IL112523A - ESTERS OF 2-HALO- 5-£TETRAHYDRO-3 (THI) OXO-1H, 3H-£1, 3, 4| THIADIAZOL £3, 4-a| PYRIDAZIN-1- YLIDEN| AMINO|- BENZOIC ACID AND HOMOLOGS THEREOF, THEIR PREPARATION AND HERBICIDAL COMPOSITIONS CONTAINING THEM - Google Patents

ESTERS OF 2-HALO- 5-£TETRAHYDRO-3 (THI) OXO-1H, 3H-£1, 3, 4| THIADIAZOL £3, 4-a| PYRIDAZIN-1- YLIDEN| AMINO|- BENZOIC ACID AND HOMOLOGS THEREOF, THEIR PREPARATION AND HERBICIDAL COMPOSITIONS CONTAINING THEM

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IL112523A
IL112523A IL112523A IL11252395A IL112523A IL 112523 A IL112523 A IL 112523A IL 112523 A IL112523 A IL 112523A IL 11252395 A IL11252395 A IL 11252395A IL 112523 A IL112523 A IL 112523A
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methyl
hydrogen
compound
oxygen
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IL112523A
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Ciba Geigy Ag
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D295/00—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms
    • C07D295/04—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms
    • C07D295/08—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms substituted by singly bound oxygen or sulfur atoms
    • C07D295/084—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms substituted by singly bound oxygen or sulfur atoms with the ring nitrogen atoms and the oxygen or sulfur atoms attached to the same carbon chain, which is not interrupted by carbocyclic rings
    • C07D295/088—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms substituted by singly bound oxygen or sulfur atoms with the ring nitrogen atoms and the oxygen or sulfur atoms attached to the same carbon chain, which is not interrupted by carbocyclic rings to an acyclic saturated chain
    • 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
    • A01N43/90—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having two or more relevant hetero rings, condensed among themselves or with a common carbocyclic ring system
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C205/00—Compounds containing nitro groups bound to a carbon skeleton
    • C07C205/49—Compounds containing nitro groups bound to a carbon skeleton the carbon skeleton being further substituted by carboxyl groups
    • C07C205/57—Compounds containing nitro groups bound to a carbon skeleton the carbon skeleton being further substituted by carboxyl groups having nitro groups and carboxyl groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton
    • C07C205/58—Compounds containing nitro groups bound to a carbon skeleton the carbon skeleton being further substituted by carboxyl groups having nitro groups and carboxyl groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton the carbon skeleton being further substituted by halogen atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C229/00—Compounds containing amino and carboxyl groups bound to the same carbon skeleton
    • C07C229/52—Compounds containing amino and carboxyl groups bound to the same carbon skeleton having amino and carboxyl groups bound to carbon atoms of six-membered aromatic rings of the same carbon skeleton
    • C07C229/54—Compounds containing amino and carboxyl groups bound to the same carbon skeleton having amino and carboxyl groups bound to carbon atoms of six-membered aromatic rings of the same carbon skeleton with amino and carboxyl groups bound to carbon atoms of the same non-condensed six-membered aromatic ring
    • C07C229/60—Compounds containing amino and carboxyl groups bound to the same carbon skeleton having amino and carboxyl groups bound to carbon atoms of six-membered aromatic rings of the same carbon skeleton with amino and carboxyl groups bound to carbon atoms of the same non-condensed six-membered aromatic ring with amino and carboxyl groups bound in meta- or para- positions
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C235/00—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by oxygen atoms
    • C07C235/02—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by oxygen atoms having carbon atoms of carboxamide groups bound to acyclic carbon atoms and singly-bound oxygen atoms bound to the same carbon skeleton
    • C07C235/04—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by oxygen atoms having carbon atoms of carboxamide groups bound to acyclic carbon atoms and singly-bound oxygen atoms bound to the same carbon skeleton the carbon skeleton being acyclic and saturated
    • C07C235/06—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by oxygen atoms having carbon atoms of carboxamide groups bound to acyclic carbon atoms and singly-bound oxygen atoms bound to the same carbon skeleton the carbon skeleton being acyclic and saturated having the nitrogen atoms of the carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C235/00—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by oxygen atoms
    • C07C235/02—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by oxygen atoms having carbon atoms of carboxamide groups bound to acyclic carbon atoms and singly-bound oxygen atoms bound to the same carbon skeleton
    • C07C235/04—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by oxygen atoms having carbon atoms of carboxamide groups bound to acyclic carbon atoms and singly-bound oxygen atoms bound to the same carbon skeleton the carbon skeleton being acyclic and saturated
    • C07C235/08—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by oxygen atoms having carbon atoms of carboxamide groups bound to acyclic carbon atoms and singly-bound oxygen atoms bound to the same carbon skeleton the carbon skeleton being acyclic and saturated having the nitrogen atom of at least one of the carboxamide groups bound to an acyclic carbon atom of a hydrocarbon radical substituted by singly-bound oxygen atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C251/00—Compounds containing nitrogen atoms doubly-bound to a carbon skeleton
    • C07C251/32—Oximes
    • C07C251/62—Oximes having oxygen atoms of oxyimino groups esterified
    • C07C251/64—Oximes having oxygen atoms of oxyimino groups esterified by carboxylic acids
    • C07C251/66—Oximes having oxygen atoms of oxyimino groups esterified by carboxylic acids with the esterifying carboxyl groups bound to hydrogen atoms, to acyclic carbon atoms or to carbon atoms of rings other than six-membered aromatic rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C259/00—Compounds containing carboxyl groups, an oxygen atom of a carboxyl group being replaced by a nitrogen atom, this nitrogen atom being further bound to an oxygen atom and not being part of nitro or nitroso groups
    • C07C259/04—Compounds containing carboxyl groups, an oxygen atom of a carboxyl group being replaced by a nitrogen atom, this nitrogen atom being further bound to an oxygen atom and not being part of nitro or nitroso groups without replacement of the other oxygen atom of the carboxyl group, e.g. hydroxamic acids
    • C07C259/06—Compounds containing carboxyl groups, an oxygen atom of a carboxyl group being replaced by a nitrogen atom, this nitrogen atom being further bound to an oxygen atom and not being part of nitro or nitroso groups without replacement of the other oxygen atom of the carboxyl group, e.g. hydroxamic acids having carbon atoms of hydroxamic groups bound to hydrogen atoms or to acyclic carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C327/00—Thiocarboxylic acids
    • C07C327/20—Esters of monothiocarboxylic acids
    • C07C327/28—Esters of monothiocarboxylic acids having sulfur atoms of esterified thiocarboxyl groups bound to carbon atoms of hydrocarbon radicals substituted by singly-bound oxygen atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C331/00—Derivatives of thiocyanic acid or of isothiocyanic acid
    • C07C331/16—Isothiocyanates
    • C07C331/26—Isothiocyanates having isothiocyanate groups bound to carbon atoms of rings other than six-membered aromatic rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D237/00—Heterocyclic compounds containing 1,2-diazine or hydrogenated 1,2-diazine rings
    • C07D237/02—Heterocyclic compounds containing 1,2-diazine or hydrogenated 1,2-diazine rings not condensed with other rings
    • C07D237/04—Heterocyclic compounds containing 1,2-diazine or hydrogenated 1,2-diazine rings not condensed with other rings having less than three double bonds between ring members or between ring members and non-ring members
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    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D513/00—Heterocyclic compounds containing in the condensed system at least one hetero ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for in groups C07D463/00, C07D477/00 or C07D499/00 - C07D507/00
    • C07D513/02—Heterocyclic compounds containing in the condensed system at least one hetero ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for in groups C07D463/00, C07D477/00 or C07D499/00 - C07D507/00 in which the condensed system contains two hetero rings
    • C07D513/04—Ortho-condensed systems
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2601/00—Systems containing only non-condensed rings
    • C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
    • C07C2601/14—The ring being saturated

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Agronomy & Crop Science (AREA)
  • Pest Control & Pesticides (AREA)
  • Plant Pathology (AREA)
  • Health & Medical Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Dentistry (AREA)
  • General Health & Medical Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Zoology (AREA)
  • Environmental Sciences (AREA)
  • Plural Heterocyclic Compounds (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)
  • Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)

Abstract

Compounds of formula (I): wherein R is C1-C6alkyl, C1-C6haloalkyl, C3-C6alkenyl, C3-C6alkynyl, C1-C4alkoxy or C3-C6cycloalkyl; R1 is halogen; R2 and R3 are each independently of the other C1-C4alkyl; R4 is halogen or a group of the formula -X-R5, -X-A-R6 or (a); R5 is hydrogen, C1-C6alkyl, C1-C8haloalkyl, C1-C4alkoxy-C1-C4alkyl, C1-C10alkylthio-C1-C4alkyl, C1-C4alkylamino-C1-C4alkyl, di-C1-C4alkylamino-C1-C4alkyl, cyano-C1-C8-alkyl, C3-C8alkenyl, C3-C8haloalkenyl, C3-C8alkynyl, C3-C6cycloalkyl, oxetanyl, C3-C7-halocycloalkyl, C3-C7cycloalkyl-C1-C4alkyl, phenyl-C1-C3alkyl that is unsubstituted or substituted in the phenyl ring by 1, 2 or 3 identical or different substituents selected from halogen, C1-C4alkyl, C1-C4haloalkyl, C1-C4alkoxy and C1-C4haloalkoxy, or R5 is an alkali metal, alkaline earth metal or ammonium ion, or is the group -N=C(CH3)2, -CH2-O-N=C(CH3)2 or -CH2CH2-O-N=C(CH3)2; X is oxygen or sulfur; A is C1-C4 alkylene; R6 is a 5- or 6-membered heterocyclic ring that contains from 1 to 3 hetero atoms selected from the group oxygen, nitrogen and sulfur and that is bonded via the carbon or nitrogen atom to the alkylene chain A, it being possible for the heterocyclic ring in turn also to be benzene-fused and mono- or di-substituted by halogen, C1-C4alkyl, C1-C3haloalkyl, C1-C3alkoxy, C1-C3haloalkoxy, di-C1-C3alkylamino, hydroxy or by an oxy function; R7 is hydrogen, C1-C6alkyl, C1-C4haloalkyl, C1-C4alkoxy, C1-C4alkoxy-C1-C4alkyl, C3-C6alkenyl, C3-C6alkynyl, C3-C8cycloalkyl, hydroxy-C1-C4alkyl or cyano-C1-C4alkyl; R8 is hydrogen, C1-C6alkyl, C1-C4haloalkyl, C1-C4alkoxy-C1-C4-alkyl, hydroxy-C1-C4-alkyl, C3-C6alkenyl, phenyl or phenyl-C1-C3alkyl, the phenyl ring being unsubstituted or mono-, di- or tri-substituted by halogen, C1-C4alkyl, C1-C4haloalkyl, C1-C4alkoxy or by C1-C4haloalkoxy; or R7 and R8, together with the nitrogen atom to which they are bonded, form a pyrrolidino, piperidino, morpholino, thiomorpholino or piperazino ring that is unsubstituted or mono- or di-substituted by C1-C3alkyl; Z is oxygen or sulfur; n is 3, 4 or 5; and n1 is 0, 1, 2 or 3, and salts of those compounds, are suitable as herbicides for controlling weeds in crops of useful plants. [WO9521174A1]

Description

112523/3 nT >N-l-)nNf1>3 [a-4,3] ¾>1ΪΝ*ΤΝ>Ϊ1 [4,3,1] -H3,Hl-1 >i71N('n)3 Esters of 2-halo-5-[tetrahydro-3(thi)oxo-lH,3H- [1,3,4] thiadia2ol[3,4-a]pyrid -1-yliden] amino] -benzoic acid and homologs thereof, their preparation and herbicidal compositions containing them Novarti s AG C. 96258 The present invention relates to novel herbicidally active phenylimino-thiadiazabicyclo alkanes, to a process for the preparation thereof, to compositions comprising those compounds, and to the use thereof in the control of weeds, especially in crops of useful plants, or in the. inhibition of plant growth.
