CA1175849A - Heterocyclic esters of phenoxybenzoic acids - Google Patents
Heterocyclic esters of phenoxybenzoic acidsInfo
- Publication number
- CA1175849A CA1175849A CA000419935A CA419935A CA1175849A CA 1175849 A CA1175849 A CA 1175849A CA 000419935 A CA000419935 A CA 000419935A CA 419935 A CA419935 A CA 419935A CA 1175849 A CA1175849 A CA 1175849A
- Authority
- CA
- Canada
- Prior art keywords
- chloro
- nitro
- trifluoromethylphenoxy
- benzoate
- tetrahydrofuryl
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
Classifications
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/02—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms
- A01N43/04—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom
- A01N43/06—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom five-membered rings
- A01N43/08—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom five-membered rings with oxygen as the ring hetero atom
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
- C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
- C07D307/04—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having no double bonds between ring members or between ring members and non-ring members
- C07D307/10—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having no double bonds between ring members or between ring members and non-ring members with substituted hydrocarbon radicals attached to ring carbon atoms
- C07D307/16—Radicals substituted by carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/02—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms
- A01N43/04—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom
- A01N43/14—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom six-membered rings
- A01N43/16—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom six-membered rings with oxygen as the ring hetero atom
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C205/00—Compounds containing nitro groups bound to a carbon skeleton
- C07C205/49—Compounds containing nitro groups bound to a carbon skeleton the carbon skeleton being further substituted by carboxyl groups
- C07C205/57—Compounds containing nitro groups bound to a carbon skeleton the carbon skeleton being further substituted by carboxyl groups having nitro groups and carboxyl groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton
- C07C205/59—Compounds containing nitro groups bound to a carbon skeleton the carbon skeleton being further substituted by carboxyl groups having nitro groups and carboxyl groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton the carbon skeleton being further substituted by singly-bound oxygen atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
- C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
- C07D307/04—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having no double bonds between ring members or between ring members and non-ring members
- C07D307/18—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having no double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D307/20—Oxygen atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D309/00—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only ring hetero atom, not condensed with other rings
- C07D309/02—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only ring hetero atom, not condensed with other rings having no double bonds between ring members or between ring members and non-ring members
- C07D309/08—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only ring hetero atom, not condensed with other rings having no double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D309/10—Oxygen atoms
- C07D309/12—Oxygen atoms only hydrogen atoms and one oxygen atom directly attached to ring carbon atoms, e.g. tetrahydropyranyl ethers
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Agronomy & Crop Science (AREA)
- Pest Control & Pesticides (AREA)
- Plant Pathology (AREA)
- Health & Medical Sciences (AREA)
- Engineering & Computer Science (AREA)
- Dentistry (AREA)
- General Health & Medical Sciences (AREA)
- Wood Science & Technology (AREA)
- Zoology (AREA)
- Environmental Sciences (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Furan Compounds (AREA)
- Pyrane Compounds (AREA)
- Plural Heterocyclic Compounds (AREA)
Abstract
ABSTRACT
The compounds of the formula:
and pharmaceutically acceptable salts and in-vivo hydrolysable esters thereof wherein R1 is a hydrogen atom or a group selected from OH, OSO3H or a pharmaceutically acceptable salt or C1-4 alkyl ester thereof, OR2, SR3, OCOR2, OCO2R3 or OCONHR3, where R2 is a C1-6 alkyl group or an optionally substituted benzyl group and R3 is a C1-6 alkyl group or an optionally substituted benzyl or an optionally substituted phenyl group; and R22 is a hydrogen atom, C1-6 alkyl, C2-6 alkenyl, C3-6 alkynyl wherein the triple bond is not present on the carbon adjacent to the sulphur atom, aralkyl, C1-6 alkanoyl, aralkanoyl, aryloxyalkanoyl or arylcarbonyl, any of such R22 groups being optionally substituted; with the proviso that when R22 is 2-aminoethyl R1 must be SR3 or OSO3H or a pharmaceutically acceptable salt or C1-4 alkyl ester thereof; have been found to be antibacterially active.
