxy, 2-methylpropylcarbonyloxy, 1,1-dimethylethylcarbonyloxy, n-pentylcarbonyloxy, 1-methyllbutylcarbonyloxy 2-methylbutylcarbonyloxy,
3-Methylbutylcarbonyloxy, 1, 1-Dimethylpropylcarbonyloxy, 1,2-Dimethylpropylcarbonyloxy, 2,2-Dimethylpropylcarbonyloxy, 1-Ethylpropylcarbonyloxy, n-Hexylcarbonyloxy, 1-Methyl pentylcarbonyloxy, 2-Methylpentylcarbonyloxy, 3-Methylpentylcarbonyloxy, 4-Methylpentylcarbonyloxy, 1,1-Dimethylbutylcarbonyloxy, 1,2-Dimethylbutylcarbonyloxy, 1,3-Dimethylbutylcarbonyloxy, 2,2-Dimethylbutylcarbonyloxy, 2,3-Dimethylbutylcarbonyloxy, 3,3-Dimethylbutylcarbonyloxy, 1-Ethylbutylcarbonyloxy, 2-Ethylbutylcarbonyloxy, 1,1,2-Trimethylpropylcarbonyloxy, 1,2,2-Trimethylpropylcarbonyloxy, 1-Ethyl-1-methylpropylcarbonyloxy und 1-Ethyl-2-methylpropylcarbonyloxy, vorzugsweise C1-C4-Alkylcarbonyloxy wie Methylcarbonyloxy und Ethylcarbonyloxy; - C1-C6-Alkylcarbamoyloxy wie Methylcarbamoyloxy, Ethylcarbamoyloxy, Propylcarbamoyloxy, 1-Methylethylcarbamoyloxy, Butylcarbamoyloxy, 1-Methylpropylcarbamoyloxy, 2-Methylpropylcarbamoyloxy, 1,1-Dimethylethylcarbamoyloxy, Pentylcarbamoyloxy, 1-Methylbutylcarbamoyloxy, 2-Methylbutylcarbamoyloxy, 3-Methylbutylcarbamoyloxy, 1,1-Dimethylpropylcarbamoyloxy, 1,2-Dimethylpropylcarbamoyloxy, 2,2-Dimethylpropylcarbamoyloxy, 1-Ethylpropylcarbamoyloxy, Hexylcarbamoyloxy, 1-Methylpentylcarbamoyloxy, 2-Methylpentylcarbamoyloxy, 3-Methylpentylcarbamoyloxy, 4-Methylpentylcarbamoyloxy, 1,1-Dimethylbutylcarbamoyloxy, 1,2-Dimethylbutylcarbamoyloxy, 1,3-Dimethylbutylcarbamoyloxy, 2,2-Dimethylbutylcarbamoyloxy, 2,3-Dimethylbutylcarbamoyloxy, 3,3-Dimethylbutylcarbamoyloxy, 1-Ethylbutylcarbamoyloxy,3-methylbutylcarbonyloxy, 1, 1-dimethylpropylcarbonyloxy, 1,2-dimethylpropylcarbonyloxy, 2,2-dimethylpropylcarbonyloxy, 1-ethylpropylcarbonyloxy, n-hexylcarbonyloxy, 1-methyl pentylcarbonyloxy, 2-methylpentylcarbonyloxy, 3-methylpentylcarbonyloxy, 4-methylpentylcarbonyloxy, 1,1-dimethylbutylcarbonyloxy, 1,2-dimethylbutylcarbonyloxy, 1,3-dimethylbutylcarbonyloxy, 2,2-dimethylbutylcarbonyloxy, 2,3-dimethylbutylcarbonyloxy, 3,3-dimethylbutylcarbonyl 1-ethylbutylcarbonyloxy, 2-ethylbutylcarbonyloxy, 1,1,2-trimethylpropylcarbonyloxy, 1,2,2-trimethylpropylcarbonyloxy, 1-ethyl-1-methylpropylcarbonyloxy and 1-ethyl-2-methylpropylcarbonyloxy, preferably C 1 -C 4 alkylcarbonyloxy such as methylcarbonyloxy and ethyl carbonyloxy; - C 1 -C 6 alkylcarbamoyloxy as methylcarbamoyloxy, ethylcarbamoyloxy, propylcarbamoyloxy, 1-Methylethylcarbamoyloxy, butylcarbamoyloxy, 1-Methylpropylcarbamoyloxy, 2-Methylpropylcarbamoyloxy, 1,1-Dimethylethylcarbamoyloxy, Pentylcarbamoyloxy, 1-Methylbutylcarbamoyloxy, 2-Methylbutylcarbamoyloxy, 3-Methylbutylcarbamoyloxy, 1 , 1-Dimethylpropylcarbamoyloxy, 1,2-Dimethylpropylcarbamoyloxy, 2,2-Dimethylpropylcarbamoyloxy, 1-Ethylpropylcarbamoyloxy, Hexylcarbamoyloxy, 1-Methylpentylcarbamoyloxy, 2-Methylpentylcarbamoyloxy, 3-Methylpentylcarbamoyyloxyamoxyloxyamoxyloxyamoxyloxyamoxyloxyamoxyloxyamoxyloxyamoxyloxyamoxyloxyamoxyloxyamoxyloxyamoxyloxyamoxyloxyamoxyloxyamoxyloxyamoxyloxyamoxyloxyamoxyloxyamoxyloxyamoxyloxyamoxyloxyamoxyloxyamoxyloxyamoxyloxyamoyloxyamoxyloxyamoxyloxyamoxyloxyamoyloxyamoxyloxyamoyloxyamoyloxyamoxyloxyamoxyoxy , 1,3-dimethylbutylcarbamoyloxy, 2,2-dimethylbutylcarbamoyloxy, 2,3-dimethylbutylcarbamoyloxy, 3,3-dimethylbutylcarbamoyloxy, 1-ethylbutylcarbamoyloxy,
2-Ethylbutylcarbamoyloxy, 1,1,2-Trimethylpropylcarbamoyloxy, 1,2,2-Trimethylpropylcarbamoyloxy, 1-Ethyl-1-methylpropylcarbamoyloxy und 1-Ethyl-2-methylpropylcarbamoyloxy, vorzugsweise C1-C4-Alkylcarbamoyloxy, insbesondere 2-ethylbutylcarbamoyloxy, 1,1,2-trimethylpropylcarbamoyloxy, 1,2,2-trimethylpropylcarbamoyloxy, 1-ethyl-1-methylpropylcarbamoyloxy and 1-ethyl-2-methylpropylcarbamoyloxy, preferably C 1 -C 4 alkylcarbamoyloxy, in particular
Methylcarbamoyloxy und Ethylcarbamoyloxy; - C1-C6-Halogenalkylcarbamoyloxy, besonders C1-C2-Halogenalkylcarbamoyloxy wie Chlormethylcarbamoyloxy, Dichlormethylcarbamoyloxy, Trichlormethylcarbamoyloxy, Fluormethylcarbamoyloxy, Difluormethzylcarbamoyloxy, Trifluormethylcarbamoyloxy, Chlorfluormethylcarbamoyloxy, Dichlorfluormethylcarbamoyloxy, Chlordifluormethylcarbamoyloxy, 1-Fluorethylcarbamoyloxy, 2-Fluorethylcarbamoyloxy, 2,2-Difluorethylcarbamoyloxy, 2,2,2-Trifluorethylcarbamoyloxy, 2-Chlor-2-fluorethylcarbamoyloxy, 2-Chlor-2,2-difluorethylcarbamoyloxy, 2,2-Dichlor-2-fluorethylcarbamoyloxy, 2,2,2-Trichlorethylcarbamoyloxy und Pentafluorethylcarbamoyloxy; - C1-C2-Halogenalkylcarbonyloxy: Chloracetyl, Dichloracetyl, Trichloracetyl, Fluoracetyl, Difluoracetyl, Trifluoracetyl, Chlorfluoracetyl, Dichlorfluoracetyl, Chlordifluoracetyl, α-Fluorpropionyl, β-Fluorpropionyl, β,β,β-Difluorpropionyl, β,β,β-Trifluorpropionyl, β-Chlor-β-fluorpropionyl, β-Chlorβ,β-difluorpropionyl, β,β-Dichlor-β-fluorpropionyl, β,β,β- Trichlorpropionyl und Pentafluorpropionyl, vorzugsweise Trichloracetyl und Trifluoracetyl; - C1-C6-Alkoxycarbonyl-C1-C6-alkyl: Methoxycarbonylmethyl, Ethoxycarbony Imethyl, n-Propoxycarbony Imethyl, (1-Methylethoxycarbonyl)methyl, n-Butoxycarbonylmethyl, (1-Methylpropoxycarbonyl)methyl, (2-Methylpropoxycarbonyl)methyl, (1,1-Dimethylethoxycarbonyl)methyl, Methoxycarbonylethyl, Ethoxycarbonylethyl, n-Propoxycarbonylethyl, (1-Methylethoxycarbonyl)ethyl, n-Butoxycarbonylethyl, (1-Methylpropoxycarbonyl)ethyl, (2-Methylpropoxycarbonyl)ethyl, (1,1-Dimethylethoxycarbony l)ethyl, 3-(Methoxycarbonyl)- propyl, 2-(Methoxycarbonyl)propyl und 2-(Ethoxycarbonyl)- propyl;, vorzugsweise C1-C4-Alkoxycarbonyl-C1-C2-alkyl wie Methoxycarbonylmethyl, Ethoxycarbonylmethyl, 2-Methoxycarbonylethyl und 2-Ethoxycarbonylethyl; - Di-(C1-C6)-alkylamino-(C1-C6)-alkoxy: N,N-Dimethylaminoethoxy, N,N-Diethylaminoethoxy, N,N-Di (n-propyl )aminoethoxy, N,N-Di-(1-methylethyl)aminoethoxy, N,N-Dibutylaminoethoxy, N,N-Di-(1-methylpropyl)aminoethoxy, N,N-Di-(2-methylpropyl)- aminoethoxy, N,N-Di-(1,1-dimethylethyl)aminoethoxy, N-EthylN-methylaminoethoxy, N-Methyl-N-propylaminoethoxy, N-Methyl¬Methyl carbamoyloxy and ethyl carbamoyloxy; - C 1 -C 6 -Halogenalkylcarbamoyloxy, especially C 1 -C 2 -Halogenalkylcarbamoyloxy as Chlormethylcarbamoyloxy, Dichlormethylcarbamoyloxy, Trichlormethylcarbamoyloxy, Fluormethylcarbamoyloxy, Difluormethzylcarbamoyloxy, Trifluormethylcarbamoyloxy, Chlorfluormethylcarbamoyloxy, Dichlorfluormethylcarbamoyloxy, Chlordifluormethylcarbamoyloxy, 1-Fluorethylcarbamoyloxy, 2-Fluorethylcarbamoyloxy, 2,2-difluoroethylcarbamoyloxy, 2,2,2-trifluoroethylcarbamoyloxy, 2-chloro-2-fluoroethylcarbamoyloxy, 2-chloro-2,2-difluoroethylcarbamoyloxy, 2,2-dichloro-2-fluoroethylcarbamoyloxy, 2,2,2-trichloroethylcarbamoyloxy and Pentafluoroethylcarbamoyloxy; - C 1 -C 2 haloalkylcarbonyloxy: chloroacetyl, dichloroacetyl, trichloroacetyl, fluoroacetyl, difluoroacetyl, trifluoroacetyl, chlorofluoroacetyl, dichlorofluoroacetyl, chlorodifluoroacetyl, α-fluoropropionyl, β-fluoropropionyl, βifluoropionyl, βif, βifluoropionyl, βif, βifluoropionyl, βif, βifluoropionyl, βif, βifluoropionyl, βif, βifluoropionyl, βif, βifluoropionyl, βif, βifluoropionyl, βif, βifluoropetyl, βif, βifluoropetyl, βif, β-fluoropro, , β-chloro-β-fluoropropionyl, β-chloroβ, β-difluoropropionyl, β, β-dichloro-β-fluoropropionyl, β, β, β-trichloropropionyl and pentafluoropropionyl, preferably trichloroacetyl and trifluoroacetyl; - C 1 -C 6 alkoxycarbonyl-C 1 -C 6 alkyl: methoxycarbonylmethyl, ethoxycarbony imethyl, n-propoxycarbony imethyl, (1-methylethoxycarbonyl) methyl, n-butoxycarbonylmethyl, (1-methylpropoxycarbonyl) methyl, (2-methylpropoxycarbonyl) methyl, (1,1-dimethylethoxycarbonyl) methyl, methoxycarbonylethyl, ethoxycarbonylethyl, n-propoxycarbonylethyl, (1-methylethoxycarbonyl) ethyl, n-butoxycarbonylethyl, (1-methylpropoxycarbonyl) ethyl, (2-methylpropoxycarbonyl) ethyl, (1,1-dimethylethoxycarbony l) ethyl, 3- (methoxycarbonyl) propyl, 2- (methoxycarbonyl) propyl and 2- (ethoxycarbonyl) propyl; preferably C 1 -C 4 alkoxycarbonyl-C 1 -C 2 alkyl such as methoxycarbonylmethyl, ethoxycarbonylmethyl, 2nd -Methoxycarbonylethyl and 2-ethoxycarbonylethyl; - Di- (C 1 -C 6 ) alkylamino- (C 1 -C 6 ) alkoxy: N, N-dimethylaminoethoxy, N, N-diethylaminoethoxy, N, N-di (n-propyl) aminoethoxy, N, N -Di- (1-methylethyl) aminoethoxy, N, N-dibutylaminoethoxy, N, N-Di- (1-methylpropyl) aminoethoxy, N, N-Di- (2-methylpropyl) - aminoethoxy, N, N-Di- ( 1,1-dimethylethyl) aminoethoxy, N-ethylN-methylaminoethoxy, N-methyl-N-propylaminoethoxy, N-methyl¬
N-(1-methy lethyl)aminoethoxy, N-Butyl-N-methylaminoethoxy, N-Methy l-N-(1-methylpropyl)aminoethoxy, N-Methy l-N-(2- methylpropyl)aminoethoxy, N-(1,1-Dimethylethyl)-N-methylaminoethoxy, N-Ethyl-N-propylaminoethoxy, N-Ethyl-N-(1- methy l-ethyl)aminoethoxy, N-Butyl-N-ethylaminoethoxy, N-Ethyl-N-(1-methylpropyl)aminoethoxy, N-Ethyl-N-(2-methylpropyl)aminoethoxy, N-Ethyl-N-(1,1-dimethylethyl)aminoethoxy, N-(1-Methylethyl)-N-propylaminoethoxy, N-Butyl-N- propylaminoethoxy, N-(1-Methylpropyl)-N-propylaminoethoxy, N-(2-Methylpropyl)-N-propylaminoethoxy, N-(1,1-Dimethylethyl)-N-propylaminoethoxy, N-Butyl-N-(1-methylethyl)aminoethoxy, N-(1-Methylethyl)-N-(1-methylpropyl)aminoethoxy, N-(1-Methylethyl)-N-(2-methylpropyl)aminoethoxy, N-(1,1-Dimethylethyl)-N-(1-methylethyl)aminoethoxy, N-Butyl-N-(1- methylpropyl)aminoethoxy, N-Butyl-N-(2-methylpropyl)aminoethoxy, N-Butyl-N-(1,1-dimethylethyl)aminoethoxy, N- (1-methylethyl) aminoethoxy, N-butyl-N-methylaminoethoxy, N-methyl 1N- (1-methylpropyl) aminoethoxy, N-methyl 1N- (2-methylpropyl) aminoethoxy, N- (1,1-dimethylethyl ) -N-methylaminoethoxy, N-ethyl-N-propylaminoethoxy, N-ethyl-N- (1-methyl-ethyl) aminoethoxy, N-butyl-N-ethylaminoethoxy, N-ethyl-N- (1-methylpropyl) aminoethoxy, N-ethyl-N- (2-methylpropyl) aminoethoxy, N-ethyl-N- (1,1-dimethylethyl) aminoethoxy, N- (1-methylethyl) -N -propylaminoethoxy, N-butyl-N-propylaminoethoxy, N- (1-methylpropyl) -N-propylaminoethoxy, N- (2-methylpropyl) -N-propylaminoethoxy, N- (1,1-dimethylethyl) -N-propylaminoethoxy, N -Butyl-N- (1-methylethyl) aminoethoxy, N- (1-methylethyl) -N- (1-methylpropyl) aminoethoxy, N- (1-methylethyl) -N- (2-methylpropyl) aminoethoxy, N- (1 , 1-dimethylethyl) -N- (1-methylethyl) aminoethoxy, N-butyl-N- (1-methylpropyl) aminoethoxy, N-butyl-N- (2-methylpropyl) aminoethoxy, N-butyl-N- (1, 1-dimethylethyl) aminoethoxy,
N-(1-Methylpropyl)-N-(2-methyl-propyl)aminoethoxy, N-(1,1- Dimethylethyl)-N-(1-methylpropyl)aminoethoxy, N-(1,1-Dimethylethyl)-N-(2-methylpropyl)aminoethoxy.  N- (1-methylpropyl) -N- (2-methylpropyl) aminoethoxy, N- (1,1-dimethylethyl) -N- (1-methylpropyl) aminoethoxy, N- (1,1-dimethylethyl) -N- (2-methylpropyl) aminoethoxy.
Die substituierten Phenylurazile I können in Form ihrer landwirtschaftlich brauchbaren Salze oder Enolether vorliegen, sofern R3 Wasserstoff bedeutet. Als landwirtschaftlich brauchbare Salze kommen im allgemeinen die Salze von solchen Basen in Betracht, welche die herbizide Wirkung von I nicht beeinträchtigen. The substituted phenylurazils I can be in the form of their agriculturally useful salts or enol ethers, provided that R 3 is hydrogen. Suitable salts which can be used in agriculture are in general the salts of bases which do not impair the herbicidal action of I.
Als basische Salze eignen sich besonders diejenigen der Alkali- metalle, vorzugsweise die Natrium- und Kaliumsalze, die der Erdalkalimetalle, vorzugsweise Calcium-, Magnesium- und Bariumsalze und die der Übergangsmetalle, vorzugsweise Mangan-, Kupfer, Zink- und Eisensalze sowie die Ammoniumsalze, die ein bis drei C1-C4- Alkyl-, Hydroxy-C1-C4-alkylsubstituenten und/oder einen Particularly suitable basic salts are those of the alkali metals, preferably the sodium and potassium salts, those of the alkaline earth metals, preferably calcium, magnesium and barium salts and those of the transition metals, preferably manganese, copper, zinc and iron salts and the ammonium salts, the one to three C 1 -C 4 alkyl, hydroxy-C 1 -C 4 alkyl substituents and / or one
Phenyl- oder Benzylsubstituenten tragen können, vorzugsweise Diisopropylammonium-, Tetramethylammonium-, Tetrabutylammonium-, Trimethylbenzylammonium- und Trimethyl-(2-hydroxyethyl)-ammonium- salze, die Phosphoniumsalze, die Sulfoniumsalze, vorzugsweise Tri-(C1-C4)alkylsufoniumsalze, und die Sulfoxoniumsalze, vorzugsweise Tri-(C1-C4)alkylsulfoxoniumsalze. Can carry phenyl or benzyl substituents, preferably diisopropylammonium, tetramethylammonium, tetrabutylammonium, trimethylbenzylammonium and trimethyl (2-hydroxyethyl) ammonium salts, the phosphonium salts, the sulfonium salts, preferably tri (C 1 -C 4 ) alkylsufoniums and the sulfoxonium salts, preferably tri (C 1 -C 4 ) alkylsulfoxonium salts.
Im Hinblick auf die Verwendung der erfindungsgemäßen 3-Phenylurazile I, Ia und Ib als herbizide, das Pflanzenwachstum regulierende und insektizid wirksame Verbindungen haben die Variablen vorzugsweise folgende Bedeutung: With regard to the use of the 3-phenylurazils I, Ia and Ib according to the invention as herbicidal, plant growth-regulating and insecticidally active compounds, the variables preferably have the following meaning:
wobei X1 und X2 unabhängig voneinander für Schwefel oder Sauerstoff stehen und die Variablen X, W, R1, R2, R3, R4, R23, R5, R56 beliebig miteinander kombiniert werden können, mit der Maßgabe, daß R4 nicht 4.27 bedeuten darf, wenn gleichzeitig R5 5,01 und W -C(R8)=C(R9)-CO-R10, wobei R8 8,01, R9 9.01 und R10 10.03-10.12 oder 10.20-10.23, bedeutet. where X 1 and X 2 independently of one another represent sulfur or oxygen and the variables X, W, R 1 , R 2 , R 3 , R 4 , R 23 , R 5 , R 56 can be combined with one another as desired, with the proviso that that R 4 must not mean 4.27 if R 5 5.01 and W -C (R 8 ) = C (R 9) -CO-R 10 , R 8 8.01, R 9 9.01 and R 10 10.03- 10.12 or 10.20-10.23 means.
Besonders bevorzugt bedeuten R1 einen Rest aus der Gruppe 1 .01 - 1.07, R 1 particularly preferably denotes a radical from the group 1.01-1.07,
R2 einen Rest aus der Gruppe 2.01 - 2.05, R 2 is a radical from the group 2.01-2.05,
R3 einen Rest aus der Gruppe 3.01 - 3.97, R 3 is a radical from the group 3.01-3.97,
R3' einen Rest aus der Gruppe 3' .01 - 3' . 17, R 3 'is a radical from group 3' .01 - 3 '. 17,
R4 einen Rest aus der Gruppe 4.01 - 4.72, R 4 is a residue from group 4.01-4.72,
R5 einen Rest aus der Gruppe 5.001 - 5.105 R 5 is a residue from the group 5.001 - 5.105
oder  or
R4 und R5 zusammen einen Rest aus der Gruppe 45.01 - 45.54 undR 4 and R 5 together form a residue from the group 45.01 - 45.54 and
W einen der folgenden Reste W1-W7: W1 -C(R8)(X3R6)(R4R7) W one of the following radicals W1-W7: W1 -C (R 8 ) (X 3 R 6 ) (R 4 R 7 )
W2 -C(R8)=X5, W2 -C (R 8 ) = X 5 ,
W3 -C(R8)=C(R9)-CO-R10, W3 -C (R 8 ) = C (R 9 ) -CO-R 10 ,
W4 -CR8=CR9-CH2-CO-R10, W4 -CR 8 = CR 9 -CH 2 -CO-R 10 ,
W5 -CR8=CR9-CR11=CR12-CO-R10, W5 -CR 8 = CR 9 -CR 11 = CR 12 -CO-R 10 ,
W6 -CR8=CR9-CH2-CHR13-CO-R10; W6 -CR 8 = CR 9 -CH 2 -CHR 13 -CO-R 10 ;
W7 -CR8=CR9-CN; wobei X3 und X4 unabhängig voneinander O oder S, W7 -CR 8 = CR 9 -CN; where X 3 and X 4 are independently O or S,
X5 O, S oder NR14, X 5 O, S or NR 14 ,
R6 und R7 unabhängig voneinander einen Rest aus der Gruppe 6.01 - 6.19, R 6 and R 7 independently of one another are a radical from group 6.01-6.19,
oder R6 und R7 zusammen einen Rest aus der Gruppe 67.01 - 67.63, R8 einen Rest aus der Gruppe 8.01 - 8.22, or R 6 and R 7 together a radical from the group 67.01-67.63, R 8 a radical from the group 8.01-8.22,
R9 und R12 einen Rest aus der Gruppe 9.01 - 9.23, R10 einen Rest aus der Gruppe 10.01 - 10.144, R 9 and R 12 are a residue from group 9.01 - 9.23, R 10 is a residue from the group 10.01 - 10.144,
R11 einen Rest aus der Gruppe 11.01 - 11.25, R 11 is a residue from group 11.01 - 11.25,
R13 einen Rest aus der Gruppe 13.01 - 13.08, R 13 is a residue from the group 13.01 - 13.08,
R14 einen Rest aus der Gruppe 14.001 - 14.162, bedeuten und alle diese Reste beliebig miteinander kombiniert werden können. R 14 is a radical from the group 14.001-14.162, and all these radicals can be combined with one another as desired.
Besonders bevorzugt sind die folgenden 3-Phenylurazile I-1 bis I-24: The following 3-phenylurazils I-1 to I-24 are particularly preferred:
wobei w in den vorstehend genannten Formeln I-1 bis I-24 jeweils für eine der folgenden Bedeutungen steht: -CHO, -COCH3, -COC2H5, -CO-n-C3H7, -CO-i-C3H7, -CO-n-C4H9,where w in the above formulas I-1 to I-24 each has one of the following meanings: -CHO, -COCH 3 , -COC 2 H 5 , -CO-nC 3 H 7 , -CO-iC 3 H 7 , -CO-nC 4 H 9 ,
-CO-i-C4H9, -CO-S-C4H9, -CO-tert.-C4H9, -CO-CH2CH=CH2, -CO-CF3, -COCCI3, -COCH2C≡CH, -CO-cyclopropyl, -CO-cyclobutyl, -CO-cyclopentyl, -CO-cyclohexyl, -CO-CN, -CO-COOCH3, -CO-COOC2H5, -CH=NH, -CH=NCH3, -CH=NC2H5, -CH=N-n-C3Hs, -CH=N-i-C3H5, -CH=N-n-C4H9, -CH=NCH2CH=CH2, -CH=NCH2CH=CH2-CH3, -CH=NCH2C≡CH, -CO-iC 4 H 9 , -CO-SC 4 H 9 , -CO-tert.-C 4 H 9 , -CO-CH 2 CH = CH 2 , -CO-CF 3 , -COCCI 3 , -COCH 2 C≡CH, -CO-cyclopropyl, -CO-cyclobutyl, -CO-cyclopentyl, -CO-cyclohexyl, -CO-CN, -CO-COOCH 3 , -CO-COOC 2 H 5 , -CH = NH, -CH = NCH 3 , -CH = NC 2 H 5 , -CH = NnC 3 Hs, -CH = NiC 3 H 5 , -CH = NnC 4 H 9 , -CH = NCH 2 CH = CH 2 , -CH = NCH 2 CH = CH 2 -CH 3 , -CH = NCH 2 C≡CH,
-CH=NCH2C≡C-CH3, -CH=N-cyclopropyl, -CH=N-cyclobutyl, -CH = NCH 2 C≡C-CH 3 , -CH = N-cyclopropyl, -CH = N-cyclobutyl,
-CH=N-cyclopentyl, -CH=N-cyclohexyl, -CH=N-cycloheptyl, -CH = N-cyclopentyl, -CH = N-cyclohexyl, -CH = N-cycloheptyl,
-CH=N-CH2-CH2Cl, -CH=N-CH2Cl, -CH=N-C6H5, -CH=N-4-Br-C6H4, -CH=N-3-F-C6H4, -CH=N-4-F-C6H4, -CH=N-2-Cl-C6H4, -CH=N-3-C1-C6H4, -CH=N-4-Cl-C6H4, -CH=N-2-Br-C6H4, -CH=N-2-F-C6H4, -CH = N-CH 2 -CH 2 Cl, -CH = N-CH 2 Cl, -CH = NC 6 H 5 , -CH = N-4-Br-C 6 H 4 , -CH = N-3- FC 6 H 4 , -CH = N-4-FC 6 H 4 , -CH = N-2-Cl-C 6 H 4 , -CH = N-3-C 1 -C 6 H 4 , -CH = N -4-Cl-C 6 H 4 , -CH = N-2-Br-C 6 H 4 , -CH = N-2-FC 6 H 4 ,
-CH=N-2-CH3-C6H4, -CH=N-3-CH3-C6H4, -CH=N-4-CH3-C6H4, -CH = N-2-CH 3 -C 6 H 4 , -CH = N-3-CH 3 -C 6 H 4 , -CH = N-4-CH 3 -C 6 H 4 ,
-CH=N-2-CF3-C6H4, -CH-N-3-CF3-C6H4, -CH=N-4-CF3-C6H4, -CH = N-2-CF 3 -C 6 H 4 , -CH-N-3-CF 3 -C 6 H 4 , -CH = N-4-CF 3 -C 6 H 4 ,
-CH=N-2-OCH3-C6H4, -CH=N-3-OCH3-C6H4, -CH=N-4-OCH3-C6H4, -CH = N-2-OCH 3 -C 6 H 4 , -CH = N-3-OCH 3 -C 6 H 4 , -CH = N-4-OCH 3 -C 6 H 4 ,
-CH=N-4-NO2-C6H4, -CH=N-4-CN-C6H4, -CH=N-2, 4-(Cl, Cl )-C6H4, -CH=N-2,4-(CH3,CH3)-C6H4, -CH=N-CH2OCH3, -CH=N-CH2OC2H5, -CH = N-4-NO 2 -C 6 H 4 , -CH = N-4-CN-C 6 H 4 , -CH = N-2, 4- (Cl, Cl) -C 6 H 4 , - CH = N-2,4- (CH 3 , CH 3 ) -C 6 H 4 , -CH = N-CH 2 OCH 3 , -CH = N-CH 2 OC 2 H 5 ,
-CH=N-CH2CH2OCH3, -CH=N-CH2CH2OC2H5, -CH=N-OH, -CH=N-OCH3, -CH=N-OC2H5, -CH=N-O-n-C3H7, -CH=N-O-i-C3H7, -CH=N-O-n-C4H9, -CH=N-O-i-C4H9, -CH=N-O-S-C4H9, -CH=N-O-tert.-C4H9, -CH=N-O-CH2CH=CH2, -CH=N-O-CH(CH3)CH=CH2, -CH=N-O-CH2C≡CH, -CH=N-O-CH(CH3)-C≡CH, -CH=N-O-CH2-CH=CH-CH3, -CH=N-O-CH2-CH2-Cl, -CH=N-O-CH2-CH2-F, -CH=N-O-CH2-CF3, -CH=N-O-CH2-CH=CHCl, -CH = N-CH 2 CH 2 OCH 3 , -CH = N-CH 2 CH 2 OC 2 H 5 , -CH = N-OH, -CH = N-OCH 3 , -CH = N-OC 2 H 5 , -CH = NOnC 3 H 7 , -CH = NOiC 3 H 7 , -CH = NOnC 4 H 9 , -CH = NOiC 4 H 9 , -CH = NOSC 4 H 9 , -CH = NO-tert.-C 4 H 9 , -CH = NO-CH 2 CH = CH 2 , -CH = NO-CH (CH 3 ) CH = CH 2 , -CH = NO-CH 2 C≡CH, -CH = NO-CH (CH 3 ) -C ≡CH, -CH = NO-CH 2 -CH = CH-CH 3 , -CH = NO-CH 2 -CH 2 -Cl, -CH = NO-CH 2 -CH 2 -F, -CH = NO-CH 2 -CF 3 , -CH = NO-CH 2 -CH = CHCl,
-CH=N-O-CH2-CCl=CH2, -CH=N-O-CH2-CBr=CH2, -CH=N-O-CH2-CH=CCl-CH3, -CH=N-OC(O)CH3, -CH=N-OC(O)C2H5, -CH=N-O-CH2-CN, -CH = NO-CH 2 -CCl = CH 2 , -CH = NO-CH 2 -CBr = CH 2 , -CH = NO-CH 2 -CH = CCl-CH 3 , -CH = N-OC (O) CH 3 , -CH = N-OC (O) C 2 H 5 , -CH = NO-CH 2 -CN,
-CH=N-O-CH2-CH=CH-CH2-O-CH3, -CH=N-O-CH2-CH=CH-CH2-O-tert.-C4H9, -CH=N-O-(CH2)3-C6H5, -CH=N-O-(CH2)4-C6H5, -CH = NO-CH 2 -CH = CH-CH 2 -O-CH 3 , -CH = NO-CH 2 -CH = CH-CH 2 -O-tert.-C 4 H 9 , -CH = NO- (CH 2 ) 3 -C 6 H 5 , -CH = NO- (CH 2 ) 4 -C 6 H 5 ,
-CH=N-O-(CH2)4-4-Cl-C6H4, -CH=N-O-(CH2)4-4-OCH3-C6H4, -CH = NO- (CH 2 ) 4 -4-Cl-C 6 H 4 , -CH = NO- (CH 2 ) 4 -4-OCH 3 -C 6 H 4 ,
-CH=N-O-(CH2)4-4-CH3-C6H4, -CH=N-O-(CH2)4-4-F-C6H4, -CH = NO- (CH 2 ) 4 -4-CH 3 -C 6 H 4 , -CH = NO- (CH 2 ) 4 -4-FC 6 H 4 ,
-CH=N-O-CH2CH=CH-C6H5, -CH=N-O-CH2CH=CH-4-F-C6H4, -CH = NO-CH 2 CH = CH-C 6 H 5 , -CH = NO-CH 2 CH = CH-4-FC 6 H 4 ,
-CH=N-O-CH2CH=CH-4-Cl-C6H4, -CH=N-O-CH2CH=CH-3-OCH3-C6H4, -CH = NO-CH 2 CH = CH-4-Cl-C 6 H 4 , -CH = NO-CH 2 CH = CH-3-OCH 3 -C 6 H 4 ,
-CH=N-O-(CH2)2CH=CH-4-F-C6H4, -CH=N-O-(CH2)CH=CH-4-Cl-C6H4, -CH=N-O-CH2CH=CHCH2-4-OCH3-C6H4, -CH=N-O-CH2-CH=C(CH3)-C6H5 -CH=N-O-(CH2)2CH=CH-3,4(Cl,Cl)-C6H3, -CH=N-O-(CH2)3C≡C-4-F-C6H4, -CH2=N-OCHOCH3, -CH=N-OC2H4OCH3, -CH=N-OCH2OC2H5, -CH = NO- (CH 2 ) 2 CH = CH-4-FC 6 H 4 , -CH = NO- (CH 2 ) CH = CH-4-Cl-C 6 H 4 , -CH = NO-CH 2 CH = CHCH2-4-OCH 3 -C 6 H 4 , -CH = NO-CH 2 -CH = C (CH 3 ) -C 6 H 5 -CH = NO- (CH 2 ) 2 CH = CH-3, 4 (Cl, Cl) -C 6 H 3 , -CH = NO- (CH 2 ) 3 C≡C-4-FC 6 H 4 , -CH 2 = N-OCHOCH 3 , -CH = N-OC 2 H 4 OCH 3 , -CH = N-OCH 2 OC 2 H 5 ,
-CH=N-OCH(CH3)OCH3, -CH=N-OCH(CH3)COOCH3, -CH = N-OCH (CH 3 ) OCH 3 , -CH = N-OCH (CH 3 ) COOCH 3 ,
-CH=N-OCH(CH3)COO-n-C4H9, -CH=N-NH2, -CH=N-NHCH3, -CH=N-NHC2H5, -CH=N-NH-n-C3H7, -CH=N-NH-i-C3H7, -CH=N-NH-n-C4H9, -CH = N-OCH (CH 3 ) COO-nC 4 H 9 , -CH = N-NH 2 , -CH = N-NHCH 3 , -CH = N-NHC 2 H 5 , -CH = N-NH- nC 3 H 7 , -CH = N-NH-iC 3 H 7 , -CH = N-NH-nC 4 H 9 ,
-CH=N-NH-i-C4H9, -CH=N-NH-S-C4H9, -CH=N-NH-tert.-C4H9, -CH = N-NH-iC 4 H 9 , -CH = N-NH-SC 4 H 9 , -CH = N-NH-tert.-C 4 H 9 ,
-CH=N-NH-cyclopropyl, -CH=N-NH-cyclobutyl, -CH=N-NH-cyclopentyl, -CH=N-NH-cyclohexyl, -CH=N-NH-cycloheptyl, -CH=N-N(CH3)2, -CH = N-NH-cyclopropyl, -CH = N-NH-cyclobutyl, -CH = N-NH-cyclopentyl, -CH = N-NH-cyclohexyl, -CH = N-NH-cycloheptyl, -CH = NN ( CH 3 ) 2 ,
-CH=N-N(C2H5)2, -CH=N-N(C3H7)2, -CH=N-N(i-C3H7)(CH3), -CH = NN (C 2 H 5 ) 2 , -CH = NN (C 3 H 7 ) 2 , -CH = NN (iC 3 H 7 ) (CH 3 ),
-CH=N-NHCH2-C=CH, -CH=N-NHCH2-C≡CH, -CH=N-N(CH3)-CH2-C≡CH, -CH = N-NHCH 2 -C = CH, -CH = N-NHCH 2 -C≡CH, -CH = NN (CH 3 ) -CH 2 -C≡CH,
-CH=N-NHCH2CF3, -CH=N-NH-CO-CH3, -CH=N-NH-CO-CH2H5, -CH = N-NHCH 2 CF 3 , -CH = N-NH-CO-CH 3 , -CH = N-NH-CO-CH 2 H 5 ,
-CH=N-NH-COOCH3, -CH=N-NH-COOC2H5, -CH=N-NH-COO-tert.-C4H9, -CH=N-pyrrolidin-1-yl, -CH=N-piperidin-1-yl, -CH = N-NH-COOCH 3 , -CH = N-NH-COOC 2 H 5 , -CH = N-NH-COO-tert.-C 4 H 9 , -CH = N-pyrrolidin-1-yl, -CH = N-piperidin-1-yl,
-CH=N-morpholin-4-yl, -CH=N-NH-C6H5, -CH=N-NH-(4-Cl-C6H4), -CH = N-morpholin-4-yl, -CH = N-NH-C 6 H 5 , -CH = N-NH- (4-Cl-C 6 H 4 ),
-CH=N-NH-(4-NO2-C6H4), -CH=N-NH-(4-F-C6H4), -CH = N-NH- (4-NO 2 -C 6 H 4 ), -CH = N-NH- (4-FC 6 H 4 ),
-CH=N-NH-(4-CH3O-C6H4), -CH=N-NH-(2,4-Cl2-C6H3), -CH = N-NH- (4-CH 3 OC 6 H 4 ), -CH = N-NH- (2,4-Cl 2 -C 6 H 3 ),
-CH=N-NH-(2,4-(NO2)2-C6H3), -CH=N-NH-CO-NH2, -CH=N-NH-CO-NHCH3, -CH=N-NH-CO-NHC2H5, -CH=N-NH-CO-N(CH3)2, -CH=CH-COOH, -CH = N-NH- (2,4- (NO 2 ) 2 -C 6 H 3 ), -CH = N-NH-CO-NH 2 , -CH = N-NH-CO-NHCH 3 , -CH = N-NH-CO-NHC 2 H 5 , -CH = N-NH-CO-N (CH 3 ) 2 , -CH = CH-COOH,
-CH=CH-CO-OCH3, -CH=CH-CO-OC2H5, -CH=CH-CO-O-n-C3H7, -CH = CH-CO-OCH 3 , -CH = CH-CO-OC 2 H 5 , -CH = CH-CO-OnC 3 H 7 ,
-CH=CH-CO-O-i-C3H7, -CH=CH-CO-O-n-C4H9, -CH=CH-CO-O-tert.-C4H9, -CH=CH-CO-O-cyclopropyl, -CH=CH-CO-O-cyclobutyl, -CH = CH-CO-OiC 3 H 7 , -CH = CH-CO-OnC 4 H 9 , -CH = CH-CO-O-tert.-C 4 H 9 , -CH = CH-CO-O- cyclopropyl, -CH = CH-CO-O-cyclobutyl,
-CH=CH-CO-O-cyclopentyl, -CH=CH-CO-O-cyclohexyl, -CH = CH-CO-O-cyclopentyl, -CH = CH-CO-O-cyclohexyl,
-CH=CH-CO-O-cycloheptyl, -CH=C(CH3)-COOH, -CH=C(CH3)-CO-OCH3, -CH=C(CH3)-CO-OC2H5, -CH=C(CH3)-CO-O-n-C3H7, -CH = CH-CO-O-cycloheptyl, -CH = C (CH 3 ) -COOH, -CH = C (CH 3 ) -CO-OCH 3 , -CH = C (CH 3 ) -CO-OC 2 H 5 , -CH = C (CH 3 ) -CO-OnC 3 H 7 ,
-CH=C(CH3)-CO-O-i-C3H7, -CH=C(CH3)-CO-O-n-C4H9, -CH = C (CH 3 ) -CO-OiC 3 H 7 , -CH = C (CH 3 ) -CO-OnC 4 H 9 ,
-CH=C(CH3)-CO-O-tert.-C4H9, -CH=C(CH3)-CO-O-cyclopropyl, -CH = C (CH 3 ) -CO-O-tert-C 4 H 9 , -CH = C (CH 3 ) -CO-O-cyclopropyl,
-CH=C(CH3)-CO-O-cyclobutyl, -CH=C(CH3)-CO-O-cyclopentyl, -CH=C(CH3)-CO-O-cyclohexyl, -CH=C(CH3)-CO-O-cycloheptyl, -CH = C (CH 3 ) -CO-O-cyclobutyl, -CH = C (CH 3 ) -CO-O-cyclopentyl, -CH = C (CH 3 ) -CO-O-cyclohexyl, -CH = C (CH 3 ) -CO-O-cycloheptyl,
-CH=C(C2H5)-COOH, -CH=C(C2H5)-CO-OCH3, -CH=C(C2H5)-CO-OC2H5, -CH=C(C2H5)-CO-O-n-C3H7, -CH=C(C2H5)-CO-O-i-C3H7, -CH = C (C 2 H 5 ) -COOH, -CH = C (C 2 H 5 ) -CO-OCH 3 , -CH = C (C 2 H 5 ) -CO-OC 2 H 5 , -CH = C (C 2 H 5 ) -CO-OnC 3 H 7 , -CH = C (C 2 H 5 ) -CO-OiC 3 H 7 ,
-CH=C(C2H5)-CO-O-n-C4H9, -CH=C(C2H5)-CO-O-tert.-C4H9, -CH = C (C 2 H 5 ) -CO-OnC 4 H 9 , -CH = C (C 2 H 5 ) -CO-O-tert.-C 4 H 9 ,
-CH=C(C2H5)-CO-O-cyclopropyl, -CH=C(C2H5)-CO-O-cyclobutyl, -CH=C(C2H5)-CO-O-cyclopentyl, -CH=C(C2H5)-CO-O-cyclohexyl, -CH=C(C2H5)-CO-O-cyclθheptyl, -CH=C(Cl)-COOH, -CH=C(Cl)-CO-OCH3, -CH=C(Cl)-CO-OC2H5, -CH=C(Cl)-CO-O-n-C3H7, -CH=C(Cl)-CO-O-i-C3H7, -CH=C(Cl)-CO-O-n-C4H9, -CH=C(Cl)-CO-O-tert.-C4H9, -CH = C (C 2 H 5 ) -CO-O-cyclopropyl, -CH = C (C 2 H 5 ) -CO-O-cyclobutyl, -CH = C (C 2 H 5 ) -CO-O-cyclopentyl , -CH = C (C 2 H 5 ) -CO-O-cyclohexyl, -CH = C (C 2 H 5 ) -CO-O-cyclθheptyl, -CH = C (Cl) -COOH, -CH = C ( Cl) -CO-OCH 3 , -CH = C (Cl) -CO-OC 2 H 5 , -CH = C (Cl) -CO-OnC 3 H 7 , -CH = C (Cl) -CO-OiC 3 H 7 , -CH = C (Cl) -CO-OnC 4 H 9 , -CH = C (Cl) -CO-O-tert.-C 4 H 9 ,
-CH=C(Cl)-CO-O-cyclopropyl, -CH=C(Cl)-CO-O-cyclobutyl,  -CH = C (Cl) -CO-O-cyclopropyl, -CH = C (Cl) -CO-O-cyclobutyl,
-CH=C(Cl)-CO-O-cyclopentyl, -CH=C(Cl)-CO-O-cyclohexyl,  -CH = C (Cl) -CO-O-cyclopentyl, -CH = C (Cl) -CO-O-cyclohexyl,
-CH=C(Cl)-CO-O-cycloheptyl, -CH=C(Br)-COOH, -CH=C(Br)-CO-OCH3, -CH=C(Br)-CO-OC2H5, -CH=C(Br)-CO-O-n-C3H7, -CH=C(Br)-CO-O-i-C3H7, -CH=C(Br)-CO-O-n-C4H9, -CH=C(Br)-CO-O-tert.-C4H9, -CH = C (Cl) -CO-O-cycloheptyl, -CH = C (Br) -COOH, -CH = C (Br) -CO-OCH 3 , -CH = C (Br) -CO-OC 2 H 5 , -CH = C (Br) -CO-OnC 3 H 7 , -CH = C (Br) -CO-OiC 3 H 7 , -CH = C (Br) -CO-OnC 4 H 9 , -CH = C (Br) -CO-O-tert.-C 4 H 9 ,
-CH=C(Br)-CO-O-cyclopropyl, -CH=C(Br)-CO-O-cyclobutyl,  -CH = C (Br) -CO-O-cyclopropyl, -CH = C (Br) -CO-O-cyclobutyl,
-CH=C(Br)-CO-O-cyclopentyl, -CH=C(Br)-CO-O-cyclohexyl,  -CH = C (Br) -CO-O-cyclopentyl, -CH = C (Br) -CO-O-cyclohexyl,
-CH=C(Br)-CO-O-cyclθheptyl, -CH=C(CN)-COOH, -CH=C(CN)-CO-OCH3, -CH=C(CN)-CO-OC2H5, -CH=C(CN)-CO-O-n-C3H7, -CH=C(CN)-CO-O-i-C3H7, -CH=C(CN)-CO-O-n-C4H9, -CH=C(CN)-CO-O-tert.-C4H9, -CH = C (Br) -CO-O-cyclθheptyl, -CH = C (CN) -COOH, -CH = C (CN) -CO-OCH 3 , -CH = C (CN) -CO-OC 2 H 5 , -CH = C (CN) -CO-OnC 3 H 7 , -CH = C (CN) -CO-OiC 3 H 7 , -CH = C (CN) -CO-OnC 4 H 9 , -CH = C (CN) -CO-O-tert.-C 4 H 9 ,
-CH=C(CN)-CO-O-cyclopropyl, -CH=C(CN)-CO-O-cyclobutyl,  -CH = C (CN) -CO-O-cyclopropyl, -CH = C (CN) -CO-O-cyclobutyl,
-CH=C(CN)-CO-O-cyclopentyl, -CH=C(CN)-CO-O-cyclohexyl,  -CH = C (CN) -CO-O-cyclopentyl, -CH = C (CN) -CO-O-cyclohexyl,
-CH=C(CN)-CO-O-cycloheptyl, -CH=CH-CO-OCH2-OCH3, -CH = C (CN) -CO-O-cycloheptyl, -CH = CH-CO-OCH 2 -OCH 3 ,
-CH=CH-CO-OCH2-OC2H5, -CH=CH-CO-OCH2-O-n-C3H5, -CH = CH-CO-OCH 2 -OC 2 H 5 , -CH = CH-CO-OCH 2 -OnC 3 H 5 ,
-CH=CH-CO-OCH2-O-i-C3H5, -CH=CH-CO-OCH(CH3)-OCH3, -CH = CH-CO-OCH 2 -OiC 3 H 5 , -CH = CH-CO-OCH (CH 3 ) -OCH 3 ,
-CH=CH-CO-OCH(CH3)-OC2H5, -CH=CH-CO-O-CH2CH2-OCH3, -CH = CH-CO-OCH (CH 3 ) -OC 2 H 5 , -CH = CH-CO-O-CH 2 CH 2 -OCH 3 ,
-CH=CH-CO-O-CH2CH2-OC2H5, -CH=C(CH3)-CO-OCH2-OCH3, -CH = CH-CO-O-CH 2 CH 2 -OC 2 H 5 , -CH = C (CH 3 ) -CO-OCH 2 -OCH 3 ,
-CH=C(CH3)-CO-OCH2-OC2H5, -CH=C(CH3)-CO-OCH2-O-n-C3H5, -CH = C (CH 3 ) -CO-OCH 2 -OC 2 H 5 , -CH = C (CH 3 ) -CO-OCH 2 -OnC 3 H 5 ,
-CH=C(CH3)-CO-OCH2-O-i-C3H5, -CH=C(CH3)-CO-OCH(CH3)-OCH3, -CH = C (CH 3 ) -CO-OCH 2 -OiC 3 H 5 , -CH = C (CH 3 ) -CO-OCH (CH 3 ) -OCH 3 ,
-CH=C(CH3)-CO-OCH(CH3)-OC2H5, -CH=C(CH3)-CO-O-CH2CH2-OCH3, -CH = C (CH 3 ) -CO-OCH (CH 3 ) -OC 2 H 5 , -CH = C (CH 3 ) -CO-O-CH 2 CH 2 -OCH 3 ,
-CH=C(CH3)-CO-O-CH2CH2-OC2H5, -CH=C(C2H5)-CO-OCH2-OCH3, -CH = C (CH 3 ) -CO-O-CH 2 CH 2 -OC 2 H 5 , -CH = C (C 2 H 5 ) -CO-OCH 2 -OCH 3 ,
-CH=C(C2H5)-CO-OCH2-OC2H5, -CH=C(C2H5)-CO-OCH2-O-n-C3H5, -CH = C (C 2 H 5 ) -CO-OCH 2 -OC 2 H 5 , -CH = C (C 2 H 5 ) -CO-OCH 2 -OnC 3 H 5 ,
-CH=C(C2H5)-CO-OCH2-O-i-C3H5, -CH=C(C2H5)-CO-OCH(CH3)-OCH3, -CH=C(C2H5)-CO-OCH(CH3)-OC2H5, -CH=C(C2H5)-CO-O-CH2CH2-OCH3, -CH=C(C2H5)-CO-O-CH2CH2-OC2H5, -CH=C(Cl)-CO-OCH2-OCH3, -CH = C (C 2 H 5 ) -CO-OCH 2 -OiC 3 H 5 , -CH = C (C 2 H 5 ) -CO-OCH (CH 3 ) -OCH 3 , -CH = C (C 2 H 5 ) -CO-OCH (CH 3 ) -OC 2 H 5 , -CH = C (C 2 H 5 ) -CO-O-CH 2 CH 2 -OCH 3 , -CH = C (C 2 H 5 ) -CO-O-CH 2 CH 2 -OC 2 H 5 , -CH = C (Cl) -CO-OCH 2 -OCH 3 ,
-CH=C(Cl)-CO-OCH2-OC2H5, -CH=C(Cl)-CO-OCH2-O-n-C3H5, -CH = C (Cl) -CO-OCH 2 -OC 2 H 5 , -CH = C (Cl) -CO-OCH 2 -OnC 3 H 5 ,
-CH=C(Cl)-CO-OCH2-O-i-C3H5, -CH=C(Cl)-CO-OCH(CH3)-OCH3, -CH = C (Cl) -CO-OCH 2 -OiC 3 H 5 , -CH = C (Cl) -CO-OCH (CH 3 ) -OCH 3 ,
-CH=C(Cl)-CO-OCH(CH3)-OC2H5, -CH=C(Cl)-CO-O-CH2CH2-OCH3, -CH = C (Cl) -CO-OCH (CH 3 ) -OC 2 H 5 , -CH = C (Cl) -CO-O-CH 2 CH 2 -OCH 3 ,
-CH=C(Cl)-CO-O-CH2CH2-OC2H5, -CH=C(Br)-CO-OCH2-OCH3, -CH = C (Cl) -CO-O-CH 2 CH 2 -OC 2 H 5 , -CH = C (Br) -CO-OCH 2 -OCH 3 ,
-CH=C(Br)-CO-OCH2-OC2H5, -CH=C(Br)-CO-OCH2-O-n-C3H5, -CH = C (Br) -CO-OCH 2 -OC 2 H 5 , -CH = C (Br) -CO-OCH 2 -OnC 3 H 5 ,
-CH=C(Br)-CO-OCH2-O-i-C3H5, -CH=C(Br)-CO-OCH(CH3)-OCH3, -CH =C(Br)-CO-OCH(CH3)-OC2H5, -CH=C(Br)-CO-O-CH2CH2-OCH3, -CH = C (Br) -CO-OCH 2 -OiC 3 H 5 , -CH = C (Br) -CO-OCH (CH 3 ) -OCH 3 , -CH = C (Br) -CO-OCH (CH 3 ) -OC 2 H 5 , -CH = C (Br) -CO-O-CH 2 CH 2 -OCH 3 ,
-CH =C(Br)-CO-O-CH2CH2-OC2H5, -CH=C(CN)-CO-OCH2-OCH3, -CH = C (Br) -CO-O-CH 2 CH 2 -OC 2 H 5 , -CH = C (CN) -CO-OCH 2 -OCH 3 ,
-CH =C(CN)-CO-OCH2-OC2H5, -CH=C(CN)-CO-OCH2-O-n-C3H5, -CH = C (CN) -CO-OCH 2 -OC 2 H 5 , -CH = C (CN) -CO-OCH 2 -OnC 3 H 5 ,
-CH=C(CN)-CO-OCH2-O-i-C3H5, -CH=C(CN)-CO-OCH(CH3)-OCH3, -CH = C (CN) -CO-OCH 2 -OiC 3 H 5 , -CH = C (CN) -CO-OCH (CH 3 ) -OCH 3 ,
-CH=C(CN)-CO-OCH(CH3)-OC2H5, -CH=C(CN)-CO-O-CH2CH2-OCH3, -CH = C (CN) -CO-OCH (CH 3 ) -OC 2 H 5 , -CH = C (CN) -CO-O-CH 2 CH 2 -OCH 3 ,
-CH=C(CN)-CO-O-CH2CH2-OC2H5, -CH=CH-CO-OCH2-CF3, -CH = C (CN) -CO-O-CH 2 CH 2 -OC 2 H 5 , -CH = CH-CO-OCH 2 -CF 3 ,
-CH=CH-CO-OCH2-CCl3, -CH=CH-CO-OCH2-oxiranyl, -CH = CH-CO-OCH 2 -CCl 3 , -CH = CH-CO-OCH 2 -oxiranyl,
-CH=CH-CO-O(CH2)3-Br, -CH=CH-CO-OCH2-CH=CH2, -CH=CH-CO-OCH2-C=CH,-CH = CH-CO-O (CH 2 ) 3 -Br, -CH = CH-CO-OCH 2 -CH = CH 2 , -CH = CH-CO-OCH 2 -C = CH,
-CH=CH-CO-OCH2-CN, -CH=CH-CO-O(CH2)2-CN, -CH=C(CH3)-CO-OCH2-CF3, -CH=C(CH3)-CO-OCH2-CCl3, -CH=C(CH3)-CO-OCH2-oxiranyl, -CH = CH-CO-OCH 2 -CN, -CH = CH-CO-O (CH 2 ) 2 -CN, -CH = C (CH 3 ) -CO-OCH 2 -CF 3 , -CH = C ( CH 3 ) -CO-OCH 2 -CCl 3 , -CH = C (CH 3 ) -CO-OCH 2 -oxiranyl,
-CH=C(CH3)-CO-O(CH2)3-Br, -CH=C(CH3)-CO-OCH2-CH=CH2, -CH = C (CH 3 ) -CO-O (CH 2 ) 3 -Br, -CH = C (CH 3 ) -CO-OCH 2 -CH = CH 2 ,
-CH=C(CH3)-CO-OCH2-C=CH, -CH=C(CH3)-CO-OCH2-CN, -CH = C (CH 3 ) -CO-OCH 2 -C = CH, -CH = C (CH 3 ) -CO-OCH 2 -CN,
-CH=C(CH3)-CO-O(CH2)2-CN, -CH=C(C2H5)-CO-OCH2-CF3, -CH = C (CH 3 ) -CO-O (CH 2 ) 2 -CN, -CH = C (C 2 H 5 ) -CO-OCH 2 -CF 3 ,
-CH=C(C2H5)-CO-OCH2-CCl3, -CH=C(C2H5)-CO-OCH2-oxiranyl, -CH = C (C 2 H 5 ) -CO-OCH 2 -CCl 3 , -CH = C (C 2 H 5 ) -CO-OCH 2 -oxiranyl,
-CH=C(C2H5)-CO-O(CH2)3-Br, -CH=C(C2H5)-CO-OCH2-CH=CH2, -CH = C (C 2 H 5 ) -CO-O (CH 2 ) 3 -Br, -CH = C (C 2 H 5 ) -CO-OCH 2 -CH = CH 2 ,
-CH=C(C2H5)-CO-OCH2-C≡CH, -CH=C(C2H5)-CO-OCH2-CN, -CH = C (C 2 H 5 ) -CO-OCH 2 -C≡CH, -CH = C (C 2 H 5 ) -CO-OCH 2 -CN,
-CH=C(C2H5)-CO-O(CH2)2-CN, -CH=C(Cl)-CO-OCH2-CF3, -CH = C (C 2 H 5 ) -CO-O (CH 2 ) 2 -CN, -CH = C (Cl) -CO-OCH 2 -CF 3 ,
-CH=C(Cl)-CO-OCH2-CCl3, -CH=C(Cl)-CO-OCH2-oxiranyl, -CH = C (Cl) -CO-OCH 2 -CCl 3 , -CH = C (Cl) -CO-OCH 2 -oxiranyl,
-CH=C(Cl)-CO-O(CH2)3-Br, -CH=C(Cl)-CO-OCH2-CH=CH2, -CH = C (Cl) -CO-O (CH 2 ) 3 -Br, -CH = C (Cl) -CO-OCH 2 -CH = CH 2 ,
-CH=C(Cl)-CO-OCH2-C≡CH, -CH=C(Cl)-CO-OCH2-CN, -CH = C (Cl) -CO-OCH 2 -C≡CH, -CH = C (Cl) -CO-OCH 2 -CN,
-CH=C(Cl)-CO-O(CH2)2-CN, -CH=C(Br)-CO-OCH2-CF3, -CH = C (Cl) -CO-O (CH 2 ) 2 -CN, -CH = C (Br) -CO-OCH 2 -CF 3 ,
-CH=C(Br)-CO-OCH2-CCl3, -CH=C(Br)-CO-OCH2-oxiranyl, -CH = C (Br) -CO-OCH 2 -CCl 3 , -CH = C (Br) -CO-OCH 2 -oxiranyl,
-CH=C(Br)-CO-O(CH2)3-Br, -CH=C(Br)-CO-OCH2-CH=CH2, -CH = C (Br) -CO-O (CH 2 ) 3 -Br, -CH = C (Br) -CO-OCH 2 -CH = CH 2 ,
-CH=C(Br)-CO-OCH2-C≡CH, -CH=C (Br)-CO-OCH2-CN, -CH = C (Br) -CO-OCH 2 -C≡CH, -CH = C (Br) -CO-OCH 2 -CN,
-CH=C(Br)-CO-O(CH2)2-CN, -CH=C(CN)-CO-OCH2-CF3, -CH = C (Br) -CO-O (CH 2 ) 2 -CN, -CH = C (CN) -CO-OCH 2 -CF 3 ,
-CH=C(CN)-CO-OCH2-CCl3, -CH=C(CN)-CO-OCH2-oxiranyl, -CH = C (CN) -CO-OCH 2 -CCl 3 , -CH = C (CN) -CO-OCH 2 -oxiranyl,
-CH=C(CN)-CO-O(CH2)3-Br, -CH=C(CN)-CO-OCH2-CH=CH2, -CH = C (CN) -CO-O (CH 2 ) 3 -Br, -CH = C (CN) -CO-OCH 2 -CH = CH 2 ,
-CH=C(CN)-CO-OCH2-C≡CH, -CH=C(CN)-CO-OCH2-CN, -CH = C (CN) -CO-OCH 2 -C≡CH, -CH = C (CN) -CO-OCH 2 -CN,
-CH=C(CN)-CO-O(CH2)2-CN, -CH=CH-CO-CH3, -CH=CH-CO-C2H5, -CH = C (CN) -CO-O (CH 2 ) 2 -CN, -CH = CH-CO-CH 3 , -CH = CH-CO-C 2 H 5 ,
-CH= CH-CO-n-C3H7, -CH=CH-CO-i-C3H7, -CH=CH-CO-n-C4H9, -CH = CH-CO-nC 3 H 7 , -CH = CH-CO-iC 3 H 7 , -CH = CH-CO-nC 4 H 9 ,
-CH= CH-CO-tert.-C4H9, -CH=CH-CO-CH2Cl, -CH=CH-CO-CH2Br, -CH = CH-CO-tert.-C 4 H 9 , -CH = CH-CO-CH 2 Cl, -CH = CH-CO-CH 2 Br,
-CH=CH-CO-CHCl2, -CH=CH-CO-CH2-OCH3, -CH=CH-CO-CH(OCH3)2, -CH = CH-CO-CHCl 2 , -CH = CH-CO-CH 2 -OCH 3 , -CH = CH-CO-CH (OCH 3 ) 2 ,
-CH=CH-CO-CH2-SCH3, -CH=C(CH3)-CO-CH3, -CH=C(CH3)-CO-C2H5, -CH = CH-CO-CH 2 -SCH 3 , -CH = C (CH 3 ) -CO-CH 3 , -CH = C (CH 3 ) -CO-C 2 H 5 ,
