GB1587221A - Herbicidally active sulphonates processes for their preparation and compositions containing them - Google Patents

Herbicidally active sulphonates processes for their preparation and compositions containing them Download PDF

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GB1587221A
GB1587221A GB4847/77A GB484777A GB1587221A GB 1587221 A GB1587221 A GB 1587221A GB 4847/77 A GB4847/77 A GB 4847/77A GB 484777 A GB484777 A GB 484777A GB 1587221 A GB1587221 A GB 1587221A
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compound
methanesulphonate
dihydro
alkyl
phenyl
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GB4847/77A
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Fisons Ltd
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Fisons Ltd
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Priority to GB4847/77A priority Critical patent/GB1587221A/en
Priority to BE184756A priority patent/BE863471A/en
Priority to DE19782803991 priority patent/DE2803991A1/en
Priority to IL53951A priority patent/IL53951A/en
Priority to DK48278A priority patent/DK48278A/en
Priority to NL7801189A priority patent/NL7801189A/en
Priority to ZA00780634A priority patent/ZA78634B/en
Priority to NZ186379A priority patent/NZ186379A/en
Priority to US05/875,189 priority patent/US4162154A/en
Priority to AU32986/78A priority patent/AU519345B2/en
Priority to DD78203553A priority patent/DD136690A5/en
Priority to HUFI000663 priority patent/HU179470B/en
Priority to IT7819951A priority patent/IT1092374B/en
Priority to FR7803076A priority patent/FR2379514A1/en
Priority to CA296,259A priority patent/CA1115720A/en
Priority to AR27096478A priority patent/AR223457A1/en
Priority to IE235/78A priority patent/IE46549B1/en
Priority to PL1978204448A priority patent/PL111137B1/en
Priority to JP1155678A priority patent/JPS5398936A/en
Priority to US06/022,599 priority patent/US4222767A/en
Priority to GT198061589A priority patent/GT198061589A/en
Publication of GB1587221A publication Critical patent/GB1587221A/en
Expired legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
    • C07D307/77—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom ortho- or peri-condensed with carbocyclic rings or ring systems
    • C07D307/78—Benzo [b] furans; Hydrogenated benzo [b] furans
    • C07D307/79—Benzo [b] furans; Hydrogenated benzo [b] furans with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to carbon atoms of the hetero ring
    • 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
    • A01N41/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a sulfur atom bound to a hetero atom
    • A01N41/02—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a sulfur atom bound to a hetero atom containing a sulfur-to-oxygen double bond
    • A01N41/04—Sulfonic acids; Derivatives thereof
    • 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
    • A01N41/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a sulfur atom bound to a hetero atom
    • A01N41/02—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a sulfur atom bound to a hetero atom containing a sulfur-to-oxygen double bond
    • A01N41/04—Sulfonic acids; Derivatives thereof
    • A01N41/06—Sulfonic acid amides
    • 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
    • A01N41/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a sulfur atom bound to a hetero atom
    • A01N41/02—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a sulfur atom bound to a hetero atom containing a sulfur-to-oxygen double bond
    • A01N41/04—Sulfonic acids; Derivatives thereof
    • A01N41/08—Sulfonic acid halides; alpha-Hydroxy-sulfonic acids; Amino-sulfonic acids; Thiosulfonic acids; Derivatives thereof
    • 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
    • A01N43/02—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms
    • A01N43/04—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom
    • A01N43/06—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom five-membered rings
    • A01N43/12—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom five-membered rings condensed with a carbocyclic ring
    • 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
    • A01N43/02—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms
    • A01N43/24—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with two or more hetero atoms
    • A01N43/32—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with two or more hetero atoms six-membered rings
    • 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
    • A01N43/72—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms
    • A01N43/88—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms six-membered rings with three ring hetero atoms
    • 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
    • A01N57/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds
    • A01N57/36—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds having phosphorus as a ring member
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C309/00—Sulfonic acids; Halides, esters, or anhydrides thereof
    • C07C309/63—Esters of sulfonic acids
    • C07C309/64—Esters of sulfonic acids having sulfur atoms of esterified sulfo groups bound to acyclic carbon atoms
    • C07C309/65—Esters of sulfonic acids having sulfur atoms of esterified sulfo groups bound to acyclic carbon atoms of a saturated carbon skeleton
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C309/00—Sulfonic acids; Halides, esters, or anhydrides thereof
    • C07C309/63—Esters of sulfonic acids
    • C07C309/64—Esters of sulfonic acids having sulfur atoms of esterified sulfo groups bound to acyclic carbon atoms
    • C07C309/65—Esters of sulfonic acids having sulfur atoms of esterified sulfo groups bound to acyclic carbon atoms of a saturated carbon skeleton
    • C07C309/66—Methanesulfonates
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
    • C07D307/94—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom spiro-condensed with carbocyclic rings or ring systems, e.g. griseofulvins
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D321/00—Heterocyclic compounds containing rings having two oxygen atoms as the only ring hetero atoms, not provided for by groups C07D317/00 - C07D319/00
    • C07D321/02—Seven-membered rings
    • C07D321/10—Seven-membered rings condensed with carbocyclic rings or ring systems
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    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D327/00—Heterocyclic compounds containing rings having oxygen and sulfur atoms as the only ring hetero atoms
    • C07D327/10—Heterocyclic compounds containing rings having oxygen and sulfur atoms as the only ring hetero atoms two oxygen atoms and one sulfur atom, e.g. cyclic sulfates
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
    • C07F9/6564—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms
    • C07F9/6571—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and oxygen atoms as the only ring hetero atoms
    • C07F9/6574—Esters of oxyacids of phosphorus
    • C07F9/65744—Esters of oxyacids of phosphorus condensed with carbocyclic or heterocyclic rings or ring systems

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Description

(54) HERBICIDALLY ACTIVE SULPHONATES, PROCESSES FOR THEIR PREPARATION, AND COMPOSITIONS CONTAINING THEM (71) We, FISONS LIMITED, a British Company, of Fison House, 9 Grosvenor Street, London WIX OAH, do hereby declare the invention, for which we pray that a patent may be granted to us, and the method by which it is to be performed, to be particularly described in and by the following statement:- This invention concerns herbicidally active sulphonates, processes for their preparation, and compositions containing them.
In one aspect, this invention provides the sulphonates of the formula:
wherein X represents a group -CHR3-OR4 or Y represents a group -OR5, or X and Y together represent a group -CHR3-O- or -CHR3-O-Z-O-, the free oxygen atom of which is attached to the benzene ring; R1, R2 and R3, which may be the same or different, each represent hydrogen or alkyl, or R1 and R2 together or R2 and R3 together form an alkylene chain; R4 and R5, which may be the same or different, each represent hydrogen, alkyl, alkenyl, alkynyl, aryl, a group C(=O)R10 or a group -SO2R11; R6, R7 and R8, which may be the same or different, each represent hydrogen, alkyl, halogen, cyano, carboxylic acid or alkoxy; R9 represents alkyl, aryl or aralkyl (each of which may be substituted or unsubstituted), cycloalkyl, alkylamino or dialkylamino; R10 represents alkyl, alkenyl, alkynyl, aryl, alkoxy, alkenyloxy, alkynyloxy, aryloxy, alkylamino, arylamino or dialkylamino, (each of which may be substituted or unsubstituted); R11 represents alkyl, aryl, alkylamino or dialkylamino (each of which may be substituted or unsubstituted); Z represents a group of formula \(= )ns CR12R13 or P(-Q)(OR14)-; n represents 1 or 2; R12 and R'3, which may be the same or different each represent hydrogen, alkyl, alkenyl, alkynyl, alkoxy, aryl, aryloxy, cyano or alkoxycarbonyl, or R12 and R'3 together represent an oxygen atom, a sulphur atom, an alkylene chain or an alkylamino or arylimino group; R'4 represents alkyl; and Q represents oxygen or sulphur.
R' preferably represents alkyl of I to 6 carbon atoms, especially I to 4 carbon atoms, for example methyl or ethyl.
R2 preferably represents alkyl of I to 6 carbon atoms, especially I to 4 carbon atoms, for example methyl or ethyl.
R3 preferably represents hydrogen. When, however, it represents alkyl, it is preferably of I to 6 carbon atoms, especially I to 4 carbon atoms, for example methyl or ethyl.
When R1 and R2 together or R2 and R3 together represent an alkylene chain, it is preferably of 3 to 6, especially 4 or 5 carbon atoms.
R4 and R5 are preferably the same as each other. When one or both of them represents alkyl it is preferably of I to 6 carbon atoms, especially methyl or ethyl.
Preferred alkenyl and alkynyl groups which each may represent are of 2 to 6 carbon atoms, for example allyl or propargyl. When one or both of them represents aryl it is preferably phenyl. When one or both of R4 and R5 represents a group C(=O)R'O or --SO,R", the group R'O or R" is preferably such that any alkyl moiety thereof has from I to 6 carbon atoms, especially methyl or ethyl, any alkenyl or alkynyl moiety thereof has from 2 to 6 carbon atoms, especially allyl or propargyl, and any aryl moiety thereof is phenyl. Preferably the group which R'O or R" represents is unsubstituted. However, when it represents a substituted group, the substituent(s) thereon are preferably halogen, especially chlorine or alkoxy, especially of 1 to 4 carbon atoms, for example methoxy.
Specific preferred groups which R4 and/or R5 may represent include hydrogen, methyl, ethyl, allyl, propargyl, phenyl, acetyl, isobutyryl, methylcarbamoyl, chloroacetyl, pentanoyl, benzoyl, ethoxycarbonyl, 4-chloro-2-butynyloxycarbonyl, 2-chloroethoxycarbonyl, methylsulphonyl, benzoyl, methoxycarbonyl, trichloroacetyl, crotonyl and phenylcarbamoyl.
R6, R7 and R8 independently preferably represent hydrogen. When one or more thereof is other than hydrogen, however, it is preferably alkyl of 1 to 6 carbon atoms (e.g. methyl or ethyl), chlorine, bromine, cyano, carboxylic acid of 2 to 6 carbon atoms (e.g. acetyl) or alkoxy of 1 to 4 carbon atoms (e.g. methoxy or ethoxy).
R9 preferably represents alkyl of I to 6 carbon atoms, especially l to 4 carbon atoms, which is unsubstituted or substituted by one or more halogen atoms, for example methyl, ethyl, n-propyl, isopropyl, n-butyl, i-butyl or s-butyl (either unsubstituted or substituted by a chlorine or bromine atom). Further preferred values for R9 are phenyl and phenylalkyl of 7 to 10 carbon atoms (especially benzyl), each of which may be unsubstituted or substituted by one or more chlorine or bromine atoms, alkyl or alkoxy groups of I to 4 carbon atoms (e.g. methyl or methoxy) or nitro groups, for example 4-chlorophenyl, 4-bromobenzyl, p-tolyl, 2 methoxyphenyl, 3-nitrophenyl or 3,4-dichlorophenyl, and cycloalkyl of 5 to 7 carbon atoms (especially cyclopentyl or cyclohexyl), alkylamino and dialkylamino, especially where the alkyl moieties thereof have from 1 to 4 carbon atoms, e.g. methylamino, ethylamino or dimethylamino.
Z preferably represents a group -CR12R13 as defined hereinbefore.
When Z represents a group ~CR'2R'3, the group R12 or R13 is preferably such that any alkyl moiety thereof has from l to 6 carbon atoms, e.g. methyl or ethyl, any alkenyl or alkynyl moiety thereof has from 2 to 6 carbon atoms, especially allyl or propargyl, and any aryl moiety thereof is phenyl. When R12 and R'3 together represent an alkylene chain, it is preferably of from 3 to 6, especially 4 to 5 carbon atoms.
Specific preferred groups R'2 and R'3 are hydrogen, methyl, ethyl, n-propyl, isopropyl, chloromethyl, bromomethyl, methoxy, ethoxy, phenyl, tetramethylene and pentamethylene.
When Z represents a group --P(=Q)(OR'4), R'4 is preferably of I to 6 carbon atoms, for example methyl or ethyl.
A preferred sub-group of compounds within formula I (hereinafter referred to assub-group A) comprises those compounds wherein X and Y together represent a group -CHR3-O-.
Within sub-group A, in a preferred class of compounds, R' represents alkyl of I to 4 carbon atoms, R2 represents alkyl of I to 4 carbon atoms, R3 represents hydrogen or alkyl of l to 4 carbon atoms, R6, R7 and R8 each represent hydrogen, and K9 represents methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl or s-butyl (each of which is unsubstituted or substituted by a chlorine or bromine atom), phenyl or benzyl (each of which is unsubstituted or substituted by one or more chlorine or bromine atoms or methyl, methoxy or nitro groups), cyclopentyl, cyclohexyl, methylamino, ethylamino or dimethylamino.
A further preferred class within sub-group A comprises those compounds of formula I wherein R' represents methyl or ethyl, R2 represents methyl or ethyl, R3, R6, R7 and R8 each represent hydrogen, and R9 represents methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, s-butyl, chloromethyl, 3-chloropropyl, phenyl, benzyl, p-tolyl, cyclopentyl, cyclohexyl, methylamino, ethylamino or dimethylamino.