Their use is described as are processes for their preparation.
The compounds of the formula:
and pharmaceutically acceptable salts and in-vivo hydrolysable esters thereof wherein R1 is a hydrogen atom or a group selected from OH, OSO3H or a pharmaceutically acceptable salt or C1-4 alkyl ester thereof, OR2, SR3, OCOR2, OCO2R3 or OCONHR3, where R2 is a C1-6 alkyl group or an optionally substituted benzyl group and R3 is a C1-6 alkyl group or an optionally substituted benzyl or an optionally substituted phenyl group; and R22 is a hydrogen atom, C1-6 alkyl, C2-6 alkenyl, C3-6 alkynyl wherein the triple bond is not present on the carbon adjacent to the sulphur atom, aralkyl, C1-6 alkanoyl, aralkanoyl, aryloxyalkanoyl or arylcarbonyl, any of such R22 groups being optionally substituted; with the proviso that when R22 is 2-aminoethyl R1 must be SR3 or OSO3H or a pharmaceutically acceptable salt or C1-4 alkyl ester thereof; have been found to be antibacterially active.
Their use is described as are processes for their preparation.
Description
` ~ ~ VCC-50~6 ,.
Heterocyc1ic Esters o~
;~ ~henoxybenzoic Acids Spacification ; This invention relates to new compositions of matter and : 5 more specifically relates to new chemical compound.s of the formula:
Q
~' ~ ~ ~H2)n : (I) i wherein X is halogen or tri.fluorome~hyl; Y is selected from the ! group consisting of hydrogen, halogen, nitro and cyano; R is selected Erom the group consisting of nitro, alkylthio, halogen 1 10 and cyano; and n is the integer 1 or 2.
i The compounds of the present invention are unexpectedly useful as selective herbicides.
In a preferred embodiment of the present invention X is -' chlorine, bromine or trifluoromethyl; Y is hydrogen, chlorine, bromine, nitro or cyano; and R is nitro, methylthio, chlorine, :1 . bromine and cyano.
The compounds of the present inventi~n can be prepared by reacting acid chloride of the formula ~ 11 .
Y C - Cl . . . I / .
_ ! wherein X, Y and R are as heretofore described, with an alcohol , ~ '-i~ , , C? ~!
of the formula o ~III) wherein n is the integer 1 or 2, in the presence oE an acid acceptor such as a tertiary amine. This reaction can be ~ffect~d by combining about equimolar ~mounts of the acid chloride and alcohol in an inert organic reaction medium such as toluene.
Preferably, excess molar amounts of acid acceptor is used to ensure removal of the hydrogen chloride that is formed. Typically, the reaction is carried out at room temperature with agitation. After completion of the reaction the desired product can be recovered by first removing acid acceptor salt followed by evaporation of the solvent used as the reaction medium. This product can then be used as such or can be further purified by conventional techniques.
The acid chloride of formula II usef~ll in preparing the compounds of this invention can be readily prepared from the corresponding acids by reaction with thionyl chloride.
Exemplary precursor acid for the acid chlorides of formu}a II
are 2-nitro-5-(2-chloro-4-trifluoromethylphenoxy)benzoic acid, 2-nitro-5-(2-bromo-4-trifluoromethylphenoxy)benzoic acid, 2-nitro-5-(2,4-dichlorophenoxy)benzoic acid, 2-nitro-5-(2-nitro-4-chloro-phenoxy)benzoic acid, 2-nitro-5-(2-cyano-4-trifluoromethylphenoxyJ-benzoic acid, 2-nitro-5-(4-trifluoromethylphenoxy~benzoic acid,
Heterocyc1ic Esters o~
;~ ~henoxybenzoic Acids Spacification ; This invention relates to new compositions of matter and : 5 more specifically relates to new chemical compound.s of the formula:
Q
~' ~ ~ ~H2)n : (I) i wherein X is halogen or tri.fluorome~hyl; Y is selected from the ! group consisting of hydrogen, halogen, nitro and cyano; R is selected Erom the group consisting of nitro, alkylthio, halogen 1 10 and cyano; and n is the integer 1 or 2.
i The compounds of the present invention are unexpectedly useful as selective herbicides.