-CH=C(CH3)-CO-n-C3H7, -CH=C(CH3)-CO-i-C3H7, -CH=C(CH3)-CO-n-C4H9,-CH = C (CH 3 ) -CO-nC 3 H 7 , -CH = C (CH 3 ) -CO-iC 3 H 7 , -CH = C (CH 3 ) -CO-nC 4 H 9 ,
-CH=C(CH3)-CO-tert.-C4H9, -CH=C(CH3)-CO-CH2Cl, -CH = C (CH 3 ) -CO-tert-C 4 H 9 , -CH = C (CH 3 ) -CO-CH 2 Cl,
-CH=C(CH3)-CO-CH2Br, -CH=C(CH3)-CO-CHCl2, -CH=C(CH3)-CO-CH2-OCH3,-CH = C (CH 3 ) -CO-CH 2 Br, -CH = C (CH 3 ) -CO-CHCl 2 , -CH = C (CH 3 ) -CO-CH 2 -OCH 3 ,
-CH=C(CH3)-CO-CH(OCH3)2, -CH=C(CH3)-CO-CH2-SCH3, -CH = C (CH 3 ) -CO-CH (OCH 3 ) 2 , -CH = C (CH 3 ) -CO-CH 2 -SCH 3 ,
-CH=C(C2H5)-CO-CH3, -CH=C(C2H5)-CO-C2H5, -CH=C(C2H5)-CO-n-C3H7,-CH = C (C 2 H 5 ) -CO-CH 3 , -CH = C (C 2 H 5 ) -CO-C 2 H 5 , -CH = C (C 2 H 5 ) -CO-nC 3 H 7 ,
-CH=C(C2H5)-CO-i-C3H7, -CH=C(C2H5)-CO-n-C4H9, -CH = C (C 2 H 5 ) -CO-iC 3 H 7 , -CH = C (C 2 H 5 ) -CO-nC 4 H 9 ,
-CH=C(C2H5)-CO-tert.-C4H9, -CH=C(C2H5)-CO-CH2Cl, -CH=C(C2H5)-CO-CH2Br, -CH=C(C2H5)-CO-CHCl2, -CH = C (C 2 H 5 ) -CO-tert.-C 4 H 9 , -CH = C (C 2 H 5 ) -CO-CH 2 Cl, -CH = C (C 2 H 5 ) -CO-CH 2 Br, -CH = C (C 2 H 5 ) -CO-CHCl 2 ,
-CH=C(C2H5)-CO-CH2-OCH3, -CH=C(C2H5)-CO-CH(OCH3)2, -CH = C (C 2 H 5 ) -CO-CH 2 -OCH 3 , -CH = C (C 2 H 5 ) -CO-CH (OCH 3 ) 2 ,
-CH=C(C2H5)-CO-CH2-SCH3, -CH=C(Cl)-CO-CH3, -CH=C(Cl)-CO-C2H5, -CH=C(Cl)-CO-n-C3H7, -CH=C(Cl)-CO-i-C3H7, -CH=C(Cl)-CO-n-C4H9, -CH=C(Cl)-CO-tert.-C4H9, -CH=C(Cl)-CO-CH2Cl, -CH=C(Cl)-CO-CH2Br, -CH=C(Cl)-CO-CHCl2, -CH=C(Cl)-CO-CH2-OCH3, -CH = C (C 2 H 5 ) -CO-CH 2 -SCH 3 , -CH = C (Cl) -CO-CH 3 , -CH = C (Cl) -CO-C 2 H 5 , -CH = C (Cl) -CO-nC 3 H 7 , -CH = C (Cl) -CO-iC 3 H 7 , -CH = C (Cl) -CO-nC 4 H 9 , -CH = C (Cl) - CO-tert-C 4 H 9 , -CH = C (Cl) -CO-CH 2 Cl, -CH = C (Cl) -CO-CH 2 Br, -CH = C (Cl) -CO-CHCl 2 , -CH = C (Cl) -CO-CH 2 -OCH 3 ,
-CH=C(Cl)-CO-CH(OCH3)2, -CH=C(Cl)-CO-CH2-SCH3, -CH=C(Br)-CO-CH3, -CH=C(Br)-CO-C2H5, -CH=C(Br)-CO-n-C3H7, -CH=C(Br)-CO-i-C3H7, -CH=C(Br)-CO-n-C4H9, -CH=C(Br)-CO-tert.-C4H9, -CH=C(Br)-CO-CH2Cl, -CH=C(Br)-CO-CH2Br, -CH=C(Br)-CO-CHCl2, -CH=C(Br)-CO-CH2-OCH3, -CH=C(Br)-CO-CH(OCH3)2, -CH=C(Br)-CO-CH2-SCH3, -CH=C(CN)-CO-CH3, -CH=C(CN)-CO-C2H5, -CH=C(CN)-CO-n-C3H7, -CH=C(CN)-CO-i-C3H7, -CH=C(CN)-CO-n-C4H9, -CH=C(CN)-CO-tert.-C4H9, -CH=C(CN)-CO-CH2Cl, -CH=C(CN)-CO-CH2Br, -CH=C(CN)-CO-CHCl2, -CH=C(CN)-CO-CH2-OCH3, -CH=C(CN)-CO-CH(OCH3)2, -CH=C(CN)-CO-CH2-SCH3, -CH=CH-CO-C6H5, -CH=CH-CO-(4-Cl-C6H4), -CH=C(CH3)-CO-C6H5, -CH = C (Cl) -CO-CH (OCH 3 ) 2 , -CH = C (Cl) -CO-CH 2 -SCH 3 , -CH = C (Br) -CO-CH 3 , -CH = C (Br) -CO-C 2 H 5 , -CH = C (Br) -CO-nC 3 H 7 , -CH = C (Br) -CO-iC 3 H 7 , -CH = C (Br) -CO -nC 4 H 9 , -CH = C (Br) -CO-tert.-C 4 H 9 , -CH = C (Br) -CO-CH 2 Cl, -CH = C (Br) -CO-CH 2 Br, -CH = C (Br) -CO-CHCl 2 , -CH = C (Br) -CO-CH 2 -OCH 3 , -CH = C (Br) -CO-CH (OCH 3 ) 2 , -CH = C (Br) -CO-CH 2 -SCH 3 , -CH = C (CN) -CO-CH 3 , -CH = C (CN) -CO-C 2 H 5 , -CH = C (CN) - CO-nC 3 H 7 , -CH = C (CN) -CO-iC 3 H 7 , -CH = C (CN) -CO-nC 4 H 9 , -CH = C (CN) -CO-tert.- C 4 H 9 , -CH = C (CN) -CO-CH 2 Cl, -CH = C (CN) -CO-CH 2 Br, -CH = C (CN) -CO-CHCl 2 , -CH = C (CN) -CO-CH 2 -OCH 3 , -CH = C (CN) -CO-CH (OCH 3 ) 2 , -CH = C (CN) -CO-CH 2 -SCH 3 , -CH = CH- CO-C 6 H 5 , -CH = CH-CO- (4-Cl-C 6 H 4 ), -CH = C (CH 3 ) -CO-C 6 H 5 ,
-CH=C(CH3)-CO-(4-Cl-C6H4), -CH=C(C2H5)-CO-C6H5, -CH = C (CH 3 ) -CO- (4-Cl-C 6 H 4 ), -CH = C (C 2 H 5 ) -CO-C 6 H 5 ,
-CH=C(C2H5)-CO-(4-Cl-C6H4), -CH=C(Cl)-CO-C6H5, -CH=C(Br)-CO-C6H5, -CH=C(CN)-CO-C6H5 -CH=CH-CO-NH2, -CH=CH-CO-NHCH3, -CH = C (C 2 H 5 ) -CO- (4-Cl-C 6 H 4 ), -CH = C (Cl) -CO-C 6 H 5 , -CH = C (Br) -CO-C 6 H 5 , -CH = C (CN) -CO-C 6 H 5 -CH = CH-CO-NH 2 , -CH = CH-CO-NHCH 3 ,
-CH=CH-CO-N(CH3)2, -CH=CH-CO-NH-C2H5, -CH=CH-CO-N(C2H5)2, -CH = CH-CO-N (CH 3 ) 2 , -CH = CH-CO-NH-C 2 H 5 , -CH = CH-CO-N (C 2 H 5 ) 2 ,
-CH=CH-CO-NH-n-C3H7, -CH=CH-CO-NH-i-C3H7, -CH = CH-CO-NH-nC 3 H 7 , -CH = CH-CO-NH-iC 3 H 7 ,
-CH=CH-CO-NH-tert.-C4H9, -CH=CH-CO-NH-cyclopropyl, -CH = CH-CO-NH-tert-C 4 H 9 , -CH = CH-CO-NH-cyclopropyl,
-CH=CH-CO-NH-cyclobutyl, -CH=CH-CO-NH-cyclopentyl,  -CH = CH-CO-NH-cyclobutyl, -CH = CH-CO-NH-cyclopentyl,
-CH=CH-CO-NH-cyclohexyl, -CH=CH-CO-NH-cycloheptyl, -CH = CH-CO-NH-cyclohexyl, -CH = CH-CO-NH-cycloheptyl,
-CH=CH-CO-NH-cyclooctyl, -CH=CH-CO-pyrrolidin-1-yl, -CH = CH-CO-NH-cyclooctyl, -CH = CH-CO-pyrrolidin-1-yl,
-CH=CH-CO-piperidin-1-yl, -CH=CH-CO-morpholin-4-yl, -CH = CH-CO-piperidin-1-yl, -CH = CH-CO-morpholin-4-yl,
-CH=CH-CO-NH-CH2CH=CH2, -CH=CH-CO-NH-CH2C≡CH, -CH = CH-CO-NH-CH 2 CH = CH 2 , -CH = CH-CO-NH-CH 2 C≡CH,
-CH=CH-CO-N(CH3)-CH2C≡CH, -CH=CH-CO-NH-(CH2)2Cl, -CH = CH-CO-N (CH 3 ) -CH 2 C≡CH, -CH = CH-CO-NH- (CH 2 ) 2 Cl,
-CH=CH-CO-NH-C6H5, -CH=C(CH3)-CO-NH2, -CH=C(CH3)-CO-NHCH3, -CH = CH-CO-NH-C 6 H 5 , -CH = C (CH 3 ) -CO-NH 2 , -CH = C (CH 3 ) -CO-NHCH 3 ,
-CH=C(CH3)-CO-N(CH3)2, -CH=C(CH3)-CO-NH-C2H5, -CH = C (CH 3 ) -CO-N (CH 3 ) 2 , -CH = C (CH 3 ) -CO-NH-C 2 H 5 ,
-CH=C(CH3)-CO-N(C2H5)2, -CH=C(CH3)-CO-NH-n-C3H7, -CH = C (CH 3 ) -CO-N (C 2 H 5 ) 2 , -CH = C (CH 3 ) -CO-NH-nC 3 H 7 ,
-CH=C(CH3)-CO-NH-i-C3H7, -CH=C(CH3)-CO-NH-tert.-C4H9, -CH = C (CH 3 ) -CO-NH-iC 3 H 7 , -CH = C (CH 3 ) -CO-NH-tert.-C 4 H 9 ,
-CH=C(CH3)-CO-NH-cyclopropyl, -CH=C(CH3)-CO-NH-cyclobutyl, -CH = C (CH 3 ) -CO-NH-cyclopropyl, -CH = C (CH 3 ) -CO-NH-cyclobutyl,
-CH=C(CH3)-CO-NH-cyclopentyl, -CH=C(CH3)-CO-NH-cyclohexyl, -CH = C (CH 3 ) -CO-NH-cyclopentyl, -CH = C (CH 3 ) -CO-NH-cyclohexyl,
-CH=C(CH3)-CO-NH-cycloheptyl, -CH=C(CH3)-CO-NH-cyclooctyl, -CH = C (CH 3 ) -CO-NH-cycloheptyl, -CH = C (CH 3 ) -CO-NH-cyclooctyl,
-CH=C(CH3)-CO-pyrrolidin-1-yl, -CH=C(CH3)-CO-piperidin-1-yl, -CH=C(CH3)-CO-morpholin-4-yl, -CH=C(CH3)-CO-NH-CH2CH=C(CH3)2, -CH=C(CH3)-CO-NH-CH2C≡CH, -CH=C(CH3)-CO-N(CH3)-CH2C=CH, -CH = C (CH 3 ) -CO-pyrrolidin-1-yl, -CH = C (CH 3 ) -CO-piperidin-1-yl, -CH = C (CH 3 ) -CO-morpholin-4-yl , -CH = C (CH 3 ) -CO-NH-CH 2 CH = C (CH 3 ) 2 , -CH = C (CH 3 ) -CO-NH-CH 2 C≡CH, -CH = C (CH 3 ) -CO-N (CH 3 ) -CH 2 C = CH,
-CH=C(CH3)-CO-NH-(CH2)2Cl, -CH=C(CH3)-CO-NH-C6H5, -CH = C (CH 3 ) -CO-NH- (CH 2 ) 2 Cl, -CH = C (CH 3 ) -CO-NH-C 6 H 5 ,
-CH=C(C2H5)-CO-NH2, -CH=C(C2H5)-CO-NHCH3, -CH=C(C2H5)-CO-N(CH3)2, -CH=C(C2H5)-CO-NH-C2H5, -CH=C (C2H5) -CO-N (C 2H5) 2, -CH = C (C 2 H 5 ) -CO-NH 2 , -CH = C (C 2 H 5 ) -CO-NHCH 3 , -CH = C (C 2 H 5 ) -CO-N (CH 3 ) 2 , -CH = C (C 2 H 5 ) -CO-NH-C 2 H 5 , -CH = C (C 2 H 5 ) -CO-N (C 2 H 5 ) 2 ,
-CH=C (C2H5) -CO-NH-n-C3H7, -CH=C (C2H5) -CO-NH-i-C3H7, -CH = C (C 2 H 5 ) -CO-NH-nC 3 H 7 , -CH = C (C 2 H 5 ) -CO-NH-iC 3 H 7 ,
-CH=C (C 2H5) -CO-NH-tert . -C4H9, -CH=C (C 2H5)-CO-NH-cyclopropy1, -CH=C (C 2H5) -CO-NH-cyc 1obuty 1 , -CH=C (C 2H5)-CO-NH-cyclopenty1 , -CH=C(C2H5)-CO-NH-cyclohexyl, -CH=C(C2H5)-CO-NH-cyclohepty 1, -CH=C(C2H5)-CO-NH-cyclooctyl, -CH=C(C2H5)-CO-pyrrol idin-l-y 1, -CH=C(C2H5)-CO-piperidin-l-yl, -CH=C(C2H5)-CO-morphol in-4-y 1, -CH=C(C2H5)-CO-NH-CH2CH=C(C2H5) 2, -CH=C(C2H5)-CO-NH-CH2C≡CH, -CH=C(C2H5)-CO-N(CH3)-CH2C≡CH, -CH=C (C2H5)-CO-NH- (CH2) 2C1, -CH=C(C2H5)-CO-NH-C6H5, -CH=C(Cl)-CO-NH2, -CH=C(Cl)-CO-NHCH3, -CH=C(Cl)-CO-N(CH3)2, -CH=C(Cl)-CO-NH-C2H5, -CH = C (C 2 H 5 ) -CO-NH-tert. -C 4 H 9 , -CH = C (C 2 H 5 ) -CO-NH-cyclopropy1, -CH = C (C 2 H 5 ) -CO-NH-cyc 1obuty 1, -CH = C (C 2 H 5 ) -CO-NH-cyclopenty1, -CH = C (C 2 H 5 ) -CO-NH-cyclohexyl, -CH = C (C 2 H 5 ) -CO-NH-cyclohepty 1, -CH = C (C 2 H 5 ) -CO-NH-cyclooctyl, -CH = C (C 2 H 5 ) -CO-pyrrole idin-ly 1, -CH = C (C 2 H 5 ) -CO-piperidin-l-yl, - CH = C (C 2 H 5 ) -CO-morphol in-4-y 1, -CH = C (C 2 H 5 ) -CO-NH-CH 2 CH = C (C 2 H5) 2 , -CH = C (C 2 H 5 ) -CO-NH-CH 2 C≡CH, -CH = C (C 2 H 5 ) -CO-N (CH 3 ) -CH 2 C≡CH, -CH = C (C 2 H 5 ) -CO-NH- (CH 2 ) 2 C1, -CH = C (C 2 H 5 ) -CO-NH-C 6 H 5 , -CH = C (Cl) -CO-NH 2 , -CH = C (Cl) -CO-NHCH 3 , -CH = C (Cl) -CO-N (CH 3 ) 2 , -CH = C (Cl) -CO-NH-C 2 H 5 ,
-CH=C(Cl)-CO-N(C2Hs)2, -CH=C(Cl )-CO-NH-n-C3H7, -CH = C (Cl) -CO-N (C 2 Hs) 2 , -CH = C (Cl) -CO-NH-nC 3 H 7 ,
-CH=C(Cl )-CO-NH-i-C3H7, -CH=C(Cl )-CO-NH-tert. -C4H9, -CH = C (Cl) -CO-NH-iC 3 H 7 , -CH = C (Cl) -CO-NH-tert. -C 4 H 9 ,
-CH=C(Cl )-CO-NH-cyclopropyl, -CH=C(Cl )-CO-NH-cyclobutyl, -CH = C (Cl) -CO-NH-cyclopropyl, -CH = C (Cl) -CO-NH-cyclobutyl,
-CH=C(Cl )-CO-NH-cyclopentyl, -CH=C(Cl )-CO-NH-cyclohexy 1, -CH = C (Cl) -CO-NH-cyclopentyl, -CH = C (Cl) -CO-NH-cyclohexy 1,
-CH=C (Cl)-CO-NH-cyc 1ohepty 1 , -CH=C (Cl)-CO-NH-cyc 1oocty 1 , -CH = C (Cl) -CO-NH-cyc 1ohepty 1, -CH = C (Cl) -CO-NH-cyc 1oocty 1,
-CH=C(Cl )-CO-pyrrolidin-l-yl, -CH=C(Cl )-CO-pi peridin-1-yl, -CH=C(Cl )-C0-morpholin-4-yl, -CH=C(CI)-CO-NH-CH2CH=C(CI)2, -CH=C(Cl )-CO-NH-CH2C≡CH, -CH=C (Cl )-CO-N (CH3)-CH2C=CH, -CH = C (Cl) -CO-pyrrolidin-l-yl, -CH = C (Cl) -CO-pi peridin-1-yl, -CH = C (Cl) -C0-morpholin-4-yl, - CH = C (CI) -CO-NH-CH 2 CH = C (CI) 2 , -CH = C (Cl) -CO-NH-CH 2 C≡CH, -CH = C (Cl) -CO-N (CH 3 ) -CH 2 C = CH,
-CH=C(Cl )-CO-NH-(CH2)2Cl, -CH=C(Cl)-CO-NH-C6H5, -CH=C(Br)-CO-NH2, -CH=C(Br)-CO-NHCH3, -CH=C(Br)-CO-N(CH3) 2, -CH=C(Br)-CO-NH-C2H5, -CH=C(Br)-CO-N(C2H5) 2, -CH=C(Br)-CO-NH-Ii-C3H7, -CH = C (Cl) -CO-NH- (CH 2 ) 2 Cl, -CH = C (Cl) -CO-NH-C 6 H 5 , -CH = C (Br) -CO-NH 2 , - CH = C (Br) -CO-NHCH 3 , -CH = C (Br) -CO-N (CH 3 ) 2 , -CH = C (Br) -CO-NH-C 2 H 5 , -CH = C (Br) -CO-N (C 2 H 5 ) 2 , -CH = C (Br) -CO-NH-Ii-C 3 H 7 ,
-CH=C(Br)-CO-NH-I-C3H7, -CH=C (Br)-CO-NH-tert .-C4H9, -CH = C (Br) -CO-NH-IC 3 H 7 , -CH = C (Br) -CO-NH-tert-C 4 H 9 ,
-CH=C(Br)-CO-NH-cyclopropyl, -CH=C(Br)-CO-NH-cyclobutyl, -CH = C (Br) -CO-NH-cyclopropyl, -CH = C (Br) -CO-NH-cyclobutyl,
-CH=C(Br)-CO-NH-cyclopentyl, -CH=C(Br)-CO-NH-cyclohexyl, -CH = C (Br) -CO-NH-cyclopentyl, -CH = C (Br) -CO-NH-cyclohexyl,
-CH=C ( Br) -CO-NH-cyc 1ohepty 1 , -CH=C (Br ) -CO-NH-cyc 1oocty 1 , -CH = C (Br) -CO-NH-cyc 1ohepty 1, -CH = C (Br) -CO-NH-cyc 1oocty 1,
-CH=C (Br) -CO-pyrrolidin-1-yl, -CH=C(Br)-CO-piperidin-l-yl, -CH=C (Br)-C0-morphol in-4-y 1, -CH=C(Br)-CO-NH-CH2CH=C(Br)2, -CH=C (Br )-CO-NH-CH 2C≡CH, -CH=C (Br )-CO-N (CH3)-CH2C=CH, -CH = C (Br) -CO-pyrrolidin-1-yl, -CH = C (Br) -CO-piperidin-l-yl, -CH = C (Br) -C0-morphol in-4-y 1, -CH = C (Br) -CO-NH-CH 2 CH = C (Br) 2 , -CH = C (Br) -CO-NH-CH 2 C≡CH, -CH = C (Br) -CO- N (CH 3 ) -CH 2 C = CH,
-CH=C(Br)-CO-NH-(CH2) 2CI, -CH=C(Br)-CO-NH-C6H5, -CH=C(CN)-CO-NH2, -CH=C(CN)-CO-NHCH3, -CH=C(CN)-CO-N(CH3) 2, -CH=C(CN)-CO-NH-C2H5, -CH=C(CN)-CO-N(C2H5)2, -CH=C (CN)-CO-NH-n-C3H7, -CH = C (Br) -CO-NH- (CH 2 ) 2CI, -CH = C (Br) -CO-NH-C 6 H 5 , -CH = C (CN) -CO-NH 2 , -CH = C (CN) -CO-NHCH 3 , -CH = C (CN) -CO-N (CH 3 ) 2 , -CH = C (CN) -CO-NH-C 2 H 5 , -CH = C ( CN) -CO-N (C 2 H 5 ) 2 , -CH = C (CN) -CO-NH-nC 3 H 7 ,
-CH=C(CN)-CO-NH-I-C3H7, -CH=C (CN)-CO-NH-tert .-C4H9, -CH = C (CN) -CO-NH-IC 3 H 7 , -CH = C (CN) -CO-NH-tert-C 4 H 9 ,
-CH=C (CN)-CO-NH-cyclopropyl, -CH=C (CN) -CO-NH-cyclobutyl, -CH = C (CN) -CO-NH-cyclopropyl, -CH = C (CN) -CO-NH-cyclobutyl,
-CH=C(CN)-CO-NH-cyclopentyl, -CH=C(CN)-CO-NH-cyclohexyl, -CH = C (CN) -CO-NH-cyclopentyl, -CH = C (CN) -CO-NH-cyclohexyl,
-CH=C (CN) -CO-NH-cyc loheptyl, -CH=C(CN)-CO-NH-cyclooctyl, -CH = C (CN) -CO-NH-cycloheptyl, -CH = C (CN) -CO-NH-cyclooctyl,
-CH=C (CN)-CO-pyrrolidin-1-yl, -CH=C (CN)-CO-pi peridin-1-yl, -CH=C(CN)-CO-morpholin-4-yl, -CH=C(CN)-CO-NH-CH2CH=C(CN)2, -CH=C(CN)-CO-NH-CH2C=CH, -CH=C (CN)-CO-N (CH3)-CH2C=CH, -CH = C (CN) -CO-pyrrolidin-1-yl, -CH = C (CN) -CO-pi peridin-1-yl, -CH = C (CN) -CO-morpholin-4-yl, - CH = C (CN) -CO-NH-CH 2 CH = C (CN) 2 , -CH = C (CN) -CO-NH-CH 2 C = CH, -CH = C (CN) -CO-N (CH 3 ) -CH 2 C = CH,
-CH=C(CN)-CO-NH-(CH2) 2C1, -CH=C(CN)-CO-NH-C6H5, -CH=CH-CO-SCH3, -CH=CH-CO-SC2H5, -CH=CH-CO-S-n-C3H7, -CH=CH-CO-S-i-C3H7, -CH = C (CN) -CO-NH- (CH 2 ) 2 C1, -CH = C (CN) -CO-NH-C 6 H 5 , -CH = CH-CO-SCH 3 , -CH = CH-CO-SC 2 H 5 , -CH = CH-CO-SnC 3 H 7 , -CH = CH-CO-SiC 3 H 7 ,
-CH=CH-CO-S-n-C4H9, -CH=CH-CO-S-tert.-C4H9, -CH=C(CH3)-CO-SCH3, -CH=C(CH3)-CO-SC2H5, -CH=C(CH3)-CO-S-n-C3H7, -CH = CH-CO-SnC 4 H 9 , -CH = CH-CO-S-tert.-C 4 H 9 , -CH = C (CH 3 ) -CO-SCH 3 , -CH = C (CH 3 ) -CO-SC 2 H 5 , -CH = C (CH 3 ) -CO-SnC 3 H 7 ,
-CH=C(CH3)-CO-S-i-C3H7, -CH=C(CH3)-CO-S-n-C4H9, -CH = C (CH 3 ) -CO-SiC 3 H 7 , -CH = C (CH 3 ) -CO-SnC 4 H 9 ,
-CH=C(CH3)-CO-S-tert.-C4H9, -CH=C(C2H5)-CO-SCH3, -CH = C (CH 3 ) -CO-S-tert.-C 4 H 9 , -CH = C (C 2 H 5 ) -CO-SCH 3 ,
-CH=C(C2H5)-CO-SC2H5, -CH=C(C2H5)-CO-S-n-C3H7, -CH = C (C 2 H 5 ) -CO-SC 2 H 5 , -CH = C (C 2 H 5 ) -CO-SnC 3 H 7 ,
-CH=C(C2H5)-CO-S-i-C3H7, -CH=C(C2H5)-CO-S-n-C4H9, -CH = C (C 2 H 5 ) -CO-SiC 3 H 7 , -CH = C (C 2 H 5 ) -CO-SnC 4 H 9 ,
-CH=C(C2H5)-CO-S-tert.-C4H9, -CH=C(Cl)-CO-SCH3, -CH = C (C 2 H 5 ) -CO-S-tert-C 4 H 9 , -CH = C (Cl) -CO-SCH 3 ,
-CH=C(Cl)-CO-SC2H5, -CH=C(Cl)-CO-S-n-C3H7, -CH=C(Cl)-CO-S-i-C3H7, -CH=C(Cl)-CO-S-n-C4H9, -CH=C(Cl)-CO-S-tert.-C4H9, -CH = C (Cl) -CO-SC 2 H 5 , -CH = C (Cl) -CO-SnC 3 H 7 , -CH = C (Cl) -CO-SiC 3 H 7 , -CH = C ( Cl) -CO-SnC 4 H 9 , -CH = C (Cl) -CO-S-tert.-C 4 H 9 ,
-CH=C(Br)-CO-SCH3, -CH=C(Br)-CO-SC2H5, -CH=C(Br)-CO-S-n-C3H7, -CH=C(Br)-CO-S-i-C3H7, -CH=C(Br)-CO-S-n-C4H9, -CH = C (Br) -CO-SCH 3 , -CH = C (Br) -CO-SC 2 H 5 , -CH = C (Br) -CO-SnC 3 H 7 , -CH = C (Br) -CO-SiC 3 H 7 , -CH = C (Br) -CO-SnC 4 H 9 ,
-CH=C(Br)-CO-S-tert.-C4H9, -CH=C(CN)-CO-SCH3, -CH=C(CN)-CO-SC2H5, -CH=C(CN)-CO-S-n-C3H7, -CH=C(CN)-CO-S-i-C3H7, -CH = C (Br) -CO-S-tert.-C 4 H 9 , -CH = C (CN) -CO-SCH 3 , -CH = C (CN) -CO-SC 2 H 5 , -CH = C (CN) -CO-SnC 3 H 7 , -CH = C (CN) -CO-SiC 3 H 7 ,
-CH=C(CN)-CO-S-n-C4H9, -CH=C(CN)-CO-S-tert.-C4H9, -CH = C (CN) -CO-SnC 4 H 9 , -CH = C (CN) -CO-S-tert.-C 4 H 9 ,
-CH=C(COCH3)-CO-OCH3, -CH=C(COC2H5)-CO-OCH3, -CH = C (COCH 3 ) -CO-OCH 3 , -CH = C (COC 2 H 5 ) -CO-OCH 3 ,
-CH=C(CO-n-C3H7)-CO-OCH3, -CH=C(COCH3)-CO-OC2H5, -CH = C (CO-nC 3 H 7 ) -CO-OCH 3 , -CH = C (COCH 3 ) -CO-OC 2 H 5 ,
-CH=C(COC2H5)-CO-OC2H5, -CH=C(CO-n-C3H7)-CO-OC2H5, -CH = C (COC 2 H 5 ) -CO-OC 2 H 5 , -CH = C (CO-nC 3 H 7 ) -CO-OC 2 H 5 ,
-CH=C(COCH3)-CO-O-n-C3H7, -CH=C(COC2H5)-CO-O-n-C3H7, -CH = C (COCH 3 ) -CO-OnC 3 H 7 , -CH = C (COC 2 H 5 ) -CO-OnC 3 H 7 ,
-CH=C(CO-n-C3H7)-CO-O-n-C3H7, -CH=C(CF3)-CO-OCH3, -CH = C (CO-nC 3 H 7 ) -CO-OnC 3 H 7 , -CH = C (CF 3 ) -CO-OCH 3 ,
-CH=C(CF3)-CO-OC2H5, -CH=C(CF3)-CO-O-n-C3H7, -CH = C (CF 3 ) -CO-OC 2 H 5 , -CH = C (CF 3 ) -CO-OnC 3 H 7 ,
-CH=C(CF3)-CO-O-i-C3H7, -CH=C(CF3)-CO-O-n-C4H9, -CH = C (CF 3 ) -CO-OiC 3 H 7 , -CH = C (CF 3 ) -CO-OnC 4 H 9 ,
-CH=C(CF3)-CO-O-tert.-C4H9, -CH=C(COOCH3)2, -CH=C(COOC2H5)2, -CH=C(COOCH3)-CO-OC2H5, -CH=C(COO-n-C3H7)-CO-OCH3, -CH = C (CF 3 ) -CO-O-tert.-C 4 H 9 , -CH = C (COOCH 3 ) 2 , -CH = C (COOC 2 H 5 ) 2 , -CH = C (COOCH 3 ) -CO-OC 2 H 5 , -CH = C (COO-nC 3 H 7 ) -CO-OCH 3 ,
-CH=C(COO-n-C3H7)-CO-OC2H5, -CH=C(COO-n-C3H7)2, -CH = C (COO-nC 3 H 7 ) -CO-OC 2 H 5 , -CH = C (COO-nC 3 H 7 ) 2 ,
-CH=CH-CH=CH-COOH, -CH=CH-CH=CH-CO-OCH3, -CH=CH-CH=CH-CO-OC2H5, -CH=CH-CH=C(COOCH3)2, -CH=CH-CH=C(CN)-CO-OCH3, -CH = CH-CH = CH-COOH, -CH = CH-CH = CH-CO-OCH 3 , -CH = CH-CH = CH-CO-OC 2 H 5 , -CH = CH-CH = C ( COOCH 3 ) 2 , -CH = CH-CH = C (CN) -CO-OCH 3 ,
-CH=CH-CH=C(CN)-CO-OC2H5, -CH=C(CH3)-CH=C(CN)-CO-OCH3, -CH = CH-CH = C (CN) -CO-OC 2 H 5 , -CH = C (CH 3 ) -CH = C (CN) -CO-OCH 3 ,
-CH=C(CH3)-CH=C(CN)-CO-OC2H5, -CH=C(CH3)-CH=C(CH3)-CO-OCH3, -CH=C(CH3)-CH=C(Cl)-CO-OCH3, -CH=C(CH3)-CH=C(Br)-CO-OCH3, -CH = C (CH 3 ) -CH = C (CN) -CO-OC 2 H 5 , -CH = C (CH 3 ) -CH = C (CH 3 ) -CO-OCH 3 , -CH = C ( CH 3 ) -CH = C (Cl) -CO-OCH 3 , -CH = C (CH 3 ) -CH = C (Br) -CO-OCH 3 ,
-CH=C(CH3)-CH=C(CH3)-CO-OC2H5, -CH=C(CH3)-CH=C(Cl)-CO-OC2H5, -CH=C(CH3)-CH=C(Br)-CO-OC2H5, -CH=C(CH3)-CH=C(CN)-CO-NH2, -CH = C (CH 3 ) -CH = C (CH 3 ) -CO-OC 2 H 5 , -CH = C (CH 3 ) -CH = C (Cl) -CO-OC 2 H 5 , -CH = C (CH 3 ) -CH = C (Br) -CO-OC 2 H 5 , -CH = C (CH 3 ) -CH = C (CN) -CO-NH 2 ,
-CH=C(CH3)-CH=C(CN)-CO-NH-CH3, -CH=CH-(CH2)2-COOH, -CH = C (CH 3 ) -CH = C (CN) -CO-NH-CH 3 , -CH = CH- (CH 2 ) 2 -COOH,
-CH=CH-(CH2)2-CO-OCH3, -CH=CH-(CH2)2-CO-OC2H5, -CH = CH- (CH 2 ) 2 -CO-OCH 3 , -CH = CH- (CH 2 ) 2-CO-OC 2 H 5 ,
-CH=CH-CH2-CH(COOCH3)2, -CH=CH-CH2-CH(COOC2H5)2, -CH = CH-CH 2 -CH (COOCH 3 ) 2 , -CH = CH-CH 2 -CH (COOC 2 H 5 ) 2 ,
-CH=CH-CH2-CH(CN)-CO-OCH3, -CH=CH-CH2-CH(CN)-CO-OC2H5, -CH = CH-CH 2 -CH (CN) -CO-OCH 3 , -CH = CH-CH 2 -CH (CN) -CO-OC 2 H 5 ,
-CH=CH-CH2-CH(CH3)-CO-OCH3, -CH=CH-CH2-CH(CH3)-CO-OC2H5, -CH = CH-CH 2 -CH (CH 3 ) -CO-OCH 3 , -CH = CH-CH 2 -CH (CH 3 ) -CO-OC 2 H 5 ,
-CH=CH-(CH2)2-CO-NH2, -CH=CH-(CH2)2-CO-NH-CH3, -CH=CH-CH2-COOH, -CH=CH-CH2-CO-OCH3, -CH=CH-CH2-CO-OC2H5, -CH = CH- (CH 2 ) 2 -CO-NH 2 , -CH = CH- (CH 2 ) 2 -CO-NH-CH 3 , -CH = CH-CH 2 -COOH, -CH = CH-CH 2 -CO-OCH 3 , -CH = CH-CH 2 -CO-OC 2 H 5 ,
-CH=C(COOCH3)-CH2-CO-OCH3, -CH=C(COOCH3)-CH2-CO-OC2H5, -CH=CH-CH2-CO-NH2, -CH=CH-CH2-CO-NH-CH3, -CH=CH-CH2-CO-N(CH3)2, -CH(OCH3)2, -CH(SCH3)2, -CH(OC2H5)2, -CH(SC2H5)2, -CH (O-n-C3H7) 2, -CH(O-i-C3H7)2, -CH(S-n-C3H7)2, -CH(S-i-C3H7)2, -CH(O-n-C4H9)2, -CH(O-i-C4H9)2, -CH(O-S-C4H9)2, -CH(O-tert.-C4H9)2, -CH = C (COOCH 3 ) -CH 2 -CO-OCH 3 , -CH = C (COOCH 3 ) -CH 2 -CO-OC 2 H 5 , -CH = CH-CH 2 -CO-NH 2 , -CH = CH-CH 2 -CO-NH-CH 3 , -CH = CH-CH 2 -CO-N (CH 3 ) 2 , -CH (OCH 3 ) 2 , -CH (SCH 3 ) 2 , -CH (OC 2 H 5 ) 2 , -CH (SC 2 H 5 ) 2 , -CH (OnC 3 H 7 ) 2 , -CH (OiC 3 H 7 ) 2 , -CH (SnC 3 H 7 ) 2 , -CH (SiC 3 H 7 ) 2 , -CH (OnC 4 H 9 ) 2 , -CH (OiC 4 H 9 ) 2 , -CH (OSC 4 H 9 ) 2 , -CH (O-tert-C 4 H 9 ) 2 ,
-CH(S-n-C4H9)2, -CH(S-i-C4H9)2, -CH(S-S-C4H9)2, -CH (SnC 4 H 9 ) 2 , -CH (SiC 4 H 9 ) 2 , -CH (SSC 4 H 9 ) 2 ,
-CH(S-tert.-C4H9)2, -CH(OC5Hn)2, 1,3-Dioxolan-2-yl, 1,3-Dithiolan-2-yl, 1,3-Oxathiolan-2-yl, 4-Methyl-1,3-dioxolan-2-yl, 4-Methyl-1,3-dithiolan-2-yl, 4-Methyl-1,3-oxathiolan-2-yl, 5-Methyl-1,3-oxathiolan-2-yl, 4-Ethyl-1,3-dioxolan-2-yl, 4-Ethyl1,4-dithiolan-2-yl, 4-Ethyl-1,3-oxathiolan-2-yl, 5-Ethyl-1,3-oxathiolan-2-yl, 4, 5-Dimethyl-1,3-dioxolan-2-yl, 4,4-Dimethyl-1,3- dioxolan-2-yl, 4, 5-Dimethyl-1,3-dithiolan-2-yl, 5,5-Dimethyl-1,3- dithiolan-2-yl, 4,5-Dimethyl-1,3-oxathiolan-2-yl, 5,5-Dimethyl1,3-oxathiolan-2-yl, 4,4-Dimethyl-1,3-oxathiolan-2-yl, 4-vinyl1,3-dioxolan-2-yl, 4-Vinyl-1,3-dithiolan-2-yl, 4-Vinyl-1,3-oxathiolan-2-yl, 5-Vinyl-1,3-oxathiolan-2-yl, 4-Chlormethyl-1,3- dioxolan-2-yl, 4-Chlormethyl-1,3-dithiolan-2-yl, 4-Chlormethyl1,3-oxathiolan-2-yl, 5-Chlormethyl-1,3-oxathiolan-2-yl, -CH (S-tert-C 4 H 9 ) 2 , -CH (OC 5 H n ) 2 , 1,3-dioxolan-2-yl, 1,3-dithiolan-2-yl, 1,3-oxathiolane -2-yl, 4-methyl-1,3-dioxolan-2-yl, 4-methyl-1,3-dithiolan-2-yl, 4-methyl-1,3-oxathiolan-2-yl, 5-methyl -1,3-oxathiolan-2-yl, 4-ethyl-1,3-dioxolan-2-yl, 4-ethyl1,4-dithiolan-2-yl, 4-ethyl-1,3-oxathiolan-2-yl , 5-ethyl-1,3-oxathiolan-2-yl, 4,5-dimethyl-1,3-dioxolan-2-yl, 4,4-dimethyl-1,3-dioxolan-2-yl, 4,5 -Dimethyl-1,3-dithiolan-2-yl, 5,5-dimethyl-1,3-dithiolan-2-yl, 4,5-dimethyl-1,3-oxathiolan-2-yl, 5,5-dimethyl1 , 3-oxathiolan-2-yl, 4,4-dimethyl-1,3-oxathiolan-2-yl, 4-vinyl1,3-dioxolan-2-yl, 4-vinyl-1,3-dithiolan-2-yl , 4-vinyl-1,3-oxathiolan-2-yl, 5-vinyl-1,3-oxathiolan-2-yl, 4-chloromethyl-1,3-dioxolan-2-yl, 4-chloromethyl-1,3 dithiolan-2-yl, 4-chloromethyl-1,3-oxathiolan-2-yl, 5-chloromethyl-1,3-oxathiolan-2-yl,
4-Hydroxymethyl-1,3-dioxolan-2-yl, 4-Hydroxymethyl-1,3-dithiolan-2-yl, 4-Hydroxymethyl-1,3-oxathiolan-2-yl, 5-Hydroxymethyl1,3-oxathiolan-2-yl, 4-Methoxymethyl-1,3-dioxolan-2-yl, 4-Allyloxymethyl-1,3-dioxolan-2-yl, 4-Propargyloxymethyl-1,3-dioxolan- 2-yl, 4-Acetoxymethyl-1,3-dioxolan-2-yl, 4-Methoxymethyl-1,3- dithiolan-2-yl, 4-Allyloxymethyl-1,3-dithiolan-2-yl, 4-Propargyloxymethyl-1,3-dithiolan-2-yl, 4-Acetoxymethyl-1,3-dithiolan-2-yl, 4-Methoxymethyl-1,3-oxathiolan-2-yl, 5-Methoxymethyl-1,3-oxathiolan-2-yl, 4-Allyloxymethyl-1,3-oxathiolan-2-yl, 5-Allyloxymethyl-1,3-oxathiolan-2-yl, 4-Propargyloxymethyl-1,3-oxathiolan2-yl, 5-Propargyloxymethyl-1,3-oxathiolan-2-yl, 4-Acetoxymethyl1,3-oxathiolan-2-yl, 5-Acetoxymethyl-1,3-oxathiolan-2-yl, 4-hydroxymethyl-1,3-dioxolan-2-yl, 4-hydroxymethyl-1,3-dithiolan-2-yl, 4-hydroxymethyl-1,3-oxathiolan-2-yl, 5-hydroxymethyl1,3-oxathiolan- 2-yl, 4-methoxymethyl-1,3-dioxolan-2-yl, 4-allyloxymethyl-1,3-dioxolan-2-yl, 4-propargyloxymethyl-1,3-dioxolan- 2-yl, 4-acetoxymethyl- 1,3-dioxolan-2-yl, 4-methoxymethyl-1,3-dithiolan-2-yl, 4-allyloxymethyl-1,3-dithiolan-2-yl, 4-propargyloxymethyl-1,3-dithiolan-2- yl, 4-acetoxymethyl-1,3-dithiolan-2-yl, 4-methoxymethyl-1,3-oxathiolan-2-yl, 5-methoxymethyl-1,3-oxathiolan-2-yl, 4-allyloxymethyl-1, 3-oxathiolan-2-yl, 5-allyloxymethyl-1,3-oxathiolan-2-yl, 4-propargyloxymethyl-1,3-oxathiolan2-yl, 5-propargyloxymethyl-1,3-oxathiolan-2-yl, 4- Acetoxymethyl1,3-oxathiolan-2-yl, 5-acetoxymethyl-1,3-oxathiolan-2-yl,
4-Methylthiomethyl-1,3-dioxolan-2-yl, 4-Methylthiomethyl-1,3- dithiolan-2-yl, 4-Carboxy-1,3-dioxolan-2-yl, 4-Carboxy-1,3- dithiolan-2-yl, 4-Methoxycarbonyl-1,3-dioxolan-2-yl, 4-Ethoxycarbonyl-1,3-dioxolan-2-yl, 4-n-Butoxycarbonyl-1,3-dioxolan-2-yl, 4-Methoxycarbonyl-1,3-dithiolan-2-yl, 4-Ethoxycarbonyl-1,3-dithiolan-2-yl, 4-n-Butoxycarbonyl-1,3-dithiolan-2-yl, 4-Methoxycarbonyl-4-methyl-1,3-dioxolan-2-yl, 4-Methoxycarbonyl-4-methyl1,3-dithiolan-2-yl, 4-Ethoxycarbonyl-4-methyl-1,3-dioxolan-2-yl, 4-Ethoxycarbonyl-4-methyl-1,3-dithiolan-2-yl, 4-n-Butoxycarbonyl4-methyl-1,3-dioxolan-2-yl, 4-n-Butoxycarbonyl-4-methyl-1,3-di thiolan-2-yl, 4-Cyanomethy l-1,3-dioxolan-2-yl, 4-Cyanomethyl-1,3- dithiolan-2-yl, 1,3-Dioxan-2-yl, 1,3-Dithian-2-yl, 1,3-Oxathian2-yl, 5-Methyl-1,3-dioxan-2-yl, 5-Methyl-1,3-dithian-2-yl, 5-Methy l-1,3-oxathian-2-yl, 5,5-Dimethyl-1,3-dioxan-2-yl, 4,6-Dimethy l-1,3-dioxan-2-yl, 4,4-Dimethyl-1,3-dioxan-2-yl, 5,5-Dimethyl-1,3-dithian-2-yl, 4,6-Dimethyl-1,3-dithian-2-yl, 4,4-Dimethyl-1,3-dithian-2-yl, 5,5-Dimethyl-1,3-oxathian-2-yl, 4,4-Dimethyl-1,3-oxathian-2-yl, 6,6-Dimethyl-1,3-oxathian-2-yl, 4-methylthiomethyl-1,3-dioxolan-2-yl, 4-methylthiomethyl-1,3-dithiolan-2-yl, 4-carboxy-1,3-dioxolan-2-yl, 4-carboxy-1,3- dithiolan-2-yl, 4-methoxycarbonyl-1,3-dioxolan-2-yl, 4-ethoxycarbonyl-1,3-dioxolan-2-yl, 4-n-butoxycarbonyl-1,3-dioxolan-2-yl, 4-methoxycarbonyl-1,3-dithiolan-2-yl, 4-ethoxycarbonyl-1,3-dithiolan-2-yl, 4-n-butoxycarbonyl-1,3-dithiolan-2-yl, 4-methoxycarbonyl-4- methyl-1,3-dioxolan-2-yl, 4-methoxycarbonyl-4-methyl1,3-dithiolan-2-yl, 4-ethoxycarbonyl-4-methyl-1,3-dioxolan-2-yl, 4-ethoxycarbonyl- 4-methyl-1,3-dithiolan-2-yl, 4-n-butoxycarbonyl4-methyl-1,3-dioxolan-2-yl, 4-n-butoxycarbonyl-4-methyl-1,3-di thiolan-2-yl, 4-cyanomethyl 1-1,3-dioxolan-2-yl, 4-cyanomethyl-1,3-dithiolan-2-yl, 1,3-dioxan-2-yl, 1,3-dithiane -2-yl, 1,3-oxathian2-yl, 5-methyl-1,3-dioxan-2-yl, 5-methyl-1,3-dithian-2-yl, 5-methyl l-1,3- oxathian-2-yl, 5,5-dimethyl-1,3-dioxan-2-yl, 4,6-dimethyl-1,3-dioxan-2-yl, 4,4-dimethyl-1,3-dioxane -2-yl, 5,5-dimethyl-1,3-dithian-2-yl, 4,6-dimethyl-1,3-dithian-2-yl, 4,4-dimethyl-1,3-dithian-2 -yl, 5,5-dimethyl-1,3-oxathian-2-yl, 4,4-dimethyl-1,3-oxathian-2-yl, 6,6-dimethyl-1,3-oxathian-2-yl ,
4-Hydroxymethyl-1,3-dioxan-2-yl, 4-Methoxymethyl-1,3-dioxan-2-yl, 4-Allyloxymethyl-1,3-dioxan-2-yl, 4-Acetoxymethyl-1,3-dioxan-2- yl, 4-Hydroxymethyl-1,3-dithian-2-yl, 4-Methoxymethyl-1,3-dithian-2-yl, 4-Allyloxymethyl-1,3-dithian-2-yl, 4-Acetoxymethyl1,3-dithian-2-yl, 4-Chlormethyl-1,3-dioxan-2-yl, 4-Chlormethyl1,3-dithian-2-yl, 1,3-Dioxepan-2-yl, 1,3-Dithiepan-2-yl, 1,3-Dioxep-5-en-2-yl, 4-Methoxycarbonyl-1,3-dioxan-2-yl, 4-Ethoxycarbonyl-1,3-dioxan-2-yl, 4-n-Butoxycarbonyl-1,3-dioxan-2-yl, 4-Methoxycarbonyl-1,3-dithian-2-yl, 4-Ethoxycarbonyl-1,3-dithian2-yl, 4-n-Butoxycarbonyl-1,3-dithian-2-yl, 4-Methoxycarbonyl-4- methyl-1,3-dioxan-2-yl, 4-Ethoxycarbonyl-4-methyl-1,3-dioxan-2- yl, 4-n-Butoxycarbonyl-4-methyl-1,3-dioxan-2-yl, 4-Methoxycarbonyl-4-methyl-1,3-dithian-2-yl, 4-Ethoxycarbonyl-4-methyl- 1,3-dithian-2-yl, 4-n-Butoxycarbonyl-4-methyl-1,3-dithian-2-yl, -C(CH3)(OCH3)2, -C(CH3)(SCH3)2, -C(CH3)(OC2H5)2, -C(CH3)(SC2H5)2, -C(CH3)(O-n-C3H7)2, -C(CH3)(O-i-C3H7)2, -C(CH3)(S-n-C3H7)2, -C(CH3)(S-i-C3H7)2, -C(CH3)(O-n-C4H9)2, -C(CH3)(O-i-C4H9)2, -C(CH3)(O-s-C4H9)2, -C(CH3)(O-tert.-C4H9)2, -C(CH3)(S-n-C4H9)2, -C(CH3)(S-i-C4H9)2, -C(CH3)(S-S-C4H9)2, -C(CH3)(S-tert.-C4H9)2, -C(CH3)(O-n-C5H11)", 2-Methyl-1,3-dixolan-2-yl, 2-Methyl-1,3-dithiolan-2-yl, 2-Methyl-1,3-oxathiolan-2-yl, 2,4-Dimethyl-1,3- dixolan-2-yl, 2,4-Dimethyl-1,3-dithiolan-2-yl, 2,4-Dimethyl-1,3- oxathiolan-2-yl, 2,5-Dimethyl-1,3-oxathiolan-2-yl, 4-Ethyl-2- methyl-1,3-dioxolan-2-yl, 4-Ethyl-2-methyl-1,3-dithiolan-2-yl, 4-Ethyl-2-methyl-1,3-oxathiolan-2-yl, 5-Ethyl-2-methyl-1,3- oxathiolan-2-yl, 2,4,5-Trimethyl-1,3-dioxolan-2-yl, 2,4,4-Trimethyl-1,3-dioxolan-2-yl, 2,4,5-Trimethyl-1,3-dithiolan-2-yl,4-hydroxymethyl-1,3-dioxan-2-yl, 4-methoxymethyl-1,3-dioxan-2-yl, 4-allyloxymethyl-1,3-dioxan-2-yl, 4-acetoxymethyl-1,3- dioxan-2-yl, 4-hydroxymethyl-1,3-dithian-2-yl, 4-methoxymethyl-1,3-dithian-2-yl, 4-allyloxymethyl-1,3-dithian-2-yl, 4- Acetoxymethyl1,3-dithian-2-yl, 4-chloromethyl-1,3-dioxan-2-yl, 4-chloromethyl1,3-dithian-2-yl, 1,3-dioxepan-2-yl, 1,3- Dithiepan-2-yl, 1,3-dioxep-5-en-2-yl, 4-methoxycarbonyl-1,3-dioxan-2-yl, 4-ethoxycarbonyl-1,3-dioxan-2-yl, 4- n-butoxycarbonyl-1,3-dioxan-2-yl, 4-methoxycarbonyl-1,3-dithian-2-yl, 4-ethoxycarbonyl-1,3-dithian2-yl, 4-n-butoxycarbonyl-1,3- dithian-2-yl, 4-methoxycarbonyl-4-methyl-1,3-dioxan-2-yl, 4-ethoxycarbonyl-4-methyl-1,3-dioxan-2-yl, 4-n-butoxycarbonyl-4- methyl-1,3-dioxan-2-yl, 4-methoxycarbonyl-4-methyl-1,3-dithian-2-yl, 4-ethoxycarbonyl-4-methyl-1,3-dithian-2-yl, 4- n-Butoxycarbonyl-4-methyl-1,3-dithian-2-yl, -C (CH 3 ) (OCH 3 ) 2 , -C (CH 3 ) (SCH 3 ) 2 , -C (CH 3 ) (OC 2 H 5 ) 2 , -C (CH 3 ) (SC 2 H 5 ) 2 , -C (CH 3 ) (OnC 3 H 7 ) 2 , -C (CH 3 ) (OiC 3 H 7 ) 2 , -C (CH 3 ) (SnC 3 H 7 ) 2 , -C (CH 3 ) (SiC 3 H 7 ) 2 , -C (CH 3 ) (OnC 4 H 9 ) 2 , -C (CH 3 ) (OiC 4 H 9 ) 2 , -C (CH 3 ) (OsC 4 H 9 ) 2 , -C (CH 3 ) (O-tert.-C 4 H 9 ) 2 , - C (CH 3 ) (SnC 4 H 9 ) 2 , -C (CH 3 ) (SiC 4 H 9 ) 2 , -C (CH 3 ) (SSC 4 H 9 ) 2 , -C (CH 3 ) (S- tert-C 4 H 9 ) 2 , -C (CH 3 ) (OnC 5 H 11 ) ", 2-methyl-1,3-dixolan-2-yl, 2-methyl-1,3-dithiolan-2- yl, 2-methyl-1,3-oxathiolan-2-yl, 2,4-dimethyl-1,3-dixolan-2-yl, 2,4-dimethyl-1,3-dithiolan-2-yl, 2, 4-dimethyl-1,3-oxathiolan-2-yl, 2,5-dimethyl-1,3-oxathiolan-2-yl, 4-ethyl-2-methyl-1,3-dioxolan-2-yl, 4- Ethyl-2-methyl-1,3-dithiolan-2-yl, 4-ethyl-2-methyl-1,3-oxathiolan-2-yl, 5-ethyl-2-methyl-1,3-oxathiolan-2- yl, 2,4,5-trimethyl-1,3-dioxolan-2-yl, 2,4,4-trimethyl-1,3-dioxolan-2-yl, 2,4,5-trimethyl-1,3- dithiolan-2-yl,
2,4,4-Trimethyl-1,3-dithiolan-2-yl, 2,4,5-Trimethyl-1,3-oxathiolan-2-yl, 2,4,4-Trimethyl-1,3-oxathiolan-2-yl, 2-Methyl-4-vinyll,3-dioxolan-2-yl, 2-Methyl-4-vinyl-1,3-dithiolan-2-yl, 2-Methyl4-vinyl-1,3-oxathiolan-2-yl, 2-Methyl-5-vinyl-1,3-oxathiolan-2- yl, 4-Chlormethyl-2-methyl-1,3-dioxolan-2-yl, 4-Chlormethyl-2- methyl-1,3-dithiolan-2-yl, 4-Chlormethyl-2-methyl-1,3-oxathiolan-2-yl, 5-Chlormethyl-2-methyl-1,3-oxathiolan-2-yl, 4-Hydroxymethyl-2-methyl-1,3-dioxolan-2-yl, 4-Hydroxymethyl-2-methyl-1,3- dithiolan-2-yl, 4-Hydroxymethyl-2-methyl-1,3-oxathiolan-2-yl, 5-Hydroxymethyl -2-methyl -1,3-oxath i ol an-2-yl, 4-Methoxymethyl -2- methyl-1,3-dioxolan-2-yl, 4-Allyloxymethyl-2-methyl-1,3-dioxolan- 2-yl, 2-Methyl-4-propargyloxymethyl-1,3-dioxolan-2-yl, 4-Acetoxy- 2-methyl-1,3-dioxolan-2-yl, 4-Methoxymethyl-2-methyl-1,3- dithiolan-2-yl, 4-Allyloxymethyl-2-methyl-1,3-dithiolan-2-yl, 2-Methyl-4-propargyloxymethyl-1,3-dithiolan-2-yl, 4-Acetoxy-2- methyl-1,3-dithiolan-2-yl, 4-Methoxymethyl-2-methyl-1,3-oxathiolan-2-yl, 5-Methoxymethyl-2-methyl-1,3-oxathiolan-2-yl, 4-Allyloxymethyl-2-methyl-1,3-oxathiolan-2-yl, 5-Allyloxymethyl-2- methyl-1,3-oxathiolan-2-yl, 2-Methyl-4-propargyloxymethyl-1,3- oxathiolan-2-yl, 2-Methyl-5-propargyloxymethyl-1,3-oxathiolan-2- yl, 4-Acetoxy-2-methyl-1,3-oxathiolan-2-yl, 5-Acetoxy-2-methyl- 1,3-oxathiolan-2-yl, 2-Methyl-4-methylthiomethyl-1,3-dioxolan-2- yl, 2-Methyl-4-methy lthiomethyl-1,3-dithiolan-2-yl, 4-Carboxy-2- methyl-1,3-dioxolan-2-yl, 4-Carboxy-2-methyl-1,3-dithiolan-2-yl, 4-Methoxycarbonyl-2-methyl-1,3-dioxolan-2-yl, 4-Ethoxycarbonyl-2- methyl-1,3-dioxolan-2-yl, 4-n-Butoxycarbonyl-2-methyl-1,3-dioxolan-2-yl, 4-Methoxycarbonyl-2-methyl-1,3-dithiolan-2-yl, 4-Ethoxycarbonyl-2-methyl-1,3-dithiolan-2-yl, 4-n-Butoxycarbonyl-2- methyl-1,3-dithiolan-2-yl, 2,4-Dimethyl-4-methoxycarbonyl-1,3-dioxolan-2-yl, 2,4-Dimethyl-4-methoxycarbonyl-1,3-dithiolan-2-yl, 2,4-Dimethyl-4-ethoxycarbonyl-1,3-dioxolan-2-yl, 2,4-Dimethyl-4- ethoxycarbonyl-1,3-dithiolan-2-yl, 2,4-Dimethyl-4-n-butoxycarbonyl-1,3-dioxolan-2-yl, 2,4-Dimethyl-4-n-butoxycarbonyl-1,3- dithiolan-2-yl, 4-Cyanomethyl-2-methyl-1,3-dioxolan-2-yl, 2,4,4-trimethyl-1,3-dithiolan-2-yl, 2,4,5-trimethyl-1,3-oxathiolan-2-yl, 2,4,4-trimethyl-1,3-oxathiolan- 2-yl, 2-methyl-4-vinyll, 3-dioxolan-2-yl, 2-methyl-4-vinyl-1,3-dithiolan-2-yl, 2-methyl4-vinyl-1,3-oxathiolan- 2-yl, 2-methyl-5-vinyl-1,3-oxathiolan-2-yl, 4-chloromethyl-2-methyl-1,3-dioxolan-2-yl, 4-chloromethyl-2- methyl-1,3-dithiolan-2-yl, 4-chloromethyl-2-methyl-1,3-oxathiolan-2-yl, 5-chloromethyl-2-methyl-1,3-oxathiolan-2-yl, 4- Hydroxymethyl-2-methyl-1,3-dioxolan-2-yl, 4-hydroxymethyl-2-methyl-1,3-dithiolan-2-yl, 4-hydroxymethyl-2-methyl-1,3-oxathiolan-2- yl, 5-hydroxymethyl -2-methyl -1,3-oxathio ol-2-yl, 4-methoxymethyl -2-methyl-1,3-dioxolan-2-yl, 4-allyloxymethyl-2-methyl-1 , 3-dioxolan- 2-yl, 2-methyl-4-propargyloxymethyl-1,3-dioxolan-2-yl, 4-acetoxy-2-methyl-1,3-dioxolan-2-yl, 4-methoxymethyl-2 -methyl-1,3-dithiolan-2-yl, 4-allyloxymethyl-2-methyl-1,3-dithiolan-2-yl, 2-methyl-4-propargyloxymethyl-1,3-dithiolan-2-yl, 4 Acetoxy-2-methyl-1,3-dithiolan-2-yl, 4-methoxymethyl-2-methyl-1,3-oxathiolan-2-yl, 5-methoxymethyl-2-methyl-1,3-oxathiolan-2 -yl, 4-allyloxymethyl-2-methyl-1,3-oxathiolan-2-yl, 5-allyloxymethyl-2-methyl-1,3-oxathiolan-2-yl, 2-methyl-4-propargyloxymethyl-1,3 - oxathiolan-2-yl, 2-methyl-5-propargyloxymethyl-1,3-oxathiolan-2-yl, 4-acetoxy-2-methyl-1,3-oxathiolan-2-yl, 5-ace toxy-2-methyl-1,3-oxathiolan-2-yl, 2-methyl-4-methylthiomethyl-1,3-dioxolan-2-yl, 2-methyl-4-methylthiomethyl-1,3-dithiolan-2 -yl, 4-carboxy-2-methyl-1,3-dioxolan-2-yl, 4-carboxy-2-methyl-1,3-dithiolan-2-yl, 4-methoxycarbonyl-2-methyl-1,3 -dioxolan-2-yl, 4-ethoxycarbonyl-2-methyl-1,3-dioxolan-2-yl, 4-n-butoxycarbonyl-2-methyl-1,3-dioxolan-2-yl, 4-methoxycarbonyl-2 -methyl-1,3-dithiolan-2-yl, 4-ethoxycarbonyl-2-methyl-1,3-dithiolan-2-yl, 4-n-butoxycarbonyl-2-methyl-1,3-dithiolan-2-yl , 2,4-dimethyl-4-methoxycarbonyl-1,3-dioxolan-2-yl, 2,4-dimethyl-4-methoxycarbonyl-1,3-dithiolan-2-yl, 2,4-dimethyl-4-ethoxycarbonyl -1,3-dioxolan-2-yl, 2,4-dimethyl-4-ethoxycarbonyl-1,3-dithiolan-2-yl, 2,4-dimethyl-4-n-butoxycarbonyl-1,3-dioxolan-2 -yl, 2,4-dimethyl-4-n-butoxycarbonyl-1,3-dithiolan-2-yl, 4-cyanomethyl-2-methyl-1,3-dioxolan-2-yl,
4-Cyanomethyl-2-methyl-1,3-dithiolan-2-yl, 2-Methyl-1,3-dioxan-2- yl, 2-Methyl-1,3-dithian-2-yl, 2-Methyl-1,3-oxathian-2-yl, 2,5- Dimethyl-1,3-dioxan-2-yl, 2,5-Dimethyl-1,3-dithian-2-yl, 2,5-Dimethyl-1,3-oxathian-2-yl, 2,5,5-Trimethyl-1,3-dioxan-2-yl, 2,4,6- Trimethyl-1,3-dioxan-2-yl, 2,4,4-Trimethyl-1,3-dioxan-2-yl, 2,5,5-Trimethyl-1,3-dithian-2-yl, 2,4,6-Trimethyl-1,3-dithian-2- yl, 2,4,4-Trimethyl-1,3-dithian-2-yl, 2,5,5-Trimethyl-1,3-oxathian-2-yl, 2,4,4-Trimethyl-1,3-oxathian-2-yl, 2,6,6-Trimethyl- 1,3-oxathian-2-yl, 4-Hydroxymethyl-2-methyl-1,3-dioxan-2-yl, 4-Methoxymethyl-2-methyl-1,3-dioxan-2-yl, 4-Allyloxymethyl-2- methyl-1,3-dioxan-2-yl, 4-Acetoxymethyl-2-methyl-1,3-dioxan-2-yl, 4-Hydroxymethyl-2-methyl-1,3-dithian-2-yl, 4-Methoxymethyl-2- methyl-1,3-dithian-2-yl, 4-Allyloxymethyl-2-methyl-1,3-dithian-2- yl, 4-Acetoxymethyl-2-methyl-1,3-dithian-2-yl, 4-Chlormethyl-2- methyl-1,3-dioxan-2-yl, 4-Chlormethyl-2-methyl-1,3-dithian-2-yl, -C(CH3)=NH, -C(CH3)=N-CH3, -C (CH3)=N-C2H5, -C(CH3)=N-n-C3H7, -C(CH3)=N-i-C3H7, -C(CH3)=N-n-C4H9, -C(CH3) =N-CH2CH=CH2, 4-cyanomethyl-2-methyl-1,3-dithiolan-2-yl, 2-methyl-1,3-dioxan-2-yl, 2-methyl-1,3-dithian-2-yl, 2-methyl 1,3-oxathian-2-yl, 2,5-dimethyl-1,3-dioxan-2-yl, 2,5-dimethyl-1,3-dithian-2-yl, 2,5-dimethyl-1, 3-oxathian-2-yl, 2,5,5-trimethyl-1,3-dioxan-2-yl, 2,4,6-trimethyl-1,3-dioxan-2-yl, 2,4,4- Trimethyl-1,3-dioxan-2-yl, 2,5,5-trimethyl-1,3-dithian-2-yl, 2,4,6-trimethyl-1,3-dithian-2-yl, 2, 4,4-trimethyl-1,3-dithian-2-yl, 2,5,5-trimethyl-1,3-oxathian-2-yl, 2,4,4-trimethyl-1,3-oxathian-2- yl, 2,6,6-trimethyl-1,3-oxathian-2-yl, 4-hydroxymethyl-2-methyl-1,3-dioxan-2-yl, 4-methoxymethyl-2-methyl-1,3- dioxan-2-yl, 4-allyloxymethyl-2-methyl-1,3-dioxan-2-yl, 4-acetoxymethyl-2-methyl-1,3-dioxan-2-yl, 4-hydroxymethyl-2-methyl-1,3-dithian-2-yl, 4-methoxymethyl-2-methyl-1,3-dithian-2-yl, 4-allyloxymethyl-2-methyl-1,3-dithian- 2-yl, 4-acetoxymethyl-2-methyl-1,3-dithian-2-yl, 4-chloromethyl-2-methyl-1,3-dioxan-2-yl, 4-chloromethyl-2-methyl-1, 3-dithian-2-yl, -C (CH 3 ) = NH, -C (CH 3 ) = N-CH 3 , -C (CH 3 ) = NC 2 H 5 , -C (CH 3 ) = NnC 3 H 7 , -C (CH 3 ) = NiC 3 H 7 , -C (CH 3 ) = NnC 4 H 9 , -C (CH 3 ) = N-CH 2 CH = CH 2 ,
-C(CH3)=N-CH2CH=CH2-CH3, -C(CH3)=N-CH2C≡CH, -C(CH3)=N-CH2C≡C-CH3, -C(CH3)=N-cyclopropyl, -C(CH3)=N-cyclobutyl, -C(CH3)=N-cyclopentyl, -C(CH3)=N-cyclohexyl, -C(CH3)=N-cycloheptyl, -C (CH 3 ) = N-CH 2 CH = CH 2 -CH 3 , -C (CH 3 ) = N-CH 2 C≡CH, -C (CH 3 ) = N-CH 2 C≡C-CH 3 , -C (CH 3 ) = N-cyclopropyl, -C (CH 3 ) = N-cyclobutyl, -C (CH 3 ) = N-cyclopentyl, -C (CH 3 ) = N-cyclohexyl, -C (CH 3 ) = N-cycloheptyl,
-C(CH3)=N-CH2-CH2Cl, -C(CH3)=N-CH2Cl, -C(CH3)=N-C6H5, -C (CH 3 ) = N-CH 2 -CH 2 Cl, -C (CH 3 ) = N-CH 2 Cl, -C (CH 3 ) = NC 6 H 5 ,
-C(CH3)=N-(2-F-C6H4), -C(CH3)=N-(3-F-C6H4), -C(CH3)=N-(4-F-C6H4), -C(CH3)=N-(2-Cl-C6H4), -C(CH3)=N-(3-Cl-C6H4), -C (CH 3 ) = N- (2-FC 6 H 4 ), -C (CH 3 ) = N- (3-FC 6 H 4 ), -C (CH 3 ) = N- (4-FC 6 H 4 ), -C (CH 3 ) = N- (2-Cl-C 6 H 4 ), -C (CH 3 ) = N- (3-Cl-C 6 H 4 ),
