CA1149392A - Heterocyclic phenoxyalkanoic acid derivatives - Google Patents
Heterocyclic phenoxyalkanoic acid derivativesInfo
- Publication number
- CA1149392A CA1149392A CA000346284A CA346284A CA1149392A CA 1149392 A CA1149392 A CA 1149392A CA 000346284 A CA000346284 A CA 000346284A CA 346284 A CA346284 A CA 346284A CA 1149392 A CA1149392 A CA 1149392A
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- alkyl
- formula
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- alkoxy
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-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D263/00—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings
- C07D263/52—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings condensed with carbocyclic rings or ring systems
- C07D263/54—Benzoxazoles; Hydrogenated benzoxazoles
- C07D263/56—Benzoxazoles; Hydrogenated benzoxazoles with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached in position 2
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/48—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
- A01N43/50—1,3-Diazoles; Hydrogenated 1,3-diazoles
- A01N43/52—1,3-Diazoles; Hydrogenated 1,3-diazoles condensed with carbocyclic rings, e.g. benzimidazoles
-
- 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
- A01N43/74—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 five-membered rings with one nitrogen atom and either one oxygen atom or one sulfur atom in positions 1,3
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D235/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, condensed with other rings
- C07D235/02—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, condensed with other rings condensed with carbocyclic rings or ring systems
- C07D235/04—Benzimidazoles; Hydrogenated benzimidazoles
- C07D235/06—Benzimidazoles; Hydrogenated benzimidazoles with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached in position 2
- C07D235/12—Radicals substituted by oxygen atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D277/00—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings
- C07D277/60—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings condensed with carbocyclic rings or ring systems
- C07D277/62—Benzothiazoles
- C07D277/64—Benzothiazoles with only hydrocarbon or substituted hydrocarbon radicals attached in position 2
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- Organic Chemistry (AREA)
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Health & Medical Sciences (AREA)
- Environmental Sciences (AREA)
- Engineering & Computer Science (AREA)
- Dentistry (AREA)
- General Health & Medical Sciences (AREA)
- Wood Science & Technology (AREA)
- Zoology (AREA)
- Plant Pathology (AREA)
- Pest Control & Pesticides (AREA)
- Agronomy & Crop Science (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Plural Heterocyclic Compounds (AREA)
- Heterocyclic Carbon Compounds Containing A Hetero Ring Having Nitrogen And Oxygen As The Only Ring Hetero Atoms (AREA)
Abstract
ABSTRACT OF THE DISCLOSURE
Substituted phenoxyalkanoic acid derivatives of the formula (I)
Substituted phenoxyalkanoic acid derivatives of the formula (I)
Description
This invention provides novel substituted heterocyclic phenoxyalkanoic acid derivatives of the formula I
(R) _ ~ ~ ~ C-X- ~O ~ O-C-Z (I) in which , 3, NO2, CN, NH2, (Cl - C4)alkyl, (Cl - C )alkoxy (Cl - C4)alkylthio, or phenoxy which is optionally mono-, di- or tri-substituted by halogen, CF3, (Cl - C4)alkyl or NO2, n is zero or an integer from 1 to 4, A is O, S, NH, or N-(Cl - C4)alkyl, X is -CH2- or -CH2-CH2, Rl is H or (Cl - C4)alkyl, Z is a group of the formula " 3 " 4 " 5 " ' ~ "
-C-OR , -C-S-R , -C-NH-R , -C-N-N ~ 7 ~ -C-NH2l CN, o -CH2OH, -CH2-0-C-R or -CH2-0-S02-R
R is H, (Cl - C12)alkyl optionally substituted by 1 to 6 halogen atoms, preferably F, Cl, Br, and/or by OH, (Cl - C6)alkoxy, (Cl - C4)alkylthio, (Cl - C6)alkoxy (C2 - C6)alkoxy, halo(Cl - C2)-alkoxy, methoxyethoxyethoxy, (Cl - C4)alkylamino, di(Cl - C4)-alkylamino, (Cl - C4)alkoxycarbonyl, phenyl and phenoxy which in turn may be mono- or disubstituted by halogen or (Cl - C4)alkyl, (C5 - C6)cycloalkyl or halo(C2 - C6)alkyl;
(C3 - C6)alkenyl, halo(C3- C6)alkenyl or (C5 - C6)cycloalkenyl;
(R) _ ~ ~ ~ C-X- ~O ~ O-C-Z (I) in which , 3, NO2, CN, NH2, (Cl - C4)alkyl, (Cl - C )alkoxy (Cl - C4)alkylthio, or phenoxy which is optionally mono-, di- or tri-substituted by halogen, CF3, (Cl - C4)alkyl or NO2, n is zero or an integer from 1 to 4, A is O, S, NH, or N-(Cl - C4)alkyl, X is -CH2- or -CH2-CH2, Rl is H or (Cl - C4)alkyl, Z is a group of the formula " 3 " 4 " 5 " ' ~ "
-C-OR , -C-S-R , -C-NH-R , -C-N-N ~ 7 ~ -C-NH2l CN, o -CH2OH, -CH2-0-C-R or -CH2-0-S02-R
R is H, (Cl - C12)alkyl optionally substituted by 1 to 6 halogen atoms, preferably F, Cl, Br, and/or by OH, (Cl - C6)alkoxy, (Cl - C4)alkylthio, (Cl - C6)alkoxy (C2 - C6)alkoxy, halo(Cl - C2)-alkoxy, methoxyethoxyethoxy, (Cl - C4)alkylamino, di(Cl - C4)-alkylamino, (Cl - C4)alkoxycarbonyl, phenyl and phenoxy which in turn may be mono- or disubstituted by halogen or (Cl - C4)alkyl, (C5 - C6)cycloalkyl or halo(C2 - C6)alkyl;
(C3 - C6)alkenyl, halo(C3- C6)alkenyl or (C5 - C6)cycloalkenyl;
- 2 -g~
(C3 - C4)alkinyl, optionally mono- or disubstituted by (Cl - C6)-alkyl, phenyl, halogen, or (Cl - C2)alkoxy; phenyl optionally mono-, di-, or trisubstituted by (Cl - C4)alkyl, (Cl - C4)alkoxy, halogen, N02, or CF3i or an alkali metal or alkaline earth metal cation;
R4 is (Cl - C6)alkyl optionally substituted by (Cl - C4)alkoxy, halogen or phenyl which in turn may be mono-, di- or trisubstituted by (Cl - C4)alkyl and halogen;
(C3 - C6)alkenyl or phenyl which is optionally mono-, di- or tri-substituted by (Cl - C4)alkyl and/or halogen;
R5 is H, ( C1 - C6 ) alkyl, hydroxy(Cl - C6)alkyl, or ( C5 - C6 ) cyclo-alkyl;
R is H or CH3;
R is H, CH3 or C2H5;
R8 is H, CH3, C2H5, or phenyl;
R is (C1 - C6)alkyl, (C1 - C4)haloalkyl, C3-, C5-, or C6- cyclo-alkyl, (C3 - C6) alkenyl, phenyl, (Cl - C4)alkylphenyl, (Cl - C4)-alkoxyphenyl, halophenyl, trifluoromethylphenyl, or nitrophenyl; and R is (C1 - C4)alkyl or phenyl which is optionally mono-, di-, or trisubstituted by halogen, CF3, N02, or (Cl - C4)alkyl.