In a preferred embodiment of the present invention X is -' chlorine, bromine or trifluoromethyl; Y is hydrogen, chlorine, bromine, nitro or cyano; and R is nitro, methylthio, chlorine, :1 . bromine and cyano.
The compounds of the present inventi~n can be prepared by reacting acid chloride of the formula ~ 11 .
Y C - Cl . . . I / .
_ ! wherein X, Y and R are as heretofore described, with an alcohol , ~ '-i~ , , C? ~!
of the formula o ~III) wherein n is the integer 1 or 2, in the presence oE an acid acceptor such as a tertiary amine. This reaction can be ~ffect~d by combining about equimolar ~mounts of the acid chloride and alcohol in an inert organic reaction medium such as toluene.
Preferably, excess molar amounts of acid acceptor is used to ensure removal of the hydrogen chloride that is formed. Typically, the reaction is carried out at room temperature with agitation. After completion of the reaction the desired product can be recovered by first removing acid acceptor salt followed by evaporation of the solvent used as the reaction medium. This product can then be used as such or can be further purified by conventional techniques.
The acid chloride of formula II usef~ll in preparing the compounds of this invention can be readily prepared from the corresponding acids by reaction with thionyl chloride.
Exemplary precursor acid for the acid chlorides of formu}a II
are 2-nitro-5-(2-chloro-4-trifluoromethylphenoxy)benzoic acid, 2-nitro-5-(2-bromo-4-trifluoromethylphenoxy)benzoic acid, 2-nitro-5-(2,4-dichlorophenoxy)benzoic acid, 2-nitro-5-(2-nitro-4-chloro-phenoxy)benzoic acid, 2-nitro-5-(2-cyano-4-trifluoromethylphenoxyJ-benzoic acid, 2-nitro-5-(4-trifluoromethylphenoxy~benzoic acid,
2-methylthio-5-(2-chloro-4-trifluoromethylphenoxyJbenzoic acid 2-chloro-5-(2-chloro-4-trifluoromethylphe`noxyj benzoic acid 2-bromo-5-(2-chloro-4-trifluoromethylphenoxy)benzoic acid 2-ethylthio-5-(2-chloro-4-trifluoromethylphenoxy)benzoic acid 2-propylthio-5-~2-chloro-4-trifluoromethylphenoxy)benzoic acid . ~
.
7~
2-cyano-5-~2-chloro-4-trifluoromethylphenoxy)benzoic acid the }ike.
Exemplary alcohols of formula III useful in preparing the compounds of the present invention are 3-hydro~ytetrahydrofuran~
.
7~
2-cyano-5-~2-chloro-4-trifluoromethylphenoxy)benzoic acid the }ike.
Exemplary alcohols of formula III useful in preparing the compounds of the present invention are 3-hydro~ytetrahydrofuran~
3-hydroxytetrahydropyran 7 4-hydroxytetrahydropyran and the like.
The compounds of the present invention wherein the tetrahydro-furan or tetrahydropyran moieties are attached to the carboxylic acid group in the 2 position are preferably prepared by reacting the acid corresponding to formula II with dihydrofuran or 3,4-di-hydropyran. This reaction can be efEected by combining the acidand the dihydrofuran or dihydropyran a~ room te~l~perature in the presence of a catalytic amount of p-toluenesulfonic acid. The u~
of excess pyran or furan is preferred. After the reaction i8 completed the mixture can be washed and s~ripped of excess s~ar~ing material -to yield the desired product.
The manner in which the compounds of this invention can be prepared is more specifically illustrated in the following examples.