-C(CH3)=N-(4-Cl-C6H4), -C(CH3)=N-(2-CH3-C6H4), -C (CH 3 ) = N- (4-Cl-C 6 H 4 ), -C (CH 3 ) = N- (2-CH 3 -C 6 H 4 ),
-C(CH3)=N-(3-CH3-C6H4), -C(CH3)=N-(4-CH3-C6H4), -C (CH 3 ) = N- (3-CH 3 -C 6 H 4 ), -C (CH 3 ) = N- (4-CH 3 -C 6 H 4 ),
-C(CH3)=N-(2-CF3-C6H4), -C(CH3)=N-(3-CF3-C6H4), -C (CH 3 ) = N- (2-CF 3 -C 6 H 4 ), -C (CH 3 ) = N- (3-CF 3 -C 6 H 4 ),
-C(CH3)=N-(4-CF3-C6H4), -C(CH3)=N-(2-OCH3-C6H4), -C (CH 3 ) = N- (4-CF 3 -C 6 H 4 ), -C (CH 3 ) = N- (2-OCH 3 -C 6 H 4 ),
-C(CH3)=N-(3-OCH3-C6H4), -C(CH3)=N-(4-OCH3-C6H4), -C (CH 3 ) = N- (3-OCH 3 -C 6 H 4 ), -C (CH 3 ) = N- (4-OCH 3 -C 6 H 4 ),
-C(CH3)=N-(4-NO2-C6H4), -C(CH3)=N-(4-CN-C6H4), -C (CH 3 ) = N- (4-NO 2 -C 6 H 4 ), -C (CH 3 ) = N- (4-CN-C 6 H 4 ),
-C(CH3)=N-(2,4-Cl2-C6H3), -C(CH3)=N-(2,4-(CH3)2-C6H3), -C (CH 3 ) = N- (2,4-Cl 2 -C 6 H 3 ), -C (CH 3 ) = N- (2,4- (CH 3 ) 2 -C 6 H 3 ),
-C(CH3)=N-CH2-OCH3, -C(CH3)=N-CH2-OC2H5, -C(CH3)=N-CH2CH2-OCH3, -C(CH3)=N-CH2CH2-OC2H5, -C(CH3)=N-OH, -C(CH3)=N-OCH3, -C (CH 3 ) = N-CH 2 -OCH 3 , -C (CH 3 ) = N-CH 2 -OC 2 H 5 , -C (CH 3 ) = N-CH 2 CH 2 -OCH 3 , - C (CH 3 ) = N-CH 2 CH 2 -OC 2 H 5 , -C (CH 3 ) = N-OH, -C (CH 3 ) = N-OCH 3 ,
-C(CH3)=N-OC2H5, -C(CH3)=N-O-n-C3H7, -C(CH3)=N-O-i-C3H7, -C (CH 3 ) = N-OC 2 H 5 , -C (CH 3 ) = NOnC 3 H 7 , -C (CH 3 ) = NOiC 3 H 7 ,
-C(CH3)=N-O-n-C4H9, -C(CH3)=N-O-i-C4H9, -C(CH3)=N-O-S-C4H9, -C(CH3)=N-O-tert.-C4H9, -C(CH3)=N-OCH2-CH=CH2, -C (CH 3 ) = NOnC 4 H 9 , -C (CH 3 ) = NOiC 4 H 9 , -C (CH 3 ) = NOSC 4 H 9 , -C (CH 3 ) = NO-tert.-C 4 H 9 , -C (CH 3 ) = N-OCH 2 -CH = CH 2 ,
-C(CH3)=N-OCH(CH3)-CH=CH2, -C(CH3)=N-OCH2-C=CH, -C (CH 3 ) = N-OCH (CH 3 ) -CH = CH 2 , -C (CH 3 ) = N-OCH 2 -C = CH,
-C(CH3)=N-CH(CH3)-C=CH, -C(CH3)=N-OCH2-CH=C-CH3, -C (CH 3 ) = N-CH (CH 3 ) -C = CH, -C (CH 3 ) = N-OCH 2 -CH = C-CH 3 ,
-C(CH3)=N-OCH2CH2-Cl, -C(CH3)=N-OCH2CH2-F, -C(CH3)=N-OCH2-CF3, -C(CH3)=N-OCH2-CH=CHCl, -C(CH3)=N-OCH2-C(Cl)=CH2, -C (CH 3 ) = N-OCH 2 CH 2 -Cl, -C (CH 3 ) = N-OCH 2 CH 2 -F, -C (CH 3 ) = N-OCH 2 -CF 3 , -C ( CH 3 ) = N-OCH 2 -CH = CHCl, -C (CH 3 ) = N-OCH 2 -C (Cl) = CH 2 ,
-C(CH3)=N-OCH2-C(Br)=CH2, -C(CH3)=N-OCH2-CH=C(Cl)-CH3, -C (CH 3 ) = N-OCH 2 -C (Br) = CH 2 , -C (CH 3 ) = N-OCH 2 -CH = C (Cl) -CH 3 ,
-C(CH3)=N-O-CO-CH3, -C(CH3)=N-O-CO-C2H5, -C(CH3)=N-OCH2-CN, -C(CH3)=N-OCH2-CH=CH-CH2-OCH3, -C (CH 3 ) = NO-CO-CH 3 , -C (CH 3 ) = NO-CO-C 2 H 5 , -C (CH 3 ) = N-OCH 2 -CN, -C (CH 3 ) = N-OCH 2 -CH = CH-CH 2 -OCH 3 ,
-C(CH3)=N-OCH2-CH=CH-CH2-O-tert.-C4H9, -C(CH3)=N-O-(CH2)3-C6H5, -C(CH3)=N-O-(CH2)4-C6H5, -C(CH3)=N-O-(CH2)4-(4-Cl-C6H4), -C (CH 3 ) = N-OCH 2 -CH = CH-CH 2 -O-tert.-C 4 H 9 , -C (CH 3 ) = NO- (CH 2 ) 3 -C 6 H 5 , - C (CH 3 ) = NO- (CH 2 ) 4 -C 6 H 5 , -C (CH 3 ) = NO- (CH 2 ) 4 - (4-Cl-C 6 H 4 ),
-C(CH3)=N-O-(CH2)4-(4-CH3O-C6H4), -C (CH 3 ) = NO- (CH 2 ) 4 - (4-CH 3 OC 6 H 4 ),
-C(CH3)=N-O-(CH2)4-O-CH3-C6H4), -C(CH3)=N-O-(CH2)4-(4-F-C6H4), -C(CH3)=N-OCH2-CH=CH-C6H5, -C(CH3)=N-OCH2-CH=CH-(4-F-C6H4), -C(CH3)=N-OCH2-CH=CH-(4-Cl-C6H4), -C (CH 3 ) = NO- (CH 2 ) 4 -O-CH 3 -C 6 H 4 ), -C (CH 3 ) = NO- (CH 2 ) 4 - (4-FC 6 H 4 ), -C (CH 3 ) = N-OCH 2 -CH = CH-C 6 H 5 , -C (CH 3 ) = N-OCH 2 -CH = CH- (4-FC 6 H 4 ), -C (CH 3 ) = N-OCH 2 -CH = CH- (4-Cl-C 6 H 4 ),
-C(CH3)=N-OCH2-CH=CH-(3-CH3O-C6H4), -C (CH 3 ) = N-OCH 2 -CH = CH- (3-CH 3 OC 6 H 4 ),
-C(CH3)=N-O-(CH2)2-CH=CH-(4-F-C6H4), -C (CH 3 ) = NO- (CH 2 ) 2 -CH = CH- (4-FC 6 H 4 ),
-C(CH3)=N-O-(CH2)2-CH=CH-(4-Cl-C6H4), -C(CH3)=N-OCH2-CH=CH-CH2-(4-CH3O-C6H4), -C (CH 3 ) = NO- (CH 2 ) 2 -CH = CH- (4-Cl-C 6 H 4 ), -C (CH 3 ) = N-OCH 2 -CH = CH-CH 2 - (4-CH 3 OC 6 H 4 ),
-C(CH3)=N-OCH2-CH=C(CH3)-C6H5, -C (CH 3 ) = N-OCH 2 -CH = C (CH 3 ) -C 6 H 5 ,
-C(CH3)=N-O-(CH2)2-CH=CH-(3,4-Cl2-C6H3), -C (CH 3 ) = NO- (CH 2 ) 2 -CH = CH- (3,4-Cl 2 -C 6 H 3 ),
-C(CH3)=N-O-(CH2)3-C≡C-(4-F-C6H4), -C(CH3)=N-OCH2-OCH3, -C (CH 3 ) = NO- (CH 2 ) 3 -C≡C- (4-FC 6 H 4 ), -C (CH 3 ) = N-OCH 2 -OCH 3 ,
-C(CH3)=N-OCH2CH2-OCH3, -C(CH3)=N-OCH2-OC2H5, -C (CH 3 ) = N-OCH 2 CH 2 -OCH 3 , -C (CH 3 ) = N-OCH 2 -OC 2 H 5 ,
-C(CH3)=N-OCH(CH3)-OCH3, -C(CH3)=N-OCH(CH3)-CO-OCH3, -C (CH 3 ) = N-OCH (CH 3 ) -OCH 3 , -C (CH 3 ) = N-OCH (CH 3 ) -CO-OCH 3 ,
-C(CH3)=N-OCH(CH3)-CO-O-n-C4H9, -C(CH3)=N-NH2, -C(CH3)=N-NH-CH3, -C(CH3)=N-NH-C2H5, -C(CH3)=N-NH-n-C3H7, -C(CH3)=N-NH-i-C3H7, -C(CH3)=N-NH-n-C4H9, -C(CH3)=N-NH-i-C4H9, -C(CH3)=N-NH-S-C4H9, -C(CH3)=N-NH-tert.-C4H9, -C(CH3)=N-NH-cyclopropyl, -C(CH3)=N-NH- cyclobutyl, -C(CH3)=N-NH-cyclopentyl, -C(CH3)=N-NH-cyclohexyl, -C(CH3)=N-NH-cycloheptyl, -C(CH3)=N-N(CH3)2, -C(CH3)=N-N(C2H5)2, -C(CH3)=N-N(n-C3H7)2, -C(CH3)=N-N(i-C3H7)2, -C (CH 3 ) = N-OCH (CH 3 ) -CO-OnC 4 H 9 , -C (CH 3 ) = N-NH 2 , -C (CH 3 ) = N-NH-CH 3 , -C (CH 3 ) = N-NH-C 2 H 5 , -C (CH 3 ) = N-NH-nC 3 H 7 , -C (CH 3 ) = N-NH-iC 3 H 7 , -C (CH 3 ) = N-NH-nC 4 H 9 , -C (CH 3 ) = N-NH-iC 4 H 9 , -C (CH 3 ) = N-NH-SC 4 H 9 , -C (CH 3 ) = N-NH-tert.-C 4 H 9 , -C (CH 3 ) = N-NH-cyclopropyl, -C (CH 3 ) = N-NH-cyclobutyl, -C (CH 3 ) = N-NH- cyclopentyl, -C (CH 3 ) = N-NH-cyclohexyl, -C (CH 3 ) = N-NH-cycloheptyl, -C (CH 3 ) = NN (CH 3 ) 2 , -C (CH 3 ) = NN (C 2 H 5 ) 2 , -C (CH 3 ) = NN (nC 3 H 7 ) 2 , -C (CH 3 ) = NN (iC 3 H 7 ) 2 ,
-C(CH3)=N-NH-CH2-C=CH, -C(CH3)=N-NH-CH2-C=CH, -C (CH 3 ) = N-NH-CH 2 -C = CH, -C (CH 3 ) = N-NH-CH 2 -C = CH,
-C(CH3)=N-N(CH3)-CH2-C=CH, -C(CH3)=N-NH-CH2CF3, -C (CH 3 ) = NN (CH 3 ) -CH 2 -C = CH, -C (CH 3 ) = N-NH-CH 2 CF 3 ,
-C(CH3)=N-NH-CO-CH3, -C(CH3)=N-NH-CO-C2H5, -C(CH3)=N-NH-CO-OCH3, -C(CH3)=N-NH-CO-OC2H5, -C(CH3)=N-NH-CO-O-tert.-C4H9, -C(CH3)=N- pyrrolidin-1-yl, -C(CH3)=N-piperidin-1-yl, -C(CH3)=N-morpholin- 4-yl, -C(CH3)=N-NH-C6H5, -C(CH3)=N-NH-(4-Cl-C6H4), -C (CH 3 ) = N-NH-CO-CH 3 , -C (CH 3 ) = N-NH-CO-C 2 H 5 , -C (CH 3 ) = N-NH-CO-OCH 3 , -C (CH 3 ) = N-NH-CO-OC 2 H 5 , -C (CH 3 ) = N-NH-CO-O-tert.-C 4 H 9 , -C (CH 3 ) = N- pyrrolidin-1-yl, -C (CH 3 ) = N-piperidin-1-yl, -C (CH 3 ) = N-morpholin-4-yl, -C (CH 3 ) = N-NH-C 6 H 5 , -C (CH 3 ) = N-NH- (4-Cl-C 6 H 4 ),
-C(CH3)=N-NH-(4-NO2-C6H4), -C(CH3)=N-NH-(4-F-C6H4), -C (CH 3 ) = N-NH- (4-NO 2 -C 6 H 4 ), -C (CH 3 ) = N-NH- (4-FC 6 H 4 ),
-C(CH3)=N-NH-(4-CH3O-C6H4), -C(CH3)=N-NH-(2,4-Cl2-C6H3), -C (CH 3 ) = N-NH- (4-CH 3 OC 6 H 4 ), -C (CH 3 ) = N-NH- (2,4-Cl 2 -C 6 H 3 ),
-C(CH3)=N-NH-(2,4-(NO2)2-C6H3), -C(CH3)=N-NH-CO-NH2, -C (CH 3 ) = N-NH- (2,4- (NO 2 ) 2 -C 6 H 3 ), -C (CH 3 ) = N-NH-CO-NH 2 ,
-C(CH3)=N-NH-CO-NHCH3, -C(CH3)=N-NH-CO-NHC2H5, -C (CH 3 ) = N-NH-CO-NHCH 3 , -C (CH 3 ) = N-NH-CO-NHC 2 H 5 ,
-C(CH3)=N-NH-CO-N(CH3)2, -C(CH3)=CH-COOH, -C(CH3)=CH-CO-OCH3, -C(CH3)=CH-CO-OC2H5, -C(CH3)=CH-CO-O-n-C3H7, -C (CH 3 ) = N-NH-CO-N (CH 3 ) 2 , -C (CH 3 ) = CH-COOH, -C (CH 3 ) = CH-CO-OCH 3 , -C (CH 3 ) = CH-CO-OC 2 H 5 , -C (CH 3 ) = CH-CO-OnC 3 H 7 ,
-C(CH3)=CH-CO-i-C3H7, -C(CH3)=CH-CO-O-n-C4H9, -C (CH 3 ) = CH-CO-iC 3 H 7 , -C (CH 3 ) = CH-CO-OnC 4 H 9 ,
-C(CH3)=CH-CO-O-tert.-C4H9, -C(CH3)=CH-CO-O-cyclopropyl, -C (CH 3 ) = CH-CO-O-tert.-C 4 H 9 , -C (CH 3 ) = CH-CO-O-cyclopropyl,
-C(CH3)=CH-CO-O-cyclobutyl, -C(CH3)=CH-CO-O-cyclopentyl, -C (CH 3 ) = CH-CO-O-cyclobutyl, -C (CH 3 ) = CH-CO-O-cyclopentyl,
-C(CH3)=CH-CO-O-cyclohexyl, -C(CH3)=CH-CO-O-cycloheptyl, -C (CH 3 ) = CH-CO-O-cyclohexyl, -C (CH 3 ) = CH-CO-O-cycloheptyl,
-C(CH3)=C(CH3)-COOH, -C(CH3)=C(CH3)-CO-OCH3, -C (CH 3 ) = C (CH 3 ) -COOH, -C (CH 3 ) = C (C H3 ) -CO-OCH 3 ,
-C(CH3)=C(CH3)-CO-OC2H5, -C(CH3)=C(CH3)-CO-O-n-C3H7, -C (CH 3 ) = C (CH 3 ) -CO-OC 2 H 5 , -C (C H3 ) = C (CH 3 ) -CO-OnC 3 H 7 ,
-C(CH3)=C(CH3)-CO-i-C3H7, -C(CH3)=C(CH3)-CO-O-n-C4H9, -C (CH 3 ) = C (CH 3 ) -CO-iC 3 H 7 , -C (CH 3 ) = C (CH 3 ) -CO-OnC 4 H 9 ,
-C(CH3)=C(CH3)-CO-O-tert.-C4H9, -C(CH3)=C(CH3)-CO-O-cyclopropyl, -C(CH3)=C(CH3)-CO-O-cyclobutyl, -C(CH3)=C(CH3)-CO-O-cyclopentyl, -C(CH3)=C(CH3)-CO-O-cyclohexyl, -C(CH3)=C(CH3)-CO-O-cycloheptyl, -C(CH3)=C(C2H5)-COOH, -C(CH3)=C(C2H5)-CO-OCH3, -C (CH 3 ) = C (CH 3 ) -CO-O-tert.-C 4 H 9 , -C (CH 3 ) = C (CH 3 ) -CO-O-cyclopropyl, -C (CH 3 ) = C (CH 3 ) -CO-O-cyclobutyl, -C (CH 3 ) = C (CH 3 ) -CO-O-cyclopentyl, -C (CH 3 ) = C (CH 3 ) -CO-O-cyclohexyl , -C (CH 3 ) = C (CH 3 ) -CO-O-cycloheptyl, -C (CH 3 ) = C (C 2 H 5 ) -COOH, -C (CH 3 ) = C (C 2 H 5 ) -CO-OCH 3 ,
-C(CH3)=C(C2H5)-CO-OC2H5, -C(CH3)=C(C2H5)-CO-O-n-C3H7, -C (CH 3 ) = C (C 2 H 5 ) -CO-OC 2 H 5 , -C (CH 3 ) = C (C 2 H 5 ) -CO-OnC 3 H 7 ,
-C(CH3)=C(C2H5)-CO-i-C3H7, -C(CH3)=C(C2H5)-CO-O-n-C4H9, -C (CH 3 ) = C (C 2 H 5 ) -CO-iC 3 H 7 , -C (CH 3 ) = C (C 2 H 5 ) -CO-OnC 4 H 9 ,
-C(CH3)=C(C2H5)-CO-O-tert.-C4H9, -C(CH3)=C(C2H5)-CO-O-cyclopropyl, -C(CH3)=C(C2H5)-CO-O-cyclobutyl, -C(CH3)=C(C2H5)-CO-O- cyclopentyl, -C(CH3)=C(C2H5)-CO-0-cyclohexyl, -C (CH 3 ) = C (C 2 H 5 ) -CO-O-tert.-C 4 H 9 , -C (CH 3 ) = C (C 2 H 5 ) -CO-O-cyclopropyl, -C (CH 3 ) = C (C 2 H 5 ) -CO-O-cyclobutyl, -C (CH 3 ) = C (C 2 H 5 ) -CO-O- cyclopentyl, -C (CH 3 ) = C (C 2 H 5 ) -CO-0-cyclohexyl,
-C(CH3)=C(C2H5)-CO-O-cycloheptyI, -C(CH3)=CH-COOH, -C (CH 3 ) = C (C 2 H 5 ) -CO-O-cycloheptyI, -C (CH 3 ) = CH-COOH,
-C(CH3)=CH-CO-OCH3, -C(CH3)=CH-CO-OC2H5, -C (CH 3 ) = CH-CO-OCH 3 , -C (CH 3 ) = CH-CO-OC 2 H 5 ,
-C(CH3)=C(Cl)-CO-O-n-C3H7, -C(CH3)=C(Cl)-CO-i-C3H7, -C (CH 3 ) = C (Cl) -CO-OnC 3 H 7 , -C (CH 3 ) = C (Cl) -CO-iC 3 H 7 ,
-C(CH3)=C(Cl)-CO-O-n-C4H9, -C(CH3)=C(Cl )-CO-O-tert.-C4Hg, -C (CH 3 ) = C (Cl) -CO-OnC 4 H 9 , -C (CH 3 ) = C (Cl) -CO-O-tert.-C 4 Hg,
-C(CH3)=C(ClJ-CO-O-cyclopropyl, -C(CH3)=C(ClJ-CO-O-cyclobutyl, -C(CH3)=C(Cl)-CO-0-cyclopentyl, -C(CH3)=C(ClJ-CO-0-cyclohexyl, -C(CH3)=C(ClJ-CO-O-cycloheptyl, -C(CH3)=C(Br)-COOH, -C (CH 3 ) = C (ClJ-CO-O-cyclopropyl, -C (CH 3 ) = C (ClJ-CO-O-cyclobutyl, -C (CH 3 ) = C (Cl) -CO-0- cyclopentyl, -C (CH 3 ) = C (ClJ-CO-0-cyclohexyl, -C (CH 3 ) = C (ClJ-CO-O-cycloheptyl, -C (CH 3 ) = C (Br) -COOH,
-C(CH3)=C(Br)-CO-OCH3, -C(CH3)=C(Br)-CO-OC2H5, -C (CH 3 ) = C (Br) -CO-OCH 3 , -C (CH 3 ) = C (Br) -CO-OC 2 H 5 ,
-C(CH3)=C(Br)-CO-O-n-C3H7, -C(CH3)=C(Br)-CO-i-C3H7, -C (CH 3 ) = C (Br) -CO-OnC 3 H 7 , -C (CH 3 ) = C (Br) -CO-iC 3 H 7 ,
-C(CH3)=C(Br)-C0-0-n-C4Hg, -C(CH3)=C(BrJ-CO-0-tert.-C4Hg, -C (CH 3 ) = C (Br) -C0-0-nC 4 Hg, -C (CH 3 ) = C (BrJ-CO-0-tert.-C 4 Hg,
-C(CH3)=C(Br)-CO-0-cyclopropyl, -C(CH3)=C(Br)-CO-0-cyclobutyl, -C(CH3)=C(BrJ-CO-0-cyclopentyl, -C(CH3)=C(Br)-CO-0-cyclohexyl, -C(CH3)=C(Br)-CO-0-cycloheptyl, -C(CH3)=C(CN)-COOH, -C (CH 3 ) = C (Br) -CO-0-cyclopropyl, -C (CH 3 ) = C (Br) -CO-0-cyclobutyl, -C (CH 3 ) = C (BrJ-CO-0 -cyclopentyl, -C (CH 3 ) = C (Br) -CO-0-cyclohexyl, -C (CH 3 ) = C (Br) -CO-0-cycloheptyl, -C (CH 3 ) = C (CN) -COOH,
-C(CH3)=C(CN)-CO-OCH3, -C(CH3)=C(CN)-CO-OC2H5, -C (CH 3 ) = C (CN) -CO-OCH 3 , -C (CH 3 ) = C (CN) -CO-OC 2 H 5 ,
-C(CH3)=C(CN)-CO-O-n-C3H7, -C(CH3)=C(CN)-CO-i-C3H7, -C (CH 3 ) = C (CN) -CO-OnC 3 H 7 , -C (CH 3 ) = C (CN) -CO-iC 3 H 7 ,
-C(CH3)=C(CN)-C0-0-n-C4Hg, -C(CH3)=C(CN)-CO-O-tert.-C4Hg, -C (CH 3 ) = C (CN) -C0-0-nC 4 Hg, -C (CH 3 ) = C (CN) -CO-O-tert.-C 4 Hg,
-C(CH3)=C(CN)-CO-O-cyclopropyl, -C(CH3)=C(CN)-CO-O-cyclobutyl-, -C(CH3)=C(CN)-CO-0-cyclopentyl, -C(CH3)=C(CN)-CO-0-cyclohexyI, -C(CH3)=C(CN)-CO-O-cycloheptyl, -C(CH3)=CH-CO-OCH2-OCH3, -C (CH 3 ) = C (CN) -CO-O-cyclopropyl, -C (CH 3 ) = C (CN) -CO-O-cyclobutyl-, -C (CH 3 ) = C (CN) -CO -0-cyclopentyl, -C (CH 3 ) = C (CN) -CO-0-cyclohexyl, -C (CH 3 ) = C (CN) -CO-O-cycloheptyl, -C (CH 3 ) = CH- CO-OCH 2 -OCH 3 ,
-C(CH3)=CH-CO-OCH2-0C2H5, -C(CH3)=CH-CO-OCH2-0-n-C3H7, -C (CH 3 ) = CH-CO-OCH 2 -0C 2 H 5 , -C (CH 3 ) = CH-CO-OCH 2 -0-nC 3 H 7 ,
-C(CH3)=CH-CO-O-i-C3H7, -C(CH3)=CH-CO-OCH(CH3)-OCH3, -C (CH 3 ) = CH-CO-OiC 3 H 7 , -C (CH 3 ) = CH-CO-OCH (CH 3 ) -OCH 3 ,
-C(CH3)=CH-C0-0CH(CH3)-OC2H5, -C(CH3)=CH-CO-OCH2CH2-0CH3, -C (CH 3 ) = CH-C0-0CH (CH 3 ) -OC 2 H 5 , -C (CH 3 ) = CH-CO-OCH 2 CH 2 -0CH 3 ,
-C(CH3)=CH-CO-OCH2CH2-OC2H5, -C(CH3)=C(CH3)-CO-OCH2-OCH3, -C (CH 3 ) = CH-CO-OCH 2 CH 2 -OC 2 H 5 , -C (CH 3 ) = C (CH 3 ) -CO-OCH 2 -OCH 3 ,
-C(CH3)=C(CH3)-CO-OCH2-OC2H5, -C(CH3)=C(CH3)-CO-OCH2-O-n-C3H7, -C(CH3)=C(CH3)-CO-O-i-C3H7, -C(CH3)=C(CH3)-C0-0CH(CH3)-0CH3, -C(CH3)=C(CH3)-CO-OCH(CH3)-OC2H5, -C(CH3)=C(CH3)-CO-OCH2CH2-OCH3, -C(CH3)=C(CH3)-CO-OCH2CH2-OC2H5, -C(CH3)=C(C2H5J-CO-OCH2-OCH3, -C(CH3)=C(C2H5J-CO-OCH2-OC2H5, -C(CH3)=C(C2H5J-CO-OCH2-O-Ii-C3H7, -C(CH3)=C(C2H5J-CO-O-I-C3H7; -C(CH3)=C(C2H5)-CO-OCH(CH3)-OCH3, -C(CH3)=C(C2HS)-CO-OCH(CH3)-OC2H5, -C (CH 3 ) = C (CH 3 ) -CO-OCH 2 -OC 2 H 5 , -C (CH 3 ) = C (CH 3 ) -CO-OCH 2 -OnC 3 H 7 , -C (CH 3 ) = C (CH 3 ) -CO-OiC 3 H 7 , -C (CH 3 ) = C (CH 3 ) -C0-0CH (CH 3 ) -0CH 3 , -C (CH 3 ) = C (CH 3 ) -CO-OCH (CH 3 ) -OC 2 H 5 , -C (CH 3 ) = C (CH 3 ) -CO-OCH 2 CH 2 -OCH 3 , -C (CH 3 ) = C (CH 3 ) -CO-OCH 2 CH 2 -OC 2 H 5 , -C (CH 3 ) = C (C 2 H 5 J-CO-OCH 2 -OCH 3 , -C (CH 3 ) = C (C 2 H 5 J-CO-OCH 2 -OC 2 H 5 , -C (CH 3 ) = C (C 2 H 5 J-CO-OCH 2 -O-Ii-C 3 H 7 , -C (CH 3 ) = C ( C 2 H 5 J-CO-OIC 3 H 7 ; -C (CH 3 ) = C (C 2 H 5 ) -CO-OCH (CH 3 ) -OCH 3 , -C (CH 3 ) = C (C 2 HS) -CO-OCH (CH 3 ) -OC 2 H 5 ,
-C(CH3)=C(C2H5)-CO-OCH2CH2-OCH3, -C (CH 3 ) = C (C 2 H 5 ) -CO-OCH 2 CH 2 -OCH 3 ,
-C(CH3)=C(C2H5J-CO-OCH2CH2-OC2H5, -C(CH3)=C(C1)-CO-OCH2-OCH3, -C(CH3)=C(CI)-CO-OCH2-OC2H5, -C(CH3)=C(CI)-CO-OCH2-O-n-C3H7, -C(CH3)=C(Cl)-CO-O-i-C3H7, -C(CH3)=C(Cl)-CO-OCH(CH3)-0CH3, -C (CH 3 ) = C (C 2 H 5 J-CO-OCH 2 CH 2 -OC 2 H 5 , -C (CH 3 ) = C (C1) -CO-OCH 2 -OCH 3 , -C ( CH 3 ) = C (CI) -CO-OCH 2 -OC 2 H 5 , -C (CH 3 ) = C (CI) -CO-OCH 2 -OnC 3 H 7 , -C (CH 3 ) = C ( Cl) -CO-OiC 3 H 7 , -C (CH 3 ) = C (Cl) -CO-OCH (CH 3 ) -0CH 3 ,
-C(CH3)=C(C1)-CO-OCH(CH3)-OC2H5, -C(CH3)=C(ClJ-CO-OCH2CH2-OCH3, -C(CH3)=C(CIJ-CO-OCH2CH2-OC2H5, -C(CH3)=C(Br)-CO-OCH2-OCH3, -C(CH3)=C(BrJ-CO-OCH2-OC2H5, -C(CH3)=C(Br)-CO-OCH2-O-Ii-C3H7, -C(CH3)=C(Br)-CO-O-i-C3H7, -C(CH3)=C(Br)-CO-OCH(CH3)-OCH3, -C (CH 3 ) = C (C1) -CO-OCH (CH 3 ) -OC 2 H 5 , -C (CH 3 ) = C (ClJ-CO-OCH 2 CH 2 -OCH 3 , -C (CH 3 ) = C (CIJ-CO-OCH 2 CH 2 -OC 2 H 5 , -C (CH 3 ) = C (Br) -CO-OCH 2 -OCH 3 , -C (CH 3 ) = C (BrJ- CO-OCH 2 -OC 2 H 5 , -C (CH 3 ) = C (Br) -CO-OCH 2 -O-Ii-C 3 H 7 , -C (CH 3 ) = C (Br) -CO- OiC 3 H 7 , -C (CH 3 ) = C (Br) -CO-OCH (CH 3 ) -OCH 3 ,
-C(CH3)=C(Br)-CO-OCH(CH3)-OC2H5, -C(CH3)=C(Br)-CO-OCH2CH2-OCH3, -C(CH3)=C(Br)-CO-OCH2CH2-OC2H5, -C (CH3)=C (CN)-CO-OCH2-OCH3, -C (CH3)=C(CN)-CO-OCH2-OC2H5, -C(CH3)=C (CN)-CO-OCH2-O-Ii-C3H7, -C(CH3)=C (CN)-CO-O-1-C3H7, -C (CH3)=C(CN)-CO-OCH (CH3)-OCH3, -C(CH3)=C (CN)-CO-OCH(CH3)-OC2H5, -C(CH3)=C(CN)-CO-OCH2CH2-OCH3, -C(CH3)=C(CN)-CO-OCH2CH2-OC2H5, -C(CH3)=CH-CO-OCH2-CF3, -C (CH 3 ) = C (Br) -CO-OCH (CH 3 ) -OC 2 H 5 , -C (CH 3 ) = C (Br) -CO-OCH 2 CH 2 -OCH 3 , -C (CH 3 ) = C (Br) -CO-OCH 2 CH 2 -OC 2 H 5 , -C (CH 3 ) = C (CN) -CO-OCH 2 -OCH 3 , -C (CH 3 ) = C (CN) -CO-OCH 2 -OC 2 H 5 , -C (CH 3 ) = C (CN) -CO-OCH 2 -O-Ii-C 3 H 7 , -C (CH 3 ) = C (CN) -CO-O-1-C 3 H 7 , -C (CH 3 ) = C (CN) -CO-OCH (CH 3 ) -OCH 3 , -C (CH 3 ) = C (CN) - CO-OCH (CH 3 ) -OC 2 H 5 , -C (CH 3 ) = C (CN) -CO-OCH 2 CH 2 -OCH 3 , -C (CH 3 ) = C (CN) -CO-OCH 2 CH 2 -OC 2 H 5 , -C (CH 3 ) = CH-CO-OCH 2 -CF 3 ,
-C(CH3)=CH-CO-OCH2-CCI3, -C(CH3)=CH-CO-OCH2-oxiranyl, -C (CH 3 ) = CH-CO-OCH 2 -CCI 3 , -C (CH 3 ) = CH-CO-OCH 2 -oxiranyl,
-C(CH3)=CH-CO-O-(CH2) 3-Br, -C (CH3)=CH-CO-OCH2-CH=CH2, -C (CH 3 ) = CH-CO-O- (CH 2 ) 3 -Br, -C (CH 3 ) = CH-CO-OCH 2 -CH = CH 2 ,
-C(CH3)=CH-CO-OCH2-C=CH, -C(CH3)=CH-CO-OCH2-CN, -C (CH 3 ) = CH-CO-OCH 2 -C = CH, -C (CH 3 ) = CH-CO-OCH 2 -CN,
-C(CH3)=CH-CO-OCH2CH2-CN, -C(CH3)=C(CH3)-CO-OCH2-CF3, -C (CH 3 ) = CH-CO-OCH 2 CH 2 -CN, -C (CH 3 ) = C (CH 3 ) -CO-OCH 2 -CF 3 ,
-C(CH3)=C(CH3)-CO-OCH2-CC13, -C (CH3)=C (CH3)-CO-OCH2-oxiranyl, -C(CH3)=C(CH3)-CO-O-(CH2)3-Br, -C(CH3)=C(CH3)-CO-OCH2-CH=CH2, -C(CH3)=C(CH3)-CO-OCH2-C=CH, -C(CH3)=C(CH3)-CO-OCH2-CN, -C (CH 3 ) = C (CH 3 ) -CO-OCH 2 -CC1 3 , -C (CH 3 ) = C (CH 3 ) -CO-OCH 2 -oxiranyl, -C (CH 3 ) = C ( CH 3 ) -CO-O- (CH 2 ) 3 -Br, -C (CH 3 ) = C (CH 3 ) -CO-OCH 2 -CH = CH 2 , -C (CH 3 ) = C (CH 3 ) -CO-OCH 2 -C = CH, -C (CH 3 ) = C (CH 3 ) -CO-OCH 2 -CN,
-C(CH3)=C(CH3)-CO-OCH2CH2-CN, -C(CH3)=C(C2H5J-CO-OCH2-CF3, -C(CH3)=C(C2H5J-CO-OCH2-CCl3, -C (CH3)=C(C2H5J-CO-OCH2-oxiranyl, -C(CH3)=C(C2H5J-CO-O-(CH2) 3-Br, -C(CH3)=C(C2H5)-CO-OCH2-CH=CH2, -C(CH3)=C(C2H5J-CO-OCH2-C=CH, -C(CH3)=C(C2H5J-CO-OCH2-CN, -C(CH3)=C(C2H5)-CO-OCH2CH2-CN, -C(CH3)=C(C1 )-CO-OCH2-CF3, -C(CH3)=C(CI)-CO-OCH2-CCI3, -C(CH3)=C (Cl )-CO-OCH2-oxiranyl, -C(CH3)=C(Cl)-CO-O-(CH2J3-Br, -C(CH3)=C(C1)-CO-OCH2-CH=CH2, -C(CH3)=C(Cl)-CO-OCH2-C=CH, -C(CH3)=C(Cl)-CO-OCH2-CN, -C (CH 3 ) = C (CH 3 ) -CO-OCH 2 CH 2 -CN, -C (CH 3 ) = C (C 2 H 5 J-CO-OCH 2 -CF 3 , -C (CH 3 ) = C (C 2 H 5 J-CO-OCH 2 -CCl 3 , -C (CH 3 ) = C (C 2 H 5 J-CO-OCH 2 -oxiranyl, -C (CH 3 ) = C (C 2 H 5 J-CO-O- (CH 2 ) 3 -Br, -C (CH 3 ) = C (C 2 H 5 ) -CO-OCH 2 -CH = CH 2 , -C (CH 3 ) = C (C 2 H 5 J-CO-OCH 2 -C = CH, -C (CH 3 ) = C (C 2 H 5 J-CO-OCH 2 -CN, -C (CH 3 ) = C (C 2 H 5 ) -CO-OCH 2 CH 2 -CN, -C (CH 3 ) = C (C1) -CO-OCH 2 -CF 3 , -C (CH 3 ) = C (CI) -CO-OCH 2 -CCI 3 , -C (CH 3 ) = C (Cl) -CO-OCH 2 -oxiranyl, -C (CH 3 ) = C (Cl) -CO-O- (CH 2 J 3 -Br, -C (CH 3 ) = C (C1) -CO-OCH 2 -CH = CH 2 , -C (CH 3 ) = C (Cl) -CO-OCH 2 -C = CH, -C (CH 3 ) = C (Cl) - CO-OCH 2 -CN,
-C(CH3)=C(Cl)-CO-OCH2CH2-CN, -C(CH3)=C(Br)-CO-OCH2-CF3, -C (CH 3 ) = C (Cl) -CO-OCH 2 CH 2 -CN, -C (CH 3 ) = C (Br) -CO-OCH 2 -CF 3 ,
-C(CH3)=C{Br)-CO-OCH2-CCI3, -C(CH3)=C(Br)-CO-OCH2-oxirany1, -C(CH3)=C(Br)-CO-O-(CH2) 3-Br, -C(CH3)=C(Br)-CO-OCH2-CH=CH2, -C(CH3)=C(Br)-CO-OCH2-C≡CH, -C(CH3)=C(Br)-CO-OCH2-CN, -C (CH 3 ) = C {Br) -CO-OCH 2 -CCI 3 , -C (CH 3 ) = C (Br) -CO-OCH 2 -oxirany1, -C (CH 3 ) = C (Br) -CO-O- (CH 2 ) 3 -Br, -C (CH 3 ) = C (Br) -CO-OCH 2 -CH = CH 2 , -C (CH 3 ) = C (Br) -CO-OCH 2 -C≡CH, -C (CH 3 ) = C (Br) -CO-OCH 2 -CN,
-C(CH3)=C(Br)-CO-OCH2CH2-CN, -C(CH3)=C(CN)-CO-OCH2-CF3, -C (CH 3 ) = C (Br) -CO-OCH 2 CH 2 -CN, -C (CH 3 ) = C (CN) -CO-OCH 2 -CF 3 ,
-C(CH3)=C(CN)-CO-OCH2-CCl 3, -C (CH3)=C (CN)-CO-OCH2-oxiranyl, -C(CH3)=C(CN)-CO-O-(CH2)3-Br, -C(CH3)=C(CN)-CO-OCH2-CH=CH2, -C(CH3)=C(CN)-CO-OCH2-C=CH, -C(CH3)=C(CN)-CO-OCH2-CN, -C (CH 3 ) = C (CN) -CO-OCH 2 -CCl 3 , -C (CH 3 ) = C (CN) -CO-OCH 2 -oxiranyl, -C (CH 3 ) = C (CN) -CO-O- (CH 2 ) 3 -Br, -C (CH 3 ) = C (CN) -CO-OCH 2 -CH = CH 2 , -C (CH 3 ) = C (CN) -CO-OCH 2 -C = CH, -C (CH 3 ) = C (CN) -CO-OCH 2 -CN,
-C(CH3)=C(CNJ-CO-OCH2CH2-CN, -C(CH3)=CH-CO-CH3, -C (CH 3 ) = C (CNJ-CO-OCH 2 CH 2 -CN, -C (CH 3 ) = CH-CO-CH 3 ,
-C(CH3)=CH-CO-C2H5, -C(CH3)=CH-CO-n-C3H7, -C(CH3)=CH-CO-I-C3H7, -C(CH3)=CH-CO-n-C4Hg, -C(CH3)=CH-CO-tert.-C4Hg, -C (CH 3 ) = CH-CO-C 2 H 5 , -C (CH 3 ) = CH-CO-nC 3 H 7 , -C (CH 3 ) = CH-CO-IC 3 H 7 , -C (CH 3 ) = CH-CO-nC 4 Hg, -C (CH 3 ) = CH-CO-tert.-C 4 Hg,
-C(CH3)=CH-CO-CH2Cl, -C(CH3)=CH-CO-CH2Br, -C(CH3)=CH-CO-CHCl2, -C(CH3)=CH-CO-CH2-OCH3, -C(CH3)=CH-CO-CH(OCH3) 2, -C (CH 3 ) = CH-CO-CH 2 Cl, -C (CH 3 ) = CH-CO-CH 2 Br, -C (CH 3 ) = CH-CO-CHCl 2 , -C (CH 3 ) = CH-CO-CH 2 -OCH 3 , -C (CH 3 ) = CH-CO-CH (OCH 3 ) 2 ,
-C(CH3)=CH-CO-CH2-SCH3, -C(CH3)=C(CH3)-CO-CH3, -C (CH 3 ) = CH-CO-CH 2 -SCH 3 , -C (CH 3 ) = C (CH 3 ) -CO-CH 3 ,
-C(CH3)=C(CH3)-CO-C2H5, -C(CH3)=C(CH3)-CO-n-C3H7, -C (CH 3 ) = C (CH 3 ) -CO-C 2 H 5 , -C (CH 3 ) = C (CH 3 ) -CO-nC 3 H 7 ,
-C(CH3)=C(CH3)-CO-I-C3H7, -C (CH3)=C(CH3)-CO-n-C4H9, -C (CH 3 ) = C (CH 3 ) -CO-IC 3 H 7 , -C (CH 3 ) = C (CH 3 ) -CO-nC 4 H 9 ,
-C(CH3)=C (CH3)-CO-tert.-C4Hg, -C(CH3)=C(CH3)-CO-CH2CI, -C (CH 3 ) = C (CH 3 ) -CO-tert-C 4 Hg, -C (CH 3 ) = C (CH 3 ) -CO-CH 2 CI,
-C(CH3)=C(CH3)-CO-CH2Br, -C(CH3)=C(CH3)-CO-CHC12, -C (CH 3 ) = C (CH 3 ) -CO-CH 2 Br, -C (CH 3 ) = C (CH 3 ) -CO-CHC1 2 ,
-C(CH3)=C(CH3)-CO-CH2-OCH3, -C(CH3)=C(CH3)-CO-CH(OCH3) 2, -C (CH 3 ) = C (CH 3 ) -CO-CH 2 -OCH 3 , -C (CH 3 ) = C (CH 3 ) -CO-CH (OCH 3 ) 2 ,
-C(CH3)=C(CH3)-CO-CH2-SCH3, -C(CH3)=C(C2H5)-CO-CH3, -C(CH3)=C(C2Hs)-CO-C2H5, -C(CH3)=C(C2H5)-CO-n-C3H7, -C (CH 3 ) = C (CH 3 ) -CO-CH 2 -SCH 3 , -C (CH 3 ) = C (C 2 H 5 ) -CO-CH 3 , -C (CH 3 ) = C (C 2 Hs) -CO-C 2 H 5 , -C (CH 3 ) = C (C 2 H 5 ) -CO-nC 3 H 7 ,
-C (CH3)=C(C2H5) -CO-I-C3H7, -C (CH3)=C(C2H5) -CO-n-C4H9, -C (CH 3 ) = C (C 2 H 5 ) -CO-IC 3 H 7 , -C (CH 3 ) = C (C 2 H 5 ) -CO-nC 4 H 9 ,
-C(CH3)=C (C2H5) -CO-tert. -C4Hg, -C(CH3)=C (C2H5) -CO-CH2Cl, -C (CH 3 ) = C (C 2 H 5 ) -CO-tert. -C 4 Hg, -C (CH 3 ) = C (C 2 H 5 ) -CO-CH 2 Cl,
-C(CH3)=C(C2H5)-CO-CH2Br, -C(CH3)=C(C2H5)-CO-CHC12, -C (CH 3 ) = C (C 2 H 5 ) -CO-CH 2 Br, -C (CH 3 ) = C (C 2 H 5 ) -CO-CHC1 2 ,
-C(CH3)=C(C2H5)-CO-CH2-OCH3, -C(CH3)=C(C2H5)-CO-CH(OCH3J2, -C(CH3)=C(C2Hs)-CO-CH2-SCH3, -C(CH3)=C(Cl)-CO-CH3, -C (CH 3 ) = C (C 2 H 5 ) -CO-CH 2 -OCH 3 , -C (CH 3 ) = C (C 2 H 5 ) -CO-CH (OCH 3 J 2 , -C ( CH 3 ) = C (C 2 Hs) -CO-CH 2 -SCH 3 , -C (CH 3 ) = C (Cl) -CO-CH 3 ,
-C(CH3)=C(Cl)-CO-C2H5, -C(CH3)=C(Cl )-CO-n-C3H7, -C (CH 3 ) = C (Cl) -CO-C 2 H 5 , -C (CH 3 ) = C (Cl) -CO-nC 3 H 7 ,
-C(CH3)=C(Cl)-CO-i-C3H7, -C(CH3)=C(Cl )-CO-n-C4H9, -C (CH 3 ) = C (Cl) -CO-iC 3 H 7 , -C (CH 3 ) = C (Cl) -CO-nC 4 H 9 ,
-C (CH3 )=C (Cl J -CO-tert. -C4H9, -C(CH3)=C(Cl)-CO-CH2Cl, -C (CH 3 ) = C (Cl J -CO-tert. -C 4 H 9 , -C (CH 3 ) = C (Cl) -CO-CH 2 Cl,
-C(CH3)=C(C1)-CO-CHCl2, -C(CH3)=C(Cl)-CO-CH2-OCH3, -C (CH 3 ) = C (C1) -CO-CHCl 2 , -C (CH 3 ) = C (Cl) -CO-CH 2 -OCH 3 ,
-C (CH 3)=C (Cl)-CO-CH (OCH 3)2, -C(CH3)=C(Cl)-CO-CH2-SCH3, -C (CH 3 ) = C (Cl) -CO-CH (OCH 3 ) 2 , -C (CH 3 ) = C (Cl) -CO-CH 2 -SCH 3 ,
-C(CH3)=C(Br)-CO-CH3, -C(CH3)=C(Br)-CO-C2H5, -C (CH 3 ) = C (Br) -CO-CH 3 , -C (CH 3 ) = C (Br) -CO-C 2 H 5 ,
-C(CH3)=C(Br)-CO-n-C3H7, -C(CH3)=C(Br)-CO-i-C3H7, -C (CH 3 ) = C (Br) -CO-nC 3 H 7 , -C (CH 3 ) = C (Br) -CO-iC 3 H 7 ,
-C(CH3)=C(Br)-CO-n-C4Hg, -C(CH3)=C(Br)-CO-tert.-C4H9, -C (CH 3 ) = C (Br) -CO-nC 4 Hg, -C (CH 3 ) = C (Br) -CO-tert.-C 4 H 9 ,
-C(CH3)=C(Br)-CO-CH2Cl, -C(CH3)=C(Br)-CO-CH2Br, -C (CH 3 ) = C (Br) -CO-CH 2 Cl, -C (CH 3 ) = C (Br) -CO-CH 2 Br,
-C(CH3)=C(Br)-CO-CH2-OCH3, -C(CH3)=C(Br)-CO-CH(OCH3) 2, -C (CH 3 ) = C (Br) -CO-CH 2 -OCH 3 , -C (CH 3 ) = C (Br) -CO-CH (OCH 3 ) 2 ,
-C(CH3)=C(Br)-CO-CH2-SCH3, -C(CH3)=C(CN)-CO-CH3, -C (CH 3 ) = C (Br) -CO-CH 2 -SCH 3 , -C (CH 3 ) = C (CN) -CO-CH 3 ,
-C(CH3)=C(CN)-CO-C2H5, -C(CH3)=C(CN)-CO-n-C3H7, -C (CH 3 ) = C (CN) -CO-C 2 H 5 , -C (CH 3 ) = C (CN) -CO-nC 3 H 7 ,
-C(CH3)=C(CN)-CO-I-C3H7, -C(CH3)=C(CN)-CO-n-C4Hg, -C (CH 3 ) = C (CN) -CO-IC 3 H 7 , -C (CH 3 ) = C (CN) -CO-nC 4 Hg,
-C(CH3)=C(CN)-CO-tert.-C4Hg, -C(CH3)=C(CN)-CO-CH2Cl, -C (CH 3 ) = C (CN) -CO-tert-C 4 Hg, -C (CH 3 ) = C (CN) -CO-CH 2 Cl,
-C(CH3)=C(CN)-CO-CH2Br, -C(CH3)=C(CN)-CO-CHCl2, -C (CH 3 ) = C (CN) -CO-CH 2 Br, -C (CH 3 ) = C (CN) -CO-CHCl 2 ,
-C(CH3)=C(CN)-CO-CH2-OCH3, -C (CH 3)=C (CN J -CO-CH (OCH3 J 2, -C (CH 3 ) = C (CN) -CO-CH 2 -OCH 3 , -C (CH 3 ) = C (CN J -CO-CH (OCH 3 J 2 ,
-C(CH3)=C(CN)-CO-CH2-SCH3, -C(CH3)=CH-CO-C6H5, -C (CH 3 ) = C (CN) -CO-CH 2 -SCH 3 , -C (CH 3 ) = CH-CO-C 6 H 5 ,
-C(CH3)=CH-C0-(4-Cl-C6H4), -C(CH3)=C(CH3)-CO-C6H5, -C (CH 3 ) = CH-C0- (4-Cl-C 6 H 4 ), -C (CH 3 ) = C (CH 3 ) -CO-C 6 H 5 ,
-C(CH3)=C(CH3)-C0-(4-Cl-C6H4), -C(CH3)=C(C2H5)-CO-C6H5, -C (CH 3 ) = C (CH 3 ) -C0- (4-Cl-C 6 H 4 ), -C (CH 3 ) = C (C 2 H 5 ) -CO-C 6 H 5 ,
-C(CH3)=C(C2H5)-C0-(4-Cl-C6H4), -C(CH3)=C(Cl)-CO-C6H5, -C (CH 3 ) = C (C 2 H 5 ) -C0- (4-Cl-C 6 H 4 ), -C (CH 3 ) = C (Cl) -CO-C 6 H 5 ,
-C(CH3)=C(Br)-CO-C6H5, -C(CH3)=C(CN)-CO-C6H5, -C(CH3)=CH-CO-NH2, -C(CH3)=CH-CO-NHCH3, -C (CH3 )=CH-CO-N(CH3) 2, -C (CH 3 ) = C (Br) -CO-C 6 H 5 , -C (CH 3 ) = C (CN) -CO-C 6 H 5 , -C (CH 3 ) = CH-CO-NH 2 , -C (CH 3 ) = CH-CO-NHCH 3 , -C (CH 3 ) = CH-CO-N (CH 3 ) 2 ,
-C(CH3)=CH-CO-NH-C2H5, -C(CH3)=CH-CO-N(C2H5) 2, -C (CH 3 ) = CH-CO-NH-C 2 H 5 , -C (CH 3 ) = CH-CO-N (C 2 H 5 ) 2 ,
-C(CH3)=CH-CO-NH-n-C3H7, -C(CH3)=CH-CO-NH-I-C3H7, -C (CH 3 ) = CH-CO-NH-nC 3 H 7 , -C (CH 3 ) = CH-CO-NH-IC 3 H 7 ,
-C (CH 3 ) =CH-CO-NH-tert . -C4H9 , -C (CH 3 ) =CH-CO-NH-cyc lopropy I , -C(CH3)=CH-CO-NH-cyclobutyl, -C(CH3)=CH-CO-NH-cyclopentyl, -C(CH3)=CH-CO-NH-cyclohexyl, -C(CH3)=CH-CO-NH-cycloheptyl, -C(CH3)=CH-CO-NH-cyclooctyl, -C(CH3)=CH-CO-pyrrolidin-l-yl, -C(CH3)=CH-CO-piperτdin-l-yl, -C(CH3)=CH-C0-morpholin-4-yl, -C ( CH 3 ) =CH-CO-NH-CH 2CH=CH 2, -C ( CH 3 J =CH-CO-NH-CH 2C≡CH, -C (CH 3 ) = CH-CO-NH-tert. -C 4 H 9 , -C (CH 3 ) = CH-CO-NH-cyclopropyl I, -C (CH 3 ) = CH-CO-NH-cyclobutyl, -C (CH 3 ) = CH-CO-NH -cyclopentyl, -C (CH 3 ) = CH-CO-NH-cyclohexyl, -C (CH 3 ) = CH-CO-NH-cycloheptyl, -C (CH 3 ) = CH-CO-NH-cyclooctyl, -C (CH 3 ) = CH-CO-pyrrolidin-l-yl, -C (CH 3 ) = CH-CO-piperτdin-l-yl, -C (CH 3 ) = CH-CO-morpholin-4-yl, - C (CH 3 ) = CH-CO-NH-CH 2 CH = CH 2 , -C (CH 3 J = CH-CO-NH-CH 2 C≡CH,
-C ( CH 3 J =CH-CO-N ( CH 3 J -CH 2C≡CH , -C ( CH 3 ) =CH-CO-NH- ( CH 2 ) 2C I , -C (CH 3 J = CH-CO-N (CH 3 J -CH 2 C≡CH, -C (CH 3 ) = CH-CO-NH- (CH 2 ) 2 CI,
-C(CH3)=CH-CO-NH-C6H5, -C(CH3)=C(CH3)-CO-NH2, -C (CH 3 ) = CH-CO-NH-C 6 H 5 , -C (CH 3 ) = C (CH 3 ) -CO-NH 2 ,
-C(CH3)=C(CH3)-CO-NHCH3, -C(CH3)=C(CH3)-CO-N(CH3J2, -C (CH 3 ) = C (CH 3 ) -CO-NHCH 3 , -C (CH 3 ) = C (CH 3 ) -CO-N (CH 3 J 2 ,
-C(CH3)=C(CH3)-CO-NH-C2H5, -C(CH3)=C(CH3)-CO-N(C2H5) 2, -C(CH3)=C(CH3)-CO-NH-n-C3H7, -C(CH3)=C(CH3)-CO-NH-i-C3H7, -C (CH 3 ) = C (CH 3 ) -CO-NH-C 2 H 5 , -C (CH 3 ) = C (CH 3 ) -CO-N (C 2 H 5 ) 2 , -C (CH 3 ) = C (CH 3 ) -CO-NH-nC 3 H 7 , -C (CH 3 ) = C (CH 3 ) -CO-NH-iC 3 H 7 ,
-C(CH3)=C(CH3)-CO-NH-tert.-C4H9, -C(CH3)=C(CH3)-CO-NH- cyclopropyl, -C(CH3)=C(CH3)-CO-NH-cyclobutyl, -C (CH 3 ) = C (CH 3 ) -CO-NH-tert-C 4 H 9 , -C (CH 3 ) = C (CH 3 ) -CO-NH-cyclopropyl, -C (CH 3 ) = C (CH 3 ) -CO-NH-cyclobutyl,
-C(CH3)=C(CH3)-CO-NH-cyclopentyl, -C(CH3)=C(CH3)-CO-NH- cyclohexyl, -C(CH3)=C(CH3)-CO-NH-cycloheptyl, -C (CH 3 ) = C (CH 3 ) -CO-NH-cyclopentyl, -C (CH 3 ) = C (CH 3 ) -CO-NH-cyclohexyl, -C (CH 3 ) = C (CH 3 ) -CO-NH-cycloheptyl,
-C(CH3)=C(CH3)-CO-NH-cyclooctyl, -C(CH3)=C(CH3)-CO- pyrrolidin-1-yl, -C(CH3)=C(CH3)-CO-piperidin-1-yl, -C (CH 3 ) = C (CH 3 ) -CO-NH-cyclooctyl, -C (CH 3 ) = C (CH 3 ) -CO-pyrrolidin-1-yl, -C (CH 3 ) = C (CH 3 ) -CO-piperidin-1-yl,
-C(CH3)=C(CH3)-CO-morpholin-4-yl, -C (CH 3 ) = C (CH 3 ) -CO-morpholin-4-yl,
-C(CH3)=C(CH3)-CO-NH-CH2CH=C(CH3)2, -C(CH3)=C(CH3)-CO-NH-CH2C≡CH, -C(CH3)=C(CH3)-CO-N(CH3)-CH2C≡CH, -C(CH3)=C(CH3)-CO-NH-(CH2)2Cl, -C(CH3)=C(CH3)-CO-NH-C6H5, -C(CH3)=C(C2H5)-CO-NH2, -C (CH 3 ) = C (CH 3 ) -CO-NH-CH 2 CH = C (CH 3 ) 2 , -C (CH 3 ) = C (CH 3 ) -CO-NH-CH 2 C≡CH , -C (CH 3 ) = C (CH 3 ) -CO-N (CH 3 ) -CH 2 C≡CH, -C (CH 3 ) = C (CH 3 ) -CO-NH- (CH 2 ) 2 Cl, -C (CH 3 ) = C (CH 3 ) -CO-NH-C 6 H 5 , -C (CH 3 ) = C (C 2 H 5 ) -CO-NH 2 ,
-C(CH3)=C(C2H5)-CO-NHCH3, -C(CH3)=C(C2H5)-CO-N(CH3)2, -C (CH 3 ) = C (C 2 H 5 ) -CO-NHCH 3 , -C (CH 3 ) = C (C 2 H 5 ) -CO-N (CH 3 ) 2 ,
-C(CH3)=C(C2H5)-CO-NH-C2H5, -C(CH3)=C(C2H5)-CO-N(C2H5)2, -C (CH 3 ) = C (C 2 H 5 ) -CO-NH-C 2 H 5 , -C (CH 3 ) = C (C 2 H 5 ) -CO-N (C 2 H 5 ) 2 ,
-C(CH3)=C(C2H5)-CO-NH-n-C3H7, -C(CH3)=C(C2H5)-CO-NH-i-C3H7, -C(CH3)=C(C2H5)-CO-NH-tert.-C4H9, -C(CH3)=C(C2H5)-CO-NH- cyclopropyl, -C(CH3)=C(C2H5)-CO-NH-cyclobutyl, -C (CH 3 ) = C (C 2 H 5 ) -CO-NH-nC 3 H 7 , -C (CH 3 ) = C (C 2 H 5 ) -CO-NH-iC 3 H 7 , -C (CH 3 ) = C (C 2 H 5 ) -CO-NH-tert-C 4 H 9 , -C (CH 3 ) = C (C 2 H 5 ) -CO-NH-cyclopropyl, -C (CH 3 ) = C (C 2 H 5 ) -CO-NH-cyclobutyl,
-C(CH3)=C(C2H5)-CO-NH-cyclopentyl, -C(CH3)=C(C2H5)-CO-NH-cyclohexyl, -C(CH3)=C(C2H5)-CO-NH-cycloheptyl, -C(CH3)=C(C2H5)-CO-NH- cyclooctyl, -C(CH3)=C(C2H5)-CO-pyrrolidin-1-yl, -C (CH 3 ) = C (C 2 H 5 ) -CO-NH-cyclopentyl, -C (CH 3 ) = C (C 2 H 5 ) -CO-NH-cyclohexyl, -C (CH 3 ) = C (C 2 H 5 ) -CO-NH-cycloheptyl, -C (CH 3 ) = C (C 2 H 5 ) -CO-NH-cyclooctyl, -C (CH 3 ) = C (C 2 H 5 ) -CO -pyrrolidin-1-yl,
-C(CH3)=C(C2H5)-CO-piperidin-1-yl, -C(CH3)=C(C2H5)-CO- morpholin-4-yl, -C(CH3)=C(C2H5)-CO-NH-CH2CH=C(C2H5)2, -C (CH 3 ) = C (C 2 H5) -CO-piperidin-1-yl, -C (CH 3 ) = C (C 2 H 5 ) -CO-morpholin-4-yl, -C (CH 3 ) = C (C 2 H 5 ) -CO-NH-CH 2 CH = C (C 2 H 5 ) 2 ,
-C(CH3)=C(C2H5)-CO-NH-CH2C=CH, -C(CH3)=C(C2H5)-CO-N(CH3)-CH2C=CH, -C(CH3)=C(C2H5)-CO-NH-(CH2)2Cl, -C(CH3)=C(C2H5)-CO-NH-C6H5, -C(CH3)=C(Cl)- CO-NH2, -C(CH3)=C(Cl)-CO-NHCH3, -C (CH 3 ) = C (C 2 H 5 ) -CO-NH-CH 2 C = CH, -C (CH 3 ) = C (C 2 H 5 ) -CO-N (CH 3 ) -CH 2 C = CH, -C (CH 3 ) = C (C 2 H 5 ) -CO-NH- (CH 2 ) 2 Cl, -C (CH 3 ) = C (C 2 H 5 ) -CO-NH-C 6 H5, -C (CH 3 ) = C (Cl) - CO-NH 2 , -C (CH 3 ) = C (Cl) -CO-NHCH 3 ,
-C(CH3)=C(Cl)-CO-N(CH3)2, -C(CH3)=C(Cl)-CO-NH-C2H5, -C (CH 3 ) = C (Cl) -CO-N (CH 3 ) 2 , -C (CH 3 ) = C (Cl) -CO-NH-C 2 H 5 ,
-C(CH3)=C(Cl)-CO-N(C2H5)2, -C(CH3)=C(Cl)-CO-NH-n-C3H7, -C (CH 3 ) = C (Cl) -CO-N (C 2 H 5 ) 2 , -C (CH 3 ) = C (Cl) -CO-NH-nC 3 H 7 ,
-C(CH3)=C(Cl)-CO-NH-i-C3H7, -C(CH3)=C(Cl)-CO-NH-tert.-C4H9, -C(CH3)=C(Cl)-CO-NH-cyclopropyl, -C(CH3)=C(Cl)-CO-NH-cyclobutyl, -C(CH3)=C(Cl)-CO-NH-cyclopentyl, -C(CH3)=C(Cl)-CO-NH-cyclohexyl, -C(CH3)=C(Cl)-CO-NH-cycloheptyl, -C(CH3)=C(Cl)-CO-NH-cyclooctyl, -C(CH3)=C(Cl)-CO-pyrrolidin-1-yl, -C(CH3)=C(Cl)-CO-piperidi- 1- yl, -C(CH3)=C(Cl)-CO-morpholin-4-yl, -C (CH 3 ) = C (Cl) -CO-NH-iC 3 H 7 , -C (CH 3 ) = C (Cl) -CO-NH-tert.-C 4 H 9 , -C (CH 3 ) = C (Cl) -CO-NH-cyclopropyl, -C (CH 3 ) = C (Cl) -CO-NH-cyclobutyl, -C (CH 3 ) = C (Cl) -CO-NH-cyclopentyl, - C (CH 3 ) = C (Cl) -CO-NH-cyclohexyl, -C (CH 3 ) = C (Cl) -CO-NH-cycloheptyl, -C (CH 3 ) = C (Cl) -CO-NH -cyclooctyl, -C (CH 3 ) = C (Cl) -CO-pyrrolidin-1-yl, -C (CH 3 ) = C (Cl) -CO-piperidi- 1-yl, -C (CH 3 ) = C (Cl) -CO-morpholin-4-yl,
-C(CH3)=C(Cl)-CO-NH-CH2CH=C(Cl)2, -C(CH3)=C(Cl)-CO-NH-CH2C≡CH, -C(CH3)=C(Cl)-CO-N(CH3)-CH2C=CH, -C(CH3)=C(Cl)-CO-NH-(CH2)2Cl, -C(CH3)=C(Cl)-CO-NH-C6H5, -C(CH3)=C(Br)-CO-NH2, -C (CH 3 ) = C (Cl) -CO-NH-CH 2 CH = C (Cl) 2 , -C (CH 3 ) = C (Cl) -CO-NH-CH 2 C≡CH, -C (CH 3 ) = C (Cl) -CO-N (CH 3 ) -CH 2 C = CH, -C (CH 3 ) = C (Cl) -CO-NH- (CH 2 ) 2 Cl, -C ( CH 3 ) = C (Cl) -CO-NH-C 6 H 5 , -C (CH 3 ) = C (Br) -CO-NH 2 ,
-C(CH3)=C(Br)-CO-NHCH3, -C(CH3)=C(Br)-CO-N(CH3)2, -C (CH 3 ) = C (Br) -CO-NHCH 3 , -C (CH 3 ) = C (Br) -CO-N (CH 3 ) 2 ,
-C(CH3)=C(Br)-CO-NH-C2H5, -C(CH3)=C(Br)-CO-N(C2H5)2, -C (CH 3 ) = C (Br) -CO-NH-C 2 H 5 , -C (CH 3 ) = C (Br) -CO-N (C 2 H 5 ) 2 ,
-C(CH3)=C(Br)-CO-NH-n-C3H7, -C(CH3)=C(Br)-CO-NH-i-C3H7, -C (CH 3 ) = C (Br) -CO-NH-nC 3 H 7 , -C (CH 3 ) = C (Br) -CO-NH-iC 3 H 7 ,
-C(CH3)=C(Br)-CO-NH-tert.-C4H9, -C(CH3)=C(Br)-CO-NH-cyclopropyl, -C(CH3)=C(Br)-CO-NH-cyclobutyl, -C(CH3)=C(Br)-CO-NH-cyclopentyl, -C(CH3)=C(Br)-CO-NH-cyclohexyl, -C(CH3)=C(Br)-CO-NH-cycloheptyl, -C(CH3)=C(Br)-CO-NH-cyclooctyl, -C(CH3)=C(Br)-CO-pyrrolidin-1-yl, -C(CH3)=C(Br)-CO-piperidin-1-yl, -C(CH3)=C(Br)-CO-morpholin-4-yl, -C(CH3)=C(Br)-CO-NH-CH2CH=C(Br)2, -C(CH3)=C(Br)-CO-NH-CH2C≡CH, -C(CH3)=C(Br)-CO-N(CH3)-CH2C≡CH, -C(CH3)=C(Br)-CO-NH-(CH2)2Cl, -C(CH3)=C(Br)-CO-NH-C6H5, -C(CH3)=C(CN)-CO-NH2, -C (CH 3 ) = C (Br) -CO-NH-tert-C 4 H 9 , -C (CH 3 ) = C (Br) -CO-NH-cyclopropyl, -C (CH 3 ) = C (Br) -CO-NH-cyclobutyl, -C (CH 3 ) = C (Br) -CO-NH-cyclopentyl, -C (CH 3 ) = C (Br) -CO-NH-cyclohexyl, -C (CH 3 ) = C (Br) -CO-NH-cycloheptyl, -C (CH 3 ) = C (Br) -CO- NH-cyclooctyl, -C (CH 3 ) = C (Br) -CO-pyrrolidin-1-yl, -C (CH 3 ) = C (Br) -CO-piperidin-1-yl, -C (CH 3 ) = C (Br) -CO-morpholin-4-yl, -C (CH 3 ) = C (Br) -CO-NH-CH 2 CH = C (Br) 2 , -C (CH 3 ) = C (Br ) -CO-NH-CH 2 C≡CH, -C (CH 3 ) = C (Br) -CO-N (CH 3 ) -CH 2 C≡CH, -C (CH 3 ) = C (Br) - CO-NH- (CH 2 ) 2 Cl, -C (CH 3 ) = C (Br) -CO-NH-C 6 H 5 , -C (CH 3 ) = C (CN) -CO-NH 2 ,
-C(CH3)=C(CN)-CO-NHCH3, -C(CH3)=C(CN)-CO-N(CH3)2, -C (CH 3 ) = C (CN) -CO-NHCH 3 , -C (CH 3 ) = C (CN) -CO-N (CH 3 ) 2 ,
-C(CH3)=C(CN)-CO-NH-C2H5, -C(CH3)=C(CN)-CO-N(C2H5)2, -C (CH 3 ) = C (CN) -CO-NH-C 2 H 5 , -C (CH 3 ) = C (CN) -CO-N (C 2 H 5 ) 2 ,
-C(CH3)=C(CN)-CO-NH-n-C3H7, -C(CH3)=C(CN)-CO-NH-i-C3H7, -C (CH 3 ) = C (CN) -CO-NH-nC 3 H 7 , -C (CH 3 ) = C (CN) -CO-NH-iC 3 H 7 ,
-C(CH3)=C(CN)-CO-NH-tert.-C4H9, -C(CH3)=C(CN)-CO-NH-cyclopropyl, -C(CH3)=C(CN)-CO-NH-cyclobutyl, -C(CH3)=C(CN)-CO-NH-cyclopentyl, -C(CH3)=C(CN)-CO-NH-cyclohexyl, -C(CH3)=C(CN)-CO-NH-cycloheptyl, -C(CH3)=C(CN)-CO-NH-cyclooctyl, -C(CH3)=C(CN)-CO-pyrrolidin-1-yl, -C(CH3)=C(CN)-CO-piperidin-1-yl, -C(CH3)=C(CN)-CO-morpholin-4-yl, -C(CH3)=C(CN)-CO-NH-CH2CH=C(CN)2, -C(CH3)=C(CN)-CO-NH-CH2C=CH, -C(CH3)=C(CN)-CO-N(CH3)-CH2C≡CH, -C(CH3)=C(CN)-CO-NH-(CH2)2Cl, -C(CH3)=C(CN)-CO-NH-C6H5, -C(CH3)=CH-CO-SCH3, -C (CH 3 ) = C (CN) -CO-NH-tert-C 4 H 9 , -C (CH 3 ) = C (CN) -CO-NH-cyclopropyl, -C (CH 3 ) = C (CN) -CO-NH-cyclobutyl, -C (CH 3 ) = C (CN) -CO-NH-cyclopentyl, -C (CH 3 ) = C (CN) -CO-NH-cyclohexyl, -C (CH 3 ) = C (CN) -CO-NH-cycloheptyl, -C (CH 3 ) = C (CN) -CO-NH-cyclooctyl, -C (CH 3 ) = C (CN) -CO-pyrrolidin-1- yl, -C (CH 3 ) = C (CN) -CO-piperidin-1-yl, -C (CH 3 ) = C (CN) -CO-morpholin-4-yl, -C (CH 3 ) = C (CN) -CO-NH-CH 2 CH = C (CN) 2 , -C (CH 3 ) = C (CN) -CO-NH-CH 2 C = CH, -C (CH 3 ) = C (CN ) -CO-N (CH 3 ) -CH 2 C≡CH, -C (CH 3 ) = C (CN) -CO-NH- (CH 2 ) 2 Cl, -C (CH 3 ) = C (CN) -CO-NH-C 6 H 5 , -C (CH 3 ) = CH-CO-SCH 3 ,
-C(CH3)=CH-CO-SC2H5, -C(CH3)=CH-CO-S-n-C3H7, -C (CH 3 ) = CH-CO-SC 2 H 5 , -C (CH 3 ) = CH-CO-SnC 3 H 7 ,
-C(CH3)=CH-CO-S-i-C3H7, -C(CH3)=CH-CO-S-n-C4H9, -C (CH 3 ) = CH-CO-SiC 3 H 7 , -C (CH 3 ) = CH-CO-SnC 4 H 9 ,
-C(CH3)=CH-CO-S-tert.-C4H9, -C(CH3)=C(CH3)-CO-SCH3, -C (CH 3 ) = CH-CO-S-tert.-C 4 H 9 , -C (CH 3 ) = C (CH 3 ) -CO-SCH 3 ,
-C(CH3)=C(CH3)-CO-SC2H5, -C(CH3)=C(CH3)-CO-S-n-C3H7, -C (CH 3 ) = C (CH 3 ) -CO-SC 2 H 5 , -C (CH 3 ) = C (CH 3 ) -CO-SnC 3 H 7 ,
-C(CH3)=C(CH3)-CO-S-i-C3H7, -C(CH3)=C(CH3)-CO-S-n-C4H9, -C (CH 3 ) = C (CH 3 ) -CO-SiC 3 H 7 , -C (CH 3 ) = C (CH 3 ) -CO-SnC 4 H 9 ,
-C(CH3)=C(CH3)-CO-S-tert.-C4H9, -C(CH3)=C(C2H5)-CO-SCH3, -C (CH 3 ) = C (CH 3 ) -CO-S-tert-C 4 H 9 , -C (CH 3 ) = C (C 2 H 5 ) -CO-SCH 3 ,
-C(CH3)=C(C2H5)-CO-SC2H5, -C(CH3)=C(C2H5)-CO-S-n-C3H7, -C (CH 3 ) = C (C 2 H 5 ) -CO-SC 2 H 5 , -C (CH 3 ) = C (C 2 H 5 ) -CO-SnC 3 H 7 ,
-C(CH3)=C(C2H5)-CO-S-i-C3H7, -C(CH3)=C(C2H5)-CO-S-n-C4H9, -C (CH 3 ) = C (C 2 H 5 ) -CO-SiC 3 H 7 , -C (CH 3 ) = C (C 2 H 5 ) -CO-SnC 4 H 9 ,