The compounds according to the invention are valuable herbicides which exhibit a special effect against weed grasses.
GB-PS 1,157,558 discloses certain compounds of the formula I in which Z denotes different carboamido and carbanilido radicals (not claimed in this specification) having vasodilatory properties. Nothing is said about any herbicidal effect. Experi-ments have revealed, however, that they do have a certain herbicidal activity.
Alkyl, alkenyl or alkinyl groups occurring in the radicals R1 to R5, R9 and R10 can be linear as well as branched.
Preferred compounds of the formula I are those in which R is halogen or (Cl - C2)alkyl, n is zero or 1 or 2, A is 0, S or (N-(Cl - C4)alkyl, X is -CH2- or -CH2-CH2-, Rl is H or CH3, Z is a group of the formula O O S
-COR , -C-NH-R -CNH2 or -CN
R3 is H, (C1 - C8)alkyl optionally substituted by halogen or (Cl - C6)alkoxy, or an alkali metal or alkaline earth metal cation, R is H or (Cl ~ C4)alkyl.
Especially preferred compounds of the formula I are those in which R is chlorine or bromine, n is zero or 1, A is O or S, X is -CH2, Rl is -CH3, Z is -CooR3, and R3 is Hl (Cl - C6)alkyl optionally substituted by (Cl - C4)alkoxy, Cl or Br, or is an alkali metal or alkaline earth metal cation.
The compounds of the formula I can be produced from start-ing materials known per se or obtainable by known methods. Theprocesses of the invention are characterized in that a) a compound of the formula II
(R)n ~ ~H2 (II) is reacted with a compound of the formula III
" ~ Rl (III), ~9~9z in which Q is hydroxy, alkoxy or halogen and Z' is lower alkoxy-carbonyl;
b) a compound of the formula IV
n ~ J ~ ~ ~ (IV) is reacted with a compound of the formula V
~ i Rl W-CH-Z (V), in which W is halogen, toluenesulfonyl Qr methanesulfonyl radical;
c) a compound of the formula I in which Z is -CooR3 is hydro-genated and the alcohol obtained (Z = CH20H) is optionally converted into the corresponding carboxylic acid ester (Z = CH2-0-,C,-R ) by reaction with a carboxylic acid, carboxylic acid halide or carboxylic anhydride, or is converted into the sulfonic acid ester (Z= -CH2-0-S02-R10) by reaction with a sulfonic acid halide;
d) a compound of the formula I in which Z is an ester group is converted in known manner into a salt (Z = CooR3) in which R3 is a cation as defined above or the free acid (Z = COOH);
e) a compound of the formula I in which Z is -CooR3 is reacted with ammonia, an amine or hydrazine to give the corresponding acid amide (Z = CONHR ) or acid hydrazide (Z = -CO-N(R )-N ~ 7 R
f) a compound of the formula I in which Z is -COOH is converted into the corresponding acid halide which is then converted into the acid amide, acid hydrazide or ester by reaction with an amine, a ny~razine or an alcohol;
(C3 - C4)alkinyl, optionally mono- or disubstituted by (Cl - C6)-alkyl, phenyl, halogen, or (Cl - C2)alkoxy; phenyl optionally mono-, di-, or trisubstituted by (Cl - C4)alkyl, (Cl - C4)alkoxy, halogen, N02, or CF3i or an alkali metal or alkaline earth metal cation;
R4 is (Cl - C6)alkyl optionally substituted by (Cl - C4)alkoxy, halogen or phenyl which in turn may be mono-, di- or trisubstituted by (Cl - C4)alkyl and halogen;
(C3 - C6)alkenyl or phenyl which is optionally mono-, di- or tri-substituted by (Cl - C4)alkyl and/or halogen;
R5 is H, ( C1 - C6 ) alkyl, hydroxy(Cl - C6)alkyl, or ( C5 - C6 ) cyclo-alkyl;
R is H or CH3;
R is H, CH3 or C2H5;
R8 is H, CH3, C2H5, or phenyl;
R is (C1 - C6)alkyl, (C1 - C4)haloalkyl, C3-, C5-, or C6- cyclo-alkyl, (C3 - C6) alkenyl, phenyl, (Cl - C4)alkylphenyl, (Cl - C4)-alkoxyphenyl, halophenyl, trifluoromethylphenyl, or nitrophenyl; and R is (C1 - C4)alkyl or phenyl which is optionally mono-, di-, or trisubstituted by halogen, CF3, N02, or (Cl - C4)alkyl.
The compounds according to the invention are valuable herbicides which exhibit a special effect against weed grasses.
GB-PS 1,157,558 discloses certain compounds of the formula I in which Z denotes different carboamido and carbanilido radicals (not claimed in this specification) having vasodilatory properties. Nothing is said about any herbicidal effect. Experi-ments have revealed, however, that they do have a certain herbicidal activity.
Alkyl, alkenyl or alkinyl groups occurring in the radicals R1 to R5, R9 and R10 can be linear as well as branched.
Preferred compounds of the formula I are those in which R is halogen or (Cl - C2)alkyl, n is zero or 1 or 2, A is 0, S or (N-(Cl - C4)alkyl, X is -CH2- or -CH2-CH2-, Rl is H or CH3, Z is a group of the formula O O S
-COR , -C-NH-R -CNH2 or -CN
R3 is H, (C1 - C8)alkyl optionally substituted by halogen or (Cl - C6)alkoxy, or an alkali metal or alkaline earth metal cation, R is H or (Cl ~ C4)alkyl.
Especially preferred compounds of the formula I are those in which R is chlorine or bromine, n is zero or 1, A is O or S, X is -CH2, Rl is -CH3, Z is -CooR3, and R3 is Hl (Cl - C6)alkyl optionally substituted by (Cl - C4)alkoxy, Cl or Br, or is an alkali metal or alkaline earth metal cation.