Specific preferred compounds within sub-group A are: 2,3-dihydro-3,3-dimethylbenzofuran-5-yl methanesulphonate, 2,3-dihydro-3,3-dimethylbenzofuran-5-yl ethanesulphonate, 2,3-dihydro-3,3-dimethylbenzofuran-5-yl propanesulphonate, 2,3-dihydro-3, 3-dimethylbenzofuran-5-yl I -butanesulphonate, 2,3-dihydro-3,3-dimethylbenzofuran-5-yl 2-propanesulphonate, 2,3-dihydro-3,3-dimethylbenzofuran-5-yl 2-butanesulphonate, 2,3-dihydro-3,3-dimethylbenzofuran-5.-yl 2-methyl-l-propanesulphonate, 2,3-dihydro-3,3-dimethylbenzofuran-5-yl chloromethanesulphonate, 2,3-dihydro-3,3-dimethylbenzofuran-5-yl 3-chloro- 1 -propanesulphonate, 2,3-dihydro-3,3-dimethylbenzofuran-5-yl cyclohexane sulphonate, 2,3-dihydro-3,3-dimethylbenzofuran-5-yl p-toluenesulphonate, 2,3-dihydro-3,3-dimethylbenzofuran-5-yl a-toluenesulphonate, 2,3-dihydro-3,3-dimethylbenzofuran-5-yl methylsulphamate, and spiro[benzofuran-3(2H), l '-cyclopentan]-5-yl methanesulphonate.
Specific preferred compounds of formula I wheren X and Y together represent a group -CHR3-O-Z-O (hereinafter referred to as sub-group B) are: 4,5-dihydro-5 , 5-dimethyl-2-oxido- 1,3 ,2-benzodioxathiepin-7-yl methanesulphonate; 4,5-dihydro-2,2,5,5-tetramethyl- I ,3-benzodioxepin-7-yl methanesulphonate; 4,5-dihydro-2-methoxy-5,5-dimethyl-l ,3-benzodioxepin-7-yl methanesulphonate; 2-ethyl-4,5-dihydro-2,5,5-trimethyl- 1 ,3-benzodioxepin-7-yl methanesulphonate; 2,2-diethyl-4,5-dihydro-5,5-dimethyl- 1 ,3-benzodioxepin-7-yl methanesulphonate; 4,5-dihydro-2-isopropyl-2,5,5-trimethyl- 1 ,3-benzodioxepin-7-yl methanesulphonate; 4,5-dihydro-5,5-dimethyl- I ,3-benzodioxepin-7-yl methanesulphonate; 4,5-dihydro-2,5,5-trimethyl- 1 ,3-benzodioxepin-7-yl methanesulphonate; 4,5-dihydro-5,5-dimethyl-2-phenyl- 1 ,3-benzodioxepin-7-yl methanesulphonate; 4,5-dihydro-2,5,5-trimethyl-2-phenyl-1,3-benzodioxepin-7-yl methanesulphonate; 4,5-dihydro-5,5-dimethylspiro[ l ,3-benzodioxepin-2, l '-cyclohexan]-7-yl me thanesulphonate; 4,5-dihydro-5,5-dimethylspiro[ 1 ,3-benzodioxepin-2, 1 '-cyclopentan]-7-yl me thanesulphonate; 2-chloromethyl-4,5-dihydro-2,5, 5-trimethyl- 1, 3-benzodioxepin-7-yl methane sulphonate; 2-bromomethyl-4,5-dihydro-5,5-dimethyl- l ,3-benzodioxepin-7-yl methanesul- phonate; 2-ethoxy-4,5-dihydro-5,5-dimethyl-1,3-benzodioxepin-7-yl methanesulphonate; 2-ethyl-4,5-dihydro-2-methoxy-5,5-dimethyl-1,3-benzodioxepin-7-yl methane sulphonate; and 2 - ethoxy-4,5-dihydro-5,5-dimethyl-2-oxo-1,3,2-benzodioxaphosphepin - 7 yl methanesulphonate.
Specific preferred compounds of formula I wherein X represents -CHR3-OR4 and Y represents --OR5 (hereinafter referred to as sub-group C) are: 4-hydroxy-3-(2-hydroxy- 1,1 -dimethylethyl)phenyl methanesulphonate; 4-hydroxy-3-(2-hydroxy- 1,1 -dimethylethyl)phenyl ethanesulphonate (this compound being particularly preferred); 4-acetoxy-3-(2-acetoxy- ,I-dimethylethyl)phenyl methanesulphonate; 4-isobutyryloxy-3-(2-isobutyryloxy- 1,1 -dimethyiethyl)phenyl methanesulphonate; 4-methylcarbamoyloxy-3-(2-methylcarbamoyloxy 1,1 -dimethylethyl)phenyl methanesulphonate; 4-hydroxy-3-( I -hydroxymethyl)cyclopentyl)phenyl methanesulphonate; 4-hydroxy-3-(l-(hydroxymethyl)cyclohexyl)phenyl methanesulphonate; 4-chloroacetyloxy-3-(2-chloroacetyloxy- 1,1 -dimethylethyl)phenyl methanesulphonate; 4-pentanoyloxy-3-(2-pentanoyloxy- 1,1 -dimethylethyl)phenyl methanesulphonate; 4-benzoyloxy-3-(2-benzoyloxy- 1,1 -dimethylethyl)phenyl methanesulphonate; 4-(ethoxycarbonyloxy)-3-(2-(ethoxycarbonyloxy)-l,l-dimethylethyl)phenyl methanesulphonate; 4- (4- chloro- 2- butynyloxycarbonyloxy) - 3- (2- (4- chloro- 2butynyloxycarbonyloxy) - 1,1 - dimethylethyl)phenyl methanesulphonate; 4 - (2 - chloroethoxycarbonyloxy) - 3 - (2 - (2 - chloroethoxycarbonyloxy) - 1,1 dimethylethyl)phenyl methanesulphonate; 4-methansulphonyloxy-3-(2-methanesulphonyloxy- 1,1 -dimethylethyl)phenyl methanesulphonate; 3-(2-benzyloxy- 1,1 -dimethylethyl)-4-hydroxyphenyl methanesulphonate; 4-methoxycarbonyloxy-3-(2-(methoxycarbonyloxy)-l ,l-dimethylethyl)phenyl methanesulphonate; 4-(trichloroacetyloxy)-3-(2 (trichloroacetyloxy)- 1,1 -dimethylethyl)phenyl methanesulphonate; 4-crotonyloxy-3-(2-crotonyloxy- 1,1 -dimethylethyl)phenyl methanesulphonate; 4-(phenylcarbamoyloxy)-3-(2-(phenylcarbamoyloxy)- 1,1 -dimethylethyl)phenyl methanesulphonate; The compounds of formula I possess, when R3 is other than hydrogen or R' and R2 are not identical, at least one asymmetric carbon atom. They may therefore exist as distinct stereoisomeric forms or as mixtures thereof. The activities of the stereoisomeric forms of a single compound may be different.
The compounds of sub-group C of formula I in which R4 and R5 both represent hydrogen may be prepared by a process in which a carbonyl compound of the formula:
(wherein R', R2, R3, R6, R7, Re and R9 are as defined hereinbefore and M represents an alkali-metal) is reduced, followed by acidification, to give the desired compound of formula I.
The reduction may be effected in any appropriate manner for reducing carbonyl groups without affecting the other groups in the molecule. Preferably, sodium borohydride is employed as the reducing agent.
The alkali-metal which M represents is preferably sodium or potassium.
The acidification may be effected by means of a mineral acid, e.g. hydrochloric acid.
The carbonyl compounds of formula II wherein R9 represents alkylamino or dialkylamino are themselves novel compounds and this invention provides them per se.
The compounds of formula II may be prepared by a process in which a 2hydroxy-benzo-furanyl sulphonate of the formula:
(wherein R', R2, R3, R6, R7, RS and R9 are as defined hereinbefore) is treated with an alkali-metal hydroxide to give the desired compound of formula ll.
The compounds of formula III are either known compounds or may be prepared from known compounds by techniques which will be familiar to those skilled in organic synthesis.
The compounds of sub-group C of formula l in which one of R4 and R5 is other than hydrogen or both of R4 and R5 are identical and other than hydrogen may be prepared from the corresponding compounds where R4 and R5 both represent hydrogen by reaction with one or two moles, as appropriate, of a halide of formula R4Hal (where Hal represents halogen, e.g. bromide, and R4 is as defined hereinbefore). Alternatively, where R4 and/or R5 in the desired compound represents carboxylic acid, an anhydride of formula R40R4 (where R4 represents carboxylic acyl) may be employed instead of the halide. Alternatively, where R4 and/or R5 in the desired compound represents a group C(=O)R'O where R'O represents alkylamino or arylamino, an alkyl or aryl isocyanate, as appropriate, may be employed instead of the halide.
The compounds of sub-group C of formula I in which R4 and R5 are different may be prepared from the corresponding compounds where R4 and R5 both represent hydrogen by reaction with an appropriate amount of a halide, anhydride or alkyl or aryl isocyanate as above to give the corresponding compound wherein R5 is hydrogen and R4 is other than hydrogen, followed by reaction of the formed compound with an appropriate amount of a different halide, anhydride or alkyl or aryl isocyanate to give the corresponding compound where R4 and RS are different and are both other than hydrogen.
The compounds of sub-group B of formula I may be prepared by a process in which a compound of sub-group C of formula I wherein R4 and R5 both represent hydrogen is reacted with a dihalide of formula Hal-Z-Hal (where Z is as defined hereinbefore, and Hal represents halogen, e.g. chlorine) in the presence of a base if necessary or desired to give the corresponding compound of sub-group B of formula 1.
The reaction is desirably carried out in an appropriate solvent or suspension medium, other than a dialkylamide, e.g. an aromatic hydrocarbon, e.g. toluene.
Alternatively, where Z represents a group -CR12R13- as defined hereinbefore, the dihalide may be replaced by a dialkoxy compound of formula R'50ZOR'5 (where R'5 represents an alkyl group, especially of 1-6 carbon atoms) in the presence of an acid catalyst, e.g. p-toluenesulphonic acid.
The compounds of sub-group A of formula I may be prepared by a process in which a compound of sub-group C of formula I wherein R4 and R5 both represent hydrogen is cyclised and dehydrated to give the desired compound.
The cyclisation and dehydration may conveniently be effected by means of a dehydrating agent, for example phosphorous pentoxide or dicyclohexylcarbodiimide or, more preferably, a Vilsmeier reagent, for example of the formula:
Alkyl + I-laW I Alkyl or Aryl Rx (where Rx represents hydrogen or alkyl, and Hal represents chlorine or bromine) to give the corresponding compound of sub-group A of formula 1.
The Vilsmeier reagent, where Hal preferably represents chlorine, Rx preferably represents hydrogen, and each alkyl preferably represents methyl may be generated in situ by the reaction of a thionyl, phosphoryl or carbonyl chloride or bromide and a dialkylamide. It is preferred to employ thionyl chloride and dimethylformamide. The anion in the Vilsmeier reagent may be any suitable anion, for example Cl- or Br-.
As will be apparent to those skilled in synthetic organic chemistry, the dehydration may be effected in several ways, e.g. by replacement of the group R4 by a good leaving group, e.g. a halogen atom, followed by elimination of that group with the hydrogen atom which Ra represents. Such processes are all encompassed by the term 'dehydration' as used herein.
The compounds of sub-group A of formula I may alternatively be prepared by a process in which a compound of sub-group B of formula I is heated in an appropriate dialkylamide solvent medium in the presence of an ionic salt to give the desired compound of sub-group A.
The solvent medium is desirably dimethylformamide.
The ionic salt is conveniently an alkali-metal salt, e.g. a halide, for example a chloride. Specifically preferred is sodium chloride.
The compounds of sub-group A of formula I may alternatively be prepared by a process in which a S-hydroxybenzofuranyl compound of the formula:
(wherein R', R2, R3, Ra, R7 and Ra are as defined hereinbefore) is reacted with a sulphonyl halide of the formula R9SO2Hal (where Hal represents a halogen atom) pr an anhydride of the formula (RaSO2)2O, Ra being as defined hereinbefore, to give the desired compound of formula I.
The reaction is desirably effected in the presence of an organc base, for example an amine such as triethylamine.
The 5-hydroxybenzofuranyl compounds of formula VI may themselves be prepared by a multi-step process schematically represented as follows:
R6 R2 Br - + R18 (VII) R7 R16 (VIII) IC Step (a) R6 Br < 1R .CHR3Hal (Ix) ibR16 8 D Step &commat;) 2/ Step (c) 6 1 R6 B R12 < 9 2 R7 -R3 R7 3 R8 (X) R8 / (Xl) Step (d) 6 Ho 2 R7 R3 S R3 (Vl) In the above scheme, R1, R2, R3, Ra, R7 and Ra are as defined hereinbefore, R'6 and R'7 represent lower (i.e. C l to 6) alkyl groups, R13 represents a divalent group formed by the removal of an alpha-hydrogen atom from a group R', and Hal represents a halogen atom (e.g. chlorine).
Step (d) is conveniently effected by dealkylating the compound of formula XI, preferably using as the dealkylating agent a salt of a mercaptan, in an appropriate solvent medium which is preferably of high boiling point, e.g. dimethylformamide.
