CA1091240A - Phenoxy-phenoxy-alkanecarboxylic acid derivatives having a herbicidal action, their production, compositions containing them, and their use - Google Patents
Phenoxy-phenoxy-alkanecarboxylic acid derivatives having a herbicidal action, their production, compositions containing them, and their useInfo
- Publication number
- CA1091240A CA1091240A CA320,024A CA320024A CA1091240A CA 1091240 A CA1091240 A CA 1091240A CA 320024 A CA320024 A CA 320024A CA 1091240 A CA1091240 A CA 1091240A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D213/72—Nitrogen atoms
- C07D213/75—Amino or imino radicals, acylated by carboxylic or carbonic acids, or by sulfur or nitrogen analogues thereof, e.g. carbamates
-
- 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
- A01N39/00—Biocides, pest repellants or attractants, or plant growth regulators containing aryloxy- or arylthio-aliphatic or cycloaliphatic compounds, containing the group or, e.g. phenoxyethylamine, phenylthio-acetonitrile, phenoxyacetone
- A01N39/02—Aryloxy-carboxylic 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
- A01N39/00—Biocides, pest repellants or attractants, or plant growth regulators containing aryloxy- or arylthio-aliphatic or cycloaliphatic compounds, containing the group or, e.g. phenoxyethylamine, phenylthio-acetonitrile, phenoxyacetone
- A01N39/02—Aryloxy-carboxylic acids; Derivatives thereof
- A01N39/04—Aryloxy-acetic acids; Derivatives thereof
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C205/00—Compounds containing nitro groups bound to a carbon skeleton
- C07C205/27—Compounds containing nitro groups bound to a carbon skeleton the carbon skeleton being further substituted by etherified hydroxy groups
- C07C205/35—Compounds containing nitro groups bound to a carbon skeleton the carbon skeleton being further substituted by etherified hydroxy groups having nitro groups and etherified hydroxy groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton
- C07C205/36—Compounds containing nitro groups bound to a carbon skeleton the carbon skeleton being further substituted by etherified hydroxy groups having nitro groups and etherified hydroxy groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton to carbon atoms of the same non-condensed six-membered aromatic ring or to carbon atoms of six-membered aromatic rings being part of the same condensed ring system
- C07C205/38—Compounds containing nitro groups bound to a carbon skeleton the carbon skeleton being further substituted by etherified hydroxy groups having nitro groups and etherified hydroxy groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton to carbon atoms of the same non-condensed six-membered aromatic ring or to carbon atoms of six-membered aromatic rings being part of the same condensed ring system the oxygen atom of at least one of the etherified hydroxy groups being further bound to a carbon atom of a six-membered aromatic ring, e.g. nitrodiphenyl ethers
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C327/00—Thiocarboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C43/00—Ethers; Compounds having groups, groups or groups
- C07C43/02—Ethers
- C07C43/257—Ethers having an ether-oxygen atom bound to carbon atoms both belonging to six-membered aromatic rings
- C07C43/29—Ethers having an ether-oxygen atom bound to carbon atoms both belonging to six-membered aromatic rings containing halogen
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C43/00—Ethers; Compounds having groups, groups or groups
- C07C43/02—Ethers
- C07C43/257—Ethers having an ether-oxygen atom bound to carbon atoms both belonging to six-membered aromatic rings
- C07C43/295—Ethers having an ether-oxygen atom bound to carbon atoms both belonging to six-membered aromatic rings containing hydroxy or O-metal groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C59/00—Compounds having carboxyl groups bound to acyclic carbon atoms and containing any of the groups OH, O—metal, —CHO, keto, ether, groups, groups, or groups
- C07C59/40—Unsaturated compounds
- C07C59/58—Unsaturated compounds containing ether groups, groups, groups, or groups
- C07C59/64—Unsaturated compounds containing ether groups, groups, groups, or groups containing six-membered aromatic rings
- C07C59/66—Unsaturated compounds containing ether groups, groups, groups, or groups containing six-membered aromatic rings the non-carboxylic part of the ether containing six-membered aromatic rings
- C07C59/68—Unsaturated compounds containing ether groups, groups, groups, or groups containing six-membered aromatic rings the non-carboxylic part of the ether containing six-membered aromatic rings the oxygen atom of the ether group being bound to a non-condensed six-membered aromatic ring
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D295/00—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms
- C07D295/16—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms acylated on ring nitrogen atoms
- C07D295/18—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms acylated on ring nitrogen atoms by radicals derived from carboxylic acids, or sulfur or nitrogen analogues thereof
- C07D295/182—Radicals derived from carboxylic acids
- C07D295/185—Radicals derived from carboxylic acids from aliphatic carboxylic acids
Abstract
ABSTRACT OF THE DISCLOSURE
Novel phenoxy-phenoxy-alkanecarboxylic acid derivatives having a herbicidal action and an action regulatlng plant growth, their production, compositions containing them, and the use thereof are described. The acid derivatives correspond to the formula
Novel phenoxy-phenoxy-alkanecarboxylic acid derivatives having a herbicidal action and an action regulatlng plant growth, their production, compositions containing them, and the use thereof are described. The acid derivatives correspond to the formula
Description
-lO9~Z40 Case 5-11548/=
NOVEL PHENOXY-PHENOXY-ALKANECARBOXYLIC ACID DERIVATIVES
HAVING A HERBICIDAL ACTION, THEIR PRODUCTION~
COMPOSITIONS CONTAINI~C IH~M~ AND THEIR USE_ The present invention relates to novel phenoxy-phenoxy-alkanecarboxylic acid derivatives which have a herbicidal action and an action regulating plant growth, to processes for producing them, to compositions containing these derivatives as active substances, and also to the use of these phenoxy-phenoxy-alkanecarboxylic acid derivatives, or of compositions containing them~ for regulating plant growth.
The phenoxy-phenoxy-alkanecarboxylic acid derivatives are novel compounds and correspond to the formula I
; ' C~ o-~ -B .(I) P
in which Rl is hydrogen, Cl-C4 alkyl or C2-C3 alkoxyalkyl, A is the cyano group or a radical -COR, wherein R is a radical -OR3, SR4-NR5R6 or -N-R2, wherein ~3 is hydrogen or ~k .: . . ,. .. : : ~ . :
~ .
..
.
.
,.. ~ .
~C~91 2 40
NOVEL PHENOXY-PHENOXY-ALKANECARBOXYLIC ACID DERIVATIVES
HAVING A HERBICIDAL ACTION, THEIR PRODUCTION~
COMPOSITIONS CONTAINI~C IH~M~ AND THEIR USE_ The present invention relates to novel phenoxy-phenoxy-alkanecarboxylic acid derivatives which have a herbicidal action and an action regulating plant growth, to processes for producing them, to compositions containing these derivatives as active substances, and also to the use of these phenoxy-phenoxy-alkanecarboxylic acid derivatives, or of compositions containing them~ for regulating plant growth.
The phenoxy-phenoxy-alkanecarboxylic acid derivatives are novel compounds and correspond to the formula I
; ' C~ o-~ -B .(I) P
in which Rl is hydrogen, Cl-C4 alkyl or C2-C3 alkoxyalkyl, A is the cyano group or a radical -COR, wherein R is a radical -OR3, SR4-NR5R6 or -N-R2, wherein ~3 is hydrogen or ~k .: . . ,. .. : : ~ . :
~ .
..
.
.
,.. ~ .
~C~91 2 40
- 2 -the cation of a base 1 M m ~3 wherein M is an alkali metal cation or alkaline-earth metal cation, or an Fe, Cu, Zn, Mn or Ni cation, or an ammonium group ~- N -Rd ~ and /\
Rb Rc m as integer 1, 2 or 3 takes into account the valency of the cation, whilst Ra~ Rb, Rc and Rd independently of one another are hydrogen, benzyl or a Cl-C4 alkyl group unsubstituted or substituted by -OH, -NH2 or Cl-C4 alkoxy, and in addition R3 is a Cl-C12 alkyl group which is unsubstituted or :
substituted by halogen, nitro, cyano, Cl-C8 alkoxy, .
Cl-C8 alkylthio, C2-C8 alkanoyl, bis (Cl-C4 alkyl) ~.
amino, tris (Cl-C4 alkyl) ammonium, C3-C8 cycloalkyl, C3-C8 cycloalkenyl, or by a phenyl, phenoxy or 5- or 6-membered heterocyclic radical having 1 to 3 hetero :~
atoms, each of which is unsubstituted or for its part mono- or polysubstituted by halogen, Cl-C4 alkyl or Cl-C4 alkoxy, or R3 is an unsubstituted or substituted C3-C18 alkenyl group, :
a C3-C8 alkynyl group, a C3-C12 cycloalkyl group unsubstituted or substituted by halogen or Cl-C4 alkyl, or R3 is a phenyl group which is unsubstituted or mono- or polysubstituted by halogen, Cl-C4 alkyl, Cl-C4 alkoxy, Cl-C4 alkylthio, N02 or CF3, or R3 is a S- or 6-membered heterocyclic ring having 1 to 3 hetero at s, and R4 is the same as R3, R5 and R6 independently of one another are each hydrogen, or an alkyl group which can be unsubstituted or .. . . ., . - : .
.-: ~ -- , . - ~ .. .
. - ,, . -~: ' . ; '' -.
i 109~240 substituted by hydroxyl or alkoxy, or they are each alkoxy, alkenyl, alkynyl, phenyl or benzyl, and the phenyl rings can be mono- or polysubstituted by halogen, alkyl, alkoxy, alkylthio, cyano or nitro, or R5 and R6 together with the nitrogen atom to which they are bound can form a 5- or 6-membered heterocycle, which can also contain a second hetero atom, nitrogen oxygen or sulfur, R2 is a preferably branched-chain alkylene group bound by a double bond to the nitrogen atom, B is a hydrogen or halogen atom, or a cyano or nitro group, C is halogen, cyano, nitro or trifluoromethyl, D is hydrogen, halogen, or a cyano, nitro or trifluoromethyl group, E is a halogen atom or a Cl-C4 alkyl group, and P is the number 1 or 2.
In this formula, the alkyl groups are both branched-chain and straight-chain and contain the given number of carbon atoms. The radicals R5 and R6 are preferably hydrogen and Cl-C4 alkyl groups. Some among them can however also be substituted alkyl groups, or one of them can be an unsubstituted or substituted phenyl group or benzyl, or together with the nitrogen atom to which they are bound they can also form a heterocycle pre-ferably containing 5 or 6 ring members.
This invention discloses a novel group of phenoxy-phenoxy-and phenoxy-phenylthio-alkanecarboxylic acid derivatives, respectively, which in small applied amounts already exhibit a strong herbicidal action ~ 3 ~
.
.
. . ' , . -:
lO91Z~O
and/or are able to regulate plant growth in some other manner useful in agriculture.
The novel active substances cf the formula I can be used as herbicides in the pre-emergence process but mainly - 3a -,,,~ , ~
, ' " ' '` ' .~ ' ' ' ~ .
in the post-emergence process. They have a good action against broad-leaved plants (dicotyledons).
The derivatives according to the invention also have a favourable growth-regulating action (growth inhibition).
They inhibit the growth in particular of dicotyledonous plants, and can be used in a profitable manner for example as follows:
- reduction of vegetative growth in the case of soya-bean plants and similar leguminosae, an effect which leads to an increase in the yield of these crops;
- reduction of the undesirable growth of side shoots on tobacco plants, the leading shoots of which have been cut, an effect which promotes the formation of larger and better leaves; and - reduction of the growth of grass and of dicotyledonous plants, such as fruit trees, ornamental trees, shrubs and hedges, for the purpose of economising in the amount of cutting work.
The compounds of the present invention are negligibly toxic to warm-blooded animals, and application of the compounds presents no problems. The suggested amounts to apply are between 0.1 and 5 kg per hectare.
Phenoxy-phenoxy-alkanecarboxylic acid derivatives having a herbicidal action and similar chemical structure have already become known from a series of recent publications. Reference is made in this respect to the German Offenlegungsschriften Nos. 2,311,638, 2,609,461, 2,623,558, 2,639,796, 2,643,438, 2,652,384 and 2,730,591, and also to C.A. 86 (1977) 134 874x. The present compounds are different from those mentioned in these publications, and exhibit, in spite of their pronounced action on dicotyledonous weeds, excellent selectivity with respect to .
.
broad-leaved cultivated plants, such as sugar beet and soya-bean plants.
The novel compounds of the formula I are produced by methods known per se for the synthesis of phenoxy-phenoxy-alkanecarboxylic acids and derivatives thereof.