PreDaration of 2-Nitro-5-~2-chloro-4-tri-20fiuoromethylphenoxy)benzoyl chloride 2-Nitro-5-(2-chloro-4-trifluoromethylphenoxy)benzoic acid (80 grams~ and toluene (80 ml) were charged into a reaction vessel equipped with a mechanical stirrer, thermometer and reflux condenser. Thion~l chloride (80 ml) was slowly added at room temperature with stirring. After the addition was completed the mixture was heated at reflux with continued stirring for a period of one hour. Stirring was therafter continued at room temperature overnight. After this time the reaction mixture was stripped of toluene to yield the desired product as an oil.
- 3 - :
Preparation of 3-Tetrahydrofuryl~2-Nitro 5-2-chloro-4-trifluoromethylphenoxy ben~oate 3-Hydroxytetrahydrofuran (1.76 grams; 0,02 mole), tolucne (50 ml) and triethylamine ~2.0 grams; 0.02 mole) ~ere charged into a glass reaction vessel equipped with a mechanical stirr~r and addition funnel. A solution of 2-nitro-5~(2-chloro-4-trifluoro-methylphenoxy)benzoyl chloride (7.60 grams; 0.02 mole) in toluene (10 ml) was slowly added with stirring. After the addition was completed stirring was continued overnight. After this time the reaction mixture was washed with water and dried over anhydrous sodium sulfate. The dried solution was then stripped of solvent under reduced pressure leaving a brown oil. This oil was puri~ied by silica gel chromatography using toluene and ethyl acetatettoluene mixtures as the eluant. The puri~ied oil was triturated in etXanol to yield the de~ired product 3-tetrahydrofuryl 2-nitro 5-~2-chloro-
The compounds of the present invention wherein the tetrahydro-furan or tetrahydropyran moieties are attached to the carboxylic acid group in the 2 position are preferably prepared by reacting the acid corresponding to formula II with dihydrofuran or 3,4-di-hydropyran. This reaction can be efEected by combining the acidand the dihydrofuran or dihydropyran a~ room te~l~perature in the presence of a catalytic amount of p-toluenesulfonic acid. The u~
of excess pyran or furan is preferred. After the reaction i8 completed the mixture can be washed and s~ripped of excess s~ar~ing material -to yield the desired product.
The manner in which the compounds of this invention can be prepared is more specifically illustrated in the following examples.
PreDaration of 2-Nitro-5-~2-chloro-4-tri-20fiuoromethylphenoxy)benzoyl chloride 2-Nitro-5-(2-chloro-4-trifluoromethylphenoxy)benzoic acid (80 grams~ and toluene (80 ml) were charged into a reaction vessel equipped with a mechanical stirrer, thermometer and reflux condenser. Thion~l chloride (80 ml) was slowly added at room temperature with stirring. After the addition was completed the mixture was heated at reflux with continued stirring for a period of one hour. Stirring was therafter continued at room temperature overnight. After this time the reaction mixture was stripped of toluene to yield the desired product as an oil.
- 3 - :
Preparation of 3-Tetrahydrofuryl~2-Nitro 5-2-chloro-4-trifluoromethylphenoxy ben~oate 3-Hydroxytetrahydrofuran (1.76 grams; 0,02 mole), tolucne (50 ml) and triethylamine ~2.0 grams; 0.02 mole) ~ere charged into a glass reaction vessel equipped with a mechanical stirr~r and addition funnel. A solution of 2-nitro-5~(2-chloro-4-trifluoro-methylphenoxy)benzoyl chloride (7.60 grams; 0.02 mole) in toluene (10 ml) was slowly added with stirring. After the addition was completed stirring was continued overnight. After this time the reaction mixture was washed with water and dried over anhydrous sodium sulfate. The dried solution was then stripped of solvent under reduced pressure leaving a brown oil. This oil was puri~ied by silica gel chromatography using toluene and ethyl acetatettoluene mixtures as the eluant. The puri~ied oil was triturated in etXanol to yield the de~ired product 3-tetrahydrofuryl 2-nitro 5-~2-chloro-
4-trifluoromethylphenoxy)benzoate as a white solid melting point at 55C.