Step (c) is conveniently effected by means of an alkoxide (suitably an alkali metal alkoxide, especially of l to 6 carbon atoms), in -the presence of a suitable catalyst, e.g. a transition metal salt, for example a copper or nickel salt, especially cuprous iodide. Generally, the alkanol employed to generate the alkoxide acts as solvent medium for the reaction. Other- solvents, e.g. dimethylformamide or xylene, may additionally be employed e.g. in order to raise the boiling point thereof.
Step (b) is a combined dealkylation and cyclisation. It is conveniently effected by heating the compound of formula IX with a mild dealkylating and cyclising agent, e.g. a pyridine salt such as pyridine hydrochloride.
Step (a) is an alkylation reaction which is conveniently effected by reacting the compounds of formula Vil and VILLI in the presence of an acid.
The compounds of formulae X, XI and VI are themselves novel compounds, with the exception of 3,3-dimethylbenzofuran-5-ol, and this invention provides them per se, together with processes for their preparation as described hereinbefore.
This invention extends, naturally, to the compounds of formula I whenever prepared by a process as described hereinbefore.
In a further aspect, this invention provides a method of combating weeds at a locus infested or liable to be infested with them which method comprises applying to the locus at which they are growing an effective amount of one or more compounds of formula I.
The present compounds are normally employed in the form of compositions, which can be prepared by admixing the ingredients. Usually the compositions are initially produced in the form of concentrates, e.g. containing 0.5-85%, preferably 10 to 50%, by weight of the present compounds, and these are diluted with water or hydrocarbon, usually water, for application, generally such that the concentration of the compound is 0.055%. Percentages and parts in this specification are by weight unless otherwise indicated.
The compositions normally contain a surface active agent and/or a carrier.
The carrier may be a liquid, e.g. water (e.g. water used to dilute a concentrate for application). If water is employed as carrier in a concentrate, an organic solvent may also be present as carrier, though this is not usually employed. A surface active agent may advantageously be present.
The carrier may be a solid, which may be finely divided. Examples of suitable solids are limestone, clays, sand, mica, chalk, attapulgite, diatomite, perlite, sepiolite, silicas, silicates, lignosulphonates and solid fertilizers. The carrier can be of natural or synthetic origin or can be a modified natural material.
Wettable powders soluble or dispersible in water may be formed by admixing the compound in particulate form with a particulate carrier or spraying molten compound on to the particulate carrier, admixing a wetting agent and a dispersing agent and finely grinding the whole powder mixture.
An aerosol composition may be formed by admixing the compound with a propellant e.g. a polyhalogenated alkane such as dichloridifluoromethane, and suitably also with a solvent.
A flowable suspension concentrate may be formed by grinding the compound with water, a wetting agent and a suspending agent.
Thus the present composition can for example be solid (e.g. dust or granules) and contain a solid carrier, or liquid (e.g. an emulsifiable concentrate) and contain a liquid carrier which may for example be a ketone or a hydrocarbon which boils within the range 130--270"C.
The term 'surface active agent' is used in the broad sense to include materials variously called emulsifying agents, dispersing agents and wetting agents. Such agents are well known in the art.
The surface active agents used may comprise anionic surface acive agents, for example mono- or di-esters of phosphoric acid with fatty alcohol ethxylate or salts of such esters, fatty alcohol sulphates such as sodium dodecyl sulphate, ethoxylated fatty alcohol sulphates, ethoxylated alkylphenol sulphates, lignin sulphonates, petroleum sulphonates, alkylaryl sulphonates such as alkyl-benzene sulphonates or lower alkyl-naphthalene sulphonates, salts of sulphonated naphthaleneformaldehyde condensates, salts of sulphonated phenol-formaldehyde condensates, or more complex sulphonates such as the amide sulphonates, e.g. the sulphonated condensation product of oleic acid and N-methyl taurine or the dialkyl sulphosuccinate e.g. the sodium sulphonate of dioctyl succinate.
The surface active agents may also comprise non-ionic agents, for example condensation products of fatty acid esters, fatty alcohols, fatty acid amides or alkylsubstituted phenols with ethylene oxide, fatty esters of polyhydric alcohol ethers e.g. sorbitan fatty acid esters, condensation products of such esters with ethylene oxide e.g. polyoxyethylene sorbitan fatty acid esters, block copolymers of ethylene oxide and propylene oxide, acetylenic glycols such as 2,4,7,9-tetramethyl-5-decyn4,7-diol, or ethoxylated acetylenic glycols.
The surface active agents may also comprise cationic agents, for example alkyl- and/or aryl-substituted quaternary ammonium compounds such as cetyl trimethylammonium bromide, or ethoxylated tertiary fatty amines.
Preferred surface active agents include ethoxylated fatty alcohol sulphates, lignin sulphonates, alkyl-aryl sulphonates, salts of sulphonated napthaleneformaldehyde condensates, salts of sulphonated phenol-formaldehyde condensates, sodium oleyl N-methyltauride, dialkyl sulphosuccinates, alkyl phenol ethoxylates, and fatty alkyl ethoxylates.
The present active compounds, particularly those specifically identified hereinbefore, and especiallyd 2,3-dihydro-3,3-dimethylbenzofuran-5-yl ethanesulphonate, methanesulphonate, 2-methyl-I -propanesulphonate, or 2propanesulphonate, or 4-hydroxy-3-(2-hydroxy- 1,1 -dimethylethyl)phenyl ethanesulphonate or methanesulphonate, may be admixed with another pesticide, e.g. herbicide, insecticide or fungicide, or with a plant growth regulant or with a fertilizer. Particular advantages are obtained with mixtures with a second herbicide, e.g. one herbicide applied before planting or before emergence of a crop and the other herbicide applied after emergence of the crop.
The second herbicide employed in admixture or sequentially with the compounds of the present invention may be, for example, a substituted benzofuran herbicide, a phenoxyaliphatic acid, substituted urea, triazine, phenol, nitrile, bipyridylium compound, substituted benzoic acid, halogenated aliphatic acid, carbamate, thiocarbamate, chloroacetamide , diazine, arsenic compound or other herbicidal compound. In respect of selective herbicidal compositions for postemergence use, the second herbicide is preferably a substituted phenoxyaliphatic acid; in respect of selective herbicidal compositions for pre-emergence use, the second herbicide is preferably a substituted benzofuran, a substituted urea or tri azine.
The substituted benzofuran herbicide is preferably a compound of the formula:
where Ria represents alkoxy (especially ethoxy, propoxy or isopropoxy), and R20 represents alkyl (especially methyl) or a group R21R22N- where R2' and R22, which may be the same or different, each represent hydrogen, alkyl (especially methyl) or carboxylic acyl (especially acetyl).
A particularly preferred substituted benzofuranyl compound for admixture with the compounds of the present invention, especially with those specifically identified herein, is 2-ethoxy-2,3-dihydro-3,3-dimethylbenzofuran-5-yl methanesulphonate (common name ethofumesate).
The phenoxyaliphatic acid generally comprises alkyl and/or halogen substituted phenoxyaliphatic acids, and their salts, for example alkali metal, amine and alkanolamine salts, and functional
where T is a halogen or a group -OR6 or -SR6 where Re is an alkyl group, and Ra, Rb, Rc and Rd are hydrogen or alkyl.
Specific compounds with which the compounds of the present invention, especially those specifically identified herein, may be admixed are as follows, all common names being as set out in the Pesticide Manual, 4th edition, issued by the British Crop Protection Council: alachlor, allidochlor, ametryne, aminotriazole (ATA), ancymidol, asulam, atrazine, aziprotryne, barban, benazolin, benfluralin, bensulide, bentazon, benthiocarb, bentranil, benzadox, benzoylprop-ethyl, benzthiazuron, bifenox, bromacil, bromofenoxim, bromoxynil, bromoxynil octanoate, brompyrazone, butachlor, buturon, butylate, carbetamide, chinonamid, chloramben, chloranocryl, chlorburomuron, chlorbufam, chlorfenac, chlorfenprop-methyl, chlorflurecol methyl, chlormequat, chloroxuron, chlorphonium, chlorpropham, chlorthal dimethyl, chlorthiamid, chlortoluron, credazine, cyanazine, cycloate, cycluron, cyprazine, 2,4-D, dalapon, dalapon sodium, diaminozide, 2,4 DB, delachlor, desmedipham, desmetryne, diallate, dicamba, dichlobenil, dichlorprop, dimethametryn, difenzoquat, difenzoquat methylsulphate, dimexan, dinitramine, dinoseb, dinoseb acetate, dinoterb, dinoterb acetate, diphenamid, dipropetryn, diquat, diuron, DNOC, DSMA, endothal, EPTC, erbon, ethiolate, EXD, fenoprop, fenuron; flamprop-isopropyl, fluometuron, fluorodifen, flumezin, flurecol-butyl, glyphosate, hexaflurate, ioxynil, ioxynil octanoate, isonoruron, isopropalin, isoproturon, karbutilate, lenacil, linuron, MCPA, MCPB, mecoprop, medinoterb acetate, merphos, methabenzthiazuron, methazole, methoprotryne, metobromuron, metoxuron, metribuzin, molinate, monalide, monolinuron, monuron, monuron-TCA, MSMA, napropamide, naptalam, neburon, nitralin, nitrofen, norflurazon, noruron, oryzalin, paraquat, pebulate, pentanochlor, phenmedipham, phenmedipham-ethyl, phenobenzuron, picloram, piperophos, profluralin, prometon, prometryne, propachlor, propanil, propazine, propham, propyzamide, pyrazon, secbumeton, siduron, simazine, simetryne, sulfallate, swep, 2,4,5-T, 2,3,6-TBA, TCA, terbacil, terbucarb, terbumeton, terbuthylazine, terbutryne, thiafluron, triallate, trietazine, trifluralin, and vernolate, N - (a,a, - dimethylbenzyl)- N' - p - tolylurea, 3,4,5- tribromo- N,N - dimethylpyrazole- 1 - acetamide (U 27267), N - methyl - N - cyclohexyldithio - N' - o - fluorophenyl urea, N - benzyl - N - (3,4 - dichlorophenyl) - N',N' - dimethyl urea, ethyl N,N diisobutylthiolcarbamate, 4 - (methylsulphonyl) - 2,6 - dinitro - N,N - dipropyl aniline, 5(6) - chloro - 2 - isopropylbenzimidazole, I - (3,4 - dichlorophenyl) - 3 methyl - 2 - pyrrolidinone, N - (p - bromophenyl) - N' - methyl - N' - methoxyurea, 3 - (2,4 - dichlorophenyl) - 5 - t - butyl - 1,3,4 - oxadiazol - 2 - one, N - (3,4 - dichloro phenyl) - cyclopropanecarboxamide, 2,3,5 - trichloro - 4 - pyridinol, 2 - chloro isopropylacetanilide, 2,6 - dichlorothiobenzamide, 1,1' - bis(3,5 - dimethyl morpholinocarbonylmethyl) - 4,4'- bipyridylium dichloride, sodium cis- 3 chloroacrylate, 4,5,7- trichloro- 2,1,3- benzthiadiazole, N- (3- chloro- 4 methylphenyl) - 2 - methylpentanamide, n - propyl ethyl - n - butylthiocarbamate, 3,4- dichloropropionanilide, N- cyclooctyl- N',N'- dimethylurea, butyl m chlorophenylcarbamate, 2- chloro- N- (1,3- dioxolan- 2- ylmethyl)- 2',6' dimethylacetanilide, tetrahydrofurfuryl isothiocyanate, N - chloroacetyl - N - (2,6 diethylphenyl) - glcyine