One of these processes comprises reacting according to the invention an appropriately substituted halogeno-phenol of the formula II
- D
C ~ Hal (II) , in which "Hal" is a halogen atom, preferably chlorine or .
bromine, and C and ~ have the meanings defined under the formula I, with an appropriately substituted hydroxy-phenoxy-alkanecarboxylic acid derivative of the .. . - ~
formula III 1 ,, 0 -.C - A
HO ~ B 2 (III), r ~
Ep in which B, E, p, Rl, R2 and A are as defined ~1nder the formula I, in the presence of a base.
A second process comprises using according to the invention an appropriately substituted m-hydroxy-diphenyl ether of the formula IV
D OH
B (IV), Ep in which B, C, D, E and p are as defined under the formula I, as the starting material, and reacting this with an - . ~ . . . ~.
1o~g1 2 4~
a-halogenoalkanoic acid derivative of the formula V
Hal - C - A (V) in which "Hal" is a halogen atom, preferably chlorine or bromine, and Rl, R2 and A are as defined under the formula I, in the presence of a base.
If in these processes there is used as starting material (A=COOH) Gf the formulae III and V, respec~ively, a carboxylic acid, this group can subsequently be converted, for example by esterification, and so forth, into another derivative of the formula I as defined. Conversely, it is possible with use of an ester of the formulae III and V, respectively, to finally convert the ester group by saponi-fication into the free carboxylic acid or into a salt thereof.
The reactions mentioned can be performed in the presence or absence of solvents or diluents inert to the reactants.
Polar organic solvents such as methyl ethyl ketone, dimethyl-formamide, dimethylsulfoxide, and so forth, are preferred.
The reaction temperatures are between O and 200C, and the duration of the reaction, depending on starting material, the chosen reaction temperature and the solvent, is between 1 hour and several days. The reaction is performed as a rule at normal pressure. The customary bases (condensation agents), for example KOH, NaOCH3, NaHC03, H2C03, potassium-tert-butylate, and so forth, are suitable for the reaction, but also organic bases are suitable, such as triethylamine, and the like.
The starting materials of the formulae II to V are in some cases known. Starting materials of these formulae which have still not been described can be readily produced ...
'~
~09lZ40 by customary processes and techniques. Phenoxyphenols of the formula IV can be produced for example by the methods described in J.A.C.S. 61, 2702 (1939), or in Chem. Abstracts 54, 922h (1960).
The following Examples illustrate the processes according to the invention. Further active substances produced in a corresponding manner are listed in the Table which follows. Temperature values are given in degrees Centigrade, and percentages in per cent by weight.
, - - . ~ ., :
, . ~ - . ' ' ~, , , 1~)91Z40 Example 1 a- [3-(2'-Cnloro-4'-trifluoromethylphenoxy)-4-chloro-phenoxy]-propionic acid methyl ester , O-C~I-COOCH3 '' '' Cl Cl a) 11.5 g o~ 2-chloro-4-trifluoromethyl-2'-chloro-S'-hydroxydiphenyl ether is dissolved in 50 ml of 2-butanone, and, after the addition of 30 ml of 2-bromopropionic acid methyl ester, 12 g of potassium carbonate and a spatula-tip of potassium iodide, the whole is stirred overnight at 80C. The reaction product is diluted with 100 ml of acetone and filtered off. The solvent is distilled off, and the residue is distilled under high vacuum to yield 12.8 g of the above-mentioned product, which has a boiling point of 147C at 0.04 Torr.
The starting product, 2-chloro-4-trifluoromethyl-2'-chloro-5'-hydroxydiphenyl ether, is produced as follows:
b) 20 g (0.33 mol) of pulverised potassium hydroxide is placed into 200 ml of dimethyl sulfoxide, and 48 g (0.3 mol) of 2-chloro-3-methoxyphenol is added in portions. After everything has gone into solution, 70 g (0.33 mol) of
Rb Rc m as integer 1, 2 or 3 takes into account the valency of the cation, whilst Ra~ Rb, Rc and Rd independently of one another are hydrogen, benzyl or a Cl-C4 alkyl group unsubstituted or substituted by -OH, -NH2 or Cl-C4 alkoxy, and in addition R3 is a Cl-C12 alkyl group which is unsubstituted or :
substituted by halogen, nitro, cyano, Cl-C8 alkoxy, .
Cl-C8 alkylthio, C2-C8 alkanoyl, bis (Cl-C4 alkyl) ~.
amino, tris (Cl-C4 alkyl) ammonium, C3-C8 cycloalkyl, C3-C8 cycloalkenyl, or by a phenyl, phenoxy or 5- or 6-membered heterocyclic radical having 1 to 3 hetero :~
atoms, each of which is unsubstituted or for its part mono- or polysubstituted by halogen, Cl-C4 alkyl or Cl-C4 alkoxy, or R3 is an unsubstituted or substituted C3-C18 alkenyl group, :
a C3-C8 alkynyl group, a C3-C12 cycloalkyl group unsubstituted or substituted by halogen or Cl-C4 alkyl, or R3 is a phenyl group which is unsubstituted or mono- or polysubstituted by halogen, Cl-C4 alkyl, Cl-C4 alkoxy, Cl-C4 alkylthio, N02 or CF3, or R3 is a S- or 6-membered heterocyclic ring having 1 to 3 hetero at s, and R4 is the same as R3, R5 and R6 independently of one another are each hydrogen, or an alkyl group which can be unsubstituted or .. . . ., . - : .
.-: ~ -- , . - ~ .. .
. - ,, . -~: ' . ; '' -.
i 109~240 substituted by hydroxyl or alkoxy, or they are each alkoxy, alkenyl, alkynyl, phenyl or benzyl, and the phenyl rings can be mono- or polysubstituted by halogen, alkyl, alkoxy, alkylthio, cyano or nitro, or R5 and R6 together with the nitrogen atom to which they are bound can form a 5- or 6-membered heterocycle, which can also contain a second hetero atom, nitrogen oxygen or sulfur, R2 is a preferably branched-chain alkylene group bound by a double bond to the nitrogen atom, B is a hydrogen or halogen atom, or a cyano or nitro group, C is halogen, cyano, nitro or trifluoromethyl, D is hydrogen, halogen, or a cyano, nitro or trifluoromethyl group, E is a halogen atom or a Cl-C4 alkyl group, and P is the number 1 or 2.
In this formula, the alkyl groups are both branched-chain and straight-chain and contain the given number of carbon atoms. The radicals R5 and R6 are preferably hydrogen and Cl-C4 alkyl groups. Some among them can however also be substituted alkyl groups, or one of them can be an unsubstituted or substituted phenyl group or benzyl, or together with the nitrogen atom to which they are bound they can also form a heterocycle pre-ferably containing 5 or 6 ring members.
This invention discloses a novel group of phenoxy-phenoxy-and phenoxy-phenylthio-alkanecarboxylic acid derivatives, respectively, which in small applied amounts already exhibit a strong herbicidal action ~ 3 ~
.
.
. . ' , . -:
lO91Z~O
and/or are able to regulate plant growth in some other manner useful in agriculture.
The novel active substances cf the formula I can be used as herbicides in the pre-emergence process but mainly - 3a -,,,~ , ~
, ' " ' '` ' .~ ' ' ' ~ .
in the post-emergence process. They have a good action against broad-leaved plants (dicotyledons).
The derivatives according to the invention also have a favourable growth-regulating action (growth inhibition).
They inhibit the growth in particular of dicotyledonous plants, and can be used in a profitable manner for example as follows:
- reduction of vegetative growth in the case of soya-bean plants and similar leguminosae, an effect which leads to an increase in the yield of these crops;
- reduction of the undesirable growth of side shoots on tobacco plants, the leading shoots of which have been cut, an effect which promotes the formation of larger and better leaves; and - reduction of the growth of grass and of dicotyledonous plants, such as fruit trees, ornamental trees, shrubs and hedges, for the purpose of economising in the amount of cutting work.
The compounds of the present invention are negligibly toxic to warm-blooded animals, and application of the compounds presents no problems. The suggested amounts to apply are between 0.1 and 5 kg per hectare.
Phenoxy-phenoxy-alkanecarboxylic acid derivatives having a herbicidal action and similar chemical structure have already become known from a series of recent publications. Reference is made in this respect to the German Offenlegungsschriften Nos. 2,311,638, 2,609,461, 2,623,558, 2,639,796, 2,643,438, 2,652,384 and 2,730,591, and also to C.A. 86 (1977) 134 874x. The present compounds are different from those mentioned in these publications, and exhibit, in spite of their pronounced action on dicotyledonous weeds, excellent selectivity with respect to .
.
broad-leaved cultivated plants, such as sugar beet and soya-bean plants.
The novel compounds of the formula I are produced by methods known per se for the synthesis of phenoxy-phenoxy-alkanecarboxylic acids and derivatives thereof.
One of these processes comprises reacting according to the invention an appropriately substituted halogeno-phenol of the formula II
- D
C ~ Hal (II) , in which "Hal" is a halogen atom, preferably chlorine or .
bromine, and C and ~ have the meanings defined under the formula I, with an appropriately substituted hydroxy-phenoxy-alkanecarboxylic acid derivative of the .. . - ~
formula III 1 ,, 0 -.C - A
HO ~ B 2 (III), r ~
Ep in which B, E, p, Rl, R2 and A are as defined ~1nder the formula I, in the presence of a base.
A second process comprises using according to the invention an appropriately substituted m-hydroxy-diphenyl ether of the formula IV
D OH
B (IV), Ep in which B, C, D, E and p are as defined under the formula I, as the starting material, and reacting this with an - . ~ . . . ~.
1o~g1 2 4~
a-halogenoalkanoic acid derivative of the formula V
Hal - C - A (V) in which "Hal" is a halogen atom, preferably chlorine or bromine, and Rl, R2 and A are as defined under the formula I, in the presence of a base.
If in these processes there is used as starting material (A=COOH) Gf the formulae III and V, respec~ively, a carboxylic acid, this group can subsequently be converted, for example by esterification, and so forth, into another derivative of the formula I as defined. Conversely, it is possible with use of an ester of the formulae III and V, respectively, to finally convert the ester group by saponi-fication into the free carboxylic acid or into a salt thereof.
The reactions mentioned can be performed in the presence or absence of solvents or diluents inert to the reactants.
Polar organic solvents such as methyl ethyl ketone, dimethyl-formamide, dimethylsulfoxide, and so forth, are preferred.
The reaction temperatures are between O and 200C, and the duration of the reaction, depending on starting material, the chosen reaction temperature and the solvent, is between 1 hour and several days. The reaction is performed as a rule at normal pressure. The customary bases (condensation agents), for example KOH, NaOCH3, NaHC03, H2C03, potassium-tert-butylate, and so forth, are suitable for the reaction, but also organic bases are suitable, such as triethylamine, and the like.
The starting materials of the formulae II to V are in some cases known. Starting materials of these formulae which have still not been described can be readily produced ...
'~
~09lZ40 by customary processes and techniques. Phenoxyphenols of the formula IV can be produced for example by the methods described in J.A.C.S. 61, 2702 (1939), or in Chem. Abstracts 54, 922h (1960).
The following Examples illustrate the processes according to the invention. Further active substances produced in a corresponding manner are listed in the Table which follows. Temperature values are given in degrees Centigrade, and percentages in per cent by weight.
, - - . ~ ., :
, . ~ - . ' ' ~, , , 1~)91Z40 Example 1 a- [3-(2'-Cnloro-4'-trifluoromethylphenoxy)-4-chloro-phenoxy]-propionic acid methyl ester , O-C~I-COOCH3 '' '' Cl Cl a) 11.5 g o~ 2-chloro-4-trifluoromethyl-2'-chloro-S'-hydroxydiphenyl ether is dissolved in 50 ml of 2-butanone, and, after the addition of 30 ml of 2-bromopropionic acid methyl ester, 12 g of potassium carbonate and a spatula-tip of potassium iodide, the whole is stirred overnight at 80C. The reaction product is diluted with 100 ml of acetone and filtered off. The solvent is distilled off, and the residue is distilled under high vacuum to yield 12.8 g of the above-mentioned product, which has a boiling point of 147C at 0.04 Torr.