The compounds of the formula I can be produced from start-ing materials known per se or obtainable by known methods. Theprocesses of the invention are characterized in that a) a compound of the formula II
(R)n ~ ~H2 (II) is reacted with a compound of the formula III
" ~ Rl (III), ~9~9z in which Q is hydroxy, alkoxy or halogen and Z' is lower alkoxy-carbonyl;
b) a compound of the formula IV
n ~ J ~ ~ ~ (IV) is reacted with a compound of the formula V
~ i Rl W-CH-Z (V), in which W is halogen, toluenesulfonyl Qr methanesulfonyl radical;
c) a compound of the formula I in which Z is -CooR3 is hydro-genated and the alcohol obtained (Z = CH20H) is optionally converted into the corresponding carboxylic acid ester (Z = CH2-0-,C,-R ) by reaction with a carboxylic acid, carboxylic acid halide or carboxylic anhydride, or is converted into the sulfonic acid ester (Z= -CH2-0-S02-R10) by reaction with a sulfonic acid halide;
d) a compound of the formula I in which Z is an ester group is converted in known manner into a salt (Z = CooR3) in which R3 is a cation as defined above or the free acid (Z = COOH);
e) a compound of the formula I in which Z is -CooR3 is reacted with ammonia, an amine or hydrazine to give the corresponding acid amide (Z = CONHR ) or acid hydrazide (Z = -CO-N(R )-N ~ 7 R
f) a compound of the formula I in which Z is -COOH is converted into the corresponding acid halide which is then converted into the acid amide, acid hydrazide or ester by reaction with an amine, a ny~razine or an alcohol;
3~
g) a compound of the formula I in which Z is a low molecular weight ester group is transesterified with an alcohol of the formula R OH;
h) a compound of the formula I in which Z is -CO-NH2 is dehy-drated and the nitrile obtained (Z - CN) is converted, if desired, into the corresponding thioamide (Z = CS-NH2) by addition of H2S.
Item a): Preferably the free acids (Q = OH) or the acid halides (Q = Cl) are used as starting compounds III. The reaction may be carried out in the presence or absence of a solvent at a temperature of from 100 to 200C. Preferred solvents are xylene, chlorobenzene, dichlorobenzene. The water formed in the reaction is distilled off.
Item b): The reaction is preferably carried out in inert aprotic solvents such as aliphatic or aromatic hydrocarbons, for example benzene, toluene, acetonitrile, acetone, dimethy] sulfoxide, or dimethyl formamide at temperatures of from 50C to the boiling point of the solvent used, in the presence of a base, for example an alkali metal carbonate, alkali metal hydroxide or a tertiary organic base. W denotes halogen or a sulfonic acid radical selected from tosyl and mesyl radicals.
Item c): The reduction of acids or esters to give alcohols is preferably carried out with a complex metal hydride such as LiAlH4, in ethereal, anhydrous solvents. In general, the reaction is exothermic and, therefore, heating from the outside is unnecessary.
The subsequent esterification with acid anhydrides or halides is carried out in an inert solvent (as used in method a) at a temper-ature between 0C and the boiling point of the solvent used with ;, addition of an organic or inorganic base, for example Na2C03, K2C03, pyridine or triethylamine. The esterification with carboxylic acids is carried out either with the addition of a water binding agent such as P205 or by extractive azeotropic distillation of the acidified components.
- 6a -Item e): The reaction is preferably carried out in a solvent as specified in b), the reaction temperature being in the range of from 40C to reflux temperature.
Item f): The acids of the formula I are converted into the acid halide in known manner. The same applies to the subsequent reaction with ammonia, amines or hydrazines. To bind the hydrogen halide set free an at least one molar excess of the base used is necessary.
Item g): The reaction proceeds by means of acid or basic catalysis. The alcohol used for transesterification is preferably added in an excess and the lower boiling alcohol set free is distilled off as it is formed.
It,em h): The dehydration of amides to give nitriles is preferably carried out in an aromatic hydrocarbon at a temperature between 50C and boiling temperature. The subsequent addition of H2S is expediently performed in an autoclave in the presence of catalytic amounts of a base, preferably ethanol amine, at temperatures between 50 and 150C.
The heterocyclic phenols of formula IV used for the manufacture of the compounds of formula I are preferably prepared by condensation of aminophenols, aminothiophenols and diaminobenzenes with 4-hydroxyphenylacetic acid or 3-(4'-hydroxyphenyl)-propionic acid while distilling off 25 water at reaction temperatures of 120 to 200C.
The compounds of the formula I according to the in-vention exhibit a very good herbicidal effect in pre-emer-gence and post-emergence application against a broad spec-trum of monocotyledonous weeds while, at the same time, they are excellently tolerated by dicotyledonous crop plants and some cereals.
The compounds can, therefore, be used, irter alia, for the selective control of weed grasses in crop plants.
It is, therfore, another object of the present invention to provide herbicidal compositions containing a carrier and a herbicidally effective amount of a compound of the formula I.
'3~
The compositions of the invention generally contain from 2 to 95 % by weight of the compounds of the formula I
as active substance. The compositions can be formulated as wettable powders, emulsifiable concentrates, sprayable so-lutions, dusts and granules, together with the usual addi-tives.
Wettable powders are formulations which are uniformly dispersible in water and which, in addition to the active compound and a diluent or inert material, also contain wetting agents, for example polyoxethylated alkylphenols, polyoxethylated oleyl- or stearylamines, alkylsulfonates or alkylphenylsulfonates, and dispersing agents, for example sodium ligninsulfonate, sodium-2,2'-dinaphthylmethane-6,6'-disulfonate or the sodium salt of oleoylmethyl taurine.
Emulsifiable concentrates are obtained by dissolving the active compound in an organic solvent, for example bu-tanol, cyclohexanone, dimethyl formamide, xylene or even higher boiling aromatics, and adding a non ionic emul-sifier, for example a polyoxethylated alkylphenol or a polyoxethylated oleyl-or stearylamine.
Dusts are obtained by grinding the active compound together with finely divided solid substances, for example talc, natural clays such as kaolin, bentonite, pyrophillite or diatomaceous earth.
Granules can be manufactured either by spraying the active compound onto adsorbent, granular inert material or by applying active compound concentrates by means of adhe-sives, for example polyvinyl alcohol, sodium polyacrylate or even mineral oils, onto the surfaces of carriers, such as sand, kaolinites or granular inert material. Suitable formulations can also be manufactured by the customary me-thods of manufacture of fertilizer granules, if desired in admixture with fertilizers.
In the herbicidal compositions the conentrations of the active compounds in the commercial formulations may vary. In wettable powders, the active compound concentra-tion varies, for example, between about 10 and 95 %, the remainder consisting of the abovementioned formulation ad-ditives. In the case of emulsifiable concentrates, the ac-tive compound concentration is about 10 % to 80 %. Dust formulations usually contain 5 - 20 % of active compound, and sprayable solutions about 2 - 20 ~. In the case of granules, the active compound content in part depends on whether the active compound is in a liquid or solid form and what granulation auxiliaries, fillers and the like are used.
The commercial concentrates are diluted prior to appli-cation in the usual manner, for example by means of water in the case of wettable powders and emulsifiable concentra-tes. Dusts, granules and sprayable solutions need not be diluted with further inert material prior to use. The amount of active ingredients necessary for obtaining the desired result depends on external conditions such as tem-perature, humidity and the like. It may vary within wide limits, for example between 0.05 and 10.0 kg of active sub-stance per hectare, preferably however, between 0.1 and 5 kgihectare.
The active compounds according to the invention can be combined with other herbicides, insecticides and fun-gicides.
The following examples illustrate the invention.
EXAMPLES OF MANUFACTURE
E x a m p l e 2-/ 4' (2"-Benzthiazolylmethyl)-phenoxy_7-propionic acid eth l ester y 24.1 g (0.1 mol) of 4-(2'-benzthiazolyolmethyl)-phe-30 nol, 16.6 g (0.12 mol) of potassium carbonate and 19.9 g (0.11 mol) of 2-bromopropionic acid ethyl ester in 100 cc of acetonitrile are refluxed for 8 hours. Inorganic salts are filtered off, acetonitrile is distilled off under re-duced pressure and the residue is distilled in high vaccum.