isopropyl ester, N - chloroacetyl - N - (2,6 - diethyl phenyl) - glycine ethyl ester, N - chloroacetyl - N - (2 - methyl - 6 - ethylphenyl) glycine isopropyl ester, (1 - methylethyl)O - methyl - O - (4 - methyl - 2 - nitro phenyl) - phosphoramidothioate, 1,1 - dimethylhexahydropyridazinium bromide, dimethylpiperidinium chloride, I - [2- (2,4- dichlorophenyl)- 1,3- dioxolan- 2 methyl]imidazole, 3'- (tri-fluoromethyl)- phthalanilic acid, 3,6 - dichlor propicolinic acid, benzyl 3,5 - dichloro - 2,6 - difluoro - 4 - pyridyl ether, ethyl N (2,4- dichlorophenyl)- N- (tritluoromethanesulphonyl) - carbamate, N - (p - chlorophenyl)- N- (trifluoromethanesulphonyl) - carbamate, N- (p chlorophenyl)- 3,4,5,6- tetrahydrophthalimide, tributyiL(5- chioro- 2 - thienyl) - methyl]phosphonium chloride, N - pyrrolidinosuccinamic acid, methyl - 3,6 - dichloro - o - anisate, ethyl 5 - (4 - chlorophenyl - 2 - H - tetrazol - 2 - yl acetate, 2 (4 - ethylamino - 6 - methylthio - s - triazin - 2 - yl) - amino - 2 - methylpropionitrile, 3 - cyclohexyl - 6 - dimethylamino - 1 - methyl - 1,3,5 - triazine - 2,4 - (1H,3H) - dione, 1 - (N - ethyl - N - propylcarbamoyl) - 3 - propyl - sulphonyl - 1H - 1,2,4 - triazole, N - ethyl - N - (2 - methyl - 2 - propenyl) - 2,6 - dinitro - 4 - (trifluoromethyl) - benz amine, 2 - ethyl - 6 - methyl - N - (1' - methyl - 2' - methoxyethyl) - chloro acetanilide, 2 - (3 - chlorophenoxy) - propionic acid, N - n - propyl - N - cyclo propylmethyl - 4 - trifluoromethyl - 2,6 - dinitro - aniline, N - benzyl - N - isopropyl 3,5- dimethylbenzamide, N- phenyldiethanolamine - bis(2 - methoxy- 3,6- dichlorobenzoate), [(3,5,6 - trichloro - 2 - pyridinyl)oxy]-acetic acid, 3,3a - dihydro 2 - (p - methoxyphenyl) - 8H - pyrazolo - 5,1 - a - isoindol - 8 - one, r - 2 - ethyl - 5 methyl - c - 5 - (2 - methylbenzyloxy) - 1,3 - dioxane, 3 - (1 - N - ethoxyamido) propyliden - 6 - ethyl - 3,4 - dihydro - 2H - pyran - 2,4 - dione, N - (5 - n - butylsulphonyl - 1,3,4 - thiadiazolyl) - N,N' - dimethyl urea, 1,1 - dimethyl - 3 - (m chloro - p - tri - fluoromethoxyphenyl) - urea, 2',6' - dimethyl - N - (2 - methoxyethyl) - 2 - chloroacetanilide, 1 - (&alpha;,&alpha; - dimethylbenzyl) - 3 - methyl - 3 - phenyl urea, 1 - (o - fluorophenyl) - 3 - methyl - 5 - imino - hydantoin, N - methyl - N - 2 chlorocyclohexylthio - N' - (2 - fluorophenyl) urea, 1 - (3,4 - dichlorophenyl) - 3 methyl - 3 - (1 - formyloxy - 2,2,2 - trichloroethyl) - urea, N - methyl - N cyclohexyldithio - N' - o - fluorophenyl urea, N - carboxymethoxymethyl - 2,6 diethyl - chloroacetanilide, 6 - t - butyl - 4,5 - dihydro - 3 - isopropylpyridino - [4,5 c]isothiazole - 4 - one, 6 - t - butyl - 4,5 - dihydro - 3 - isopropylpyrimido - [5,4 - d] isoxazol - 4 - one, O - (5 - chloro - 1 - isopropyl - 1,2,4 - triazol - 3 - yl) O,O - diethyl phosphorothioate, 2,4 - dichlorophenyl 3 - methoxy - 4 - nitrophenyl ether, 2 ethyl - 5 - methyl - 5 - (2 - methylbenzyloxy) - 1,3 - dioxan, N - (1 - ethylpropyl) - 2,6 dinitro- 3,4- xylidene, hexafluoroacetone trihydrate, methyl tetrachloro- N methoxy - N - methylterephthalamate, S,S,S - tributyl phosphorotrithioate, N - sec butyl - 2,6 - dinitro - 3,4 - xylidine, N,N - dimethyl - 2 - (3,4,5 - tribromo - 1 pyrazolyl) - propionamide, &alpha; - (2,2,2 - trichloroethyl) - styrene, 2 - isopropyl - 5 methyl - 5 - (2 - methylbenzyloxy)1,3 - dioxane, O - (methylsulphamoyl) - N,N hexamethyleneglycollamide, O - (methylsulphamoyl) - N - isopropylglycollanilide, isobutyl 2 - [4 - (4 - chlorophenoxy) - phenoxyl - propionate, methyl 2 - [4 - (2.4 - dichlorophenoxy)- phenoxy]- propionate, 6- chloro- 2- trifluoromethylimidazo(4,5 - b)pyridine, pentachlorophenyl, N' - p - chlorophenyl - O,N,N trimethylisourea, 2 - chloro - N - (but - 1 - yn - 3 - yl) - acetanilide, 2 - bromo - 2' methyl - 6' - t - butylacetanilide, 2 - bromo - N - (methoxymethyl) - 2' - methyl - 6' t - butyl - acetanilide, 2 - chloro - N - (ethoxycarbonyloxymethyl) - 2',6' - diethyl acetanilide, O - (isopropylsulphamoyl) - N - (but - 1 - yn - 3 - yl) - glycollanilide, ethyleneglycol bis - (trichloroacetate), hexachloroacetone, potassium cyanate, sodium chlorate, sodium metaborate, trichlorobenzyl chloride, undecylenic acid, N - (1 - ethylpropyl) - 3,4 - dimethyl - 2,6 - dinitrobenzeneamine, tris(2 - methoxyethoxy) - 2' - chloroethylsilane, N - [2,4 - dimethyl - 5[[(trifluoromethyl) sulphonyl] - amino] - phenyl] - acetamide, 6 - t - butyl - 4 - isobutylideneamino - 3 methylthio - 1,2,4 - triazin - 5(4H) - one, S - (4 - methoxybenzyl - N,N - diethylcarbamothioate, 2 - chloro - 1 - (3 - ethoxy - 4 - nitrophenoxy) - 4 - trifluoromethylbenzene, 3 - (3 - chloro - 4 - trifluoromethoxyphenyl) - 1,1 - dimethyl urea, N isobutyl - 2 - oxoimidazolidine - 1 - carboxamide, O - ethyl O - (3 - methyl - 6 nitrophenyl) - N - sec - butyl - phosphorthioamide, 2,6 - dichlorobenzyl, (2,2 dimethyl - 4 - ethyldioxolan - 4 - yl)methyl ether, 3',5' - dinitro - 4 - (di - n propylamino) - acetophenone, N - chloroacetyl - N - (2,6 - diethylphenyl) glycine ethyl ester, 2,3:4,6 - di - O - isopropylidene - 2 - keto - L - gulonate, 1 - m - trifluoromethylphenyl - 4 - dimethylamino - 5 - chloropyridazone, 4 - amino - 3 - methyl - 6 phenyl - 1,2,4 - triazin - 5 - (4H) - one, N - (2 methoxy - I - methylethyl) - 2' - ethyl 6' - methyl - 2- chloroacetanilide, O- (N- phenylcarbamoyl)- propane oxime, N (4- methyl- 3- (trifluoromethylsulphonylamino)phenyl)acetamide, 2,2,3,3tetrafluoropropionic acid, O - methyl O - (4 - methyl - 2 - nitrophenyl) (1 - methylethyl)phosphoramidothioate, N - benzyl - N - isopropyl - 3,5 - dimethylbenzamide, 2 - chloro - 6 - (2 - cyano - 1 - methyl - ethylamino) - 4 - cyclopropylamino - s triazine, 2,2 - dimethyl - N - benzyl - N - isopropylpropionamide, 3 - [5 - (1,1 dimethylethyl)- 1,3,4- thiadiazol- 2- yl]- 4- hydroxy- 1- methyl- 2imidazolidinone, N- (3- chloro- 4- ethoxyphenyl)- N',N' - dimethylurea, 1methyl- 4- phenylpyridinium chloride, N- [5- (2- chloro- 1,1- dimethylethyl)1,3,4 - thiadiazol - 2 - yl]cyclopropane carboxamide, 4 - t - butyl - N - s - butyl - 2,6 dinitroaniline, 1,1' - di(diethylcarbamoylmethyl) - 4,4' - bipyridylium dichloride, 2 t - butyl - 4 - (2 - chloro - 4 - (3,3 - dimethylureido)phenyl) - 1,3,4 - oxadiazolin - 5 one, 2',6' - dimethyl - N - (2 - methoxyethyl) - 2 - chloroacetanilide, N - ethyl - N propyl - 3 - (propylsulphonyl) - 1H - 1,2,4 - triazole - 1 - carboxamide, tris - (2 methoxyethyl) - 2' - chloroethylsilane, N - ethyl - N - (2 - methyl - 2 - propenyl) 2,6 - dinitro - 4 - (trifluoromethyl)aniline, N - (2 - chloroethyl) - 2,6 - dinitro - N propyl - 4 - (trifluoromethyl)aniline, methyl N - benzoyl - N - (3 - chloro - 4 fluorophenyl) - 2 - aminopropionate, 2,4 - dichloro - 6 - fluorophenyl 4 - nitrophenyl ether, N- 3- (1',1',2',2'- tetrafluoroethoxy)phenyl- N',N'- dimethylurea, 1methyl - 3 - phenyl - 5 - [3 - (trifluoromethyl)phenyl] - 4 - (1H) - pyridinone, 2 amino - 4 - isopropylamino - 6 - chloropyrimidine, 6 - t - butyl - 4 - isobutylideneamino - 3 - methylthio - 1,2,4 - triazin - 5 - (4H) - one, &alpha; - (4 - chlorophenyl) - &alpha; - (1 - methylethyl) - 5 - pyrimidinemethanol, 2 - (2,4,5 - trichlorophenoxy)ethanol, 2 chloroethyl - tris(methoxy)silane + &alpha;,# - bis(2 - chloroethyl) - &alpha;,&alpha;,#, - tetramethoxypoly[(2 - chloroethyl)methoxy]siloxane, O - ethyl O - (3 - methyl - 6 nitrophenyl) N - s - butylphosphorothioamidate, N - (2' - methoxy - 1' methylethyl) - 2' - ethyl - 6' - methyl - 2 - chloro - acetanilide, N - (2 - methyl - 2 propenyl) - 2,6 - dinitro - N - propyl - 4 - (trifluoromethyl)aniline, N - (1 - phenyl - 5 bromo - 6 - oxypyridazin - 4 - yl) oxamic acid sodium salt, 1,1,1 - trifluoro - N - [2 methyl - 4 - (phenylsulphonyl)phenyl]methane sulphonamide, 3 - ethoxycarbonylaminophenyl N - phenylcarbamate, ammonium ethyl carbamoylphosphonate, 1 allyl - 1 - tetrahydrogeranylpiperidinium bromide, N - ((4 - dipropylamino) - 3,5 - dinitrophenyl)sulphonyl) - S,S - dimethylsulphilimine, 2 - chloro - N - (1 - methyl - 2 propynyl)acetanilide, N - (5 - butylsulphonyl - 1,3,4 - thiadiazol - 2 - yl) - N,N' dimethylurea, 1,3- dimethyl- 1 - (5 - dimethylsulphamoyl - 1,3,4- thiadiazol- 2yl)urea, I - (5 - ethylsulphonyl - 1,3,4 - thiadiazol - 2 - yl) - 1,3 - dimethylurea, 1 - (5 - t - butyl - 1,3,4 - thiadiazol - 2 - yl) - 1,3 - dimethylurea, N - butoxymethyl) - 2 chloro - N - (2 - (1,1 - dimethylethyl) - 6 - methylphenyl)acetamide, 3 - (3 - chloro 4 - chlorodifluoromethylthiophenyl) - 1,1 - dimethylurea, [(3,5,6 - trichloro - 2 pyridinyl)oxy] acetic acid, 2- [4- (4 - trifluoromethylphenoxy)phenoxy)]propionic acid methyl ester, and 3 - cyclohexyl - 6 - (dimethylamino) - I - methyl - s - triazine 2,4- (lH,3H)- dione.
The invention also provides a two-container pack in which one or more compounds of formula I are provided in a first container and one or more further pesticides, plant growth regulants or fertilizers are provided in a second container, especially in relative proportions as described hereinafter. Desirably, the twocontainer pack bears or contains instructions, either separate or in conjunction with one of the containers, for mixing the contents of the containers or separately applying the contents thereof.
The ratio by weight of the compound(s) of the present invention to the second herbicide may vary over a wide range according to the particular compounds employed and the intended use. In general, however, the ratio by weight of the compound(s) of the present invention to the second herbicidal component will be from 10:1 to 1:15, more preferably from 5:1 to 1:5, and especially from 3:1 to 1:3.
The compounds of the present invention may, if desired, be employed in admixture with non-phytotoxic oils.
The compounds of the present invention are of herbicidal activity, and may be applied to plants, the soil, land or aquatic areas. They are of special use as selective herbicides in crops, e.g. cotton, ryegrass, safflower, sorghum, millets, sunflowers, tobacco, or a food crop such as cereals, sugar beet, peas, beans (e.g. navy beans, soya beans and field beans), carrots, peanuts, maize, rice and potatoes. They may be applied pre- or post-planting of the crop? and may be employed postemergence or preferably pre-emergence. When used in cereals, they are preferably applied with one or more piant-gr6wth hormones.
The compounds of formula I are preferably applied in an amount in total of from 0.1 to 20 kg/ha, more preferably 1 to 10 kg/ha, especially 2.5 to 8 kg/ha.
The invention will now be further described, though only by way of illustration, in the following Examples, in which all 'parts' are by weight.
Example 1.
4-Hydroxy-3-(2-hydroxy-1,1-dimethylethyl)phenyl methanesulphonate 2,3-Dihydro-2-hydroxy-3,3-dimethylbenzofuran-5-yl methane sulphonate (129 parts) was added to a solution of sodium hydroxide (120 parts) in water (1200 parts) and methanol (320 parts). Sodium borohydride (19 parts) was added portionwise with vigorous stirring at 15-20 C. The mixture was stirred for three hours, then acidified with hydrochloric acid and filtered to give 4-hydroxy-3-(2-hydroxy-1,1-di methylethyl)phenyl methansulphonate (117 parts, 90% yield). Recrystallisation from 1,2-dichloroethane gave the pure product, melting point 122-124 C.