The starting product, 2-chloro-4-trifluoromethyl-2'-chloro-5'-hydroxydiphenyl ether, is produced as follows:
b) 20 g (0.33 mol) of pulverised potassium hydroxide is placed into 200 ml of dimethyl sulfoxide, and 48 g (0.3 mol) of 2-chloro-3-methoxyphenol is added in portions. After everything has gone into solution, 70 g (0.33 mol) of
3,4-dichlorobenzotrifluoride is added dropwise fairly quickly, and stirring is maintained for about 12 hours at 150C (bath temperature). The reaction product is poured into ice/water, and extracted with toluene/ethyl acetate (1:1). The solvent is distilled off to leave 91 g of 2-chloro-4-trifluoromethyl-2'-chloro-5'-methoxydiphenyl ether in the form of oil, which is distilled under high vacuum; boiling point 119-123C at 0.25 Torr; yield 59.5 g .. , .,, , ... .. . , , , ~, . _, _ . _ .. . _ . , ... . .... , . .. ., . .. , .. . , . .. .. , .. , . , . ,, _ .. _ .
.. .. . .. .. .
.. , :
.
, ~,, "~
.. - - .
~' ' . .
IQ91~40 (59% of theory).
c) 32 g of 2-chloro-4-trifluoromethyl-2'-chloro-5'-methoxydipheny~ ether is diss~lved in 700 ml of glacial acetic acid, and 170 ml of 48% hydrobromic acid is added.
The mixture is refluxed for 60 hours with stirring at a bath temperature of 120C, and the glacial acetic acid is subsequently distilled off. The oil remaining behind is taken up in toluene, and washed with a solution of sodium bicarbonate/sodium thiosulfate. The solvent is distilled off to leave 28 g of 2-chloro-4-trifluoromethyl-2'-chloro-5~-hydroxydiphenyl ether in the form of viscous oil, which is distilled under high vacuum; yield 19.5 g;
boiling point 132C at 0.25 Torr.
Example 2 a-l3-(4'-Trifluoromethylphenoxy)-4,6-dichlorophenoxy]-propionic acid methyl ester 0-CH-COOC~3 CF3 ~ 0 ~ 1 Cl 34 g (0.1 mol) of 3-(4'-trifluoromethylphenoxy)-a-(phenoxy)-propionic acid methyl ester (produced analogously to Example 1) is dissolved in 100 ml of glacial acetic acid, and at 40C chlorine is fed in in excess. The reac-tion is followed by means of gas-chromatography. After the reaction has ended, the reaction mixture is stirred for a further half hour, and excess chlorine is removed by the introduction of nitrogen. The solvent is distilled off, and the oil thus obtained is distilled under high vacuum to yield 34.5 g of the above product in the form .
. ~ .
....
of oil, which is distilled under high vacuum; boiling point 163-165C at 0.07 Torr.
Example 3 a- [ 3-(4'-Trifluoromethylphenoxy)-S-methylphenoxy]-propionic acid methyl ester CF3 ~ o ~ CH3 CH
a) 13.0 g (0.0485 mol) of 5-(4-trifluoromethylphenoxy)-m-cresol, 7.6 g (0.055 mol) of potassium carbonate and 50 ml of methyl ethyl ketone are refluxed for 2 hours with stirring. There is then added at 50C 8.4 g (0.05 mol) of 2-bromopropionic acid methyl ester, and the mixture is stirred at 50C for 15 hours. After cooling, it is filtered, and the filtrate is concentrated in vacuo.
The residue is filtered with methylene chloride through a small column to obtain 16.1 g (93.6% of theory) of the above product in the form of a clear light-yellow oil having a refractive index of nD = 1.5104. The starting material, 5-(4-trifluoromethylphenoxy-m-cresol, is produced as follows:
b) 35.5 g ~0.25 mol) of orcinol.H20 (3,5-dihydroxytoluene) is dissolved in 200 ml of dimethyl sulfoxide, and 31.3 g (0.5 mol) of potassium hydroxide (90%), which is finely pulverised, is added. As soon as everything has gone into solution, 45.1 g (0.25 mol) of 4- chlorobenzenetriflu-oride is added, and the reaction mixture is stirred at 150C for 20 hours. It is then cooled, 200 ml of 10% HCl is added, and extraction is performed with methylene chloride. The organic phase is dried, and concentrated ~7 , . . .,, . .. .. , . . ~ . ~ , .
- . , - . . -- - , , - - .. . ..
........ .. . .
- , , .
,., . . , , . , :
, by evaporation. The residue is separated through a small silica gel column with methylene chloride. There is obtained as the main fraction 29.8 g (44.4/O of theory) of 5-(4-trifluoromethylphenoxy)-m-cresol in the form of clear light-yellow oil having a refractive index of nD - 1.5322.
Example 4 a-[3-(4'-Trifluoromethylphenoxy)-5-methyl-6-chlorophenoxyl-propionic acid methyl ester O -CH -COOCH
CF3 ~ ~ Cl 3 a) 1.7 g (0.0056 mol) of 5-(4'-trifluoromethylphenoxy)-2-chloro-m-cresol is stirred with 0.23 g (0.0062 mol) of potassium carbonate in 20 ml of ethyl methyl ketone for 2 hours under reflux. There is then added at 50C 1.0 g ~0.0062 mol) of 2-bromopropionic acid methyl ester, and the mixture is stirred at 60C for 15 hours. It is sub-sequently filtered and the filtrate is concentrated by evaporation. The residue is filtered with methylene chloride through a small column, and the main fraction is concentrated by evaporation to yield 1.6 g (76.2% of theory) of thP above product in the form of yellow oil having the refractive index nD - 1.5119.
The 5-(4'-trifluoromethylphenoxy)-2-chloro-m-cresol used as starting material is produced as follows:
b) 13.4 g (0.05 mol) of 5-(4-trifluoromethylphenoxy)-m-cresol (for production of this see Example 3b) is dissolved in 50 ml of glacial acetic acid. To this solution is added droFwise at 15C 3.8 g of chlorine (0.055 mol) in 25 ml of J
..... ~ .. . ... .. .... ... . . .. . .. . .. .. ... ...
- : ' - ~ . -, :-. . ~ ., 109~Z40 glacial acetic acid, in the course of which the tempera-ture is held at 15C. The internal temperature is subsequently allowed to rise to room temperature. After 15 minutes, the reaction mixture is poured into water; it is extracted with methylene chloride, the organic phase is dried with sodium sulfate and is concentrated in vacuo.
The residue is chromatographed with hexane through a small silica gel column. The main fraction yields a clear light-coloured oil, which crystallises on being triturated with petroleum ether. There is thus obtained 1.7 g (11.3 % of theory) of 5-(4-trifluoromethylphenoxy)-2-chloro-m-cresol as a white product having a melting point of 106-110C.
Example 5 l~
a-[3-(4'-Trifluoromethylphenoxy)-5-methyl]-propionitrile ;~
CF3 ~ ~ CH3 13.0 g (0.0485 mol) of 5-(4'-trifluoromethylphenoxy)-m-cresol (for production of this see Example 3b), 7.6 g (0.055 mol) of potassium carbonate and 50 ml of methyl ethyl ketone are refluxed for 2 hours. There is then added at 40C 6.7 g (0.05 mol) of 2-bromopropionitrile, and the mixture is stirred at 60C for 15 hours. It is subsequently cooled and filtered, and the filtrate is concentrated in vacuo. The residue is filtered with methylene chloride through a small silica gel column to thus yield 14.4 g (90.0% of theory) of the above product in the form of a clPar brown oil having the refractive index nD s 1.5174.
~"
- . .
~ ;' ' ' . ' ' ~ "
~: , .' .
~09lZ40 Example 6 ~-[3-(4'-Trifluoromethylphenyl)-5-methylphenoxy]-propionic acid O - CH-COOH
CF3 ~ ~ CH3 39.0 g (O.ll mol) of a- 13-(4'-trifluoromethylphenoxy)-3-methylphenoxy]-propionic acid methyl ester (for its production see Example 3a) is dissolved in lOO ml o~
methanol, and a solution of lO.l g of sodium hydroxide (100%) in lO ml of water is added, in the course of which the temperature rises. The mixture is stirred at 50C - -for one further hour; lOO ml of ice/water is added to the reaction mixture, and the whole is acidified with concen- , trated hydrochloric acid. The produc~ which has precipitated is taken up in 200 ml of methylene chloride and dried. It is concentrated by evaporation to yield 23.8 g (63.4% of theory) of the above product in the form of a light-yellow crystalline powder having a melting point of 88-90C.
ExamPle 7 -[3-(4'-Trifluoromethylphenoxy)-5-methylphenoxy]-propionic acid allylamide OCH-CONEICH2-CH~CH2 a) 7.0 g (O.Ol9 mol) of a-13-(4'-trifluoromethylphenoxy)-5-methylphenoxy-propionic acid chloride is dissolved in 20 ml _ _ _ ,, .____. _ _ . ,. . . , , . . . ~ . ., .. _ _.. , .. . ~.. . ... .... .
. . . :
. .
. , of methylene chloride, and at 10C is added 2.8 g (0.042 mol) of allylamine. After 1 hour, 100 ml of water is added; the organic phase is then separated, and dried with sodium sulfate. ~t is concentrated by evaporation to obtain a clear light-yellow oil, which crystallises on being triturated with petroleum ether. In this manner is obtained the above product in the form of white crystals in a yield of 5.0 g (69.4% of theory3; melting point 94-96C. The acid chloride used as starting product is produced as follows:
b) 20 ml of thionyl chloride is added at room temperature to 13.8 g (0.04 mol) of a-(3-(4'-trifluoromethylphenoxy)-5-methylphenoxy)-propionic acid (for production of this see Example 6), and the temperature is then raised to 50C.
The reaction mixture is left to stand at this temperature for 2 hours, and is subsequently concentrated by evapor-ation; to the residue is added 50 ml of toluene, and the whole is evaporated to dryness in a good vacuum to thus yield, in the form of clear dark-brown oil, 14.3 g (100%
of theory) of a-(3-(4'-trifluoromethylphenoxy)-5-methyl-phenoxy)-propionic acid chloride.
ExamPle 8 a-l3-(2'-Chloro-4'-trifluoromethylphenoxy)-6-chlorophenoxy]-propionic acid methyl ester Cl O~H-COOCH3 CF3-~ O--~ ~--Cl 35.9 g of 3-(2'-chloro-4'-trifluoromethylphenoxy)~a-phenoxy-propionic acid methyl ester is dissolved in 100 ml of glacial acetic acid. Into this solution is then passed, . .
- ~ :
.. , . . . ~ ,: .
.
1(~91240 with thorough stirring, the theoretically required amount of chlorine, with the temperature being held at 40C. The reaction mixture is stirred for half an hour and the solvent is distilled off. Ligroin is added to the oily residue, and the crystals which have precipitated are filtered off. The title product thus obtained has a melting point of 79-80C~
Example 9 a-[3-(2'-Chloro-4'-trifluoromethyl)-6-chloro-4-iodophenoxy)-propionic acid methyl ester CH3 Cl O~H-COOCH
cF3~ o~
Cl 41 g of 3-(2'-chloro-4'-trifluoromethylphenoxy)-a-6-chlorophenoxy-propionic acid methyl ester is dissolved in 150 ml of glacial acetic acid. To this solution is added dropwise a solution of 20.5 g of iodine chloride in 30 ml of glacial acetic acid, and the reaction mixture is allowed to fully react for 15 minutes (slightly exothermic reaction) and, after the addition of 200 ml of water, the mixture is heated at 90C for 3 hours. There is then added a 5%
sodium bisulfite solution until the mixture is decolorised, a~d the oil which has precipitated is extracted with toluene/ethyl acetate (1:1). The solvent is distilled off to leave 47 g of oil which crystallises after the addition of ligroin. The crystals are filtered off to yield 32 g of the title product in the form of a white crystalline mass having a melting point of 102-105C.
'' ' , ' . ~
. , . ~ , . .
.
, , ~O~lZ~O
Example 10 a-l3-(2'-Chloro-4'-trifluoromethylphenoxy~-6-chloro-4-cyanophenoxyl-propionic acid methyl ester Cl 0-~H-COOCH3 CF3~ ._0~ - CN
Cl 27 g of 3-(2'-chloro-4'-trifluoromethylphenoxy)-a-6-chloro-4-iodophenoxy-propionic acid methyl ester is dissolved in 50 ml of N-methyl-2-pyrrolidone. There is then added, with slow stirring, 6 g of copper-I-cyanide.
Under a weak flow of nitrogen, the reaction mixture is heated to 140C bath temperature, and is stirred for 3 hours at this temperature. After cooling, the copper-I-iodide which has precipitated is filtered off, and the filtrate is slowly introduced into a mixture of 25 ml of 25% ammonia and 75 g of ice. The crystals which have precipitated are filtered off and dried. The yield is 21 g of the crystalline title product having a melting point of 121-124C.