35 30 g _ 88 ~ of theory of 2-/ 4'-(2"-benzthiazolylmethyl)-phenoxy_7-propionic acid ethyl ester are obtained (boil-ing point 205 - 208C, 0.07 mbar).
9 ~ Z
- 10 - HOE 7~/F 039 ~ ~CH2-~)-OCHC02C2H5 E x a m p l e 2 2-/ 4'-t2"-Benzthiazolylmethyl)-phenoxy_7-propionic acid _________________________________________________________ 34.1 g (o.1 mol) of 2-/ 4'-(2"-benzthiazolylmethyl)-phenoxy_7-propionic acid ethyl ester, 4,4 g (0.11 mol) of sodium hydroxide, 200 cc of water and 50 cc of methanol are stirred for 16 hours at room temperature. The reaction mixture is acidified with 15 cc of concentrated hydrochlor-ic acid, the precipitate formed is filtered off and dried.
30 g = 96 % of theory of 2-/ 4l-(2~'-benzthiazolylmethyl)-phenoxy_7-propionic acid melting at 154 to 156C are ob-tained.
~ ~CH2-~-OCHCOOH
The following compounds are prepared in analogous manner.
x. No. compound accord. b.p./m.p.
to Ex.
(process) __________________________________________________________ N CH
3 ~ / 2 ~ 2 3 m.p. 63C
N CH
g) a compound of the formula I in which Z is a low molecular weight ester group is transesterified with an alcohol of the formula R OH;
h) a compound of the formula I in which Z is -CO-NH2 is dehy-drated and the nitrile obtained (Z - CN) is converted, if desired, into the corresponding thioamide (Z = CS-NH2) by addition of H2S.
Item a): Preferably the free acids (Q = OH) or the acid halides (Q = Cl) are used as starting compounds III. The reaction may be carried out in the presence or absence of a solvent at a temperature of from 100 to 200C. Preferred solvents are xylene, chlorobenzene, dichlorobenzene. The water formed in the reaction is distilled off.
Item b): The reaction is preferably carried out in inert aprotic solvents such as aliphatic or aromatic hydrocarbons, for example benzene, toluene, acetonitrile, acetone, dimethy] sulfoxide, or dimethyl formamide at temperatures of from 50C to the boiling point of the solvent used, in the presence of a base, for example an alkali metal carbonate, alkali metal hydroxide or a tertiary organic base. W denotes halogen or a sulfonic acid radical selected from tosyl and mesyl radicals.
Item c): The reduction of acids or esters to give alcohols is preferably carried out with a complex metal hydride such as LiAlH4, in ethereal, anhydrous solvents. In general, the reaction is exothermic and, therefore, heating from the outside is unnecessary.
The subsequent esterification with acid anhydrides or halides is carried out in an inert solvent (as used in method a) at a temper-ature between 0C and the boiling point of the solvent used with ;, addition of an organic or inorganic base, for example Na2C03, K2C03, pyridine or triethylamine. The esterification with carboxylic acids is carried out either with the addition of a water binding agent such as P205 or by extractive azeotropic distillation of the acidified components.
- 6a -Item e): The reaction is preferably carried out in a solvent as specified in b), the reaction temperature being in the range of from 40C to reflux temperature.
Item f): The acids of the formula I are converted into the acid halide in known manner. The same applies to the subsequent reaction with ammonia, amines or hydrazines. To bind the hydrogen halide set free an at least one molar excess of the base used is necessary.
Item g): The reaction proceeds by means of acid or basic catalysis. The alcohol used for transesterification is preferably added in an excess and the lower boiling alcohol set free is distilled off as it is formed.
It,em h): The dehydration of amides to give nitriles is preferably carried out in an aromatic hydrocarbon at a temperature between 50C and boiling temperature. The subsequent addition of H2S is expediently performed in an autoclave in the presence of catalytic amounts of a base, preferably ethanol amine, at temperatures between 50 and 150C.
The heterocyclic phenols of formula IV used for the manufacture of the compounds of formula I are preferably prepared by condensation of aminophenols, aminothiophenols and diaminobenzenes with 4-hydroxyphenylacetic acid or 3-(4'-hydroxyphenyl)-propionic acid while distilling off 25 water at reaction temperatures of 120 to 200C.
The compounds of the formula I according to the in-vention exhibit a very good herbicidal effect in pre-emer-gence and post-emergence application against a broad spec-trum of monocotyledonous weeds while, at the same time, they are excellently tolerated by dicotyledonous crop plants and some cereals.
The compounds can, therefore, be used, irter alia, for the selective control of weed grasses in crop plants.
It is, therfore, another object of the present invention to provide herbicidal compositions containing a carrier and a herbicidally effective amount of a compound of the formula I.
'3~
The compositions of the invention generally contain from 2 to 95 % by weight of the compounds of the formula I
as active substance. The compositions can be formulated as wettable powders, emulsifiable concentrates, sprayable so-lutions, dusts and granules, together with the usual addi-tives.
Wettable powders are formulations which are uniformly dispersible in water and which, in addition to the active compound and a diluent or inert material, also contain wetting agents, for example polyoxethylated alkylphenols, polyoxethylated oleyl- or stearylamines, alkylsulfonates or alkylphenylsulfonates, and dispersing agents, for example sodium ligninsulfonate, sodium-2,2'-dinaphthylmethane-6,6'-disulfonate or the sodium salt of oleoylmethyl taurine.
Emulsifiable concentrates are obtained by dissolving the active compound in an organic solvent, for example bu-tanol, cyclohexanone, dimethyl formamide, xylene or even higher boiling aromatics, and adding a non ionic emul-sifier, for example a polyoxethylated alkylphenol or a polyoxethylated oleyl-or stearylamine.
Dusts are obtained by grinding the active compound together with finely divided solid substances, for example talc, natural clays such as kaolin, bentonite, pyrophillite or diatomaceous earth.
Granules can be manufactured either by spraying the active compound onto adsorbent, granular inert material or by applying active compound concentrates by means of adhe-sives, for example polyvinyl alcohol, sodium polyacrylate or even mineral oils, onto the surfaces of carriers, such as sand, kaolinites or granular inert material. Suitable formulations can also be manufactured by the customary me-thods of manufacture of fertilizer granules, if desired in admixture with fertilizers.
In the herbicidal compositions the conentrations of the active compounds in the commercial formulations may vary. In wettable powders, the active compound concentra-tion varies, for example, between about 10 and 95 %, the remainder consisting of the abovementioned formulation ad-ditives. In the case of emulsifiable concentrates, the ac-tive compound concentration is about 10 % to 80 %. Dust formulations usually contain 5 - 20 % of active compound, and sprayable solutions about 2 - 20 ~. In the case of granules, the active compound content in part depends on whether the active compound is in a liquid or solid form and what granulation auxiliaries, fillers and the like are used.