Phenylimino-thiadiazabicyclononane compounds having herbicidal acdvity are known are described, for example, in EP-A-238,711. EP-A-480,871 and US 4,816,063 both disclose phenyliminothiadiazabicyclononanone derivatives with an alkoxycarbonyl-alkoxycarbonyl group as phenyl substituent. Neither of them describes the quaternary methylene bridge linking the benzoyloxy moiety and the carbonyl group of the second ester function. US 5,135,562 discloses tetrahydro- lH,3H-( l,3,4)thiadiazolo[3,4-a]pyridazine derivatives with a tertiary methylene group bridging the double-ester function and a different substitution pattern on the benzoyl-ring moiety.
Novel phenylimino-thiadiazabicycloalkanes having herbicidal and growth-inhibiting properties have now been found.
The present invention therefore relates to compounds of formula I wherein R is CrC6alkyl, CrC6haloalkyl, C3-C6alkenyl, C3-C6alkynyl, CrC4alkoxy or C3-C6-cycloalkyl; Ri is halogen; R2 and R3 are each independently of the other Q-Qalkyl; R4 is halogen or a group of the formula -X-R5, -X-A-R6 or — ; Rs R5 is hydrogen, CrC6aIkyl, CrC8haloalkyl, CrC4alkoxy-CrC4alkyl, CrCl0aLkylthio-C1-C4alkyl, CpQalkylamino-CpQalkyl, di-C1-C alkylamino-C1-C4alkyl( cyano-CrC8-alk l, C3-C8alkenyl, C3-C8haioaIkenyI, C3-C8aUcynyl, C3-C6cycloaIkyl, oxetanyl, C3-C7- halocycloalkyl, C3-C7cycloalkyl-C1-C4alkyl, phenyl-C Csalk l that is unsubstituted or substituted in the phenyl ring by 1, 2 or 3 identical or different substituents selected from halogen, C rC4alkyl, C rC4haloalkyl, CrC4alkoxy and CrC4haloalkoxy, or R5 is an alkali metal, alkaline earth metal or ammonium ion, or is the group -N=C(CH3)2, -CH2-0- =C(CH3)2 or -CH2CH2-0- =C(CH3)2; X is oxygen or sulfur; A is CL-C4alkylene; R6 is a 5- or 6-membered heterocyclic ring that contains from 1 to 3 hetero atoms selected from the group oxygen, nitrogen and sulfur and that is bonded via the carbon or nitrogen atom to the alkylene chain A, it being possible for the heterocyclic ring in turn also to be benzene-fused and mono- or di-substi utsd by halogen, CrC4aIl yl, C1-C3haloalkyl, Y" CrC3alkoxy, C1-C3haloaIk:oxy, di-CrC3alkylamino, hydroxy or by an oxo function ' R7 is hydrogen, CrC0alleyl, CrC4haloalkyl, CrC4alkoxy, C1-C4alkoxy-C1-C4allcyl, C3-C6alkenyl, C3-C6alkynyl, C3-C8cycloalkyl, hydroxy-CrC4alkyl or cyano-C1-C4alkyl; R8 is hydrogen, CrC6allcyl, C^haloalkyl, C1-C4al] oxy-CrC4all-yl, hydroxy-CrC4- alkyl, C3-C6alkenyl, phenyl or phenyl-C1-C3ali yl, the phenyl ring being unsubstituted or mono-, di- or tri-substituted by halogen, CrC4aI! yl, C1-C4haloallcyl, CrC4aIkoxy or by CrC4haloaIkoxy; or R7 and R8, together with the nitrogen atom to which they are bonded, form a pyrrolidino, piperidino, morpholino, thiomorpholino or piperazino ring that is unsubstituted or mono- or di-substituted by CrC3alkyl; Z is oxygen or sulfur; n is 3, 4 or 5; and nL is O, 1, 2 or 3, and to salts of those compounds.
The alkyl groups that occur in the definitions of the substituents may be straight-chained or branched and are, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl and the various isomers of pentyl and hexyl radicals. Methyl, ethyl, n-propyl, isopropyl and n-butyl are preferred.
Halogen is to be understood as being iodine, preferably fluorine, chlorine and bromine.
As haloalkyl there come into consideration alkyl groups that are mono- or poly-substituted, especially mono-, di- or tri-substituted, by halogen, the individual meanings of halogen being iodine and especially fluorine, chlorine and bromine, for example fluoro- methyl, difluoromethyl, trifluoromethyl, chloromethyl, dichloromethyl, trichloromethyl, 2,2,2-trifluoroethyl, 2-fluoroethyl, 2-chloroethyl and 2,2,2-trichloroethyl; preferably di- fluorochloromethyl, trifluoromethyl, dichlorofluoromeihyl and 2-chloroethyl.
Alkoxy is, for example, methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy and tert-butoxy; preferably methoxy, ethoxy and isopropoxy.
Haloalkoxy is, for example, fluoromethoxy, difluoromethoxy, trifluoromethoxy, 2,2,2-tri-fluoroethoxy, 1,1,2,2-tetrafluoroethoxy, 2-fluoroethoxy, 2-chloroethoxy and 2,2,2-tri-chloroethoxy; preferably difluoromethoxy, trifluoromethoxy and 2-chloroethoxy.
Alkenyl is to be understood as being straight-chained or branched alkenyl, for example allyl, 1-methylallyl, methallyl, but-2-en-l-yl, pentenyl, 2-hexenyl and 3-heptenyl.
Alkenyl radicals having a chain length of 3 and 4 carbon atoms are preferred.
As haloalkenyl there come into consideration alkenyl groups that are mono- or poly-substituted by halogen, the individual meanings of halogen being bromine, iodine and, especially, fluorine and chlorine, for example 2- and 3-fluoroallyl, 2- and 3-chloroallyl, 2,3,3-trifluoroallyl, 2,3,3-trichloroallyl, 4,4,4-trifluoro-but-2-en-l-yl and 4,4,4-trichloro-but-2-en-l-yl. 2- and 3-chloroallyl are preferred.
The alkynyl radicals that occur in the definitions of the substituents may be straight-chained or branched, for example propargyl, 3-butynyl, l-methylpropargyl, 1-pentynyl or 2-hexynyl. Propargyl and l-methylpropargyl are preferred.
Cycloalkyl is, for example, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl or cyclooctyl.
Halocycloalkyl is, for example, 2,2-dichlorocyclopropyl and pentachlorocyclohexyl.
Alkoxyalkyl is, for example, methoxymethyl, ethoxymethyl, propoxymethyl, methoxy-ethyl, ethoxyethyl, propoxyethyl, butoxyethyl, methoxypropyl, ethoxypropyl and propoxy-propyl.
Alkylthioalkyl is, for example, methylthiomethyl, ethylthiomethyl, methylthioethyl, methylthio-prop-2-yl, ethylthioethyl, ethylthio-prop-2-yl, propylthio-prop-2-yl, isopropyl-thioethyl, isopropylthio-prop-2-yl, n-butylthio-prop-2-yl and n-pentylthio-prop-2-yl.
Alkylamino is, for example, methylamino, ethylamino and the isomers of propyl- and butyl-amino.
Dialkylamino is, for example, dimethylamino, methylethylamino, diethylamino and the isomers of dipropyl- and dibutyl-amino.
Cyanoalkyl is, for example, cyanomethyl, cyanoethyl, cyanoeth-l-yl and cyanopropyl.
Hydroxyalkyl is, for example, hydroxymethyl, hydroxyethyl and 3-hydroxypropyl.
Phenyl, including part of a substituent such as phenylalkyl, may generally be unsubstituted or substituted. In the latter case, the substituents may be in the ortho-, meta- and/or para-position with respect to the ring linkage site. Preferred positions for the substituents are the ortho- and para-positions. Preferred substituents are halogen atoms and alkyl, halo-alkyl, alkoxy and haloalkoxy groups.
A as an alkylene chain may be straight-chained or branched and is, for example, methylene, ethylene, methylethylene, propylene, 1-methyl-propylene and butylene; preferably methylene and ethylene.
R6 as a 5- or 6-membered heterocyclic ring is an unsaturated or completely or partially saturated heterocycle, for example 2-, 3- or 4-pyridyl, N-piperidyl, 2-thienyl, 2-furyl, 2-tetrahydrothienyl, 2-tetrahydrofuryl, N-morpholinyl and N-imidazolyl. Those hetero-cycles may in turn be substituted, for example l-methyl-4-pyrazolyl, 4-methyl-5-thiazolyl and 2-pyrrolidon-l-yl.
The substituents in definitions composed of several elements, for example cycloalkyl-alkyl, alkylamino-alkyl and dialkylamino-alkyl, may also be given corresponding meanings.
The salts of compounds of formula I containing acid protons, especially the salts of the derivatives containing carboxylic acid groups (R4 is the group of the formula -X-R5, wherein X is oxygen and R5 is hydrogen), are, for example, alkali metal salts, e.g. sodium and potassium salts; alkaline earth metal salts, e.g. calcium and magnesium salts; ammonium salts, i.e. unsubstituted ammonium salts and mono- or poly-substituted ammonium salts, e.g. triethylammonium and methylammonium salts; or salts with other organic bases.
Of the alkali metal and alkaline earth metal hydroxides as salt-forming substances, special mention is to be made of the hydroxides of lithium, sodium, potassium, magnesium and calcium, but especially those of sodium and potassium.
Examples of amines that are suitable for the formation of ammonium salts are both ammonia and primary, secondary and tertiary amines and C2-C4a]Jcoxyalkylamines, for example methylamine, ethylamine, n-propyl-amine, isopropylamine, the four isomers of butylamine, n-amylamine, isoamylamine, hexylamine, heptylamine, octylamine, nonylamine, decylamine, pentadecylamine, hexa-decylamine, heptadecylamine, octadecylamine, methyl-ethylamine, methyl-isopropyl-amine, methyl-hexylamine, methyl-nonylamine, methyl-pentadecylamine, methyl-octa-decylamine, ethyl-butylamine, ethyl-heptylamine, ethyl-octylamine, hexyl-heptylamine, hexyl-octylamine, dimethylamine, diethylamine, di-n-propylamine, diisopropylamine, di-n-butylamine, di-n-amylamine, diisoamylamine, dihexylamine, diheptylamine, dioctyl-amine, ethanolamine, n-propanolamine, isopropanolamine, Ν,Ν-diethanolamine, N-ethyl-propanolamine, N-butylethanolamine, allylamine, n-butenyl-2-amine, n-pentenyl-2-amine, 2,3-dimethylbutenyl-2-amine, dibutenyl-2-amine, n-hexenyl-2-amine, propylenediamine, trimethylamine, triethylamine, tri-n-propylamine, triisopropylamine, tri-n-butylamine, tri-isobutylamine, tri-sec-butylamine, tri-n-amylamine, methoxyethylamine and ethoxyethyl-amine; heterocyclic amines, for example pyridine, quinoline, isoquinoline, moi holine, thiomorpholine, N-methylmorpholine, N-methyl-thiomoφholine, piperidine, pyrrolidine, indoline, quinuclidine and azepine; primary arylamines, for example anilines, methoxy-anilines, ethoxyanilines, o-, m- and p-toluidines, phenylenediamines, benzidines, naph-thylamines and o-, m- and p-chloroanilines; but especially triethylamine, isopropylamine and diisopropylamine.