.
- :: :- .
' . ~ . , l~)9~Z~(~
C-~ -0--\ ~ B
.. .. . .. .. .
.. , :
.
, ~,, "~
.. - - .
~' ' . .
IQ91~40 (59% of theory).
c) 32 g of 2-chloro-4-trifluoromethyl-2'-chloro-5'-methoxydipheny~ ether is diss~lved in 700 ml of glacial acetic acid, and 170 ml of 48% hydrobromic acid is added.
The mixture is refluxed for 60 hours with stirring at a bath temperature of 120C, and the glacial acetic acid is subsequently distilled off. The oil remaining behind is taken up in toluene, and washed with a solution of sodium bicarbonate/sodium thiosulfate. The solvent is distilled off to leave 28 g of 2-chloro-4-trifluoromethyl-2'-chloro-5~-hydroxydiphenyl ether in the form of viscous oil, which is distilled under high vacuum; yield 19.5 g;
boiling point 132C at 0.25 Torr.
Example 2 a-l3-(4'-Trifluoromethylphenoxy)-4,6-dichlorophenoxy]-propionic acid methyl ester 0-CH-COOC~3 CF3 ~ 0 ~ 1 Cl 34 g (0.1 mol) of 3-(4'-trifluoromethylphenoxy)-a-(phenoxy)-propionic acid methyl ester (produced analogously to Example 1) is dissolved in 100 ml of glacial acetic acid, and at 40C chlorine is fed in in excess. The reac-tion is followed by means of gas-chromatography. After the reaction has ended, the reaction mixture is stirred for a further half hour, and excess chlorine is removed by the introduction of nitrogen. The solvent is distilled off, and the oil thus obtained is distilled under high vacuum to yield 34.5 g of the above product in the form .
. ~ .
....
of oil, which is distilled under high vacuum; boiling point 163-165C at 0.07 Torr.
Example 3 a- [ 3-(4'-Trifluoromethylphenoxy)-S-methylphenoxy]-propionic acid methyl ester CF3 ~ o ~ CH3 CH
a) 13.0 g (0.0485 mol) of 5-(4-trifluoromethylphenoxy)-m-cresol, 7.6 g (0.055 mol) of potassium carbonate and 50 ml of methyl ethyl ketone are refluxed for 2 hours with stirring. There is then added at 50C 8.4 g (0.05 mol) of 2-bromopropionic acid methyl ester, and the mixture is stirred at 50C for 15 hours. After cooling, it is filtered, and the filtrate is concentrated in vacuo.
The residue is filtered with methylene chloride through a small column to obtain 16.1 g (93.6% of theory) of the above product in the form of a clear light-yellow oil having a refractive index of nD = 1.5104. The starting material, 5-(4-trifluoromethylphenoxy-m-cresol, is produced as follows:
b) 35.5 g ~0.25 mol) of orcinol.H20 (3,5-dihydroxytoluene) is dissolved in 200 ml of dimethyl sulfoxide, and 31.3 g (0.5 mol) of potassium hydroxide (90%), which is finely pulverised, is added. As soon as everything has gone into solution, 45.1 g (0.25 mol) of 4- chlorobenzenetriflu-oride is added, and the reaction mixture is stirred at 150C for 20 hours. It is then cooled, 200 ml of 10% HCl is added, and extraction is performed with methylene chloride. The organic phase is dried, and concentrated ~7 , . . .,, . .. .. , . . ~ . ~ , .
- . , - . . -- - , , - - .. . ..
........ .. . .
- , , .
,., . . , , . , :
, by evaporation. The residue is separated through a small silica gel column with methylene chloride. There is obtained as the main fraction 29.8 g (44.4/O of theory) of 5-(4-trifluoromethylphenoxy)-m-cresol in the form of clear light-yellow oil having a refractive index of nD - 1.5322.
Example 4 a-[3-(4'-Trifluoromethylphenoxy)-5-methyl-6-chlorophenoxyl-propionic acid methyl ester O -CH -COOCH
CF3 ~ ~ Cl 3 a) 1.7 g (0.0056 mol) of 5-(4'-trifluoromethylphenoxy)-2-chloro-m-cresol is stirred with 0.23 g (0.0062 mol) of potassium carbonate in 20 ml of ethyl methyl ketone for 2 hours under reflux. There is then added at 50C 1.0 g ~0.0062 mol) of 2-bromopropionic acid methyl ester, and the mixture is stirred at 60C for 15 hours. It is sub-sequently filtered and the filtrate is concentrated by evaporation. The residue is filtered with methylene chloride through a small column, and the main fraction is concentrated by evaporation to yield 1.6 g (76.2% of theory) of thP above product in the form of yellow oil having the refractive index nD - 1.5119.
The 5-(4'-trifluoromethylphenoxy)-2-chloro-m-cresol used as starting material is produced as follows:
b) 13.4 g (0.05 mol) of 5-(4-trifluoromethylphenoxy)-m-cresol (for production of this see Example 3b) is dissolved in 50 ml of glacial acetic acid. To this solution is added droFwise at 15C 3.8 g of chlorine (0.055 mol) in 25 ml of J
..... ~ .. . ... .. .... ... . . .. . .. . .. .. ... ...
- : ' - ~ . -, :-. . ~ ., 109~Z40 glacial acetic acid, in the course of which the tempera-ture is held at 15C. The internal temperature is subsequently allowed to rise to room temperature. After 15 minutes, the reaction mixture is poured into water; it is extracted with methylene chloride, the organic phase is dried with sodium sulfate and is concentrated in vacuo.
The residue is chromatographed with hexane through a small silica gel column. The main fraction yields a clear light-coloured oil, which crystallises on being triturated with petroleum ether. There is thus obtained 1.7 g (11.3 % of theory) of 5-(4-trifluoromethylphenoxy)-2-chloro-m-cresol as a white product having a melting point of 106-110C.
Example 5 l~
a-[3-(4'-Trifluoromethylphenoxy)-5-methyl]-propionitrile ;~
CF3 ~ ~ CH3 13.0 g (0.0485 mol) of 5-(4'-trifluoromethylphenoxy)-m-cresol (for production of this see Example 3b), 7.6 g (0.055 mol) of potassium carbonate and 50 ml of methyl ethyl ketone are refluxed for 2 hours. There is then added at 40C 6.7 g (0.05 mol) of 2-bromopropionitrile, and the mixture is stirred at 60C for 15 hours. It is subsequently cooled and filtered, and the filtrate is concentrated in vacuo. The residue is filtered with methylene chloride through a small silica gel column to thus yield 14.4 g (90.0% of theory) of the above product in the form of a clPar brown oil having the refractive index nD s 1.5174.
~"
- . .
~ ;' ' ' . ' ' ~ "
~: , .' .
~09lZ40 Example 6 ~-[3-(4'-Trifluoromethylphenyl)-5-methylphenoxy]-propionic acid O - CH-COOH
CF3 ~ ~ CH3 39.0 g (O.ll mol) of a- 13-(4'-trifluoromethylphenoxy)-3-methylphenoxy]-propionic acid methyl ester (for its production see Example 3a) is dissolved in lOO ml o~
methanol, and a solution of lO.l g of sodium hydroxide (100%) in lO ml of water is added, in the course of which the temperature rises. The mixture is stirred at 50C - -for one further hour; lOO ml of ice/water is added to the reaction mixture, and the whole is acidified with concen- , trated hydrochloric acid. The produc~ which has precipitated is taken up in 200 ml of methylene chloride and dried. It is concentrated by evaporation to yield 23.8 g (63.4% of theory) of the above product in the form of a light-yellow crystalline powder having a melting point of 88-90C.
ExamPle 7 -[3-(4'-Trifluoromethylphenoxy)-5-methylphenoxy]-propionic acid allylamide OCH-CONEICH2-CH~CH2 a) 7.0 g (O.Ol9 mol) of a-13-(4'-trifluoromethylphenoxy)-5-methylphenoxy-propionic acid chloride is dissolved in 20 ml _ _ _ ,, .____. _ _ . ,. . . , , . . . ~ . ., .. _ _.. , .. . ~.. . ... .... .
. . . :
. .
. , of methylene chloride, and at 10C is added 2.8 g (0.042 mol) of allylamine. After 1 hour, 100 ml of water is added; the organic phase is then separated, and dried with sodium sulfate. ~t is concentrated by evaporation to obtain a clear light-yellow oil, which crystallises on being triturated with petroleum ether. In this manner is obtained the above product in the form of white crystals in a yield of 5.0 g (69.4% of theory3; melting point 94-96C. The acid chloride used as starting product is produced as follows:
b) 20 ml of thionyl chloride is added at room temperature to 13.8 g (0.04 mol) of a-(3-(4'-trifluoromethylphenoxy)-5-methylphenoxy)-propionic acid (for production of this see Example 6), and the temperature is then raised to 50C.
The reaction mixture is left to stand at this temperature for 2 hours, and is subsequently concentrated by evapor-ation; to the residue is added 50 ml of toluene, and the whole is evaporated to dryness in a good vacuum to thus yield, in the form of clear dark-brown oil, 14.3 g (100%
of theory) of a-(3-(4'-trifluoromethylphenoxy)-5-methyl-phenoxy)-propionic acid chloride.
ExamPle 8 a-l3-(2'-Chloro-4'-trifluoromethylphenoxy)-6-chlorophenoxy]-propionic acid methyl ester Cl O~H-COOCH3 CF3-~ O--~ ~--Cl 35.9 g of 3-(2'-chloro-4'-trifluoromethylphenoxy)~a-phenoxy-propionic acid methyl ester is dissolved in 100 ml of glacial acetic acid. Into this solution is then passed, . .
- ~ :
.. , . . . ~ ,: .
.
1(~91240 with thorough stirring, the theoretically required amount of chlorine, with the temperature being held at 40C. The reaction mixture is stirred for half an hour and the solvent is distilled off. Ligroin is added to the oily residue, and the crystals which have precipitated are filtered off. The title product thus obtained has a melting point of 79-80C~
Example 9 a-[3-(2'-Chloro-4'-trifluoromethyl)-6-chloro-4-iodophenoxy)-propionic acid methyl ester CH3 Cl O~H-COOCH
cF3~ o~
Cl 41 g of 3-(2'-chloro-4'-trifluoromethylphenoxy)-a-6-chlorophenoxy-propionic acid methyl ester is dissolved in 150 ml of glacial acetic acid. To this solution is added dropwise a solution of 20.5 g of iodine chloride in 30 ml of glacial acetic acid, and the reaction mixture is allowed to fully react for 15 minutes (slightly exothermic reaction) and, after the addition of 200 ml of water, the mixture is heated at 90C for 3 hours. There is then added a 5%
sodium bisulfite solution until the mixture is decolorised, a~d the oil which has precipitated is extracted with toluene/ethyl acetate (1:1). The solvent is distilled off to leave 47 g of oil which crystallises after the addition of ligroin. The crystals are filtered off to yield 32 g of the title product in the form of a white crystalline mass having a melting point of 102-105C.
'' ' , ' . ~
. , . ~ , . .
.
, , ~O~lZ~O
Example 10 a-l3-(2'-Chloro-4'-trifluoromethylphenoxy~-6-chloro-4-cyanophenoxyl-propionic acid methyl ester Cl 0-~H-COOCH3 CF3~ ._0~ - CN
Cl 27 g of 3-(2'-chloro-4'-trifluoromethylphenoxy)-a-6-chloro-4-iodophenoxy-propionic acid methyl ester is dissolved in 50 ml of N-methyl-2-pyrrolidone. There is then added, with slow stirring, 6 g of copper-I-cyanide.
Under a weak flow of nitrogen, the reaction mixture is heated to 140C bath temperature, and is stirred for 3 hours at this temperature. After cooling, the copper-I-iodide which has precipitated is filtered off, and the filtrate is slowly introduced into a mixture of 25 ml of 25% ammonia and 75 g of ice. The crystals which have precipitated are filtered off and dried. The yield is 21 g of the crystalline title product having a melting point of 121-124C.
.
- :: :- .