Analysis: Found: C, 50.94; H, 5.95; S, 12.05% CttHteO5Srequires: C, 50.75; H, 6.20; S, 12.32% Example 2.
The following compound was prepared by a method analogous to that of Example I but starting with the corresponding ethansulphonate: 4-hydroxy-3-(2hydroxy-1,1-dimethylethyl)phenyl ethanesulphonate, mp 127-129 C. Its structure was confirmed by elemental analysis and IR and NMR spectra.
Example 3.
4-Acetoxy-3-(2-acetoxy- 1, -dimethylethyl)phenyl methanesulphonate The product of Example 1(10 parts) was boiled under reflux with acetic acid anhydride (50 parts) for six hours. The excess nhydride was then evaporated off under reduced pressure and the residue treated with water. The product was extracted with ether and the ether extracts were washed with aqueous sodium bicarbonate solution and with water and dried over magnesium sulphate. The ether was then evaporated off to give 4-acetoxy-3-(2-acetoxy- 1,1 -dimethylethyl)phenyl methanesulphonate (11.6 parts, 88% yield) as an orange oil which solidified on standing to a pink solid, melting point 49--510C.
Analysis: Found: C,52.42; H, 5.97; S, 9.21% C15H2007S requires: C, 52.31; H, 5.85; S, 9.31% Example 4.
4-lsobutyryloxy-3-(2-isobutyryloxy- 1,1 -dimethylethyl)phenyl methanesulphonate.
Isobutyryl chloride (11.7 parts) was added dropwise with stirring at 5-100C to a solution of the product of Example 1(13 parts) and triethylamine (11.2 parts) in acetonitrile (80 parts). The mixture was stirred for three hoprs, then added to water (500 parts). The product was extracted into ether and the ether extracts were washed with dilute sodium hydroxide solution and with water and dried over magnesium sulphate. The ether was then evaporated off to give 4-isobutyryloxy-3 (2-isobutyryloxy-1,1-dimethylethyl)phenyl methanesulphonate (13.7 parts, 69% yield) as a yellow oil.
Analysis: Found: C, 57.00; H, 6.97; S, 7.71% C1aH2aO7S requires: C, 56.98; H, 7.05; S, 8.01% Example 5.
4-Methylcarbamoyloxy-3-(2-methylcarbamoyloxy- 1,1 -dimethylethyl)phenyl methanesulphonate Methyl isocyanate (68 parts) and triethylamine (2 parts) were added to a solution of the product of Example 1(130 parts) in acetonitrile (400 parts). The mixture was kept for 20 hours at rom temperature and then filtered. The filtrate was added to water (3000 parts) and the product isolated by ether extraction, washing and drying. The ether was evaporated off to give 4-methylcarbamoyloxy-3 (2-methylcarbamoyloxy- 1,1 -dimethylethyl)phenyl methanesulphonate (58 parts, 31% yield) as a colourless glass-like solid.
Examples 6-7.
The following compounds were prepared by analogous methods to that described in Example I. Structures were confirmed by their spectra and elemental analysis.
6. 4 - hydroxy - 3 - (1 - hydroxymethyl)cyclopentyl)phenyl methanesulphonate, melting point l3l-1330C.
7. 4- hydroxy- 3 - (1 - hydroxymethyl)cyclohexyl)phenyl methanesulphonate, melting point 119-122 C.
Examples 8-17.
The following compounds were prepared by analogous methods to that described in Example 4. Structures were confirmed by their spectra and elemental analysis.
8. 4 - chloroacetyloxy - 3 - (2 - chloroacetyloxy - 1,1 - dimethylethyl)phenyl methanesulphonate, low melting solid.
9. 4 - pentanoyloxy - 3 - (2 - pentanoyloxy - 1,1 - dimethylethyl)phenyl methanesulphonate, orange liquid.
10. 4- benzoyloxy - 3 - (2 - benzoyloxy- 1,1 - dimethylethyl)phenyl methanesulphonate, melting point 98-100 C.
11. 4 - (ethoxycarbonyloxy) - 3 - (2 - ethoxycarbonyloxy) - 1,1 - dimethylethyl)phenyl methanesulphonate, melting point 69-70 C.
12. 4 - (4 - chloro - 2 - butynyloxycarbonyloxy) - 3 - (2 - (4 - chloro - 2 butynyloxycarbonyloxy) - 1,1 - dimethylethyl)phenyl methanesulphonate, 13. 4- (2- chloroethoxycarbonyloxy) - 3(2 - (2 - chloroethoxycarbonyloxy) - 1,1 dimethylethyl)phenyl methanesulphonate, viscous yellow liquid.
14 . 4 - methanesulphonyloxy - 3 - (2 - methanesulphonyloxy - 1,1 - dimethyl ethyl)phenyl methanesulphonate, melting point 82-84 C.
15. 4 - (methoxycarbonyloxy) - 3 - (2 - methoxycarbonyloxy) - 1,1 - dimethylethyl)phenyl methanesulphonate, melting point 76-77 C.
16. 4 - (trichloroacetoxy)- 3 - (2 - trichloroacetyloxy) - 1,1 - dimethylethyl)phenyl methanesulphonate, viscous red-brown liquid.
17. 4 - crotonyloxy - 3 - (2 - crotonyloxy - 1,1- dimethylethyl)phenyl methane sulphonate, melting point < 300 C.
Example 18.
3-(2-Benzoyloxy-1,1-dimethyl-ethyl)-4-hydroxyphenyl methanesulphonate Benzoyl chloride (5.6g) in diethyl ether (50 ml) was added dropwise with vigorous stirring to a solution of 3-(2-hydroxy-1,1-dimethylethyl)-4-hydroxyphenyl methanesulphonate in aqueous sodium hydroxide solution (1.6g in 100 ml water).
The mixture was stirred for three hours at room temperature, then separated, and the ether solution washed with dilute sodium hydroxide solution followed by water.
Drying over magnesium sulphate and running down gave 4.5g of an oil.
Crystallisation from ethanol gave 0.7g of 3-(2-benzyloxy-1,1-dimethyl-ethyl)-4benzoyloxyphenyl)methanesulphonate, m.p. 100-101 C. Removal of the solvent from the mother liquors gave 2.5g of 3-(2-benzoyloxy-l,l-dimethyl-ethyl)-4hydroxyphenyl methanesulphonate as a viscous oil.
Analysis: C1aH20OaS required: C, 59.32; H, 5.53 S, 8.80% Found: C, 59.61; H, 5.34 S, 8.90% The following compound was prepared by a method analogous to that of Example 5: 4-(phenylcarbamoyloxy)-3-(2-(phenylcarbamoyloxy-1,1-dimethylethyl)phenyl methanesulphonate, mp 59-62 C.
Example 20.
4,5-Dihydro-5,5-dimethyl-2-oxido-1,3,2-benzodioxathiepin-7-yl methanesulphonate Thionyl chloride (12 parts) was added dropwise at room temperature to a suspension of 4-hydroxy-3-(2-hydroxy- 1,1 -dimethylethyl)phenyl methanesulphonate (5 parts) (from Example 1) in toluene (50 parts). The mixture was gently warmed to 50 C when reaction commenced, then maintained at this temperature for 15 minutes. The temperature was then raised to boiling point and the mixture boiled under reflux for 2 hours. The solvent was then evaporated off under reduced pressure to give crude 4,5-dihydro-5,5-dimethyl-2-oxido-1,3,2-benzodioxathiepin7-yl methanesulphonate (5.2 parts, 90% yield). Recrystallisation from ethanol gave the pure product (2.4 parts), melting point 96-98 C.
Analysis: Found: C, 43.51; H, 5.07; S, 21.16% C11H14O6S2requires:: C, 43.12; H, 4.61; S, 20.93% Example 21.
4,5-Dihydro-2,2,5,5-tetramethyl- 1 ,3-benzodioxepin-7-yl methanesulphonate A mixture of 4-hydroxy-3-(2-hydroxy- 1,1 -dimethylethyl)phenyl methylsulphonate (10 parts) (from Example 1), 2,2-dimethoxypropane (17 parts) and p toluenesulphonic acid (0.1 parts) was heated in toluene (90 parts) with distillation of low boiling fraction and slow addition of further 2,2-dimethoxypropane (17 parts) for 1 hour. The resulting solution was cooled, washed with aqueous sodium hydroxide solution and with water, dried over magnesium sulphate and the solvent evaporated off under reduced pressure. The crude product was distilled yielding 9 parts of 4,5-dihydro-2,2,5,5-tetramethyl-1,3-benzodioxepin-7-yl methanesulphonate, boiling point 130-142 C/0.2 mm Hg. Recrystallisation from aqueous ethanol gave the pure product (4.8 parts), melting point 65-67 C.
Analysis: Found: C, 55.89; H, 6.72; S, 10.44% C14H2005Srequire: C, 55.98; H, 6.71; S, 10.67% Example 22.
4,5-Dihydro-2-methoxy-5,5-dimethyl-1,3-benzodioxepin-7-yl methanesulphonate 4-Hydroxy-3-(2-hydroxy- 1,1 -dimethylethyl)phenyl methanesulphonate (10.4 parts) (from Example 1) was reacted with trimethyl orthoformate (127 parts) in the presence of p-toluenesulphonic acid (0.05 parts) as in Example 20 to produce 4,5 dihydro-2-methoxy-5,5-dimethyl- 1 ,3-benzodioxepin-7-yl methanesulphonate (9.5 parts, 79% yield) as a colourless oil.
Analysis: Found: C, 52.00; H, 6.05; S, 10.21% Ci3HiaOaS requires: C, 51.64; H, 6.00; S, 10.60% Examples 23-35.
The following compounds were prepared by analogous methods to those described in Examples 21 and 22. Structures were confirmed by their spectra and elemental analysis.
23. 2 - ethyl - 4,5 - dihydro - 2,5,5 - trimethyl - 1,3 - benzodioxepin - 7 - yl methane sulphonate, m.p. 75-76 C.
24. 2,2 - diethyl - 4,5 - dihydro - 5,5 - dimethyl - 1,3 - benzodioxepin-- 7 - yl me thanesulphonate, viscous yellow liquid.
25. 4,5 - dihydro - 2 - isopropyl - 2,5,5 - trimethyl - 1,3 - benzodioxepin - 7 - yl methanesulphonate, m.p. 92-93 C.
26. 4,5 - dihydro - 5,5 - dimethyl - 1,3 - benzodioxepin - 7 - yl methanesulphonate, m.p. 69-71 C.
27. 4,5 - dihydro - 2,5,5 - trimethyl - 1,3 - benzodioxepin - 7 - yl methanesulphonate, m.p. 4450C.
28. 4,5 - dihydro - 5,5 - dimethyl - 2 - phenyl - 1,3 - benzodioxepin - 7 - yl methanesulphonate, m.p. 86-87 C.
29. 4,5 - dihydro - 2,5,5 - trimethyl - 2 - phenyl - 1,3 - benzodioxepin - 7 - yl methanesulphonate, m.p. 85-86 C.
30. 4,5 - dihydro - 5,5 - dimethylspiro[1,3 - benzodioxepin - 2,1' - cyclohexan] - 7 yl methanesulphonate, m.p. 82-830C.
31. 4,5 - dihydro - 5,5 - dimethylspiro[l,3 - beniodioxepin - 2,1' - cyclopentani - 7 yl methanesulphonate, m.p. 59--610C.
32. 2 - chloromethyl - 4,5 - dihydro - 2,5,5 - trimethyl - 1,3 - benzodioxepin - 7 - yl methanesulphonate, m.p. 85-87 C.
33. 2 - bromomethyl - 4,5 - dihydro - 5,5 - dimethyl - 1,3 - benzodioxepin - 7 yl methanesulphonate, m.p. 68690 C.
34. 2 - ethoxy - 4,5 - dihydro - 5,5 - dimethyl - 1,3 - benzodioxepin - 7 - yl methane sulphonate, light brown viscous liquid.
35. 2 - ethyl - 4,5 - dihydro - 2 - methoxy - 5,5 - dimethyl - 1,3 - benzodioxepin - 7 yl methanesulphonate, m.p. 596l0C.
Example 36.
2-Ethoxy-4,5-dihydro-5,5-dimethyl-2-oxo-1,3,2-benzodioxaphosphepin-7-yl methanesulphonate 4-Hydroxy-3-(2-hydroxy- 1,1 -dimethylethyl)phenyl methanesulphonate (10g) from Example I was suspended in acetonitrile (100 ml) and triethylamine (8g) was added. The mixture was cooled in ice, and ethyl phosphorodichloridate (6.9g) was added dropwise with vigorous stirring. Stirring was continued for 6 hburs prior to the addition of dichloromethane (200 ml), after which the solution was washed with water, dilute sodium hydroxide solution and water again, dried over magnesium sulphate and run down. The crude product was recrystallised from toluene, yielding 6.0g of the desired product, melting point 113-Il 50C.
Analysis: C, 44.57 H, 5.47 C13H ia107PS requires: C, 44.35 H, 5.79% Example 37.