The possible presence of at least one asymmetric carbon atom in the compounds of formula I, for example in the ester derivatives containing substituted aliphatic and alicyclic groups ( — i ci — o — J c* — t and the substituents R5, A and R6 may contain asymmetric carbon atoms), means that the compounds may be obtained either as optically active individual isomers or in the form of racemic mixtures. In the present invention, the compounds of formula I are to be understood as including both the pure optical antipodes and the racemates. Unless specific reference is made to the individual optical antipodes, the given formula is to be understood as meaning those racemic mixtures that are formed in the preparation process indicated. If an aliphatic C=C or C=N-0 double bond (syn/anti) is present, then geometrical isomerism may also occur.
Preference is given to compounds of formula I wherein n is 3 or 4. Of those compounds of formula I, those wherein n is 4 are especially preferred.
Preference is given also to compounds of formula I wherein nt is 0, 1 or 2 and R is C C3-alkyl.
Also preferred are compounds of formula I wherein R4 is the group -X-R5. Of those compounds of formula I, those wherein X is oxygen are especially preferred.
Of those compounds, special preference is given to those wherein R5 is C^Qalkyl.
Also preferred are compounds of formula I wherein R2 and R3 are methyl.
Preferred compounds of formula I are also those wherein nj is 0, 1 or 2; R is methyl; Ri is chlorine or bromine; R2 and R3 are methyl; R4 is the group -X-R5; R5 is C^Qa-lcyl; and X and Z are oxygen.
Preference is given also to compounds of formula I wherein R4 is the group -X-A-R6. Of those compounds of formula I, those wherein X is oxygen and A is a C or C2-alkylene bridge are especially preferred.
Preferred compounds are those wherein ^ is 0, 1 or 2; R is methyl; Rt is chlorine or bromine; R2 and R3 are methyl; R4 is the group -X-A-R6; and X and Z are oxygen.
Also preferred are compounds of formula I wherein R4 is the group — N Also preferred are compounds of formula I wherein ^ is 0, 1 or 2; R is methyl; Rt is chlorine or bromine; R2 and R3 are methyl; R4 is the group ; and Z is oxygen.
There are suitable compounds of formula la wherein Ri is chlorine or bromine; R5 is hydrogen, Ci-C5alkyl, C2chloroalkyl, or C2-alkoxy-C2- or -C3-alkyl, Q-Csalkyl-thio-C2- or -C3-alkyl, di-C or -C2-alkylamino-C3alkyl, cyano-Cr or -C2-alkyl, C3- or C4-alkenyl, C3chloroalkenyl, C3- or C4-alkynyl, C5- or C6-cycloalkyl, C3- or C5-cyclo-alkyl-Cr or -C2-alkyl, phenyl-Cj- or -C2-alkyl that is unsubstituted or monosubstituted in the phenyl ring by chlorine or by methyl, or R5 is the group -N=C(CH3)2 or -CH2CH2-0-N=C(CH3)2, or is a sodium, potassium, ammonium, diethylammonium, tri-ethylammonium, ethanolammonium, diethanolammonium, triethanolammonium, morpholinium, thiomorpholinium, pyrrolidinium or piperidinium ion; and X is oxygen or sulfur: Also suitable are compounds of formula lb wherein Ri is chlorine or bromine; X is oxygen; A is Cr or C2-alkylene; and R6 is 2-furyl, 2-tetrahydrofuryl, 2-thienyl, 2-, 3- or 4-pyridyl, 4-methyl-5-thiazolyl, pyrrolidin-2-on-l-yl, N-morpholinyl, N-piperidyl, 1-imidazolyl or l-methyl-4-pyrazolyl.
Further suitable compounds are those of formula Ic wherein Ri is chlorine or bromine; R7 is hydrogen, C3alkenyl, methoxy, C3-C8cycloalkyl or cyano- or hydroxy-C2alkyl; and R8 is hydrogen, CrC5alkyl, C2chloroalkyl, methoxy-C2alkyl, hydroxy-C2alkyl, C3- or C4-alkenyl, C3chloroalkenyl, C3- or C4-all ynyl, phenyl, phenyl monosubstituted by chlorine, methyl, methoxy or by trifluoromethyl, benzyl or benzyl monosubstituted in the phenyl ring by chlorine or by methyl; or R7 and R8, together with the nitrogen atom to which they are bonded, form a pyrrolidino, morpholino, thiomorpholino, N-methylpiperazino or 3,5-dimethylmorpholino ring.
Also suitable are compounds of formula Id wherein R is hydrogen or methyl; Rj is chlorine; X is oxygen or sulfur; and R5 is hydrogen, Cx-QaUeyl, C3- or C4-alkenyl, C3chloroalkenyl, C3alkynyl, C or C2-alkoxy-C2alkyl or C or C2-alkylthio-C3alkyl.
There are also suitable compounds of formula Ie wherein Ri is chlorine; X is oxygen; and R5 is Cj-C^alkyl, C3- or C4-alkenyl, C3chloroalkenyl, C3alkynyl, methylthio-C3alkyl, C6-cycloalkyl or the group -N=C(CH3)2.
Also suitable are compounds of formula If wherein Ri is chlorine or bromine; X is oxygen; A is Cr or C2-alkylene; and R6 is 2-furyl, 2-tetrahydrofuryl, 4-methyl-5-thiazolyl, N-piperidyl, N-methylpiperazinyl or N-morpholinyl.
There are suitable compounds of formula Ig wherein R is hydrogen or methyl; Ri is chlorine or bromine; R7 is hydrogen, C1-C4alkyl, C3alkenyl, methoxy or C3cycloalkyl; and R8 is hydrogen, C1-C4alkyl, C3alkenyl, C3chloroalkenyl, C3alkynyl, phenyl, chlorophenyl or phenyl-Cr or -C2-alkyl.
Also suitable are compounds of formula Di wherein Ri is chlorine; R7 is hydrogen, methyl, methoxy, C3alkenyl or C3cycloalkyl; and R8 is hydrogen, C1-C alkyl or C3- or C4-alkenyl; or R7 and R8, together with the nitrogen atom to which they are bonded, form a morpholino ring.
There are also suitable compounds of formula Ii wherein R is hydrogen or methyl; Ri is chlorine or bromine; X is oxygen or sulfur; and R5 is hydrogen, -C^alkyl, methoxy-C2alkyl, C2- or C3-alkylthio-C3alkyl, C3- or C4-alkenyl, C3chloroalkenyl, C3alkynyl, Qcycloalkyl, C3cycloalkyl-C2alkyl, phenyl-C^- or -C2-alkyl or the group -N=C(CH3)2.
Suitable compounds are also those of formula Ij wherein R is hydrogen or methyl; Ri is chlorine or bromine; X is oxygen; A is Ci- or C2-alkylene; and R6 is 2-furyl, 2-tetrahydrofuryl, 2-tetrahydrothienyl, N-morpholinyl, N-piperidyl, 2-, 3- or 4-pyridyl or 4-methyl-5-thiazolyl.
There are also suitable compounds of formula Dc R is hydrogen or methyl; Rt is chlorine or bromine; R7 is hydrogen, methyl, methoxy, C3cycloalkyl or C3alkenyl; and R8 is hydrogen, C^^alkyl, hydroxy-C2alkyl, C3alkenyl, C3chloroalkenyl, C3- or C4-alkynyl, phenyl, fluorophenyl, methoxyphenyl or benzyl; or R7 and R8, together with the nitrogen atom to which they are bonded, form a morpholino ring.
A very especially preferred individual compound within the scope of formula I is 2-metoyl-2-[2^hloro-5-[(tetrahyaxo-3-oxo-m ylidene)amino]-benzoyloxy]-propionic acid 2-chloro-2-propenyl ester.
The process according to the invention for the preparation of the compounds of formula I is carried out analogously to known processes and comprises reacting an aniline derivative of formula Π with thiophosgene to form the isothiocyanate of formula ΠΙ the radicals Ri to R4 in the compounds of formulae Π and ΙΠ being as defined under formula I, and converting the isothiocyanate with a compound of formula V wherein R, n and nt are as defined under formula I, into the compound of formula IV wherein R, Rx to R4, n and are as defined, and then reacting the compound of formula IV with a compound of formula VI CZCl (VI), wherein Z is oxygen or sulfur, if desired in the presence of a base.
The reaction of the aniline derivatives of formula Π to form the isothiocyanates of formula ΙΠ is carried out analogously to known processes, for example as described in EP-A-0 304 920, EP-A-0238 711, EP-A-0409025, EP-A-0 372461, EP-A-0 311 135 and DE-OS-3 724098.
The reaction of the isothiocyanates of formula ΠΙ with the compounds of formula V is advantageously carried out in a solvent that is inert towards the reaction, at temperatures of from -5°C to the boiling temperature of the solvent, especially from 0 to +50°C, especially preferably at room temperature. Suitable solvents for this reaction are, for example, toluene, xylene, ethyl acetate and acetonitrile.
The reaction of the compound of formula IV with the compound of formula VI is advantageously carried out in an inert organic solvent at low temperatures, preferably at from 0 to +50°C, especially preferably at from 0 to +15°C. Suitable bases for this reaction are, for example, pyridine, triethylamine and N,N-dimethylaniline. Suitable solvents are, for example, 1,2-dichloroethane, dichloromethane and toluene.
The aniline derivatives of formula II, the isothiocyanates of formula ΠΙ and the compounds of formula IV are novel and have been developed specifically for the synthesis of the compounds of formula I. The present invention therefore relates also thereto.
The novel intermediates of formula IV are also distinguished by herbicidal activity, with selectivity in the case of certain cultivated plants.
For the intermediates of formulae Π, ΙΠ and IV, the same preferences as those given for the compounds of formula I apply with respect to R, Ri to R4, n and The starting materials of formula V, wherein R is alkyl and η is as defined under formula I, required for the preparation process according to the invention are known and can be prepared analogously to processes known in the literature. The preparation of such compounds from dibromoalkanes and hydrazine is described, for example, in Archiv der Pharmazie 295 (7), 526 (1962), J. Org. Chem. 46, 442 (1981), Bull. Soc. Chim. France 1957, 704; EP-A-0 304920, pages 9-11 (schemes 2-4), EP-A-0 468 924, page 19, last section, page 20, first section and page 28, Example H18, and J. Am. Chem. Soc. 88, 3959 (1966).
Compounds of formula Va (dihydrobromide) wherein R and nj are as defined under formula I, can be prepared in accordance with reaction scheme 1.
Reaction scheme 1 : p-tolyl IXX D Xb HBr Va (dihydrobromide) In reaction scheme 1, formulae DCX, IXXa and IXXb are each an unbranched aliphatic pentane chain to the terminal carbon atoms and C5 of which there is bonded a hydroxy group (DCX) or a group RQSC^O (DCXb) or bromine (DCXa). The radical R may be linked 0, 1, 2 or 3 times, if desired also geminally, with all five carbon atoms in the n-pentane chain.