Preparation of 3-Tetrahydrofuryl 2-Nitro-5-(2-bromo-4-trifluoromethyl~henoxy benzoate 3-Hydrotetrahydrofuran (0.04 mole), toluene ~50 ml) and triethylamine tO.04 mole) are charged into a glass reaction vessel equipped with a mechanical stirrer and addition funnel. A solution of 2-nitro-5-(2-bromo-4-trifluoromethylphenoxy)ben~oyl chloride tO.04 mole) in toluene (20 ml) is slowly added at room temperature with stirring. After ~.he addition is completed stirring is continued for a period of about 8 hours. After this time the reaction ~ixture is washed with water and dried over anhydrous magnesium sulfate.
The dried solution is then stripped of solvent under reduced pressure ! leaving a residue. This residue is purified by silica gel chromato-... . .
.' ,; , , .
.
' -~ graphy using toluene'and ethyl acetate/toluene mixture as the eluant to yield the desired product 3-tetrahydrofuryl 2-nitro-5-~2-~ bromo-4-trifluoromethylphenoxy)benzoate.
,. EXAMPLE 4 Praparation of 3-Tetrahydrofurvl 2-Nitro-S-t2-nitro-4-trifluoromethylphenoxy benzoat_ 3-Hydroxytetrahydrofuran (0.04 mole), toluene (50 ml) and tri ethylamine (0.04 mole) are charged into a glass reaction ves~el equipped with a mechanical stirrer and addition funnel. A solution of 2-nitro-5-(2-nitro~4-trifluoromethylphenoxy)benzoyl ~hloride (0.04 mole) in toluene (20 ml) is slowly added at room temperature ' with stirring. After the addition is completed stirr:ing is continued for a period of abou-t a hours. After this time the reaction , j mixture is washed with water and dried over anhydrous magnesium; 15 sulfate. The dried solution i5 then stripped of solvent under - reduced presRure leaving a residue. This residue is purified by silica gel chromatography using toluene and ethyl acetate/toluene mixture as the eluant to yield the desired product 3-tetrahydro-_ furyl 2-nitro-5,-(2-nitro-4-trifluoromethylphenoxy)benzoate.
; Pre~aration of 3-TetrahydrofurY1 2-Nitro-5-(2-cYano-4-trifluoromethylphenoxyJbenzoate 3-Hydroxytetrahydrofuran (D.04 mole), toluene (5U ml) and triethylamine (0.04 mole) are charged into a glass reaction ~essel equipped with a mechanical stirrer and addition funnel. A solution of 2-nitro-5-(2-cyano-4-trifluoromethylphenoxy?benzoyl chloride (0.04 mole~ in toluene (20 ml) is slowly added at room temperature with stirring. After the addition is completed stirring is continued for a per,~iod of about 8 hours. After this time the -- .
- , . _ . -- - ~
_ _ _ _ _ . _ _ _ reaction mixture is washed with water and dried over anhydrous magnesium sulf~te. The dried solution is then stripped of solv~nt under reduced pressure leaving a residue. This residue is purifisd by silica gel chromatography using toluene and ethyl acetate/toluene mixture as the eluant to yield the desired product 3-tetrahydrofuryl 2-nitro-5-t2-cyano-4-trifluoromethylphenoxy)benzoate.
Pre aration of 3-Te ~ -~ -trifluoromethylphenoxy)benzoat_ 3-Hydroxytetrahydrofuran (0.04 mole), toluene (50 ml) and triethylamine (0.04 mole) are charged into a glass reaction vessel equipped with a mechanical stirrer and addition funnel. A
solution of 2-methylthio-S-t4-trifluoromethylphenoxy)benzoyl chloride (0.04 mole) in toluene (20 ml) is slowly added at room temperature with stirring. After the addition is completed stirring is continued ~or a p~riod of about 8 hour~. After this ti~
the reaction mixture is washed with water and dried over anhydrous magnesium sulfate. The dried solution is then stripped of solvent under reduced pressure leaving a residue. This residue is purified by silica gel chromatography using toluene and ethyl acetate/toluene mixture as the eluant to yield the desired product 3-tetrahydrofuryl 2-methylthio-5-(4-trifluoromethylphenoxy)benzoate.