2,3-Dihydro-3,3-dimethylbenzofuran-5-yl methanesulphonate (a) 2-Methallyl chloride (108 parts) was added dropwise to a mixture of 4bromoanisole (240 parts) and a concentrated sulphuric acid (20 parts) over a period of 2 hours at a temperature of 25--35"C. Stirring was continued for 5 hours and the mixture was then kept for 24 hours at room temperature. Ether (400 parts) was then added and the resulting solution washed with water, aqueous sodium bicarbonate solution and water again. After drying with sodium sulphate and evaporating off the solvent the brown oil which remained was distilled yielding 4-bromo-2-(2 chloro-l,l-dimethylethyl)anisole (118 parts), boiling point 106--1200/0.4 mm Hg.
Recrystallisation from petroleum ether (b.p. 80--100"C) gave the pure product (98 parts), melting point 86-880C.
This product was heated with pyridine hydrochloride (235 parts) at 2000C with stirring for 1 hour and then poured into iced dilute hydrochloric acid. Isolation through ether and distillation gave a crude product (50 parts), b.p. 135--140"C/31 mm Hg. Purification gave pure 5-bromo-2,3- which was filtered off and recrystallised from aqueous ethanol to give 2,3-dihydro3,3-dimethylbenzofuran-5-yl methansulphonate (65.2 parts) identical with the product of Example 37(a) above.
Example 38.
2,3-Dihydro-3,3-dimethylbenzofuran-5-yl ethanesulphonate Thionyl chloride (4.3g) was added dropwise to dimethylformamide (13 ml) maintained at about 5 C. To this was quickly added 4-hydroxy-3-(2-hydroxy-1,1-di methylethyl)phenyl ethanesulphonate (9.5g) from Example 2 in dimethylformamide (13 ml). The reaction mixture was then heated to 100 C and maintained at that temperature for 4-5 hours, after which it was cooled and poured into water (100 ml). The oil was extracted with diethyl ether, washed with water, dried over magnesium sulphate and evaporated down to give 6.2g of a brownish oil.
Analysis: Found: C, 56.28 H, 6.47% C12H,604S requires: C, 56.23 H, 6.29% The same compound was also prepared by reacting 2,3-dihydro-3,3-dimethyl 5-benzofuranol with ethanesulphonyl chloride in the presence of triethylamine in an analogous way to that described in Example 37(a).
Examples 39-49.
The following compounds were prepared by analogous methods to that described in the final stage of Example 37(a), by reacting 2,3-dihydro-3,3-dimethyl-5-benzofuranol with the appropriate sulphonyl chloride in the presence of triethylamine: 39. 2,3- dihydro- 3,3- dimethylbenzofuran- 5 - yl methylsulphamate, melting point 52--54"C.
40. 2,3- dihydro- 3,3- dimethylbenzofuran- 5 - yl 1- propanesulphonate, oil.
41. 2,3 - dihydro- 3,3- dimethylbenzofuran- 5 - yl I - butanesulphonate, oil.
42. 2,3 - dihydro - 3,3 - dimethylbenzofuran - 5 - yl p - toluenesulphonate, mp 103-105 C.
43. 2,3 - dihydro - 3,3 - dimethylbenzofuran - 5 - yl &alpha; - toluenesulphonate, mp 129-131 C.
44. 2,3 - dihydro - 3,3 - dimethylbenzofuran - 5 - yl 3 - chloro - 1 propanesulphonate, oil.
45. 2,3- dihydro- 3,3- dimethylbenzofuran- 5 - yl 2 - methyl - 1 - propanesulphonate, oil.
46. 2,3 - dihydro - 3,3 - dimethylbenzofuran - 5 - yl 2 - propanesulphonate, oil.
47. 2,3 - dihydro - 3,3 - dimethylbenzofuran - 5 - yl cyclohexanesulphonate.
48. 2,3 - dihydro - 3,3 - dimethylbenzofuran chloromethanesulphonate, oil.
49. 2,3- dihydro- 3,3- dimethylbenzofuran 2- butanesulphonate, oil.
Example 50.
Spiro[benzofuran-3(2H), 1 '-cyclopentan]-5-yl methanesulphonate The product of Example 6 (6.7 g) in dimethylformamide (20 ml) was added in portions to thionyl chloride in 5 ml of dimethyl formamide with cooling to 200 C.
The reactants were stirred at that temperature for 30 minutes and were then heated to 100 C and maintained there for 5 hours. The mixture was then poured into water and extracted into diethyl ether three times. The extracts were combined, washed with water, sodium bicarbonate solution and water twice more and were then dried over magnesium sulphate, filtered and evaporated down leaving an oil which was taken up in diethyl ether. It was then cooled in solid carbon dioxide/acetone to give a white solid which was filtered off to give 1.2g of product, mp 75-770C.
Example 51.
A 20% emulsifiable concentrate was prepared from the following: 2,3-dihydro-3,3-dimethylbenzofuran-5-yl methanesulphonate 200g 'Arylan CA' (70% alcoholic solution of calcium dodecylbenzenesulphonate) 25g 'Ethylan C40 AH' (condensation product of castor oil with 40 moles of ethylene oxide) 25g Isophorone(to I litre) approx. 750ml (Ethylene is a Registered Trade Mark) Example 52.
A 50% wettable powder was prepared from the following: by wt 4-hydroxy-3-(l -(hydroxymethyl)cyclopentylphenyl 50% methanesulphonate 'Reax 45L' (combined wetting and dispersing agent based on lignin sulphonate) 5% China Clay 45% Examples 53-54.
Formulations equivalent to those of Examples 51 and 52 with the exception that the active ingredient employed was 2,3-dihydro-3 ,3-dimethylbenzofuran-5-yl ethanesulphonate were also prepared.
Example A.
The compounds listed below were formulated as an attaclay/sand dust and incorporated into John Innes No I potting compost at a rate of 26 parts per million weight/volume of compound to soil and placed in anodised aluminium pans, 20 cm long x 10 cm wide x 5 cm deep. This rate is approximately equivalent to a soil surface application of 11.2 kg of compound per hectare cultivated to a depth of 5 cm. Seeds of pea (Pisum sativum), mustard (Sinapis alba), linseed (Linum usitatissimum), maize (Zea mays), oats (Avena sativa) and ryegrass (Lolium sp.) were then sown in the treated soil, one species to each pan, watered and kept in a controlled environment room (temperature 22"C, relative humidity 6585%, 14 hours per day artificial illumination of 13000 lux) for 21 days.
The plants were then assessed visually for any growth regulatory or herbicidal effect, difference from untreated controls being assessed on a scale from 0 to 9 in which 0 signifies no effect and 9 signifies complete suppression. The results are listed below: Compound Herbicidal Activity Product of ExampleNo. Pea Mustard Linseed Ryegrass Oats Maize 1 7 9 8 9 9 8 2 7 9 8 9 9 9 3 5 7 8 8 9 8 4 5 7 8 8 9 8 6 3 9 9 9 9 8 7 1 3 5 8 8 2 8 2 4 6 5 8 3 9 6 8 9 9 9 9 11 3 8 7 9 9 5 13 2 6 6 8 9 6 15 4 6 8 8 8 4 16 3 7 8 8 .8 5 17 5 9 8 9 9 7 18 6 8 8 8 9 9 Compound Herbicidal Activity Product of Example No. Pea Mustard Linseed Ryegrass Oats Maize 20 6 9 9 9 9 9 21 5 6 9 8 8 9 22 3 6 8 7 9 9 23 4 6 9 9 9 9 24 6 8 8 8 9 7 25 4 8 8 8 9 8 29 4 7 8 7 9 6 30 1 4 6 4 9 1 31 7 9 9 9 9 9 34 7 8 8 9 9 9 35 6 8 9 9 9 9 37 7 9 8 7 9 9 38 7 8 8 9 9 9 39 6 9 7 9 8 7 40 5 6 6 9 8 8 45 4 9 7 9 9 9 46 6 9 8 9 9 9 Example B.
Pre-emergence The compounds listed below formulated as: (I) an attaclay/sand dust and incorporated in John Innes potting I compost at a rate equivalent to 6.5 ppm weight/volume of active ingredient to soil and placed in anodised aluminium pans, 19 cm long x 9.5 cm wide x 5 cm high. This is approximately equivalent to a surface application of 2.8 kg active ingredient per hectare cultivated to a depth of 5 cm.
Seeds of the species listed below were sown in the treated soil, one species per pan, watered and placed in a controlled environment room (220 C; 65-86% R.H. and 14 hours artificial illumination at 1600 foot candles) for 21 days (II) An aqueous suspension together with l000ppm of the wetting agent Lissapol NX (Lissapol is a Registered Trade Mark). The surfaces of an additional set of pans with seeds already sown were then sprayed with 2.8 kg/ha in 450 litres/hectare. The plants were then visually assessed for any growth regulatory or herbicidal effects. All differences from an untreated control were scored on a scale from Q--100, where 0 signifies no effect and 100 signifies complete suppression. The results are summarised in the following table:
Example No.
20 21 22 23 24 25 28 29 Species I II I II I II I II I II I II I II I II Chickweed (Stellaria media) 9 9 9 9 9 9 9 9 9 9 8 9 8 8 9 9 Mustard (Sinapis alba) 5 6 6 6 6 5 7 6 2 2 4 3 2 2 3 3 Cotton (Gossypium sp) 4 6 7 6 5 4 6 3 3 1 4 1 3 2 4 1 Tomato (Lycopersicon esculentum) 6 7 7 7 8 7 8 8 7 7 6 6 3 3 7 7 Fathen (Chenonpodium album) 7 9 8 9 8 9 8 9 8 9 7 9 6 8 8 8 Carrot (Daucus carota) 5 7 4 7 6 8 6 7 5 5 2 6 2 3 5 5 Wheat (Triticum aestivum) 9 8 9 8 9 8 9 6 8 7 8 6 8 5 9 8 Barley (Hordeum vulgare) 8 6 9 8 9 5 8 5 7 4 6 3 8 2 8 7 Wild Oat (Avena fatua) 6 7 7 9 8 7 8 7 7 6 6 8 6 2 8 5 Blackgrass (Alopecurus 8 9 8 8 7 6 6 5 6 4 3 2 4 3 8 7 myosuroides) Barnyardgrass (Echinochloa 6 6 8 7 8 7 6 2 4 7 3 4 1 1 8 6 crus-galli) Grabgrass (Digitaria sanguinalis) 9 9 9 9 9 9 9 9 8 9 5 8 5 6 9 9
Example No.
31 34 35 37 38 40 45 46 Species I II I II I II I II I II I II I II I II Chickweed (Stellaria media) 9 8 8 9 9 9 9 9 9 9 9 9 8 9 9 9 Mustard (Sinapis alba) 6 4 4 3 5 3 8 9 7 6 5 6 2 0 7 7 Cotton (Gossypium sp) 5 4 4 2 6 4 8 6 4 3 0 2 2 0 4 3 Tomato (Lycopersicon esculentum) 6 7 6 6 7 6 8 8 8 8 9 9 7 7 8 8 Fathen (Chenopodium album) 7 9 7 8 8 8 8 9 9 9 8 9 0 7 7 8 Carrot (Daucus carota) 4 6 4 6 5 6 4 5 1 3 3 4 0 0 2 2 Wheat (Triticum aestivum) 9 9 9 9 9 8 9 8 9 9 6 7 6 3 8 8 Barley (Hordeum vulgare) 9 8 9 8 9 7 9 9 9 9 4 4 4 3 8 8 Wild Oat (Avena fatua) 8 8 8 8 8 9 7 9 7 8 0 6 3 8 8 9 Blackgrass (Alopecurus 9 8 9 9 9 9 9 9 8 9 6 9 6 9 7 8 myosuroides) Barnyardgrass (Echinochloa 9 8 9 8 9 8 8 9 9 9 4 9 8 8 8 9 crus-galli) Crabgrass (Digitaria sanguinalis) 9 9 9 9 9 9 8 9 9 9 7 9 7 9 9 9

Claims (125)

  1. WHAT WE CLAIM IS:- 1. The sulphonates of the formula:
    wherein X represents a group H R3O R4 and Y represents a group -OR5, or X and Y together represent a group -CHR3-O- or a group - CHR3-O-Z-O-, the free oxygen atom of which is attached to the benzene ring; R1, R2 and R3, which may be the same or different, each represent hydrogen or alkyl, or R' and R2 together or R2 and R3 together form an alkylene chain; R4 and R5, which may be the same or different, each represent hydrogen, alkyl, alkenyl, alkynyl, aryl, a group C(=O)R or a group - SO2R11; RB, R7 and Ra, which may be the same or different, each represent hydrogen, alkyl, halogen, cyano, carboxylic acyl or alkoxy; Ra represents alkyl, aryl or aralkyl (each of which may be substituted or unsubstituted), cycloalkyl, alkylamino or dialkylamino; R'O represents alkyl, alkenyl, alkynyl, aryl, alkoxy, alkenyloxy, alkynyloxy, aryloxy, alkylamino, arylamino or dialkylamino (each of which may be substituted or unsubstituted); R" represents alkyl, aryl, alkylamino or dialkylamino (each of which may be substituted or unsubstituted); Z represents a group of formula - S(=O)n, -CR12R13 or -P(=Q)(OR14)-; n represents 1 or 2; R12 and R13, which may be the same or different, each represent hydrogen, alkyl, alkenyl, alkynyl, alkoxy, aryl, aryloxy, cyano or alkoxycarbonyl, or R12 and R'3 together represent an oxygen atom, a sulphur atom, an alkylene chain or an alkylimino or arylimino group; R4 represents alkyl; and Q represents oxygen or sulphur.