The aniline derivatives of formula II required for the preparation process according to the invention can be prepared analogously to known processes.
Those preparation processes are illustrated in greater detail in reaction scheme 2 below. Reaction scheme 2: a) l) SOCl2 Ed He d) The starting materials of formulae VII, VHI, X, ΧΠ, ΧΙΠ and XV, wherein Rj to R3, R5 to R8, X and A are as defined above, are known and can be prepared according to the disclosed processes, as described, for example, in US-A-5 183 492 and EP-A-0 408 382.
The nitrobenzoic acid ester derivatives of formulae XI, XVI and XVIII are novel and have been developed specifically for the synthesis of the compounds of formula I. The present invention therefore relates also thereto.
The reactions to form compounds of formula I are advantageously carried out in aprotic, inert organic solvents. Such solvents are pure hydrocarbons, such as benzene, toluene, xylene or cyclohexane, chlorinated hydrocarbons, such as dichloromethane, trichloro-methane, tetrachloromethane, ethylene chloride or chlorobenzene, ethers, such as diethyl ether, tert-butyl methyl ether, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, tetrahydrofuran or dioxane, nitriles, such as acetonitrile or propionitrile, and ketones, such as acetone or methyl ethyl ketone. The reduction of the nitrobenzoic acid ester derivatives of formulae XI, XVI and XVin is advantageously carried out in dioxane or protic, organic solvents, for example alcohols, such as methanol, ethanol or propanol, in the presence of an organic or inorganic acid, for example hydrochloric acid. The isothio-cyanates of formula ΠΙ are advantageously prepared in a two-phase system, for example a solvent mixture of ethylene chloride and water. The reaction temperatures are from -10°C to the reflux temperature of the reaction mixture, preferably in the temperature range of from 0°C to 120°C.
The end products of formula I can be isolated in customary manner by concentration and/or evaporation of the solvent and can be purified by recrystallisation or trituration of the solid residue in solvents in which they are not readily soluble, such as ethers, aromatic hydrocarbons or chlorinated hydrocarbons, by distillation or by means of column chromatography and a suitable eluant.
For the use according to the invention of the compounds of formula I or of compositions comprising them, there come into consideration all methods of application customarily used in agriculture, for example preemergence application, postemergence application and seed dressing, as well as different methods and techniques, for example controlled release of the active ingredient. For that purpose, the active ingredient is applied in solution to granulated mineral carriers or polymerised granules (urea/formaldehyde) and is dried. Where appropriate, a coating may additionally be applied (coated granules), which allows the active ingredient to be released in metered amounts over a particular period of time.
The compounds of formula I can be used in unmodified form, i.e. as obtained in the synthesis, but preferably they are formulated in customary manner together with the adjuvants conventionally employed in formulation technology to form e.g. emulsifiable concentrates, directly sprayable or dilutable solutions, dilute emulsions, wettable powders, soluble powders, dusts, granules or microcapsules. As with the nature of the compositions, the methods of application, such as spraying, atomising, dusting, wetting, scattering or pouring, are chosen in accordance with the intended objectives and the prevailing circumstances.
The formulations, i.e. the compositions, preparations or mixtures comprising the compound (active ingredient) of formula I or at least one compound of formula I and, where appropriate, one or more solid or liquid formulation adjuvants, are prepared in known manner, e.g. by homogeneously mixing and/or grinding the active ingredients with the formulation adjuvants, e.g. solvents or solid carriers. In addition, surface-active compounds (surfactants) may also be used in the preparation of the formulations.
Suitable solvents are: aromatic hydrocarbons, preferably the fractions containing 8 to 12 carbon atoms, such as mixtures of alkylbenzenes, e.g. xylene mixtures or alkylated naphthalenes; aliphatic and cycloaliphatic hydrocarbons, such as paraffins, cyclohexane or tetrahydronaphthalene; alcohols, such as ethanol, propanol or butanol; glycols and their ethers and esters, such as propylene glycol or dipropylene glycol ether; ketones, such as cyclohexanone, isophorone or diacetone alcohol; strongly polar solvents, such as N-methyl-2-pyrrolidone, dimethyl sulfoxide or water; vegetable oils and their esters, such as rape oil, castor oil or soybean oil; and, where appropriate, also silicone oils.
The solid carriers used, e.g. for dusts and dispersible powders, are normally natural mineral fillers, such as calcite, talcum, kaolin, montmorillonite or attapulgite. In order to improve the physical properties it is also possible to add highly dispersed silicic acid or highly dispersed absorbent polymers. Suitable granulated adsorptive carriers are porous types, for example pumice, broken brick, sepiolite or bentonite; and suitable nonsorbent carriers are, for example, calcite or sand. In addition, a great number of pregranulated materials of inorganic or organic nature can be used, e.g. especially dolomite or pulverised plant residues.
Depending on the nature of the compound of formula I to be formulated, suitable surface-active compounds are non-ionic, cationic and/or anionic surfactants having good emulsifying, dispersing and wetting properties. The term "surfactants" will also be understood as comprising mixtures of surfactants.
Both so-called water-soluble soaps and water-soluble synthetic surface-active compounds are suitable anionic surfactants.
Suitable soaps are the alkali metal salts, alkaline earth metal salts or unsubstituted or substituted ammonium salts of higher fatty acids (C10-C22), e.g. the sodium or potassium salts of oleic or stearic acid, or of natural fatty acid mixtures which can be obtained e.g. from coconut oil or tallow oil. Mention may also be made of fatty acid methyltaurin salts.
More frequently, however, so-called synthetic surfactants are used, especially fatty alcohol sulfonates, fatty alcohol sulfates, sulfonated benzimidazole derivatives or alkylarylsulfonates.
The fatty alcohol sulfonates or sulfates are usually in the form of alkali metal salts, alkaline earth metal salts or unsubstituted or substituted ammonium salts and contain a C8-C22alkyl radical, which also includes the alkyl moiety of acyl radicals, e.g. the sodium or calcium salt of lignosulfonic acid, of dodecyl sulfate or of a mixture of fatty alcohol sulfates obtained from natural fatty acids. These compounds also comprise the salts of sulfated and sulfonated fatty alcohol/ethylene oxide adducts. The sulfonated benzimidazole derivatives preferably contain 2 sulfonic acid groups and one fatty acid radical containing 8 to 22 carbon atoms. Examples of alkylarylsulfonates are the sodium, calcium or triethanolamine salts of dodecylbenzenesulfonic acid, dibutylnaphthalenesulfonic acid, or of a condensate of naphthalenesulfonic acid and formaldehyde.
Also suitable are corresponding phosphates, e.g. salts of the phosphoric acid ester of an adduct of p-nonylphenol with 4 to 14 mol of ethylene oxide, or phospholipids.
Non-ionic surfactants are preferably polyglycol ether derivatives of aliphatic or cycloaliphatic alcohols, saturated or unsaturated fatty acids and alkylphenols, said derivatives containing 3 to 30 glycol ether groups and 8 to 20 carbon atoms in the (aliphatic) hydrocarbon moiety and 6 to 18 carbon atoms in the alkyl moiety of the alkylphenols.
Further suitable non-ionic surfactants are the water-soluble adducts of polyethylene oxide with polypropylene glycol, ethylenediaminopolypropylene glycol and alkylpolypropylene glycol containing 1 to 10 carbon atoms in the alkyl chain, which adducts contain 20 to 250 ethylene glycol ether groups and 10 to 100 propylene glycol ether groups. These compounds usually contain 1 to 5 ethylene glycol units per propylene glycol unit.
Representative examples of non-ionic surfactants are nonylphenol polyethoxyethanols, castor oil polyglycol ethers, polypropylene/polyethylene oxide adducts, tributylphenoxy-polyethoxyethanol, polyethylene glycol and octylphenoxypolyethoxyethanol.
Fatty acid esters of polyoxyethylene sorbitan, e.g. polyoxyethylene sorbitan trioleate, are also suitable non-ionic surfactants.
Cationic surfactants are preferably quaternary ammonium salts which contain, as N-substituent, at least one C8-C22alkyl radical and, as further substituents, unsubstituted or halogenated lower alkyl, benzyl or hydroxy-lower alkyl radicals. The salts are preferably in the form of halides, methyl sulfates or ethyl sulfates, e.g. stearyltrimethylammonium chloride or benzyldi(2-chloroethyl)ethylammonium bromide.
The surfactants customarily employed in formulation technology, which may also be used in the compositions according to the invention, are described inter alia in "McCutcheon's Detergents and Emulsifiers Annual", MC Publishing Corp., Ridgewood New Jersey, 1981, Stache, H., "Tensid-Taschenbuch", Carl Hanser Verlag, Munich/Vienna, 1981 and M. and J. Ash, "Encyclopedia of Surfactants", Vol. Ι-ΙΠ, Chemical Publishing Co., New York, 1980-1981.
The herbicidal compositions usually comprise 0.1 to 99 %, preferably 0.1 to 95 %, of a compound of formula 1, 1 to 99.9 % of a solid or liquid formulation adjuvant, and 0 to 25 , preferably 0.1 to 25 %, of a surfactant.
Whereas commercial products will preferably be formulated as concentrates, the end user will normally employ dilute formulations.
The compositions may also comprise further auxiliaries such as stabilisers, e.g. vegetable oils or epoxidised vegetable oils (epoxidised coconut oil, rape oil or soybean oil), antifoams, e.g. silicone oil, preservatives, viscosity regulators, binders, tackifiers as well as fertilisers or other active ingredients.
Preferred formulations have especially the following composition (throughout, percentages are by weight): Emulsifiable concentrates: active ingredient: 1 to 90 %, preferably 5 to 50 % surface-active agent: 5 to 30 , preferably 10 to 20 % solvent: 15 to 94 %, preferably 70 to 85 % Dusts: active ingredient: 0.1 to 50 , preferably 0.1 to 1 % solid carrier: 99.9 to 90 %, preferably 99.9 to 99 % Suspension concentrates: active ingredient: 5 to 75 %, preferably 10 to 50 % water: 94 to 24 %, preferably 88 to 30 % surface-active agent: 1 to 40 %, preferably 2 to 30 % Wettable powders: active ingredient: 0.5 to 90 %, preferably 1 to 80 % surface-active agent: 0.5 to 20 %, preferably 1 to 15 % solid carrier: 5 to 95 %, preferably 15 to 90 % Granules: active ingredient: 0.5 to 30%, preferably 0.5 to 15% •solid carrier: 99.5 to 70 %, preferably 97 to 85 % The compounds of formula I are generally employed successfully on the plant or the locus thereof at rates of application of from 0.001 to 2 kg/ha, especially from 0.005 to 1 kg/ha. The rate of application required to achieve the desired effect may be determined by experiments. It is dependent on the type of action, the stage of development of the cultivated plant and of the weeds, and on the application (place, time, method) and, in dependence on those parameters, may vary within a wide range.
The compounds of formula I are distinguished by herbicidal and growth-inhibiting properties, which render them excellendy suitable for use in crops of useful plants.
Crops are to be understood as including crops which have been rendered tolerant to herbicides or classes of herbicides by conventional cultivation or genetic engineering methods.
The following Examples illustrate the invention in greater detail but do not limit the invention.