-C(CH3)=C(C2H5)-CO-S-tert.-C4H9, -C(CH3)=C(Cl)-CO-SCH3, -C (CH 3 ) = C (C 2 H 5 ) -CO-S-tert-C 4 H 9 , -C (CH 3 ) = C (Cl) -CO-SCH 3 ,
-C(CH3)=C(Cl)-CO-SC2H5, -C(CH3)=C(Cl)-CO-S-n-C3H7, -C (CH 3 ) = C (Cl) -CO-SC 2 H 5 , -C (CH 3 ) = C (Cl) -CO-SnC 3 H 7 ,
-C(CH3)=C(Cl)-CO-S-i-C3H7, -C(CH3)=C(Cl)-CO-S-n-C4H9, -C (CH 3 ) = C (Cl) -CO-SiC 3 H 7 , -C (CH 3 ) = C (Cl) -CO-SnC 4 H 9 ,
-C(CH3)=C(Cl)-CO-S-tert.-C4H9, -C(CH3)=C(Br)-CO-SCH3, -C (CH 3 ) = C (Cl) -CO-S-tert-C 4 H 9 , -C (CH 3 ) = C (Br) -CO-SCH 3 ,
-C(CH3)=C(Br)-CO-SC2H5, -C(CH3)=C(Br)-CO-S-n-C3H7, -C (CH 3 ) = C (Br) -CO-SC 2 H 5 , -C (CH 3 ) = C (Br) -CO-SnC 3 H 7 ,
-C(CH3)=C(Br)-CO-S-i-C3H7, -C(CH3)=C(Br)-CO-S-n-C4H9, -C (CH 3 ) = C (Br) -CO-SiC 3 H 7 , -C (CH 3 ) = C (Br) -CO-SnC 4 H 9 ,
-C(CH3)=C(Br)-CO-S-tert.-C4H9, -C(CH3)=C(CN)-CO-SCH3, -C (CH 3 ) = C (Br) -CO-S-tert-C 4 H 9 , -C (CH 3 ) = C (CN) -CO-SCH 3 ,
-C(CH3)=C(CN)-CO-SC2H5, -C(CH3)=C(CN)-CO-S-n-C3H7, -C (CH 3 ) = C (CN) -CO-SC 2 H 5 , -C (CH 3 ) = C (CN) -CO-SnC 3 H 7 ,
-C(CH3)=C(CN)-CO-S-i-C3H7, -C(CH3)=C(CN)-CO-S-n-C4H9, -C (CH 3 ) = C (CN) -CO-SiC 3 H 7 , -C (CH 3 ) = C (CN) -CO-SnC 4 H 9 ,
-C(CH3)=C(CN)-CO-S-tert.-C4H9, -C(CH3)=C(COCH3)-CO-OCH3, -C (CH 3 ) = C (CN) -CO-S-tert-C 4 H 9 , -C (CH 3 ) = C (COCH 3 ) -CO-OCH 3 ,
-C(CH3)=C(COC2H5)-CO-OCH3, -C(CH3)=C(CO-n-C3H7)-CO-OCH3, -C (CH 3 ) = C (COC 2 H 5 ) -CO-OCH 3 , -C (CH 3 ) = C (CO-nC 3 H 7 ) -CO-OCH 3 ,
-C(CH3)=C(COCH3)-CO-OC2H5, -C(CH3)=C(COC2H5)-CO-OC2H5, -C (CH 3 ) = C (COCH 3 ) -CO-OC 2 H 5 , -C (CH 3 ) = C (COC 2 H 5 ) -CO-OC 2 H 5 ,
-C(CH3)=C(CO-n-C3H7)-CO-OC2H5, -C(CH3)=C(COCH3)-CO-O-n-C3H7, -C(CH3)=C(COC2H5)-CO-O-n-C3H7, -C(CH3)=C(CO-n-C3H7)-CO-O-n-C3H7, -C(CH3)=C(CF3)-CO-OCH3, -C(CH3)=C(CF3)-CO-OC2H5, -C(CH3)=C(CF3)-CO-O-n-C3H7, -C(CH3)=C(CF3)-CO-O-i-C3H7, -C (CH 3 ) = C (CO-nC 3 H 7 ) -CO-OC 2 H 5 , -C (CH 3 ) = C (COCH 3 ) -CO-OnC 3 H 7 , -C (CH 3 ) = C (COC 2 H 5 ) -CO-OnC 3 H 7 , -C (CH 3 ) = C (CO-nC 3 H 7 ) -CO-OnC 3 H 7 , -C (CH 3 ) = C (CF 3 ) -CO-OCH 3 , -C (CH 3 ) = C (CF 3 ) -CO-OC 2 H 5 , -C (CH 3 ) = C (CF 3 ) -CO-OnC 3 H 7 , -C (CH 3 ) = C (CF 3 ) -CO-OiC 3 H 7 ,
-C(CH3)=C(CF3)-CO-O-n-C4H9, -C(CH3)=C(CF3)-CO-O-tert.-C4H9, -C(CH3)=C(COOCH3)2, -C(CH3)=C(COOC2H5)2, -C (CH 3 ) = C (CF 3 ) -CO-OnC 4 H 9 , -C (CH 3 ) = C (CF 3 ) -CO-O-tert.-C 4 H 9 , -C (CH 3 ) = C (COOCH 3 ) 2 , -C (CH 3 ) = C (COOC 2 H 5 ) 2 ,
-C(CH3)=C(COOCH3)-CO-OC2H5, -C(CH3)=C(COO-n-C3H7)-CO-OCH3, -C(CH3)=C(COO-n-C3H7)-CO-OC2H5, -C(CH3)=C(COO-n-C3H7)2, -C (CH 3 ) = C (COOCH 3 ) -CO-OC 2 H 5 , -C (CH 3 ) = C (COO-nC 3 H 7 ) -CO-OCH 3 , -C (CH 3 ) = C (COO-nC 3 H 7 ) -CO-OC 2 H 5 , -C (CH 3 ) = C (COO-nC 3 H 7 ) 2 ,
-C(CH3)=CH-CH=CH-COOH, -C(CH3)=CH-CH=CH-CO-OCH3, -C (CH 3 ) = CH-CH = CH-COOH, -C (CH 3 ) = CH-CH = CH-CO-OCH 3 ,
-C(CH3)=CH-CH=CH-CO-OC2H5, -C(CH3)=CH-CH=C(COOCH3)2, -C (CH 3 ) = CH-CH = CH-CO-OC 2 H 5 , -C (CH 3 ) = CH-CH = C (COOCH 3 ) 2 ,
-C(CH3)=CH-CH=C(CN)-CO-OCH3, -C(CH3)=CH-CH=C(CN)-CO-OC2H5, -C(CH3)=C(CH3)-CH=C(CN)-CO-OCH3, -C (CH 3 ) = CH-CH = C (CN) -CO-OCH 3 , -C (CH 3 ) = CH-CH = C (CN) -CO-OC 2 H 5 , -C (CH 3 ) = C (CH 3 ) -CH = C (CN) -CO-OCH 3 ,
-C(CH3)=C(CH3)-CH=C(CN)-CO-OC2H5, -C (CH 3 ) = C (CH 3 ) -CH = C (CN) -CO-OC 2 H 5 ,
-C(CH3)=C(CH3)-CH=C(CH3)-CO-OCH3, -C (CH 3 ) = C (CH 3 ) -CH = C (CH 3 ) -CO-OCH 3 ,
-C(CH3)=C(CH3)-CH=C(Cl)-CO-OCH3, -C(CH3)=C(CH3)-CH=C(Br)-CO-OCH3, -C(CH3)=C(CH3)-CH=C(CH3)-CO-OC2H5, -C (CH 3 ) = C (CH 3 ) -CH = C (Cl) -CO-OCH 3 , -C (CH 3 ) = C (CH 3 ) -CH = C (Br) -CO-OCH 3 , -C (CH 3 ) = C (CH 3 ) -CH = C (CH 3 ) -CO-OC 2 H 5 ,
-C(CH3)=C(CH3)-CH=C(Cl)-CO-OC2H5, -C (CH 3 ) = C (CH 3 ) -CH = C (Cl) -CO-OC 2 H 5 ,
-C(CH3)=C(CH3)-CH=C(Br)-CO-OC2H5, -C(CH3)=C(CH3)-CH=C(CN)-CO-NH2, -C(CH3)=C(CH3)-CH=C(CN)-CO-NH-CH3, -C(CH3)=CH-(CH2)2-COOH, -C (CH 3 ) = C (CH 3 ) -CH = C (Br) -CO-OC 2 H 5 , -C (CH 3 ) = C (CH 3 ) -CH = C (CN) -CO-NH 2 , -C (CH 3 ) = C (CH 3 ) -CH = C (CN) -CO-NH-CH 3 , -C (CH 3 ) = CH- (CH 2 ) 2 -COOH,
-C(CH3)=CH-(CH2)2-CO-OCH3, -C(CH3)=CH-(CH2)2-CO-OC2H5, -C (CH 3 ) = CH- (CH 2 ) 2 -CO-OCH 3 , -C (CH 3 ) = CH- (CH 2 ) 2 -CO-OC 2 H 5 ,
-C(CH3)=CH-CH2-CH(COOCH3)2, -C(CH3)=CH-CH2-CH(COOC2H5)2, -C (CH 3 ) = CH-CH 2 -CH (COOCH 3 ) 2 , -C (CH 3 ) = CH-CH 2 -CH (COOC 2 H 5 ) 2 ,
-C(CH3)=CH-CH2-CH(CN)-CO-OCH3, -C(CH3)=CH-CH2-CH(CN)-CO-OC2H5, -C(CH3)=CH-CH2-CH(CH3)-CO-OCH3, -C(CH3)=CH-CH2-CH(CH3)-CO-OC2H5, -C(CH3)=CH-(CH2)2-CO-NH2, -C(CH3)=CH-(CH2)2-CO-NH-CH3, -C (CH 3 ) = CH-CH 2 -CH (CN) -CO-OCH 3 , -C (CH 3 ) = CH-CH 2 -CH (CN) -CO-OC 2 H 5 , -C (CH 3 ) = CH-CH 2 -CH (CH 3 ) -CO-OCH 3 , -C (CH 3 ) = CH-CH 2 -CH (CH 3 ) -CO-OC 2 H 5 , -C (CH 3 ) = CH- (CH 2 ) 2 -CO-NH 2 , -C (CH 3 ) = CH- (CH 2 ) 2 -CO-NH-CH 3 ,
-C(CH3)=CH-CH2-COOH, -C(CH3)=CH-CH2-CO-OCH3, -C (CH 3 ) = CH-CH 2 -COOH, -C (CH 3 ) = CH-CH 2 -CO-OCH 3 ,
-C(CH3)=CH-CH2-CO-OC2H5, -C(CH3)=C(COOCH3)-CH2-CO-OCH3, -C (CH 3 ) = CH-CH 2 -CO-OC 2 H 5 , -C (CH 3 ) = C (COOCH 3 ) -CH 2 -CO-OCH 3 ,
-C(CH3)=C(COOCH3)-CH2-CO-OC2H5, -C(CH3)=CH-CH2-CO-NH2, -C (CH 3 ) = C (COOCH 3 ) -CH 2 -CO-OC 2 H 5 , -C (CH 3 ) = CH-CH 2 -CO-NH 2 ,
-C(CH3)=CH-CH2-CO-NH-CH3, -C(CH3)=CH-CH2-CO-N(CH3)2. -C (CH 3 ) = CH-CH 2 -CO-NH-CH 3 , -C (CH 3 ) = CH-CH 2 -CO-N (CH 3 ) 2 .
Ganz besonders bevorzugt sind Verbindungen I, wobei X1 und X2 Sauerstoff, R1 Halogen, R2 Wasserstoff oder Fluor, R3 C1-C6- Alkyl, partiell oder vollständig halogeniertes C1-C2-Alkyl, R4 C1-C6-Alkyl, partiell oder vollständig halogeniertes C1-C2-Alkyl; R5 Wasserstoff oder R4 und R5 zusammen eine Tetramethylenkette bedeuten. Compounds I are very particularly preferred, where X 1 and X 2 are oxygen, R 1 is halogen, R 2 is hydrogen or fluorine, R 3 is C 1 -C 6 -alkyl, partially or completely halogenated C 1 -C 2 -alkyl, R4 is C 1 -C 6 alkyl, partially or fully halogenated C 1 -C 2 alkyl; R 5 is hydrogen or R 4 and R 5 together represent a tetramethylene chain.
Die substituierten 3-Phenylurazi le sind auf verschiedene Weise erhältlich, und zwar vorzugsweise nach einem der folgenden The substituted 3-phenylurazils are available in various ways, preferably one of the following
Verfahren: a) Cyclisierung eines Enamin-esters der Formel II oder eines Enamin-carboxylats der Formel III Method: a) Cyclization of an enamine ester of the formula II or an enamine carboxylate of the formula III
L1 bedeutet niedermolekulares Alkyl, vorzugsweise C1-C4-Alkyl, oder Phenyl. L 1 means low molecular weight alkyl, preferably C 1 -C 4 alkyl, or phenyl.
In der Regel arbeitet man in einem inerten Lösungs- oder Verdünnungsmittel, vorzugsweise in Gegenwart einer Base. Als Lösungs- oder Verdünnungsmittel eignen sich inerte aprotische organische Lösungsmittel, beispielsweise aliphatische oder cyclische Ether wie 1,2-Dimethoxyäthan, Tetrahydrofuran und Dioxan, aromatische Kohlenwasserstoffe wie Benzol, Toluol und Xylole, sowie inerte polare organische Lösungsmittel wie Dimethy Iformamid oder Dimethylsulfoxid, oder auch Wasser, wobei die polaren Lösungsmittel gegebenenfalls auch als Mischung mit einem unpolaren Kohlenwasserstoff wie n-Hexan verwendet werden können. As a rule, one works in an inert solvent or diluent, preferably in the presence of a base. Suitable solvents or diluents are inert aprotic organic solvents, for example aliphatic or cyclic ethers such as 1,2-dimethoxyethane, tetrahydrofuran and dioxane, aromatic hydrocarbons such as benzene, toluene and xylenes, and inert polar organic solvents such as dimethylformamide or dimethyl sulfoxide, or else Water, where the polar solvents can optionally also be used as a mixture with a non-polar hydrocarbon such as n-hexane.
Als Basen kommen vorzugsweise Alkalimetallalkoholate, insbesondere Natriumalkoholate wie Natriummethanolat und Natriumethanolat, Alkalimetallhydroxide, insbesondere Natriumhydroxid und Kaliumhydroxid, Alkalimetallcarbonate, insbesondere Natriumcarbonat und Kaliumcarbonat, sowie Alkalimetallhydride, insbesondere Natriumhydrid, in Betracht. Suitable bases are preferably alkali metal alcoholates, especially sodium alcoholates such as sodium methoxide and sodium ethanolate, alkali metal hydroxides, especially sodium hydroxide and potassium hydroxide, alkali metal carbonates, especially sodium carbonate and potassium carbonate, and alkali metal hydrides, especially sodium hydride.
Bei der Verwendung von Natriumhydrid ist das Lösungsmittel besonders bevorzugt ein al iphatischer oder cyclischer Ether wie Tetrahydrofuran sowie Dimethy Iformamid und Dimethylsulfoxid. Die Menge an Base liegt vorzugsweise zwischen der 0,5- und 2-molaren Menge, bezogen auf die Menge an II oder III. When sodium hydride is used, the solvent is particularly preferably an aliphatic or cyclic ether such as tetrahydrofuran and dimethylformamide and dimethyl sulfoxide. The amount of base is preferably between the 0.5 and 2 molar amount, based on the amount of II or III.
Im allgemeinen empfiehlt sich eine Reaktionstemperatur zwischen (-78)°C und der Siedetemperatur des Reaktionsgemisches, insbesondere zwischen (-60) und 60°C. In general, a reaction temperature between (-78) ° C and the boiling point of the reaction mixture is recommended, in particular between (-60) and 60 ° C.
Produkte I, in denen R3 Wasserstoff bedeutet, liegen nach der Cyclisierung je nach der Natur der verwendeten Base in Form des entsprechenden Metallsalzes der allgemeinen Formel lc Products I in which R 3 is hydrogen are after the cyclization, depending on the nature of the base used, in the form of the corresponding metal salt of the general formula Ic
(M⊕ = ein Äquivalent eines Metallions, insbesondere ein Alkalimetallion wie Natrium) vor, beispielsweise im Falle der vorstehend genannten bevorzugten Alkalimetall enthaltenden Basen in Form des entsprechenden Alkalimetallsalzes. Das Salz kann in an sich bekannter Weise isoliert und gereinigt werden, beispielsweise durch Umkristallisation. (M ⊕ = one equivalent of a metal ion, in particular an alkali metal ion such as sodium) before, for example in the case of the abovementioned preferred bases containing alkali metal in the form of the corresponding alkali metal salt. The salt can be isolated and purified in a manner known per se, for example by recrystallization.
Produkte I, in denen R3 Wasserstoff bedeutet, erhält man durch Ansäuern des nach der Cyclisierung erhaltenen Reaktionsgemisches, z.B. mit Salzsäure. b) Alkylierung oder Acylierung eines substituierten Products I in which R 3 is hydrogen are obtained by acidifying the reaction mixture obtained after the cyclization, for example with hydrochloric acid. b) alkylation or acylation of a substituted
3-Phenylurazils I, wobei R3 Wasserstoff bedeutet 3-phenylurazil I, where R 3 is hydrogen
Die Alkylierung erfolgt normalerweise mit dem Halogenid, vorzugsweise dem Chlorid oder Bromid, oder dem Sulfat eines Alkans, Alkens, Alkins, Cycloalkans, Cyanoalkans, Halogenalkans, Phenylalkans oder Alkoxyalkans. The alkylation normally takes place with the halide, preferably the chloride or bromide, or the sulfate of an alkane, alkene, alkyne, cycloalkane, cyanoalkane, haloalkane, phenylalkane or alkoxyalkane.
Als Acylierungsmittel kommen z.B. Ameisensäure-, Alkancarbonsäure- oder Alkoxycarbonsäurehalogenide in Betracht, wobei jeweils die Chloride und Bromide bevorzugt sind. Die Alkylierung erfolgt zweckmaβigerweise in Gegenwart eines inerten organischen Lösungsmittels und einer Base, beispielsweise in einem protischen Lösungsmittel wie niederen Alkoholen, vorzugsweise Ethanol, gegebenenfalls im Gemisch mit Wasser, oder in einem aprotischen Lösungsmittels wie aliphatische oder cyclische Ether, vorzugsweise 1,2-Dimethoxyethan, Tetrahydrofuran und Dioxan, aliphatischen Ketonen, vorzugsweise Aceton, Amiden, vorzugsweise Dimethylformamid, oder Sulfoxiden, vorzugsweise Dimethylsulfoxid. Als Base eignen sich beispielsweise Alkoholate wie Natriummethanolat, Natriumethanolat und Kalium-tert.-butanolat, Suitable acylating agents are e.g. Formic acid, alkane carboxylic acid or alkoxy carboxylic acid halides into consideration, the chlorides and bromides being preferred in each case. The alkylation is conveniently carried out in the presence of an inert organic solvent and a base, for example in a protic solvent such as lower alcohols, preferably ethanol, optionally in a mixture with water, or in an aprotic solvent such as aliphatic or cyclic ethers, preferably 1,2-dimethoxyethane, Tetrahydrofuran and dioxane, aliphatic ketones, preferably acetone, amides, preferably dimethylformamide, or sulfoxides, preferably dimethyl sulfoxide. Suitable bases are, for example, alcoholates such as sodium methoxide, sodium ethoxide and potassium tert-butoxide,
Hydroxide wie Natriumhydroxid, Kaliumhydroxid und Calziumhydroxid, Carbonate wie Natrium- und Kaliumcarbonat, und  Hydroxides such as sodium hydroxide, potassium hydroxide and calcium hydroxide, carbonates such as sodium and potassium carbonate, and
Alkalimetallhydroxide wie Natriumhydrid.  Alkali metal hydroxides such as sodium hydride.
In einer besonders bevorzugten Ausführungsform alkyliert man das als Salz vorliegende Produkt der Cyclisierung (Methode a) ohne vorherige Isolierung aus der Reaktionsmischung, wobei in diesem Fall noch aus der Cyclisierung der Verbindung II oder III stammende, überschüssige Base, beispielsweise Natriumhydrid, ein Natriumalkoholat oder Natriumcarbonat, vorhanden sein kann. Diese Base wirkt jedoch nicht störend; gewünschtenfalls kann auch noch eine weitere Menge des Verdünnungsmittel, das auch zur Cyclisierung der Verbindung II oder III verwendet wurde, zugesetzt werden. In a particularly preferred embodiment, the cyclization product present as a salt (method a) is alkylated without prior isolation from the reaction mixture, in which case excess base, for example sodium hydride, a sodium alcoholate or sodium carbonate, still originating from the cyclization of the compound II or III , may be present. However, this base does not interfere; if desired, a further amount of the diluent which was also used for the cyclization of the compound II or III can also be added.
Die Acylierung mit einem Halogenid kann auf analoge Weise erfolgen, wobei in diesem Fall besonders bevorzugt in einem The acylation with a halide can be carried out in an analogous manner, in which case it is particularly preferred in one
aprotischen Lösungsmittel und in Gegenwart von Natriumhydrid als Base gearbeitet wird. Die Reaktionstemperatur liegt im allgemeinen zwischen 0°C und ca. 100°C, vorzugsweise zwischen 0 und 40°C. aprotic solvent and in the presence of sodium hydride as the base. The reaction temperature is generally between 0 ° C and about 100 ° C, preferably between 0 and 40 ° C.
Sofern nicht unmittelbar durch die als Methode a) beschriebene Cyclisierung unter basischen Bedingungen herstellbar, können die Salze derjenigen Verbindungen I, in denen R3 Wasserstoff bedeutet, auch in an sich bekannter Weise aus den Produkten der vorliegenden Methode d) erhalten werden. Zu diesem Zweck versetzt man beispielsweise die wässrige Lösung einer anorganischen oder organischen Base mit dem substituierten 3-Phenylurazil I, bei dem R3 für Wasserstoff steht. Die Salzbildung erfolgt normalerweise bereits bei 20-25°C mit ausreichender Geschwindigkeit. Unless it can be prepared directly under basic conditions by the cyclization described as method a), the salts of those compounds I in which R 3 is hydrogen can also be obtained in a manner known per se from the products of the present method d). For this purpose, for example, the aqueous solution of an inorganic or organic base is mixed with the substituted 3-phenylurazil I, in which R 3 is hydrogen. Salt formation normally takes place at 20-25 ° C with sufficient speed.
Besonders vorteilhaft ist es, das Natriumsalz durch Auflösen des 3-Phenyluracils I (R3 = Wasserstoff), in wäβriger Natriumhydroxidlösung bei 20-25°C herzustellen, wobei äquivalente Mengen an 3-Phenylurazil und Natriumhydroxid eingesetzt werden. Das Salz des 3-Phenylurazils kann dann z.B. durch Fällen mit einem geeigneten inerten Lösungsmittel oder durch Abdampfen des Lösungsmittels isoliert werden. It is particularly advantageous to prepare the sodium salt by dissolving the 3-phenyluracil I (R 3 = hydrogen) in aqueous sodium hydroxide solution at 20-25 ° C., using equivalent amounts of 3-phenylurazil and sodium hydroxide. The salt of 3-phenylurazil can then be isolated, for example by precipitation with a suitable inert solvent or by evaporation of the solvent.
Salze der 3-Phenylurazile, deren Metallion kein Alkalimetallion ist, können üblicherweise durch Umsalzen des entsprechenden Alkalimetallsalzes in wässriger Lösung hergestellt werden. Auf diese Weise lassen sich im allgemeinen 3-Phenyluracil-MetalIsalze herstellen, die in Wasser unlöslich sind. c) Substitution eines Halogenatoms am Phenylteil der substituierten 3-Phenylurazile I (R1 = Halogen) durch die Cyanogruppe Salts of 3-phenyluracil, the metal ion of which is not an alkali metal ion, can usually be prepared by salting the corresponding alkali metal salt in aqueous solution. In this way, 3-phenyluracil metal salts which are insoluble in water can generally be prepared. c) Substitution of a halogen atom on the phenyl part of the substituted 3-phenylurazile I (R 1 = halogen) by the cyano group
Hal bedeutet Halogen, vorzugsweise Chlor oder Brom. Die Umsetzung erfolgt vorteilhaft in Gegenwart eines aprotischen, polaren Lösungsmittels, beispielsweise eines Alkylnitrils wie Acetonitril, Propionitril und Butyronitril, eines Alkylharnstoffes wie N,N,N',N'-Tetramethylharnstoff, eines Dialkylamids wie Dimethylformamid, eines Dialkylsulfoxids wie Dimethylsulfoxid oder in N-Methyl-2-pyrrolidon, 1,2-Dimethyl-imidazolidin-2-on, 1,2-Dimethyl-3,4,5,6-tetrahydro-2(1H)-pyrimidinon oder Hexamethylphosphorsäuretriamid. Normalerweise führt man die Reaktion unter Verwendung einesHal means halogen, preferably chlorine or bromine. The reaction is advantageously carried out in the presence of an aprotic, polar solvent, for example an alkyl nitrile such as acetonitrile, propionitrile and butyronitrile, an alkyl urea such as N, N, N ', N'-tetramethyl urea, a dialkyl amide such as dimethylformamide, a dialkyl sulfoxide such as dimethyl sulfoxide or in N- Methyl-2-pyrrolidone, 1,2-dimethyl-imidazolidin-2-one, 1,2-dimethyl-3,4,5,6-tetrahydro-2 (1H) -pyrimidinone or hexamethylphosphoric triamide. Usually the reaction is carried out using a
Metallcyanides, insbesondere eines übergangsmetallcyanides wie Kupfer (I)cyanid, bei erhöhten Temperaturen, vorzugsweise zwischen 150 und 250°C, durch. Zweckmäβig werden die Edukte in stöchiotnetri sehen Mengen eingesetzt, jedoch kann auch ein Überschuβ an Metallcyanid, etwa bis zur 4-fachen molaren Menge (bezogen auf die Menge an Edukt I mit R1 = Halogen), vorteilhaft sein. d) Überführung eines Pyrimidonderivat der Formel IVa oder IVb in einen Enolether Ia oder Ib Metal cyanides, in particular a transition metal cyanide such as copper (I) cyanide, at elevated temperatures, preferably between 150 and 250 ° C. The starting materials are expediently used in stoichiometric amounts, but an excess of metal cyanide, up to about 4 times the molar amount (based on the amount of starting material I with R 1 = halogen), can also be advantageous. d) converting a pyrimidone derivative of the formula IVa or IVb into an enol ether Ia or Ib
Hal bedeutet Chlor oder Brom;  Hal means chlorine or bromine;
Me⊕ bedeutet ein Äquivalent eines Metallions, insbesondere eines Übergangsmetall ions, eines Alkalimetallions wie Natrium und Me ⊕ means an equivalent of a metal ion, especially a transition metal ion, an alkali metal ion such as sodium and
Kalium, oder eines Erdalkalimetallions wie Kalzium und Magnesium. Besonders bevorzugt ist Natrium. Die Umsetzung der Pyrimidonderi vate IVa oder IVb mit Alkanolen, Alkenolen, Alkinolen (R3'-OH) oder Alkanthiolen, Alkenthiolen, Alkinthiolen (R3'-SH) erfolgt vorteilhaft in Gegenwart einer organischen Base, wobei Pyridin besonders bevorzugt ist. Potassium, or an alkaline earth metal ion such as calcium and magnesium. Sodium is particularly preferred. The reaction of the pyrimidone derivatives IVa or IVb with alkanols, alkenols, alkynols (R 3 ' -OH) or alkanethiols, alkenthiols, alkyne diols (R 3' -SH) is advantageously carried out in the presence of an organic base, pyridine being particularly preferred.
Die Menge an Base ist nicht kritisch; normalerweise ist die 0,5- bis 2-fache molare Menge, bezogen auf die Menge an IVa oder IVb, ausreichend. Die Umsetzungen von IVa mit H-X1-R3' und von IVb mit H-X2-R3' kann entweder ohne Lösungsmittel in einem Überschuß an R3'-OH bzw. R3'-SH oder in einem geeigneten inerten organischen Lösungsmittel, z.B. in einem Aromaten wie Toluol und Xylol, in einem Ether wie Diethylether, Tetrahydrofuran und 1,2-Dimethoxyethan, oder in einem halogenierten Kohlenwasserstoff wie Dichlormethan und Chlorbenzol, vorgenommen werden. The amount of base is not critical; normally 0.5 to 2 times the molar amount, based on the amount of IVa or IVb, is sufficient. The reactions of IVa with HX 1 -R 3 ' and of IVb with HX 2 -R 3' can be carried out either without solvent in an excess of R 3 ' -OH or R 3' -SH or in a suitable inert organic solvent, for example in an aromatic such as toluene and xylene, in an ether such as diethyl ether, tetrahydrofuran and 1,2-dimethoxyethane, or in a halogenated hydrocarbon such as dichloromethane and chlorobenzene.
Bei Einsatz der Verbindung R3'-OH arbeitet man vorzugsweise ohne Lösungsmittel, und zwar unter Verwendung der 1- bis ca. When using the compound R 3 ' -OH, one preferably works without a solvent, using the 1- to approx.
150-fachen Menge an R3'-OH, bezogen auf die Menge an Pyrimidonderivat IVa oder IVb. 150 times the amount of R 3 ' -OH, based on the amount of pyrimidone derivative IVa or IVb.
Be i der Reakt i onsführung mit einem Salz der Formel M⊕ ΘO-R3' oder M⊕ ΘS-R3' empfehlen sich äquimolare Mengen an Pyrimidonderivat und Salz, jedoch kann auch ein Überschuß an Salz, bis etwa 20 mol-% (bezogen auf die Menge an Pyrimidonderivat), vorteilhaft sein. When carrying out the reaction with a salt of the formula M ⊕ Θ OR 3 ' or M ⊕ Θ SR 3' , equimolar amounts of pyrimidone derivative and salt are recommended, but an excess of salt, up to about 20 mol% (based on the amount of pyrimidone derivative).
Normalerweise ist eine Reaktionstemperatur zwischen 0 und 50°C, bevorzugt zwischen 10 und 30°C, ausreichend. e) Acetalisierung einer Verbindung I, wobei W eine Gruppe A reaction temperature between 0 and 50 ° C., preferably between 10 and 30 ° C., is normally sufficient. e) acetalization of a compound I, where W is a group
-C(=O)-R8 bedeutet Means -C (= O) -R 8
I (W = -C(R8)=0) I (W = -C(R8)(X3R6)(X4R7)) Die Acetalisierung erfolgt allgemein in einem inerten aprotischen organischen Lösungsmittel, beispielsweise in einem aliphatischen oder cyclischen Ether wie Diethylether, 1,2-Dimethoxyethan, Tetrahydrofuran und Dioxan, in einem aromatischen Kohlenwasserstoff wie Benzol, Toluol, o-, m-, p-Xylol und Mesitylen, oder in einem chlorierten Kohlenwasserstoff wie Methylenchlorid, Chloroform und Chlorbenzol, sofern sie nicht ohne Lösungsmittel in einem Überschuß an H-X3R6, H-X4R7 oder H-X3(R6R7)X4-H durchgeführt wird. I (W = -C (R 8 ) = 0) I (W = -C (R 8 ) (X 3 R 6 ) (X 4 R 7 )) The acetalization is generally carried out in an inert aprotic organic solvent, for example in an aliphatic or cyclic ether such as diethyl ether, 1,2-dimethoxyethane, tetrahydrofuran and dioxane, in an aromatic hydrocarbon such as benzene, toluene, o-, m-, p-xylene and Mesitylene, or in a chlorinated hydrocarbon such as methylene chloride, chloroform and chlorobenzene, unless it is carried out without solvent in an excess of HX 3 R 6 , HX 4 R 7 or HX 3 (R 6 R 7 ) X 4 -H.
Entstehendes Reaktionswasser kann wie üblich aus dem Reaktionsgemisch entfernt werden, z.B. mittels Wasserabscheidung. Resulting water of reaction can be removed from the reaction mixture as usual, e.g. by means of water separation.
Vorzugsweise führt man die Acetalisierung in Gegenwart einer organischen Säure wie p-Toluolsulfonsäure und/oder einer Lewissäure wie Zinntetrachlorid, Zinn-II-chlorid, Eisen-III-chlorid, Tellurtetrachlorid und Bortrifluoroetherat oder eines geeigneten Katalysators wie Montmorillonit-K 10 durch, wobei die Menge an Säure normalerweise zwischen 0,5 und 100 mol-%, bezogen auf die Menge an zu acetalisierendem Edukt, liegt. The acetalization is preferably carried out in the presence of an organic acid such as p-toluenesulfonic acid and / or a Lewis acid such as tin tetrachloride, tin II chloride, iron III chloride, tellurium tetrachloride and boron trifluoroetherate or a suitable catalyst such as montmorillonite K 10, the The amount of acid is usually between 0.5 and 100 mol%, based on the amount of starting material to be acetalized.
Die Mengenverhältnisse sind nicht kritisch. Für eine vollständige Umsetzung werden alle Reaktionspartner in etwa stöchiometrischem Verhältnis eingesetzt, bevorzugt verwendet man jedoch einen Überschuβ an H-X3R6 und H-X4R7 bzw. H-X3(R6R7)X4-H. verwendet man die Edukte H-X3R6 und H-X4R7 bzw. H-X3(R6R7)X4-H gleichzeitig als Verdünnungsmittel, so liegen sie in einem größeren Überschuß vor. The proportions are not critical. For a complete reaction, all reactants are used in an approximately stoichiometric ratio, but an excess of HX 3 R 6 and HX 4 R 7 or HX 3 (R 6 R 7 ) X 4 -H is preferably used. if the reactants HX 3 R 6 and HX 4 R 7 or H-X3 (R 6 R 7 ) X 4 -H are used simultaneously as diluents, they are present in a large excess.
Im allgemeinen arbeitet man bei einer Temperatur zwischen (-78) und 180°C, vorzugsweise zwischen (-40) und 150°C. In general, a temperature between (-78) and 180 ° C, preferably between (-40) and 150 ° C.
Werden Produktgemische erhalten, z.B. wenn R6 und R7 keinen gemeinsamen Rest bilden und X3R6 und X4R7 nicht gleich sind, so können diese gewünschtenfalls nach an sich bekannten Methoden wie Kristallisation und Chromatographie gereinigt und getrennt werden. Insbesondere Verbindungen der Formel I, wobei W für eine Gruppe -C(R8) (X3R6) (X4R7) steht, in der R6 und R7 keinen gemeinsamen Rest bilden und X3R6 und X4R7 nicht gleich sind, können auch nach anderen literaturbekannten Methoden dargestellt werden (vgl. z.B. Tetrahedron Lett. 32, 467-470 (1991) sowie die dort zitierte Literatur). If product mixtures are obtained, for example if R 6 and R 7 do not form a common radical and X 3 R 6 and X 4 R 7 are not the same, they can, if desired, be purified and separated by methods known per se, such as crystallization and chromatography. In particular, compounds of the formula I, where W is a group -C (R 8 ) (X 3 R 6 ) (X 4 R 7 ), in which R 6 and R 7 do not have a common one Form the rest and X 3 R 6 and X 4 R 7 are not the same, can also be prepared by other methods known from the literature (see, for example, Tetrahedron Lett. 32, 467-470 (1991) and the literature cited therein).
In einigen Fällen kann es auch vorteilhaft sein, die Acetalisierung über den Umweg einer Acetalisierung zum Dialkylacetal, vorzugsweise Dimethylacetal, und anschlieβende Umacetalisierung in Gegenwart eines geeigneten Katalysators durchzuführen. Die für die Umacetal isierung verwendeten Lösungsmittel, Katalysatoren und sonstigen Reaktionsbedingungen entsprechen den bereits oben für die Acetalisierung aufgeführten. In some cases, it may also be advantageous to carry out the acetalization via the detour of acetalization to the dialkylacetal, preferably dimethylacetal, and subsequent transacetalization in the presence of a suitable catalyst. The solvents, catalysts and other reaction conditions used for the umacetalization correspond to those already listed above for the acetalization.
Eine weiter erfindungsgemäße Variante ist die Umsetzung einer Verbindung I (W=CHO) mit einem reaktiven Derivat R2C(X3R6)(X4R7) unter Umacetalisierungsbedingungen (Bedingungen s.o.). Als reaktive Derivate eignen sich z.B. Acetale und Orthoester. f) Acetalspaltung einer Verbindung I, wobei W eine Gruppe Another variant according to the invention is the reaction of a compound I (W = CHO) with a reactive derivative R 2 C (X 3 R 6 ) (X 4 R 7 ) under transacetalization conditions (conditions see above). Examples of suitable reactive derivatives are acetals and orthoesters. f) acetal cleavage of a compound I, where W is a group
-C(R8) (X3R6) (X4R7) bedeutet -C (R 8 ) (X 3 R 6 ) (X 4 R 7 )
I (W = -C(R8) (X3R6)(X4R7)) I (W = -C(R8)=X5) I (W = -C (R 8 ) (X 3 R 6 ) (X 4 R 7 )) I (W = -C (R 8 ) = X 5 )
Die Acetalspaltung kann ohne Säurezusatz, in Gegenwart einer Säure, z.B. einer Mineralsäure wie Salzsäure und Schwefelsäure, einer organischen Carbonsäure wie Ameisensäure, Essigsäure, Oxalsäure und Trifluoressigsäure, in Gegenwart eines sauren Ionenaustauschers, wie Amberlite® (Warenzeichen der Fa. "Aldrich") IR120 oder IRC84, oder in Gegenwart eines Übergangsmetallsalzes wie Quecksilber-(II)-oxid, Kupfer-(I)-oxid und Eisen-(III)-chlorid, durchgeführt werden. The acetal can be used without the addition of acid, in the presence of an acid, eg a mineral acid such as hydrochloric acid and sulfuric acid, an organic carboxylic acid such as formic acid, acetic acid, oxalic acid and trifluoroacetic acid, in the presence of an acidic ion exchanger such as Amberlite ® (trademark of the company. "Aldrich") IR120 or IRC84, or in the presence of a transition metal salt such as mercury (II) oxide, copper (I) oxide and iron (III) chloride.
Als Lösungs- oder Verdünnungsmittel eignen sich beispielsweise Aromaten wie Benzol, Toluol und o-, m-, p-Xylol, aliphatische oder cyclische Ether wie 1,2-Dimethoxyethan, Diethylether, Tetrahydrofuran und Dioxan, Alkohole wie Methanol, Ethanol und Isopropanol, polare organische Lösungsmittel wie Dimethylformamid, Dimethylsulfoxid und Acetonitril, Ketone wie Aceton und Butanon, oder auch Wasser. Examples of suitable solvents or diluents are aromatics such as benzene, toluene and o-, m-, p-xylene, aliphatic or cyclic ethers such as 1,2-dimethoxyethane, diethyl ether, tetrahydrofuran and dioxane, alcohols such as methanol, ethanol and isopropanol, polar organic solvents such as dimethylformamide, dimethyl sulfoxide and acetonitrile, ketones such as acetone and butanone, or water.
Vorzugsweise arbeitet man ohne Lösungsmittel in einem Überschuß der zur Acetalspaltung verwendeten Säure, wobei Ameisensäure besonders bevorzugt ist. It is preferred to work without a solvent in an excess of the acid used for the acetal cleavage, formic acid being particularly preferred.
Für eine vollständige Umsetzung werden die Edukte I, wobei W eine Gruppe -C(R8) (X3R6) (X4R7) bedeutet, und H2X5 in mindestens stöchiometrischen Verhältnis eingesetzt, jedoch ist auch ein Überschuß an H2X5, bis etwa 200 mol-%, möglich. For a complete reaction, the starting materials I, where W is a group —C (R 8 ) (X 3 R 6 ) (X 4 R 7 ), and H 2 X 5 are used in at least a stoichiometric ratio, but there is also an excess H 2 X 5 , up to about 200 mol%, possible.
Die Menge an Säure, Ionenaustauscher oder Übergangsmetallsalz ist nicht kritisch. Im allgemeinen ist eine Menge bis etwa 300 mol-%, bezogen auf die Menge an H2X5, ausreichend. In der Regel liegt die Reaktionstemperatur zwischen (-78) und 180°C, vorzugsweise zwischen 0°C und der Siedetemperatur des jeweiligen Verdünnungsmittels. The amount of acid, ion exchanger or transition metal salt is not critical. In general, an amount of up to about 300 mol%, based on the amount of H 2 X 5 , is sufficient. In general, the reaction temperature is between (-78) and 180 ° C, preferably between 0 ° C and the boiling point of the respective diluent.
Weitere zur Herstellung der substituierten 3-Phenylurazi le I brauchbare Methoden können Houben-Weyl, Handbuch der Org. Chemie, 4. Auflage, Bd E3, S. 362ff entnommen werden. g) Olefinierung von Verbindungen I (W = -C(R8)=0 ) Further methods which can be used to prepare the substituted 3-phenylurazi le I can be found in Houben-Weyl, Handbuch der Org. Chemie, 4th edition, Vol E3, p. 362ff. g) olefination of compounds I (W = -C (R 8 ) = 0)
Die Reaktion kann mit den folgenden Phosphoryliden Va bis Vd, Phosphoniumsalze VIa bis VId und Phosphonate Vlla bis Vlld durchgeführt werden: Phosphorylide V: R3P=c(R9)-CO-R10 Va,The reaction can be carried out with the following phosphorylides Va to Vd, phosphonium salts VIa to VId and phosphonates Vlla to Vlld: Phosphorylide V: R 3 P = c (R 9 ) -CO-R 10 Va,
R3P=C(R9)-CH2-CO-R10 Vb,R 3 P = C (R 9 ) -CH 2 -CO-R 10 Vb,
R3P=c(R9)-C(R11)=C(R12)-CO-R10 Vc,R 3 P = c (R 9 ) -C (R 11 ) = C (R 12 ) -CO-R 10 Vc,
R3P=c(R9)-CH2-CH(R13)-CO-R10 Vd; R 3 P = c (R 9 ) -CH 2 -CH (R 13 ) -CO-R 10 Vd;
Phosphoniumsalze VI: R3P⊕-CH(R9)-CO-R10 HalΘ VIa, Phosphonium salts VI: R 3 P ⊕ -CH (R 9 ) -CO-R 10 Hal Θ VIa,
R3P⊕-CH(R9)-CH2-CO-R10 HalΘ VIb,R 3 P ⊕ -CH (R 9 ) -CH 2 -CO-R 10 Hal Θ VIb,
R3P⊕-CH(R9)-CR11=CR12-CO-R10 HalΘ VIc,R 3 P ⊕ -CH (R 9 ) -CR 11 = CR 12 -CO-R 10 Hal Θ VIc,
R3P⊕-CH(R9)-CH2-CHR13-CO-R10 HalΘ VId; R 3 P ⊕ -CH (R 9 ) -CH 2 -CHR 13 -CO-R 10 Hal Θ VId;
Phosphonate VII: (RO)2PO-CH(R9)-CO-R10 Vlla, Phosphonates VII: (RO) 2 PO-CH (R 9 ) -CO-R 10 Vlla,
(RO)2PO-CH(R9)-CH2-CO-R10 Vllb, (RO)2PO-CH(R9)-CRH=CR12-CO-R10 VIIc, (RO)2PO-CH(R9)-CH2-CHR13-CO-R10 Vlld. (RO) 2 PO-CH (R 9 ) -CH 2 -CO-R 10 Vllb, (RO) 2 PO-CH (R 9 ) -CRH = CR 12 -CO-R 10 VIIc, (RO) 2 PO- CH (R 9 ) -CH 2 -CHR 13 -CO-R 10 Vlld.