  2. 2. A compound according to Claim 1 wherein R represents alkyl of 1 to 6 carbon atoms.
  3. 3. A compound according to Claim 2 wherein R' represents alkyl of 1 to 4 carbon atoms.
  4. 4. A compound according to Claim 3 wherein R' represents methyl or ethyl.
  5. 5. A compound according to any of Claims 1 to 4 wherein R2 represents alkyl of I to 6 carbon atoms.
  6. 6. A compound according to Claim 5 wherein R2 represents alkyl of 1 to 4 carbon atoms.
  7. 7. A compound according to Claim 6 wherein R2 represents methyl or ethyl.
  8. 8. A compound according to Claim 1 wherein R1 and R2 together represent an alkylene chain of 3 to 6 carbon atoms.
  9. 9. A compound according to any of Claims I to 8 wherein R3 represents hydrogen.
  10. 10. A compound according to any of Claims I to 8 wherein R3 represents alkyl of I to 6 carbon atoms.
  11. I I. A compound according to Claim 10 wherein R3 represents methyl or ethyl.
  12. 12. A compound according to Claim 1 wherein R2 and R3 together represent an alkylene chain of 3 to 6 carbon atoms.
  13. 13. A compound according to any of Claims 1 to 12 wherein Ra, R7 and Ra each represent hydrogen, alkyl of 1 to 6 carbon atoms, chlorine, bromine, cyano, carboxylic acyl of 2 to 6 carbon atoms or alkoxy of 1 to 4 carbon atoms.
  14. 14. A compound according to Claim 13 wherein Ra, R7 and Ra each represent hydrogen, methyl, ethyl, chlorine, bromine, cyano, acetyl, methoxy or ethoxy.
  15. 15. A compound according to any of Claims 1 to 14, wherein Ra represents alkyl of I to 6 carbon atoms (which is unsubstituted or substituted by one or more halogen atoms), phenyl or phenylalkyl of 7 to 10 carbon atoms (each of which is unsubstituted or substituted by one or more chlorine or bromine atoms, alkyl groups of 1 to 4 carbon atoms, alkoxy groups of I to 4 carbon atoms, or nitro groups), cycloalkyl of 5 to 7 carbon atoms, alkylamino of 1 to 4 carbon atoms or dialkylamino, each of the alkyl moieties of which are of 1 to 4 carbon atoms.
  16. 16. A compound according to Claim 15, wherein R9 represents methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl or s-butyl (each of which is unsubstituted or substituted by a chlorine or bromine atom), phenyl or benzyl (each of which is unsubstituted or substituted by one or more chlorine or bromine atoms or methyl, methoxy or nitro groups), cyclopentyl, cyclohexyl, methylamino, ethylamino or dimethylamino.
  17. 17. A compound according to any of Claims 1 to 16 wherein X represents a group -CHR3-OR4 and Y represents a group -OR5 where R3, R4 and R5 are as defined in Claim 1.
  18. 18. A compound according to Claim 17 wherein R4 and Ra are the same
  19. 19. A compound according to Claim 17 or Claim 18 wherein R4 and/or R5 represents hydrogen, alkyl of 1 to 6 carbon atoms, alkenyl or alkynyl of 2 to 6 carbon atoms, phenyl or a group C(=O)R10 or -SO3R11 where R10 or R11 is such that any alkyl moiety thereof has from 1 to 6 carbon atoms, any alkenyl or alkynyl moiety thereof has from I to 6 carbon atoms, and any aryl moiety thereof is phenvl.
  20. 20. A compound according to any of Claims 17 to 19, wherein R4 and/or Ra represents hydrogen, methyl, ethyl, allyl, propargyl, phenyl, acetyl, isobutyryl, methylcarbamoyl, chloroacetyl, pentanoyl, benzoyl, ethoxycarbonyl, 4-chloro-2butynyloxycarbonyl, 2-chloroethoxycarbonyl, methanesulphonyl, benzoyl, methoxycarbonyl, trichloroacetyl, crotonyl or phenylcarbamoyl.
  21. 21. 4- Hydroxy- 3- (2- hydroxy- 1,1- dimethylethyl)phenyl methanesulphonate.
  22. 22. 4 - Hydroxy - 3 - (2 - hydroxy - 1,1 - dimethylethyl)phenyl ethanesulphonate.
  23. 23. 4 - Acetoxy - 3 - (2 - acetoxy - 1,1 - dimethylethyl)phenyl methane sulphonate.
  24. 24. 4 - Isobutyryloxy - 3 - (2 - isobutyryloxy - 1,1 - dimethylethyl)phenyl methanesulphonate.
  25. 25. 4- Methylcarbamoyloxy- 3 - (2 - methylcarbamoyloxy- 1,1 - dimethyl- ethyl)phenyl methanesulphonate.
  26. 26. 4- Hydroxy - 3- (1- (hydroxymethyl)cyclopentyl)phenyl methanesulphonate.
  27. 27. 4 - Hydroxy - 3 - ( I - (hydroxymethyl)cyclohexyl)phenyl methanesulphonate.
  28. 28. 4 - Chloroacetyloxy - 3 - (2 - chloroacetyloxy- 1,1- dimethylethyl)phenyl methanesulphonate.
  29. 29. 4 - Pentanoyloxy - 3 - (2 - pentanoyloxy - 1,l - dimethylethyl)phenyl methanesulphonate.
  30. 30. 4 - Benzoloxy - 3 - (2 - benzoyloxy - 1,1 - dimethylethyl)phenyl methanesulphonate.
  31. 31. 4 - (Ethoxycarbonyloxy) - 3 - (2 - (ethoxycarbonyloxy) - 1,1 - dimethylethyl)phenyl methanesulphonate.
  32. 32. 4 - (4 - Chloro - 2 - butynyloxycarbonyloxy) - 3 - 2 - (4- chloro - 2 - butynyl oxycarbonyloxy) - 1,1 - dimethylethyl)phenyl methanesulphonate.
  33. 33. 4- (2- Chloroethoxycarbonyloxy) - 3(2- (2- chloroethoxycarbonyloxy) 1,1 dimethylethyl)phenyl methanesulphonate.
  34. 34. 4 - Methanesulphonyloxy - 3 - (2 - methanesulphonyloxy - 1,1 - dimethyl ethyl)phenyl. methanesulphonate.
  35. 35. 3 - (2 - Benzoyloxy- 1,1- dimethylethyl)- 4 - hydroxyphenyl methanesulphonate.
  36. 36. 4- Methoxycarbonyloxy)- 3- (2- methoxycarbonyloxy) - 1,1 - dimethyl- ethyl)phenyl methanesulphonate.
  37. 37. 4- (Trichloroacetyloxy) - 3 - (2 - trichloroacetyloxy) - 1,1 - dimethylethyl)phenyl methanesulphonate.
  38. 38. 4 - Crotonyloxy - 3 - (2 - crotonyloxy - 1,1 - dimethylethyl)phenyl methanesulphonate.
  39. 39. 4- (Phenylcarbamoyloxy)- 3- (2- (phenylcarbamoyloxy) - 1,1 - dimethyl- ethyl)phenyl methanesulphonate.
  40. 40. A compound according to any of Claims 1 to 16 wherein X and Y together represent a group -CH R3-O-Z-O- where R3 and Z are as defined in Claim 1.
  41. 41. A compound according to Claim 40 wherein Z represents a group -CR12R13, wherein R'2 and/or R13 represents groups wherein any alkyl moiety thereof has from I to 6 carbon atoms, any alkenyl or alkynyl moiety thereof has from 2 to 6 carbon atoms, and any aryl moiety thereof is phenyl, or together represent an alkylene chain of 3 to 6 carbon atoms.
  42. 42. A compound according to Claim 41 wherein R12 and/or R'3 separately represent hydrogen, methyl, ethyl, n-propyl, isopropyl, chloromethyl, bromomethyl, methoxy, ethoxy or phenyl, or together represent tetramethylene or pentamethylene.
  43. 43. A compound according to Claim 40 wherein Z represents a group -P(-Q)(0 R14) where R'4 represents alkyl of I to 6 carbon atoms.
  44. 44. 4,5- Dihydro- 5,5- dimethyl- 2- oxido- 1,3,2- benzodioxathiepin- 7- yl methanesulphonate.
  45. 45. 4,5- Dihydro- 2,2,5,5- tetramethyl- 1,3- benzodioxepin- 7- yl methanesulphonate.
  46. 46. 4,5- Dihydro- 2- methoxy- 5,5- dimethyl- 1,3- benzodioxepin- 7- yl methanesulphonate.
  47. 47. 2- Ethyl- 4,5- dihydro- 2,5,5- trimethyl- 1,3- benzodioxepin- 7- yl methanesulphonate.
  48. 48. 2,2- Diethyl- 4,5- dihydro- 5,5- dimethyl- 1,3- benzodioxepin- 7- yl methanesulphonate.
  49. 49. 4,5 - Dihydro- 2 - isopropyl - 2,5,5- trimethyl- 1,3 - benzodioxepin - 7 - yi methanesulphonate.
  50. 50. 4,5 - Dihydro - 5,5 - dimethyl - 1,3 - benzodioxepin - 7 - yl methanesul phonate.
  51. 51.4,5 - Dihydro - 2,5,5 - trimethyl - 1,3 - benzodioxepin - 7 - yl methanesul phonate.
  52. 52. 4,5- Dihydro- 5,5- dimethyl- 2 - phenyl - 1,3- benzodioxepin- 7- yl methanesulphonate.
  53. 53. 4,5- Dihydro- 2,5,5- trimethyl- 2- phenyl- 1,3- benzodioxepin- 7- yl methanesulphonate.
  54. 54. 4,5- Dihydro- 5,5- dimethylspiro[l,3- benzodioxepin- 2,1' - cyclohexan] - 7yl methanesulphonate.
  55. 55. 4,5 - Dihydro- 5,5 - dimethylspiro[l,3 - benzodioxepin- 2,1' - cyclopentani - 7 - yl methanesulphonate.
  56. 56. 2 - Chloromethyl - 4,5 - dihydro - 2,5,5 - trimethyl - 1,3 - benzodioxepin - 7 yl methanesulphonate.
  57. 57. 2 - Bromomethyl - 4,5 - dihydro - 5,5 - dimethyl - 1,3 - benzodioxepin - 7 - yl methanesulphonate.
  58. 58. 2- Ethoxy- 4,5- dihydro- 5,5- dimethyl- 1,3- benzodioxepin- 7- yl methanesulphonate.
  59. 59. 2 - Ethyl - 4,5 - dihydro - 2 - methoxy - 5,5 - dimethyl - 1,3 - benzodioxepin 7 - yl methanesulphonate.
  60. 60. 2-Ethoxy - 4,5 - dihydro - 5,5 - dimethyl - 2 - oxo - 1,3,2 - benzodioxa phosphepin - 7 - yl methanesulphonate.
  61. 61. A compound according to any of claims 1 to 16 wherein X and Y together represent a group -CHR3O- where R3 is as defined in claim 1.
  62. 62. A compound according to claim 61, wherein R' represents alkyl of 1 to 4 carbon atoms, R2 represents akyl of 1 to 4 carbon atoms, R3 represents hydrogen or alkyl of 1 to 4 carbon atoms, Ra, R7 and R8 each represent hydrogen, and R9 represents methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl or s-butyl (each of which is unsubstituted or substituted by a chlorine or bromine atom) phenyl or benzyl (each of which is unsubstituted or substituted by one or more chlorine or bromine atoms or methyl, methoxy or nitro groups), cyclopentyl, cyclohexyl, methylamino, ethylamino or dimethylamino.
  63. 63. A compound according to claim 62, wherein R' represents methyl or ethyl, R2 represents methyl or ethyl, R3, Ra, R7 and Ra each represent hydrogen, and Ra represents methyl, ethyl, n-propyl, isopropyl, n-butyl isobutyl, s-butyl, chloromethyl, 3-chloropropyl, phenyl, benzyl, p-tolyl, cyclopentyl, cyclohexyl, methylamino, ethylamino or dimethylamino.
  64. 64. 2,3 - Dihydrd - 3,3 - dimethylbenzofuran - S - yI methanesulphonate.
  65. 65. 2,3-Dihydro-3,3-dimethylbenzofuran-5-yl ethanesulphonate.
  66. 66. 2,3-Dihydro-3,3-dimethylbenzofuran-5-yl 1-propanesulphonate.
  67. 67. 2,3-Dihydro-3,3-dimethylbenzofuran-5-yl 1-butanesulphonate.
  68. 68. 2,3-Dihydro-3,3-dimethylbenzofuran-5-yl 2-propanesulphonate.
  69. 69. 2,3-Dihydro-3,3-dimethylbenzofuran-5-yl 2-butanesulphonate.
  70. 70. 2,3 - Dihydro - 3,3 - dimethylbenzofuran - 5 - yl 2 - methyl - 1 - propane sulphonate.
  71. 71. 2,3- Dihydro- 3,3 - dimethylbenzofuran - 5 - yl chloromethanesulphonate.