Preparation Examples: Example PI: 2-Chloro-5-nitrobenzoic acid l-(2-chloroallyloxycarbonyl)-l -methyl ethyl ester (intermediate) 4.0 ml of 2,3-dichloro-l-propene are added dropwise at 20°C to a mixture of 12.0 g of 2-chloro-5-nitrobenzoic acid l-(oxycarbonyl)-l-methyl ethyl ester and 6.3 g of potassium carbonate in 200 ml of methyl ethyl ketone (exothermic reaction). The resulting reaction mixture is stirred overnight at 20°C. The inorganic components are then filtered off and washed with methyl ethyl ketone. The resulting organic phase is concentrated by evaporation and the residue is purified by means of column chromatography on silica gel (eluant hexane/ethyl acetate 1/1), yielding 7.7 g of the desired product having a refractive index ° 1.5312 .
Example P2: 2-Chloro-5-aminobenzoic acid l-(2-chloroallyloxycarbonyl)-l-methyl ethyl ester (intermediate) A solution of 7.7 g of 2-chloro-5-nitrobenzoic acid l-(2-chloroallyloxycarbonyl)-l -methyl ethyl ester (Example PI) in 50 ml of ethanol is added dropwise to a mixture, heated to boiling temperature, consisting of 5.0 g of iron powder, 2.0 ml of concentrated hydrochloric acid in 50 ml of water and 50 ml of ethanol, and the reaction mixture is stirred for 6 hours at boiling temperature. After cooling the reaction mixture, the inorganic components are filtered off, the filtrate is rendered alkaline with aqueous sodium hydrogen carbonate solution, and extraction is carried out with ethyl acetate. The combined extracts are dried over sodium sulfate and concentrated by evaporation, yielding 6.5 g of 2-chloro-5-aminobenzoic acid l-(2-chloroallyloxycarbonyl)-l -methyl ethyl ester having a refractive index nD 1.5439 Example P3: 2-Chloro-5-isothiocyanatobenzoic acid l-(2-chloroallyloxycarbonyl)-l-methyl ethyl ester (intermediate) CH (15.003) A solution of 6.5 g of 2-chloro-5-amino-l-(2-chloroallyloxycarbonyl)-l-methyl ethyl ester in 20 ml of ethylene chloride is added dropwise at 20°C, with stirring, to a mixture of 4.0 g of calcium carbonate, 2.0 ml of thiophosgene in 30 ml of ethylene chloride and 30 ml of water, and the mixture is stirred for a further 6 hours. The inorganic components are then filtered off and the organic phase is dried over calcium chloride and is then concentrated by evaporation, yielding 7.3 g of the desired product in the form of an oil.
Example P4: 2-Chloro-5-r(l-hexahvdropyridazinyl)-thiocarbonylamino1-benzoic acid 1-(2-chloroallyloxycarbonyl)-l-methyl ethyl ester (intermediate) A solution of 7.3 g of 2-chloro-5-isothiocyanatobenzoic acid l-(2-chloroallyloxy-carbonyl)-l -methyl ethyl ester in 30 ml of ethylene chloride is added dropwise at 5°C, with stirring, to a solution of 2.0 g of hexahydropyridazine in 30 ml of ethanol, and the mixture is stirred for a further 3 hours at 20°C. The reaction mixture is then concentrated by evaporation in vacuo, yielding 8.3 g of the desired product having a refractive index 20 nD 1.5738 · 112523/2 - 25 - Example P5: 2-Methyl-2-r2-chloro-5-r(tetrahvdro-3-oxo-lH.3H-n.3.41thiadiazolor3.4-a1-pyridazin-l-ylidene)amino1-benzoyloxy1-propionic acid 2-chloro-2-propenyl ester A solution of 6.0 g of 2-chloro-5-[(l-hexahydropyridazinyl)-thiocarbonylamino]-benzoic acid l-(2-chloroallyloxycarbonyl)-l-methyl ethyl ester in 30 ml of ethylene chloride is added dropwise to a solution of 6.5 ml of 20 % phosgene in toluene at a temperature of 0-5°C. The reaction mixture is then stirred for 6 hours at 20°C and is then poured into ice-water. The organic phase is separated off and dried over sodium sulfate.
Concentration of the organic phase by evaporation yields 5.5 g of the desired product in 20 the form of an oil; refractive index nD 1.5811 · The compounds listed in the following Tables can be prepared in an analogous manner.
Table 1: Compounds of formula la H m.p. 150°C CH3 C2H5 η β 1.5576 C3H7(n) C3H7(i) m.p. 98-99°C 20 C4H9(n) 1.5592 — CH — C2Hg CH3 -CH2-CH(CH3)2 C4H9(t) C5Hn(n) 20 -CH2CH2OCH3 n D 1.5651 1.012 CI O -CH2CH2OC2H5 1.014 CI O -CH2-CH2C1 1.015 CI O -CH2CH2-S-CH3 1.016 CI O — CH-CH2-S-CH3 CH 3 Comp. No. R{ X Phys. data 1.017 CI o CH-CH2-S*C2Hg CH3 20 1.018 CI o — CH-CH2-S-C3H7(n) η β 1.5634 CH3 1.019 CI o — CH-CH2-S-C3H7(i) CH3 1.020 CI o — CH-CH2-S-C4H9(n) CH3 1.021 CI o — CH-CHg-S-CgHn in) CH3 1.022 CI o - CH-CH2-N(CH3)2 CH3 1.023 CI o - CH-CH2-N(C2H5)2 CH3 1.024 CI 0 -CH2-CN m.p. 125-127°C 1.025 CI o — CH-CN m.p. 128-130°C I CH3 1.026 CI o -CH2CH2CN 1.027 CI o — CH2- CH=CH2 n D 1.5566 1.028 CI o -CH2-CH=CH-CH3 n o 1.5499 1.029 CI o — CH-CH=CH∑ n D 1.5572 CH3 1.030 CI o — CH2— C — — CH2 n D 1.5676 CH3 1.031 CI o -CH2CH=CHC1 n D 1.5741 Comp. No. R, Phys. data -CH2-C = CH2 nD 1.5811 CI -CH2-C≡CH m.p.83-84°C -CHC = CH I CH3 CI O -CH^ ] resin CH, 1.043 CI 0 -CH2CH; 1.044 CI 0 Na 1.045 CI 0 K 1.046 CI 0 NH4 Comp. No. Ri X Phys. data 1.047 CI o H3N-CH2CH2OH 1.050 CI 0 H2N(CH2CH2OH)2 1.051 CI 0 HN(CH2CH2OH)3 1.054 CI 0 Η2Ν((¼Η5)2 1.055 CI 0 ΗΝ((¼Η5)3 1.056 CI s CH3 1.057 CI s <¾Η5 1.058 CI s C3H7(n) 1.059 CI s C3H7(i) 1.060 CI s - CH2- CH=CH2 1.062 CI 0 -N=C(CH3)2 1.063 CI 0 -CH2-CH2-0-N=C(CH3)2 1.064 Br 0 -CH2-CH=CH2 n∞ 1.5561 1.065 Br 0 -CH2-CH=CH-CH3 1.066 Br 0 -CH2-C=CH 1.067 CI o Li 1.068 CI 0 Mg 1.069 CI 0 Ca 1.070 CI 0 (CH3)2NH2 1.071 CI 0 (CH3)3NH Comp. No. Ri X Phys. data 1.072 CI 0 C2H5NH3 1.073 CI 0 1.074 CI 0 (C4H9)4N 1.075 CI 0 C6H5-CH2NH3 1.076 CI O C6H5-NH3 1.080 CI 0 HC = C - CH2NH3 1.082 Br 0 Na 1.083 Br 0 NH4 1.084 CI 0 H2C=CH-CH2NH3 1.085 CI 0 CH3NH3 1.086 Br 0 K 1.087 Br 0 H3N-CH2CH2OH 1.088 Br 0 H2N 1.090 Br 0 ΗΝ((¾Η5)3 1.091 Br 0 H Comp. No. Rj X Phys. data 2.011 CI O -CH2CH2- — J* resin 2.015 Br O -CH2CH2- ~ N. ° Table 3: Compounds of formula Ic Comp. No. Rj R7 R« Phys. data 3.001 CI H H 3.002 CI H CH3 3.003 CI H C2H5 3.004 CI H C3H7(n) 3.005 CI H C3H7(i) 3.006 CI H C4H9(n) 3.007 CI H * CH — CH2— CHg CHg 3.008 CI H -CH2-CH(CH3)2 3.009 CI H C4H9(t) 3.010 CI H C5HH(n) 3.011 CI H -CH2CH2-CI 3.012 CI H -CH2-CH2-0-CH3 3.013 CI H -CH2-CH2-OH 3.014 CI H -CH2-CH=CH2 3.015 CI H -CH2-C≡CH 3.016 CI OCH3 H 3.018 CI H - CH2→Q- Comp. No. R7 R8 Phys. data 3.030 CI H 3.042 CI CH3 - CH- C ≡ CH CHg 3.043 CI -CH2-CH2CN CH3 3.044 CI -CH2CH2-OH -CH2CH2-OH 3.045 CI CH3 -■*- 3.048 CI -CH2-CH=CH2 -CH2-CH=CH2 3.049 CI C2H5 -CH2- CH=CH2 3.050 CI C3H7(n) - CH2- CH=CH2 Comp. No. Ri R7 R8 Phys. data 3.051 CI C3H7(i) -CH2-CH=CH2 3.052 CI C2H5 • CH2 — C — CH2 ΠΙ 3.054 CI C3H7(n) C3H7(n) 3.055 CI CH3 3.056 CI -o CH3 3.057 CI C4H9(n) -CH2-CH=CH2 3.058 Br H - CH2- CH=CH2 3.059 Br H CH3 3.060 Br H C2H5 3.061 Br H C3H7(n) 3.062 Br H C4H9(n) 3.063 Br CH3 - CH2 CH— CH2 3.065 Br - CH2- CH=CH2 - CH2" CH=CH2 21 3.066 CI — N nD 1.5736 3.069 CI ■ N N — CH3 Corap. No. Rj R7 Phys. data 3.071 Br — N O 3.072 Br - N S Table 4: Compounds of formula Id Comp. No. R Ri X Rs Phys. data 4.001 H CI 0 CH3 4.002 H CI 0 C2H5 4.003 H CI 0 C3H7(n) 4.004 H CI o C3H7(i) 4.005 H CI 0 -CH2-CH=CH2 4.006 H CI o -CH2-CH=CH-CH3 4.007 H Ci 0 - CH- CH= CH2 CH3 4.008 H CI 0 - CH — C — CH2 CH3 4.009 H CI 0 - CHo— C — CHo 1 CI 4.010 H CI 0 -CH2-CH=CH-C1 4.011 H CI 0 -CH2-C≡CH 4.012 H CI 0 -CH2-CH2-0-CH3 4.013 H CI 0 CH CH2- S C2H5 CH3 4.014 H CI o H m.p. 125 4.015 CH3 CI 0 H foam 4.016 CH3 CI o - CH2" CH=CH2 4.017 CH3 CI 0 -CH2-CH=CH-CH3 4.018 CH3 CI 0 - CH- CH= CH2 CH, Comp. No. R Ri X Phys. data 4.019 CH3 CI 0 - CH2— C — CH2 CH3 4.020 CH3 CI 0 - CH2— C — CH2 CI 4.021 CH3 CI 0 -CH2-CH=CH-C1 4.022 CH3 CI 0 -CH2-CH O-CH3 4.023 CH3 CI 0 -CH2-CH2-O-C2H5 4.024 CH3 CI 0 - CH— CH2" S CH3 CH3 4.025 CH3 CI s -CH2-CH=CH2 4.026 H CI 0 Na 4.027 H CI 0 Η,Ν O 4.028 H CI 0 Li 4.029 H CI 