' . ~ . , l~)9~Z~(~
C-~ -0--\ ~ B
4 Ep5 No. C D B Ep Rl ... __ Physical . . _ - . . _ constants 1 CF3 _ 5 CH3 CH3 ~ CH=CH2 m.p. 94-96 2 CF3 _ Cl 4 Cl CH3 COOCH3 b.p.163-5/0.07 3 CF3 ~ ~ 5 CH3 CH3 COOCH3 nD1.5104 4 CF3 ~ Cl 5 CH3 c~3 COOCH3 n21.5119 CF3 ~ ~ 5 CH3 C~I3 CN n21.5174 6 CF3 _ _ 5 CH3 CH3 COOH m.p. 88-90 7 CF3 Cl _ 4 Cl CH3 COOCH3 b.p.147/0.04 Torr 8 CF3 Cl _ 4 Cl CH3 COOH m.p. 129-132 9 CF3 Cl _ 5 Cl C~3 COOCH3 b.p. 153-5/0.02 Torr CF3 Cl Cl 4 Cl CH3 COOCH3 m.p. 79-80 11 CF3 Cl CN 4 Cl CH3 COOCH3 m.p. 121-124 12 CF3 Cl No2 4 Cl CH3 COOH
13 CF3 Cl No2 4 Cl CH3 COOCH3 m.p. 106-10 14 CF3 Cl No2 4 Cl c~3 COS--~ ~._, 1 CF3 Cl No2 4 Br CH3 COOCH3 -16 CF3 Cl N2 4 Br CH3 o~H2-CH=CH2 17 ~F3 Cl NQ2 4 Br CH3 CONHC2H5 18 CF3 Cl CN 4 Cl CH3 CN oil 19 CF3 Cl CN 4 Cl CH3 COOH
CF3 Cl CN 4 Cl CH3 COSC2H5 .
' ~
No. C D B ~p 1 Physical constants _ - . _. _ . __ . , 21 CF3 Cl _ 5 CH3 CH3 COOCH3 22 CF3 Cl _ 5 CH3 CH3 COOH
23 CF3 Cl _ 5 CH3 CH3 O~H2-CH=CH2 24 CF3 Cl Br 4 Br CH3 COOCH3 CF3 Cl Br 4 Br CH3 oxxH2c-=cH
26 CF3 Cl Br 4 Br CH3 COOCH2~ , ~XH3 27 CF3 Cl Cl 4 Cl CH3 COOC2H5 m.p. 49-51 28 CF3 Cl Cl 4 Cl CH3 ~ CH-CH2 m.p. 47-So 29 CF3 Cl Cl 4 Cl CH3 ~ CH=CH2 oil CF3 Cl Cl 4 Cl CH3 iso C3H7 31 CF3 Cl Cl 4 Cl CH3 CCN(CH3)0CH3 oil 32 CF3 Cl Cl 4 Cl CH3 COO--\ H \- m.p. 53-55 33 CF3 Cl Cl 4 Cl CH3 COS--~ ~. m.p. 86-890 34 CF3 Cl Cl 4 Cl CH3 COO-~ ~. m.p. 118.119 CF3 Cl Cl 4 Cl CH3 COOH m.p. 147-149 36 CF3 Cl Cl 4 Cl CH3 4 9 m.p. 49-52 37 CF3 Cl Cl 4 Cl CH3 COOisoC4Hg m.p. 58-Sgo 38 CF3 Cl Cl 4 Cl CH3 ~ 2CHC2H5 oil :
39 CF3 Cl Cl 4 Cl CH3 ox~H C=CH m.p. 47-49 CF3 Cl Cl 4 Cl CH3 COOC2H4Cl oil ~;
._. . _,. _ __ _ __ ., . _ . ~ . _ . _ ~.
., , ~ ; , ~ i . .
,'.'' "~ ' . ' ' .
. ' . . ` , , ':
~' '' ' ~ ~ ' ' ' ', 3.091~40 No. C ¦ D B Ep Rl A -- Physical . _ . con~tants 41 CF3 Cl Cl 4 Cl CH COON=(CH3)2 oil 42 CF3 Cl Cl 4 Cl CH ~X~2H4CN m.p. 75-79 43 CF3 Cll Cl 4 Cl CH3 ~ CH20CH3 oil 44 CF3 Cl ¦ Cl 4 Cl CH3 OOOC2H40CH3 oil .
CF3 Cl Cl 4 Cl CH3 COOC H N/ \o oil 46 CF3 Cl Cl 4 Cl CH3 CONH2 m.p. 94-96 47 CF3 Cl Cl 4 Cl CH3 CON\ /- m.p.115-117 48 CF3 Cl Cl 4 Cl CH3 2 4 3 m.p.89-91 49 CF3 Cl Cl 4 Cl CH3 COOCH2CF3 m.p. 48-51 ,.~-\.
. 50 CP3 Cl Cl 4 Cl CE3 CONH ~ m.p. 124-125' 51 CF3 Cl Cl 4 Cl CH3 T`. .~- oil C,CH
52 CF3 Cl No2 4 Cl CH3 COSCH3 oil 53 ¦ CF3 Cl _ 4 N02 CH3 COOCH3 b.p.190~0.04 Tor~
54 I CF3 Cl Br 4 Cl CH3 COOCH3 m.p. 88-91 55 CF3 Cl I 4 Cl CH3 COOCH3 m.p. 102-105 , . ... .. ~
105~Z40 _ _ . . .
No. C D BEp Rl A Phys ical l . cons tants . ¦
56 CF3 Cl - 2 Cl 4 _ . CH3 -COOCH3 b.p.162/0.05 Torr 57 CF3 CN _ 4 Cl CH3 COOCH3 m.p. 104-108 58 CF3 CN Cl 4 Cl c~3 COOCH3 m.p. 105-107 59 CF3 N02 ~4 Cl C~3 COOCH3 b p 183-5/0 05 60 CF3 No2 Cl 4 Cl CH3 CN oil 61 CF3 No2 Cl 4 Cl CH3 COOH
62 CF3 No2 Cl 4 Cl CH3 COS--\ H \-63 CF3 No2 No2 4 Cl CH3 COOCH3 b.p.> 200/0 01 64 CF3 N2 N02 4 Cl CH3 COOC2H40CH3 65 CF3 N2 N02 4 Cl CH3 o~C2H40CH3 66 Cl CN Cl 4 Cl CH3 COOCH3 m.p. 113-4 67 Cl CN Cl 4 Cl CH3 COOC2H5 68 Cl CN Cl 4 Cl CH3 COOH m.p. 115 69 Cl CN Cl 4 Cl CH3 CCOisoC4Hg oil .
70 Cl CN Cl 4 Cl CH3 COOnC4Hg oil :~
71 Cl CN Cl 4 Cl H COOCH3 m.p. 114-116 72 Cl CN Cl 4 Cl CH3~ ~ H2 OE 2H3 oil 73 Cl CN Cl 4 Br CH3¦COOnC3H7 oil _ _ .. ,, .. ___ . ............ ~................. _ ,, .
, , . . -109124(~
_ . _ .... . _ . ....... __ No. C D ~¦Ep Rl A , Physical cons tants 75 Cl CN Br4 BrC~3 COOCH3 m.p. 107-9 76 Cl CN _5 Cl CH3 COOCH3 l n251.5736 77 Cl No2 _ 4 Cl CH3 COOCH3 78 Cl No2 _ S Cl CH3 COOCH3 79 Cl No2 Cl 4 Cl CH3 COOCH3 resin 80 Cl Cl CN 4 Cl CH3 COOCH3 81 Cl Cl I 4 Cl CH3 COOCH3 82 Cl Cl Cl 4 Cl CH3 COOCH3 b.p. 190/o.ool Torr 83 Cl Cl Cl 4 Cl CH3 COO~ .
84 Cl Cl Cl 4 Cl CH3 ~X~H2CH=CH2 oil Cl Cl NO 4 Cl CH3 CCOC2H4Cl ~--~ . ' 86 Cl Cl NO 4 Cl CH3 ~X~H2 \ /
87 Cl Cl No2 Cl CH3 ~OOisoC3H7 88 Cl Cl _ 4 Cl CH3 COOCH3 oil B9 Cl Cl No2 4 Cl CH3 COOCH3 m.p. 95-6 90 Cl Cl Cl 4 Br CH3 COOCH3 b.p. 200o/0 001 31 Cl Br N02 2 Cl 4 Cl H CONH2 32 Cl Br N02 2 Cl 4 Cl CH3 XX~H2 (CH3)2 33 Cl Br No2 2 Cl 4 Cl H COOH
",;
_ _ _ ___. . _. . . ... ~ .
_ _ _ . . _ _ . _ _ . , ... . . .. , . .. . ..... .. . _ __ - - . .
r , ~ , ' ' `` lC~91Z40 _ _ __ _ .. _ . _ , ~o. C D 3 Ep Rl A Phys iGal constants __ . l 94 Cl 3r N02 C1 4 !E cos ~
95 Cl 8r N02~ Cl 4 Cl H COSC2H4SCH3 96 Cl Br N22 Cl 4 Cl H COOC2EI4SCH3 97 Cl Br N022 Cl 4 Cl H CN
98 Br Br No2 4 Cl CH3 COOCH3 99 Br Br N2 4 Cl CH3 CONHCH3 3r 3 ~2 Cl ~3 ON\ /0 101 Cl Cl Cl 4 Cl CH3 OoXH2 2 oilb.po,OOl 200 102 Cl Cl Cl 4 Cl CH3 CON(CH3)0CH3 oil 103 Cl Cl Cl 4 Cl CH3 COC2H4Cl oil 104 Cl Cl Cl 4 Cl CH3 COOfHC2H5 oil b.p.O,OOl 210 105 Cl Cl Cl 4 Cl c~3 COOC2H40CX3 oil b.p.O,OOl 230 10~ Cl Cl Cl 4 Cl CH3 2 4 oil 107 Cl Cl Cl 4 Cl c~3 2 4 3 oil 108 Cl Cl Cl 4 Cl CH3 COOC2H4N(CH3)2 oil 109 No2 _ _ 4 Cl CH3 COOCH3 oil :
110 ~2 ~ N02 4 Cl ca3 COOCH3 111 No2 _ _ 5 Cl CH3 COOCH3 112 No2 Cl Cl 4 Cl CH3 COOCH3 m.p. 98-99 11' No2 Cl _ 5 Cl CH3 COOCH3 resin 114CN _ N02 4 Cl CH3 COOCH3 .
-- -: : - ' --, "' '` ' :
- ,. ..
.: , . .
~ ' .. ~ .
1091i~40 The compositions according to the invention are produced in a manner known per se by the intimate mixing and grinding of the active substances of the formula I
with suitable carriers and/or distributing agents, optionally with the addition of antifoaming agents, wet-ting agents, dispersing agents and/or solvents, all inert to the active substances. The active substances can be obtained and used in the following forms:
solid preparations: dusts, scattering agents, granules (coated granules, impregnated granules and homogeneous granules);
water-dispersible concentrates of active substance:
wettable powders, pastes, emulsions a~d emulsion concentrates; and liquid preparations: solutions.
The concentration of active substance in the compo-sitions according to the invention is 1 to 80 per cent by weight, and when being applied the compositions can if necessary contain the active substances also at a lower concentration, such as about 0.05 to l per cent by weight.
Other biocidal active substances or compositions can be added to the compositions according to the invention.
Thus, the novel compositions can contain, in addition to the stated compounds of the formula I, for example insecticides, fungicides, bactericides, fungistatics, bacteriostatics, nematocides or further herbicides, in order to widen the sphere of action.
The production of the compositions according to the invention is further illustrated by the following formu-lation examples.
___ . _ ... . . .. , .. . . . , , _., .. , . ... , . ;.. , .. , . . . . -- . _ .. . .
. : '' :, ..
, , Wettable powder The following constituents are used to produce a) a 70% wettable powder and b) a 10% wettable powder:
a) 70 parts of active substance, parts of sodium dibutyl-naphthalene sulfonate, 3 parts of naphthalenesulfonic acid/phenolsulfonic acid/formaldehyde condensate (3:2:1), parts of kaolin, and 12 parts of Champagne chalk; and b) 10 parts of one of the active substances of the formula I, 3 parts of a mixture of the sodium salts of , saturated fatty alcohol sulfates, parts of naphthalenesulfonic acid/formaldehyde condensate, and 82 parts of kaolin.
The given active substance is absorbed onto the appro- -priate carriers (kaolin and chalk), and the material is subsequently mixed and ground with the remaining constituents.
Wettable powders having excellent wetting and suspension properties are obtained. It is possible to obtain from wettable powders of this kind suspensions containing 0.1 to 8% of active substance, and these suspensions are suitable for combating weeds in crops of cultivated plants.
Paste The following materials are used to produce a 45% paste:
parts of an active substance of the formula I, parts of sodium aluminium silicate, 14 parts of cetyl polyglycol ether having 8 mols of ethylene oxide, 1 part of oleyl polyglycol ether having 5 mols ~ j .
~, : , - . .
, ~ .. , , . - . , - . , . .
: ~ - - .. .-- . . - :. , . -: -..
