EP0604491A1 - Substituierte-3-phenylurazile als herbizide - Google Patents

Substituierte-3-phenylurazile als herbizide

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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
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German (de)
English (en)
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/de
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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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JP3253299B2 (ja) 2002-02-04
DE4131038A1 (de) 1993-04-01
BR9206518A (pt) 1995-04-25
KR100260011B1 (ko) 2000-08-01
JPH06510992A (ja) 1994-12-08
MX9205306A (es) 1993-04-01
ZA927153B (en) 1994-03-18
CA2119036A1 (en) 1993-04-01

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