0 K 4.030 H CI 0 Mg 4.031 H CI 0 Ca 4.032 H CI 0 NH4 4.033 H CI 0 CH3NH3 4.034 H CI 0 (CH3)2NH2 4.035 H CI 0 (CH3)3NH 4.036 H CI 0 C2H5NH3 4.037 H CI 0 (C2H5)2NH2 4.038 H CI 0 (C2H5)3NH 4.039 CH3 CI 0 (C2H5)3NH 4.040 CH3 CI 0 C4H9NH3 4.041 CH3 CI 0 (C4H9)4N 4.042 CH3 CI 0 HOCH2CH2NH3 4.043 CH3 CI 0 (HOCH2CH2)2NH2 4.044 CH3 CI 0 (HOCH2CH2)3NH 4.045 CH3 CI 0 C6H5CH2NH3 4.046 CH3 CI 0 C6H5-NH3 4.047 CH3 CI 0 H5C20CO-CH2NH3 Comp. No. R R, X R5 Phys. data 4.051 CH3 CI 0 4.052 CH3 CI 0 H2C=CH-CH2NH3 4.053 CH3 CI 0 HC≡C-CH2NH3 4.056 H CI 0 ■Ό 4.057 H CI 0 HC≡C-CH2NH3 4.058 H CI 0 Table 5: Compounds of formula Ie Comp. No. Phys. data CH3 C2H5 C3H7(i) CH~ CHg" S ™* CHg CH3 -CH2-CH=CH2 -CH2-CH=CH-CH3 -CH-CH=CH2 CH3 -CH2-C = CH2 I CH3 -CH2-CH=CH-C1 -CH2-C≡CH 5.013 CI O -N=C(CH3)2 5.014 CI O Na 5.015 CI O ¾N o Comp. No. Ri X R5 Phys. data 5.016 CI 0 Li 5.017 CI 0 K 5.018 CI 0 Mg 5.019 CI 0 Ca 5.020 CI o NH 5.021 CI 0 CH3NH3 5.022 CI o (CH3)2NH2 5.023 CI o (CH3)3NH 5.024 CI 0 C2H5NH3 5.025 CI 0 (¾Η5)2ΝΗ2 5.026 CI 0 (¾Η5)3ΝΗ 5.027 CI 0 C4H9NH3 5.028 CI 0 (C4H9)4N 5.029 CI o HOCH2CH2NH3 5.030 CI o (ΗΟΟ½α¾)2ΝΗ2 5.031 CI o (Ηοα¼α½)3ΝΗ 5.032 CI 0 CgHs-CHzNHa 5.033 CI o C6H5-NH3 5.036 CI 0 5.040 CI 0 HC=C-CH2 H3 5.042 CI 0 H m.p. 148-150°C Table 6: Compounds of formula If Comp. No. R-i X Phys. data 6.004 CI O -CH2CH2- - N N — CH3 6.005 CI O -CH2CH2- -O 6.006 CI O -CH2CH2- ~ N. .° 6.007 Br O -CH2CH2- -O Table 7: Compounds of formula Ig Comp. No. R Rt R7 Phys. data 7.001 H CI H H 7.002 H CI CH3 H 7.003 H CI C2H5 H 7.004 H CI C4H9(n) H 7.005 H CI -CH2"CH=CH2 H 7.007 H CI CH3 -CH2CH=CH2 7.008 H CI C2H5 -CH2CH=CH2 7.009 H CI CH3 ■ CH2— C — CH2 CI 7.010 H CI -CH2CH=CH2 -CH2CH=CH2 7.011 H CI OCH3 CH3 7.012 H CI C2H5 C4H9(n) 7.013 H CI -< CH3 CH3 CI H 7.017 CH3 CI H CH3 7.018 CH3 CI H C2H5 7.019 CH3 CI H C3H7(i) Comp. No. R R, R^ R« Phys. data 7.020 CH3 CI H C4H9(n) 7.021 CH3 CI H -CH2-CH=CH2 7.022 CH3 CI H -CH2-C≡CH 7.023 CH3 CI H -CH2CHg-^~^ 7.024 CH3 CI H 7.025 CH3 CI - H 7.026 CH3 CI ~<\ CH3 7.027 CH3 CI OCH3 CH3 7.028 CH3 CI OCH3 H 7.029 CH3 Br H -CH2"CH=CH2 Table 8: Compounds of formula Ih Comp. No. R-! R7 R8 Phys. data 8.001 CI H H 8.002 CI H CH3 8.003 CI H C2H5 8.004 CI H C3H7(i) 8.005 CI H -CH2-CH=CH2 8.006 CI CH3 -CH2"CH=CH2 8.007 CI -CH2-CH=CH2 -CH2-CH=CH2 8.008 CI CH3 - CH- CH= CH2 CH3 8.009 CI OCH3 CH3 8.010 CI CH3 C4H9(n) 8.011 CI ~<\ H 8.012 CI - CH3 8.013 CI Table 9: Compounds of formula Ii Comp.No. R Rl X R5 Phys. data 9.001 H CI 0 H 9.002 H CI s H 9.003 H CI 0 CH3 9.004 H CI 0 C2H5 9.005 H CI 0 C3H7(i) m.p. 120-123°C 9.006 H CI 0 -CH2CH2OCH3 9.007 H CI 0 - CH-CH2-S-C2H5 CH3 9.008 H CI 0 - CH-CH2-S-C3H7(n) 1 CH3 9.009 H CI 0 -CH2"CH=CH2 resin 9.010 H CI 0 -CH2-CH=CH-CH3 9.011 H CI 0 - CH2- C = CH2 CI 9.012 H CI 0 -CH2-CH=CH-C1 9.013 H CI 0 - CH- CH= CH2 CH3 9.014 H CI 0 - CH2 C = CH2 CH3 9.017 H CI 0 - CH- ] CH, Comp.No. R Ri X R5 Phys. data 9.018 H CI 0 .020 H CI 0 -N=C(CH3)2 9.021 H CI s -CH2"CH=CH2 9.022 CH3 CI 0 H 9.023 CH3 CI 0 CH3 9.024 CH3 CI 0 C2H5 9.025 CH3 CI 0 C3H7(i) 9.026 CH3 CI 0 -CH2-CH2-0-CH3 9.027 CH3 CI 0 - CH-CH2-S-C3H7(n) I CH3 25 9.028 CH3 CI 0 -CH2-CH=CH2 9.029 CH3 CI 0 -CH2-CH=CH-CH3 9.030 CH3 CI 0 -CH2-C=CH CI 9.031 CH3 CI 0 -CH2-CH=CH-C1 9.032 CH3 CI 0 - CH- CH: CH2 1 * CH3 9.033 CH3 CI 0 -CH2-C=CH2 CH3 9.036 CH3 CI 0 CH3 9.037 CH3 CI 0 Comp.No. R R, X R< Phys. data 9.039 CH3 CI 0 -N=C(CH3)2 9.040 CH3 CI s -CH2_CH=CH2 9.041 CH3 Br 0 -CH2"CH=CH2 9.042 CH3 Br 0 -CH2-CH=CH-CH3 9.043 H CI 0 Na 9.044 H r~\ CI s H2N 0 \ / 9.045 H CI 0 Li 9.046 H CI 0 K 9.047 H CI 0 Mg 9.048 H CI 0 Ca 9.049 H CI 0 NH4 9.050 H CI 0 CH3NH3 9.051 H CI 0 (CH3)2NH2 9.052 H CI 0 (CH3)3NH 9.053 H CI 0 C2H5NH3 9.054 H CI 0 (C2H5)2NH2 9.055 H CI 0 (C2H5)3NH 9.056 H CI 0 C4H9NH3 9.057 H CI 0 (C4H9)4N 9.058 H CI 0 HOCH2CH2NH3 9.059 H CI 0 (HOCH2CH2)2NH2 9.060 H CI 0 (HOCH2CH2)3NH 9.061 H CI 0 C6H5-CH2NH3 9.062 H CI 0 C6H5-NH3 9.063 H CI s H5C2OCO-CH2NH3 9.064 CH3 CI 0 O 9.065 CH3 CI 0 Comp.No. R X Phys. data 9.066 CH3 CI 0 O H3 -^^ 9.068 CH3 CI 0 9.069 CH3 CI 0 9.070 CH3 CI 0 M S 9.075 H CI 0 9.076 H CI 0 9.077 H CI 0 H,N 9.078 CH3 CI 0 9.079 CH3 CI 0 O H2N 9.080 CH3 CI 0 9.081 CH3 CI 0 Table 10: Compounds of formula Ij Comp.No. R Ri X A R6 Phys. data 10.001 H CI 0 -CH2- -Q 10.002 H CI 0 -CH2- 10.003 H CI 0 -CH2CH2- -Q 10.010 H Br 0 -CH2CH2- — N 0 \ / 10.011 CH3 CI 0 -CH2CH2- Comp.No. R Rj X A R6 Phys. data / — \ 10.012 CH3 CI O -CH2CH2- N Table 11: Compounds of formula He Comp.No. R Ri R7 R8 Phys. data 11.001 H CI H H 11.002 H CI H CH3 11.003 H CI H C2H5 11.004 H CI H C3H7(i) 11.005 H CI H C4H9(n) 11.006 H CI H -CH2-CH2-OH 11.007 H CI H -CH2-CH=CH2 11.008 H CI OCH3 H 11.010 H CI H 11.011 H CI H ~~ -OCH3 Comp.No. R Ri R7 R» Phys. data 11.013 H CI - H 11.016 H CI CH3 C2H5 11.017 H CI CH3 C3H7(n) 11.018 H CI CH3 C4H9(n) 11.019 H CI OCH3 CH3 11.020 H CI CH3 -CH2"CH=CH2 11.021 H CI CH3 -CH2_C=CH2 CI 11.022 H CI CH3 -CH-C≡CH CH, 11.023 H CI -CH2_CH=CH2 -CH2_CH=CH2 11.024 H Br H -CH2-CH=CH2 11.025 CH3 CI H H 11.026 CH3 CI H CH3 11.027 CH3 CI H C2H5 11.028 CH3 CI H C3H7(i) 11.029 CH3 CI H C4H9(n) 11.030 CH3 CI H -CH2-CH=CH2 11.031 CH3 CI OCH3 H 11.032 CH3 CI H 11.033 CH3 CI H 11.034 CH3 CI - N O -o \ / Table 12: Compounds of formula Ila Comp.No. Ri X Phys. data 12.001 CI 0 -CH2_CH=CH2 12.002 CI 0 -CH2-CH=CH-CH3 nD20 1.5261 12.003 CI 0 nD20 1.5439 12.004 CI 0 -CH2-CH=CH-C1 nD20 1.4732 12.005 CI 0 -CH=CH2 nD20 1.5391 3 12.006 CI 0 -CH2-C=CH2 nD20 L5329 CH3 12.007 CI 0 -CH2-C≡CH nD20 1.5413 12.008 CI 0 -CH2-S-CH3 3 12.010 CI 0 3' 12.011 CI 0 o Table 13: Compounds of formula lib Comp.No. Ri X A R6 Phys. data 13.007 CI 0 -CH2CH2- -O Table 14: Compounds of formula lie Comp.No. Ri R7 R8 14.001 CI H H 14.002 CI H CH3 14.003 CI H C4H9(n) 14.004 CI H -CH2-CH2OH 14.005 CI H -CH2"CH=CH2 14.006 CI H -CH2-C≡CH 14.007 CI OCH3 H 14.008 CI -CH2_CH=CH2 -CH2-CH=CH2 Table 15: Compounds of formula Ilia Comp. No. Rx Phys. data 15.001 CI 0 -CH2-CH=CH2 oil 15.002 CI 0 -CH2-CH=CH-CH3 oil 15.003 CI 0 • CH - C — CH oil 01 15.004 CI 0 -CH2-CH=CH-C1 oil 15.005 CI 0 • CH CH= CH2 CH3 15.006 CI 0 • CH2" C = CH2 oil CH3 15.007 CI 0 -CH2-CsCH 15.008 CI 0 • CH* CH2S CHg CH3 15.010 CI 0 -N=C(CH3)2 15.011 CI 0 -O Table 16: Compounds of formula Illb Comp. No. Ri X A R6 Phys. data 16.002 CI O -CH2- ^ i 16.003 CI O -CH2CH2- ^J s 16.004 CI O -CH2CH2- 16.005 CI O -CH2CH2- — 16.007 CI O -CH2CH2- — ^ 16.008 CI O -CH2CH2- Table 17: Compounds of formula IIIc Comp. No. Rj R7 Phys. data 17.001 CI H H 17.002 CI H CH3 17.003 CI H C4H9(n) 17.004 CI H -CH2-CH2-OH 17.005 CI H -CH2-CH=CH2 17.006 CI OCH3 H 17.007 CI OCH3 CH3 17.008 CI -CH2_CH=CH2 -CH2_CH=CH2 Table 18: Compounds of formula IVa Comp.No. Rx X R5 Phys. data 18.001 CI 0 -CH2-CH=CH2 m.p. 64-66°C 18.002 CI 0 -CH2-CH=CH-CH3 m.p. 65-70°C 18.003 CI 0 -CH2-^=CH2 nD20 1.5738 18.004 CI 0 -CH2-CH=CH-C1 nD20 1.4379 18.005 CI 0 -CH-CH=CH2 nD20 1.5776 CH3 18.006 CI 0 -CH2-C=CH2 nD20 L5599 CH3 18.007 CI 0 -CH2-C≡CH 18.008 CI 0 -CH-CH2-S-CH3 18.009 CI O -CH2 -^^ 18.010 CI O -N=C(CH3)2 18.011 CI O Table 19: Compounds of formula IVb Comp. No. Rj X A R6 Phys. data 19.002 CI O -CH2- ^JC 19.004 CI O -CH2CH2- 19.005 CI O -CH2CH2- ~N ^J° Table 20: Compounds of formula IVc Comp. No. Ri R7 R8 Phys. data 20.001 CI H H 20.002 CI H CH3 20.003 CI H C4H9(n) 20.004 CI H -CH2-CH2-OH 20.005 CI H -CH2-CH=CH2 oil 20.006 CI OCH3 H 20.007 CI OCH3 CH3 20.008 CI -CH2"CH=CH2 -CH2-CH=CH2 Formulation Examples for compounds of formula I (throughout, percentages are by weight) Fl. Emulsifiable concentrates a) b) c ) d) a compound of Tables 1-11 5 % 10 % 25 % 50 % calcium dodecylbenzenesulfonate 6 % 8 % 6 % 8 % castor oil polyglycol ether 4 % - 4 % 4 % (36 mol of ethylene oxide) octylphenol polyglycol ether - 4 % - 2 % (7-8 mol of ethylene oxide) cyclohexanone - - 10 % 20 % aromatic hydrocarbon mixture 85 % 78 % 55 % 16 % C9-C12 Emulsions of any desired concentration can be produced from such concentrates by dilution with water.