.
:-: ~ -~091240 of ethylene oxide 2 parts of spindle oil, parts of polyethylene glycol, and 23 parts of water.
The active substance is intimately mixed and ground with the additives in apparatus suitable for the purpo~e.
There is o~tained a paste from which can be produced, by dilution with water, suspensions of any desired concentration.
Emulsion concentrate The following constituents are mixed together to produce a 25% emulsion concentrate:
parts of an active substance of the formula I, parts of a mixture of nonylphenolpolyoxyethylene and calcium dodecylbenzene sulfonate, parts of cyclohexanone, and parts of xylene.
This concentrate can be diluted with water to give emulsions of suitable concentration, e.g. 0.1%, and such emulsions are suitable for combating weeds in crops of cultivated plants.
The novel phenoxy-a-phenoxyalkanecarboxylic acids and their derivatives of the formula I, and also the compo-sitions containing them, have an excellent selectively herbicidal action against weeds in the widest variety of cultivated crops. They also have an action regulating the growth of plants.
Although the novel active substances of the formula I
are effective both for pre-emergence and post-emergence application, the post-emergence application of these active substances as contact herbicides appears to deserve preferenc~; however, the pre-emergence application thereof is also of interest. The novel active substances of the '~ ' :' ' :.
lO91Z40 fonmula I are preferably applied to the crops of cultivated plants after emergence of the plants, with the active substances being formulated for example as 25% wettable powders, or for e~ample as 20% emulsifiable concentrates, and diluted with water.
The following test methods serve ~o verify the suitability of the novel active substances of the formula I as herbicides (pre- and post^emergence), and to prove the superiority of them over known active substances of similar structure.
Pre-emer~ence herbicidal action (inhibition of germination) Immediately after sowing the test plants in seed trays in a greenhouse, the surface of the soil is treated with aqueous dispersions of the active substance, which have been prepared from a 25% emulsion concentrate, and from a 25% wettable powder containing active substances which cannot be produced as emulsion concentrates owing to inadequate solubility. Four different concentration series are used, corresponding to 4, 2, 1 and 0.5 kg of active ~ -substance per hectare. The seed trays are left in the greenhouse at 22-25C with 50-70% relative humidity, and the test is evaluated after 3 weeks, with the results being assessed according to the following scale of ratings:
1 = plants have not germinated or have fully died off, 2-3 ~ very intense action, 4-6 = moderate action, 7-8 - slight action, 9 = no action (as in the case of untreated control plants).
The following are used as test plants:
Hordeum (barley) Setaria italica Triticum (wheat) Echinochloa crus galli Zea (maize) Beta vulgaris ;;J
_ _ . ., . . . .. . . _. ~ _ .. , .. _ .... . ,. ... .. . . .. _.. ,_ .. .. __ ..... .
~- : -l~)9~Z40 Sorghum hybr. (millet) Sida spinosa Oryza (rice) Sesbania exaltata Glycine (soya bean) Amaranthus retroflexus Gossypium (cotton) Sinapis alba Avena fatua Ipomoea purpurea Lolium perenne Galium aparine Alopecurus myosuroides Pastinaca sativa Bromus tectorum Rumex sp.
Cyperus esculentus Chrysanthemum leucum Rottboellia exaltata Abutilon sp.
Digitaria sanguinalis Solanium nigrum Post-emer~ence herbicidal action (contact herbicide) A largish number (at least 7) of weeds and of culti-vated plants, both monocotyledonous and dicotyledonous, are sprayed after emergence (in the 4- to 6-leaf stage) with an aqueous active-substance dispersion in dosage amounts of 0.06, 0.125, 0.25 and 0.5 kg of active substance per hectare, and they are then kept at 24-26C
with 45-60% relative humidity. The test is evaluated at least 15 days after treatment, and the results are assessed according to the same scale of ratings as used in the pre-emergence test.
The tested compounds according to the present invention exhibited on some plants a pronounced contact-herbicidal action, and effected on many plants a cessation of growth, a sign of the growth-inhibiting properties of these compounds.
Reduction of ~rowth of grasse~
Seeds of the grasses Lolium perenne, Poa pratensis, Festuca ovina and Dactylis glomerata are sown in a soil/
peat/sand mixture (6:3:1) in plas~ic trays and watered in the usual manner. The emerged grasses are cut back each ~:, ~' '~" .
. ' :.
.
, .
11)91;~40 week to a height of 4 cm, and are sprayed 40 days after sowing and 1 day after the last cutting with aqueous spray liquors of an active substance of the formula I.
The amount of active substance is equivalent to 5 kg of active substance per hectare. The growth of the grasses is evaluated lO and 21 days after application.
Reduction of ~rowth of cereals Spring wheat (Triticum aestivum), spring barley (Hordeum vulgare) and rye (Secale) are sown in sterilised soil in plastic trays and are grown in a greenhouse.~ The shoots of the cereals are treated, 5 days after sowing, with a spray liquor of the active substance. This leaf application is equivalent to 6 ~g of active substance per hectare. An evaluation is made after 21 days.
The tested active substances according to the invention produce an appreciable reduction in growth both of the grasses and of the cereals.
~,J
.. . , . , , ~
' ' : ' :' .:
- , .
' ' ' ~ ' ~ ' '
13 CF3 Cl No2 4 Cl CH3 COOCH3 m.p. 106-10 14 CF3 Cl No2 4 Cl c~3 COS--~ ~._, 1 CF3 Cl No2 4 Br CH3 COOCH3 -16 CF3 Cl N2 4 Br CH3 o~H2-CH=CH2 17 ~F3 Cl NQ2 4 Br CH3 CONHC2H5 18 CF3 Cl CN 4 Cl CH3 CN oil 19 CF3 Cl CN 4 Cl CH3 COOH
CF3 Cl CN 4 Cl CH3 COSC2H5 .
' ~
No. C D B ~p 1 Physical constants _ - . _. _ . __ . , 21 CF3 Cl _ 5 CH3 CH3 COOCH3 22 CF3 Cl _ 5 CH3 CH3 COOH
23 CF3 Cl _ 5 CH3 CH3 O~H2-CH=CH2 24 CF3 Cl Br 4 Br CH3 COOCH3 CF3 Cl Br 4 Br CH3 oxxH2c-=cH
26 CF3 Cl Br 4 Br CH3 COOCH2~ , ~XH3 27 CF3 Cl Cl 4 Cl CH3 COOC2H5 m.p. 49-51 28 CF3 Cl Cl 4 Cl CH3 ~ CH-CH2 m.p. 47-So 29 CF3 Cl Cl 4 Cl CH3 ~ CH=CH2 oil CF3 Cl Cl 4 Cl CH3 iso C3H7 31 CF3 Cl Cl 4 Cl CH3 CCN(CH3)0CH3 oil 32 CF3 Cl Cl 4 Cl CH3 COO--\ H \- m.p. 53-55 33 CF3 Cl Cl 4 Cl CH3 COS--~ ~. m.p. 86-890 34 CF3 Cl Cl 4 Cl CH3 COO-~ ~. m.p. 118.119 CF3 Cl Cl 4 Cl CH3 COOH m.p. 147-149 36 CF3 Cl Cl 4 Cl CH3 4 9 m.p. 49-52 37 CF3 Cl Cl 4 Cl CH3 COOisoC4Hg m.p. 58-Sgo 38 CF3 Cl Cl 4 Cl CH3 ~ 2CHC2H5 oil :
39 CF3 Cl Cl 4 Cl CH3 ox~H C=CH m.p. 47-49 CF3 Cl Cl 4 Cl CH3 COOC2H4Cl oil ~;
._. . _,. _ __ _ __ ., . _ . ~ . _ . _ ~.
., , ~ ; , ~ i . .
,'.'' "~ ' . ' ' .
. ' . . ` , , ':
~' '' ' ~ ~ ' ' ' ', 3.091~40 No. C ¦ D B Ep Rl A -- Physical . _ . con~tants 41 CF3 Cl Cl 4 Cl CH COON=(CH3)2 oil 42 CF3 Cl Cl 4 Cl CH ~X~2H4CN m.p. 75-79 43 CF3 Cll Cl 4 Cl CH3 ~ CH20CH3 oil 44 CF3 Cl ¦ Cl 4 Cl CH3 OOOC2H40CH3 oil .
CF3 Cl Cl 4 Cl CH3 COOC H N/ \o oil 46 CF3 Cl Cl 4 Cl CH3 CONH2 m.p. 94-96 47 CF3 Cl Cl 4 Cl CH3 CON\ /- m.p.115-117 48 CF3 Cl Cl 4 Cl CH3 2 4 3 m.p.89-91 49 CF3 Cl Cl 4 Cl CH3 COOCH2CF3 m.p. 48-51 ,.~-\.
. 50 CP3 Cl Cl 4 Cl CE3 CONH ~ m.p. 124-125' 51 CF3 Cl Cl 4 Cl CH3 T`. .~- oil C,CH
52 CF3 Cl No2 4 Cl CH3 COSCH3 oil 53 ¦ CF3 Cl _ 4 N02 CH3 COOCH3 b.p.190~0.04 Tor~
54 I CF3 Cl Br 4 Cl CH3 COOCH3 m.p. 88-91 55 CF3 Cl I 4 Cl CH3 COOCH3 m.p. 102-105 , . ... .. ~
105~Z40 _ _ . . .
No. C D BEp Rl A Phys ical l . cons tants . ¦
56 CF3 Cl - 2 Cl 4 _ . CH3 -COOCH3 b.p.162/0.05 Torr 57 CF3 CN _ 4 Cl CH3 COOCH3 m.p. 104-108 58 CF3 CN Cl 4 Cl c~3 COOCH3 m.p. 105-107 59 CF3 N02 ~4 Cl C~3 COOCH3 b p 183-5/0 05 60 CF3 No2 Cl 4 Cl CH3 CN oil 61 CF3 No2 Cl 4 Cl CH3 COOH
62 CF3 No2 Cl 4 Cl CH3 COS--\ H \-63 CF3 No2 No2 4 Cl CH3 COOCH3 b.p.> 200/0 01 64 CF3 N2 N02 4 Cl CH3 COOC2H40CH3 65 CF3 N2 N02 4 Cl CH3 o~C2H40CH3 66 Cl CN Cl 4 Cl CH3 COOCH3 m.p. 113-4 67 Cl CN Cl 4 Cl CH3 COOC2H5 68 Cl CN Cl 4 Cl CH3 COOH m.p. 115 69 Cl CN Cl 4 Cl CH3 CCOisoC4Hg oil .
70 Cl CN Cl 4 Cl CH3 COOnC4Hg oil :~
71 Cl CN Cl 4 Cl H COOCH3 m.p. 114-116 72 Cl CN Cl 4 Cl CH3~ ~ H2 OE 2H3 oil 73 Cl CN Cl 4 Br CH3¦COOnC3H7 oil _ _ .. ,, .. ___ . ............ ~................. _ ,, .
, , . . -109124(~
_ . _ .... . _ . ....... __ No. C D ~¦Ep Rl A , Physical cons tants 75 Cl CN Br4 BrC~3 COOCH3 m.p. 107-9 76 Cl CN _5 Cl CH3 COOCH3 l n251.5736 77 Cl No2 _ 4 Cl CH3 COOCH3 78 Cl No2 _ S Cl CH3 COOCH3 79 Cl No2 Cl 4 Cl CH3 COOCH3 resin 80 Cl Cl CN 4 Cl CH3 COOCH3 81 Cl Cl I 4 Cl CH3 COOCH3 82 Cl Cl Cl 4 Cl CH3 COOCH3 b.p. 190/o.ool Torr 83 Cl Cl Cl 4 Cl CH3 COO~ .
84 Cl Cl Cl 4 Cl CH3 ~X~H2CH=CH2 oil Cl Cl NO 4 Cl CH3 CCOC2H4Cl ~--~ . ' 86 Cl Cl NO 4 Cl CH3 ~X~H2 \ /
87 Cl Cl No2 Cl CH3 ~OOisoC3H7 88 Cl Cl _ 4 Cl CH3 COOCH3 oil B9 Cl Cl No2 4 Cl CH3 COOCH3 m.p. 95-6 90 Cl Cl Cl 4 Br CH3 COOCH3 b.p. 200o/0 001 31 Cl Br N02 2 Cl 4 Cl H CONH2 32 Cl Br N02 2 Cl 4 Cl CH3 XX~H2 (CH3)2 33 Cl Br No2 2 Cl 4 Cl H COOH
",;
_ _ _ ___. . _. . . ... ~ .