Wenig geeignet sind diejenigen Phosphorylide Vb und Vd, Phosphoniumsalze VIb und VId sowie Phosphonate Vllb und Vlld, bei denen R10 Wasserstoff, Alkyl oder Cycloalkyl bedeutet. Die Reste R am Phosphor können gleich oder verschieden sein und stehen beispielsweise für verzweigte oder unverzweigte C1-C8- Alkylgruppen, C5- oder C6-Cycloalkylgruppen und insbesondere für Phenyl, das weitere (für die Umsetzung inerte Substituenten, beispielsweise C1-C4-Alkyl wie Methyl, Ethyl und tert. Butyl, C1-C4-Alkoxy wie Methoxy oder Halogen wie Fluor, Chlor und Brom) tragen kann. Bevorzugt sind unsubstituierte Phenylreste, da der für die Herstellung der Phosphoryl ide v und Phosphoniumsalze VI verwendete Ausgangsstoff Triphenylphosphin besonders kostengünstig ist und zudem das bei den Umsetzungen das sehr reaktionsträge und gut abtrennbare, feste Triphenylphosphinoxid entsteht. Those phosphorylides Vb and Vd, phosphonium salts VIb and VId and phosphonates Vllb and Vlld in which R 10 is hydrogen, alkyl or cycloalkyl are not very suitable. The radicals R on the phosphorus may be the same or different and represent, for example, branched or unbranched C 1 -C 8 -alkyl groups, C 5 - or C 6 -cycloalkyl groups and in particular phenyl, the further (for the reaction inert substituents, for example C 1 -C 4 alkyl such as methyl, ethyl and tert-butyl, C 1 -C 4 alkoxy such as methoxy or halogen such as fluorine, chlorine and bromine) can carry. Unsubstituted phenyl radicals are preferred, since the starting material triphenylphosphine used for the preparation of the phosphoryl ide v and phosphonium salts VI is particularly inexpensive and, moreover, the very inert and easily separable, solid triphenylphosphine oxide is formed in the reactions.
Zur Herstellung der Phosphonate VII eignen sich beispielsweise die in Houben-Weyl, Methoden der Organischen Chemie, Band E2, 1982, S. 345ff. beschriebenen Methoden. Suitable for the preparation of the phosphonates VII are, for example, those in Houben-Weyl, Methods of Organic Chemistry, Volume E2, 1982, pp. 345ff. described methods.
Als Lösungsmittel kommen inerte organische Lösungsmittel, z.B. Aromaten wie Toluol und o-, m-, p-Xylol, Ether wie 1,2-Dimethoxyethan, Diethylether, Tetrahydrofuran und Dioxan, polare organische Lösungsmittel wie Dimethylformamid und Dimethylsulfoxid, oder Alkohole wie Methanol, Ethanol und isopropanol, in Betracht. Bei der Olefinierung von I, wobei W -C(R8)=0 bedeutet, mit einem Phosphoniumsalz VI oder einem Phosphonat VII arbeitet man in Gegenwart einer Base, wobei Alkalimetallalkyle wie n-Butyllithium, Alkalimetallhydride und -alkoholate wie Natriumhydrid, Natriumethanolat und Kalium-tert.-butanolat, sowie Alkalimetall- und Erdalkalimetallhydroxide wie Calciumhydroxid, besonders gut geeignet sind. Inert organic solvents, for example aromatics such as toluene and o-, m-, p-xylene, ethers such as 1,2-dimethoxyethane, diethyl ether, tetrahydrofuran and dioxane, polar organic solvents such as dimethylformamide and dimethyl sulfoxide, or alcohols such as methanol, ethanol are used as solvents and isopropanol. The olefination of I, where W is -C (R 8 ) = 0, with a phosphonium salt VI or a phosphonate VII is carried out in the presence of a base, alkali metal alkyls such as n-butyllithium, alkali metal hydrides and alcoholates such as sodium hydride, sodium ethanolate and potassium tert-butanolate, as well as alkali metal and alkaline earth metal hydroxides such as calcium hydroxide, are particularly suitable.
Für eine vollständige Umsetzung werden alle Reaktionspartner in etwa stöchiometrischem Verhältnis eingesetzt, bevorzugt verwendet man jedoch einen Überschuß an Base bis etwa 10 mol-%. For a complete reaction, all reactants are used in an approximately stoichiometric ratio, but an excess of base of up to approximately 10 mol% is preferably used.
Im allgemeinen liegt die Reäktionstemperatur zwischen (-40) und 150°C. In general, the reaction temperature is between (-40) and 150 ° C.
Die Verbindungen der Formel V, VI und VII sind bekannt oder lassen sich in auf bekannte Weise darstellen (vgl. z.B. Houben- Weyl, Methoden d. Org. Chemie, Bd E1, S. 636ff, Georg Thieme Verlag, Stuttgart 1982, Chem. Ber. 95, 3993 (1962) oder Houben- Weyl, Methoden d. Org. Chemie Bd. E2, S. 345 ff, Georg Thieme Verlag, Stuttgart 1982). The compounds of the formulas V, VI and VII are known or can be prepared in a known manner (see, for example, Houben-Weyl, Methods of Org. Chemistry, Vol E1, p. 636ff, Georg Thieme Verlag, Stuttgart 1982, Chem. Ber. 95, 3993 (1962) or Houben-Weyl, Methods of Org. Chemistry, Vol. E2, p. 345 ff, Georg Thieme Verlag, Stuttgart 1982).
Eine weitere Möglichkeit zur Darstellung von 3-Phenylurazilen I, wobei W -CR8=CR9-CO-R10 bedeutet und R10 Wasserstpff, Alkyl, Alkenyl, Haloalkyl, Cycloalkyl, Phenyl oder Alkoxyalkyl bedeuten, besteht in der an sich bekannte Aldolkondensation. Hierfür geeignete Bedingungen sind z.B. Nielsen, Org.React. 16, Iff. (1968) zu entnehmen. Als weitere Methode zur Synthese von Verbindungen der Formel I, wobei W -C(R8)=C(R9)-CO-R10, -CH(R8)=CH(R9)-CO-R10, Another possibility for the preparation of 3-phenylurazilene I, where W is -CR 8 = CR 9 -CO-R 10 and R 10 is water, alkyl, alkenyl, haloalkyl, cycloalkyl, phenyl or alkoxyalkyl, consists in the aldol condensation known per se . Suitable conditions for this are, for example, Nielsen, Org.React. 16, Iff. (1968). As a further method for the synthesis of compounds of the formula I, where W -C (R 8 ) = C (R 9 ) -CO-R 10, -CH (R 8 ) = CH (R 9 ) -CO-R 10 ,
-CR8=CR11-CH2-CO-R12, -CR8=CRU-CR13=CR14-CO-R10 oder -CR 8 = CR 11 -CH 2 -CO-R 12 , -CR 8 = CRU-CR 13 = CR 14 -CO-R 10 or
-CR8=CRH-CH2-CHR15-CO-R12 wobei R9 oder R11 Wasserstoff, Cyano, Alkoxycarbonyl oder Alkylcarbonyl bedeuten, kommen sowohl die Knoevenagel-Kondensation als auch die Perkin-Kondensation in-CR 8 = CRH-CH 2 -CHR 15 -CO-R 12 where R 9 or R 11 are hydrogen, cyano, alkoxycarbonyl or alkylcarbonyl, both the Knoevenagel condensation and the Perkin condensation are suitable
Betracht. Geeignete Bedingungen sind z. B. aus Org. React. 1967, 15, 204ff (Knoevenagel) bzw. Johnson, Org. React. 1942, 1, 210ff (Perkin) ersichtlich. Verbindungen in denen R10 -NR18R19 oder -SR17 bedeuten, lassen sich z.B. in an sich bekannter Weise dadurch herstellen, daβ man Verbindungen, in denen R10 für Hydroxyl steht, in die entsprechenden Säurehalogenide (R10 bedeutet Halogen) überführt und die Verfahrensprodukte anschließend mit einem entsprechenden Amin H-NR18R19 oder Thiol H-SR17 oder mit einem reaktiven Derivat dieser Verbindungen umsetzt. h) Umsetzung von Verbindungen I (W = -C(R8)=0 ) mit Aminen, Hydroxylaminen oder Hydrazinen Consideration. Suitable conditions are e.g. B. from Org. React. 1967, 15, 204ff (Knoevenagel) and Johnson, Org. React. 1942, 1, 210ff (Perkin). Compounds in which R 10 denotes -NR 18 R 19 or -SR 17 can be prepared, for example, in a manner known per se by Compounds in which R 10 stands for hydroxyl are converted into the corresponding acid halides (R 10 means halogen) and the process products are then reacted with an appropriate amine H-NR 18 R 19 or thiol H-SR 17 or with a reactive derivative of these compounds. h) reaction of compounds I (W = -C (R 8 ) = 0) with amines, hydroxylamines or hydrazines
Die Umsetzung erfolgt normalerweise in einem inerten organischen Lösungs- oder Verdünnungsmittel, z.B. in einem Aromaten wie Toluol und Xylol, in einem chlorierten Kohlenwasserstoff wie Dichlormethan, Chloroform und Chlorbenzol, in einem Ether wie Diethylether, 1,2-Dimethoxyether und Tetrahydrofuran, in einem Alkohol wie Methanol und Ethanol, oder in einem Gemisch der genannten Lösungsmittel.  The reaction is usually carried out in an inert organic solvent or diluent, e.g. in an aromatic such as toluene and xylene, in a chlorinated hydrocarbon such as dichloromethane, chloroform and chlorobenzene, in an ether such as diethyl ether, 1,2-dimethoxy ether and tetrahydrofuran, in an alcohol such as methanol and ethanol, or in a mixture of the solvents mentioned.
Liegen die Amine H2N-R14 als Salze, z.B. als Hydrochloride oder Oxalate vor, so ist zu ihrer Freisetzung die Zugabe einer Base wie vorzugsweise Natriumcarbonat, Kaliumcarbonat, Natriumhydrogencarbonat, Triethylamin und Pyridin, empfehlenswert. If the amines H 2 NR 14 are present as salts, for example as hydrochlorides or oxalates, the addition of a base such as preferably sodium carbonate, potassium carbonate, sodium hydrogen carbonate, triethylamine and pyridine is recommended for their release.
Das entstehende Reaktionswasser kann gegebenenfalls destillativ oder mit Hilfe eines Wasserabscheiders aus dem Reaktionsgemisch entfernt werden. üblicherweise liegt die Reaktionstemperatur zwischen (-30) und 150°C, bevorzugt zwischen 0 und 130°C. i) Spaltung von Verbindungen I, wobei W -C(R8)=N-R14 bedeutet The water of reaction formed can optionally be removed from the reaction mixture by distillation or with the aid of a water separator. The reaction temperature is usually between (-30) and 150 ° C., preferably between 0 and 130 ° C. i) Cleavage of compounds I, where W is -C (R 8 ) = NR 14
Die Spaltung erfolgt lösungsmittelfrei oder in einem inerten Lösungs- oder Verdünnungsmittel mit Wasser oder einem reaktionsfähigen Derivat des Wassers.  The cleavage is carried out without solvent or in an inert solvent or diluent with water or a reactive derivative of water.
Die Umsetzung kann hydrolytisch oder unter oxidativen Bedingungen durchgeführt werden, wobei sich eine Reaktionstemperatur zwischen (-78) und 180°C, vorzugsweise zwischen 0°C und dem Siedepunkt des Verdünnungsmittels empfiehlt. The reaction can be carried out hydrolytically or under oxidative conditions, a reaction temperature between (-78) and 180 ° C., preferably between 0 ° C. and the boiling point of the diluent being recommended.
Als Lösungs- oder Verdünnungsmittel kommen z.B. Aromaten wie Benzol, Toluol und o-, m-, p-Xylol, chlorierte Kohlenwasserstoffe wie Dichlormethan, Chloroform und Chlorbenzol, Ether wie Dialkylether, 1,2-Dimethoxyethan, Tetrahydrofuran und Dioxan, Alkohole wie Methanol und Ethanol, Ketone wie Aceton, Ester organischer Säuren wie Essigsäureethylester oder Wasser sowie Gemische der genannten Lösungsmittel, in Betracht. Zweckmäβigerweise arbeitet man in Gegenwart einer Mineralsäure wie Salzsäure, Bromwasserstoffsäure und Schwefelsäure, einer Carbonsäure wie Essigsäure und Trifluoressigsäure oder einer Sulfonsäure wie p-Toluolsulfonsäure. Um das bei der Hydrolyse anfallende H2N-R14 abzufangen bzw. Examples of solvents or diluents are aromatics such as benzene, toluene and o-, m-, p-xylene, chlorinated hydrocarbons such as dichloromethane, chloroform and chlorobenzene, ethers such as dialkyl ether, 1,2-dimethoxyethane, tetrahydrofuran and dioxane, alcohols such as methanol and Ethanol, ketones such as acetone, esters of organic acids such as ethyl acetate or water, and mixtures of the solvents mentioned. It is advantageous to work in the presence of a mineral acid such as hydrochloric acid, hydrobromic acid and sulfuric acid, a carboxylic acid such as acetic acid and trifluoroacetic acid or a sulfonic acid such as p-toluenesulfonic acid. In order to intercept the H 2 NR 14 obtained during hydrolysis or
aus dem Gleichgewicht zu entfernen, kann es vorteilhaft sein, in Gegenwart einer anderen Carbonylverbindung, wie z.B. Aceton, Formaldehyd, Glyoxalsäure oder Phenylglyoxylsäure, bevorzugt Formaldehyd, zu arbeiten, die eine stabilere Verbindung mit H2N-R14 eingeht als I(W=CHO). to remove from equilibrium, it can be advantageous to work in the presence of another carbonyl compound, such as acetone, formaldehyde, glyoxalic acid or phenylglyoxylic acid, preferably formaldehyde, which forms a more stable compound with H 2 NR 14 than I (W = CHO) .
Bei der Arbeitsweise unter oxidativen Bedingungen eignen sich insbesondere Oxidationsmittel wie Bleitetraacetat, Natriumhypochlorid und Wasserstoffperoxid. Gewünschtenfalls kann die Reaktionsführung zusätzlich in Gegenwart eines Katalysators wie Kupfer-(II)-sulfat, Titantetrachlorid und Bortrifluoretherat erfolgen. Die Mengen an Säure, Oxidationsmittel und Katalysator können in weiten Bereichen variiert werden. Normalerweise liegen sowohl Säure- als auch Katalysatormenge zwischen 5 und 200 mol-%, und die Menge an Oxidationsmittel zwischen 25 und 400 mol-%, bezogen auf die Menge der zu oxidierenden Verbindung, sie können aber auch in erhebel ich größerem Überschuß verwendet werden. k) Umsetzung eines substituierten 3-Phenylurazils I, wobei When working under oxidative conditions, oxidizing agents such as lead tetraacetate, sodium hypochlorite and hydrogen peroxide are particularly suitable. If desired, the reaction can additionally be carried out in the presence of a catalyst such as copper (II) sulfate, titanium tetrachloride and boron trifluoroetherate. The amounts of acid, oxidizing agent and catalyst can be varied within a wide range. Normally, both the amount of acid and catalyst are between 5 and 200 mol%, and the amount of oxidizing agent is between 25 and 400 mol%, based on the amount of the compound to be oxidized, but they can also be used in a substantial excess. k) implementation of a substituted 3-phenylurazil I, wherein
X2 Sauerstoff bedeutet, mit einem Schwefelungsreagenz X 2 means oxygen with a sulfurization reagent
Die Umsetzung erfolgt in der Regel in einem inerten Lösungsmittel, beispielsweise in einem aromatischen Kohlenwasserstoff wie Toluol und o-, m-, p-Xylol, in einem Ether wie Diethylether, 1,2-Dimethoxyethan und Tetrahydrofuran, oder in einem organischen Amin wie Pyridin. The reaction is usually carried out in an inert solvent, for example in an aromatic hydrocarbon such as toluene and o-, m-, p-xylene, in an ether such as diethyl ether, 1,2-dimethoxyethane and tetrahydrofuran, or in an organic amine such as pyridine .
Als Schwefelungsreagenz eignen sich besonders gut Phosphor(V)- sulfid und 2,4-Bis(4-methoxyphenyl)-1,3,2,4-dithiadiphosphetan- 2,4-dithion ("Lawessons Reagenz"). Die Menge an Schwefelungsreagenz ist nicht kritisch; normalerweise verwendet man die 1- bis 5-fache molare Menge, bezogen auf das zu schwefelnde 3-Phenylurazil. Phosphorus (V) sulfide and 2,4-bis (4-methoxyphenyl) -1,3,2,4-dithiadiphosphetane-2,4-dithione ("Lawesson's reagent") are particularly suitable as the sulfurization reagent. The amount of sulfurization reagent is not critical; normally 1 to 5 times the molar amount, based on the 3-phenylurazil to be sulfurized.
Normalerweise liegt die Reaktionstemperatur zwischen 20 und 200°C, vorzugsweise zwischen 40°C und dem Siedepunkt des Usually the reaction temperature is between 20 and 200 ° C, preferably between 40 ° C and the boiling point of the
Lösungsmittels. l) Halogenierung eines substituierten 3-Phenylurazils I, wobei R5 Wasserstoff bedeutet Solvent. l) Halogenation of a substituted 3-phenylurazil I, where R 5 is hydrogen
Die Halogenierung erfolgt in der Regel in einem inerten organischen Lösungs- oder Verdünnungsmittel. Für die Chlorierung und Bromierung kommen beispielsweise aliphatische Carbonsäure wie Essigsäure, oder chlorierte aliphatische Kohlenwasserstoffe wie Methylenchlorid, Chloroform und Tetrachlorkohlenstoff, in Betracht. Für die Jodierung sind niedrig siedendende aliphatischen Carbonsäuren wie Essigsäure besonders bevorzugt.  The halogenation is usually carried out in an inert organic solvent or diluent. For chlorination and bromination, for example, aliphatic carboxylic acid such as acetic acid, or chlorinated aliphatic hydrocarbons such as methylene chloride, chloroform and carbon tetrachloride are suitable. Low-boiling aliphatic carboxylic acids such as acetic acid are particularly preferred for iodination.
Für die Chlorierung und Bromierung eignen sich insbesondere elementares Chlor bzw. Brom sowie Sulfurylchlorid bzw. Sulfurylbromid, wobei sich eine Reaktionstemperatur zwischen 0 und 60°C, vorzugsweise zwischen 10 und 30°C, empfiehlt. Elemental chlorine or bromine and sulfuryl chloride or sulfuryl bromide are particularly suitable for chlorination and bromination, a reaction temperature between 0 and 60 ° C., preferably between 10 and 30 ° C., being recommended.
Gewünschtenfalls kann die Chlorierung und Bromierung in Gegenwart eines säurebindenden Mittels erfolgen, wobei Natriumacetat und tertiäre Amine wie Triethylamin, Dimethylanilin und Pyridin besonders bevorzugt sind. If desired, the chlorination and bromination can take place in the presence of an acid-binding agent, sodium acetate and tertiary amines such as triethylamine, dimethylaniline and pyridine being particularly preferred.
Als Jodierungsmittel ist elementares Jod besonders bevorzugt, wobei in diesem Fall die Reaktionstemperatur zwischen ca. 0 und 110°C, vorzugsweise zwischen 10 und 30°C, liegt. Elemental iodine is particularly preferred as the iodination agent, in which case the reaction temperature is between about 0 and 110 ° C., preferably between 10 and 30 ° C.
Besonders vorteilhaft führt man die Jodierung in Gegenwart einer Mineralsäure wie rauchende Salpetersäure durch. Die Menge an Halogenierungsmittel ist nicht kritisch; normalerweise verwendet man äquimolare Mengen an Halogenierungsmittel oder einen Überschuβ bis etwa 200 mol-%, bezogen auf das zu halogenierende Edukt. überschüssiges Jod kann beispielsweise nach der Reaktion mittels gesättigter wäßriger Natriumhydrogensulfitlösung entfernt werden. m) Reduktion eines substituierten 3-Phenylurazils I, wobei The iodination is particularly advantageously carried out in the presence of a mineral acid such as fuming nitric acid. The amount of halogenating agent is not critical; normally equimolar amounts of halogenating agent or an excess of up to about 200 mol%, based on the starting material to be halogenated, are used. Excess iodine can be removed, for example, after the reaction using saturated aqueous sodium bisulfite solution. m) reduction of a substituted 3-phenylurazil I, where
W die Cyanogruppe bedeutet  W means the cyano group
Die Umsetzung erfolgt zweckmäßig in einem inerten organischen Lösungsmittel, z.B. einem Aromaten wie Toluol und o-, m-, p-Xylol, einem aliphatischen oder cyclischen Ether wie Diethylether, tert.-Butylmethylether, Tetrahydrofuran und Dioxan, einem chlorierten Kohlenwasserstoff wie Methylenchlorid, Chloroform und Chlorbenzol, oder in einer organischen Carbonsäure wie Ameisensäure.  The reaction is conveniently carried out in an inert organic solvent, e.g. an aromatic such as toluene and o-, m-, p-xylene, an aliphatic or cyclic ether such as diethyl ether, tert-butyl methyl ether, tetrahydrofuran and dioxane, a chlorinated hydrocarbon such as methylene chloride, chloroform and chlorobenzene, or in an organic carboxylic acid such as formic acid.
Als Reduktionsmittel eignen sich beispielsweise Wasserstoff oder Metallsalze wie Zinn-(II)-chlorid, Metallhydride wie Diisobutylaluminiumhydrid, Diisopropylaluminiumhydrid, Lithium-trisethoxyaluminiumhydrid und Lithium-bisethoxy-aluminiumhydrid oder Triethylsilan. Bevorzugt ist die Verwendung von Diisobutylaluminiumhydrid, Ameisensäure oder Wasserstoff. Suitable reducing agents are, for example, hydrogen or metal salts such as tin (II) chloride, metal hydrides such as diisobutyl aluminum hydride, diisopropyl aluminum hydride, lithium trisethoxy aluminum hydride and lithium bisethoxy aluminum hydride or triethylsilane. The use of diisobutylaluminum hydride, formic acid or hydrogen is preferred.
Gewünschtenfalls kann die Reduktion in Gegenwart eines Katalysators, wie Triethyloxoniumtetrafluoroborat oder Raney-Nickel durchgeführt werden. If desired, the reduction can be carried out in the presence of a catalyst such as triethyloxonium tetrafluoroborate or Raney nickel.
Arbeitet man ohne Verdünnungsmittel in Ameisensäure als Reduktionsmittel, so kann diese auch in einem gröβeren Überschuβ vorliegen. Die vorteilhafteste Reaktionstemperatur ist abhängig vom jeweiligen Reduktionsmittel, liegt aber im allgemeinen zwischen (-78) und 150°C. n) Phosgenierung oder Thiophosgenierung eines Enaminamid der Formel VIII If a reducing agent is used in formic acid without a diluent, this can also be present in a large excess. The most advantageous reaction temperature depends on the particular reducing agent, but is generally between (-78) and 150 ° C. n) Phosgenation or thiophosgenation of an enaminamide of the formula VIII
Das Verfahren kann in einem inerten organischen Lösungsmittel mit Hilfe eines geeigneten Phosgenierungs- oder Thiophosgenierungsmittel, wie z.B. Phosgen, Thiophosgen, Chlorameisensäuretrichlormethylester oder 1,1'-Carbonyldiimidazol gegebenenfalls in  The process can be carried out in an inert organic solvent with the aid of a suitable phosgenating or thiophosgenating agent, e.g. Phosgene, thiophosgene, trichloromethyl chloroformate or 1,1'-carbonyldiimidazole optionally in
Gegenwart einer Base, wie z.B. einer organischen Stickstoffbase, z.B. Triethylamin, Pyridin oder 2, 6-Lutidin, bei Temperaturen zwischen -20 und 130°C, bevorzugt zwischen 0° und der Rückfluβtemperatur des verwendeten Lösungsmittels, durchgeführt werden. Presence of a base, e.g. an organic nitrogen base, e.g. Triethylamine, pyridine or 2, 6-lutidine, at temperatures between -20 and 130 ° C, preferably between 0 ° and the reflux temperature of the solvent used.
Als Lösungs- oder Verdünnungsmittel kommen insbesondere In particular come as solvents or diluents
aprotische, organische Lösungsmittel, beispielsweise Aromaten wie Toluol und o-, m-, p-Xylol, halogenierte Kohlenwasserstoffe wie Methylenchlorid, Chloroform, 1,2-Dichlorethan und Chlorbenzol, aliphatische oder cyclische Ether wie 1,2-Dimethoxyethan, Tetrahydrofuran und Dioxan, oder Ester wie Essigsäureethylester, aber auch, insbesondere für den Fall X1 = Schwefel, Wasser, sowie Gemische dieser Lösungsmittel in Frage. aprotic, organic solvents, for example aromatics such as toluene and o-, m-, p-xylene, halogenated hydrocarbons such as methylene chloride, chloroform, 1,2-dichloroethane and chlorobenzene, aliphatic or cyclic ethers such as 1,2-dimethoxyethane, tetrahydrofuran and dioxane, or esters such as ethyl acetate, but also, in particular for the case X 1 = sulfur, water, and mixtures of these solvents.
Die Menge des Phosgenierungs- bzw. Thiophosgenierungsmittels ist nicht kritisch und liegt normalerweise zwischen 0,9 und The amount of phosgenating or thiophosgenating agent is not critical and is usually between 0.9 and
1,3-facher molarer Menge (bezogen auf VIII), kann aber auch in einigen Fällen deutlich höher liegen (200-500 mol%). o) Meerwein-Alkyl ierung eines Diazoniumsalzes IXb 1.3 times the molar amount (based on VIII), but can also be significantly higher in some cases (200-500 mol%). o) Meerwein alkylation of a diazonium salt IXb
Die Reaktionsbedingungen der Meerwe i nreakt i on sind dem Fachmann bekannt (vgl. z.B. M.P. Doyle et al., 3. Org. Chem. 1977, 42, 2431; G. Theodoridis et al. J. Heterocyclic Chem. 1991, 28, 849; C.S. Rondestvedt Jr., Org. React. 1976, 24, 225 und dort zit. Literatur) und können in Analogie zu den in der Literatur beschriebenen auf die erfindungsgemäßen Verbindungen I übertragen werden. p) Metallkatalysierte Olefinkupplung mit einem Phenylhalogenid der Formel IXc  The reaction conditions of the seaweed reaction are known to the person skilled in the art (see, for example, MP Doyle et al., 3rd Org. Chem. 1977, 42, 2431; G. Theodoridis et al. J. Heterocyclic Chem. 1991, 28, 849 ; CS Rondestvedt Jr., Org. React. 1976, 24, 225 and literature cited therein) and can be applied to the compounds I according to the invention in analogy to those described in the literature. p) Metal-catalyzed olefin coupling with a phenyl halide of the formula IXc
Die Bedingungen dieser Heck- oder Heck-ähnlichen Reaktion sind dem Fachmann bekannt und lassen sich analog zu den in der  The conditions of this Heck- or Heck-like reaction are known to the person skilled in the art and can be analogous to those in FIG
Literatur beschriebenen (vgl. z.B. Comprehensive Organic  Literature (see e.g. Comprehensive Organic
Chemistry) auf die erfindungsgemäßen Verbindungen I übertragen. Die als Ausgangsstoffe benötigten Enamin-Ester der Formel II sind neu, es sei denn, W bedeutet eine Gruppe -CH=CH-CO-OR14 mit R14 C1-C6-Alkyl oder C3-C6-Alkenyl, wenn R4 die Trifluormethylgruppe und R5 Wasserstoff sind (vgl. US 4,979,982). Sie können ebenfalls als Herbizide eingesetzt werden. Chemistry) transferred to the compounds I according to the invention. The enamine esters of formula II required as starting materials are new, unless W denotes a group -CH = CH-CO-OR 14 with R 14 C 1 -C 6 alkyl or C 3 -C 6 alkenyl, if R 4 is the trifluoromethyl group and R 5 is hydrogen (cf. US 4,979,982). They can also be used as herbicides.
Die Enamin-Ester II können nach an sich bekannten Methoden hergestellt werden, z.B. nach einem der folgenden Verfahren: The enamine esters II can be prepared by methods known per se, e.g. one of the following:
Vorzugsweise arbeitet man im wesentlichen wasserfrei in einem inerten Lösungs- oder Verdünnungsmittel, besonders bevorzugt in Gegenwart eines sauren oder basischen Katalysators.  It is preferred to work essentially anhydrous in an inert solvent or diluent, particularly preferably in the presence of an acidic or basic catalyst.
Als Lösungs- oder Verdünnungsmittel kommen insbesondere mit Wasser azeotrop mischbare organische Lösungsmittel, beispielsweise Aromaten wie Benzol, Toluol und o-, m-, p-Xylol, halogenierte Kohlenwasserstoffe wie Methylenchlorid, Chloroform, Tetrachlorkohlenstoff und Chlorbenzol, aliphatische und cyclische Ether wie 1,2-Dimethoxyethan, Tetrahydrofuran und Dioxan, oder Cyclohexan, aber auch Alkohole wie Methanol und Ethanol, in Betracht. Suitable solvents or diluents are, in particular, water solvents which are azeotropically miscible with water, for example aromatics such as benzene, toluene and o-, m-, p-xylene, halogenated hydrocarbons such as methylene chloride, chloroform, carbon tetrachloride and chlorobenzene, aliphatic and cyclic ethers such as 1,2 -Dimethoxyethane, tetrahydrofuran and dioxane, or cyclohexane, but also alcohols such as methanol and ethanol, into consideration.
Als saure Katalysatoren eignen sich bevorzugt starke Mineralsäuren wie Schwefelsäure und Salzsäure, Phosphor enthaltende Säuren wie Orthophosphorsaure und Polyphosphorsaure, organische Säuren wie p-Toluolsulfonsäure sowie saure Kationenaustauscher wie "Amberlyst 15" (Fluka). Suitable acidic catalysts are preferably strong mineral acids such as sulfuric acid and hydrochloric acid, phosphorus-containing acids such as orthophosphoric acid and polyphosphoric acid, organic acids such as p-toluenesulfonic acid and acidic cation exchangers such as "Amberlyst 15" (Fluka).
Als basische Katalysatoren eignen sich z.B. Metallhydride wie Natriumhydrid sowie besonders bevorzugt Metallalkoholate wie Natriummethanolat und Ethanolat. Zweckmäβig setzt man den β-Ketoester XI und den Phenylharnstoff XII in stöchiometrischem Verhältnis ein oder man arbeitet mit einem geringen Überschuβ der einen oder anderen Komponente bis etwa 10 mol-%. Suitable basic catalysts are, for example, metal hydrides such as sodium hydride and particularly preferably metal alcoholates such as sodium methoxide and ethanolate. The β-ketoester XI and the phenylurea XII are expediently used in a stoichiometric ratio or one works with a slight excess of one or the other component up to about 10 mol%.
Normalerweise ist eine Katalysatormenge zwischen 0,5 und 100 mol-%, bezogen auf die Menge eines Edukts, ausreichend. Usually an amount of catalyst between 0.5 and 100 mol%, based on the amount of a starting material, is sufficient.
Im allgemeinen erfolgt die Reaktionsführung bei einer Temperatur zwischen 60 und 120°C, zur raschen Entfernung von entstehendem Wasser vorzugsweise bei der Siedetemperatur des Reaktionsgemisches. In general, the reaction is carried out at a temperature between 60 and 120 ° C., for the rapid removal of water formed, preferably at the boiling point of the reaction mixture.
L3 bedeutet C1-C4-Alkyl oder Phenyl. L 3 represents C 1 -C 4 alkyl or phenyl.
Diese Umsetzung kann beispielsweise in einem inerten, mit Wasser mischbaren, organischen Lösungsmittel, beispielsweise einem aliphatischen oder cyclischen Ether wie Diethylether, 1,2-Dimethoxyethan, Tetrahydrofuran und Dioxan, oder einem niederen Alkohol, insbesondere Ethanol, durchgeführt werden, wobei die Reaktionstemperatur normalerweise zwischen 50 und 150°C, vorzugsweise bei der Siedetemperatur des Reaktionsgemisches, liegt. This reaction can be carried out, for example, in an inert, water-miscible, organic solvent, for example an aliphatic or cyclic ether such as diethyl ether, 1,2-dimethoxyethane, tetrahydrofuran and dioxane, or a lower alcohol, in particular ethanol, the reaction temperature normally being between 50 and 150 ° C, preferably at the boiling point of the reaction mixture.
Die Reaktion kann jedoch auch in einem aromatischen Verdünnungsmittel wie Benzol, Toluol und o-, m-, p-Xylol durchgeführt werden, wobei in diesem Fall der Zusatz entweder eines sauren Katalysators wie Salzsäure und p-Toluolsulfonsäure oder einer Base, z.B. eines Alkalimetallalkoholates wie Natriummethanolat und Natriumethanolat, empfehlenswert ist. Auch bei dieser Verfahrensvariante liegt die Reaktionstemperatur normalerweise zwischen 50 und 150°C, bevorzugt jedoch zwischen 60 und 80°C. However, the reaction can also be carried out in an aromatic diluent such as benzene, toluene and o-, m-, p-xylene, in which case either the addition of an acidic catalyst such as hydrochloric acid and p-toluenesulfonic acid or a base, for example an alkali metal alcoholate such as Sodium methoxide and sodium ethanolate, is recommended. In this process variant too, the reaction temperature is normally between 50 and 150 ° C., but preferably between 60 and 80 ° C.
Die Umsetzung erfolgt zweckmäβig in Gegenwart eines im wesentlichen wasserfreien, aprotischen, organischen Lösungs- oder Verdünnungsmittel, beispielsweise eines aliphatischen oder cyclischen Ethers wie Diethylether, 1,2-Dimethoxyethan, Tetrahydrofuran und Dioxan, eines aliphatischen oder aromatischen Kohlenwasserstoffs wie n-Hexan, Benzol, Toluol und o-, m-, p-Xylol, eines halogenierten, aliphatischen Kohlenwasserstoffs wie Methylenchlorid, Chloroform, Tetrachlorkohlenstoff, 1,2-Dichlorethan und Chlorbenzol, eines aprotischen, polaren Lösungsmittel wie Dimethylformamid, Hexamethylphosphorsauretriamid und Dimethylsulfoxid, oder eines Gemisches aus den genannten  The reaction is conveniently carried out in the presence of an essentially anhydrous, aprotic, organic solvent or diluent, for example an aliphatic or cyclic ether such as diethyl ether, 1,2-dimethoxyethane, tetrahydrofuran and dioxane, an aliphatic or aromatic hydrocarbon such as n-hexane, benzene, Toluene and o-, m-, p-xylene, a halogenated, aliphatic hydrocarbon such as methylene chloride, chloroform, carbon tetrachloride, 1,2-dichloroethane and chlorobenzene, an aprotic, polar solvent such as dimethylformamide, hexamethylphosphoric acid triamide and dimethyl sulfoxide, or a mixture of the above
Solventien.  Solvents.
Gewünschtenfalls kann auch in Gegenwart einer Metallhydridbase wie Natrium- und Kaliumhydrid, eines Alkalimetall- oder Erdalkalimetallelkoholates wie Natriummethanolat, Natriumethanolat und Kalium-tert.-butanolat, oder einer organischen tertiären Base wie Triethylamin und Pyridin gearbeitet werden, wobei die organische Base gleichzeitig als Lösungsmittel dienen kann. If desired, it is also possible to work in the presence of a metal hydride base such as sodium and potassium hydride, an alkali metal or alkaline earth metal alcoholate such as sodium methoxide, sodium ethanolate and potassium tert-butoxide, or an organic tertiary base such as triethylamine and pyridine, the organic base simultaneously serving as a solvent can.
Zweckmäβig setzt man die Edukte in stöchiometrischem Verhältnis ein oder man arbeitet mit einem geringen Überschuβ der einen oder anderen Komponente bis etwa 20 mol-%. Arbeitet man ohne Lösungsmittel in Gegenwart einer organischen Base, so liegt diese in einem gröβeren Überschuß vor. The starting materials are expediently used in a stoichiometric ratio or one works with a slight excess of one or the other component up to about 20 mol%. If one works without solvent in the presence of an organic base, this is present in a large excess.
Die Reaktionstemperatur liegt vorzugsweise im Bereich zwischen (-80) und 50°C, besonders bevorzugt zwischen (-60) und 30°C. In einer besonders bevorzugten Variante dieses Verfahrens wird das erhaltene II mit überschüssiger Base direkt (d.h. in situ) gemäβ Verfahrensvariante a) in die entsprechende Verbindung I überführt. Etwaige Nebenprodukte (z.B. C-Alkylierungsprodukte bei The reaction temperature is preferably in the range between (-80) and 50 ° C, particularly preferably between (-60) and 30 ° C. In a particularly preferred variant of this process, the II obtained is converted directly (ie in situ) according to process variant a) into the corresponding compound I using excess base. Any by-products (e.g. C-alkylation products at
Verbindungen, in denen R5 für Wasserstoff steht), lassen sich mit üblichen Trennmethoden wie Kristallisation und Chromatographie entfernen. Compounds in which R 5 stands for hydrogen) can be removed using customary separation methods such as crystallization and chromatography.
L1 und L4 bedeuten C1-C4-Alkyl oder Phenyl. L 1 and L 4 represent C 1 -C 4 alkyl or phenyl.
Diese Reaktion erfolgt zweckmäβig in einem aprotischen, polaren Lösungs- oder Verdünnungsmittel wie Dimethylformamid, 2-Butanon, Dimethylsulfoxid und Acetonitril, und zwar vorteilhaft in Gegenwart einer Base, beispielsweise eines Akalimetall- oder Erdalkalimetallalkoholats, insbesondere eines Natriumalkanolates wie Natriummethanolat, eines Akalimetall- oder Erdalkalimetallcarbonates, insbesondere Natriumcarbonat, oder eines Alkalimetallhydrids wie Lithium- und Natriumhydrid. This reaction is conveniently carried out in an aprotic, polar solvent or diluent such as dimethylformamide, 2-butanone, dimethyl sulfoxide and acetonitrile, advantageously in the presence of a base, for example an alkali metal or alkaline earth metal alcoholate, in particular a sodium alkanolate such as sodium methoxide, an alkali metal carbonate or alkaline earth metal , in particular sodium carbonate, or an alkali metal hydride such as lithium and sodium hydride.
Normalerweise ist die 1- bis 2-fache molare Menge an Base, bezogen auf die Menge eines Edukts, ausreichend. Normally 1 to 2 times the molar amount of base, based on the amount of a starting material, is sufficient.
Die Reaktionstemperatur liegt im allgemeinen zwischen 80 und 180°C, vorzugsweise bei der Siedetemperatur des Reaktionsgemisches. Bezüglich der Mengenverhältnisse der Edukte gelten die Angaben für Methode q). The reaction temperature is generally between 80 and 180 ° C, preferably at the boiling point of the reaction mixture. With regard to the quantitative ratios of the educts, the information for method q) applies.
In einer besonders bevorzugten Ausführungsform verwendet man ein Natriumalkoholat als Base und destilliert den im Laufe der Reaktion entstehenden Alkohol kontinuierlich ab. Die auf diese Weise hergestellten Enamin-Ester der Formel II können ohne Isolierung aus der Reaktionsmischung gemäβ Verfahrensvariante a) zu einem Salz der substituierten 3-Phenylurazile I cyclisiert werden. In a particularly preferred embodiment, a sodium alcoholate is used as the base and the alcohol formed in the course of the reaction is distilled off continuously. The enamine esters of the formula II prepared in this way can be cyclized to a salt of the substituted 3-phenylurazils I without isolation from the reaction mixture according to process variant a).
Diese Umsetzung erfolgt vorteilhaft in Gegenwart eines im wesentlichen wasserfreien, aprotischen, organischen Lösungs- oder Verdünnungsmittels, gewünschtenfalls in Gegenwart einer Metallhydridbase wie Natrium- und Kaliumhydrid oder einer organischen tertiären Base wie Triethylamin und Pyridin, wobei die organische Base auch als Lösungsmittel dienen kann.  This reaction is advantageously carried out in the presence of an essentially anhydrous, aprotic, organic solvent or diluent, if desired in the presence of a metal hydride base such as sodium and potassium hydride or an organic tertiary base such as triethylamine and pyridine, where the organic base can also serve as a solvent.
Bezüglich der geeigneten Lösungsmittel und der Mengenverhältnisse gelten die Angaben für Methode r). With regard to the suitable solvents and the quantitative ratios, the information for method r) applies.
Die Reaktionstemperatur liegt in der Regel zwischen (-80) und 150°C, vorzugsweise zwischen (-60)°C und dem jeweiligen Siedepunkt des Lösungsmittels. The reaction temperature is generally between (-80) and 150 ° C, preferably between (-60) ° C and the particular boiling point of the solvent.
Die Umsetzung erfolgt zweckmäβig in Gegenwart eines im The reaction is conveniently carried out in the presence of an im
wesentlichen wasserfreien, aprotischen organischen Lösungs- und Verdünnungsmittel, beispielsweise eines aliphatischen oder cyclischen Ethers wie Diethylether, 1,2-Dimethoxyethan, essential anhydrous, aprotic organic solvents and diluents, for example an aliphatic or cyclic ether such as diethyl ether, 1,2-dimethoxyethane,
Tetrahydrofuran und Dioxan, eines aliphatischen oder aromatischen Kohlenwasserstoffs wie n-Hexan, Benzol, Toluol und o-, m-, p-Xylol, eines halogenierten, aliphatischen Kohlenwasserstoffs wie Methylenchlorid, Chloroform, Tetrachlorkohlenstoff, Tetrahydrofuran and dioxane, an aliphatic or aromatic hydrocarbon such as n-hexane, benzene, toluene and o-, m-, p-xylene, a halogenated aliphatic hydrocarbon such as methylene chloride, chloroform, carbon tetrachloride,
1,2-Dichlorethan und Chlorbenzol, eines aprotischen, polaren Lösungsmittel wie Dimethylformamid, Hexamethylphosphorsäuretriamid und Dimethylsulfoxid, oder eines Gemisches aus den genannten Solventen. Gewünschtenfalls kann auch in Gegenwart einer Metallhydridbase wie Natrium- und Kaliumhydrid, eines Alkalimetall- oder 1,2-dichloroethane and chlorobenzene, an aprotic, polar solvent such as dimethylformamide, hexamethylphosphoric triamide and dimethyl sulfoxide, or a mixture of the solvents mentioned. If desired, also in the presence of a metal hydride base such as sodium and potassium hydride, an alkali metal or
Erdalkal imetallalkoholates wie Natriummethanolat,  Alkaline earth metal alcoholates such as sodium methoxide,
Natriumethanolat und Kalium-tert.-butanolat, oder einer  Sodium ethanolate and potassium tert-butoxide, or one
organischen tertiären Base wie Triethylamin und Pyridin  organic tertiary base such as triethylamine and pyridine
gearbeitet werden, wobei die organische Base gleichzeitig als Lösungsmittel dienen kann.  be worked, the organic base can simultaneously serve as a solvent.
Zweckmäβig setzt man die Edukte in stöchiometrischem Verhältnis ein oder man arbeitet mit einem geringen Überschuβ der einen oder anderen Komponente bis etwa 20 mol-%. Arbeitet man ohne The starting materials are expediently used in a stoichiometric ratio or one works with a slight excess of one or the other component up to about 20 mol%. You work without
Lösungsmittel in Gegenwart einer organischen Base, so liegt diese in einem gröβeren Überschuβ vor. Die Reaktionstemperatur liegt vorzugsweise im Bereich zwischen (-80) und 150°C, besonders bevorzugt zwischen (-30) und der Rückfluβtemperatur des verwendeten Lösungsmittels.  Solvents in the presence of an organic base, this is in a large excess. The reaction temperature is preferably in the range between (-80) and 150 ° C, particularly preferably between (-30) and the reflux temperature of the solvent used.
Die Enamin-carboxylate der Formel III sind ebenfalls neu und können als Herbizide eingesetzt werden. Sie sind nach an sich bekannten Verfahren herstellbar, beispielsweise aus einem Anilinderivat der Formel XVI nach folgendem Reaktionsschema: The enamine carboxylates of formula III are also new and can be used as herbicides. They can be prepared by processes known per se, for example from an aniline derivative of the formula XVI according to the following reaction scheme:
In Gleichung (G11) bedeuten R4' und R5' Wasserstoff oder In equation (G11), R 4 ' and R 5' are hydrogen or
C1-C4-Alkyl. Die Umsetzungen nach Reaktionsgleichung 1 und 2 erfolgen vorzugsweise in einem wasserfreien inerten aprotischen Lösungsmittel, beispielsweise in einem halogenierten Kohlenwasserstoff wie Methylenchlorid, Chloroform, Tetrachlorkohlenstoff und Chlorbenzol, einem aromatischen Kohlenwasserstoff wie Benzol, Toluol und o-, m-, p-Xylol, oder einem aliphatischen oder cyclischen Aether wie Diethylether, Dibutylether, 1,2-Dimethoxyethan, C 1 -C 4 alkyl. The reactions according to reaction equations 1 and 2 are preferably carried out in an anhydrous, inert aprotic solvent, for example in a halogenated hydrocarbon such as methylene chloride, chloroform, carbon tetrachloride and chlorobenzene, an aromatic hydrocarbon such as benzene, toluene and o-, m-, p-xylene, or one aliphatic or cyclic ethers such as diethyl ether, dibutyl ether, 1,2-dimethoxyethane,
Tetrahydrofuran und Dioxan.  Tetrahydrofuran and dioxane.
Für die Umsetzung des Lactons XX mit dem Anilinderivat XIX nach Gleichung (G11) empfiehlt sich der Zusatz eines basischen Katalysators, z.B. 4-Pyrrolidinopyridin, 4-Dimethylamino-pyridin, 1,2-Diazabicyclo[2,2,2]octan, 1,5-Diazabicyclo[4,3,0]non-5-en, 1,8-Diazabicyclo[5,4,0]undec-7-en oder Diethylamin. Da die Reaktion exotherm verläuft, ist im allgemeinen eine Reaktionstemperatur zwischen (-10) und 50°C, vorzugsweise zwischen 10 und 30°C ausreichend. For the reaction of lactone XX with the aniline derivative XIX according to equation (G11), the addition of a basic catalyst is recommended, e.g. 4-pyrrolidinopyridine, 4-dimethylamino-pyridine, 1,2-diazabicyclo [2,2,2] octane, 1,5-diazabicyclo [4,3,0] non-5-ene, 1,8-diazabicyclo [5, 4.0] undec-7-ene or diethylamine. Since the reaction is exothermic, a reaction temperature between (-10) and 50 ° C, preferably between 10 and 30 ° C is generally sufficient.
Für die Reaktion der Verbindungen der Formeln XXII und XIX mit- einander nach Gleichung (G12) sind dagegen höhere Temperaturen, etwa zwischen 70 und 140°C, insbesondere zuwischen 100 und 120°C vorteilhaft. For the reaction of the compounds of formulas XXII and XIX with each other according to equation (G12), however, higher temperatures, for example between 70 and 140 ° C., in particular between 100 and 120 ° C., are advantageous.
Bei der Umsetzung nach Reaktionsgleichung (G13) handelt es sich um eine Aminolyse, die in der Regel entweder ohne Lösungsmittel [vgl. z.B. J. Soc. Dyes Col. 42, 81 (1926), Ber. 64, 970 (1931); Org. Synth., Coll. Vol. IV, 80 (1963) und J.A.C.S. 70, 2402 (1948)] oder in einem inerten wasserfreien Lösungs- oder Verdünnungsmittel, insbesondere in einem aprotischen Solvens, beispielsweise in einem gegebenenfalls halogenierte Aromaten wie Toluol, o-, m-, p-Xylol und Chlorbenzol, durchgeführt wird. Hierbei empfiehlt sich das Arbeiten in Gegenwart eines basischen Katalysators, z.B. eines höher siedenden Amins [siehe beispielsweise Helv. Chim. Acta 11, 779 (1928) und U.S. 2,416,738] oder Pyridin. The reaction according to reaction equation (G13) is an aminolysis, which is usually either without a solvent [cf. e.g. J. Soc. Dyes Col. 42, 81 (1926), Ber. 64, 970 (1931); Org. Synth., Coll. Vol. IV, 80 (1963) and JACS 70, 2402 (1948)] or in an inert anhydrous solvent or diluent, in particular in an aprotic solvent, for example in an optionally halogenated aromatic such as toluene, o-, m-, p- Xylene and chlorobenzene. It is recommended to work in the presence of a basic catalyst, eg a higher boiling amine [see for example Helv. Chim. Acta 11, 779 (1928) and US 2,416,738] or pyridine.
Vorzugsweise liegt die Reaktionstemperatur zwischen etwa 20 und 160°C. The reaction temperature is preferably between about 20 and 160 ° C.
Bei allen drei Herstellungsvarianten setzt man die Edukte zweckmäβigerweise in stöchiometrischem Verhältnis ein oder man arbeitet mit einem geringen Überschuβ der einen oder anderen Komponente bis etwa 10 mol-%. Arbeitet man in Gegenwart eines basischen Katalysators, so ist im allgemeinen eine Menge zwischen 0,5 und 200 mol-%, bezogen auf die Menge eines Edukts, ausreichend. In all three production variants, the starting materials are expediently used in a stoichiometric ratio or one works with a slight excess of one or the other component up to about 10 mol%. If one works in the presence of a basic catalyst, an amount between 0.5 and 200 mol%, based on the amount of a starting material, is generally sufficient.
Die anschlieβende Umsetzung der so hergestellten Verbindungen der Formel XXI mit der Verbindung H2N-COOL1 wird vorteilhaft in einem weitgehend wasserfreien Lösungs- oder Verdünnungsmittel bei Normaldruck durchgeführt, besonders bevorzugt in Gegenwart eines sauren Katalysators. The subsequent reaction of the compounds of the formula XXI thus prepared with the compound H 2 N-COOL 1 is advantageously carried out in a largely anhydrous solvent or diluent at atmospheric pressure, particularly preferably in the presence of an acidic catalyst.
Als Lösungs- oder Verdünnungsmittel kommen insbesondere mit Wasser azeotrop mischbare organische Flüssigkeiten, beispielsweise Aromaten wie Benzol, Toluol und o-, m-, p-Xylol oder halo- genierte Kohlenwasserstoffe wie Tetrachlorkohlenstoff und Chlorbenzol, in Betracht. Suitable solvents or diluents are, in particular, water which is azeotropically miscible with water, for example aromatics such as benzene, toluene and o-, m-, p-xylene or halogenated hydrocarbons such as carbon tetrachloride and chlorobenzene.
Geeignete Katalysatoren sind insbesondere starke Mineralsäuren wie Schwefelsäure, organische Säuren wie p-Toluolsulfonsäure, Phosphor enthaltende Säuren wie Orthophosphorsaure und Polyphosphorsaure oder saure Kationenaustauscher wie "Amberlyst 15" (Fluka). Suitable catalysts are in particular strong mineral acids such as sulfuric acid, organic acids such as p-toluenesulfonic acid, phosphorus-containing acids such as orthophosphoric acid and polyphosphoric acid or acidic cation exchangers such as "Amberlyst 15" (Fluka).
Im allgemeinen liegt die Reaktionstemperatur zwischen etwa 70 und 150°C; zur raschen Entfernung des entstehenden Reaktionswassers arbeitet man jedoch zweckmäβigerweise bei der Siedetemperatur des Solvens. w) Die Pyrimidon-Derivate IVa und IVb, von denen Methode d) ausgeht, können durch Halogenierung, vorzugsweise Chlorierung und Bromierung, von 3-Phenylurazilen I, in denen R3 Wasserstoff bedeutet, ohne Lösungsmittel oder in Gegenwart eines inerten Lösungs- oder Verdünnungsmittels erhalten werden. In general, the reaction temperature is between about 70 and 150 ° C; however, to rapidly remove the water of reaction formed, it is expedient to work at the boiling point of the solvent. w) The pyrimidone derivatives IVa and IVb, from which method d) starts, can by halogenation, preferably chlorination and bromination, of 3-phenylurazilene I, in which R 3 is hydrogen, without solvent or in the presence of an inert solvent or diluent be preserved.
Als Lösungs- oder Verdünnungsmittel kommen insbesondere aprotische organische Flüssigkeiten, beispielsweise aliphatische oder aromatische Kohlenwasserstoffe wie n-Hexan, Benzol, Toluol und o-, m-, p-Xylol, halogenierte aliphatische Kohlenwasserstoffe wie Methylenchlorid, Chloroform und 1,2-Dichlorethan, halogenierte aromatische Kohlenwasserstoffe wie Chlorbenzol, oder tertiäre Amine wie N,N-Dimethylanilin, in Betracht. Als Halogenierungsmittel eignen sich insbesondere Thionylchlorid, Phosphorpentachlorid, Phosphoroxychlorid, Phosphorpentabromid oder Phosphorylbromid. Besonders vorteilhaft kann auch ein Gemisch aus Phosphorpentachlorid und Phosphoroxychlorid oder aus Phosphorpentabromid und Phosphorylbromid sein. In particular, aprotic organic liquids, for example aliphatic or aromatic hydrocarbons such as n-hexane, benzene, toluene and o-, m-, p-xylene, halogenated aliphatic hydrocarbons such as methylene chloride, chloroform and 1,2-dichloroethane, halogenated come as solvents or diluents aromatic hydrocarbons such as chlorobenzene, or tertiary amines such as N, N-dimethylaniline. Particularly suitable halogenating agents are thionyl chloride, phosphorus pentachloride, phosphorus oxychloride, phosphorus pentabromide or phosphoryl bromide. A mixture of phosphorus pentachloride and phosphorus oxychloride or of phosphorus pentabromide and phosphoryl bromide can also be particularly advantageous.
In den meisten Fällen empfiehlt es sich, eine katalytische Menge an Dimethylformamid oder eines alkylierten Anilinderivates zuzusetzen. Die Menge an Halogenierungsmittel ist nicht kritisch; für eine vollständige Umsetzung benötigt man mindestens äquimolare Mengen an Halogenierungsmittel und zu halogenierendem Edukt. Es kann jedoch auch ein 1- bis 8-facher molarer Überschuβ an Halogenierungsmittel vorteilhaft sein. In most cases it is advisable to add a catalytic amount of dimethylformamide or an alkylated aniline derivative. The amount of halogenating agent is not critical; For a complete reaction, at least equimolar amounts of halogenating agent and starting material to be halogenated are required. However, a 1- to 8-fold molar excess of halogenating agent can also be advantageous.
Die Reaktionstemperaturen liegen im allgemeinen zwischen 0°C und der Rückflußtemperatur des Reaktionsgemisches, vorzugsweise zwischen 20 und 120°C. x) C-Acylierung eines Enamins der Formel XXIV mit einem Isocyanat oder Isothiocyanat der Formel XII 4 The reaction temperatures are generally between 0 ° C and the reflux temperature of the reaction mixture, preferably between 20 and 120 ° C. x) C-acylation of an enamine of formula XXIV with an isocyanate or isothiocyanate of formula XII 4
Φ Φ
Die Umsetzung erfolgt zweckmäβig in Gegenwart eines im  The reaction is conveniently carried out in the presence of an im
wesentlichen wasserfreien, aprotischen organischen Lösungs- und Verdünnungsmittel, beispielsweise eines aliphatischen oder cyclischen Ethers wie Diethylether, 1,2-Dimethoxyethan, essential anhydrous, aprotic organic solvents and diluents, for example an aliphatic or cyclic ether such as diethyl ether, 1,2-dimethoxyethane,
Tetrahydrofuran und Dioxan, eines aliphatischen oder aromatischen Kohlenwasserstoffs wie n-Hexan, Benzol, Toluol und o-, m-, p-Xylol, eines halogenierten, aliphatischen Kohlenwasserstoffs wie Methylenchlorid, Chloroform, Tetrachlorkohlenstoff, Tetrahydrofuran and dioxane, an aliphatic or aromatic hydrocarbon such as n-hexane, benzene, toluene and o-, m-, p-xylene, a halogenated aliphatic hydrocarbon such as methylene chloride, chloroform, carbon tetrachloride,
1,2-Dichlorethan und Chlorbenzol, eines aprotischen, polaren Lösungsmittel wie Dimethylformamid, Hexamethylphosphorsauretriamid und Dimethylsulfoxid, oder eines Gemisches aus den genannten Solventen. 1,2-dichloroethane and chlorobenzene, an aprotic, polar solvent such as dimethylformamide, hexamethylphosphoric triamide and dimethyl sulfoxide, or a mixture of the solvents mentioned.
Gewünschtenfal l s kann auch in Gegenwart einer organischen tertiären Base wie Triethylamin und Pyridin gearbeitet werden, wobei die organische Base gleichzeitig als Lösungsmittel dienen kann. If desired, it is also possible to work in the presence of an organic tertiary base such as triethylamine and pyridine, where the organic base can simultaneously serve as a solvent.
Zweckmäβig setzt man die Edukte in stöchiometrischem Verhältnis ein oder man arbeitet mit einem geringen Überschuβ der einen oder anderen Komponente bis etwa 20 mol-%. Arbeitet man ohne The starting materials are expediently used in a stoichiometric ratio or one works with a slight excess of one or the other component up to about 20 mol%. You work without
Lösungsmittel in Gegenwart einer organischen Base, so liegt diese in einem gröβeren Überschuβ vor. Die Reaktionstemperatur liegt vorzugsweise im Bereich zwischen (-80) und 150°C, besonders bevorzugt zwischen (-30) und der Rückfluβtemperatur des verwendeten Lösungsmittels. Solvents in the presence of an organic base, this is in a large excess. The reaction temperature is preferably in the range between (-80) and 150 ° C, particularly preferably between (-30) and the reflux temperature of the solvent used.
Das bei dieser Reaktion häufig anfallende Nebenprodukt The by-product that often occurs in this reaction
(Acylierung am Stickstoff, vgl. Verfahrensvariante s)), läßt sich auf übliche Weise, z.B. Kristallisation oder Chromatographie, abtrennen. Die Verbindungen der Formeln IX, XII, XIII und XIV sind ebenfalls neu. Sie können nach an sich bekannten Methoden hergestellt werden, besonders vorteilhaft aus Verbindungen der Formel XVI: (Acylation on nitrogen, cf. process variant s)), can be separated off in a customary manner, for example crystallization or chromatography. The compounds of the formulas IX, XII, XIII and XIV are also new. They can be prepared by methods known per se, particularly advantageously from compounds of the formula XVI:
Durch "Phosgenierung" und Hydolyse der Verfahrensprodukte mit Ammoniak By "phosgenation" and hydrolysis of the process products with ammonia
Das Verfahren kann in einem inerten, im wesentlichen wasserfreien Lösungs- oder Verdünnungsmittel oder ohne Lösungsmittel durchgeführt werden, wobei die Verbindungen XIX bevorzugt mit Phosgen oder Chiorameisensäuretrichlormethylester umgesetzt werden.  The process can be carried out in an inert, essentially anhydrous solvent or diluent or without a solvent, the compounds XIX preferably being reacted with phosgene or trichloromethyl chloroformate.
Als Lösungs- oder Verdünnungsmittel kommen insbesondere aprotische, organische Lösungsmittel, beispielsweise Aromaten wie Toluol und o-, m-, p-Xylol, halogenierte Kohlenwasserstoffe wie Methylenchlorid, Chloroform, 1,2-Dichlorethan und Chlorbenzol, aliphatische oder cyclische Ether wie 1,2-Dimethoxyethan, Tetrahydrofuran und Dioxan, oder Ester wie Essigsäureethylester, sowie Gemische dieser Lösungsmittel, in Betracht. Suitable solvents or diluents are, in particular, aprotic, organic solvents, for example aromatics such as toluene and o-, m-, p-xylene, halogenated hydrocarbons such as methylene chloride, chloroform, 1,2-dichloroethane and chlorobenzene, aliphatic or cyclic ethers such as 1,2 -Dimethoxyethane, tetrahydrofuran and dioxane, or esters such as ethyl acetate, and mixtures of these solvents.
Je nach eingesetztem Anilinderivat XIX kann der Zusatz einer Base wie Triethylamin vorteilhaft sein, beispielsweise in 0,5- bis 2-facher molarer Menge, bezogen auf die Menge an XIX. Durch Wahl der geeigneten Reaktionsbedingungen lassen sich sowohl die Carbaminsäurechloride XIX als auch die Phenylisocyanate XII erhalten: Depending on the aniline derivative XIX used, the addition of a base such as triethylamine can be advantageous, for example in 0.5 to 2 times the molar amount, based on the amount of XIX. By choosing the appropriate reaction conditions, both the carbamic acid chlorides XIX and the phenyl isocyanates XII can be obtained:
So erhält man bei niederen Temperaturen zwischen etwa (-40) und 50°C normalerweise die Carbaminsäurechloride XVII, während weitere Temperaturerhöhung, bis zur Siedetemperatur des Reaktionsgemisches, dagegen überwiegend zur Bildung der Phenylisocyanate XIV führt, die mit Ammoniak oder einem reaktiven Derivat des Ammoniaks zu den Phenylharnstoffderi vaten XII umgesetzt werden können.  Thus, at low temperatures between about (-40) and 50 ° C, the carbamic acid chlorides XVII are normally obtained, while a further increase in temperature up to the boiling point of the reaction mixture, on the other hand, predominantly leads to the formation of the phenyl isocyanates XIV which, with ammonia or a reactive derivative of ammonia the phenylurea derivatives XII can be implemented.
Durch Umsetzung mit Alkalimetallcyanaten By reaction with alkali metal cyanates
M⊕ steht für das Äquivalent eines Metallions, insbesondere für ein Alkalimetallion wie Natrium und Kalium. M ⊕ stands for the equivalent of a metal ion, in particular for an alkali metal ion such as sodium and potassium.
Die Umsetzung erfolgt in einem inerten Lösungs- oder Verdünnungsmittel, beispielsweise in einem aromatischen Kohlenwasserstoff wie Toluol und o-, m-, p-Xylol, in einem aliphatischen oder cyclischen Ether wie Tetrahydrofuran und Dioxan, in einem niederen Alkohol wie Methanol und Ethanol, in Wasser oder in einem Gemisch der genannten Solventien. The reaction takes place in an inert solvent or diluent, for example in an aromatic hydrocarbon such as toluene and o-, m-, p-xylene, in an aliphatic or cyclic ether such as tetrahydrofuran and dioxane, in a lower alcohol such as methanol and ethanol Water or in a mixture of the solvents mentioned.