The commercial concentrates are diluted prior to appli-cation in the usual manner, for example by means of water in the case of wettable powders and emulsifiable concentra-tes. Dusts, granules and sprayable solutions need not be diluted with further inert material prior to use. The amount of active ingredients necessary for obtaining the desired result depends on external conditions such as tem-perature, humidity and the like. It may vary within wide limits, for example between 0.05 and 10.0 kg of active sub-stance per hectare, preferably however, between 0.1 and 5 kgihectare.
The active compounds according to the invention can be combined with other herbicides, insecticides and fun-gicides.
The following examples illustrate the invention.
EXAMPLES OF MANUFACTURE
E x a m p l e 2-/ 4' (2"-Benzthiazolylmethyl)-phenoxy_7-propionic acid eth l ester y 24.1 g (0.1 mol) of 4-(2'-benzthiazolyolmethyl)-phe-30 nol, 16.6 g (0.12 mol) of potassium carbonate and 19.9 g (0.11 mol) of 2-bromopropionic acid ethyl ester in 100 cc of acetonitrile are refluxed for 8 hours. Inorganic salts are filtered off, acetonitrile is distilled off under re-duced pressure and the residue is distilled in high vaccum.
35 30 g _ 88 ~ of theory of 2-/ 4'-(2"-benzthiazolylmethyl)-phenoxy_7-propionic acid ethyl ester are obtained (boil-ing point 205 - 208C, 0.07 mbar).
9 ~ Z
- 10 - HOE 7~/F 039 ~ ~CH2-~)-OCHC02C2H5 E x a m p l e 2 2-/ 4'-t2"-Benzthiazolylmethyl)-phenoxy_7-propionic acid _________________________________________________________ 34.1 g (o.1 mol) of 2-/ 4'-(2"-benzthiazolylmethyl)-phenoxy_7-propionic acid ethyl ester, 4,4 g (0.11 mol) of sodium hydroxide, 200 cc of water and 50 cc of methanol are stirred for 16 hours at room temperature. The reaction mixture is acidified with 15 cc of concentrated hydrochlor-ic acid, the precipitate formed is filtered off and dried.
30 g = 96 % of theory of 2-/ 4l-(2~'-benzthiazolylmethyl)-phenoxy_7-propionic acid melting at 154 to 156C are ob-tained.
~ ~CH2-~-OCHCOOH
The following compounds are prepared in analogous manner.
x. No. compound accord. b.p./m.p.
to Ex.
(process) __________________________________________________________ N CH
3 ~ / 2 ~ 2 3 m.p. 63C
N CH
4 ~ ~ CH2- ~ CHc2c2H5 1 b.p.174-6C
0.013 mbar 3~Z
~ HOE 79/F 039 Ex. No. compound accord. b.p./m.p.
to Ex.
(process) __________________________________________________________ ~ ~ CH2- ~ -OCHCO2CH3 1 m.p. 70C
6 ~ N~ CH3 2 vitreous S mass Cl ~ ~ CH2- ~ -OCHCO2C2H5 8 ~ N~ CH3 1 b.p. 192C
Cl O 0.007 mbar C ~ ~ CH2- ~ -OCHC02C2H5 Cl ~ N~ CH3 b.p. 181C
0 0.005 mbar Cl ~ CH2 ~ CHc2cH2cH2cH3 N CH
12 C ~ ~ H2 ~ OCHCO2CH2CH2Cl 3~2 Ex . No. compound accord. b.p./m.p.
to Ex.
( proc es s ) ________________________________. ___________. _ ___________ 3 ~ \~CH2~-OCH2CO2CH3 1 m.p 91 -~CH2-~-OCHC02CH3 1 b.p. 226C
N O . 08 mbar (~ ~CH2~-OcHc02c2H5 1 b.p.206C
N O . 07 mbar 16 ~ ~ CH2-CH2 ~ -OCHC02CH3 1 m p 65 -7 ~ ~ CH2-CH2- ~ CHc2c2H5 1 b.p. 198C
S 0.01 mbar 18 ~ ~CH2-GH2~-ocHco2cH3 1 b.p. 190C
S O . 007 mbar 19 Cl ~ ~/ CH2~0CHc02cH2cH ( CH2 ) 2 3;~3~
Ex. No. compound accord. b.p./m.p.
to Ex.
(process) __________________________________________________________ 20Cl ~ ~ CH2- ~ -OCHCH2OH c Cl~ ~CH ~0 CH COS C 2H 5 22~ ~ CH2- ~ -o8HCoNHC2H5 23Cl ~ ~ CH ~ -OCH-CN h 24 Cl ~ N~ CH3 Cl ~ N~ CH3 5 h 3~
EXAMPLES OF FORMULATION
E x a m p l e A:
An emulsifiable concentrate is obtained from 15 parts by weight of active substance 75 parts by weight of cyclohexanone as solvent and 10 parts by weight of oxethylated nonyl phenol (10 EO) as emulsifier.
E x a m p l e B:
A wettable powder which is easily dispersible in wa-ter is obtained by mixing25 parts by weight of active substance 64 parts by weight of kaolin containing quartz as inert material, 10 parts by weight of potassium lignosulfonate and 5 1 part by weight of sodium oleoyl-methyl tauride as wet-ting and dispersing agent, and grinding the mixture in a pin mill.
E x a m p l e C:
A dust composition is obtained by mixing 10 parts by weight of active substance and 90 parts by weight of talc as inert material and grinding the mixture in a hammer mill.
E x a m p l e D:
A granular formulation consists, for example, of about 2 to 15 parts by weight of active substance and 98 to 85 parts by weight of inert granular carrier material such as attapulgite, granular pumice and quartz sand.
EXAMPLES OF APPLICATION:
E x a m p l e Various economically important weed grasses and crop plants were sown in pots and treated in pre-emergence application ~ith compounds according to the invention. The pots were then kept in the greenhouse under good growing conditions. 4 Weeks after the treatment the herbicidal effect against the weed grasses and the selectivity with respect to the crop plants were evalated by visual inspec-tion. The damage in percent in comparison with untreated plants is indicated in the following Table 1. The results show that the compounds of the invention have a good her-bicidal effect against many weed grasses and simultaneously that they do no harm or little harm only to the crop plants even in a high dosage of 2.4 kg of active substance per hectare. Hence, they can be used for selectively com-bating weeds in such cultivations.
E x a m p l e 2 In analogous manner the compounds of the invention were sprayed in a post-emergence process on some important types of weed grasses and various crop plants which had been grown in the greenhouse to a height of 8 to 15 cm.