Pre3aration of 3-Tetrahydrofuryl 2-chloro-5-(?-bromo-4-trifluoromethylehenoxy benzoate 3-Hydroxytetrahydrofuran (0.04 mole), toluene (S0 ml) and triethylamine (0.04 mole) are charged into a glass reaction vessel equipped with a mechanical stirrer and addition funnel. A solution of 2-chloro-5-(2-brQmo-4-trifluoromethylphenoxy)benzoyl chloride (0.~4 mole2 in toluene (20 ml2 is slowly added at room temperature . . . . .
, c~ c`
~7~c~
. .
i with stirring. After the addition is completed stirring i5 continued for a period of about 8 hours. After this time the reaction mi~tura : is washed with water and dried over anhydrous magnesium sulfate.
- The dried solution is then stripped of solvent under reduced pressure leaving a residue. This residue is purified by silica gel chromato-graphy using toluene and ethyl acetateltoluene mixt:ure as the eluant to yield the desired product 3-tetrahydrofuryl 2-chloro-5-(2-bromo-4-trifluoromethylphenoxy)benzoate.
EX~PLE 8 Pre~aration of 3-Tetrahydrofuryl 2-Bromo-5-(2-Chloro-4-trifluoromethylphenoxy?benzoate 3-Hydroxytetrahydrofuran (0.04 mole), toluene (50 ml) aDd ; triethylamine ~0.04 mole) are charged into a glass reaction ~essel equipped with a mechanical stirrer and addition funnel. A solution ~ 15 of 2-bromo-5-(2-chloro-4-tri~luoromethylphenoxy)ben~oyl chloride j - ~0.04 mole) in toluene ~20 ml) is slowly added at room temperature ~ith stirring. After the addition is completed stirring is continued for a period of about 8 hours. After this time the reaction mixture is washed with water and dried over anhydrous magnesium sulfate. The dried solution is then stripped of solvent under reduced pressure leaving a residue. This residue is purified by silica gel chromatography using toluene and ethyl acetatel toluene mixture as the eluant to yield the desired product 3-tetra hydrofuryl 2-bromo-5-(2-chloro-4-trifluoromethylphenoxy)ben~o3te.
; 25 EXAMPLE g Pre~aration of 3-Tetrahydrofuryl 2'Cyano-5-t2,4-di-chlorophenoxy benzoate ¦ 3-Hydroxytetrahydrofuran (0.04 mole), toluene (50 ml) and triethylamine (0.04 mole) are charged into a glass reaction vessel _ 7 _ .. .. . . . _ . . _ ... . _ . _ , .. . ... . .. _ . . .
.~ . . .
...... _ . .
! `
. ., .
equipped with a mechanical stirrer and addition fùnnel. A solution of 2-cyano-5-(2,4~dichlorophenoxy)benzoyl chlorid~ (0.04 mole) in - j toluene (20 ml~ is slowly added at room temperature with stirring.
After the addition is completed stirring is continued for a period of about 8 hours. After this time the reaction mixture is washed with water and dried over anhydrous magnesium sulfate. The dried solution is then stripped of solvent under reduced pressure leaving a residue. This residue is purified by silica gel chromatography using toluene and ethyl acetate/toluene mixture as the eluant to 10yield the desired product 3-tetrahydrofuryl 2-cyano-5-~2,4-dichloro-phenoxy~benzoate.
..
EXA~P~E 10 I Preparat.~on of 3-Tet ~hydrofuryl 2-Ethylthio-S _~--- Chloro-4-bromoPhenoxy ben~oate 153-HydroxytetrahydroPuran ~0.04 mole~, toluene ~50 ml) and - ! triethylamine (0.04 mole~ are charged into a glass reaction vessel equipped ~ith a mechanical stirrer and addition funnel. A solution of 2-ethylthio-5-(2-chloro-4-bromophenoxy)benzoyl chloride tO.04 mole`
in toluene (20 ml) is slowly added at room temperature with stirring.