_ _ _ . . _ _ . _ _ . , ... . . .. , . .. . ..... .. . _ __ - - . .
r , ~ , ' ' `` lC~91Z40 _ _ __ _ .. _ . _ , ~o. C D 3 Ep Rl A Phys iGal constants __ . l 94 Cl 3r N02 C1 4 !E cos ~
95 Cl 8r N02~ Cl 4 Cl H COSC2H4SCH3 96 Cl Br N22 Cl 4 Cl H COOC2EI4SCH3 97 Cl Br N022 Cl 4 Cl H CN
98 Br Br No2 4 Cl CH3 COOCH3 99 Br Br N2 4 Cl CH3 CONHCH3 3r 3 ~2 Cl ~3 ON\ /0 101 Cl Cl Cl 4 Cl CH3 OoXH2 2 oilb.po,OOl 200 102 Cl Cl Cl 4 Cl CH3 CON(CH3)0CH3 oil 103 Cl Cl Cl 4 Cl CH3 COC2H4Cl oil 104 Cl Cl Cl 4 Cl CH3 COOfHC2H5 oil b.p.O,OOl 210 105 Cl Cl Cl 4 Cl c~3 COOC2H40CX3 oil b.p.O,OOl 230 10~ Cl Cl Cl 4 Cl CH3 2 4 oil 107 Cl Cl Cl 4 Cl c~3 2 4 3 oil 108 Cl Cl Cl 4 Cl CH3 COOC2H4N(CH3)2 oil 109 No2 _ _ 4 Cl CH3 COOCH3 oil :
110 ~2 ~ N02 4 Cl ca3 COOCH3 111 No2 _ _ 5 Cl CH3 COOCH3 112 No2 Cl Cl 4 Cl CH3 COOCH3 m.p. 98-99 11' No2 Cl _ 5 Cl CH3 COOCH3 resin 114CN _ N02 4 Cl CH3 COOCH3 .
-- -: : - ' --, "' '` ' :
- ,. ..
.: , . .
~ ' .. ~ .
1091i~40 The compositions according to the invention are produced in a manner known per se by the intimate mixing and grinding of the active substances of the formula I
with suitable carriers and/or distributing agents, optionally with the addition of antifoaming agents, wet-ting agents, dispersing agents and/or solvents, all inert to the active substances. The active substances can be obtained and used in the following forms:
solid preparations: dusts, scattering agents, granules (coated granules, impregnated granules and homogeneous granules);
water-dispersible concentrates of active substance:
wettable powders, pastes, emulsions a~d emulsion concentrates; and liquid preparations: solutions.
The concentration of active substance in the compo-sitions according to the invention is 1 to 80 per cent by weight, and when being applied the compositions can if necessary contain the active substances also at a lower concentration, such as about 0.05 to l per cent by weight.
Other biocidal active substances or compositions can be added to the compositions according to the invention.
Thus, the novel compositions can contain, in addition to the stated compounds of the formula I, for example insecticides, fungicides, bactericides, fungistatics, bacteriostatics, nematocides or further herbicides, in order to widen the sphere of action.
The production of the compositions according to the invention is further illustrated by the following formu-lation examples.
___ . _ ... . . .. , .. . . . , , _., .. , . ... , . ;.. , .. , . . . . -- . _ .. . .
. : '' :, ..
, , Wettable powder The following constituents are used to produce a) a 70% wettable powder and b) a 10% wettable powder:
a) 70 parts of active substance, parts of sodium dibutyl-naphthalene sulfonate, 3 parts of naphthalenesulfonic acid/phenolsulfonic acid/formaldehyde condensate (3:2:1), parts of kaolin, and 12 parts of Champagne chalk; and b) 10 parts of one of the active substances of the formula I, 3 parts of a mixture of the sodium salts of , saturated fatty alcohol sulfates, parts of naphthalenesulfonic acid/formaldehyde condensate, and 82 parts of kaolin.
The given active substance is absorbed onto the appro- -priate carriers (kaolin and chalk), and the material is subsequently mixed and ground with the remaining constituents.
Wettable powders having excellent wetting and suspension properties are obtained. It is possible to obtain from wettable powders of this kind suspensions containing 0.1 to 8% of active substance, and these suspensions are suitable for combating weeds in crops of cultivated plants.
Paste The following materials are used to produce a 45% paste:
parts of an active substance of the formula I, parts of sodium aluminium silicate, 14 parts of cetyl polyglycol ether having 8 mols of ethylene oxide, 1 part of oleyl polyglycol ether having 5 mols ~ j .
~, : , - . .
, ~ .. , , . - . , - . , . .
: ~ - - .. .-- . . - :. , . -: -..
.
:-: ~ -~091240 of ethylene oxide 2 parts of spindle oil, parts of polyethylene glycol, and 23 parts of water.
The active substance is intimately mixed and ground with the additives in apparatus suitable for the purpo~e.
There is o~tained a paste from which can be produced, by dilution with water, suspensions of any desired concentration.
Emulsion concentrate The following constituents are mixed together to produce a 25% emulsion concentrate:
parts of an active substance of the formula I, parts of a mixture of nonylphenolpolyoxyethylene and calcium dodecylbenzene sulfonate, parts of cyclohexanone, and parts of xylene.
This concentrate can be diluted with water to give emulsions of suitable concentration, e.g. 0.1%, and such emulsions are suitable for combating weeds in crops of cultivated plants.
The novel phenoxy-a-phenoxyalkanecarboxylic acids and their derivatives of the formula I, and also the compo-sitions containing them, have an excellent selectively herbicidal action against weeds in the widest variety of cultivated crops. They also have an action regulating the growth of plants.
Although the novel active substances of the formula I
are effective both for pre-emergence and post-emergence application, the post-emergence application of these active substances as contact herbicides appears to deserve preferenc~; however, the pre-emergence application thereof is also of interest. The novel active substances of the '~ ' :' ' :.
lO91Z40 fonmula I are preferably applied to the crops of cultivated plants after emergence of the plants, with the active substances being formulated for example as 25% wettable powders, or for e~ample as 20% emulsifiable concentrates, and diluted with water.
The following test methods serve ~o verify the suitability of the novel active substances of the formula I as herbicides (pre- and post^emergence), and to prove the superiority of them over known active substances of similar structure.
Pre-emer~ence herbicidal action (inhibition of germination) Immediately after sowing the test plants in seed trays in a greenhouse, the surface of the soil is treated with aqueous dispersions of the active substance, which have been prepared from a 25% emulsion concentrate, and from a 25% wettable powder containing active substances which cannot be produced as emulsion concentrates owing to inadequate solubility. Four different concentration series are used, corresponding to 4, 2, 1 and 0.5 kg of active ~ -substance per hectare. The seed trays are left in the greenhouse at 22-25C with 50-70% relative humidity, and the test is evaluated after 3 weeks, with the results being assessed according to the following scale of ratings:
1 = plants have not germinated or have fully died off, 2-3 ~ very intense action, 4-6 = moderate action, 7-8 - slight action, 9 = no action (as in the case of untreated control plants).
The following are used as test plants:
Hordeum (barley) Setaria italica Triticum (wheat) Echinochloa crus galli Zea (maize) Beta vulgaris ;;J
_ _ . ., . . . .. . . _. ~ _ .. , .. _ .... . ,. ... .. . . .. _.. ,_ .. .. __ ..... .
~- : -l~)9~Z40 Sorghum hybr. (millet) Sida spinosa Oryza (rice) Sesbania exaltata Glycine (soya bean) Amaranthus retroflexus Gossypium (cotton) Sinapis alba Avena fatua Ipomoea purpurea Lolium perenne Galium aparine Alopecurus myosuroides Pastinaca sativa Bromus tectorum Rumex sp.
Cyperus esculentus Chrysanthemum leucum Rottboellia exaltata Abutilon sp.
Digitaria sanguinalis Solanium nigrum Post-emer~ence herbicidal action (contact herbicide) A largish number (at least 7) of weeds and of culti-vated plants, both monocotyledonous and dicotyledonous, are sprayed after emergence (in the 4- to 6-leaf stage) with an aqueous active-substance dispersion in dosage amounts of 0.06, 0.125, 0.25 and 0.5 kg of active substance per hectare, and they are then kept at 24-26C
with 45-60% relative humidity. The test is evaluated at least 15 days after treatment, and the results are assessed according to the same scale of ratings as used in the pre-emergence test.
The tested compounds according to the present invention exhibited on some plants a pronounced contact-herbicidal action, and effected on many plants a cessation of growth, a sign of the growth-inhibiting properties of these compounds.
Reduction of ~rowth of grasse~
Seeds of the grasses Lolium perenne, Poa pratensis, Festuca ovina and Dactylis glomerata are sown in a soil/
peat/sand mixture (6:3:1) in plas~ic trays and watered in the usual manner. The emerged grasses are cut back each ~:, ~' '~" .
. ' :.
.
, .
11)91;~40 week to a height of 4 cm, and are sprayed 40 days after sowing and 1 day after the last cutting with aqueous spray liquors of an active substance of the formula I.
The amount of active substance is equivalent to 5 kg of active substance per hectare. The growth of the grasses is evaluated lO and 21 days after application.
Reduction of ~rowth of cereals Spring wheat (Triticum aestivum), spring barley (Hordeum vulgare) and rye (Secale) are sown in sterilised soil in plastic trays and are grown in a greenhouse.~ The shoots of the cereals are treated, 5 days after sowing, with a spray liquor of the active substance. This leaf application is equivalent to 6 ~g of active substance per hectare. An evaluation is made after 21 days.
The tested active substances according to the invention produce an appreciable reduction in growth both of the grasses and of the cereals.
~,J
.. . , . , , ~
' ' : ' :' .:
- , .
' ' ' ~ ' ~ ' '
Claims (20)
1. A phenoxy-phenoxy-alkanecarboxylic acid derivative of the formula I
(I) in which R1 is hydrogen, C1-C4 alkyl or C2-C3 alkoxyalkyl, A is the cyano group or a radical -COR, wherein R is a radical -OR3, SR4-NR5R6 or -N=R2, wherein R3 is hydrogen or the cation of a base ? M m ? wherein M is an alkali metal cation or alkaline-earth metal cation, or a Fe, Cu, Zn, Mn or Ni cation, or an ammonium group , and m as integer 1, 2 or 3 takes into account the valency of the cation, whilst Ra, Rb, Rc and Rd independently of one another are hydrogen, benzyl or a C1-C4 alkyl group unsubstituted or substituted by -OH, -NH2 or C1-C4 alkoxy, and in addition R3 is a C1-C12 alkyl group which is unsubstituted or substituted by halogen, nitro, cyano, C1-C8 alkoxy, C1-C8 alkylthio, C2-C8 alkanoyl, bis (C1-C4 alkyl) amino, tris (C1-C4 alkyl)ammonium, C3-C8 cycloalkyl, C3-C8 cycloalkenyl, or by a phenyl, phenoxy or 5- or 6-membered heterocyclic radical having 1 to 3 hetero atoms, each of which is unsubstituted or for its part mono- or polysubstituted by halogen, C1-C4 alkyl or C1-C4 alkoxy, or R3 is an unsubstituted or substituted C3-C18 alkenyl group, a C3-C8 alkynyl group, a C3-C12 cycloalkyl group unsubstituted or sub-stituted by halogen or C1-C4 alkyl, or R3 is a phenyl group which is unsubstituted or mono- or polysubstituted by halogen, C1-C4 alkyl, C1-C4 alkoxy, C1-C4 alkylthio, NO2 or CF3, or R3 is a 5-or 6-membered heterocyclic ring having 1 to 3 hetero atoms, and R4 is the same as R3, R5 and R6 independently of one another are each hydrogen, or an alkyl group which can be unsubstituted or substituted by hydroxyl or alkoxy, or they are each alkoxy, alkenyl, alkynyl, phenyl or benzyl, and the phenyl rings can be mono- or polysubstituted by halogen, alkyl alkoxy, alkylthio, cyano or nitro, or R5 and R6 together with the nitrogen atom to which they are bound can form a 5-6-membered heterocycle, which can also contain a second hetero atom, nitrogen, oxygen or sulfur, R2 is a preferably branched-chain alkylene group bound by a double bond to the nitrogen atom, B is hydrogen or a halogen atom, or a cyano or nitro group, C is halogen, cyano, nitro or trifluoromethyl, D is hydrogen, halogen, cyano, nitro or trifluoromethyl, E is a halogen atom or a C1-C4 alkyl group, and P is the number 1 or 2.