4 Weeks after the treatment in the greenhouse the plants were inspected as to their damage in percent. The results listed in Table 2 show that also in a post-emergence pro-cess the compounds of the invention can be used for selec-tively combating weed grasses in crops of numerous di-cotyledonous and monocotyledonous plants, such as cotton or'rice.
i 3~2 Table 1 Herbicidal effect and selectivity of compounds of the in-vention in a pre-emergence process Effective- Selectivity in crop ness against plants (damages in %) Ex. No. kg AS/ha AL ECG SA GH GS BA
in % _ _ 2.4 100 100 100 0 2 5 0.6 100 100 95 o o O
2 2.4 98 99 95 4 5 4 0.6 g5 98 90 0 0 0 3 2.4 85 90 90 o o o 4 2.4 85 90 75 0 0 0 1 2.4 99 99 95 0 O O
o.6 98 95 90 - - -2.4 100 loO 95 o o o 0.6 98 95 92 - - -Al = Alopecurus ECG = Echinochloa SA = Setaria CH = Cotton GS = Soybean BA = Sugar beet Table 2 Herbicidal effect and selectivity in a post-emergence process ~damages in ~) Ex. No. kg AS/ha AL ECG SA GH GS BA HV OS
2.4 100 99100 0 2 1 7 4 0.6 96 9999 0 0 0 1 2 2.4 96 9595 0 2 0 0.6 92 90 - O O O - -_ HV = Barley OS - Rice
0.013 mbar 3~Z
~ HOE 79/F 039 Ex. No. compound accord. b.p./m.p.
to Ex.
(process) __________________________________________________________ ~ ~ CH2- ~ -OCHCO2CH3 1 m.p. 70C
6 ~ N~ CH3 2 vitreous S mass Cl ~ ~ CH2- ~ -OCHCO2C2H5 8 ~ N~ CH3 1 b.p. 192C
Cl O 0.007 mbar C ~ ~ CH2- ~ -OCHC02C2H5 Cl ~ N~ CH3 b.p. 181C
0 0.005 mbar Cl ~ CH2 ~ CHc2cH2cH2cH3 N CH
12 C ~ ~ H2 ~ OCHCO2CH2CH2Cl 3~2 Ex . No. compound accord. b.p./m.p.
to Ex.
( proc es s ) ________________________________. ___________. _ ___________ 3 ~ \~CH2~-OCH2CO2CH3 1 m.p 91 -~CH2-~-OCHC02CH3 1 b.p. 226C
N O . 08 mbar (~ ~CH2~-OcHc02c2H5 1 b.p.206C
N O . 07 mbar 16 ~ ~ CH2-CH2 ~ -OCHC02CH3 1 m p 65 -7 ~ ~ CH2-CH2- ~ CHc2c2H5 1 b.p. 198C
S 0.01 mbar 18 ~ ~CH2-GH2~-ocHco2cH3 1 b.p. 190C
S O . 007 mbar 19 Cl ~ ~/ CH2~0CHc02cH2cH ( CH2 ) 2 3;~3~
Ex. No. compound accord. b.p./m.p.
to Ex.
(process) __________________________________________________________ 20Cl ~ ~ CH2- ~ -OCHCH2OH c Cl~ ~CH ~0 CH COS C 2H 5 22~ ~ CH2- ~ -o8HCoNHC2H5 23Cl ~ ~ CH ~ -OCH-CN h 24 Cl ~ N~ CH3 Cl ~ N~ CH3 5 h 3~
EXAMPLES OF FORMULATION
E x a m p l e A:
An emulsifiable concentrate is obtained from 15 parts by weight of active substance 75 parts by weight of cyclohexanone as solvent and 10 parts by weight of oxethylated nonyl phenol (10 EO) as emulsifier.
E x a m p l e B:
A wettable powder which is easily dispersible in wa-ter is obtained by mixing25 parts by weight of active substance 64 parts by weight of kaolin containing quartz as inert material, 10 parts by weight of potassium lignosulfonate and 5 1 part by weight of sodium oleoyl-methyl tauride as wet-ting and dispersing agent, and grinding the mixture in a pin mill.
E x a m p l e C:
A dust composition is obtained by mixing 10 parts by weight of active substance and 90 parts by weight of talc as inert material and grinding the mixture in a hammer mill.
E x a m p l e D:
A granular formulation consists, for example, of about 2 to 15 parts by weight of active substance and 98 to 85 parts by weight of inert granular carrier material such as attapulgite, granular pumice and quartz sand.
EXAMPLES OF APPLICATION:
E x a m p l e Various economically important weed grasses and crop plants were sown in pots and treated in pre-emergence application ~ith compounds according to the invention. The pots were then kept in the greenhouse under good growing conditions. 4 Weeks after the treatment the herbicidal effect against the weed grasses and the selectivity with respect to the crop plants were evalated by visual inspec-tion. The damage in percent in comparison with untreated plants is indicated in the following Table 1. The results show that the compounds of the invention have a good her-bicidal effect against many weed grasses and simultaneously that they do no harm or little harm only to the crop plants even in a high dosage of 2.4 kg of active substance per hectare. Hence, they can be used for selectively com-bating weeds in such cultivations.
E x a m p l e 2 In analogous manner the compounds of the invention were sprayed in a post-emergence process on some important types of weed grasses and various crop plants which had been grown in the greenhouse to a height of 8 to 15 cm.
4 Weeks after the treatment in the greenhouse the plants were inspected as to their damage in percent. The results listed in Table 2 show that also in a post-emergence pro-cess the compounds of the invention can be used for selec-tively combating weed grasses in crops of numerous di-cotyledonous and monocotyledonous plants, such as cotton or'rice.