Die Menge an Cyanat ist nicht kritisch; für eine vollständige Umsetzung benötigt man mindestens aquimolare Mengen an Anilinderivat XIX und Cyanat, jedoch kann auch ein Überschuβ an Cyanat, bis etwa 100 mol-%, vorteilhaft sein. The amount of cyanate is not critical; For a complete reaction, at least equimolar amounts of aniline derivative XIX and cyanate are required, but an excess of cyanate, up to about 100 mol%, can also be advantageous.
Die Reaktionstemperatur liegt im allgemeinen zwischen 0°C und der Rückfluβtemperatur des Reaktionsgemisches. Durch Umsetzung mit Estern XX The reaction temperature is generally between 0 ° C and the reflux temperature of the reaction mixture. By implementation with Estern XX
L4 steht für C1-C4-Alkyl oder Phenyl; L 4 represents C 1 -C 4 alkyl or phenyl;
L5 steht für Halogen, vorzugsweise Chlor oder Brom, für C1-C4- Alkoxy oder Phenoxy. L 5 stands for halogen, preferably chlorine or bromine, for C 1 -C 4 alkoxy or phenoxy.
Als Lösungs- oder Verdünnungsmittel eignen sich beispielsweise aromatische Kohlenwasserstoffe wie Toluol und o-, m-, p-Xylol, halogenierten Kohlenwasserstoffe wie Methylenchlorid, Chloroform, 1,2-Dichlorethan und Chlorbenzol, aliphatische oder cyclischeExamples of suitable solvents or diluents are aromatic hydrocarbons such as toluene and o-, m-, p-xylene, halogenated hydrocarbons such as methylene chloride, chloroform, 1,2-dichloroethane and chlorobenzene, aliphatic or cyclic
Ethern, wie 1,2-Dimethoxyethan, Tetrahydrofuran und Dioxan, Ester wie Essigsäureethylester, Alkohole wie Methanol und Ethanol, oder Wasser oder Zweiphasengemische aus einem organischen Lösungsmittel und Wasser. Ethers such as 1,2-dimethoxyethane, tetrahydrofuran and dioxane, esters such as ethyl acetate, alcohols such as methanol and ethanol, or water or two-phase mixtures of an organic solvent and water.
Vorteilhaft verläuft die Umsetzung in Gegenwart einer Base, z.B. eines Alkalimetallhydroxides, -carbonates oder -alkoholates wie Natriumhydroxid, Natriumcarbonat, Natiummethanolat und Natiumethanolat oder eines tertiären Amins wie Pyridin und Triethylamin. The reaction advantageously takes place in the presence of a base, e.g. an alkali metal hydroxide, carbonate or alcoholate such as sodium hydroxide, sodium carbonate, sodium methoxide and sodium ethanolate or a tertiary amine such as pyridine and triethylamine.
Gewünschtenfalls kann auch ein Katalysator, z.B. eine Lewissäure wie Antimontrichlorid, zugesetzt werden. Zweckmäβig setzt man die Ausgangsverbindungen und die Base in stöchiometrischem Verhältnis ein, jedoch kann auch die eine oder andere Komponente in einem Überschuβ, bis etwa 100 mol-%, vorliegen. In der Regel beträgt die Katalysatormenge 1 bis 50 mol-%, bevorzugt 2 bis 30 mol-%, bezogen auf die Menge an eingesetztem If desired, a catalyst, e.g. a Lewis acid such as antimony trichloride can be added. The starting compounds and the base are expediently used in a stoichiometric ratio, but one or the other component can also be present in an excess, up to about 100 mol%. In general, the amount of catalyst is 1 to 50 mol%, preferably 2 to 30 mol%, based on the amount of used
Anilinderivat XIX. Im allgemeinen liegt die Reaktionstemperatur zwischen (-40)°C und der Siedetemperatur des Reaktionsgemisches. Aniline derivative XIX. In general, the reaction temperature is between (-40) ° C and the boiling point of the reaction mixture.
Die Ausgangsverbindungen der Formel XIX und deren Herstellung, sowie aller anderen Verbindungen, deren Herstellung nicht explizit beschrieben sind, sind aus der Literatur bekannt oder nach an sich bekannten Methoden herstellbar. The starting compounds of the formula XIX and their preparation, as well as all other compounds whose preparation is not explicitly described, are known from the literature or can be prepared by methods known per se.
Bei den vorstehend genannten Verfahren zur Synthese von substituierten Phenylurazilen I, deren Salzen, Enolethern oder Vorprodukten arbeitet man zweckmäβigerweise unter Normaldruck oder unter dem Eigendruck des jeweiligen Lösungsmittels. Geringerer oder höherer Druck ist möglich, bringt aber normalerweise keine Vorteile. In the abovementioned processes for the synthesis of substituted phenylurazils I, their salts, enol ethers or precursors, it is advantageous to work under normal pressure or under the autogenous pressure of the particular solvent. Lower or higher pressure is possible, but usually has no advantages.
Sofern nicht anders angegeben, sind die zur Herstellung der substituierten 3-Phenylurazile I, Ia und Ib benötigten Edukte und Reagenzien bekannt oder können nach an sich bekannten Methoden hergestellt werden. Unless otherwise stated, the starting materials and reagents required for the preparation of the substituted 3-phenylurazils I, Ia and Ib are known or can be prepared by methods known per se.
Die Aufarbeitung der jeweiligen Reaktionsgemische erfolgt in der Regel nach an sich bekannten Methoden, beispielsweise durch Entfernen des Lösungsmittels, Verteilen des Rückstandes in einem Gemisch aus Wasser und einem geeigneten organischen Lösungsmittel und Isolieren des Produktes der organischen Phase. The respective reaction mixtures are generally worked up by methods known per se, for example by removing the solvent, distributing the residue in a mixture of water and a suitable organic solvent and isolating the product of the organic phase.
Die substituierten 3-Phenylurazile I, Ia und Ib können bei der. Herstellung als Isomerengemische anfallen, die jedoch The substituted 3-phenylurazils I, Ia and Ib can be used in the. Production arise as mixtures of isomers, however
gewünschtenfalls nach den hierfür üblichen Methoden, z.B. durch Kristallisation oder Chromatographie (ggf. an einem optisch aktiven Adsorbat), in die reinen Isomeren getrennt werden können. Reine optisch aktive isomere lassen sich beispielsweise aus entsprechenden optisch aktiven Ausgangsmaterialien synthetisieren. if desired, according to the usual methods, e.g. by crystallization or chromatography (possibly on an optically active adsorbate) into which the pure isomers can be separated. Pure optically active isomers can be synthesized, for example, from corresponding optically active starting materials.
In der Regel lassen sich die Verbindungen der Formeln I, Ia und Ib auf den vorstehend beschriebenen- Wegen herstellen. Es ist jedoch auch in einzelnen Fällen möglich, bestimmte Verbindungen I vorteilhaft aus anderen Verbindungen I durch Esterhydrolyse, Amidierung, Veresterung, Umesterung, Veretherung, Etherspaltung, Olefinierung, Reduktion, Oxidation oder Ringschlußreaktion an den Positionen der Reste R4, R5 und W herzustellen. Die substituierten 3-Phenylurazile I, Ia und Ib eignen sich, sowohl als Isomerengemische als auch in Form der reinen isomeren, als Herbizide. Im allgemeinen sind sie verträglich und somit selektiv in breitblättrigen Kulturen sowie in monokotylen (einkeimblättrigen) Gewächsen. In general, the compounds of the formulas I, Ia and Ib can be prepared in the ways described above. However, it is also possible in individual cases to prepare certain compounds I advantageously from other compounds I by ester hydrolysis, amidation, esterification, transesterification, etherification, ether cleavage, olefination, reduction, oxidation or ring closure reaction at the positions of the radicals R 4 , R 5 and W. . The substituted 3-phenylurazils I, Ia and Ib are suitable, both as isomer mixtures and in the form of the pure isomers, as herbicides. They are generally compatible and therefore selective in broadleaved crops and in monocotyledonous plants.
In Abhängigkeit von der jeweiligen Appl ikationsmethode können die substituierten Phenylurazile Ia und Ib bzw. sie enthaltende Mittel in einer Vielzahl von Kulturplfanzen zur Beseitigung unerwünschter Pflanzen eingesetzt werden, wobei die folgenden Kulturen beispielhaft genannt seien: Depending on the respective application method, the substituted phenylurazils Ia and Ib or agents containing them can be used in a large number of crop plants for eliminating undesired plants, the following crops being mentioned as examples:
Botanischer Name Deutscher Name Botanical name German name
Allium cepa Küchenzwiebel  Allium cepa onion
Ananas comosus Ananas  Ananas comosus pineapple
Arachis hypogaea Erdnuß  Arachis hypogaea peanut
Asparagus officinalis Spargel  Asparagus officinalis asparagus
Beta vulgaris spp. altissima Zuckerrübe  Beta vulgaris spp. altissima beet
Beta vulgaris spp. rapa Futterrübe  Beta vulgaris spp. rapa beet
Brassica napus var. napus Raps  Brassica napus var.napus rape
Brassica napus var. napobrassica Kohlrübe  Brassica napus var.napobrassica turnip
Brassica rapa var. silvestris Rüben  Brassica rapa var.silvestris beets
Camellia sinensis Teestrauch  Camellia sinensis tea bush
Carthamus tinctorius Saflor - Färberdistel Carya illinoinensis Pekannußbaum  Carthamus tinctorius Safflower - safflower Carya illinoinensis pecan tree
Citrus limon Zitrone  Citrus limon lemon
Citrus sinensis Apfelsine, Orange  Citrus sinensis orange, orange
Coffea arabica (Coffea canephora, Kaffee  Coffea arabica (Coffea canephora, coffee
Coffea liberica)  Coffea liberica)
Cucumis sativus Gurke Cucumis sativus cucumber
Cynodon dactylon Bermudagras  Cynodon dactylon Bermuda grass
Daucus carota Möhre  Daucus carota carrot
Elaeis guineensis Ölpalme  Elaeis guineensis oil palm
Fragaria vesca Erdbeere  Fragaria vesca strawberry
Glycine max Sojabohne Glycine max soybean
Gossypium hirsutum (Gossypium arboreum, Baumwolle  Gossypium hirsutum (Gossypium arboreum, cotton
Gossypium herbaceum, Gossypium vitifolium)  Gossypium herbaceum, Gossypium vitifolium)
Helianthus annuus Sonnenblume  Helianthus annuus sunflower
Hevea brasiliensis Parakautschukbaum  Hevea brasiliensis para rubber tree
Hordeum vulgäre Gerste Hordeum vulgar barley
Humulus lupulus Hopfen Botanischer Name Deutscher Name Humulus lupulus hops Botanical name German name
Ipomoea batatas Süßkartoffeln  Ipomoea batatas sweet potatoes
Juglans regia Walnuβbaum  Juglans regia walnut
Lens culinaris Linse  Lens culinaris lens
Linum usitatissimum Faserlein  Linum usitatissimum fiber
Lycopersicon lycopersicum Tomate  Lycopersicon lycopersicum tomato
Malus spp. Apfel  Malus spp. Apple
Manihot esculenta Maniok  Manihot esculenta cassava
Medicago sativa Luzerne  Medicago sativa alfalfa
Musa spp. Obst- und Mehlbanane Musa spp. Fruit and flour banana
Nicotiana tabacum (N. rustica) Tabak Nicotiana tabacum (N. rustica) tobacco
Olea europaea Ölbaum  Olea europaea olive tree
Oryza sativa Reis  Oryza sativa rice
Phaseolus lunatus Mondbohne  Phaseolus lunatus broad bean
Phaseolus vulgaris Buschbohnen  Phaseolus vulgaris bush beans
Picea abies Rotfichte  Picea abies red spruce
Pinus spp. Kiefer  Pinus spp. jaw
Pisum sativum Gartenerbse  Pisum sativum garden pea
Prunus avium Süβkirsche  Prunus avium sweet cherry
Prunus persica Pfirsich  Prunus persica peach
Pyrus communis Birne  Pyrus communis pear
Ribes sylvestre Rote Johannisbeere Ribes sylvestre red currant
Ricinus communis Rizinus Ricinus communis castor
Saccharum officinarum Zuckerrohr  Saccharum officinarum sugar cane
Seeale cereale Roggen  Seeale cereal rye
Solanum tuberosum Kartoffel  Solanum tuberosum potato
Sorghum bicolor (s. vulgäre) Mohrenhirse  Sorghum bicolor (see vulgar) black millet
Theobroma cacao Kakaobaum  Theobroma cocoa cocoa tree
Trifolium pratense Rotklee  Trifolium pratense red clover
Triticum aestivum Weizen  Triticum aestivum wheat
Triticum durum Hartweizen  Triticum durum durum wheat
Vicia faba Pferdebohnen  Vicia faba horse beans
Vitis vinifera Weinrebe  Vitis vinifera grapevine
Zea mays Mais  Zea May's Corn
Des weiteren eignen sich die substituierten 3-Phenylurazile I, Ia und Ib auch zur Desiccation und Defoliation von Pflanzen. Als Dessicantien eignen sie sich insbesondere zur Austrocknung der oberirdischen Teile von Kulturpflanzen wie Kartoffel, Raps, Sonnenblume und Sojabohne. Damit wird ein vollständig mechanisiertes Beernten dieser wichtigen Kulturpflanzen ermöglicht. Von wirtschaftlichem Interesse ist ferner die Ernteerleichterung, die durch das zeitlich konzentrierte Abfallen oder Vermindern der Haftfestigkeit am Baum bei Zitrusfrüchten, Oliven oder bei anderen Arten und Sorten von Kern-, Stein- und Schalenobst ermöglicht wird. Derselbe Mechanismus, das heißt die Förderung der Ausbildung von Trenngewebe zwischen Frucht- bzw. Blatt- und Sproßteil der Pflanze ist auch für ein gut kontrollierbares Entblättern von Nutzpflanzen wie beispielsweise Baumwolle wesentlich. Auβerdem führt die Verkürzung des Zeitintervalls, in dem die einzelnen Baumwollpflanzen reif werden, zu einer erhöhten Furthermore, the substituted 3-phenylurazils I, Ia and Ib are also suitable for the desiccation and defoliation of plants. As dessicants, they are particularly suitable for drying out the aerial parts of crops such as potatoes, rapeseed, sunflower and soybeans. This enables fully mechanized harvesting of these important crops. Also of economic interest is the ease of harvesting, which is made possible by the temporally concentrated decrease or decrease in the adhesive strength on the tree in the case of citrus fruits, olives or other types and varieties of pome, stone and nuts. The same mechanism, that is, the promotion of the formation of separating tissue between the fruit or leaf and shoot part of the plant is also essential for a well controllable defoliation of useful plants such as cotton. In addition, the shortening of the time interval in which the individual cotton plants ripen leads to an increased
Faserqualität nach der Ernte.  Fiber quality after harvest.
Abgesehen von ihrer herbiziden und entblätternden Wirkung können einige der substituierten 3-Phenylurazile der Formeln I, Ia und Ib auch als Wachstumsregulatoren oder zur Bekämpfung von Schädlingen aus der Klasse der Insekten, Spinnentiere und Nematoden eingesetzt werden. Sie können im Pflanzenschutz sowie auf dem Hygiene-, Vorratsschutz- und Veterinärsektor zur Bekämpfung von Schädlingen dienen. In addition to their herbicidal and defoliate activity, some of the substituted 3-phenylurazils of the formulas I, Ia and Ib can also be used as growth regulators or for controlling pests from the class of the insects, arachnids and nematodes. They can be used to control pests in crop protection as well as in the hygiene, storage protection and veterinary sectors.
Zu den schädlichen Insekten gehören aus der Ordnung der The harmful insects include from the order of the
Schmetterlinge (Lepidoptera) beispielsweise Agrotis ypsilon, Agrotis segetum, Alabama argillacea, Anticarsia gemmatalis, Argyresthia conjugella, Autographa gamma, Bupalus piniarius, Cacoecia murinana, Capua reticulana, Cheimatobia brumata,  Butterflies (Lepidoptera), for example Agrotis ypsilon, Agrotis segetum, Alabama argillacea, Anticarsia gemmatalis, Argyresthia conjugella, Autographa gamma, Bupalus piniarius, Cacoecia murinana, Capua reticulana, Cheimatobia brumata,
Choristoneura fumiferana, Choristoneura occidentalis, Cirphis unipuncta, Cydia pomonella, Dendrolimus pini, Diaphania Choristoneura fumiferana, Choristoneura occidentalis, Cirphis unipuncta, Cydia pomonella, Dendrolimus pini, Diaphania
nitidalis, Diatraea grndiosella, Earias insulana, Elasmopalpus lignosellus, Eupoecilia ambiguella, Evetria bouliana, Feltia subterranea, Galleria mellonella, Grapholita funebrana, nitidalis, Diatraea grndiosella, Earias insulana, Elasmopalpus lignosellus, Eupoecilia ambiguella, Evetria bouliana, Feltia subterranea, Galleria mellonella, Grapholita funebrana,
Grapholita molesta, Heliothis armigera, Heliothis virescens, Heliothis zea, Hellula undalis, Hibernia defoliaria, Hyphantria cunea, Hyponomeuta malinellus, Keifferia lycopersicella, Lambdina fiscellaria, Laphygma exigua, Leucoptera coffeella, Leucoptera scitella, Lithocolletis blancardella, Lobesia botrana, Loxostege sticticalis, Lymantria dispar, Lymantria monacha, Lyonetia clerkella, Malacosoma neustria, Mamestra brassicae, Orgyia pseudotsugata, Ostrinia nubilalis, Panolis flamea, Pectinophora gossypiella, Peridroma saucia, Phalera bucephala, Phthorimaea operculella, Phyllocnistis citrella, Pieris brassicae, Plathypena scarbra, Plutella xylostella, Pseudoplusia includens, Phyacionia frustrana, Scrobipalpula absolute, Sitotroga cerelella, Grapholita molesta, Heliothis armigera, Heliothis virescens, Heliothis zea, Hellula undalis, Hibernia defoliaria, Hyphantria cunea, Hyponomeuta malinellus, Keifferia lycopersicella, Lambdina fiscellaria, Laphygma exigua, Leucoptera collellaitellaostellais, lucoptera collellaitellaostella, botella , Lymantria monacha, Lyonetia clerkella, Malacosoma neustria, Mamestra brassicae, Orgyia pseudotsugata, Ostrinia nubilalis, Panolis flamea, Pectinophora gossypiella, Peridroma saucia, Phalera bucephala, Phthorimaea operculisena plithella brassella, Phyllocnella pella scarbra, Plutella xylostella, Pseudoplusia includens, Phyacionia frustrana, Scrobipalpula absolute, Sitotroga cerelella,
Sparganothis pilleriana, Spodoptera frugiperda, Spodoptera littoralis, Spodoptera litura, Thaumatopoea pityocampa, Tortrix viridana, Trichoplusia ni, Zeiraphera canadensis. Sparganothis pilleriana, Spodoptera frugiperda, Spodoptera littoralis, Spodoptera litura, Thaumatopoea pityocampa, Tortrix viridana, Trichoplusia ni, Zeiraphera canadensis.
Aus der Ordnung der Käfer (Coleoptera) beispielsweise Agrilus sinuatus, Agriotes lineatus, Agriotes obscurus, Amphimallus solstitial is, Anisandrus dispar, Anthonomus grandis, Anthonomus pomorum, Atomaria linearis, Blastophagus piniperda, Blitophaga undata, Bruchus rufimanus, Bruchus pisorum, Bruchus lentis, Byctiscüs betulae, Cassida nebulosa, Cerotoma trifurcata, From the order of the beetles (Coleoptera), for example Agrilus sinuatus, Agriotes lineatus, Agriotes obscurus, Amphimallus solstitial is, Anisandrus dispar, Anthonomus grandis, Anthonomus pomorum, Atomaria linearis, Blastophagus piniperda, Blitophaga undata, Bruchus rufimorisus, Bruchus pusorisis, Bruchus lisusis betulae, Cassida nebulosa, Cerotoma trifurcata,
Ceuthorrhynchus assimilis, Ceuthorrynchus napi, Chaetocnema tibialis, Conoderus vespertinus, Crioceris asparagi, Diabrotica longicornis, Diabrotica 12-punctata, Diabrotica virgifera, Epilachna varivestis, Epitrix hirtipennis, Eutinobothrus brasiliensis, Hylobius abietis, Hypera brunneipennis, Hypera postica, Ips typographus, Lema bilineata, Lema melanopus, Ceuthorrhynchus assimilis, Ceuthorrynchus napi, Chaetocnema tibialis, Conoderus vespertinus, Crioceris asparagi, Diabrotica longicornis, Diabrotica 12-punctata, Diabrotica virgifera, Epilachna varivestis, Epitrix hirtobipususiensinusiliensis, hyperitipisisia, hibipotisis, brunitipis, histipotis, histipotis, histipotus, histipotus Lema melanopus,
Leptinotarsa decemlineata, Limonius californicus, Lissorhoptrus oryzophilus, Melanotus communis, Meligethes aeneus, Melolontha hippocastani, Melolontha melolontha, Onlema oryzae, Leptinotarsa decemlineata, Limonius californicus, Lissorhoptrus oryzophilus, Melanotus communis, Meligethes aeneus, Melolontha hippocastani, Melolontha melolontha, Onlema oryzae,
Ortiorrhynchus sulcatus, Otiorrhynchus ovatus, Phaedon Ortiorrhynchus sulcatus, Otiorrhynchus ovatus, Phaedon
cochleariae, Phyllotreta chrysocephala, Phyllophaga sp., cochleariae, Phyllotreta chrysocephala, Phyllophaga sp.,
Phyllopertha horticola, Phyllotreta nemorum, Phyllotreta striolata, Popillia japonica, Sitona lineatus, Sitophilus granaria. Phyllopertha horticola, Phyllotreta nemorum, Phyllotreta striolata, Popillia japonica, Sitona lineatus, Sitophilus granaria.
Aus der Ordnung der Zweiflügler (Diptera) beispielsweise Aedes aegypti, Aedes vexans, Anastrepha ludens, Anopheles maculipennis, Ceratitis capitata, Chrysomya bezziana, Chrysomya hominivorax, Chrysomya macellaria, Contarinia sorghicola, Cordylobia From the order of the two-winged species (Diptera), for example, Aedes aegypti, Aedes vexans, Anastrepha ludens, Anopheles maculipennis, Ceratitis capitata, Chrysomya bezziana, Chrysomya hominivorax, Chrysomya macellaria, Contarinia sorghicola, Cordylobia
anthropophaga, Culex pipiens, Dacus cucurbitae, Dacus oleae, Dasineura brassicae, Fannia canicularis, Gasterophilus anthropophaga, culex pipiens, dacus cucurbitae, dacus oleae, dasineura brassicae, fannia canicularis, gasterophilus
intestinalis, Glossia morsitans, Haematobia irritans, intestinalis, glossia morsitans, haematobia irritans,
Haplodiplosis equestris, Hylemyia platura, Hypoderma lineata,Haplodiplosis equestris, Hylemyia platura, Hypoderma lineata,
Liriomyza sativae, Liriomyza trifolii, Lucilia caprina, Lucilia cuprina, Lucilia sericata, Lycoria pectoralis, Mayetiola destructor, Musca domestica, Muscina stabulans, Oestrus ovis, Oscinella frit, Pegomya hysocyami, Phorbia antiqua, Phorbia brassicae, Phorbia coarctata, Rhagoletis cerasi, Rhagoletis pomonella, Tabanus bovinus, Tipula oleracea, Tipula paludosa. Aus der Ordnung der Thripse (Thysanoptera) beispielsweise Frankliniella fusca, Frankliniella occidentalis, Frankliniella tritici, Scirtothrips citri, Thrips oryzae, Thrips palmi, Thrips tabaci. Liriomyza sativae, Liriomyza trifolii, Lucilia caprina, Lucilia cuprina, Lucilia sericata, Lycoria pectoralis, Mayetiola destructor, Musca domestica, Muscina stabulans, Oestrus ovis, Oscinella frit, Pegomya hysocyami, Phorbia antiqua, Phorbia brassagaroletata, Phorbia brassagarolata, Phorbia brassagarolatais , Tabanus bovinus, Tipula oleracea, Tipula paludosa. From the order of the thrips (Thysanoptera), for example Frankliniella fusca, Frankliniella occidentalis, Frankliniella tritici, Scirtothrips citri, Thrips oryzae, Thrips palmi, Thrips tabaci.
Aus der Ordnung der Hautflügler (Hymenoptera) beispielsweise Athalia rosae, Atta cephalotes, Atta sexdens, Atta texana, Hoplocampa minuta, Hoplocampa testudinea, Monomorium pharaonis, Solenopsis geminata, Solenopsis invicta. From the order of the hymenoptera, for example Athalia rosae, Atta cephalotes, Atta sexdens, Atta texana, Hoplocampa minuta, Hoplocampa testudinea, Monomorium pharaonis, Solenopsis geminata, Solenopsis invicta.
Aus der Ordnung der Wanzen (Heteroptera) beispielsweise From the order of the bugs (Heteroptera) for example
Acrosternum hilare, Blissus leucopterus, Cyrtopeltis notatus, Dysdercus cingulatus, Dysdercus intermedius, Eurygaster integriceps, Euchistus impictiventris, Leptoglossus phyllopus, Lygus lineolaris, Lygus pratensis, Nezara viridula, Piesma quadrata, Solubea insularis, Thyanta perditbr.  Acrosternum hilare, Blissus leucopterus, Cyrtopeltis notatus, Dysdercus cingulatus, Dysdercus intermedius, Eurygaster integriceps, Euchistus impictiventris, Leptoglossus phyllopus, Lygus lineolaris, Lygus pratensis, Nezara viridula, Piesma quadratais, Solub.
Aus der Ordnung der Pflanzensauger (Homoptera) beispielsweise Acyrthosiphon onobrychis, Adelges laricis, Aphidula nasturtii; Aphis fabae, Aphis pomi, Aphis sambuci, Brachycaudus cardui, Brevicoryne brassicae, Cerosipha gossypii, Dreyfusia From the order of the plant suckers (Homoptera), for example Acyrthosiphon onobrychis, Adelges laricis, Aphidula nasturtii; Aphis fabae, Aphis pomi, Aphis sambuci, Brachycaudus cardui, Brevicoryne brassicae, Cerosipha gossypii, Dreyfusia
nordmannianae, Dreyfusia piceae, Dyasphis radicola,  nordmannianae, Dreyfusia piceae, Dyasphis radicola,
Dysaulacorthum pseudosolani, Empoasca fabae, Macrosiphum avenae, Macrosiphum euphorbiae, Macrosiphon rosae, Megoura viciae, Metopolophium dirhodum, Myzodes persicae, Myzus cerasi,  Dysaulacorthum pseudosolani, Empoasca fabae, Macrosiphum avenae, Macrosiphum euphorbiae, Macrosiphon rosae, Megoura viciae, Metopolophium dirhodum, Myzodes persicae, Myzus cerasi,
Nilaparvata lugens, Pemphigus bursarius, Perkinsiella Nilaparvata lugens, Pemphigus bursarius, Perkinsiella
saccharicida, Phorodon humuli, Psylla mali, Psylla piri, saccharicida, Phorodon humuli, Psylla mali, Psylla piri,
Rhopalomyzus ascalonicus, Rhopalosiphum maidis, Sappaphis mala, Sappaphis mali, Schizaphis graminum, Schizoneura lanuginosa, Trialeurodes vaporariorum, Viteus vitifolii. Rhopalomyzus ascalonicus, Rhopalosiphum maidis, Sappaphis mala, Sappaphis mali, Schizaphis graminum, Schizoneura lanuginosa, Trialeurodes vaporariorum, Viteus vitifolii.
Aus der Ordnung der Termiten (Isoptera) beispielsweise Calotermes flavicollis, Leucotermes flavipes, Reticulitermes lucifugus, Termes natalensis. From the order of the termites (Isoptera), for example, Calotermes flavicollis, Leucotermes flavipes, Reticulitermes lucifugus, Termes natalensis.
Aus der Ordnung der Geradflügler (Orthoptera) beispielsweise Acheta domestica, Blatta orientalis, Blattella germanica, From the order of the straight wing (Orthoptera), for example Acheta domestica, Blatta orientalis, Blattella germanica,
Forficula auricularia, Gryllotalpa gryllotalpa, Locusta Forficula auricularia, Gryllotalpa gryllotalpa, Locusta
migratoria, Melanoplus birittatus, Melanoplus femur-rubrum, Melanoplus mexicanus, Melanoplus sanguinipes, Melanoplus spretus, Nomadacris septemfasciata, Periplaneta americana, Schistocerca americana, Schistocerca peregrina, Stauronotus maroccanus, Tachycines asynamorus. Aus der Klasse der Arachnoidea beispielsweise Spinnentieremigratoria, Melanoplus birittatus, Melanoplus femur-rubrum, Melanoplus mexicanus, Melanoplus sanguinipes, Melanoplus spretus, Nomadacris septemfasciata, Periplaneta americana, Schistocerca americana, Schistocerca peregrina, Stauronotus maroccanus, Tachycines asynamorus. Arachnoid, for example, arachnids
(Acarina) wie Amblyomma americanum, Amblyomma variegatum, Argas persicus, Boophilus annulatus, Boophilus decoloratus, Boophilus microplus, Brevipalpus phoenicis, Bryobia praetiosa, Dermacentor silvarum, Eotetranychus carpini, Eriophyes sheldoni, Hyalomma truncatum, Ixodes ricinus, Ixodes rubicundus, Ornithodorus moubata, Otobins megnini, Paratetranychus pilosus, Permanyssus gallinae, Phyllocaptrata oleivora, Polyphagotarsonemus latus, Psoroptes ovis, Rhipicephalus appendiculatus, Rhipicephalus evertsi, Saccoptes scabiei, Tetranychus cinnabarinus, Tetranychus kanzawai, Tetranychus pacificus, Tetranychus telarius, (Acarina) such as Amblyomma americanum, Amblyomma variegatum, Argas persicus, Boophilus annulatus, Boophilus decoloratus, Boophilus microplus, Brevipalpus phoenicis, Bryobia praetiosa, Dermacentor silvarum, Eotetranychus carpini, Eriophyes sheldoni, Hyinomminsusodes, Hyinomminsus, Ialobinus megnini, Paratetranychus pilosus, Permanyssus gallinae, Phyllocaptrata oleivora, Polyphagotarsonemus latus, Psoroptes ovis, Rhipicephalus appendiculatus, Rhipicephalus evertsi, Saccoptes scabiei, Tetranychus cinnabarinus, Tetranychuschus tetranychus kus
Tetranychus urticae. Tetranychus urticae.
Aus der Klasse der Nematoden beispielsweise Wurzelgallen- nematoden, z.B. Meloidogyne hapla, Meloidogyne incognita, From the class of nematodes, for example, root gall nematodes, e.g. Meloidogyne hapla, Meloidogyne incognita,
Meloidogyne javanica, Zysten bildende Nematoden, z.B. Globodera rostochiensis, Heterodera avenae, Heterodera glycinae, Heterodera schatii, Heterodera trifolii, Stock- und Blattälchen, z.B. Meloidogyne javanica, cyst-forming nematodes, e.g. Globodera rostochiensis, Heterodera avenae, Heterodera glycinae, Heterodera schatii, Heterodera trifolii, stick and leaf wholes, e.g.
Belonolaimus longicaudatus, Ditylenchus destructor, Ditylenchus dipsaci, Heliocotylenchus multicinctus, Longidorus elongatus, Radopholus similis, Rotylenchus robustus, Trichodorus primitivus, Tylenchorhynchus claytoni, Tylenchorhynchus dubius, Pratylenchus neglectus, Pratylenchus penetrans, Pratylenchus curvitatus, Pratylenchus goodeyi. Die Wirkstoffe können als solche, in Form ihrer Formulierungen oder den daraus bereiteten Anwendungsformen, z.B. in Form von direkt versprühbaren Lösungen, Pulvern, Suspensionen oder Belonolaimus longicaudatus, Ditylenchus destructor, Ditylenchus dipsaci, Heliocotylenchus multicinctus, Longidorus elongatus, Radopholus similis, Rotylenchus robustus, Trichodorus primitivus, Tylenchorhynchus claytoni, Tylenchorhynchususususususususususususususususususchusususususususchusatus, Pratchylenate, Prat. The active ingredients as such, in the form of their formulations or the use forms prepared therefrom, e.g. in the form of directly sprayable solutions, powders, suspensions or
Dispersionen, Emulsionen, öldispersionen, Pasten, Stäubemitteln, Streumitteln, Granulaten durch Versprühen, Vernebeln, Verstäuben, Verstreuen oder Gieβen angewendet werden. Die Anwendungsformen richten sich ganz nach den Verwendungszwecken; sie sollten in jedem Fall möglichst die feinste Verteilung der erfindungsgemäßen Wirkstoffe gewährleisten. Die Formulierungen werden in bekannter Weise hergestellt, z.B. durch Verstrecken des Wirkstoffs mit Lösungsmitteln und/oder Trägerstoffen, gewünschtenfalls unter Verwendung von Emulgiermitteln und Dispergiermitteln, wobei im Falle von Wasser als Verdünnungsmittel auch andere organische Lösungsmittel als Hilfslösungsmittel verwendet werden können. Als inerte Hilfsstoffe kommen dafür im wesentlichen in Betracht: Mineralölfraktionen von mittlerem bis hohem Siedepunkt wie Kerosin und Dieselöl, ferner Kohlenteeröle sowie öle pflanzlichen oder tierischen Ursprungs, Lösungsmittel wie Aromaten (z.B. Toluol, Xylol), chlorierte Aromaten (z.B. Chlorbenzole), Paraffine (z.B. Erdölfraktionen), Alkohole (z.B. Methanol, Ethanol, Butanol, Cyclohexanol), Ketone (z.B. Cyclohexanon, Isophoron), Amine (z.B. Dispersions, emulsions, oil dispersions, pastes, dusts, spreading agents, granules by spraying, atomizing, dusting, scattering or pouring can be used. The application forms depend entirely on the purposes; in any case, they should ensure the finest possible distribution of the active compounds according to the invention. The formulations are prepared in a known manner, for example by stretching the active ingredient with solvents and / or carriers, if desired using emulsifiers and dispersants, and in the case of water as a diluent, other organic solvents can also be used as auxiliary solvents. The following are essentially considered as inert auxiliaries: mineral oil fractions of medium to high boiling point such as kerosene and diesel oil, furthermore coal tar oils and oils of vegetable or animal origin, solvents such as aromatics (e.g. toluene, xylene), chlorinated aromatics (e.g. chlorobenzenes), paraffins (e.g. Petroleum fractions), alcohols (e.g. methanol, ethanol, butanol, cyclohexanol), ketones (e.g. cyclohexanone, isophorone), amines (e.g.
Ethanolamin, N,N-Dimethylformamid, N-Methylpyrrolidon) und  Ethanolamine, N, N-dimethylformamide, N-methylpyrrolidone) and
Wasser; Trägerstoffe wie natürliche Gesteinsmehle (z.B. Kaoline, Tonerden, Talkum, Kreide) und synthetische Gesteinsmehle (z.B. hochdisperse Kieselsäure, Silikate); Emulgiermittel wie nichtionogene und anionische Emulgatoren (z.B. Polyoxyethylen-Fettalkohol-Ether, Alkylsulfonate und Arylsulfonate) und Dispergiermittel wie Ligninsulfitablaugen und Methylcellulose.  Water; Carriers such as natural stone powder (e.g. kaolins, clays, talc, chalk) and synthetic stone powder (e.g. highly disperse silica, silicates); Emulsifiers such as nonionic and anionic emulsifiers (e.g. polyoxyethylene fatty alcohol ethers, alkyl sulfonates and aryl sulfonates) and dispersants such as lignin sulfite liquors and methyl cellulose.
Wäßrige Anwendungsformen können aus Emulsionskonzentraten, Dispersionen, Pasten, netzbaren Pulvern oder wasserdispergierbaren Granulaten durch Zusatz von Wasser bereitet werden. Zur Herstellung von Emulsionen, Pasten oder öldispersionen können die Aqueous use forms can be prepared from emulsion concentrates, dispersions, pastes, wettable powders or water-dispersible granules by adding water. For the production of emulsions, pastes or oil dispersions
Substrate als solche oder in einem öl oder Lösungsmittel gelöst, mittels Netz-, Haft-, Dispergier- oder Emulgiermittel in Wasser homogenisiert werden. Es können aber auch aus wirksamer Substanz, Netz-, Haft-, Dispergier- oder Emulgiermittel und eventuell Lösungsmittel oder öl bestehende Konzentrate hergestellt werden, die zur Verdünnung mit Wasser geeignet sind.  Substrates as such or dissolved in an oil or solvent can be homogenized in water by means of wetting agents, adhesives, dispersants or emulsifiers. However, concentrates consisting of active substance, wetting agent, adhesive, dispersant or emulsifier and possibly solvent or oil can also be prepared which are suitable for dilution with water.
Als oberflächenaktive Stoffe kommen die Alkali-, Erdalkali-, Ammoniumsalze von aromatischen Sulfonsauren, z.B. Lignin-, The alkali, alkaline earth, ammonium salts of aromatic sulfonic acids, e.g. Lignin-,
Phenol-, Naphthalin- und Dibutylnaphthal insulfonsäure, sowie von Fettsäuren, Alkyl- und Alkylarylsulfonaten, Alkyl-, Laurylether- und Fettalkoholsulfaten, sowie Salze sulfatierter Hexa-, Hepta- und Octadecanolen, sowie von Fettalkoholglykolether, Kondensationsprodukte von sulfoniertem Naphthalin und seiner Derivate mit Formaldehyd, Kondensationsprodukte des Naphthalins bzw. der Naphthalinsulfonsäuren mit Phenol und Formaldehyd, Polyoxyethylenoctylphenolether, ethoxyliertes Isooctyl-, Octyl- oder Nonylphenol, Alkylphenol-, Tributylphenylpolyglykolether, Alkylarylpolyetheralkohole, Isotridecylalkohol, Fettalkoholethylenoxid-Kondensate, ethoxyliertes Rizinusöl, Polyoxyethylenalkylether oder Polyoxypropylen, Laurylalkoholpolyglykoletheracetat, Sorbitester, Lignin-Sulfitablaugen oder Methylcellulose in Betracht. Pulver-, Streu- und Stäubemittel können durch Mischen oder gemeinsames Vermählen der wirksamen Substanzen mit einem festen Trägerstoff hergestellt werden. Phenolic, naphthalene and dibutylnaphthalene sulfonic acid, as well as of fatty acids, alkyl and alkylaryl sulfonates, alkyl, lauryl ether and fatty alcohol sulfates, as well as salts of sulfated hexa-, hepta- and octadecanols, and of fatty alcohol glycol ethers, condensation products of sulfonated naphthalene and its derivatives with formaldehyde , Condensation products of naphthalene or Naphthalenesulfonic acids with phenol and formaldehyde, polyoxyethylene octylphenol ether, ethoxylated isooctyl, octyl or nonylphenol, alkylphenol, tributylphenyl polyglycol ether, alkylaryl polyether alcohols, isotridecyl alcohol, fatty alcohol ethylene oxide condensates, ethoxylated castor oil or lauryl ether, alcoholoxyl ether polyalkylene glycol, ethoxylated alcohol oil, polyoxyethylene ethylenedilylalkylene glycol, ethoxylated alcohol oil, polyoxyethylene ethylene glycol ethylenedilylalkylene glycol, ethoxylated alcohol, polyoxyethylene ethylenedilyl, ethoxylated alcohol, polyoxyethylene ethylene glycol, ethoxylated alcohol, polyoxyethylene ethylenediole; Powders, materials for broadcasting and dusts can be prepared by mixing or grinding the active substances together with a solid carrier.
Granulate, z.B. Umhüllungs-, Imprägnierungs- und Homogengranulate können durch Bindung der Wirkstoffe an feste Trägerstoffe hergestellt werden. Feste Trägerstoffe sind Mineralerden wie Silicagel, Kieselsäuren, Kieselgele, Silikate, Talkum, Kaolin, Kalkstein, Kalk, Kreide, Bolus, Löβ, Ton, Dolomit, Diatomeenerde, Calcium- und Magnesiumsulfat, Magnesiumoxid, gemahlene Kunststoffe, Düngemittel, wie Ammoniumsulfat, Ammoniumphosphat, Ammoniumnitrat, Harnstoffe und pflanzliche Produkte, wie Granules, e.g. Coated, impregnated and homogeneous granules can be produced by binding the active ingredients to solid carriers. Solid carriers are mineral earths such as silica gel, silicas, silica gels, silicates, talc, kaolin, limestone, lime, chalk, bolus, loess, clay, dolomite, diatomaceous earth, calcium and magnesium sulfate, magnesium oxide, ground plastics, fertilizers such as ammonium sulfate, ammonium phosphate, Ammonium nitrate, ureas and herbal products, such as
Getreidemehl, Baumrinden-, Holz- und Nuβschalenmehl, Cellulosepulver oder andere feste Trägerstoffe. Die Konzentrationen der Wirkstoffe I, Ia und Ib in den anwendungsfertigen Zubereitungen können in weiten Bereichen variiert werden, etwa zwischen 0,0001 und 95 Gew.%. Für die Anwendung als Herbizide oder das Pflanzenwachstum regulierende Mittel empfehlen sich Konzentrationen zwischen 0,01 und 95 Gew.%, vorzugsweise zwischen 0,5 und 90 Gew.%, Wirkstoff. Für die Anwendung alsCereal flour, tree bark, wood and nutshell flour, cellulose powder or other solid carriers. The concentrations of the active ingredients I, Ia and Ib in the ready-to-use preparations can be varied within a wide range, for example between 0.0001 and 95% by weight. Concentrations between 0.01 and 95% by weight, preferably between 0.5 and 90% by weight, of active ingredient are recommended for use as herbicides or for regulating plant growth. For use as
Insektizide kommen Formulierungen mit 0,0001 bis 10 Gew.%, vorzugsweise 0,01 bis 1 Gew.% Wirkstoff, in Betracht. Die Wirkstoffe werden dabei in einer Reinheit von 90 % bis 100 %, vorzugsweise 95 % bis 100 % (nach NMR-Spektrum) eingesetzt. Insecticides are formulations with 0.0001 to 10% by weight, preferably 0.01 to 1% by weight, of active ingredient. The active ingredients are used in a purity of 90% to 100%, preferably 95% to 100% (according to the NMR spectrum).
Beispiele für solche Zubereitungen sind: Examples of such preparations are:
I. eine Lösung aus 90 Gew.-Teilen der Verbindung Nr. 1.1 und 10 Gew. -Teilen N-Methyl-α-pyrrolidon, die zur Anwendung in Form kleinster Tropfen geeignet ist; II. eine Mischung aus 20 Gew.-Teilen der Verbindung Nr. 1.2, 80 Gew.-Teilen Xyiol, 10 Gew.-Teilen des Anlagerungsproduktes von 8 bis 10 Mol Ethylenoxid anI. a solution of 90 parts by weight of compound no. 1.1 and 10 parts by weight of N-methyl-α-pyrrolidone, which is suitable for use in the form of tiny drops; II. A mixture of 20 parts by weight of compound no. 1.2, 80 parts by weight of xylene, 10 parts by weight of the adduct of 8 to 10 moles of ethylene oxide
1 Mol ölsäure-N-monoethanolamid, 5 Gew. Teilen Calciumsalz der Dodecylbenzolsulfonsäure, 5 Gew. -Teilen des1 mol of oleic acid-N-monoethanolamide, 5 parts by weight of calcium salt of dodecylbenzenesulfonic acid, 5 parts by weight of
Anlagerungsproduktes und 40 Mol Ethylenoxid an 1 Mol Ricinusöl. Durch feines Verteilen des Gemisches in 100 000 Gew.-Teilen Wasser erhält man eine Dispersion, die 0,02 Gew.-% des Wirkstoffs enthält. Addition product and 40 moles of ethylene oxide with 1 mole of castor oil. By finely distributing the mixture in 100,000 parts by weight of water, a dispersion is obtained which contains 0.02% by weight of the active ingredient.
III. eine wäβrige Dispersion aus 20 Gew.-Teilen der Verbindung Nr. 3.1, 40 Gew.-Teilen Cyclohexanon, 30 Gew.- Teilen isobutanol, 20 Gew.-Teilen des Anlagerungsproduktes von 40 mol Ethylenoxid an 1 mol Ricinusöl. Die Mischung dieser Dispersion mit 100 000 Gewichtsteilen Wasser enthält 0,02 Gew.-% des Wirkstoffes. III. an aqueous dispersion of 20 parts by weight of compound no. 3.1, 40 parts by weight of cyclohexanone, 30 parts by weight of isobutanol, 20 parts by weight of the adduct of 40 mol of ethylene oxide and 1 mol of castor oil. The mixture of this dispersion with 100,000 parts by weight of water contains 0.02% by weight of the active ingredient.
IV. eine wäβrige Dispersion aus 20 Gew.-Teilen der Verbindung Nr. 2.1, 25 Gew.-Teilen Cyclohexanol, 65 Gew.- Teilen einer Mineralölfraktion vom Siedepunkt 210 bisIV. An aqueous dispersion of 20 parts by weight of compound no. 2.1, 25 parts by weight of cyclohexanol, 65 parts by weight of a mineral oil fraction from the boiling point 210 to
280°C und 10 Gew.-Teilen des Anlagerungsproduktes von 40 mol Ethylenoxid an 1 mol Ricinusöl. Die Mischung dieser Dispersion mit 100 000 Gew. -Teilen Wasser enthält 0,02 % des Wirkstoffes; 280 ° C and 10 parts by weight of the adduct of 40 moles of ethylene oxide and 1 mole of castor oil. The mixture of this dispersion with 100,000 parts by weight of water contains 0.02% of the active ingredient;
V. eine in einer Hammermühle vermahlene Mischung aus V. a mixture ground in a hammer mill
80 Gew.-Teilen der Verbindung Nr. 3.1, 3 Gew. -Teilen des Natriumsalzes der Di isobutylnaphtalin-α-sulfon- säure, 10 Gew.-Teilen des Natriumsalzes einer Ligninsulfonsäure aus einer Sulfitablauge und 7 Gew.-Teilen pulverförmigem Kieselsäuregel. Durch feines Verteilen der Mischung in 20 000 Gew.-Teilen Wasser erhält man eine Spritzbrühe, die 0,1 Gew.-% des Wirkstoffs enthält; VI. eine innige Mischung aus 3 Gew.-Teilen der Verbindung  80 parts by weight of compound no. 3.1, 3 parts by weight of the sodium salt of diisobutylnaphtaline-α-sulfonic acid, 10 parts by weight of the sodium salt of a lignosulfonic acid from a sulfite waste liquor and 7 parts by weight of powdered silica gel. By finely distributing the mixture in 20,000 parts by weight of water, a spray liquor is obtained which contains 0.1% by weight of the active ingredient; VI. an intimate mixture of 3 parts by weight of the compound
Nr. 3.2 und 97 Gew.-Teilen feinteiligem Kaolin. Dieses Stäubemittel enthält 3 Gew.-% Wirkstoff; VII. eine innige Mischung aus 30 Gew. -Teilen der Verbindung Nr. 3.3, 92 Gew. -Teilen pul verförmigem Kieselsäuregel und 8 Gew. -Teilen Paraffinöl, das auf die Oberfläche dieses Kieselsäuregels gesprüht wurde. Diese Aufbereitung gibt dem Wirkstoff eine gute Haftfähigkeit; 3.2 and 97 parts by weight of finely divided kaolin. This dust contains 3% by weight of active ingredient; VII. An intimate mixture of 30 parts by weight of compound no. 3.3, 92 parts by weight of powdered silica gel and 8 parts by weight of paraffin oil which was sprayed onto the surface of this silica gel. This preparation gives the active ingredient good adhesion;
VIII. eine stabile wäβrige Dispersion aus 40 Gew. -Teilen der VIII. A stable aqueous dispersion of 40 parts by weight of
Verbindung Nr. 4.1, 10 Gew. -Teilen des Natriumsalzes eines Phenosulfonsäure-harnstoff-formaldehyd-Konden- sates, 2 Gew. -Teilen Kieselgel und 48 Gew.-Teilen Compound No. 4.1, 10 parts by weight of the sodium salt of a phenosulfonic acid-urea-formaldehyde condensate, 2 parts by weight of silica gel and 48 parts by weight
Wasser, die weiter verdünnt werden kann; Water that can be further diluted;
IX. eine stabile ölige Dispersion aus 20 Gew.-Teilen der IX. a stable oily dispersion of 20 parts by weight of the
Verbindung Nr. 1.1, 2 Gew. -Teilen des Calciumsalzes der Dodecylbenzolsulfonsäure, 8 Gew. -Teilen Fettalkohol- polyglykolether, 20 Gew. -Teilen des Natriumsalzes eines Phenolsul fonsäure-harnstoff-formaldehydKondensates und 68 Gew.-Teilen eines paraffinischen Mineralöls; X. eine in einer Hammermühle vermahlene Mischung aus  Compound No. 1.1, 2 parts by weight of the calcium salt of dodecylbenzenesulfonic acid, 8 parts by weight of fatty alcohol polyglycol ether, 20 parts by weight of the sodium salt of a phenolsulfonic acid-urea-formaldehyde condensate and 68 parts by weight of a paraffinic mineral oil; X. a mixture ground in a hammer mill
10 Gew. -Teilen der Verbindung Nr. 2.1, 4 Gew.-Teilen des Natriumsalzes der Diisobutylnaphthalin-α-sulfonsäure, 20 Gew. -Teilen des Natriumsalzes einer Ligninsulfonsäure aus einer Sulfitablauge, 38 Gew. -Teilen Kieselsäuregel und 38 Gew.-Teilen Kaolin. Durch feines 10 parts by weight of compound no. 2.1, 4 parts by weight of the sodium salt of diisobutylnaphthalene-α-sulfonic acid, 20 parts by weight of the sodium salt of a lignin sulfonic acid from a sulfite waste liquor, 38 parts by weight of silica gel and 38 parts by weight Kaolin. By fine
Verteilen der Mischung in 10 000 Gew. -Teilen Wasser erhält man eine Spritzbrühe, die 0,1 Gew.% des Wirkstoffs enthält. Die Applikation der Wirkstoffe bzw. der herbiziden und das Distributing the mixture in 10,000 parts by weight of water gives a spray liquor which contains 0.1% by weight of the active ingredient. The application of the active ingredients or the herbicides and that
Pflanzenwachstum regulierenden Mittel kann im Vorauflauf- oder im Nachauflaufverfahren erfolgen. Normalerweise werden die Pflanzen mit den Wirkstoffen besprüht oder bestäubt oder die Samen der Testpflanzen mit den Wirkstoffen behandelt. Sind die Wirkstoffe für gewisse Kulturpflanzen weniger verträglich, so können Ausbringungstechniken angewandt werden, bei welchen die herbiziden Mittel mit Hilfe der Spritzgeräte so gespritzt werden, daβ die Blätter der empfindlichen Kulturpflanzen nach Möglichkeit nicht getroffen werden, während die Wirkstoffe auf die Blätter darunter wachsender unerwünschter Pflanzen oder die unbedeckte Bodenfläche gelangen (post-directed, lay-by). Die Aufwandmengen an Wirkstoff betragen je nach Bekämpfungsziel, Jahreszeit, Zielpflanzen und Wachstumsstadium 0,001 bis 5,0, vorzugsweise 0,01 bis 2 kg/ha aktive Substanz (a.S.). Zur Verbreiterung des Wirkungsspektrums und zur Erzielung synergistischer Effekte können die substituierten 3-Phenylurazile I, Ia und Ib mit zahlreichen Vertretern anderer herbizider oder wachstumsregulierender Wirkstoffgruppen gemischt und gemeinsam ausgebracht werden. Beispielsweise kommen als Mischungspartner Diazine, 4H-3,1-Benzoxazinderi vate, Benzothiadiazinone, 2,6-Dinitroaniline, N-Phenylcarbamate, Thiolcarbamate, Halogencarbonsäuren, Triazine, Amide, Harnstoffe, Diphenylether, Triazinone, Uracile, Benzofuranderivate, Cyclohexan-1,3-dionderivate, die in 2-Stellung z.B. eine Carboxy- oder Carbimino-Gruppe tragen, Chinolincarbonsäurederivate, Imidazolinone, Sulfonamide, Plant growth regulators can be done pre-emergence or post-emergence. The plants are usually sprayed or dusted with the active compounds or the seeds of the test plants are treated with the active compounds. If the active ingredients are less compatible with certain crop plants, application techniques can be used in which the herbicidal compositions are sprayed with the aid of sprayers in such a way that the leaves of the sensitive crop plants are not hit wherever possible, while the active ingredients are applied to the leaves of unwanted plants growing below them or the uncovered floor area (post-directed, lay-by). The application rates of active ingredient are 0.001 to 5.0, preferably 0.01 to 2 kg / ha of active substance (as), depending on the control target, season, target plants and growth stage. To broaden the spectrum of activity and to achieve synergistic effects, the substituted 3-phenylurazils I, Ia and Ib can be mixed with numerous representatives of other herbicidal or growth-regulating active compound groups and applied together. For example, diazines, 4H-3,1-benzoxazine derivatives, benzothiadiazinones, 2,6-dinitroanilines, N-phenyl carbamates, thiol carbamates, halocarboxylic acids, triazines, amides, ureas, diphenyl ethers, triazinones, uraciles, benzofuran derivatives, cyclohexane-1,3 come as mixing partners -dione derivatives which carry, for example, a carboxy or carbimino group in the 2-position, quinolinecarboxylic acid derivatives, imidazolinones, sulfonamides,
Sulfonylharnstoffe, Aryloxy-, Heteroaryloxyphenoxypropionsäuren sowie deren Salze, Ester und Amide und andere in Betracht.  Sulfonylureas, aryloxy, heteroaryloxyphenoxypropionic acids and their salts, esters and amides and others into consideration.
Die substituierten 3-Phenylurazile I, Ia und Ib können auch gemeinsam mit anderen Pflanzenschutzmitteln wie Herbiziden,The substituted 3-phenylurazils I, Ia and Ib can also be used together with other crop protection agents such as herbicides,
Wachstumsregulatoren, Schädlingsbekämpfungsmittel, Fungiziden und Bakteriziden ausgebracht werden. Diese Mittel können zu den erfindungsgemäßen Mitteln im Gewichtsverhältnis 1:100 bis 100:1 zugemischt werden, gewünschtenfalls auch erst unmittelbar vor der Anwendung (Tankmix). Von Interesse ist ferner die Mischbarkeit mit Mineralsalzlösungen, welche zur Behebung von Ernährungs- und Spurenelementmängeln eingesetzt werden. Es können auch nicht- phytotoxische öle und ölkonzentrate zugesetzt werden. Herstellungsbeispiele Growth regulators, pesticides, fungicides and bactericides are applied. These agents can be added to the agents according to the invention in a weight ratio of 1: 100 to 100: 1, if desired also only immediately before use (tank mix). Also of interest is the miscibility with mineral salt solutions, which are used to remedy nutritional and trace element deficiencies. Non-phytotoxic oils and oil concentrates can also be added. Manufacturing examples
Beispiel 1 example 1
3-[4-Chlor-3-(ethoximinomethyl)-phenyl]-2,4-dioxo-6-trifluormethyl-1,2,3,4-tetrahydropyrimidin (Verb. 1.4) 3- [4-chloro-3- (ethoximinomethyl) phenyl] -2,4-dioxo-6-trifluoromethyl-1,2,3,4-tetrahydropyrimidine (Verb.1.4)
Zu einer Suspension von 18,2 g 80-proz. Natriumhydrid in 550 ml Dimethylformamid wurden bei 0-5°C 100,7 g 3-Amino-4,4,4-trifluor-crotonsäureethylester in 150 ml Dimethylformamid getropft und ein Stunde bei 0-5 °C nachgerührt. Anschließend wurden bei (-30)-(-35)°C 123,6 g 4-Chlor-3-ethoximinomethyl-phenyl isocyanat in 150 ml Tetrahydrofuran zugetropft und 20 h bei 25°C nachgerührt. Bei 0-5°C wurden 1,7 1 Wasser in das Reaktionsgemisch eingerührt und der ausgefallene Niederschlag entfernt. Das Filtrat wurde mit 60 ml 6N HCl auf pH5 eingestellt, der To a suspension of 18.2 g 80 percent. Sodium hydride in 550 ml of dimethylformamide, 100.7 g of 3-amino-4,4,4-trifluoro-crotonic acid ethyl ester in 150 ml of dimethylformamide were added dropwise at 0-5 ° C. and the mixture was subsequently stirred at 0-5 ° C. for one hour. 123.6 g of 4-chloro-3-ethoximinomethylphenyl isocyanate in 150 ml of tetrahydrofuran were then added dropwise at (-30) - (- 35) ° C. and the mixture was stirred at 25 ° C. for 20 h. At 0-5 ° C, 1.7 l of water were stirred into the reaction mixture and the precipitate which had separated out was removed. The filtrate was adjusted to pH 5 with 60 ml of 6N HCl
ausgefallene Niederschlag isoliert, mit Wasser und Petrolether gewaschen und getrocknet. precipitate isolated, washed with water and petroleum ether and dried.
Smp.: 219-220°C. M.p .: 219-220 ° C.
Beispiel 2 Example 2
3-[4-Chlor-3-(ethoximinomethyl)-phenyl]-2,4-dioxo-6-methyl-1,2,3, 4-tetrahydropyrimidin (Verb. 1.75) 3- [4-chloro-3- (ethoximinomethyl) phenyl] -2,4-dioxo-6-methyl-1,2,3,4-tetrahydropyrimidine (Verb. 1.75)
Zu einer Suspension von 0,24 g 80-proz. Natriumhydrid in 550 ml Dimethylformamid wurden bei Raumtemperatur 3 g N-(4-Chlor3-ethoximinomethyl-phenyl)-N'-(1-ethoxycarbonyl-propen-2-yl)-harnstoff in 20 ml Dimethylformamid getropft und 3 h bei Raumtemperatur nachgerührt. Bei 10-15°C wurden 100 ml Wasser zugesetzt, mit 10-proz. HCl auf pH 5 gestellt, 30 min. bei 10-15°C nachgerührt. Der ausgefallene Niederschlag wurde isoliert, mit Wasser gewaschen und getrocknet.  To a suspension of 0.24 g 80 percent. Sodium hydride in 550 ml of dimethylformamide, 3 g of N- (4-chloro-3-ethoximinomethyl-phenyl) -N '- (1-ethoxycarbonyl-propen-2-yl) urea in 20 ml of dimethylformamide were added dropwise at room temperature and the mixture was stirred at room temperature for 3 h. At 10-15 ° C 100 ml of water were added, with 10 percent. HCl adjusted to pH 5, 30 min. stirred at 10-15 ° C. The precipitate was isolated, washed with water and dried.
Smp: >280°C. Bei sp i el 3 MP:> 280 ° C. In game 3
3-[4-Chloro-3-(ethoximi nomethyl ) -phenyl ] -2,4-di oxo-1-methy1-6- -tri fl uoromethyl-1,2,3,4-tetrahydropyrimi d i n (Verb . 1 .5 ) 3- [4-Chloro-3- (ethoximi nomethyl) phenyl] -2,4-di oxo-1-methy1-6- -trifluoromethyl-1,2,3,4-tetrahydropyrimi din (Verb. 1. 5)
Zu einer Suspension von 137,5 g 3-(4-Chloro-3-ethoximinomethylphenyl)-2,4-dioxo-6-trifluormethyl-1,2,3,4-tetrahydropyrimidin und 57,8 g Kaliumcarbonat in 600 ml Dimethylformamid wurden 26,3 ml Methyl iodid in 100 ml Dimethylformamid innerhalb lh getropft, wobei die Temperatur auf 30°C stieg. Nach 20-stündigem Rühren wurden bei 5-10°C 700 ml Wasser zugetropft, der  To a suspension of 137.5 g of 3- (4-chloro-3-ethoximinomethylphenyl) -2,4-dioxo-6-trifluoromethyl-1,2,3,4-tetrahydropyrimidine and 57.8 g of potassium carbonate in 600 ml of dimethylformamide 26.3 ml of methyl iodide in 100 ml of dimethylformamide were added dropwise within 1 hour, the temperature rising to 30 ° C. After stirring for 20 hours, 700 ml of water were added dropwise at 5-10 ° C.
ausgefallene Niederschlag isoliert, mit Wasser und Petrolether gewaschen und getrocknet.  precipitate isolated, washed with water and petroleum ether and dried.
Smp.: 133-134°C.  M.p .: 133-134 ° C.