  72. 72. 2,3- Dihydro- 3,3- dimethylbenzofuran- 5- yl 3- chloro- 1 - propane- sulphonate.
  73. 73. 2,3-Dihydro-3,3-dimethylbenzofuran-5-yl cyclohexanesulphonate.
  74. 74. 2,3-Dihydro-3,3-dimethylbenzofuran-5-yl toluenesulphonate.
  75. 75. 2,3-Dihydro-3,3-dimethylbenzofuran-5-yl a-toluenesulphonate.
  76. 76. 2,3-Dihydro-3,3-dimethylbenzofuran-5-yl methylsulphamate.
  77. 77. Spir[benzofuran-3(2H)-1'-cyclopentan]-5-yl methanesulphonate.
  78. 78. A process for the preparation of a compound as claimed in any of claims 17-22, 26 and 27 wherein R4 and Ra both represent hydrogen, in which a carbonyl compound of the formula:
    (wherein R1, R2, R5, R6, R7, R8 and R9 are as defined in claim 1 and M represents an alkali-metal) is reduced, followed by acidification, to give the desired compound.
  79. 79. A process according to claim 78 wherein the reduction is effected by means of a sodium borohydride.
  80. 80. A process according to claim 78 or claim 79 wherein the compound of formula II is itself prepared by a process in which a 2-hydroxybenzofuranyl sulphonate of the formula:
    (wherein R', R2, R3, Ra, R7, Ra and Ra are as defined in claim 1) is subjected to the action of an alkali-metal hydroxide.
  81. 81. A process for the preparation of a compound as claimed in any of claims 17-20, 23-25 and 28-29 wherein one of R4 and R5 is other than hydrogen or both of R4 and R5 are identical and other than hydrogen, in which the corresponding compound where R4 and R5 both represent hydrogen is reacted (a) with one or two molar proportions as appropriate of a halide R4Hal (where R4 is as defined hereinbefore and Hal represents halogen), or (b) where R4 and/or R6 in the desired compound represents carboxylic acyl, with an appropriate anhydride of formula (R4)2O, or (c) where R4 and/or R5 in the desired compound represents a group -C(=O)R10 where R10 represents alkylamino or arylamino, with an appropriate alkyl or aryl isocyanate respectively.
  82. 82. A process for the preparation of a compound as claimed in any of claims 17-20 wherein R4 and Ra are different and both other than hydrogen in which the corresponding compound wherein R4 and Rs both represent hydrogen is reacted with an appropriate amount of a halide, anhydride or alkyl or aryl isocyanate as defined in claim 81 to give the corresponding compound wherein Ra is R5 is hydrogen and R4 is other than hydrogen, followed by reaction with an appropriate amount of a different halide, anhydride or alkyl or aryl isocyanate as defined in claim 81 to give the desired compound.
  83. 83. A process for the preparation of a compound as claimed in any of claims 40 to 60 wherein a compound of formula I as defined in any of claims 17-22, 26 and 27 wherein R4 and R5 both represent hydrogen is reacted with a dihalide of formula Hal-Z-Hal (where Z is as defined in claim 1 and Hal represents halogen) in the presence of a base if necessary or desired.
  84. 84. A process according to claim 83 wherein the reaction is effected in a solvent medium other than a dialkylamide.
  85. 85. A process for the preparation of a compound as claimed in any of claims 40--42 and 45-59 wherein Z represents a group -CR12R13- as defined in claim 1 wherein a compound of formula I as defined in any of claims 17-22, 26 and 27 where R4 and Ra both represent hydrogen is reacted with a dialkoxy compound of formula R'sOZOR's (where Z represents a group -CR12R13 as defined in claim 1 and R'5 represents an alkyl gorup) in the presence of an acid catalyst.
  86. 86. A process according to claim 85 wherein R'5 represents an alkyl group of 1 to 6 carbon atoms.
  87. 87. A process according to claim 85 or claim 86 wherein the acid catalyst is ptoluenesulphonic acid.
  88. 88. A process according to any of claims 83 to 87 wherein the compound of formula I employed as starting material is itself prepared by a process as claimed in any of claims 78 to 80.
  89. 89. A process for the preparation of a compound as claimed in any of claims 61 to 77 wherein a compound of formula I as defined in any of claims 17-22, 26 and 27 wherein R4 and Ra both represent hydrogen is cyclised and dehydrated to give the desired compound.
  90. 90. A process according to claim 89 wherein the cyclisation and dehydration agent employed is a Vilsmeier reagent.
  91. 91. A process according to claim 90 wherein the Vilsmeier reagent employed is of the formula:
    Alkyl + Hal Hal Anion Alkyl r \ Aryl Rx (where Rx represents hydrogen or alkyl, and Hal represents chlorine or bromine).
  92. 92. A process according to claim 91 wherein Rx represents hydrogen.
  93. 93. A process according to claim 91 or claim 92 wherein each Alkyl represents methyl.
  94. 94. A process according to any of claims 91 to 93 wherein the Vilsmeier reagent is generated in situ by the reaction between a thionyl, phosphoryl or carbonyl chloride or bromide and a dialkylamide.
  95. 95. A process according to claim 94 wherein the Vilsmeier reagent is generated in situ by the reaction between thionyl chloride and dimethylformamide.
  96. 96. A process according 0 any of claims 89 to 95 wherein the compound of formula I employed as a starting material is itself prepared by a process as claimed in any of claims 78 to 80.
  97. 97. A process for the preparation of a compound as claimed in any of claims 61 to 77 wherein a compound of formula I as defined in any of claims 40 to 60 is heated in an appropriate dialkylamide solvent medium in the presence of an ionic salt.
  98. 98. A process according to claim 97 wherein the solvent medium is
  99. 99. A process according to claim 97 or claim 98 wherein the ionic salt is sodium chloride.
  100. 100. A process according to any of claims 97 to 99 wherein the compound of formula I employed as starting material is itself prepared by a process as claimed in any of claims 83 to 88.
  101. 101. A process for the preparation of a compound as claimed in any ofclaims 61 to 77 in which a 5-hydroxybenzofuran of the formula:
    (wherein R', R2, R3, R8, R7 and Ra are as defined in claim 1) is reacted with a sulphonyl halide of the formula R9SO2Hal or an anhydride of the formula (R9SO2)2O (where R9 is as defined in claim I and Hal represents halogen).
  102. 102. A process according to claim 101 wherein the reaction is effected in the presence of a bse.
  103. 103. A process according to claim 101 or claim 102 wherein the 5hydroxybenzofuran of formula VI employed as starting material is itself prepared by a process in which a 5-alkoxybenzofuran of' the formula:
    (wherein R', R2, R3, Re, R7 and Ra are as defined in claim 1 and R'7 represents alkyl of 1 to 6 carbon atoms) is dealkylated by means of an appropriate dealkylating agent.
  104. 104. A process according to claim 103 wherein the dealkylating agent is a mercaptan salt.
  105. 105. A process according to claim 103 or claim 104 wherein the 5-alkoxybenzofuran of the formula XI employed as starting material is itself prepared by a process in which a 5-bromobenzofuran of the formula:
    (wherein R1, R2, R3, Ra, R7 and Ra are as defined in claim 1) is subjected to the action of an alkali-metal alkoxide R170M (where R17 is as defined in claim 103 and M represents an alkali-metal) in the presence of copper salt as catalyst.
  106. 106. A process according to claim 105 wherein the 5-bromobenzofuran of formula X employed as starting material is itself prepared by a process in which a compound of the formula:
    (wherein R', R2, R3, R6, R7, Ra are as defined in claim 1, Ria represents alkyl of I to 6 carbon atoms, and Hal represents halogen) is dealkylated and cyclised by means of an appropriate dealkylating and cyclising agent.
  107. 107. A process according to claim 106 wherein the dealkylating and cyclising agent is pyridine hydrochloride.
  108. 108. A process according to any of claims 78 to 107, and substantially as described herein in Examples 1 to 50.
  109. 109. A compound of formula I whenever prepared by a process according to any of claims 78 to 108.
  110. 110. A method of combating weeds at a locus either infested or liable to infestation therewith, which comprises applying to said locus an effective amount of one or more compounds as claimed in claims 1 to 77 and 109.
  111. 111. A method according to claim 110 wherein the locus is a crop.
  112. 112. A process according to claim 111 wherein the crop is cotton, ryegrass, safflower, sorghum, millet, sunflower, tobacco, a cereal, sugar beet, peas, beans, carrots, peanuts, maize, rice or potatoes.
  113. 113. A method according to claim 111 or claim 112 wherein the compound(s) are applied pre-emergence of the crop.
  114. 114. A method according to any of claims 110 to 113 wherein from 0.1 to 20 kg/ha in total of the compound(s) are applied.
  115. 115. A method according to claim 114 wherein from 1 to 10 kg/ha of the compound(s) are applied.
  116. 116. A method according to claim 115 wherein from 2.5 to 8 kg/ha of the compound(s) are applied.
  117. 117. A method according to any of claims 111 to 116 and substantially as described in any one of Examples A and B.
  118. 118. A herbicidal composition which comprises one or more compounds as claimed in any of claims I to 77 and 109 in association with a carrier and/or surface active agent.
  119. 119. A composition according to claim 119 which contains from 0.5 to 85% by weight of the compound(s).
  120. 120. A composition according to claim 119 which contains from 10 to 50% by weight of the compound(s).
  121. 121. A composition according to any of claims 118 to 120 which also contains one or more further pesticides, plant growth regulants or fertilizers.
  122. 122. A composition according to claim 121 wherein the further pesticide is a herbicide.
  123. 123. A composition according to any one of claims 118 to 121 and substantially as described in Examples 51-54.
  124. 124. A method of combating weeds as claimed in any one of claims 111 to 117 employing a composition as claimed in any of claims 118 to 122.
  125. 125. A two-container pack in which one or more compounds of formula I are provided in a first container and one or more further pesticides, plant growth regulants or fertilizers are provided in a second container.
GB4847/77A 1977-02-05 1977-02-05 Herbicidally active sulphonates processes for their preparation and compositions containing them Expired GB1587221A (en)

Priority Applications (21)

Application Number Priority Date Filing Date Title
GB4847/77A GB1587221A (en) 1977-02-05 1977-02-05 Herbicidally active sulphonates processes for their preparation and compositions containing them
BE184756A BE863471A (en) 1977-02-05 1978-01-30 HERBICIDE COMPOUNDS
DE19782803991 DE2803991A1 (en) 1977-02-05 1978-01-31 SULFONATES, PROCESS FOR THEIR PREPARATION AND HERBICIDAL COMPOSITIONS
IL53951A IL53951A (en) 1977-02-05 1978-02-01 Phenyl sulphonates and heterocyclic sulphonates,their preparation and their use as herbicides
DK48278A DK48278A (en) 1977-02-05 1978-02-02 THEIR PREPARATION AND USE OF THE SULPHONATE COMPOUNDS AND COMPOSITIONS CONTAINING THESE COMPOUNDS
NL7801189A NL7801189A (en) 1977-02-05 1978-02-02 Phenyl- and heterocyclyl-sulphonate ester(s) - useful as selective, pre-emergence herbicides
ZA00780634A ZA78634B (en) 1977-02-05 1978-02-02 Herbicidal sulphonate esters
NZ186379A NZ186379A (en) 1977-02-05 1978-02-02 Sulphonates and herbicidal compositons containing them
US05/875,189 US4162154A (en) 1977-02-05 1978-02-03 Herbicidally-active sulphonates
AU32986/78A AU519345B2 (en) 1977-02-05 1978-02-03 Herbicidal esters of sulphonic and sulphamic acids
DD78203553A DD136690A5 (en) 1977-02-05 1978-02-03 HERBICIDES COMPOSITIONS
HUFI000663 HU179470B (en) 1977-02-05 1978-02-03 Process for preparing new benzofuranyl-sulphonate derivatives and selective herbicide compositions containing such compounds as active materials
IT7819951A IT1092374B (en) 1977-02-05 1978-02-03 ACTIVE SULPHONATES SUCH AS HERBICIDES, PROCEDURES FOR THEIR PREPARATION AND COMPOSITIONS CONTAINING THEM
FR7803076A FR2379514A1 (en) 1977-02-05 1978-02-03 SULPHONATE-BASED HERBICIDE COMPOUNDS AND THEIR PREPARATION AND APPLICATION METHODS
CA296,259A CA1115720A (en) 1977-02-05 1978-02-03 Herbicidally-active sulphonates
AR27096478A AR223457A1 (en) 1977-02-05 1978-02-03 HERBICIDALLY ACTIVE SULPHONATES AND CONTAINING COMPOSITIONS
IE235/78A IE46549B1 (en) 1977-02-05 1978-02-03 Herbicidally active sulphonates,processes for theri preparation,and compositions containing them
PL1978204448A PL111137B1 (en) 1977-02-05 1978-02-04 Herbicide
JP1155678A JPS5398936A (en) 1977-02-05 1978-02-06 New sulfonates * method of its production and composition containing it
US06/022,599 US4222767A (en) 1977-02-05 1979-03-21 Certain herbicidal sulfonates and sulfamates
GT198061589A GT198061589A (en) 1977-02-05 1980-01-22 HERBICIDE COMPOUNDS

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GT198061589A (en) 1981-07-15

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