F2. Solutions a) b) c ) d) a compound of Tables 1-11 5 % 10 % 50 % 90 % dipropylene glycol methyl ether 20 % 20 % polyethylene glycol 20 % 10 % (mol. wL 400) N-methyl-2-pyrrolidone 30 % 10 % aromatic hydrocarbon mixture 75 % 60 % C9-C12 These solutions are suitable for application in the form of micro-drops.
F3. Wettable powders a ) b) c ) d) a compound of Tables 1-11 5 % 25 % 50 % 80 % sodium lignosulfonate 4 % - 3 % -sodium laurylsulfate 2 % 3 % - 4 % sodium diisobutylnaphthalene- 6 % 5 % 6 % sulfonate octylphenol polyglycol ether 1 % 2 % (7-8 mol of ethylene oxide) highly dispersed silicic acid 1 % 3 % 5 % 10 % kaolin 88 % 62 % 35 % The active ingredient is thoroughly mixed with the adjuvants and the mixture is thoroughly ground in a suitable mill, affording wettable powders which can be diluted with water to give suspensions of the desired concentration.
F4. Coated granules a) b) c) a compound of Tables 1-11 0.1 % 5 % 15 % highly dispersed silicic acid 0.9 % 2 % 2 % inorganic carrier 99.0 % 93 % 83 % (diameter 0.1-1 mm) e.g. CaC03 or Si02 The active ingredient is dissolved in methylene chloride, the solution is sprayed onto the carrier, and the solvent is subsequently evaporated off in vacuo.
F5. Coated granules a) b) c) a compound of Tables 1-11 0.1 % 5 % 15 % polyethylene glycol 1.0 % 2 % 3 % (mol. wt 200) highly dispersed silicic acid 0.9 % 1 % 2 % inorganic carrier 98.0 % 92 % 80 % (diameter 0.1 - 1 mm) e.g. CaC03 or Si02 The finely ground active ingredient is uniformly applied, in a mixer, to the carrier moistened with polyethylene glycol. Non-dusty coated granules are obtained in this manner.
F6. Extruder granules a) b) c) d) a compound of Tables 1-11 0, .1 % 3 % 5 % 15 % sodium lignosulfonate 1, .5 % 2 % 3 % 4 % carboxymethylcellulose 1, .4 % 2 % 2 % 2 % kaolin 97 , .0 % 93 % 90 % 79 % The active ingredient is mixed and ground with the adjuvants, and the mixture is moistened with water. The mixture is extruded and then dried in a stream of air.
F7. Dusts a) b) c ) a compound of Tables 1-11 0 . 1 % 1 % 5 % talcum 39 .9 % 49 % 35 % kaolin 60 . 0 % 50 % 60 % Ready-for-use dusts are obtained by mixing the active ingredient with the carriers and grinding the mixture in a suitable mill.
F8. Suspension concentrates a) b) c ) d) a compound of Tables 1-11 3 % 10 % 25 % 50 % ethylene glycol 5 % 5 % 5 % 5 % nonylphenol polyglycol ether - 1 % 2 % - (15 mol of ethylene oxide) sodium lignosulfonate 3 % 3 % 4 % 5 % carboxymethylcellulose 1 % 1 % 1 % 1 % 37 % aqueous formaldehyde 0 . .2 % 0 . , 2 % 0 . .2 % 0 .2 solution silicone oil emulsion 0 , .8 % 0 , .8 % 0 . .8 % 0 .8 water 87 % 79 % 62 % 38 % The finely ground active ingredient is intimately mixed with the adjuvants, giving a suspension concentrate from which suspensions of any desired concentration can be obtained by dilution with water.
Biological Examples Example Bl: Preemergence herbicidal action Monocotyledonous and dicotyledonous test plants are sown in plastics pots in standard soil. Immediately after sowing, the plants are sprayed with an aqueous suspension of the test compounds prepared from a 25 % wettable powder (Formulation Example F3, b)), corresponding to a rate of application of 2 kg a.i ha (500 1 water/ha). The test plants are then cultivated in a greenhouse under optimum conditions. Three weeks later, the test is evaluated using a scale of nine ratings (1 = total damage, 9 = no action). Ratings of from 1 to 4 (especially from 1 to 3) indicate good to very good herbicidal action.
Test plants: Setaria, Sinapis, Solanum, Stellaria.
In this test, compounds of Tables 1 to 11 exhibit pronounced herbicidal activity.
An example of the good herbicidal activity is shown in Table Bl.
Table Bl: Preemergence action Test plant: Setaria Sinapis Solanum Stellaria "Compound no. 1.027 1 1 1 1 .
The same results are obtained when the compounds of formula I are formulated in accordance with Examples Fl, F2 and F4 to F8.
Example B2: Postemergence herbicidal action (contact herbicide) Monocotyledonous and dicotyledonous test plants are grown in a greenhouse in plastic, pots containing standard soil and are sprayed in the 4- to 6-leaf stage with an aqueous suspension of the test compounds of formula I prepared from a 25 % wettable powder (Example F3, b)), corresponding to a rate of application of 2 kg a.i7ha (500 1 water/ha). The plants are then grown on in the greenhouse under optimum conditions. About 18 days later, the test is evaluated using a scale of nine ratings (1 = total damage, 9 = no action). Ratings of from 1 to 4 (especially from 1 to 3) indicate good to very good herbicidal action.
In this test too, the compounds of formula I according to the examples in Tables 1 to 11 exhibit pronounced herbicidal activity.
An example of the good herbicidal activity of the compounds of formula I is given in Table B2.
Table B2: Postemergence action Test plant: Setaria Sinapis Solanum Stellaria Compound no. 1.027 1 1 1 1 The same results are obtained when the compounds of formula I are formulated in accordance with Examples Fl, F2 and F4 to F8.

Claims (33)

112523/2 What is claimed is:
1. A compound of formula I wherein R is C1-C6alkyl, CrC6haloalkyl( C3-C6alkenyl, C3-C6alkynyl, CrC4alkoxy or C3-C6-cycloalkyl; Rt is halogen; R2 and R3 are each independently of the other C1-C4al.kyl; R4 is halogen or a group of the formula -X-R5, -X-A-R6 or ; R5 is hydrogen, CrC6alkyl, -Cghaloalkyl, C1-C4alkoxy-C1-C4alkyl, CrC10alkylthio-C1-C4alkyl, C1-C4alkylamino-C1-C4alkyl, di-C1-C4aIkylamino-C1-C4alkyl, cyano-CrC8-alkyl, C3-C8alkenyl, C3-C8haloalkenyl, C3-C8alkynyl, C3-C6cycloalkyl, oxetanyl, C3-C7-halocycloalkyl, phenyl-CrC3alkyl that is unsubstituted or substituted in the phenyl ring by 1, 2 or 3 identical or different substituents selected from halogen, C1-C4alkyl, CrC4haloalkyl, CrC4aIk:oxy and CrC4haloalkoxy, or R5 is an alkali metal, alkaline earth metal or ammonium ion, or is the group -N=C(CH3)2, -CH2-0-N=C(CH3)2 or -CH2CH2-0-N=C(CH3)2; X is oxygen or sulfur; A is CrC4alkylene; R6 is a 5- or 6-membered heterocyclic ring that contains from 1 to 3 hetero atoms selected from the group oxygen, nitrogen and sulfur and that is bonded via the carbon or nitrogen atom to the alkylene chain A, it being possible for the heterocyclic ring in turn also to be benzene-fused and mono- or di-substituted by halogen, CpQalkyl, C1-C3haloalkyl, CrC3alkoxy, C Cshaloalkoxy, di-C1-C3alkylamino, hydroxy or by an oxo function; R7 is hydrogen, CrC6aU yl, CrC4haloalkyl, CrC4alkoxy, CrC4alkoxy-CrC4alkyl, C3-C6alkenyl, C3-C6alk:ynyl, C3-C3cycloalkyl, hydroxy-CrC4alkyl or cyano-CrC4alkyl; R8 is hydrogen, CrC6alkyl, C1-C4haloalkyl, C1-C4alkoxy-C1-C alkyl, hydroxy-C C4-alkyl, C3-C6alkenyl, phenyl or phenyl-C1-C3alkyl, the phenyl ring being unsubstituted or mono-, di- or tri-substituted by halogen, Ci-Qalkyl, Cj-Qhaloalkyl, C Qalkoxy or by Ci-Qhaloalkoxy; or R7 and R8, together with the nitrogen atom to which they are bonded, form a pyrrolidino, piperidino, morpholino, thiomorpholino or piperazino ring that is unsubstituted or mono-or di-substituted by C1-C3alkyl; Z is oxygen or sulfur; n is 3, 4 or 5; and nx is 0, 1, 2 or 3, or a salt of such a compound.