Beispiel 4 Example 4
3-(4-Chlor-3-formyl-phenyl)-2,4-dioxo-1-methyl-6-trifluormethyl-1,2,3,4-tetrahydropyrimidin (Verb. 1.1) 3- (4-chloro-3-formylphenyl) -2,4-dioxo-1-methyl-6-trifluoromethyl-1,2,3,4-tetrahydropyrimidine (Verb.1.1)
Zu einer Lösung von 1,9 g 3-(4-Chlor-3-(1,3-dioxolan-2-yl)- phenyl)-2,4-dioxo-1-methyl-6-trifluormethyl-1,2,3,4-tetrahydropyrimidin in 45 ml Eisessig wurden 5 ml Wasser gegeben. Nach 12 Std. Rühren bei ca. 20-25°C und noch 5 Std. bei 40-50°C rührte man 150 ml Wasser in die Mischung. Danach wurde der gebildete To a solution of 1.9 g of 3- (4-chloro-3- (1,3-dioxolan-2-yl) phenyl) -2,4-dioxo-1-methyl-6-trifluoromethyl-1,2, 3,4-tetrahydropyrimidine in 45 ml of glacial acetic acid was added to 5 ml of water. After stirring for 12 hours at approx. 20-25 ° C. and for a further 5 hours at 40-50 ° C., 150 ml of water were stirred into the mixture. Then the educated
Niederschlag abgetrennt, mit Wasser und Petrolether gewaschen und getrocknet. Precipitate separated, washed with water and petroleum ether and dried.
Smp.: 151-153°C. Beispiel 5 M.p .: 151-153 ° C. Example 5
3-[4-Chlor-6-fluor-3-formyl-phenyl]-2,4-dioxo-1-methy1-6-trifluormethyl-1,2,3,4-tetrahydropyrimidin (Verb. 1.67) 3- [4-chloro-6-fluoro-3-formylphenyl] -2,4-dioxo-1-methy1-6-trifluoromethyl-1,2,3,4-tetrahydropyrimidine (Verb. 1.67)
Zu einer Lösung von 58,5 g 3-[4-Chlor-6-fluor-3-(ethoximinomethyl)-phenyl]-2,4-dioxo-1-methyl-6-trifluormethyl- -1,2,3,4-tetrahydropyrimidin in 350 ml Eisessig wurden 50 ml konzentrierte Salzsäure und 50 ml 37-proz. Formaldehydlösung gegeben und 2h am Rückfluß gekocht. Nach dem Abkühlen wurde das Reaktionsgemisch eingeengt, der ölige Rückstand mit Wasser verrührt, der erhaltene kristalline Niederschlag isoliert, mit Wasser und Petrolether gewaschen und getrocknet.  To a solution of 58.5 g of 3- [4-chloro-6-fluoro-3- (ethoximinomethyl) phenyl] -2,4-dioxo-1-methyl-6-trifluoromethyl-1,2,3,4 -tetrahydropyrimidine in 350 ml of glacial acetic acid were 50 ml of concentrated hydrochloric acid and 50 ml of 37 percent. Given formaldehyde solution and refluxed for 2 hours. After cooling, the reaction mixture was concentrated, the oily residue was stirred with water, the crystalline precipitate obtained was isolated, washed with water and petroleum ether and dried.
Smp.: 172-174°C. M.p .: 172-174 ° C.
Beispiel 6 Example 6
3-[4-Chlor-3-(2-chlor-2-butoxycarbonyl-ethen-1-yl)-phenyl]-2,4- dioxo-1-methyl-6-trifluormethy1-1,2,3,4-tetrahydropyrimidin (Verb. 1.15) 3- [4-chloro-3- (2-chloro-2-butoxycarbonyl-ethen-1-yl) phenyl] -2,4-dioxo-1-methyl-6-trifluoromethyl 1-1,2,3,4- tetrahydropyrimidine (Verb 1.15)
Zu einer Lösung von 4, 4 g 3-[4-Chlor-3-(2-chlor-2-ethoxycarbonyl- ethen-1-yl)-phenyl]-2,4-dioxo-1-methyl-6-trifluormethyl-1,2,3,4- tetrahydropyrimidin in 50 ml n-Butanol wurden 50 ml einer  To a solution of 4.4 g of 3- [4-chloro-3- (2-chloro-2-ethoxycarbonylethen-1-yl) phenyl] -2,4-dioxo-1-methyl-6-trifluoromethyl- 1,2,3,4-tetrahydropyrimidine in 50 ml of n-butanol was 50 ml
Natrium-n-butanolat-Lösung in n-Butanol (hergestellt aus 0, 3 g 80-proz. Natriumhydrid und 50 ml n-Butanol) gegeben und 5 h bei Raumtemperatur nachgerührt. Dann wurde bei 0-5°C mit 10-proz. Salzsäure neutralisiert und die erhaltene Lösung bei 0-5°C in 100 ml Wasser gerührt. Die wäβrige Phase wurde mit 100 ml Toluol extrahiert, die vereinigten organischen Phasen dreimal mit je 50 ml Wasser gewaschen, über Natriumsulfat getrocknet und eingeengt. Das erhaltene öl wurde an Kieselgel chromatographiert (Dichlormethan), das daraus erhaltene öl mit Petrolether verrührt. Der erhaltene Feststoff wurde abfiltriert, mit Sodium n-butanolate solution in n-butanol (prepared from 0.3 g of 80% sodium hydride and 50 ml of n-butanol) and stirred for 5 hours at room temperature. Then was at 0-5 ° C with 10 percent. Hydrochloric acid neutralized and the solution obtained at 0-5 ° C in 100 ml of water stirred. The aqueous phase was extracted with 100 ml of toluene, the combined organic phases were washed three times with 50 ml of water each time, dried over sodium sulfate and concentrated. The oil obtained was chromatographed on silica gel (dichloromethane), and the oil obtained was stirred with petroleum ether. The solid obtained was filtered off using
Petrolether nachgewaschen und getrocknet.  Washed and dried petroleum ether.
Smp.: 109-10°C. Beispiel 7  M.p .: 109-10 ° C. Example 7
3-[4-Chlor-3-(4-chlor-3-oxo-but-1-enyl)-phenyl]-2,4-dioxo-1- methyl-6-trifluormethyl-1,2,3,4-tetrahydropyrimidin (Verb. 1.29). 3- [4-chloro-3- (4-chloro-3-oxo-but-1-enyl) phenyl] -2,4-dioxo-1-methyl-6-trifluoromethyl-1,2,3,4- tetrahydropyrimidine (Verb. 1.29).
Zu einer Lösung von 3,3 g 3-[4-Chlor-3-formyl-phenyl]-2,4-dioxo-1-methyl-6-trifluormethyl-1,2,3,4-tetrahydropyrimidin in 100 ml Methanol wurden 4, 6 g Chloracetyl-methylen-triphenylphosphoran gegeben und 10 h bei Raumtemperatur nachgerührt. Der ausgefallene Niederschlag wurde isoliert, mit Petrolether gewaschen und getrocknet. To a solution of 3.3 g of 3- [4-chloro-3-formylphenyl] -2,4-dioxo-1-methyl-6-trifluoromethyl-1,2,3,4-tetrahydropyrimidine in 100 ml of methanol 4, 6 g of chloroacetyl-methylene-triphenylphosphorane added and stirred for 10 h at room temperature. The precipitate was isolated, washed with petroleum ether and dried.
Smp.: 188-189°C.  M.p .: 188-189 ° C.
Beispiel 8 3-[4-Ch1or-3-(2-cyano-etheny l)-phenyl]-2,4-dioxo-1-methyl-6-trifluormethyl-1,2,3,4-tetrahydropyrimidin (Verb. 1.34) Example 8 3- [4-Chloro-3- (2-cyano-ethenyl) phenyl] -2,4-dioxo-1-methyl-6-trifluoromethyl-1,2,3,4-tetrahydropyrimidine (comp. 1.34 )
Zu einer Suspension von 1,8 g Diethyl-cyanomethylphosphonat und 1,5 g Kaliumcarbonat in 120 ml Dimethylformamid wurden 3,3 g 3-(4-Chlor-3-formyl-phenyl)-2,4-dioxo-1-methyl-6-trifluormethyl-1,2,3,4-tetrahydropyrimidin in 30 ml Dimethylformamid getropft und 20 h bei Raumtemperatur nachgerührt. Dann wurden 150 ml Wasser zugegeben, der ausgefallene Niederschlag isoliert, mit Wasser und Petrolether gewaschen und getrocknet. 3.3 g of 3- (4-chloro-3-formylphenyl) -2,4-dioxo-1-methyl- were added to a suspension of 1.8 g of diethyl cyanomethylphosphonate and 1.5 g of potassium carbonate in 120 ml of dimethylformamide. 6-trifluoromethyl-1,2,3,4-tetrahydropyrimidine was added dropwise in 30 ml of dimethylformamide and the mixture was stirred at room temperature for 20 h. Then 150 ml of water were added, the precipitate was isolated, washed with water and petroleum ether and dried.
Smp.: 263-265°C. Beispiel 9 M.p .: 263-265 ° C. Example 9
3-[4-Chlor-3-(2-cyano-2-methoxycarbonyl-ethenyl)-phenyl]-2,4-dioxo-1-methyl-6-trifluormethy1-1,2,3,4-tetrahydropyrimidin (Verb. 1.22) 3- [4-Chloro-3- (2-cyano-2-methoxycarbonylethenyl) phenyl] -2,4-dioxo-1-methyl-6-trifluoromethyl 1-1,2,3,4-tetrahydropyrimidine (Verb. 1.22)
Zu einer Lösung von 3,3 g 3-( 4-Ch l or-3-formyl -phenyl ) -2,4-d i oxo- -1-methyl -6-tr i fl uormethy l -1,2,3,4-tetrahydropyrimidin in 100 ml Tetrahydrofuran wurden 0,97 ml Cyanessigsäuremethylester und 0,3 ml Piperidin gegeben. Nach 5 h Rühren bei Rückflußtemperatur wurden nochmals 0,97 ml Cyanessigsäuremethylester zugegeben und nochmals 5 h am Rückfluß gekocht. Das Reaktionsgemisch wurde eingeengt, das erhaltene öl wurde chromatographiert (Dichlormethan). Der erhaltene Feststoff wurde mit Diisopropylether verrührt, isoliert, mit Petrolether gewaschen und getrocknet. Smp.: 187-188°C.  To a solution of 3.3 g of 3- (4-chloro-3-formylphenyl) -2,4-di oxo- -1-methyl -6-trifluoromethyl (-1,2,3) 4-tetrahydropyrimidine in 100 ml of tetrahydrofuran were added 0.97 ml of methyl cyanoacetate and 0.3 ml of piperidine. After stirring for 5 hours at reflux temperature, a further 0.97 ml of methyl cyanoacetate were added and the mixture was boiled under reflux for a further 5 hours. The reaction mixture was concentrated, the oil obtained was chromatographed (dichloromethane). The solid obtained was stirred with diisopropyl ether, isolated, washed with petroleum ether and dried. M.p .: 187-188 ° C.
Beispiel 10 Example 10
5-Chlor-3-[4-chlor-(2-chlor-2-ethoxycarbonyl-ethenyl)-phenyl]--2,4-dioxo-1-methyl-6-trifluormethyl-1,2,3,4-tetrahydropyrimidin (Verb. 1.42) 5-chloro-3- [4-chloro (2-chloro-2-ethoxycarbonylethenyl) phenyl] -2,4-dioxo-1-methyl-6-trifluoromethyl-1,2,3,4-tetrahydropyrimidine (Verb 1.42)
Zu einer Lösung von 4,4 g 3-[4-Chlor-3-(2-chlor-2-ethoxycarbonylethenyl)-phenyl]-2,4-dioxo-1-methyl-6-trifluormethyl-1,2,3,4- tetrahydropyrimidin in 50 mlEisessig wurden 1,5 g Sulfurylchlorid getropft. Es wurde 20 h bei Raumtemperatur, 12 h bei Rückfluβ nachgerührt, wobei nochmals 2,6 ml Sulfurylchlorid in zwei Portionen zugegeben wurde. Das Reaktionsgemisch wurde eingeengt, mit Wasser verrührt, der Niederschlag isoliert, mit Wasser und Petrolether gewaschen und getrocknet.  To a solution of 4.4 g of 3- [4-chloro-3- (2-chloro-2-ethoxycarbonylethenyl) phenyl] -2,4-dioxo-1-methyl-6-trifluoromethyl-1,2,3, 4-tetrahydropyrimidine in 50 ml of glacial acetic acid, 1.5 g of sulfuryl chloride were added dropwise. The mixture was stirred for 20 h at room temperature and 12 h at reflux, with another 2.6 ml of sulfuryl chloride being added in two portions. The reaction mixture was concentrated, stirred with water, the precipitate isolated, washed with water and petroleum ether and dried.
Smp.: 160-164°C.  M.p .: 160-164 ° C.
Beispiel 11 Example 11
3-[4-Chlor-3-(2-(2,2,2-trifluorethoxycarbonyl)-ethenyl)- -phenyl]-2,4-dioxo-1-methyl-6-trifluormethyl-1,2,3,4-tetrahydropyrimi d i n (Verb . 1 .85) 3- [4-chloro-3- (2- (2,2,2-trifluoroethoxycarbonyl) ethenyl) phenyl] -2,4-dioxo-1-methyl-6-trifluoromethyl-1,2,3,4 -tetrahydropyrimi din (Verb. 1.85)
Eine Suspension von 5,0 g 3-[4-Chlor-3-iod-phenyl]-2,4-dioxo- -1-methyl-6-trifluormethyl-1,2,3,4-tetrahydropyrimidin, 2, 0 g 2,2,2-Trifluorethylacrylat, 0,5 mg Palladiumacetat, 1,1 g  A suspension of 5.0 g of 3- [4-chloro-3-iodophenyl] -2,4-dioxo-1-methyl-6-trifluoromethyl-1,2,3,4-tetrahydropyrimidine, 2.0 g 2,2,2-trifluoroethyl acrylate, 0.5 mg palladium acetate, 1.1 g
Natriumacetat in 50 ml Dimethylformamid wurde 4 h bei 120°C gerührt, dann wurde nochmals Palladiumacetat und 2, 2, 2-Trifluormethylacrylat zugegeben und weiter 2 h bei 120°C nachgerührt. Das erkaltete Reaktionsgemisch wurde in 200 ml Wasser gegeben, der Niederschlag isoliert, mit Petrolether gewaschen und im Sodium acetate in 50 ml of dimethylformamide was stirred for 4 hours at 120 ° C., then again palladium acetate and 2,2,2-trifluoromethyl acrylate were added and stirring was continued at 120 ° C. for 2 hours. The cooled reaction mixture was poured into 200 ml of water, the precipitate was isolated, washed with petroleum ether and in
Hochvakuum getrocknet. High vacuum dried.
Smp.: 170-172°C. Beispiel 12 M.p .: 170-172 ° C. Example 12
3-[4-Chlor-3-(2-chlor-2-methoxycarbonyl-ethyl]-pheny1-2,4-dioxo-1-methyl-6-trifluormethy1-1,2,3,4-tetrahydropyrimidin (Verb. 1.86) 3- [4-Chloro-3- (2-chloro-2-methoxycarbonyl-ethyl] -pheny1-2,4-dioxo-1-methyl-6-trifluoromethy1-1,2,3,4-tetrahydropyrimidine (comp. 1.86 )
Es wurden 5,4 g tert.-ButyInitrit in 200 ml Acetonitril bei 0°C vorgelegt. Nacheinander gab man 30,1 g Acrylsäuremethy lester und 5, 9 g CuCl2 zu. Dann wurde eine Lösung von 11,2 g 3-[3-Amino- -4-chlorphenyl]-2,4-dioxo-1-methyl-6-trifluormethy1-1,2,3,4- -tetrahydropyrimidin in 100 ml Acetonitril langsam zugetropft und die Mischung über Nacht bei 25°C gerührt. Zur Aufarbeitung wurde das Lösungsmittel bei vermindertem Druck abgezogen und der Rückstand an Kieselgel (Cyclohexan/Essigester 8:1) chromatographiert. Man erhielt die Titel Verbindung als öl. 5.4 g of tert-butynitrite in 200 ml of acetonitrile were initially introduced at 0.degree. 30.1 g of methyl acrylate and 5.9 g of CuCl 2 were added in succession. Then a solution of 11.2 g of 3- [3-amino--4-chlorophenyl] -2,4-dioxo-1-methyl-6-trifluoromethyl 1-1,2,3,4- -tetrahydropyrimidine in 100 ml of acetonitrile slowly added dropwise and the mixture was stirred at 25 ° C. overnight. For working up, the solvent was removed under reduced pressure and the residue was chromatographed on silica gel (cyclohexane / ethyl acetate 8: 1). The title compound was obtained as an oil.
Beispiel 13 Example 13
3-[4-Chlor-3-(1,3-dioxan-2-yl)-phenyl]-2,4-dioxo-1-methy1-6-trifluormethyl-1,2,3,4-tetrahydropyrimidin (Verb. 2.1) 3- [4-chloro-3- (1,3-dioxan-2-yl) phenyl] -2,4-dioxo-1-methy1-6-trifluoromethyl-1,2,3,4-tetrahydropyrimidine (comp. 2.1)
Eine Lösung von 3, 5 g 3-[4-Chlor-3-formyl-phenyl]-2,4-dioxo-1- -methyl-6-trifluormethyl-1,2,3,4-tetrahydropyrimidin, 0,8 g 1,3-Propandiol, 0, 2 g p-Toluolsulfonsäure in 100 ml wasserfreiem Dichlormethan wurde 5 h am Wasserabscheider gekocht. Die Lösung wurde mit 10-proz. Natriumhydrogencarbonatlösung und Wasser gewaschen, über Natriumsulfat getrocknet und eingeengt. Der Rückstand wurde an Kieselgel (Cyclohexan/Essigester 7:3) A solution of 3.5 g of 3- [4-chloro-3-formylphenyl] -2,4-dioxo-1- methyl-6-trifluoromethyl-1,2,3,4-tetrahydropyrimidine, 0.8 g 1,3-propanediol, 0.2 g of p-toluenesulfonic acid in 100 ml of anhydrous dichloromethane was boiled for 5 hours on a water separator. The solution was with 10 percent. Sodium bicarbonate solution and water washed, dried over sodium sulfate and concentrated. The residue was on silica gel (cyclohexane / ethyl acetate 7: 3)
Chromatographiert.  Chromatographed.
Smp.: 87-92°C.  M.p .: 87-92 ° C.
Beispiel 14 Example 14
3-[4-Chlor-3-dimethoxymethy l-phenyl]-2,4-dioxo-1-methyl-6-tri- fluormethyl-1,2,3,4-tetrahydropyrimidin (Verb. 2.22) 3- [4-chloro-3-dimethoxymethyl l-phenyl] -2,4-dioxo-1-methyl-6-trifluoromethyl-1,2,3,4-tetrahydropyrimidine (comp. 2.22)
Zu einer gut gerührten Suspension von 136 g Montmorillonit-K10 in 700 ml wasserfreiem Toluol gab man 170 ml Trimethylorthoformiat und rührte 30 Minuten nach. Dann wurden 68,0 g 3-(4-Chlor- 3-formyl-phenyl)-2,4-dioxo-1-methyl-6-trifluormethyl-1,2,3,4- -tetrahydropyrimidin unter Eiskühlung zugetropft und der Ansatz über Nacht bei 25°C gerührt. Der Montmorollonit-K10 wurde abfiltriert und gut mit Toluol gewaschen. Von den vereinigten Filtraten wurde das Lösungsmittel, überschüssiger Orthoester und Ameisensäuremethylester bei vermindertem Druck abdestilliert. Das zurückbleibende öl wurde mit Petrolether zur Kristallisation gebracht.  170 ml of trimethyl orthoformate were added to a well-stirred suspension of 136 g of montmorillonite K10 in 700 ml of anhydrous toluene, and the mixture was stirred for 30 minutes. Then 68.0 g of 3- (4-chloro-3-formylphenyl) -2,4-dioxo-1-methyl-6-trifluoromethyl-1,2,3,4- -tetrahydropyrimidine were added dropwise with ice cooling and the mixture stirred overnight at 25 ° C. The montmorollonite-K10 was filtered off and washed well with toluene. The solvent, excess orthoester and methyl formate were distilled off from the combined filtrates under reduced pressure. The remaining oil was crystallized with petroleum ether.
Smp.: 92-94°C. M.p .: 92-94 ° C.
Beispiel 15 Example 15
3-[4-Chlor-3-(4,5-dimethyl-1,3-dioxolan-2-yl)-phenyl]-2,4-dioxo-1-methyl-6-trifluormethyl-1,2,3,4-tetrahydropyrimidin 3- [4-chloro-3- (4,5-dimethyl-1,3-dioxolan-2-yl) phenyl] -2,4-dioxo-1-methyl-6-trifluoromethyl-1,2,3, 4-tetrahydropyrimidine
(Verb. 2.17) (Verb 2.17)
30 g 3-(4-Chlor-3-dimethoxymethyl-phenyl)-2,4-dioxo-1-methyl- -6-trifluormethyl-1,2,3,4-tetrahydropyrimidin, 2,1 g 2,3-Dihydroxybutan und 0, 3 g p-Toluolsulfonsäure wurden in 100 ml wasserfreiem Toluol gelöst und unter Wasserausschluβ und Rühren 7 h unter Rückfluβ gekocht. Zur Aufarbeitung wurde nacheinander mit Wasser und 10 %iger NaHCO3-Lösung gewaschen, über Na2SO4 getrocknet und eingedampft. 30 g of 3- (4-chloro-3-dimethoxymethyl-phenyl) -2,4-dioxo-1-methyl-6-trifluoromethyl-1,2,3,4-tetrahydropyrimidine, 2.1 g of 2,3-dihydroxybutane and 0.3 g of p-toluenesulfonic acid were dissolved in 100 ml of anhydrous toluene and refluxed for 7 hours with the exclusion of water and stirring. For working up, the mixture was washed successively with water and 10% NaHCO 3 solution, dried over Na 2 SO 4 and evaporated.
Smp.: 149-151°C. Beispiel 16 M.p .: 149-151 ° C. Example 16
3-[4-Chlor-3-(1,3-oxothiolan-2-yl)-phenyl]-2,4-dioxo-1-methyl- -6-trifluormethyl-1,2,3,4-tetrahydropyrimidin (Verb. 2.32) 3- [4-chloro-3- (1,3-oxothiolan-2-yl) phenyl] -2,4-dioxo-1-methyl--6-trifluoromethyl-1,2,3,4-tetrahydropyrimidine (comp 2.32)
Eine Mischung von 3,0 g 3-(4-Chlor-3-formyl-phenyl)-2,4-dioxo- -1-methyl-6-trifluormethyl-1,2,3,4-tetrahydropyrimidin, 0,8 g 2-Mercaptoethanol, 0,12 g Tellurtetrachlorid in 100 ml A mixture of 3.0 g of 3- (4-chloro-3-formylphenyl) -2,4-dioxo- -1-methyl-6-trifluoromethyl-1,2,3,4-tetrahydropyrimidine, 0.8 g 2-mercaptoethanol, 0.12 g tellurium tetrachloride in 100 ml
1,2-Dichlorethan wurde 16 h bei Raumtemperatur gerührt. Es wurden 0,2 g Natriumhydrogencarbonat zugegeben, gut durchgerührt und abfiltriert. Der Niederschlag wurde mit Dichlormethan gewaschen, die vereinigten organischen Filtrate über Natriumsulfat 1,2-dichloroethane was stirred at room temperature for 16 h. 0.2 g of sodium hydrogen carbonate was added, the mixture was stirred well and filtered off. The precipitate was washed with dichloromethane, the combined organic filtrates over sodium sulfate
getrocknet und eingeengt. Der Rückstand wurde chromatographiert (Diethylether), in Toluol/Petrolether verrührt. Der erhaltene Kristalline Niederschlag wurde mit Petrolether gewaschen und getrocknet. dried and concentrated. The residue was chromatographed (diethyl ether), stirred in toluene / petroleum ether. The crystalline precipitate obtained was washed with petroleum ether and dried.
Smp.: 168-170°C. Bei sp i el 17 M.p .: 168-170 ° C. In game 17
3-[4-Chlor-3- (2-carboxy-2-chlor-ethenyl ) -phenyl] -2,4-dioxo-6-tri fluormethyl -1,2,3,4-tetrahydropyrimi d i n ( Verb . 1 .41 ) 3- [4-chloro-3- (2-carboxy-2-chloro-ethenyl) phenyl] -2,4-dioxo-6-tri fluoromethyl-1,2,3,4-tetrahydropyrimi din (Verb. 1. 41)
In einer Suspension von 0,8 g Natriumhydroxid in 100 ml Ethanol wurden 4, 4 g 3-[4-Chlor-3-(2-chlor-2-ethoxycarbonylethenyl)-phenyl]-2, 4-dioxo-6-trifluormethyl-1,2,3,4-tetrahydropyrimidin gegeben und 20 h bei Raumtemperatur nachgerührt. Das Reaktionsgemisch wurde eingeengt, der Rückstand in Wasser aufgenommen und mit 10-proz. HCl auf pH3 gestellt. Der  4.4 g of 3- [4-chloro-3- (2-chloro-2-ethoxycarbonylethenyl) phenyl] -2, 4-dioxo-6-trifluoromethyl were dissolved in a suspension of 0.8 g of sodium hydroxide in 100 ml of ethanol. 1,2,3,4-tetrahydropyrimidine and stirred for 20 h at room temperature. The reaction mixture was concentrated, the residue was taken up in water and with 10 percent. HCl adjusted to pH3. The
ausgefallene Niederschlag wurde isoliert, mit Wasser und  precipitate was isolated, with water and
Petrolether gewaschen und im Vakuum getrocknet.  Washed petroleum ether and dried in vacuo.
Smp.: >250°C.  M.p .:> 250 ° C.
Beispiel 18 Example 18
3-[4-Chlor-3-cyanomethoximinomethyl-phenyl]-2,4-dioxo-1-methyl-6-trifluormethyl-1,2,3,4-tetrahydropyrimidin 3- [4-Chloro-3-cyanomethoximinomethylphenyl] -2,4-dioxo-1-methyl-6-trifluoromethyl-1,2,3,4-tetrahydropyrimidine
(verb. 1.53)  (verb.1.53)
Zu einer Suspension von 3,3 g 3-(4-Chlor-3-formyl-phenyl)-2,4- dioxo-1-methyl-6-trifluormethyl-1,2,3,4-tetrahydropyrimidin und 1,3 g Natriumcarbonat in 150 ml Toluol wurden 1,3 g O-Cyanomethylhydroxylamin-hydrochlorid gegeben und 20 h nachgerührt. Das Reaktionsgemisch wurde dreimal mit je 50 ml Wasser gewaschen. über Natriumsulfat getrocknet und eingeengt. Der feste Rückstand wurde mit Petrolether verrührt, isoliert, mit Petrolether gewaschen und getrocknet. To a suspension of 3.3 g of 3- (4-chloro-3-formylphenyl) -2,4-dioxo-1-methyl-6-trifluoromethyl-1,2,3,4-tetrahydropyrimidine and 1.3 g Sodium carbonate in 150 ml of toluene was added 1.3 g of O-cyanomethylhydroxylamine hydrochloride and stirred for 20 h. The reaction mixture was washed three times with 50 ml of water. dried over sodium sulfate and concentrated. The solid residue was stirred with petroleum ether, isolated, washed with petroleum ether and dried.
Smp.: 171-174°C. M.p .: 171-174 ° C.
Beispiel 19 Example 19
3-[4-Chlor-3-(2-chlor-2-methoxycarbonyl-ethenyl ) -phenyl ] -2-methoxy-4-oxo-6-tr i fl uormethyl-3,4-d i hydropyrimi di n (Verb . 3. 1 ) 3- [4-chloro-3- (2-chloro-2-methoxycarbonylethenyl) phenyl] -2-methoxy-4-oxo-6-trifluoromethyl-3,4-di hydropyrimi di n (verb. 3. 1)
Zu einer Lösung von 2,2 g 2-Chlor-3-[4-chlor-3-(2-chlorethoxycarbonyl-ethenyl)-phenyl]-4-oxo-6-trifluormethyl-3,4-dihydropyrimidin in 40 ml Methanol wurden 0, 9 g Natriummethanolatlösung (30-proz. in Methanol) in 10 ml Methanol getropft und 2 h bei Raumtemperatur nachgerührt. Der Niederschlag wurde isoliert, mit Wasser und Petrolether gewaschen und getrocknet.  To a solution of 2.2 g of 2-chloro-3- [4-chloro-3- (2-chloroethoxycarbonylethenyl) phenyl] -4-oxo-6-trifluoromethyl-3,4-dihydropyrimidine in 40 ml of methanol 0.9 g of sodium methoxide solution (30% in methanol) was added dropwise to 10 ml of methanol and the mixture was stirred at room temperature for 2 h. The precipitate was isolated, washed with water and petroleum ether and dried.
Smp.: 151-52°C. M.p .: 151-52 ° C.
Beispiel 20 Example 20
3-[4-Chlor-3-(2-chlor-2-ethoxycarbonyl-ethenyl)-phenyl]-4-oxo-2- -thioxo-1,2,3,4-tetrahydro-thieno[3,4-d]-pyrimidin (Verb. 1.90) 3- [4-chloro-3- (2-chloro-2-ethoxycarbonyl-ethenyl) phenyl] -4-oxo-2- -thioxo-1,2,3,4-tetrahydro-thieno [3,4-d ] -pyrimidine (Verb. 1.90)
Zu einer Suspension von 0,11 g Natriumhydrid (80-proz.) in 50 ml Dimethylformamid wurden bei Raumtemperatur 1,8 g N-[4-Chlor- -3-(2-chlor-2-ethoxycarbonyl-ethenyl)-phenyl]-N'-(4-methoxy- carbonylthien-3-yl)-harnstoff in 10 ml Dimethylformamid gegeben und 3 h bei Raumtemperatur und 8 h bei 50°C nachgerührt. Das Reaktionsgemisch wurde auf 10-15°C abgekühlt, mit 100 ml Wasser versetzt, mit 10%iger Salzsäure neutralisiert und 1 h nachgerührt. Der erhaltene Niederschlag wurde isoliert, in Dichlormethan gelöst. Die erhaltene Lösung zweimal mit Wasser gewaschen, über Natriumsulfat getrocknet und eingeengt. Der Rückstand wurde mit Diisopropylether verrührt, isoliert und getrocknet. 1.8 g of N- [4-chloro--3- (2-chloro-2-ethoxycarbonyl-ethenyl) phenyl] were added to a suspension of 0.11 g of sodium hydride (80%) in 50 ml of dimethylformamide at room temperature. -N '- (4-methoxycarbonylthien-3-yl) urea in 10 ml of dimethylformamide and stirred for 3 h at room temperature and 8 h at 50 ° C. The reaction mixture was cooled to 10-15 ° C, mixed with 100 ml of water, neutralized with 10% hydrochloric acid and stirred for 1 h. The precipitate obtained was isolated and dissolved in dichloromethane. The solution obtained was washed twice with water, dried over sodium sulfate and concentrated. The residue was stirred with diisopropyl ether, isolated and dried.
Smp.: 278-280°C. Beispiel 21  M.p .: 278-280 ° C. Example 21
3-(4-Chlor-3-ethoxycarbonyl hydrazonomethyl-phenyl)-2,4-dioxo-1-methyl-6-trifluormethyl-1,2,3,4-tetrahydropyrimidin 3- (4-chloro-3-ethoxycarbonyl hydrazonomethyl-phenyl) -2,4-dioxo-1-methyl-6-trifluoromethyl-1,2,3,4-tetrahydropyrimidine
(Verb. 1.91)  (Verb 1.91)
Zu einer Lösung von 3,3 g 3-[4-Chlor-3-formyl-phenyl]-2,4- -dioxo-1-methyl-6-trifluormethyl-1,2,3,4-tetrahydropyrimidin und 0,1 g p-Toluolsulfonsäure in 150 ml Toluol wurden 1,0 g Hydrazincarbonsäureethylester gegeben. Nach 2 h wurde einmal mit Wasser gewaschen, die organische Phase über Natriumsulfat getrocknet, eingeengt, mit Petrolether verrührt. Der Niederschlag wurde isoliert, mit Petrolether gewaschen und getrocknet.  To a solution of 3.3 g of 3- [4-chloro-3-formylphenyl] -2,4- -dioxo-1-methyl-6-trifluoromethyl-1,2,3,4-tetrahydropyrimidine and 0.1 g of p-toluenesulfonic acid in 150 ml of toluene was added to 1.0 g of ethyl hydrazinecarboxylate. After 2 h, the mixture was washed once with water, the organic phase was dried over sodium sulfate, concentrated, and stirred with petroleum ether. The precipitate was isolated, washed with petroleum ether and dried.
Smp.: 111-116°C. Beispiel 22 M.p .: 111-116 ° C. Example 22
3-[4-Chlor-3-(2-carboxy-2-chlor-ethenyl)-phenyl]-2,4-dioxo-1- methyl-6-trifluormethyl-1,2,3,4-tetrahydropyrimidin (Verb. 1.92) 3- [4-chloro-3- (2-carboxy-2-chloroethenyl) phenyl] -2,4-dioxo-1-methyl-6-trifluoromethyl-1,2,3,4-tetrahydropyrimidine (comp. 1.92)
Zu einer Lösung von 4, 7 g 3-[4-Chlor-3-(2-tert.-butoxycarbonyl- -2-chlor-ethenyl-phenyl]-2,4-dioxo-1-methy1-6-trifluor-methyl- 1,2,3,4-tetrahydropyrimidin in 25 ml Dichlormethan wurden bei 25°C 25 ml Trifluoressigsäure gegeben und es wurde 2 h nachgerührt. Das Reaktionsgemisch wurde eingeengt, der ölige Rückstand mit Wasser verrührt, der Niederschlag isoliert, mit Wasser und Petrolether gewaschen und getrocknet. To a solution of 4.7 g of 3- [4-chloro-3- (2-tert-butoxycarbonyl--2-chloro-ethenyl-phenyl] -2,4-dioxo-1-methyl-6-trifluoromethyl - 1,2,3,4-tetrahydropyrimidine in 25 ml dichloromethane was added 25 ml trifluoroacetic acid at 25 ° C. and the mixture was stirred for 2 h, the reaction mixture was concentrated, the oily residue was stirred with water, the precipitate was isolated, with water and petroleum ether washed and dried.
Smp.: 216-217°C. Beispiel 23 M.p .: 216-217 ° C. Example 23
3-[4-Chlor-3-ethoximinomethyl-phenyl]-1-methyl-2-oxo-4-thioxo- -6-trifluormethyl-1,2,3,4-tetrahydropyrimidin (Verb. 4.1) 3- [4-chloro-3-ethoximinomethyl-phenyl] -1-methyl-2-oxo-4-thioxo- -6-trifluoromethyl-1,2,3,4-tetrahydropyrimidine (compound 4.1)
Zu einer Lösung von 3,8 g 3-[4-Chlor-3-ethoximinomethylphenyl]-2,4-dioxo-1-methyl-6-trifluormethyl-1,2,3,4-tetrahydropyrimidin in 100 ml Toluol wurden 2,4 g 2,4-Bis-(4-methoxyphenyl)-1,3-dithia-2,4-diphosphetan-2,4-disulfid (Lawessons Reagenz) gegeben und 10 h am Rückfluß nachgerührt. Nach Abkühlen und Flashchromatographie (Kieselgel, Toluol) erhielt man einen festen Rückstand, der mit Petrolether verrührt, isoliert, mit Petrolether nachgewaschen und getrocknet wurde. To a solution of 3.8 g of 3- [4-chloro-3-ethoximinomethylphenyl] -2,4-dioxo-1-methyl-6-trifluoromethyl-1,2,3,4-tetrahydropyrimidine in 100 ml of toluene, 4 g of 2,4-bis (4-methoxyphenyl) -1,3-dithia-2,4-diphosphetane-2,4-disulfide (Lawesson's reagent) were added and the mixture was stirred at reflux for 10 h. After cooling and flash chromatography (silica gel, toluene), a solid residue was obtained, which was stirred with petroleum ether, isolated, washed with petroleum ether and dried.
Smp.: 129-130°C. Beispiel 24 M.p .: 129-130 ° C. Example 24
3-[3-(2-Brom-2-methoxyethoxycarbonyl-ethenyl)-4-chlor-phenyl]- 2,4-dioxo-1-methyl-6-trifluormethyl-1,2,3,4-tetrahydropyrimidin (Verb. 1.104) 3- [3- (2-bromo-2-methoxyethoxycarbonylethenyl) -4-chlorophenyl] -2,4-dioxo-1-methyl-6-trifluoromethyl-1,2,3,4-tetrahydropyrimidine (comp. 1,104)
Zu einer Lösung von 2,27 g 3-[3-(2-Brom-2-carboxy-ethenyl)-4- -chlor-phenyl]-2,4-dioxo-1-methyl-6-trifluormethyl-1,2,3,4-tetrahydropyrimidin und 0,76 g Kaliumcarbonat in Dimethylformamid wurden 0,52 ml Methoxyethylbromid gegeben und die erhaltene Lösung 17 h nachgerührt. Dann wurden 100 ml Wasser zugegeben, die wäßrige Phase zweimal mit je 100 ml Dichlormethan extrahiert. Die vereinigten organischen Phasen wurden dreimal mit je 50 ml Wasser gewaschen über Natriumsulfat getrocknet und eingeengt. Nach Flash-Chromatographie (Dichlormethan → Dichlormethan/Ethylacetat 9:1) erhielt man die Titelverbindung als öl. To a solution of 2.27 g of 3- [3- (2-bromo-2-carboxyethenyl) -4- chlorophenyl] -2,4-dioxo-1-methyl-6-trifluoromethyl-1,2 , 3,4-tetrahydropyrimidine and 0.76 g of potassium carbonate in dimethylformamide were added to 0.52 ml of methoxyethyl bromide and the resulting solution was stirred for 17 h. Then 100 ml of water were added and the aqueous phase extracted twice with 100 ml of dichloromethane. The combined organic phases were washed three times with 50 ml of water, dried over sodium sulfate and concentrated. After flash chromatography (dichloromethane → dichloromethane / ethyl acetate 9: 1), the title compound was obtained as an oil.
Beispiel 25 Example 25
3-[3-(2-Brom-2-ethy lthioethoxycarbonyl-ethenyl)-4-chlor- -phenyl]-2,4-dioxo-1-methyl-6-trifluoromethyl-1,2,3,4tetrahydropyrimidi n (Verb. 1.105) 3- [3- (2-bromo-2-ethylthioethoxycarbonyl-ethenyl) -4-chloro-phenyl] -2,4-dioxo-1-methyl-6-trifluoromethyl-1,2,3,4tetrahydropyrimidine (comp 1.105)
Zu einer Lösung von 0,58 g 2-Ethyl-mercapto-ethanol und 0,56 g Triethylamin in 30 ml Tetrahydrofuran wurden 2,36 g  2.36 g were added to a solution of 0.58 g of 2-ethyl-mercapto-ethanol and 0.56 g of triethylamine in 30 ml of tetrahydrofuran
3-[3- (2-Brom-2-chlorcarbony l-ethenyl)-4-chlor-phenyl]-2,4-dioxo-1-methyl-6-trifluormethyl-1,2,3,4-tetrahydropyrimidin in 20 ml Tetrahydrofuran getropft und 5 h nachgerührt. Es wurden 100 ml Wasser zugegeben und die wäßrige Phase zweimal mit je 100 ml Dichlormethan extrahiert. Die vereinigten organischen Phasen wurden dreimal mit Wasser gewaschen, mit Natriumsulfat getrocknet und eingeengt. Der feste Rückstand wurde mit 3- [3- (2-bromo-2-chlorocarbonyl l-ethenyl) -4-chlorophenyl] -2,4-dioxo-1-methyl-6-trifluoromethyl-1,2,3,4-tetrahydropyrimidine in 20 ml of tetrahydrofuran were added dropwise and the mixture was stirred for 5 h. 100 ml of water were added and the aqueous phase was extracted twice with 100 ml of dichloromethane each time. The combined organic phases were washed three times with water, dried with sodium sulfate and concentrated. The solid residue was with
Diisopropylether verrührt, entfernt, mit Diisopropy lether und Petrolether nachgewaschen und getrocknet. Stirred diisopropyl ether, removed, washed with diisopropyl ether and petroleum ether and dried.
Smp.: 118-120°C. Be i sp i e l 26 M.p .: 118-120 ° C. Example 26
3-(4-Chl or-3-ethox imi nomethyl-phenyl ) -2,4-d i oxo-5-ethoxy- -c arbonyl -6-methyl -1,2,3,4-tetrahydropyrimi d i n 3- (4-chloro-3-ethoximinomethyl-phenyl) -2,4-d i oxo-5-ethoxy- -c arbonyl -6-methyl -1,2,3,4-tetrahydropyrimi d i n
Zu einer Lösung von 7 g N-(4-Chlor-3-ethoximinomethyl-phenyl)- -3-amino-2-ethoxycarbonyl-crotonamid und 4, 8 g Pyridin, 250 ml Dichlormethan wurden 1,8 ml Chlorameisensäuretrichlormethy lester in 10 ml Dichlormethan getropft. Nach 15 h Rühren wurden nochmals 0,8 ml Chlorameisensäuretrichlormethylester zugegeben. Nach 2 d Rühren bei 25°C und 3 h am Rückfluß wurde das Reaktionsgemisch dreimal mit 150 ml Wasser gewaschen, über Natriumsulfat To a solution of 7 g of N- (4-chloro-3-ethoximinomethyl-phenyl) -3-amino-2-ethoxycarbonyl-crotonamide and 4.8 g of pyridine, 250 ml of dichloromethane were added 1.8 ml of chloroformic acid trichloromethyl ester in 10 ml Dripped dichloromethane. After stirring for 15 hours, a further 0.8 ml of trichloromethyl chloroformate were added. After stirring for 2 d at 25 ° C. and 3 h at reflux, the reaction mixture was washed three times with 150 ml of water, over sodium sulfate
getrocknet und eingeengt. Man erhielt nach Chromatographie dried and concentrated. It was obtained after chromatography
(Dichlormethan - Ethylacetat) die Titelverbindung. (Dichloromethane - ethyl acetate) the title compound.
Smp.: 232-234°C. M.p .: 232-234 ° C.
Beispiel 27 Example 27
3-[4-Chlor-3-(2-chlor-2-ethoxycarbonyl-ethenyl)-phenyl]-2-methylthio-4-oxo-3,4-dihydro-thieno-[3,4-d]-pyrimidin (Verb. 3.2) 3- [4-chloro-3- (2-chloro-2-ethoxycarbonylethenyl) phenyl] -2-methylthio-4-oxo-3,4-dihydrothieno [3,4-d] pyrimidine ( Verb.3.2)
Zu einer Lösung von 0,8 g 3-[4-Chlor-3-(2-chlor-2-ethoxycarbonyl-ethenyl)-phenyl]-4-oxo-2-thioxo-1,2,3,4-tetrahydro-thieno-[3,4-d]-pyrimidin und 0,27 g Ka l i umc arbonat in 40 ml Dimethylformamid wurden 0,28 g Methyliodid in 5 ml Dimethylformamid gegeben. Nach 2 d Nachrühren wurde auf 10°C gekühlt, 80 ml Wasser zugegeben, 2 h nachgerührt. Der entstandene Niederschlag wurde entfernt, mit Wasser gewaschen und getrocknet. To a solution of 0.8 g of 3- [4-chloro-3- (2-chloro-2-ethoxycarbonylethenyl) phenyl] -4-oxo-2-thioxo-1,2,3,4-tetrahydro- thieno [3,4-d] pyrimidine and 0.27 g potassium carbonate in 40 ml dimethylformamide were added 0.28 g methyl iodide in 5 ml dimethylformamide. After stirring for 2 d, the mixture was cooled to 10 ° C. 80 ml of water were added and stirring was continued for 2 hours. The resulting precipitate was removed, washed with water and dried.
Smp.: 142-145°C. M.p .: 142-145 ° C.
In Analogie zu den in den Beispielen beschriebenen Methoden wurden weitere Verbindungen dargestellt. Diese sind zusammen mit den in den Beispielen bereits beschriebenen in den folgenden Tabellen zusammen mit ihrem Schmelzpunkt aufgeführt. Analogous to the methods described in the examples, further compounds were shown. Together with those already described in the examples, these are listed in the following tables together with their melting point.
11
1,  1,
11
- 1 - 1
1 1
1  1
1 1
1 1
Bemerkung:  Comment:
a) enthält noch 15 % isomeres Allyloxim b) Isomerengemisch  a) still contains 15% isomeric allyloxime b) mixture of isomers
c) trans-Isomer c) trans isomer
Diejenigen Verbindungen, die als öle anfielen, konnten mit Hilfe ihrer IR-Daten eindeutig charakterisiert werden, diese sind in der folgenden Tabelle angegeben. Those compounds that were obtained as oils could be clearly characterized with the help of their IR data, which are given in the following table.
Vorprodukte: Preliminary products:
Vorprodukt Beispiel 1 2-Chlor-3-[4-chlor-3-(2-chlor-2-ethoxycarbonyl-ethenyl)-phenyl]- -4-oxo-6-trifluormethyl-3,4-dihydropyrimidin Intermediate Example 1 2-Chloro-3- [4-chloro-3- (2-chloro-2-ethoxycarbonylethenyl) phenyl] -4-oxo-6-trifluoromethyl-3,4-dihydropyrimidine
Zu 12,6 g 3-[4-Chlor-3-(2-chlor-2-ethoxycarbonyl-ethenyl)- phenyl]-2,4-dioxo -6-trifluormethyl-1,2,3,4-tetrahydropyrimidin wurden 13,8 ml Phosphoroxitrichlorid getropft und 2 h bei Raumtemperatur nachgerührt. Anschließend wurden 2,1 ml Dimethylformamid zugegeben und 15 h bei 110-115°C nachgerührt. Das Reaktionsgemisch wurde im Vakuum eingeengt, in 150 ml Eiswasser gegeben und zweimal mit je 100 ml Dichlormethan extrahiert. Die vereinigten organischen Phasen wurden mit Wasser, 10-proz.  13.6 were added to 12.6 g of 3- [4-chloro-3- (2-chloro-2-ethoxycarbonylethenyl) phenyl] -2,4-dioxo -6-trifluoromethyl-1,2,3,4-tetrahydropyrimidine , 8 ml of phosphorus oxychloride and added for 2 h at room temperature. Then 2.1 ml of dimethylformamide were added and the mixture was stirred at 110-115 ° C. for 15 h. The reaction mixture was concentrated in vacuo, poured into 150 ml of ice water and extracted twice with 100 ml of dichloromethane each time. The combined organic phases were washed with water, 10 percent.
Natriumhydrogencarbonat und nochmals mit Wasser gewaschen, über Natriumsulfat getrocknet und eingeengt. Das erhaltene öl wurde Flash-chromatographiert (Dichlormethan), der daraus erhaltene kristalline Feststoff mit Petrolether verrührt, entfernt, mit wenig Petrolether nachgewaschen und getrocknet.  Sodium bicarbonate and washed again with water, dried over sodium sulfate and concentrated. The oil obtained was flash chromatographed (dichloromethane), the resulting crystalline solid was stirred with petroleum ether, removed, washed with a little petroleum ether and dried.
Smp.: 114-115°C. M.p .: 114-115 ° C.
Vorprodukt Beispiel 2 Umsetzung von 4-Chlor-3-ethoximino-phenyl isocyanat mit 3-Aminocrotonsäure-ethylester Preproduct Example 2 Reaction of 4-chloro-3-ethoximino-phenyl isocyanate with 3-aminocrotonic acid ethyl ester
Zu einer Lösung von 14,2 g 3-Amino-crotonsäureethylester in 450 ml Toluol wurden bei Rückfluβ 22,5 g 4-Chlor-3-ethoximino- -phenylisocyanat in 100 ml Toluol getropft und das Reaktionsgemisch 4 h am Rückfluβ und 2 d bei Raumtemperatur nachgerührt. Man erhielt durch Entfernen und Trocknen des entstandenen 22.5 g of 4-chloro-3-ethoximino-phenyl isocyanate in 100 ml of toluene were added dropwise to a solution of 14.2 g of 3-amino-crotonic acid ethyl ester in 450 ml of toluene at reflux and the reaction mixture was refluxed for 4 h and 2 days Stirred room temperature. It was obtained by removing and drying the resultant
Niederschlags N-(4-Chlor-3-ethoximinomethyl-phenyl)-2-amino- 2-ethoxycarbony l-crotonamid  Precipitation N- (4-chloro-3-ethoximinomethyl-phenyl) -2-amino-2-ethoxycarbony l-crotonamide
Das Filtrat wurde eingeengt und der Rückstand Chromatographiert (Dichlormethan). Nach Verreiben mit kaltem Petrolether, Entfernen und Trocknen erhielt man N-(4-Chlor-3-ethoximinomethyl-phenyl)- -N'-(1-ethoxycarbonyl-propen-2-yl)-harnstoff.  The filtrate was concentrated and the residue was chromatographed (dichloromethane). After trituration with cold petroleum ether, removal and drying, N- (4-chloro-3-ethoximinomethyl-phenyl) - -N '- (1-ethoxycarbonyl-propen-2-yl) urea was obtained.
Smp.: 126-127°C.  M.p .: 126-127 ° C.
Auf die gleiche Weise wurden folgende Vorstufen hergestellt:  The following precursors were produced in the same way:
Vorprodukte Beispiel 3 Preproducts example 3
3-Amino-4-chlor-4,4-difluor-crotonsäureester 3-amino-4-chloro-4,4-difluoro-crotonic acid ester
In 4-Chlor-4,4-difluor-acetessigesterethylester wurde bei 60°C Ammoniak bis zur Sättigung eingeleitet und 5 h bei 70°C nachgerührt, anschlieβend wurde innerhalb einer Stunde nochmals Ammoniak eingegast und erneut 2 h bei 70°C nachgerührt. Man erhielt das Produkt nach Destillation über eine 10 cm Vigreuxkolonne im Wasserstrahlvakuum. Sdp.: 129-130°C/140 h Pa. In 4-chloro-4,4-difluoro-acetoacetic ester, ammonia was introduced at 60 ° C. until saturation and stirring was continued for 5 hours at 70 ° C., then ammonia was again gassed in within one hour and stirring was continued for 2 hours at 70 ° C. The product was obtained after distillation through a 10 cm Vigreux column in a water jet vacuum. Bp: 129-130 ° C / 140 h Pa.
Auf die gleiche Weise wurde 3-Amino-4,4,4-trifluorcrotonsäureethylester hergestellt. 3-Amino-4,4,4-trifluorocrotonic acid ethyl ester was prepared in the same way.
Vorstufe Beispiel 4 Prepress example 4
4-Chloro-3-(1,3-dioxolan-2-yl)-phenylisocyanat 4-chloro-3- (1,3-dioxolan-2-yl) phenyl isocyanate
Zu einer Lösung von 3,0 g Chlorameisensäuretrichlormethylester in 50 ml Toluol wurden bei ca. 20-25°C 2,0 g 4-Chloro-3-(1,3-dioxolan-2-yl)-anilin in 25 ml Essigsäureethylester gegeben. Diese Mischung wurde 2 Std. bei 20-25°C und anschlieβend noch 5 Std. bei Rückfluβtemperatur gerührt. Anschlieβend engte man das Reaktionsgemisch ein und trocknete den Rückstand im Hochvakuum. Ausbeute: 2,0 g (öl). Vorstufe Beispiel 5 2.0 g of 4-chloro-3- (1,3-dioxolan-2-yl) aniline in 25 ml of ethyl acetate were added to a solution of 3.0 g of trichloromethyl chloroformate in 50 ml of toluene at about 20-25 ° C. . This mixture was stirred for 2 hours at 20-25 ° C and then for 5 hours at the reflux temperature. The reaction mixture was then concentrated and the residue was dried under high vacuum. Yield: 2.0 g (oil). Preliminary example 5
4-Chloro-3-(α-Chlor-acrylsäureethylester)-phenylisocyanat 4-chloro-3- (α-chloroacrylic acid ethyl ester) phenyl isocyanate
Zu einer Suspension von 130 g 4-Chlor-3-(α-Chlor-acrylsäureethylester)-anilin in 1200 ml Toluol wurden 108,8 g Chlorameisensäuretrichlormethylester gegeben. Die Mischung wurde 16 h am Rückfluβ gerührt. Nach Abtrennen des gebildeten Niederschlags wurde das Lösungsmittel unter reduziertem Druck entfernt, der Rückstand mit Petrolether verrührt, der Niederschlag entfernt und getrocknet.  108.8 g of trichloromethyl chloroformate were added to a suspension of 130 g of 4-chloro-3- (α-chloroacrylic acid ethyl ester) aniline in 1200 ml of toluene. The mixture was stirred at reflux for 16 h. After the precipitate formed had been separated off, the solvent was removed under reduced pressure, the residue was stirred with petroleum ether, the precipitate was removed and dried.
Smp. 48-50°C. Mp 48-50 ° C.
Auf die gleiche Weise wurden In the same way
4-Chlor-3-(ethoximinomethyl)-phenylisocyanat, öl und  4-chloro-3- (ethoximinomethyl) phenyl isocyanate, oil and
4-Chlor-3-(ethoximinomethyl)-6-fluor-phenylisocyanat, öl und 4-Chlor-3-(methoximinomethyl)-phenylisocyanat, öl hergestellt. 4-Chloro-3- (ethoximinomethyl) -6-fluorophenyl isocyanate, oil and 4-chloro-3- (methoximinomethyl) phenyl isocyanate, oil.
Vorstufe Beispiel 6 N-[4-Chlor-3-(2-Chlor-2-ethoxycarbonyl-ethenyl)-phenyl]-harnstoff Precursor Example 6 N- [4-chloro-3- (2-chloro-2-ethoxycarbonylethenyl) phenyl] urea
Zu einer Lösung von 14,3 g 4-Chlor-3-(2-chlor-2-ethoxycarbonylethenyl)-phenylisocyanat in 200 ml Tetrahydrofuran wurde bei 20°C Ammoniak innerhalb 1,5 h bis zur Sättigung eingegast und 1 nachgerührt. Der Niederschlag wurde entfernt und mit Ether gewaschen. Das Filtrat wurde eingeengt, mit Ether verrührt und entfernt. Die Feststoffe wurden vereinigt. To a solution of 14.3 g of 4-chloro-3- (2-chloro-2-ethoxycarbonylethenyl) phenyl isocyanate in 200 ml of tetrahydrofuran was gassed in ammonia at 20 ° C. within 1.5 h until saturation and stirring was continued. The precipitate was removed and washed with ether. The filtrate was concentrated, stirred with ether and removed. The solids were combined.
Smp. 209-210°C. Vorstufe Beispiel 7 Mp 209-210 ° C. Preliminary example 7
4-Chlor-3-(2-chlor-2-ethoxycarbonyl-ethenyl)-N-ethoxycarbonyl- -anilin 4-chloro-3- (2-chloro-2-ethoxycarbonyl-ethenyl) -N-ethoxycarbonyl-aniline
Zu einer Lösung von 13 g 4-Chlor-3-(2-chlor-2-ethoxycarbonylethenyl)-anilin in 150 g Toluol und 5,6 g Triethylamin wurden 6,0 g Chlorameisensäureethylester bei 20-40°C getropft und 5 h bei Raumtemperatur nachgerührt. Das Reaktionsgemisch wurde dreimal mit Wasser gewaschen, über Natriumsulfat getrocknet, eingeengt, der Rückstand mit Petrolether verrührt, entfernt, mit Petrolether gewaschen und getrocknet. 6.0 g of ethyl chloroformate were added dropwise to a solution of 13 g of 4-chloro-3- (2-chloro-2-ethoxycarbonylethenyl) aniline in 150 g of toluene and 5.6 g of triethylamine at 20-40 ° C. and for 5 hours Stirred room temperature. The reaction mixture was washed three times with water, dried over sodium sulfate, concentrated, the residue was stirred with petroleum ether, removed, washed with petroleum ether and dried.
Smp.: 102-104°C. Vorprodukt Beispiel 8 β-Aminozimtsäuremethylester M.p .: 102-104 ° C. Intermediate Example 8 Methyl β-aminocinnamate
Zu 7,22 g Magnesium in 20 ml Ether wurden bei Rückfluβ 47 g Brombenzol in 90 ml Ether getropft und 1 h am Rückfluβ  47 g of bromobenzene in 90 ml of ether were added dropwise to 7.22 g of magnesium in 20 ml of ether, and the mixture was refluxed for 1 h
nachgerührt. Dann wurden 9,9 g Cyanessigsäuremethylester unter Eiskühlung zugetropft, 1 h bei Raumtemperatur, 5 h bei Rückfluβ und nochmals 15 h bei Raumtemperatur nachgerührt. Zum Reaktionsgemisch wurden vorsichtig 300 ml Ammoniumchlorid gegeben, die wäβrige Phase zweimal mit Ether extrahiert, die vereinigten organischen Phasen dreimal mit Wasser gewaschen, über Natriumsulfat getrocknet und eingeengt. Der Rückstand wurde im Hochvakuum destilliert. Man erhielt 13 g β-Aminozimtsäuremethylester (110-112°C, 10,15 mbar). stirred. Then 9.9 g of methyl cyanoacetate were added dropwise with ice cooling, the mixture was stirred for 1 h at room temperature, 5 h at reflux and again for 15 h at room temperature. To the The reaction mixture was carefully added 300 ml of ammonium chloride, the aqueous phase extracted twice with ether, the combined organic phases washed three times with water, dried over sodium sulfate and concentrated. The residue was distilled in a high vacuum. 13 g of methyl β-aminocinnamate were obtained (110-112 ° C., 10.15 mbar).
Auf die gleiche Weise wurden β-Amino-4-Chlorzimtsäuremethylester (aus 1-Brom-4-chlorbenzol, amorpher Feststoff) In the same way, methyl β-amino-4-chlorocinnamate (from 1-bromo-4-chlorobenzene, amorphous solid)
β-Amino-4-methoxyzimtsäuremethylester (Sdp.: 165-167°C, 0,15 h Pa).  Methyl β-amino-4-methoxycinnamate (bp: 165-167 ° C, 0.15 h Pa).
Vorprodukt Beispiel 9 Preproduct example 9
Methyl 4-isothiocyanato-thiophen-3-carboxylat Methyl 4-isothiocyanato-thiophene-3-carboxylate
Zu einer Suspension von 7,7 ml Thiophosgen und 18,5 g Natriumhydrogencarbonat in 70 ml Wasser und 200 ml Dichlormethan wurden bei Raumtemperatur innerhalb von 30 min 19,4 g Methyl 4-aminothiophen-3-carboxylathydrochlorid gegeben und 1 h bei Raumtemperatur nachgerührt. Nach Trennung der Phasen wurde die wäβrige Phase einmal mit Dichlormethan extrahiert, die vereinigten organischen Phasen einmal mit Wasser gewaschen über Natriumsulfat getrocknet und eingeengt.  To a suspension of 7.7 ml of thiophosgene and 18.5 g of sodium hydrogen carbonate in 70 ml of water and 200 ml of dichloromethane, 19.4 g of methyl 4-aminothiophene-3-carboxylate hydrochloride were added at room temperature within 30 minutes and the mixture was stirred at room temperature for 1 h. After separation of the phases, the aqueous phase was extracted once with dichloromethane, the combined organic phases washed once with water, dried over sodium sulfate and concentrated.
Smp. 93-95°. M.p. 93-95 °.
Vorprodukt Beispiel 10 Preproduct example 10
N-[4-Chlor-3-(2-chlor-2-ethoxycarbonyl-ethenyl)-phenyl]-N'-(4- -methoxycarbony l-thien-3-yl)-thioharnstoff N- [4-Chloro-3- (2-chloro-2-ethoxycarbonylethenyl) phenyl] -N '- (4- methoxycarbonyl l-thien-3-yl) thiourea
Zu einer Lösung von 5,2 g 4-Chlor-(2-chlor-2-ethoxycarbonyl- -ethenyl)-anilin in 50 ml Toluol wurden 4 g Methyl-4-isothiocyanato-thiophen-3-carboxylat in 50 ml Toluol getropft. Das Reaktionsgemisch wurde insgesamt 78 h bei Raumtemperatur und 9 h bei 90°C gerührt. Der erhaltene Niederschlag wurde entfernt mit Toluol nachgewaschen und anschlieβend aus Ethanol umkristallisiert. 4 g of methyl 4-isothiocyanato-thiophene-3-carboxylate in 50 ml of toluene were added dropwise to a solution of 5.2 g of 4-chloro (2-chloro-2-ethoxycarbonyl-ethenyl) aniline in 50 ml of toluene. The reaction mixture was stirred for a total of 78 h at room temperature and 9 h at 90 ° C. The precipitate obtained was removed, washed with toluene and then recrystallized from ethanol.
Smp.: 158-160°C. M.p .: 158-160 ° C.
Vorprodukt Beispiel 11 Preproduct example 11
3-[3-(2-Brom-2-chlorcarbonyl-ethenyl)-4-chlor-phenyl]-2,4-dioxo- -1-methyl-6-trifluormethyl-1,2,3,4-tetrahydropyrimidin 3- [3- (2-bromo-2-chlorocarbonyl-ethenyl) -4-chlorophenyl] -2,4-dioxo-1-methyl-6-trifluoromethyl-1,2,3,4-tetrahydropyrimidine
Zu einer Lösung von 4, 5 g 3-[3-(2-Brom-2-carboxyethenyl)-4-chlorphenyl]-2,4-dioxo-1-methyl-6-trifluormethyl-1,2,3,4-tetrahydropyrimidin und 0,1 ml Dimethylformamid in 100 ml Toluol wurden 1,6 g Thionylchlorid gegeben. Die Reaktionsmischung wurde langsam bis zur Rückfluβtemperatur aufgeheizt, 5 h am Rückfluβ nachgerührt, eingeengt und im Hochvakuum getrocknet.  To a solution of 4.5 g of 3- [3- (2-bromo-2-carboxyethenyl) -4-chlorophenyl] -2,4-dioxo-1-methyl-6-trifluoromethyl-1,2,3,4- tetrahydropyrimidine and 0.1 ml of dimethylformamide in 100 ml of toluene were added to 1.6 g of thionyl chloride. The reaction mixture was slowly heated to the reflux temperature, stirred at the reflux for 5 h, concentrated and dried under high vacuum.