i 3~2 Table 1 Herbicidal effect and selectivity of compounds of the in-vention in a pre-emergence process Effective- Selectivity in crop ness against plants (damages in %) Ex. No. kg AS/ha AL ECG SA GH GS BA
in % _ _ 2.4 100 100 100 0 2 5 0.6 100 100 95 o o O
2 2.4 98 99 95 4 5 4 0.6 g5 98 90 0 0 0 3 2.4 85 90 90 o o o 4 2.4 85 90 75 0 0 0 1 2.4 99 99 95 0 O O
o.6 98 95 90 - - -2.4 100 loO 95 o o o 0.6 98 95 92 - - -Al = Alopecurus ECG = Echinochloa SA = Setaria CH = Cotton GS = Soybean BA = Sugar beet Table 2 Herbicidal effect and selectivity in a post-emergence process ~damages in ~) Ex. No. kg AS/ha AL ECG SA GH GS BA HV OS
2.4 100 99100 0 2 1 7 4 0.6 96 9999 0 0 0 1 2 2.4 96 9595 0 2 0 0.6 92 90 - O O O - -_ HV = Barley OS - Rice
Claims (12)
PROPERTY OR PRIVILEGEIS CLAIMED ARE DEFINED AS FOLLOWS:
1) A compound of the formula (I) (I) in which R is halogen, CF3, NO2, CN, NH2, (Cl - C4)alkyl, (Cl - C4)alkoxy, (Cl - C4) alkylthio, or phenoxy optionally mono-, di- or tri-substituted by halogen, CF3, (Cl - C4)alkyl or NO2, n is zero or an integer from 1 to 4, A is O, S, NH, or N-(Cl - C4)alkyl, X is -CH2- or -CH2-CH2, R1 is H or (Cl - C4)alkyl, Z is a group of the formula , ,, ,,CN, -CH2OH, or R3 is H, (Cl - C12)alkyl optionally substituted by 1 to 6 halogen atoms, and/or by OH, (Cl - C6)alkoxy, (Cl-C4)alkylthio, (Cl - C6) alkoxy-(C2 -C6)alkoxy, halo(Cl - C2)alkoxy, methoxyethoxy-ethoxy, (Cl - C4)alkylamino, di(Cl - C4)alkylamino, (Cl - C4)alkoxycarbonyl, phenyl, and phenoxy which in turn is mono- or disubstituted by halogen or (Cl - C4)alkyl, (C5 - C6)cycloalkyl or halo(C5 - C6)alkyl;
(C3 - C6)alkenyl, halo(C3 - C6)alkenyl, or (C5 - C6)-cycloalkenyl;
(C3 - C4)alkinyl optionally being mono- or disubstituted by (Cl - C6)alkyl, phenyl, halogen, or (Cl - C2)- alkoxy; phenyl optionally mono-, di-, or trisubstituted by (Cl - C4)alkyl, (Cl - C4)alkoxy, halogen, NO2, or CF3; or an alkali metal or alkaline earth metal cation;
R4 is (Cl -C6)alkyl optionally substituted by (Cl - C4)alkoxy, halogen or phenyl which in turn may be mono-, di- or trisubstituted by (Cl - C4)alkyl and halogen;
(C3 - C6)alkenyl or phenyl which is optionally mono-, di- or trisubstituted by (Cl - C4)alkyl and/or halogen;
R5 is H, (Cl - C6)alkyl, hydroxy(Cl - C6)alkyl, or (C5 - C6)cycloalkyl;
R6 is H or CH3;
R7 is H, CH3 or C2H5;
R8 is H, CH3, C2H5, or phenyl;
R9 is (Cl - C6)alkyl, (Cl - C4)haloalkyl, C3-, C5-, or C6-cycloalkyl, (C3 - C6)alkenyl, phenyl, (Cl - C4)-alkylphenyl, (Cl - C4)alkoxyphenyl, halophenyl, trifluoromethyl-phenyl, or nitrophenyl; and R10 is (Cl - C4)alkyl or phenyl which is mono-, di-, or trisubstituted by halogen, CF3, NO2, or (C1 - C4)alkyl.
(C3 - C6)alkenyl, halo(C3 - C6)alkenyl, or (C5 - C6)-cycloalkenyl;
(C3 - C4)alkinyl optionally being mono- or disubstituted by (Cl - C6)alkyl, phenyl, halogen, or (Cl - C2)- alkoxy; phenyl optionally mono-, di-, or trisubstituted by (Cl - C4)alkyl, (Cl - C4)alkoxy, halogen, NO2, or CF3; or an alkali metal or alkaline earth metal cation;
R4 is (Cl -C6)alkyl optionally substituted by (Cl - C4)alkoxy, halogen or phenyl which in turn may be mono-, di- or trisubstituted by (Cl - C4)alkyl and halogen;
(C3 - C6)alkenyl or phenyl which is optionally mono-, di- or trisubstituted by (Cl - C4)alkyl and/or halogen;
R5 is H, (Cl - C6)alkyl, hydroxy(Cl - C6)alkyl, or (C5 - C6)cycloalkyl;
R6 is H or CH3;
R7 is H, CH3 or C2H5;
R8 is H, CH3, C2H5, or phenyl;
R9 is (Cl - C6)alkyl, (Cl - C4)haloalkyl, C3-, C5-, or C6-cycloalkyl, (C3 - C6)alkenyl, phenyl, (Cl - C4)-alkylphenyl, (Cl - C4)alkoxyphenyl, halophenyl, trifluoromethyl-phenyl, or nitrophenyl; and R10 is (Cl - C4)alkyl or phenyl which is mono-, di-, or trisubstituted by halogen, CF3, NO2, or (C1 - C4)alkyl.
2). A compound according to claim 1, wherein in the formula (I), R is halogen or (Cl - C2) alkyl, n is zero, 1 or 2, A is 0, S or N-(Cl - C4)alkyl, X is -CH2 - or - CH2-CH2-, Rl is H or CH3, Z is a group of the formula , , , or - CN
R3 is H, (Cl-C8) alkyl optionally substituted by halogen or (Cl - C6)alkoxy, or an alkali metal or alkaline earth metal cation, R5 is H or (Cl - C4)alkyl.
R3 is H, (Cl-C8) alkyl optionally substituted by halogen or (Cl - C6)alkoxy, or an alkali metal or alkaline earth metal cation, R5 is H or (Cl - C4)alkyl.
3). A compound of the formula in which R is chlorine or bromine n is zero or 1, A is 0 or S, X is -CH2-, Rl is -CH3, Z is -COOR3, R3 is H, (Cl - C6)alkyl optionally substituted by (Cl - C4)alkoxy, Cl or Br, or is an alkali metal or alkaline earth metal cation.
4). A compound of the formula
5). A compound of the formula
6). A compound of the formula
7). A compound of the formula
8). A compound of the formula
9). A compound of the formula
10). A process for the manufacture of a compound as claimed in claim 1 which comprises a) reacting a compound of the formula (II) (II) in which R, n and A are as defined in claim 1, with a compound of the formula (III) (III) in which X and R1 are as defined in claim 1, Q is hydroxy, alkoxy or halogen and Z' is lower alkoxycarbonyl so as to produce a compound of the formula (I), in which Z is in which R3 is a lower alkyl radical;
b) reacting a compound of the formula IV
(IV) in which R, n, A and X are as defined in claim 1, with a compound of the formula V
(V) in which W is halogen, toluenesulfonyl or methanesulfonyl radical, Rl and Z
are as defined in claim l;
c) hydrogenating a compound of the formula (I) in which Z is -COOR3 and optionally converting the alcohol obtained (Z = CH2OH) into the correspond-ing carboxylic acid ester by reaction with a carboxylic anhydride, or into the sulfonic acid ester by reaction with a sulfonic acid halide;
d) converting a compound of the formula (I) in which Z is -COOR3 in which R3 is not hydrogen into a salt (Z = COOR3 in which R3 is a cation as defined in claim 1, or the free acid (Z = COOH);
e) reacting a compound of the formula I in which Z is -COOR3 with ammonia, an amine or hydrazine to give the acid amide (Z = CONHR5) or acid hydrazide ;
f) reacting a compound of the formula (I) in which Z is -COOH to give the acid halide and converting the latter into the acid amide, acid hydrazide or ester by reaction with an amine, a hydrazine or an alcohol;
g) transesterifying a compound of the formula (I) in which Z is a low molecular weight ester group with an alcohol of the formula R3OH;
h) dehydrating a compound of the formula (I) in which Z is -CO-NH2 and converting the nitrile obtained (Z = CN), if desired, into the corresponding thioamide (Z = CS-NH2) by addition of H2S.