After the addition is completed stirring is continued for a period ._ of about 8 hours. After this time the reaction mixture is washed with water and dried over anhydrous magnesium sulfate. The dried solution is then stripped of solvent under reduced pressure leaving a residue. This residue is purified by silica gel chromatography j 25 using toluene and ethyl acetate/toluene mixture as the eluant to ! yield the desired product 3-tetrahydrofuryl 2-ethylthio-5-(2-~ chloro-4-bromophenoxy)benzoate.
d ¦ EXAMPLE 11 PreParation of 3-Tetrahydropyranyl 2-Nitro-5-~2-chloro-j 304-trifluoromethylPhenoxy benzoate ! 3-Hydroxytetrahydropyran ~0.04 mole), toluene (50 ml) !
.
.. . .. . .. .. ._ , ,~ . ~
, and triethylamine (0.04 mole) are charged into a glass reaction vessel equipped with a mechanical stirrer and addition funnel. A
solution of 2-nitro-5-(2-chloro-4-trifluoromethylphenoxy)benzoyl chloride (0.04 mole) in toluene (20 ml) is slowly added at room temperature with stirring. After the addition is completed stirring is continued for a period of about 8 hours. After this time the reaction mixture is washed with water and dried over anhydrous magnesium sulfate. The dried solution is then stripped of solvent under reduced pressure leaving a residue. This residue is purified 13 by silica gel chromatography using toluene and ethyl acetate/toluene mixture as the eluant to yield the desired product 3 tetrahydro-pyranyl 2-nitro-5-(2-chloro-4-trifluoromethylphenoxy)benzoate.
.
Pre~aration of ~-Tetrahydropyranyl 2-Nitro-5-(2-Chloro- - r:if:luoromethylphenoxy)benzoate 4~Hydroxytetrahydropyran ~0.04 mole), toluene (S0 ml) and triethylamine (0.04 mole) are charged into a glass reaction vessel equipped with a mechanical stirrer and addi-eion funnel. A solution of 2-nitro-5-(2-chloro-4-trifluorometh~lphenoxy)benzoyl chloride (0.04 mole~ in toluene (20 ml) is slowly added at room temperature with stirring. After the addition is completed stirring is continued for a period of about 8 hour~. After this time the reaction mixture is washed with water and dried over anhydro~s magnesium sulfate.
' The dried solution is then stripped of solvent under reduced pressure leaving a residue. This residue is purified by silica gel chromato graphy using toluene and ethyl acetate/,toluene mixture as the eluant to yield the desired product 4-tetrahydropyranyl 2-nitro-
Preparation of 3-Tetrahydrofuryl 2-Nitro-5-(2-bromo-4-trifluoromethyl~henoxy benzoate 3-Hydrotetrahydrofuran (0.04 mole), toluene ~50 ml) and triethylamine tO.04 mole) are charged into a glass reaction vessel equipped with a mechanical stirrer and addition funnel. A solution of 2-nitro-5-(2-bromo-4-trifluoromethylphenoxy)ben~oyl chloride tO.04 mole) in toluene (20 ml) is slowly added at room temperature with stirring. After ~.he addition is completed stirring is continued for a period of about 8 hours. After this time the reaction ~ixture is washed with water and dried over anhydrous magnesium sulfate.
The dried solution is then stripped of solvent under reduced pressure ! leaving a residue. This residue is purified by silica gel chromato-... . .
.' ,; , , .
.
' -~ graphy using toluene'and ethyl acetate/toluene mixture as the eluant to yield the desired product 3-tetrahydrofuryl 2-nitro-5-~2-~ bromo-4-trifluoromethylphenoxy)benzoate.