Smp.: 125-127°C. M.p .: 125-127 ° C.
Anwendungsbeispiele (herbizide Wirksamkeit) Examples of use (herbicidal activity)
Die herbizide Wirkung der substituierten Phenylurazile I, Ia und Ib lieβ sich durch Gewächshausversuche zeigen: The herbicidal activity of the substituted phenylurazils I, Ia and Ib could be demonstrated by greenhouse tests:
Als Kulturgefäβe dienten Plastikblumentöpfe mit lehmigem Sand mit etwa 3,0 % Humus als Substrat. Die Samen der Testpflanzen wurden nach Arten getrennt eingesät. Plastic flower pots with loamy sand with about 3.0% humus as a substrate served as culture vessels. The seeds of the test plants were sown separately according to species.
Bei Vorauflaufbehandlung wurden die in Wasser suspendierten oder emulgierten Wirkstoffe direkt nach Einsaat mittels fein verteilender Düsen aufgebracht. Die Gefäβe wurden leicht beregnet, um Keimung und Wachstum zu fördern und anschlieβend mit durch sichtigen Plastikhauben abgedeckt, bis die Pflanzen angewachsen waren. Diese Abdeckung bewirkt ein gleichmäβiges Keimen der Testpflanzen, sofern dies nicht durch die Wirkstoffe beeinträchtigt wurde. In pre-emergence treatment, the active ingredients suspended or emulsified in water were applied directly after sowing using finely distributing nozzles. The vessels were lightly irrigated to promote germination and growth and then with through clear plastic covers until the plants had grown. This cover causes the test plants to germinate evenly, unless this was affected by the active ingredients.
Zum Zwecke der Nachauflaufbehandlung wurden die Testpflanzen bereits in den Versuchsgefäβen angezogen oder einige Tage vorher in die Versuchsgefäße verpflanzt. Die Applikation der in Wasser suspendierten oder emulgierten Wirkstoffe erfolgte je nach Wuchsform erst bei einer Wuchshöhe von 3 bis 15 cm. For the purpose of post-emergence treatment, the test plants were grown in the test vessels or transplanted into the test vessels a few days beforehand. The active ingredients suspended or emulsified in water were only applied at a height of 3 to 15 cm, depending on the growth habit.
Die Pflanzen wurden artenspezifisch bei Temperaturen von 10-25°C bzw. 20-35°C gehalten. Die Versuchsperiode erstreckte sich über 2 bis 4 Wochen. Während dieser Zeit wurden die Pflanzen gepflegt und ihre Reaktion auf die einzelnen Behandlungen wurde ausgewertet. The plants were kept at 10-25 ° C and 20-35 ° C depending on the species. The trial period lasted 2 to 4 weeks. During this time, the plants were cared for and their response to the individual treatments was evaluated.
Bewertet wurde nach einer Skala von 0 bis 100. Dabei bedeutet 100 kein Aufgang der Pflanzen bzw. völlige Zerstörung zumindest der oberirdischen Teile und 0 keine Schädigung oder normaler It was rated on a scale from 0 to 100. 100 means no emergence of the plants or complete destruction of at least the aerial parts and 0 means no damage or normal
Wachstumsverlauf.  Growth course.
Die in den Gewächshausversuchen verwendeten Pflanzen setzten sich aus folgenden Arten zusammen: The plants used in the greenhouse experiments are composed of the following types:
Botanischer Name Deutscher Name Englischer Name Botanical name German name English name
Abutilon theophrasti Chinesischer Hanf velvet leaf Abutilon theophrasti Chinese hemp velvet leaf
Amaranthus retroflexus Zurückgekrümmter redroot pigweed Amaranthus retroflexus Curved redroot pigweed
Fuchsschwanz  Foxtail
Centaurea cyanus Kornblume cornflower  Centaurea cyanus cornflower cornflower
Echinochloa crus-galli Hühnerhirse barnyardgrass Ipomoea spp Prunkwindenarten morningglory Solanum nigrum Schwarzer Nachtblack nightshade schatten Echinochloa crus-galli millet barnyardgrass Ipomoea spp morning glory morning glory Solanum nigrum black night black nightshade shade
Bei einer Aufwandmenge von 0,06 und 0,03 kg/ha lassen sich mit der Verbindung Nr. 3.1 unerwünschte breitblättrige Pflanzen im Nachauflaufverfahren sehr gut bekämpfen. Auβerdem lassen sich bei Nachauflaufanwendung von 0,5 kg/ha der Verbindungen 1.1, 1.3, 1.5, 1.11, 1.12, 1.13, 1.14, 1.15, 1.21, 1.22, 1.23, 1.24, 1.25, 1.26, 1.27, 1.36, 1.44, 2.1, 2 . 2, 2.3, 2.4, 2.7 und 2.27 im Gewächshaus unerwünschte breitblättrige Pflanzen und Gräser sehr gut bekämpfen. At a rate of 0.06 and 0.03 kg / ha, compound no. 3.1 can be used to control undesirable broad-leaved plants very well using the post-emergence method. In addition, with post-emergence application of 0.5 kg / ha of the compounds 1.1, 1.3, 1.5, 1.11, 1.12, 1.13, 1.14, 1.15, 1.21, 1.22, 1.23, 1.24, 1.25, 1.26, 1.27, 1.36, 1.44, 2.1, 2nd 2, 2.3, 2.4, 2.7 and 2.27 in the greenhouse, combat unwanted broad-leaved plants and grasses very well.
Anwendungsbeispiele (Defoliationswirkung) Examples of use (defoliation effect)
Als Vergleichsmittel diente Served as a means of comparison
A 6,7-Dihydrodipyridol(1,2-alpha:2',1'-c)pyridilium als A 6,7-dihydrodipyridol (1,2-alpha: 2 ', 1'-c) pyridilium as
Dibromid-Monohydrat-Salz (Cornmon Name: Diquat®). Dibromide monohydrate salt (Cornmon name: Diquat ® ).
Das Vergleichsmittel wurde in Form des fertig formulierten Handelsproduktes verwendet. The comparative agent was used in the form of the fully formulated commercial product.
Als Testpflanzen dienten junge, 4-blättrige (ohne Keimblätter) Baumwollpflanzen der Sorte Stoneville 825, die unter Gewächshausbedingungen angezogen wurden (rel. Luftfeuchtigkeit 50 bis 70 %; Tag-/Nachttemperatur 27/20°C). Young, 4-leaf (without cotyledons) cotton plants of the Stoneville 825 variety served as test plants, which were grown under greenhouse conditions (relative humidity 50 to 70%; day / night temperature 27/20 ° C).
Anwendungsbeispiel 1 Application example 1
Die jungen Baumwollpflanzen wurden tropfnaβ mit wässrigen Aufbereitungen der angegebenen Wirkstoffe (unter Zusatz von 0,15The young cotton plants were dripping wet with aqueous preparations of the specified active ingredients (with the addition of 0.15
Gew.-% des Fettalkoholalkoxylats Plurafac LF 700, bezogen auf die Spritzbrühe) blattbehandelt. Die ausgebrachte Wassermenge betrug umgerechnet 1000 l/ha. Nach 13 Tagen wurde die Anzahl abgeworfener Blätter und der Grad der Entblätterung in % bestimmt. Bei den unbehandelten Kontrollpflanzen trat kein Blattfall auf. % By weight of the fatty alcohol alkoxylate Plurafac LF 700, based on the spray mixture), treated with leaves. The amount of water applied was the equivalent of 1000 l / ha. After 13 days, the number of leaves dropped and the degree of defoliation in% were determined. No leaf fall occurred in the untreated control plants.
A 0A 0
Das Ergebnis zeigt, daβ die erfindungsgemäβen substituierten 3-Phenylurazile I eine sehr gute entblätternde Wirkung aufweisen und hierbei dem Handelsprodukt A überlegen sind. The result shows that the substituted 3-phenylurazils I according to the invention have a very good defoliation effect and are superior to the commercial product A.
Anwendungsbeispiele (insektizide Wirksamkeit) Examples of use (insecticidal activity)
Die Insektizide Wirkung der Verbindungen der allgemeinen The insecticidal effect of the compounds of the general
Formel I, Ia und Ib ließ sich durch folgende Versuche zeigen:  Formula I, Ia and Ib could be shown by the following experiments:
Die Wirkstoffe wurden a) als 0,1 %-ige Lösung in Aceton oder b) als 10 %-ige Emulsion in einem Gemisch aus 70 Gew.-% Cyclohexanol, 20 Gew.-% Nekanil® LN (Lutensol® AP6, Netzmittel mit Emulgier- und Dispergierwirkung auf der Basis ethoxylierter Alkylphenole) und 10 Gew.-% Emulphor® EL The active ingredients were formulated a) as a 0.1% strength solution in acetone or b) as a 10% emulsion in a mixture of 70 wt .-% of cyclohexanol, 20 wt .-% Nekanil ® LN (Lutensol ® AP6, wetting agent having Emulsifying and dispersing action based on ethoxylated alkylphenols) and 10% by weight Emulphor ® EL
(Emulan® EL, Emulgator auf der Basis ethoxyl ierter Fettalkohole) aufbereitet und entsprechend der gewünschten Konzentration mit Aceton im Fall von a) bzw. mit Wasser im Fall von b) verdünnt. Nach Abschluβ der Versuche wurde die jeweils niedrigste Konzentration ermittelt, bei der die Verbindungen im Vergleich zu unbehandelten Kontrollversuchen noch eine 80 - 100 %-ige Hemmung bzw. Mortalität hervorriefen (Wirkschwelle bzw. Minimalkonzentration). (Emulan ® EL, emulsifier based on ethoxylated fatty alcohols) prepared and diluted with acetone in the case of a) or with water in the case of b) according to the desired concentration. After the end of the tests, the lowest concentration was determined at which the compounds still caused an 80-100% inhibition or mortality compared to untreated control tests (threshold of action or minimum concentration).

Claims

Patentansprüche Claims
1. Substituierte 3-Phenylurazile der allgemeinen Formel I 1. Substituted 3-phenylurazils of the general formula I
in der die Variablen folgende Bedeutung haben: X1, X2 in which the variables have the following meaning: X 1 , X 2
Sauerstoff oder Schwefel; W  Oxygen or sulfur; W
-C(R8)=X5, -C(R8)(X3R6)(X4R7), -C(R8)=C(R9)-CN, -C (R 8 ) = X 5 , -C (R 8 ) (X 3 R 6 ) (X 4 R 7 ), -C (R 8 ) = C (R 9 ) -CN,
-C(R8)=C(R9)-CO-R10, -CH(R8)-CH(R9)-CO-R10, -C (R 8 ) = C (R 9 ) -CO-R 10 , -CH (R 8 ) -CH (R 9 ) -CO-R 10 ,
-C(R8)=C(R9)-CH2-CO-R10, -C(R8)=C(R9)-C(R11)=C(R12)-CO-R10 -C (R 8 ) = C (R 9 ) -CH 2 -CO-R 10 , -C (R 8 ) = C (R 9 ) -C (R 11 ) = C (R 12 ) -CO-R 10
Oder -C(R8)=C(R9)-CH2-CH(R13)-CO-R10 mit X3, X4 Sauerstoff oder Schwefel; X5 Sauerstoff, Schwefel oder ein Rest -NR14, mit R14 Wasserstoff, Hydroxyl, C1-C6-Alkyl, C3-C6-Or -C (R 8 ) = C (R 9 ) -CH 2 -CH (R 13 ) -CO-R 10 with X 3 , X 4 oxygen or sulfur; X 5 oxygen, sulfur or a radical -NR 14 , with R 14 hydrogen, hydroxyl, C 1 -C 6 alkyl, C 3 -C 6 -
Alkenyl, C3-C6-Alkinyl, C3-C7-Cycloalkyl, C1-C6-Halogenalkyl, C1-C6-Alkoxy-C1-C6-alkyl, C1-C6-Alkoxy, C3-C6-Alkenyloxy, C3-C6- Alkinyloxy, C5-C7-Cycloalkoxy, C5-C7-Cycloalkenyloxy, C1-C6-Halogenalkoxy, Alkenyl, C 3 -C 6 alkynyl, C 3 -C 7 cycloalkyl, C 1 -C 6 haloalkyl, C 1 -C 6 alkoxy-C 1 -C 6 alkyl, C 1 -C 6 alkoxy, C 3 -C 6 alkenyloxy, C 3 -C 6 alkynyloxy, C 5 -C 7 cycloalkoxy, C 5 -C 7 cycloalkenyloxy, C 1 -C 6 haloalkoxy,
C3-C6-Halogenalkenyloxy, Hydroxy-C1-C6- alkoxy, Cyano-C1-C6-alkoxy, C3-C7-Cycloalkyl- C1-C6-alkoxy, C1-C6-Alkoxy-C1-C6-alkoxy, C1-C6-Alkoxy-C3-C5-alkenyloxy, C 3 -C 6 haloalkenyloxy, hydroxy-C 1 -C 6 alkoxy, cyano-C 1 -C 6 alkoxy, C 3 -C 7 cycloalkyl- C 1 -C 6 alkoxy, C 1 -C 6 - Alkoxy-C 1 -C 6 -alkoxy, C 1 -C 6 -alkoxy-C 3 -C 5 -alkenyloxy,
C1-C6-Alkylcarbonyloxy, C1-C6-Halogenalkylcarbonyloxy, C1-C6-Alkylcarbamoyloxy, C1-C6- Halogenalkylcarbamoyloxy, C1-C6-Alkoxycarbonyl-C2-C6-alkoxy, C1-C6-Alkylthio-C1-C6- alkoxy, Di-(C1-C6-alkyl)-amino-C1-C6-alkoxy, Phenyl, das einen bis drei der folgenden Substituenten tragen kann: Cyano, Nitro, Halogen, C1-C6-Alkyl, C2-C6-Alkenyl, C1-C6- Halogenalkyl, C1-C6-Alkoxy und C1-C6-Alkoxycarbonyl, Phenyl-C1-C6-alkoxy, Phenyl- C3-C6-alkenyloxy oder Phenyl-C3-C6-alkinyloxy, wobei jeweils eine oder zwei Methylengruppen der Kohlenstoffketten durch -O-, -S- oder -N(C1-C6-Alkyl)- ersetzt sein können und wobei der Pheny lring jeweils einen bis drei der folgenden Substituenten tragen kann: Cyano, Nitro, Halogen, C1-C6-Alkyl, C2-C6- Alkenyl, C1-C6-Halogenalkyl, C1-C6-Alkoxy und C1-C6-Alkoxycarbonyl, Heterocyclyl, Heterocyclyl-C1-C6-alkoxy, Heterocyclyl-C3-C6- alkenyloxy, Heterocyclyl-C3-C6-alkinyloxy, wobei jeweils eine oder zwei Methylengruppen der Kohlenstoffketten durch -O-, -S- oder -N(C1-C6-Alkyl)- ersetzt sein können und wobei der Heterocyclylring drei- bis siebengliedrig, gesättigt, ungesättigt oder aromatisch sein kann und ein bis vier Heteroatome ausgewählt aus einer Gruppe von ein oder zwei Sauerstoff- oder Schwefel- und bis zu vierC 1 -C 6 alkylcarbonyloxy, C 1 -C 6 haloalkylcarbonyloxy, C 1 -C 6 alkylcarbamoyloxy, C 1 -C 6 haloalkylcarbamoyloxy, C 1 -C 6 alkoxycarbonyl-C 2 -C 6 alkoxy, C 1 -C 6 -alkylthio-C 1 -C 6 -alkoxy, di- (C 1 -C 6 -alkyl) -amino-C 1 -C 6 -alkoxy, Phenyl which can carry one to three of the following substituents: cyano, nitro, halogen, C 1 -C 6 alkyl, C 2 -C 6 alkenyl, C 1 -C 6 haloalkyl, C 1 -C 6 alkoxy and C 1 -C 6 -alkoxycarbonyl, phenyl-C 1 -C 6 -alkoxy, phenyl-C 3 -C 6 -alkenyloxy or phenyl-C 3 -C 6 -alkynyloxy, where one or two methylene groups of the carbon chains are each -O- , -S- or -N (C 1 -C 6 alkyl) - can be replaced and where the phenyl ring can each carry one to three of the following substituents: cyano, nitro, halogen, C 1 -C 6 alkyl, C 2 -C 6 alkenyl, C 1 -C 6 haloalkyl, C 1 -C 6 alkoxy and C 1 -C 6 alkoxycarbonyl, heterocyclyl, heterocyclyl-C 1 -C 6 alkoxy, heterocyclyl-C 3 -C 6 - Alkenyloxy, heterocyclyl-C 3 -C 6 -alkynyloxy, where one or two methylene groups of the carbon chains can be replaced by -O-, -S- or -N (C 1 -C 6 -alkyl) - and where the heterocyclyl ring three - can be seven-membered, saturated, unsaturated or aromatic and a bi s four heteroatoms selected from a group of one or two oxygen or sulfur and up to four
Stickstoffatomen enthalten kann und darüber hinaus ein bis drei der folgenden Substituenten tragen kann: Cyano, Nitro, Halogen, C1-C6-Alkyl, C2-C6-Alkenyl, C1-C6-Halogenalkyl, C1-C6-Alkoxy oder C1-C6-Alkoxycarbonyl, Can contain nitrogen atoms and can also carry one to three of the following substituents: cyano, nitro, halogen, C 1 -C 6 alkyl, C 2 -C 6 alkenyl, C 1 -C 6 haloalkyl, C 1 -C 6 Alkoxy or C 1 -C 6 alkoxycarbonyl,
oder -N(R15)R16, wobei or -N (R 15 ) R 16 , where
R15, R16 R 15 , R 16
Wasserstoff, C1-C6-Alkyl, C3-C6-Alkenyl, C3-C6-Alkinyl, C3-C6-Cycloalkyl, C1-C6-Halogenalkyl, C1-C6-Alkoxy-C1-C6-alkyl, C1-C6- Alky learbony l, C1-C6-Alkoxycarbonyl, Hydrogen, C 1 -C 6 alkyl, C 3 -C 6 alkenyl, C 3 -C 6 alkynyl, C 3 -C 6 cycloalkyl, C 1 -C 6 haloalkyl, C 1 -C 6 alkoxy- C 1 -C 6 alkyl, C 1 -C 6 alkyl larybony 1, C 1 -C 6 alkoxycarbonyl,
C1-C6-Alkoxycarbonyl-C1-C6-alkyl, C1-C6-Alkoxycarbonyl-C2-C6-alkenyl, wobei die Alkenylkette zusätzlich ein bis drei der folgenden Reste tragen kann: Halogen und Cyano oder Phenyl, das einen bis drei der folgenden Substituenten tragen kann: Cyano, Nitro, Halogen, C1-C6-Alkyl, C1-C6-Halogenalkyl, C3-C6-Alkenyl, C1-C6-Alkoxy und C1-C6-Alkoxycarbonyl, oder C 1 -C 6 -alkoxycarbonyl-C 1 -C 6 -alkyl, C 1 -C 6 -alkoxycarbonyl-C 2 -C 6 -alkenyl, where the alkenyl chain can additionally carry one to three of the following radicals: halogen and cyano or Phenyl which can carry one to three of the following substituents: cyano, nitro, halogen, C 1 -C 6 alkyl, C 1 -C 6 haloalkyl, C 3 -C 6 alkenyl, C 1 -C 6 alkoxy and C 1 -C 6 alkoxycarbonyl, or
R15 und R16 zusammen mit dem gemeinsamen Stickstoffatom einen gesättigten oder ungesättigten 4-7-gliedrigen Heterocyclus, wobei ein Ringglied durch -O-, -S-, -N=, -NH- oder -N(C1-C6-Alkyl)- ersetzt sein kann, bedeuten; R6, R7 C1-C6-Alkyl, C1-C6-Halogenalkyl, C3-C6-Alkenyl, R 15 and R 16 together with the common nitrogen atom form a saturated or unsaturated 4-7-membered heterocycle, a ring member being defined by -O-, -S-, -N =, -NH- or -N (C 1 -C 6 - Alkyl) - may be replaced; R 6 , R 7 C 1 -C 6 alkyl, C 1 -C 6 haloalkyl, C 3 -C 6 alkenyl,
C3-C6-Alkinyl, C1-C6-Alkoxy-C1-C6-alkyl oder C 3 -C 6 alkynyl, C 1 -C 6 alkoxy-C 1 -C 6 alkyl or
R6 und R7 zusammen eine gesättigte oder ungesättigte, zwei- bis viergliedrige Kohlenstoffkette, die einen Oxosubstituenten tragen kann, wobei einR 6 and R 7 together form a saturated or unsaturated, two- to four-membered carbon chain which can carry an oxo substituent, where a
Glied dieser Kette durch ein den Variablen X3 und X4 nicht benachbartes Sauerstoff-, Schwefel- oder Stickstoffatom ersetzt sein kann, und wobei die Kette ein bis drei der folgenden Reste tragen kann: Cyano, Nitro, Amino, Halogen, C1-C6-Alkyl,Link of this chain can be replaced by an oxygen, sulfur or nitrogen atom not adjacent to the variables X 3 and X 4 , and the chain can carry one to three of the following radicals: cyano, nitro, amino, halogen, C 1 -C 6 alkyl,
C2-C6-Alkenyl, C1-C6-Alkoxy, C2-C6-Alkenyloxy, C2-C6-Alkinyloxy, C1-C6-Halogenalkyl, Cyano-C1-C6- alkyl, Hydroxy-C1-C6-alkyl, C1-C6-Alkoxy-C1-C6- alkyl, C3-C6-Alkenyloxy-C1-C6-alkyl, C3-C6-Alkinyloxy-C1-C6-alkyl, C3-C7-Cycloalkyl, C3-C7- -Cycloalkoxy, Carboxy, C1-C6-Alkoxycarbonyl, C1-C6-Alkyl-carbonyloxy-C1-C6-alkyl und Phenyl das einen bis drei der folgenden Reste tragen kann: Halogen, Cyano, Nitro, Amino, C1-C6-Alkyl, C1-C6-Halogenalkyl, C1-C6-Alkoxy und C1-C6-Alkoxycarbonyl und wobei die Kette außerdem durch einen ankondensierten oder spiroverknüpften drei bis siebengliedrigen Ring substituiert sein kann, wobei ein bis zwei Kohlenstoffatome dieses Rings durch Sauerstoff-, Schwefel- und gegebenenfallsC 2 -C 6 alkenyl, C 1 -C 6 alkoxy, C 2 -C 6 alkenyloxy, C 2 -C 6 alkynyloxy, C 1 -C 6 haloalkyl, cyano-C 1 -C 6 alkyl, Hydroxy-C 1 -C 6 alkyl, C 1 -C 6 alkoxy-C 1 -C 6 alkyl, C 3 -C 6 alkenyloxy-C 1 -C 6 alkyl, C 3 -C 6 alkynyloxy- C 1 -C 6 alkyl, C 3 -C 7 cycloalkyl, C 3 -C 7 cycloalkoxy, carboxy, C 1 -C 6 alkoxycarbonyl, C 1 -C 6 alkylcarbonyloxy-C 1 -C 6 alkyl and phenyl which can carry one to three of the following radicals: halogen, cyano, nitro, amino, C 1 -C 6 alkyl, C 1 -C 6 haloalkyl, C 1 -C 6 alkoxy and C 1 -C 6 -alkoxycarbonyl and where the chain can also be substituted by a fused or spiro-linked three to seven-membered ring, one or two carbon atoms of this ring by oxygen, sulfur and optionally
C1-C6-Alkylsubstituierte Stickstoffatome ersetzt sein dürfen und dieser Ring ein bis zwei der folgenden Substituenten tragen kann: Cyano, C1-C6-Alkyl, C2-C6-Alkenyl, C1-C5-Alkoxy, C1-C6-Cyanoalkyl, C1-C6-Halogenalkyl und C1-C6-Alkoxycarbonyl; C 1 -C 6 alkyl substituted nitrogen atoms replaced may be and this ring may have one to two of the following substituents: cyano, C 1 -C 6 alkyl, C 2 - C6 alkenyl, C 1 -C 5 alkoxy, C 1 -C 6 cyanoalkyl, C 1 - C 6 haloalkyl and C 1 -C 6 alkoxycarbonyl;
R8 Wasserstoff, Cyano, C1-C6-Alkyl, C2-C5-Alkenyl, R 8 is hydrogen, cyano, C 1 -C 6 alkyl, C 2 -C 5 alkenyl,
C2-C6-Alkinyl, C1-C6-Halogenalkyl, C3-C7-Cycloalkyl, C1-C6-Alkoxy-C1-C6-alkyl oder C1-C6-Alkoxycarbonyl; R9, R12 Wasserstoff, Cyano, Halogen, C1-C6-Alkyl, C1-C6- Alkoxy, Halogen-C1-C6-alkyl, C1-C6-Alkylcarbonyl oder C1-C6-Alkoxycarbonyl; C 2 -C 6 alkynyl, C 1 -C 6 haloalkyl, C 3 -C 7 cycloalkyl, C 1 -C 6 alkoxy-C 1 -C 6 alkyl or C 1 -C 6 alkoxycarbonyl; R 9 , R 12 are hydrogen, cyano, halogen, C 1 -C 6 alkyl, C 1 -C 6 alkoxy, halogen C 1 -C 6 alkyl, C 1 -C 6 alkylcarbonyl or C 1 -C 6 -Alkoxycarbonyl;
R10 Wasserstoff, O-R17, S-R17, C1-C6-Alkyl, das noch einen oder zwei C1-C6-Alkoxysubstituenten tragen kann, C3-C6-Alkenyl, C3-C6-Alkinyl, C1-C6-Halogenalkyl, C3-C7-Cycloalkyl, C1-C6-Alkylthio-C1-C6- alkyl, C1-C6-Alkyliminooxy, -N(R15)R16 oder R 10 is hydrogen, OR 17 , SR 17 , C 1 -C 6 alkyl, which can also carry one or two C 1 -C 6 alkoxy substituents, C 3 -C 6 alkenyl, C 3 -C 6 alkynyl, C 1 -C 6 haloalkyl, C 3 -C 7 cycloalkyl, C 1 -C6 alkylthio-C 1 -C 6 alkyl, C 1 -C 6 alkyliminooxy, -N (R 15 ) R 16 or
Phenyl, welches einen bis drei der folgenden Substituenten tragen kann: Cyano, Nitro, Halogen, C1-C6-Alkyl, C2-C6-Alkenyl, C1-C6-Halogenalkyl, C1-C6-Alkoxy oder C1-C6-Alkoxycarbonyl, Phenyl which can carry one to three of the following substituents: cyano, nitro, halogen, C 1 -C 6 alkyl, C 2 -C 6 alkenyl, C 1 -C 6 haloalkyl, C 1 -C 6 alkoxy or C 1 -C 6 alkoxycarbonyl,
R17 Wasserstoff, C1-C6-Alkyl, C3-C6-Alkenyl, R 17 is hydrogen, C 1 -C 6 alkyl, C 3 -C 6 alkenyl,
C3-C6-Alkinyl, C3-C7-Cycloalkyl, C1-C6- Halogenalkyl, C3-C6-Halogenalkenyl, Cyano- C1-C6-alkyl, C1-C6-Alkoxy-C1-C6-alkyl, C1-C6- -Alkylthio-C1-C6-alkyl oder C1-C6-Alkyl- oximino-C1-C6-alkyl, C1-C6-Alkylcarbonyl, C1-C6-Alkoxycarbonyl, C1-C6-Alkylcarbonyl- C1-C1-alkyl, C1-C6-Alkoxycarbonyl-C1-C6- alkyl, Phenyl, Phenyl-C1-C6-alkyl, wobei der Phenylrest jeweils einen bis drei der folgenden Substituenten tragen kann: C 3 -C 6 alkynyl, C 3 -C 7 cycloalkyl, C 1 -C 6 - haloalkyl, C 3 -C 6 haloalkenyl, cyano C 1 -C 6 alkyl, C 1 -C 6 alkoxy C 1 -C 6 alkyl, C 1 -C 6 - alkylthio-C 1 -C 6 alkyl or C 1 -C 6 alkyl oximino-C 1 -C 6 alkyl, C 1 -C 6 alkylcarbonyl , C 1 -C 6 -alkoxycarbonyl, C 1 -C 6 -alkylcarbonyl- C 1 -C 1 -alkyl, C 1 -C 6 -alkoxycarbonyl-C 1 -C 6 -alkyl, phenyl, phenyl-C 1 -C 6 alkyl, where the phenyl radical can each carry one to three of the following substituents:
Cyano, Nitro, Halogen, C1-C6-Alkyl, C1-C6- Halogenalkyl, C3-C6-Alkenyl, C1-C6-Alkoxy und C1-C6-Alkoxycarbonyl; R11 Wasserstoff, Cyano, Halogen, C1-C6-Alkyl, C3-C6- Alkenyl, C3-C6-Alkinyl, C1-C6-Alkoxy-C1-C6-alkyl, C1-C6-Alky lcarbonyl, C1-C6-Al koxycarbonyl, Cyano, nitro, halogen, C 1 -C 6 alkyl, C 1 -C 6 haloalkyl, C 3 -C 6 alkenyl, C 1 -C 6 alkoxy and C 1 -C 6 alkoxycarbonyl; R 11 is hydrogen, cyano, halogen, C 1 -C 6 alkyl, C 3 -C 6 alkenyl, C 3 -C 6 alkynyl, C 1 -C 6 alkoxy-C 1 -C 6 alkyl, C 1 -C 6 -alkyl carbonyl, C 1 -C 6 -alkoxycarbonyl,
-NR18R19, wobei R18 und R19 die Bedeutungen von Rl5 und Riß haben, oder Phenyl, das noch einen bis drei der folgenden Substituenten tragen kann: -NR 18 R 19 , where R 18 and R 19 have the meanings of Rl5 and Riß, or phenyl, which can also carry one to three of the following substituents:
Cyano, Nitro, Halogen, C1-C6-Alkyl, C1-C6-Halogenalkyl, C3-C6-Alkenyl, C1-C6-Alkoxy und C1-C6-Alkoxycarbonyl; Cyano, nitro, halogen, C 1 -C 6 alkyl, C 1 -C 6 haloalkyl, C 3 -C 6 alkenyl, C 1 -C 6 alkoxy and C 1 -C 6 alkoxycarbonyl;
R13 Wasserstoff, Cyano, C1-C6-Alkyl oder C1-C6-Alkoxycarbonyl; oder R9 und R10 zusammen eine zwei- bis fünfgliedrige R 13 is hydrogen, cyano, C 1 -C 6 alkyl or C 1 -C 6 alkoxycarbonyl; or R 9 and R 10 together form a two- to five-membered group
Kohlenstoffkette, wobei ein Kohlenstoffatom dieser Kette durch Sauerstoff, Schwefel oder gegebenenfalls C1-C6-Alkyl substituiertes Stickstoff ersetzt sein kann, Carbon chain, it being possible for one carbon atom of this chain to be replaced by oxygen, sulfur or optionally C 1 -C 6 -alkyl-substituted nitrogen,
R1 R 1
Halogen, Cyano, Nitro oder Trifluormethyl; Halogen, cyano, nitro or trifluoromethyl;
R2 R 2
Wasserstoff oder Halogen; R3 Hydrogen or halogen; R 3
Wasserstoff, Nitro, C1-C6-Alkyl, C3-C6-Alkenyl, Hydrogen, nitro, C 1 -C 6 alkyl, C 3 -C 6 alkenyl,
C3-C6-Alkinyl, C3-C8-Cycloalkyl, C3-C8-Cycloalkylcarbonyl, Cyano-C1-C6alkyl, C1-C6-Halogenalkyl, C1-C6-Alkoxy-C1-C5- alkyl, Formyl, C1-C6-Alkanoyl, C1-C6-Alkoxycarbonyl, C 3 -C 6 alkynyl, C 3 -C 8 cycloalkyl, C 3 -C 8 cycloalkylcarbonyl, cyano-C 1 -C 6 alkyl, C 1 -C 6 haloalkyl, C 1 -C 6 alkoxy-C 1 -C 5 alkyl, formyl, C 1 -C 6 alkanoyl, C 1 -C 6 alkoxycarbonyl,
C1-C6-Halogenalkylcarbonyl, C1-C6-Alkylcarbonyl-C1-C6-alkyl, C1-C6-Alkoxycarbonyl-C1-C6-alkyl eine Gruppe -N(R20)R21, wobei R20 und R21 für eine der Bedeutungen von R15 und R16 stehen, C 1 -C 6 haloalkylcarbonyl, C 1 -C 6 alkylcarbonyl-C 1 -C 6 alkyl, C 1 -C 6 alkoxycarbonyl-C 1 -C 6 alkyl a group -N (R 20 ) R 21 , where R 20 and R 21 represent one of the meanings of R 15 and R 16 ,
Phenyl oder Phenyl-C1-C6-alkyl, wobei der Phenylring jeweils einen bis drei der folgenden Reste tragen kann: Cyano, Nitro, Halogen, C1-C6-Alkyl, C2-C6-Alkenyl, C1-C6-Halogenalkyl, C1-C6-Alkoxy und C1-C6-Alkoxycarbonyl; R4 Phenyl or phenyl-C 1 -C 6 -alkyl, where the phenyl ring can each carry one to three of the following radicals: cyano, nitro, halogen, C 1 -C 6 -alkyl, C 2 -C 6 -alkenyl, C 1 - C 6 haloalkyl, C 1 -C 6 alkoxy and C 1 -C 6 alkoxycarbonyl; R 4
Wasserstoff, Cyano, Nitro, Halogen, C1-C6-Alkyl, C2-C6- Alkenyl, C2-C6-Alkinyl, C3-C8-Cycloalkyl, C1-C6-Halogenalkyl, C1-C6-Hydroxyalkyl, Cyano-C1-C6-alkyl, C1-C6-Alkoxy, C!-Ce-Alkylthio, C1-C6-Alkoxy-C1-C6-alkyl, C1-C6-Alkyl- thio-C1-C6-alkyl oder Phenyl, welches einen bis drei der folgenden Reste tragen kann: Cyano, Nitro, Halogen, C1-C6- Alkyl, C2-C6-Alkenyl, C1-C6-Halogenalkyl, C1-C6-Alkoxy und C1-C6-Alkoxycarbonyl; Hydrogen, cyano, nitro, halogen, C 1 -C 6 alkyl, C 2 -C 6 alkenyl, C 2 -C 6 alkynyl, C 3 -C 8 cycloalkyl, C 1 -C 6 haloalkyl, C 1 -C 6 hydroxyalkyl, cyano-C 1 -C 6 alkyl, C 1 -C 6 alkoxy, C ! -C e alkylthio, C 1 -C 6 alkoxy-C 1 -C 6 alkyl, C 1 -C 6 alkyl thio-C 1 -C 6 alkyl or phenyl, which carry one to three of the following radicals can: cyano, nitro, halogen, C 1 -C 6 alkyl, C 2 -C 6 alkenyl, C 1 -C 6 haloalkyl, C 1 -C 6 alkoxy and C 1 -C 6 alkoxycarbonyl;
R5 R 5
Wasserstoff, Cyano, Nitro, Halogen, C1-C6-Alkyl, C2-C6- Alkenyl, C2-C6-Alkinyl, C3-C7-Cycloalkyl, C1-C6-Halogen- alkyl, C1-C6-Hydroxyalkyl, Cyano-C1-C6-alkyl, C1-C6-Alkoxy- C1-C6-alkyl, C1-C6-Alkylthio-C1-C6-alkyl, Formyl, C1-C6- Alky lcarbonyl, C1-C6-Halogenalkylcarbonyl, C1-C6-Alkoxycarbonyl, C1-C6-Alkoxycarbonyl-C2-C6-alkenyl, -N(R22)R23, wobei R22 und R23 für eine der Bedeutungen von R15 und R16 stehen, Phenyl, welches einen bis drei der folgenden Reste tragen kann: Cyano, Nitro, Halogen, C1-C6-Alkyl, C2-C6-Hydrogen, cyano, nitro, halogen, C 1 -C 6 alkyl, C 2 -C 6 alkenyl, C 2 -C 6 alkynyl, C 3 -C 7 cycloalkyl, C 1 -C 6 haloalkyl, C 1 -C 6 hydroxyalkyl, cyano-C 1 -C 6 alkyl, C 1 -C 6 alkoxy- C 1 -C 6 alkyl, C 1 -C 6 alkylthio-C 1 -C 6 alkyl, Formyl, C 1 -C 6 alkylcarbonyl, C 1 -C 6 haloalkylcarbonyl, C 1 -C 6 alkoxycarbonyl, C 1 -C 6 alkoxycarbonyl-C 2 -C 6 alkenyl, -N (R 22 ) R 23 , where R 22 and R 23 stand for one of the meanings of R 15 and R 16 , phenyl, which can carry one to three of the following radicals: cyano, nitro, halogen, C 1 -C 6 alkyl, C 2 -C 6 -
Alkenyl, C1-C6-Halogenalkyl, C1-C6-Alkoxy und C1-C6-Alkoxycarbonyl, oder Alkenyl, C 1 -C 6 haloalkyl, C 1 -C 6 alkoxy and C 1 -C 6 alkoxycarbonyl, or
R4 und R5 zusammen eine gesättigte oder ungesättigte 3- oder 4-gliedrige Kohlenstoffkette, welche ein bis drei der folgenden Heteroatome enthalten kann: 1 oder 2 Sauerstoffatomen, 1 oder 2 Schwefelatomen und 1 bis 3 Stickstoffatomen, wobei die Kette noch ein bis drei der folgenden Reste tragen kann: Cyano, Nitro, Amino, Halogen, C1-C6- Alkyl, C2-C6-Alkenyl, C1-C6-Alkoxy, C1-C6-Alkylthio und C1-C6-Alkoxycarbonyl; mit der Maβgabe, daβ nicht gleichzeitig R4 die Trifluor- methylgruppe R5 Wasserstoff sein können, wenn W eine Gruppe -CH=CH-CO-R10 mit R10 C1-C6-Alkoxy oder C3-C7-Cycloalkoxy bedeutet, und mit der Maßgabe, daβ R4 und R5 nicht gleichzeitig Wasserstoff bedeuten, wenn W für CH(R8)-CH(R9)- CO-R10 und R9 nicht für Halogen stehen, sowie die Salze und Enolether derjenigen Verbindungen I, bei denen R3 Wasserstoff bedeutet. R 4 and R 5 together form a saturated or unsaturated 3 or 4-membered carbon chain, which can contain one to three of the following heteroatoms: 1 or 2 oxygen atoms, 1 or 2 sulfur atoms and 1 to 3 nitrogen atoms, the chain still one to three of the following radicals can carry: cyano, nitro, amino, halogen, C 1 -C 6 alkyl, C 2 -C 6 alkenyl, C 1 -C 6 alkoxy, C 1 -C 6 alkylthio and C 1 -C 6 -alkoxycarbonyl; with the proviso that R 4 cannot simultaneously be the trifluoromethyl group R 5 if W is a group -CH = CH-CO-R 10 with R 10 C 1 -C 6 alkoxy or C 3 -C 7 cycloalkoxy means, and with the proviso that R 4 and R 5 are not simultaneously hydrogen if W is CH (R 8 ) -CH (R 9 ) - CO-R 10 and R 9 are not halogen, and the salts and enol ethers those compounds I in which R 3 is hydrogen.
2. Verbindungen der allgemeinen Formeln Ia oder Ib 2. Compounds of the general formulas Ia or Ib
in denen die Variablen R1, R2, R4, R5, X1, X2 und W die in Anspruch 1 gegebene Bedeutung haben und R3' für eine der folgenden Gruppen steht: in which the variables R 1 , R 2 , R 4 , R 5 , X 1 , X 2 and W have the meaning given in claim 1 and R 3 'represents one of the following groups:
R3' R 3 '
C1-C6-Alkyl, C3-C6-Alkenyl oder C3-C6-Alkinyl; mit der Maβgabe, daβ nicht gleichzeitig R4 die Trifluormethylgruppe R5 Wasserstoff sein können, wenn W eine Gruppe -CH=CH-CO-R10 mit R10 C1-C6-Alkoxy oder C3-C6-Cycloalkoxy bedeutet. 3. Verbindungen nach Anspruch 1 oder 2, wobei W -C(R8)=X5, -C(R8)(X3R6)(X4R7), -C(R8)=C(R9)-CO-R10 oder C 1 -C 6 alkyl, C 3 -C 6 alkenyl or C 3 -C 6 alkynyl; with the proviso that R 4 cannot simultaneously be the trifluoromethyl group R 5 if W is a group -CH = CH-CO-R 10 with R 10 C 1 -C 6 alkoxy or C 3 -C 6 cycloalkoxy. 3. Compounds according to claim 1 or 2, wherein W -C (R 8 ) = X 5 , -C (R 8 ) (X 3 R 6 ) (X 4 R 7 ), -C (R 8 ) = C (R 9 ) -CO-R 10 or
-CH(R8)-CH(R9)-CO-R10 bedeutet. -CH (R 8 ) -CH (R 9 ) -CO-R 10 .
4. Verbindungen nach Anspruch 1 oder 2, wobei R3 C1-C6-Alkyl bedeutet. 4. Compounds according to claim 1 or 2, wherein R 3 is C 1 -C 6 alkyl.
5. Verbindungen nach Anspruch 1 oder 2, wobei R2 Wasserstoff oder Fluor bedeutet. 6. Verbindungen nach Anspruch 1 oder 2, wobei R1 Chlor oder Brom bedeutet. 5. Compounds according to claim 1 or 2, wherein R 2 is hydrogen or fluorine. 6. Compounds according to claim 1 or 2, wherein R 1 is chlorine or bromine.
7. Verbindungen nach Anspruch 1 oder 2, wobei R4 7. Compounds according to claim 1 or 2, wherein R 4
C1-C6-Halogenalkyl bedeutet. Enamin-Ester der allgemeinen Formel II C 1 -C 6 haloalkyl. Enamine esters of the general formula II
in der die Variablen R1, R2, R3, R4, R5, X1 und W die in Anspruch 1 gegebene Bedeutung haben und L1 für C1-C6-Alkyl oder Phenyl steht. in which the variables R 1 , R 2 , R 3 , R 4 , R 5 , X 1 and W have the meaning given in claim 1 and L 1 is C 1 -C 6 -alkyl or phenyl.
9. Enamin-Carboxylate der allgemeinen Formel III 9. Enamine carboxylates of the general formula III
in der die Variablen R1, R2, R3, R4, R5, X2 und W die in Anspruch 1 gegebene Bedeutung haben und L1 für C1-C6-Alkyl oder Phenyl steht. in which the variables R 1 , R 2 , R 3 , R 4 , R 5 , X 2 and W have the meaning given in claim 1 and L 1 is C 1 -C 6 -alkyl or phenyl.
10. Pyrimidon-Derivate der allgemeinen Formel IVa oder IVb 10. Pyrimidone derivatives of the general formula IVa or IVb
in der die Variablen R1, R2, R4, R5, X1, X2 und w die in Anspruch 1 gegebene Bedeutung haben und Hal für Halogen steht. in which the variables R 1 , R 2 , R 4 , R 5 , X 1 , X 2 and w have the meaning given in claim 1 and Hal represents halogen.
11. Enaminamide der Formel VIII VI11 11. Enaminamide the formula VIII V I11
in der die Variablen R1, R2, R3, R4, R5, X2 und W die in Anspruch 1 gegebene Bedeutung haben. in which the variables R 1 , R 2 , R 3 , R 4 , R 5 , X 2 and W have the meaning given in claim 1.
12. Herbizides Mittel enthaltend einen inerten flüssigen oder festen Trägerstoff und eine herbizid wirksame Menge mindestens eines substituierten 3-Phenylurazils der Formel I gemäβ Anspruch 1 oder Ia oder Ib gemäβ Anspruch 2 oder ein Salz oder einen Enolether derjenigen Verbindungen I, in denen R3 Wasserstoff bedeutet. 12. Herbicidal composition comprising an inert liquid or solid carrier and a herbicidally effective amount of at least one substituted 3-phenylurazil of the formula I according to claim 1 or Ia or Ib according to claim 2 or a salt or an enol ether of those compounds I in which R 3 is hydrogen means.
13. Verfahren zur Bekämpfung von unerwünschtem Pflanzenwuchs, dadurch gekennzeichnet, daβ man eine herbizid wirksame Menge eines substituierten 3-Phenylurazils der Formel I gemäβ Anspruch 1 oder Ia oder Ib gemäβ Anspruch 2 oder ein Salz oder einen Enolether derjenigen Verbindungen I, in denen R3 Wasserstoff bedeutet, auf Pflanzen, deren Lebensraum oder auf Saatgut einwirken läβt. 13. A method for controlling unwanted vegetation, characterized in that a herbicidally effective amount of a substituted 3-phenylurazil of the formula I according to claim 1 or Ia or Ib according to claim 2 or a salt or an enol ether of those compounds I in which R 3 Hydrogen means on plants, their habitat or on seeds.
14. Mittel zur Desiccation und Defoliation von Pflanzen, enthaltend neben üblichen Zusatzstoffen eine defoliant und/oder desiccant wirksame Menge mindestens eines substituierten 3-Phenylurazils der Formel I gemäβ Anspruch 1 oder Ia oder Ib gemäβ Anspruch 2 oder ein Salz oder einen Enolether derjenigen Verbindungen I, in denen R3 Wasserstoff bedeutet. 14. Agents for the desiccation and defoliation of plants containing, in addition to conventional additives, a defoliant and / or desiccant effective amount of at least one substituted 3-phenylurazil of the formula I according to claim 1 or Ia or Ib according to claim 2 or a salt or an enol ether of those compounds I in which R 3 is hydrogen.
15. Verfahren zur Desiccation und Defoliation von Pflanzen, 15. Process for the desiccation and defoliation of plants,
dadurch gekennzeichnet, daβ man eine defoliant und/oder desiccant wirksame Menge eines substituierten 3-Phenylurazils I gemäβ Anspruch 1 Ia oder Ib gemäβ Anspruch 2 auf die Pflanzen einwirken läβt. 16. Verfahren nach Anspruch 15, dadurch gekennzeichnet, daβ man Baumwolle entlaubt. characterized in that a defoliant and / or desiccant effective amount of a substituted 3-phenylurazil I according to Claim 1 Ia or Ib according to Claim 2 is allowed to act on the plants. 16. The method according to claim 15, characterized in that cotton is defoliated.
17. Schädlingsbekämpfungsmittel, enthaltend inerte Trägerstoffe und eine pestizid wirksame Menge mindestens eines substituierten 3-Phenylurazils der Formel I gemäβ Anspruch 1 oder Ia oder Ib gemäβ Anspruch 2 oder eines Salzes oder eines Enolethers derjenigen Verbindungen I, in denen R3 Wasserstoff bedeutet. 17. pesticides containing inert carriers and a pesticidally effective amount of at least one substituted 3-phenylurazil of the formula I according to claim 1 or Ia or Ib according to claim 2 or a salt or an enol ether of those compounds I in which R 3 is hydrogen.
18. Verfahren zur Bekämpfung von Schädlingen, dadurch gekennzeichnet, daβ man eine pestizid wirksame Menge eines substituierten 3-Phenylurazils der Formel I gemäβ Anspruch 1 oder Ia oder Ib gemäβ Anspruch 2 oder eines Salzes oder eines Enolethers derjenigen Verbindungen I, in denen R3 Wasserstoff bedeutet auf Schädlinge bzw. ihren Lebensraum einwirken läβt. 18. Process for combating pests, characterized in that a pesticidally effective amount of a substituted 3-phenylurazil of the formula I according to claim 1 or Ia or Ib according to claim 2 or a salt or an enol ether of those compounds I in which R 3 is hydrogen means to affect pests or their habitat.
19. Verfahren zur Herstellung von substituierten 3-Phenylurazilen I gemäβ Anspruch 1 oder Ia oder Ib gemäβ 19. A process for the preparation of substituted 3-phenylurazils I according to claim 1 or Ia or Ib according
Anspruch 2, dadurch gekennzeichnet, daβ man: a) einen Enamin-Ester der Formel II oder ein Enamin-Carboxylat der Formel III  Claim 2, characterized in that: a) an enamine ester of the formula II or an enamine carboxylate of the formula III
wobei L1für C1-C6-Alkyl oder Phenyl steht, cyclisiert, und gewünschtenfalls aus dem erhaltenen Metallsalz mittels Säure das substituierte 3-Phenylurazil I, wobei R3 Wasserstoff bedeutet, freisetzt, oder b) ein 3-Phenylurazil I, wobei R3 für Wasserstoff steht, alkyliert oder acyliert, oder c) ein 3-Phenylurazil I, wobei R1 für Halogen steht, mit einem Metallcyanid umsetzt, oder d) ein Pyrimidon-Derivat der Formel IVa oder IVb where L 1 is C 1 -C 6 alkyl or phenyl, cyclized, and if desired releases from the metal salt obtained by means of acid the substituted 3-phenylurazil I, where R 3 is hydrogen, or b) a 3-phenylurazil I, where R 3 represents hydrogen, alkylated or acylated, or c) a 3-phenylurazil I, where R 1 represents halogen, is reacted with a metal cyanide, or d) a pyrimidone derivative of the formula IVa or IVb
wobei Hal Halogen bedeutet,  where Hal is halogen,
mit einer Verbindung HO-R3', HS-R3', Me⊕ ΘOR3' oderwith a compound HO-R 3 ' , HS-R 3' , Me ⊕ Θ OR 3 ' or
Me⊕ ΘSR3', wobei Me⊕ ein Äquivalent eines Metallions bedeutet, umsetzt, oder e) ein 3-Phenylurazil I, wobei W eine Gruppe -CO-R8 Me ⊕ Θ SR 3 ' , where Me ⊕ is an equivalent of a metal ion, or e) a 3-phenylurazil I, where W is a group -CO-R 8
bedeutet, mit Verbindungen H-X3R6, H-X4R7 odermeans with compounds HX 3 R 6 , HX 4 R 7 or
H-X3(R6R7)X4-H acetalisiert, oder f) ein 3-Phenylurazil I, wobei W eine Gruppe HX 3 (R 6 R 7 ) X 4 -H acetalized, or f) a 3-phenylurazil I, where W is a group
-C(R8)(X3R6)(X4R7) bedeutet, einer Acetalspaltung unterwirft, oder g) ein 3-Phenylurazil I, wobei W eine Gruppe -C(R8)=O bedeutet, mit einem Phosphoryl id der Formel Va bis Vd R3P=CR9-CO-R10 Va, -C (R 8 ) (X 3 R 6 ) (X 4 R 7 ) means subject to acetal cleavage, or g) a 3-phenylurazil I, where W is a group -C (R 8 ) = O, with a phosphoryl id of the formula Va to Vd R 3 P = CR 9 -CO-R 10 Va,
R3P=C(R9)-CH2-CO-R10 Vb, R 3 P = C (R 9 ) -CH 2 -CO-R 10 Vb,
R3P=C(R9)-C(RH)=C(R12)-CO-R10 Vc, R 3 P = C (R 9 ) -C (RH) = C (R 12 ) -CO-R 10 Vc,
R3P=C(R9)-CH2-CHR13-CO-R10 Vd, wobei R für einen C-organischen Substituenten steht, oder mit einem Phosphoniumsalz der Formel VIa bis VId R 3 P = C (R 9 ) -CH 2 -CHR 13 -CO-R 10 Vd, where R is a C-organic substituent, or with a phosphonium salt of the formula VIa to VId
R3P⊕-CH(R9)-CO-R10 HalΘ VIa, R3P⊕-CH(R9)-CH2-CO-R10 HalΘ VIb, R3P⊕-CH(R9)-CR11=CR12-CO-R10 HalΘ VIc,R 3 P ⊕ -CH (R 9 ) -CO-R 10 Hal Θ VIa, R 3 P ⊕ -CH ( R9 ) -CH 2 -CO-R 10 Hal Θ VIb, R 3 P ⊕ -CH (R 9 ) -CR 11 = CR 12 -CO-R 10 Hal Θ VIc,
R3P⊕-CH(R9)-CH2-CHR13-CO-R10 HalΘ VId, wobei Hal für Halogen steht, R 3 P ⊕ -CH (R 9 ) -CH 2 -CHR 13 -CO-R 10 Hal Θ VId, where Hal is halogen,
oder mit einem Phosphonat der Formel Vlla bis Vlld (RO)2PO-CH(R9)-CO-R10 Vlla, or with a phosphonate of the formula VIII to VIII (RO) 2 PO-CH (R 9 ) -CO-R 10 Vlla,
(RO)2PO-CH(R9)-CH2-CO-R10 Vllb, (RO) 2 PO-CH (R 9 ) -CH 2 -CO-R 10 Vllb,
(RO)2PO-CH(R9)-CRH=CR12-CO-R10 VIIc, (RO) 2 PO-CH (R 9 ) -CRH = CR 12 -CO-R 10 VIIc,
(RO) 2PO-CH(R9)-CH2-CHR13-CO-R10 Vlld, umsetzt, oder h) ein 3-Phenylurazil I, wobei W eine Gruppe -C(R8)=O mit einem Amin, Hydroxylamin oder Hydrazin H2N-R14 umsetzt, oder i) ein 3-Phenylurazil I, wobei W eine Gruppe -C(R8)=N-R14 bedeutet, in eine Verbindung I, wobei W für eine Gruppe -C(R8)=O steht, spaltet, oder k) ein 3-Phenylurazil I, wobei X2 Sauerstoff bedeutet, mit einem Schwefelungsreagenz umsetzt, oder l) ein 3-Phenylurazil I, wobei R5 Wasserstoff bedeutet, halogeniert, oder m) ein 3-Phenylurazil I, wobei W die Cyanogruppe bedeutet, reduktiv in eine Verbindung I, wobei W für die (RO) 2 PO-CH (R 9 ) -CH 2 -CHR 13 -CO-R 10 Vlld, or h) a 3-phenylurazil I, where W is a group -C (R 8 ) = O with an amine , Hydroxylamine or hydrazine H 2 NR 14 , or i) a 3-phenylurazil I, where W is a group -C (R 8 ) = NR 14 , into a compound I, where W is a group -C (R 8 ) = O, cleaves, or k) a 3-phenylurazil I, where X 2 is oxygen, is reacted with a sulfurization reagent, or l) a 3-phenylurazil I, where R 5 is hydrogen, halogenates, or m) a 3-phenylurazil I, where W is the cyano group, reductively into a compound I, where W is for the
Formylgruppe steht, überführt, oder n) ein Enamid VIII, gemäβ Anspruch 11, mit einem  Formyl group, transferred, or n) an enamide VIII, according to claim 11, with a
Phosgenierungs- oder Thiophosgenierungsmittel  Phosgenating or thiophosgenating agents
cyclisiert, oder o) ein 3-Phenylurazil I, gemäβ Anspruch 1, in dem W für cyclized, or o) a 3-phenylurazil I, according to claim 1, in which W for
Amino steht, nach dem Meerweinverfahren alkyl iert, oder p) ein 3-Phenylurazil I, gemäβ Anspruch 1, in dem W fürAmino is alkylated by the sea wine process, or p) a 3-phenylurazil I, according to claim 1, in which W is
Brom, Jod oder O-SO2CF3 steht unter Metall-Katalyse mit einem Olefin kuppelt. Substituierte 3-Phenylurazile Bromine, iodine or O-SO 2 CF 3 is coupled with an olefin under metal catalysis. Substituted 3-phenylurazile
Zusammenfassung Substituierte 3-Phenylurazile I Summary Substituted 3-phenylurazile I
(X1-X4 = O,S; (X 1 -X 4 = O, S;
W = geg. subst. -CH=O, -CH=S, -CH=NH, -CH(X3R6 ) (X4R7), W = against subst. -CH = O, -CH = S, -CH = NH, -CH (X 3 R 6 ) (X 4 R 7 ),
R6, R7 = C1-C6-Alkyl, C3-C6-Alkenyl, C3-C6-Alkinyl, C1-C6-Alkoxy- C1-C6-alkyl oder zusammen C-Kette; R10 = H, OH, SH, Ether-, Thioethergruppe, geg. subst. R 6 , R 7 = C 1 -C 6 alkyl, C 3 -C 6 alkenyl, C 3 -C 6 alkynyl, C 1 -C 6 alkoxy- C 1 -C 6 alkyl or together C chain ; R 10 = H, OH, SH, ether, thioether, against subst.
C1-C6-Alkyl, C3-C6-Alkenyl, C3-C6-Alkinyl, C3-C7-Cycloalkyl, geg. subst. Amino, geg. subst. Phenyl; C 1 -C 6 alkyl, C 3 -C 6 alkenyl, C 3 -C 6 alkynyl, C 3 -C 7 cycloalkyl, against subst. Amino, opp. Subst. Phenyl;
R1 = Halogen, CN, NO2, CF3; R2 = H, Halogen; R 1 = halogen, CN, NO 2 , CF 3 ; R 2 = H, halogen;
R3 = H, C1-C6-Alkyl, C3-C6-Alkenyl, C3-C6-Alkinyl, C3-C8-Cycloalkyl, C3-C8-Cycloalkylcarbonyl, C1-C6-Cyanoalkyl, C1-C6-Halogenalkyl, C1-C6-Alkoxy-C1-C6-alkyl, CHO, C1-C6-Alkanoyl, C1-C6-Alkoxycarbonyl, C1-C6-Halogenalkylcarbonyl, geg. subst. Amino, geg. subst. Phenyl oder Phenyl-C1-C6-alkyl; R 3 = H, C 1 -C 6 alkyl, C 3 -C 6 alkenyl, C 3 -C 6 alkynyl, C 3 -C 8 cycloalkyl, C 3 -C 8 cycloalkylcarbonyl, C 1 -C 6 Cyanoalkyl, C 1 -C 6 haloalkyl, C 1 -C 6 alkoxy-C 1 -C 6 alkyl, CHO, C 1 -C 6 alkanoyl, C 1 -C 6 alkoxycarbonyl, C 1 -C 6 -Halogenalkylcarbonyl, against subst. Amino, opp. Subst. Phenyl or phenyl-C 1 -C 6 alkyl;
R4, R5 = H, CN, Halogen, geg. subst. C1-C6-Alkyl, C2-C6-Alkenyl, C2-C6-Alkinyl, C3-C7-Cycloalkyl, geg. subst. Phenyl; R 4 , R 5 = H, CN, halogen, against subst. C 1 -C 6 alkyl, C 2 -C 6 alkenyl, C 2 -C 6 alkynyl, C 3 -C 7 cycloalkyl, against subst. Phenyl;
R5 = zusätzlich NO2, CHO, C1-C6-Alkylcarbonyl, C1-C6-Halogenalkylcarbonyl, C1-C6-Alkoxycarbonyl, geg. subst. Amino oder R4+R5 = geg. subst. Kohlenstoffkette; ausgenommen R4 = CF3 und gleichzeitig R5 = H, wenn w = R 5 = additionally NO 2 , CHO, C 1 -C 6 alkylcarbonyl, C 1 -C 6 haloalkylcarbonyl, C 1 -C 6 alkoxycarbonyl, against subst. Amino or R 4 + R 5 = against subst. Carbon chain; except R 4 = CF 3 and at the same time R 5 = H if w =
-CH=CH-CO-R10 mit R10 = C1-C6-Alkoxy oder C3-C7-Cycloalkoxy; sowie die Salze und Enolether vonflimit R3 = H. -CH = CH-CO-R 10 with R 10 = C 1 -C 6 alkoxy or C 3 -C 7 cycloalkoxy; as well as the salts and enol ethers of limit R 3 = H.
Verwendung: Desiccation/Defoliation von Pflanzen; Insektizide; Herbizide. Use: Desiccation / defoliation of plants; Insecticides; Herbicides.
GEANDERTE ANSPRUCHE CHANGED CLAIMS
[beim Internationalen Büro am 14. Januar 1993 (14.01.93) eingegangen;  [Received at the International Bureau on January 14, 1993 (January 14, 1993);
ursprünglicher Anspruch 11 geändert;  original claim 11 amended;
übrige Ansprüche unverändert (1 Seite)]  other claims unchanged (1 page)]
11. Enaminamide der Formel VIII 11. Enaminamides of the formula VIII
in der die Variablen R1, R2, R3, R4, R5, X2 und W die in in which the variables R 1 , R 2 , R 3 , R 4 , R 5 , X 2 and W the in
Anspruch 1 gegebene Bedeutung haben, ausgenommen diejenigen  Claim 1 have given meaning, except those
Verbindungen VIII, bei denen R1 für Halogen, Nitro oder Compounds VIII in which R 1 is halogen, nitro or
Trifluormethyl, R3 für Wasserstoff, R4 für Trifluormethyl, R5 Trifluoromethyl, R 3 for hydrogen, R 4 for trifluoromethyl, R 5
für Cyano, X2 für Sauerstoff und W für -CH=N-R14 mit R14 = C1-C6-Alkoxy stehen. stand for cyano, X 2 for oxygen and W for -CH = NR 14 with R 14 = C 1 -C 6 alkoxy.
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