2. A compound according to claim 1, wherein n is 3 or 4.
3. A compound according to claim 2, wherein n is 4.
4. A compound according to claim 1, wherein ηχ is 0, 1 or 2 and R is C^^a-kyl.
5. A compound according to claim 1, wherein R,^ is the group -X-R5.
6. A compound according to claim 5, wherein X is oxygen.
7. A compound according to claim 5, wherein R5 is C C^a-kyl.
8. A compound according to claim 1, wherein R2 and R3 are methyl.
9. A compound according to claim 1, wherein nj is 0, 1 or 2; R is methyl; Rx is chlorine or bromine; R2 and R3 are methyl; R4 is the group -X-R5; R5 is Ci-C6alkyl; and X and Z are oxygen.
10. A compound according to claim 1, wherein R4 is the group -X-A-R^
11. A compound according to claim 10, wherein X is oxygen and A is a Cj- or C2-alkylene bridge .
12. A compound according to claim 1, wherein ^ is 0, 1 or 2; R is methyl; Rj is chlorine or bromine; R2 and R3 are methyl; R4 is the group -X-A-R6; and X and Z are oxygen.
13. A compound according to claim 1, wherein R4 is the group
14. A compound according to claim 1, wherein nt is 0, 1 or 2; R is methyl; Rt is chlorine or bromine; R2 and R3 are methyl; R4 is the group — ; and Z is oxygen.
15. A compound according to claim 1 of formula la wherein Ri is chlorine or bromine; R5 is hydrogen, CrC5alkyl, C2chloroalkyl, Cr or C2-alkoxy-C2- or -C3-alkyl, Cj-Csalkyl-thio-C2- or -C3-alkyl, di-C or -C2-alkylamino-C3alkyl, cyano-Cr or -C2-alkyl, C3- or C -alkenyl, C3chloroalkenyl, C3- or C4-alkynyl, C5- or C6-cycloalkyl, C3- or C5-cyclo-alkyl-Ci- or -C2-aU yl, phenyl-Cj- or -C2-alkyl that is unsubstituted or monosubstituted in the phenyl ring by chlorine or by methyl, or R5 is the group -N=C(CH3)2 or -CH2CH2-0-N=C(CH3)2, or is a sodium, potassium, ammonium, diethylammonium, tri-ethylammonium, ethanolammonium, diethanolammonium, triethanolammonium, morpholinium, thiomorpholinium, pyrrolidinium or piperidinium ion; and X is oxygen or sulfur.
16. A compound according to claim 1 of formula lb wherein Ri is chlorine or bromine; X is oxygen; A is Cr or C2-alkylene; and R6 is 2-furyl, 2-tetrahydrofuryl, 2-thienyl, 2-, 3- or 4-pyridyl, 4-methyl-5-thiazolyl, pyrrolidin-2-on-l-yl, N-morpholinyl, N-piperidyl, 1-imidazolyl or l-methyl-4-pyrazolyl.
17. A compound according to claim 1 of formula Ic wherein Ri is chlorine or bromine; R7 is hydrogen, CrC4alkyl, C3alkenyl, methoxy, C3-C8cycloalkyl or cyano- or hydroxy-C2alkyl; and R8 is hydrogen, C Csalkyl, C2chloroalkyl, methoxy-C2alkyl, hydroxy-C2alkyl, C3- or C4-alkenyl, C3chloroalkenyl, C3- or C4-alkynyl, phenyl, phenyl monosubstituted by chlorine, methyl, methoxy or by trifluoromethyl, benzyl or benzyl monosubstituted in the phenyl ring by chlorine or by methyl; or R7 and R8, together with the nitrogen atom to which they are bonded, form a pyrrolidino, morpholino, thiomorpholino, N-methylpiperazino or 3,5-dimethylmorpholino ring.
18. A compound according to claim 1 of formula Id wherein R is hydrogen or methyl; Ri is chlorine; X is oxygen or sulfur; and R5 is hydrogen, C C^-kyl, C3- or C4-alkenyl, C3chloroalkenyl, C3alkynyl, C or C2-alkoxy-C2alkyl or Cr or C2-alkylthio-C3alkyl.
19. A compound according to claim 1 of formula le wherein Rx is chlorine; X is oxygen; and R5 is CrC3alkyl, C3- or C4-alkenyl, C3chloroalkenyl, C3alkynyl, methylthio-C3alkyl, C6-cycloalkyl or the group -N=C(CH3)2.
20. A compound according to claim 1 of formula If wherein Rj is chlorine or bromine; X is oxygen; A is Ci- or C2-alkylene; and R6 is 2-furyl, 2-tetrahydrofuryl, 4-methyl-5-thiazolyl, N-piperidyl, N-methylpipera N-morpholinyl.
21. A compound according to claim 1 of formula Ig wherein R is hydrogen or methyl; is chlorine or bromine; R7 is hydrogen, C1-C4alkyl, C3alkenyl, methoxy or C3cycloalkyl; and R8 is hydrogen, C1-C4alkyl, C3alkenyl, C3chloroalkenyl, C3alkynyl, phenyl, chlorophenyl or phenyl-Cr or -C2-alkyl.
22. A compound according to claim 1 of formula Di wherein is chlorine; R7 is hydrogen, methyl, methoxy, C3alkenyl or C3cycloalkyl; and R8 is hydrogen, CrC4alkyl or C3- or C4-alkenyl; or R7 and R8, together with the nitrogen atom to which they are bonded, form a morpholino ring.
23. A compound according to claim 1 of formula Ii wherein R is hydrogen or methyl; Rj is chlorine or bromine; X is oxygen or sulfur; and R5 is hydrogen, C1-C3alkyl, methoxy-C2alkyl, C2- or C3-alkylthio-C3alkyl, C3- or C4-alkenyl, C3chloroalkenyl, C3alkynyl, C6cycloalkyl, C3cycloalkyl-C2alkyl, phenyl-C or -C2-alkyl or the group -N=C(CH3)2.
24. A compound according to claim 1 of formula Ij wherein R is hydrogen or methyl; Rj is chlorine or bromine; X is oxygen; A is C or C2-alkylene; and R6 is 2-furyl, 2-tetrahydrofuryl, 2-tetrahydrothienyl, N-morpholinyl, N-piperidyl, 2-, 3- or 4-pyridyl or 4-methyl-5-thiazolyl.
25. A compound according to claim 1 of formula H wherein R is hydrogen or methyl; Ri is chlorine or bromine; R7 is hydrogen, methyl, methoxy, C3cycloalkyl or C3alkenyl; and R8 is hydrogen, CrC4alkyl, hydroxy-C2alkyl, C3alkenyl, C3chloroalkenyl, C3- or C4-alkynyl, phenyl, fluorophenyl, methoxyphenyl or benzyl; or R7 and R8, together with the nitrogen atom to which they are bonded, form a morpholino ring.
26. 2-Methyl-2-[2-chloro-5-[(tetrahydro-3-oxo-lH,3H-[l,3,4]thiadiazolo[3,4-a]pyridazin-l-ylidene)amino]-benzoyloxy]-propionic acid 2-chloro-2-propenyl ester according to claim 1. 112523/2 - 76 -
27. A process for the preparation of a compound of formula I according to claim 1, which process comprises reacting a compound of formula Π with thiophosgene to form the compound of formula ΙΠ the radicals Rx to R in the compounds of formulae Π and ΙΠ being as defined in claim 1, and converting the compound of formula ΙΠ with a compound of formula V wherein R, n and nj are as defined in claim 1, into the compound of formula IV wherein R, Rj to R4, n and x are as defined, and then reacting the compound of formula IV with a compound of formula VI CZC12 (VI), wherein Z is oxygen or sulfur, if desired in the presence of a base.
28. A herbicidal and plant-growth-inhibiting composition which comprises one or more compounds of formula I according to claim 1 and solid or liquid formulation adjuvants. 112523/3 - 77 -
29. A composition according to claim 28, which comprises from 0.1 % to 95 % of a compound of formula I according to claim 1.
30. A method of controlling undesired plant growth, which method comprises applying an effective amount of a compound of formula I according to claim 1 , or of a composition comprising such a compound, to the plant or the locus thereof.
31. A method according to claim 30, wherein from 0.001 to 2 kg of active ingredient are applied per hectare.
32. A method of inhibiting plant growth, which method comprises applying an effective amount of a compound of formula I according to claim 1, or of a composition comprising such a compound, to the plant or the locus thereof.
33. A composition according to claim 28, for use as an agent in the selective control of weeds in crops of useful plants. For the Applicants, REINHOLD COHN AND PARTNERS *r-
IL112523A 1994-02-04 1995-02-02 ESTERS OF 2-HALO- 5-£TETRAHYDRO-3 (THI) OXO-1H, 3H-£1, 3, 4| THIADIAZOL £3, 4-a| PYRIDAZIN-1- YLIDEN| AMINO|- BENZOIC ACID AND HOMOLOGS THEREOF, THEIR PREPARATION AND HERBICIDAL COMPOSITIONS CONTAINING THEM IL112523A (en)

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CA (1) CA2181583A1 (en)
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US4439229A (en) * 1981-06-29 1984-03-27 Rohm And Haas Company Substituted phthalimides herbicides
DE3675931D1 (en) * 1986-03-25 1991-01-10 Kumiai Chemical Industry Co THIADIAZABICYCLONONE DERIVATIVES, METHOD FOR THE PRODUCTION THEREOF AND HERBICIDAL COMPOSITIONS.
CA2033990C (en) * 1989-06-29 2000-12-12 Milos Suchy Herbicidal 3-aryluracils
EP0457714A1 (en) * 1990-03-22 1991-11-21 Ciba-Geigy Ag Thiadiazabicyclononane derivatives, process for their preparation, intermediates and their use as herbicides
JPH06507607A (en) * 1991-06-06 1994-09-01 ノバルティス　アクチエンゲゼルシャフト New herbicide
US5817602A (en) * 1993-06-23 1998-10-06 Novartis Corporation Herbicidal thiadiazabicyclodecanes

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CA2181583A1 (en) 1995-08-10
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ZA95864B (en) 1995-08-04

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