b) reacting a compound of the formula IV
(IV) in which R, n, A and X are as defined in claim 1, with a compound of the formula V
(V) in which W is halogen, toluenesulfonyl or methanesulfonyl radical, Rl and Z
are as defined in claim l;
c) hydrogenating a compound of the formula (I) in which Z is -COOR3 and optionally converting the alcohol obtained (Z = CH2OH) into the correspond-ing carboxylic acid ester by reaction with a carboxylic anhydride, or into the sulfonic acid ester by reaction with a sulfonic acid halide;
d) converting a compound of the formula (I) in which Z is -COOR3 in which R3 is not hydrogen into a salt (Z = COOR3 in which R3 is a cation as defined in claim 1, or the free acid (Z = COOH);
e) reacting a compound of the formula I in which Z is -COOR3 with ammonia, an amine or hydrazine to give the acid amide (Z = CONHR5) or acid hydrazide ;
f) reacting a compound of the formula (I) in which Z is -COOH to give the acid halide and converting the latter into the acid amide, acid hydrazide or ester by reaction with an amine, a hydrazine or an alcohol;
g) transesterifying a compound of the formula (I) in which Z is a low molecular weight ester group with an alcohol of the formula R3OH;
h) dehydrating a compound of the formula (I) in which Z is -CO-NH2 and converting the nitrile obtained (Z = CN), if desired, into the corresponding thioamide (Z = CS-NH2) by addition of H2S.
11). A method of combating weeds which comprises applying to the locus of weed growth an effective amount of a compound as claimed in claim 1.
12). A method according to claim 11 wherein the compound is the compound according to claim 4 or 5.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEP2907089.1 | 1979-02-23 | ||
| DE19792907089 DE2907089A1 (en) | 1979-02-23 | 1979-02-23 | HERBICIDAL AGENTS |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1149392A true CA1149392A (en) | 1983-07-05 |
Family
ID=6063752
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000346284A Expired CA1149392A (en) | 1979-02-23 | 1980-02-22 | Heterocyclic phenoxyalkanoic acid derivatives |
Country Status (19)
| Country | Link |
|---|---|
| EP (1) | EP0015005B1 (en) |
| JP (1) | JPS55120568A (en) |
| AR (1) | AR228252A1 (en) |
| AT (1) | ATE7227T1 (en) |
| AU (1) | AU529343B2 (en) |
| BR (1) | BR8001048A (en) |
| CA (1) | CA1149392A (en) |
| DD (1) | DD149152A5 (en) |
| DE (2) | DE2907089A1 (en) |
| EG (1) | EG14164A (en) |
| ES (1) | ES488659A1 (en) |
| GR (1) | GR82631B (en) |
| HU (1) | HU185875B (en) |
| IL (1) | IL59440A (en) |
| MA (1) | MA18753A1 (en) |
| PL (1) | PL222199A1 (en) |
| PT (1) | PT70862A (en) |
| ZA (1) | ZA801039B (en) |
| ZW (1) | ZW4180A1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4831152A (en) * | 1984-06-15 | 1989-05-16 | Fuji Photo Film Co., Ltd. | 5-halo-6-nitro-2-substituted benzoxazole compounds |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH03173874A (en) * | 1989-09-29 | 1991-07-29 | Mitsubishi Kasei Corp | New heterocyclic compound |
| DE60118748T2 (en) * | 2000-07-04 | 2007-05-16 | Kyoyu Agri Co., Ltd., Kawasaki | BENZOXAZOLE COMPOUNDS, PROCESS FOR THEIR PREPARATION AND HERBICIDES |
| US20050250831A1 (en) * | 2002-02-21 | 2005-11-10 | Gibson Tracey A | Peroxisome proliferator activated receptor modulators |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1157556A (en) * | 1966-06-09 | 1969-07-09 | Egyt Gyogyszervegyeszeti Gyar | Novel Benzazole Derivatives and the Preparation thereof |
| BE754245A (en) * | 1969-08-01 | 1970-12-31 | Sumitomo Chemical Co | PHENOXY CARBOXYLIC ACID DERIVATIVES |
| DE2640730C2 (en) * | 1976-09-10 | 1983-08-25 | Hoechst Ag, 6230 Frankfurt | Benzoxazolyloxy and benzothiazolyloxyphenoxy compounds and herbicidal agents containing them |
-
1979
- 1979-02-23 DE DE19792907089 patent/DE2907089A1/en not_active Withdrawn
-
1980
- 1980-02-15 ES ES488659A patent/ES488659A1/en not_active Expired
- 1980-02-21 AR AR280048A patent/AR228252A1/en active
- 1980-02-21 GR GR61255A patent/GR82631B/el unknown
- 1980-02-21 IL IL59440A patent/IL59440A/en unknown
- 1980-02-21 ZW ZW41/80A patent/ZW4180A1/en unknown
- 1980-02-21 DD DD80219199A patent/DD149152A5/en unknown
- 1980-02-22 DE DE8080100876T patent/DE3067603D1/en not_active Expired
- 1980-02-22 CA CA000346284A patent/CA1149392A/en not_active Expired
- 1980-02-22 AT AT80100876T patent/ATE7227T1/en not_active IP Right Cessation
- 1980-02-22 ZA ZA00801039A patent/ZA801039B/en unknown
- 1980-02-22 EP EP80100876A patent/EP0015005B1/en not_active Expired
- 1980-02-22 PT PT70862A patent/PT70862A/en unknown
- 1980-02-22 HU HU80419A patent/HU185875B/en unknown
- 1980-02-22 MA MA18951A patent/MA18753A1/en unknown
- 1980-02-22 BR BR8001048A patent/BR8001048A/en unknown
- 1980-02-22 JP JP2066980A patent/JPS55120568A/en active Pending
- 1980-02-22 PL PL22219980A patent/PL222199A1/xx unknown
- 1980-02-22 AU AU55805/80A patent/AU529343B2/en not_active Ceased
- 1980-02-23 EG EG104/80A patent/EG14164A/en active
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4831152A (en) * | 1984-06-15 | 1989-05-16 | Fuji Photo Film Co., Ltd. | 5-halo-6-nitro-2-substituted benzoxazole compounds |
Also Published As
| Publication number | Publication date |
|---|---|
| DE3067603D1 (en) | 1984-05-30 |
| EG14164A (en) | 1983-03-31 |
| AR228252A1 (en) | 1983-02-15 |
| IL59440A (en) | 1985-09-29 |
| AU5580580A (en) | 1980-08-28 |
| EP0015005B1 (en) | 1984-04-25 |
| PL222199A1 (en) | 1980-12-15 |
| AU529343B2 (en) | 1983-06-02 |
| DD149152A5 (en) | 1981-07-01 |
| ZA801039B (en) | 1981-03-25 |
| EP0015005A1 (en) | 1980-09-03 |
| MA18753A1 (en) | 1980-10-01 |
| JPS55120568A (en) | 1980-09-17 |
| PT70862A (en) | 1980-03-01 |
| BR8001048A (en) | 1980-10-29 |
| ZW4180A1 (en) | 1980-09-10 |
| DE2907089A1 (en) | 1980-09-04 |
| ATE7227T1 (en) | 1984-05-15 |
| HU185875B (en) | 1985-04-28 |
| GR82631B (en) | 1985-02-07 |
| ES488659A1 (en) | 1980-09-16 |
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