(I) in which R1 is hydrogen, C1-C4 alkyl or C2-C3 alkoxyalkyl, A is the cyano group or a radical -COR, wherein R is a radical -OR3, SR4-NR5R6 or -N=R2, wherein R3 is hydrogen or the cation of a base ? M m ? wherein M is an alkali metal cation or alkaline-earth metal cation, or a Fe, Cu, Zn, Mn or Ni cation, or an ammonium group , and m as integer 1, 2 or 3 takes into account the valency of the cation, whilst Ra, Rb, Rc and Rd independently of one another are hydrogen, benzyl or a C1-C4 alkyl group unsubstituted or substituted by -OH, -NH2 or C1-C4 alkoxy, and in addition R3 is a C1-C12 alkyl group which is unsubstituted or substituted by halogen, nitro, cyano, C1-C8 alkoxy, C1-C8 alkylthio, C2-C8 alkanoyl, bis (C1-C4 alkyl) amino, tris (C1-C4 alkyl)ammonium, C3-C8 cycloalkyl, C3-C8 cycloalkenyl, or by a phenyl, phenoxy or 5- or 6-membered heterocyclic radical having 1 to 3 hetero atoms, each of which is unsubstituted or for its part mono- or polysubstituted by halogen, C1-C4 alkyl or C1-C4 alkoxy, or R3 is an unsubstituted or substituted C3-C18 alkenyl group, a C3-C8 alkynyl group, a C3-C12 cycloalkyl group unsubstituted or sub-stituted by halogen or C1-C4 alkyl, or R3 is a phenyl group which is unsubstituted or mono- or polysubstituted by halogen, C1-C4 alkyl, C1-C4 alkoxy, C1-C4 alkylthio, NO2 or CF3, or R3 is a 5-or 6-membered heterocyclic ring having 1 to 3 hetero atoms, and R4 is the same as R3, R5 and R6 independently of one another are each hydrogen, or an alkyl group which can be unsubstituted or substituted by hydroxyl or alkoxy, or they are each alkoxy, alkenyl, alkynyl, phenyl or benzyl, and the phenyl rings can be mono- or polysubstituted by halogen, alkyl alkoxy, alkylthio, cyano or nitro, or R5 and R6 together with the nitrogen atom to which they are bound can form a 5-6-membered heterocycle, which can also contain a second hetero atom, nitrogen, oxygen or sulfur, R2 is a preferably branched-chain alkylene group bound by a double bond to the nitrogen atom, B is hydrogen or a halogen atom, or a cyano or nitro group, C is halogen, cyano, nitro or trifluoromethyl, D is hydrogen, halogen, cyano, nitro or trifluoromethyl, E is a halogen atom or a C1-C4 alkyl group, and P is the number 1 or 2.
2. A compound of the formula I, Claim 1, in which C is the trifluoromethyl group, and D is hydrogen, and A, B, E, p and R1 are as defined under the formula I.
3. A compound of the formula I, Claim 1, in which C is the trifluoromethyl group, D is a halogen atom, and A, B, C, p and R1 are as defined under the formula I.
4. A compound of the formula I, Claim 1, in which C and D are halogen atoms, and A, B, E, p and R1 are as defined under the formula I.
5. A compound of the formula I, Claim 1, in which C is the trifluoromethyl group, D is a cyano or nitro group, and A, B, E, p and R1 are as defined under the formula I.
6. A compound of the formula I, Claim 1, in which C is a halogen atom, D is the cyano group, and A, B, E, p and R1 are as defined under the formula I.
7. A compound of the formula I, Claim 1, in which B, C, D and E are each a halogen atom, p is the number 1, and A is as defined under the formula I.
8. A compound of the formula I, Claim 1, in which B, D and E are each a halogen atom, C is the trifluoro-methyl group, p is the number 1, and A is as defined under the formula I, Claim 1.
9. As a compound according to Claim 1:
.alpha.-[3-(2',4'-dichlorophenoxy)-4,6-dichlorophenoxy)-propionic acid methyl ester.
.alpha.-[3-(2',4'-dichlorophenoxy)-4,6-dichlorophenoxy)-propionic acid methyl ester.
10. As a compound according to Claim 1:
.alpha.-[3-(2'-chloro-4-trifluoromethylphenoxy)-4,6-dichloro-phenoxy]-propionic acid methyl ester.
.alpha.-[3-(2'-chloro-4-trifluoromethylphenoxy)-4,6-dichloro-phenoxy]-propionic acid methyl ester.
11. .alpha.-[3-(2'-Chloro-4'-trifluoromethylphenoxy)-4,6-dichlorophenoxy]-propionic acid isopropyl ester.
12. .alpha.-[3-(2'-Chloro-4'-trifluoromethylphenoxy)-4,6-dichlorophenoxy]
propionic acid-N-methyl-N-methoxyamide.
propionic acid-N-methyl-N-methoxyamide.
13. .alpha.-[3-(2'-Chloro-4'-trifluoromethylphenoxy)-4,6-dichlorophenoxy]-propionic acid-N-(.beta.-methoxyethyl)-amide.
14. .alpha.-[3-(2'-Chloro-4'-trifluoromethylphenoxy)-4-chloro-6-cyano-phenoxy]-propionic acid methyl ester.
15. A process for producing phenoxy-phenoxy-alkanecarboxylic acid derivatives of formula I as defined in claim 1, which process comprises react-ing in a manner known per se (a) an appropriately substituted halogenobenzene of the formula II
(II) in which "Hal" is a halogen atom and C and D are as defined in claim 1, with an appropriately substituted hydroxyphenoxyalkanecarboxylic acid derivative of the formula III
(III) in which A, E, p and R1 are as defined in claim 1, in a solvent in the pres-ence of a base; or (b) an appropriately substituted 3-hydroxy-diphenyl ether of the formula IV
(IV) in which A, C, D, E and p are as defined in claim 1, with an .alpha.-halogeno-carboxylic acid derivative of the formula V
(V) in which "Hal" is a halogen atom, and A and R1 are as defined in claim 1, in a solvent in the presence of a base.
(II) in which "Hal" is a halogen atom and C and D are as defined in claim 1, with an appropriately substituted hydroxyphenoxyalkanecarboxylic acid derivative of the formula III
(III) in which A, E, p and R1 are as defined in claim 1, in a solvent in the pres-ence of a base; or (b) an appropriately substituted 3-hydroxy-diphenyl ether of the formula IV
(IV) in which A, C, D, E and p are as defined in claim 1, with an .alpha.-halogeno-carboxylic acid derivative of the formula V
(V) in which "Hal" is a halogen atom, and A and R1 are as defined in claim 1, in a solvent in the presence of a base.
16. A process according to claim 15, wherein "Hal" represents chlorine or bromine.
17. A process according to claim 15 or 16, which comprises converting a compound of the formula I in which A is a free carboxyl group, by treatment with an inorganic or organic base, into a salt.
18. A process according to claim 15 or 16, which comprises converting a compound of the formula I, in which A is a free carboxyl group, into an acid halide, and subsequently converting this, by reaction with an alkanol, a thiol or an amide, into another acid derivative corresponding to the defin-ition of A.
19. The use of the phenoxy-phenoxy-alkanecarboxylic acid derivatives of the formula I, claim 1, or of compositions containing them, as herbicides.
20. The use of the phenoxy-phenoxy-alkanecarboxylic acid derivatives of the formula I, claim 1, or of compositions containing them, for regulating plant growth.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CH624/78-9 | 1978-01-20 | ||
| CH62478 | 1978-01-20 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1091240A true CA1091240A (en) | 1980-12-09 |
Family
ID=4191335
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA320,024A Expired CA1091240A (en) | 1978-01-20 | 1979-01-22 | Phenoxy-phenoxy-alkanecarboxylic acid derivatives having a herbicidal action, their production, compositions containing them, and their use |
Country Status (8)
| Country | Link |
|---|---|
| EP (1) | EP0003295B1 (en) |
| JP (1) | JPS54125624A (en) |
| BR (1) | BR7900354A (en) |
| CA (1) | CA1091240A (en) |
| DE (1) | DE2961372D1 (en) |
| ES (1) | ES476990A1 (en) |
| IL (1) | IL56458A (en) |
| PH (1) | PH15584A (en) |
Families Citing this family (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2850902A1 (en) * | 1978-11-24 | 1980-06-12 | Hoechst Ag | NEW PHENOXY-PHENOXI-PROPIONIC ACID AMIDES AND THEIR USE AS HERBICIDES |
| DE2906237A1 (en) * | 1979-02-17 | 1980-08-28 | Bayer Ag | PHENOXYCARBONIC ACID AMIDES, METHOD FOR THE PRODUCTION THEREOF AND THEIR USE AS HERBICIDES |
| EP0018324A1 (en) * | 1979-04-12 | 1980-10-29 | Ciba-Geigy Ag | Herbicidal, substituted diphenyl-ether derivatives, process for their preparation, as well as herbicidal compositions and their use |
| DE3269621D1 (en) * | 1981-08-07 | 1986-04-10 | Ciba Geigy Ag | Phenoxyphenyl-aminocarboxylic-acid derivatives, their preparation, compositions containing them and their use |
| KR840003613A (en) * | 1982-02-12 | 1984-09-15 | 아르놀트 자일러 에른스트 알테르 | Manufacturing method of herbicide |
| US4547218A (en) * | 1982-10-18 | 1985-10-15 | The Dow Chemical Company | Certain 3-nitro-6-phenoxy-2-pyridyl-oxy-propionates having herbicidal activity |
| DE3571432D1 (en) * | 1984-05-18 | 1989-08-17 | Asahi Chemical Ind | 2-nitro-5-(2'-chloro-4'trifluoromethylphenoxy)phenylacetic ester, thioester and amide, process for preparation therof, herbicidal composition, and method for destruction of undesirable weeds |
| US4710582A (en) * | 1986-07-14 | 1987-12-01 | Ppg Industries, Inc. | Herbicidally active substituted diphenyl ether oxime derivatives |
| GB8827262D0 (en) * | 1988-11-22 | 1988-12-29 | Ici Plc | Herbicidal compounds |
| CA2084874A1 (en) * | 1990-06-11 | 1991-12-12 | Shizuo Azuma | Optical isomer or r-form of diphenyl ether derivative and herbicide containing the same as active ingredient |
| MX2009008934A (en) * | 2007-02-26 | 2009-08-28 | Dow Agrosciences Llc | Process for the preparation of certain substituted sulfilimines. |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4070178A (en) * | 1975-09-03 | 1978-01-24 | Rohm And Haas Company | Herbicidal diphenyl ethers |
| JPS5814402B2 (en) * | 1975-09-27 | 1983-03-18 | 石原産業株式会社 | old man |
| JPS5934705B2 (en) * | 1976-03-05 | 1984-08-24 | 石原産業株式会社 | Phenoxyphenoxyalkane nitrile derivatives and herbicides containing them |
| JPS5828262B2 (en) * | 1976-03-17 | 1983-06-15 | 石原産業株式会社 | Phenoxyphenoxyalkane carboxylic acid derivatives and herbicides containing them |
| NZ181994A (en) | 1975-09-27 | 1978-09-20 | Ishihara Sangyo Kaisha | (2-chloro-4-trifluorom-ethylphenoxy)-phenoxy acids,esters,ethers,amides and nitriles and herbicidal compositions |
| GB1565972A (en) * | 1976-04-15 | 1980-04-23 | Sori Soc Rech Ind | M-substituted phenoxypropionic acid dervatives |
-
1979
- 1979-01-12 DE DE7979100087T patent/DE2961372D1/en not_active Expired
- 1979-01-12 EP EP79100087A patent/EP0003295B1/en not_active Expired
- 1979-01-18 IL IL56458A patent/IL56458A/en unknown
- 1979-01-19 BR BR7900354A patent/BR7900354A/en unknown
- 1979-01-19 PH PH22082A patent/PH15584A/en unknown
- 1979-01-19 ES ES476990A patent/ES476990A1/en not_active Expired
- 1979-01-20 JP JP650579A patent/JPS54125624A/en active Pending
- 1979-01-22 CA CA320,024A patent/CA1091240A/en not_active Expired
Also Published As
| Publication number | Publication date |
|---|---|
| ES476990A1 (en) | 1979-06-16 |
| BR7900354A (en) | 1979-08-14 |
| JPS54125624A (en) | 1979-09-29 |
| DE2961372D1 (en) | 1982-01-28 |
| EP0003295A1 (en) | 1979-08-08 |
| PH15584A (en) | 1983-02-17 |
| IL56458A0 (en) | 1979-03-12 |
| IL56458A (en) | 1983-02-23 |
| EP0003295B1 (en) | 1981-11-25 |
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