,. EXAMPLE 4 Praparation of 3-Tetrahydrofurvl 2-Nitro-S-t2-nitro-4-trifluoromethylphenoxy benzoat_ 3-Hydroxytetrahydrofuran (0.04 mole), toluene (50 ml) and tri ethylamine (0.04 mole) are charged into a glass reaction ves~el equipped with a mechanical stirrer and addition funnel. A solution of 2-nitro-5-(2-nitro~4-trifluoromethylphenoxy)benzoyl ~hloride (0.04 mole) in toluene (20 ml) is slowly added at room temperature ' with stirring. After the addition is completed stirr:ing is continued for a period of abou-t a hours. After this time the reaction , j mixture is washed with water and dried over anhydrous magnesium; 15 sulfate. The dried solution i5 then stripped of solvent under - reduced presRure leaving a residue. This residue is purified by silica gel chromatography using toluene and ethyl acetate/toluene mixture as the eluant to yield the desired product 3-tetrahydro-_ furyl 2-nitro-5,-(2-nitro-4-trifluoromethylphenoxy)benzoate.
; Pre~aration of 3-TetrahydrofurY1 2-Nitro-5-(2-cYano-4-trifluoromethylphenoxyJbenzoate 3-Hydroxytetrahydrofuran (D.04 mole), toluene (5U ml) and triethylamine (0.04 mole) are charged into a glass reaction ~essel equipped with a mechanical stirrer and addition funnel. A solution of 2-nitro-5-(2-cyano-4-trifluoromethylphenoxy?benzoyl chloride (0.04 mole~ in toluene (20 ml) is slowly added at room temperature with stirring. After the addition is completed stirring is continued for a per,~iod of about 8 hours. After this time the -- .
- , . _ . -- - ~
_ _ _ _ _ . _ _ _ reaction mixture is washed with water and dried over anhydrous magnesium sulf~te. The dried solution is then stripped of solv~nt under reduced pressure leaving a residue. This residue is purifisd by silica gel chromatography using toluene and ethyl acetate/toluene mixture as the eluant to yield the desired product 3-tetrahydrofuryl 2-nitro-5-t2-cyano-4-trifluoromethylphenoxy)benzoate.
Pre aration of 3-Te ~ -~ -trifluoromethylphenoxy)benzoat_ 3-Hydroxytetrahydrofuran (0.04 mole), toluene (50 ml) and triethylamine (0.04 mole) are charged into a glass reaction vessel equipped with a mechanical stirrer and addition funnel. A
solution of 2-methylthio-S-t4-trifluoromethylphenoxy)benzoyl chloride (0.04 mole) in toluene (20 ml) is slowly added at room temperature with stirring. After the addition is completed stirring is continued ~or a p~riod of about 8 hour~. After this ti~
the reaction mixture is washed with water and dried over anhydrous magnesium sulfate. The dried solution is then stripped of solvent under reduced pressure leaving a residue. This residue is purified by silica gel chromatography using toluene and ethyl acetate/toluene mixture as the eluant to yield the desired product 3-tetrahydrofuryl 2-methylthio-5-(4-trifluoromethylphenoxy)benzoate.
Pre3aration of 3-Tetrahydrofuryl 2-chloro-5-(?-bromo-4-trifluoromethylehenoxy benzoate 3-Hydroxytetrahydrofuran (0.04 mole), toluene (S0 ml) and triethylamine (0.04 mole) are charged into a glass reaction vessel equipped with a mechanical stirrer and addition funnel. A solution of 2-chloro-5-(2-brQmo-4-trifluoromethylphenoxy)benzoyl chloride (0.~4 mole2 in toluene (20 ml2 is slowly added at room temperature . . . . .
, c~ c`
~7~c~
. .
i with stirring. After the addition is completed stirring i5 continued for a period of about 8 hours. After this time the reaction mi~tura : is washed with water and dried over anhydrous magnesium sulfate.
- The dried solution is then stripped of solvent under reduced pressure leaving a residue. This residue is purified by silica gel chromato-graphy using toluene and ethyl acetateltoluene mixt:ure as the eluant to yield the desired product 3-tetrahydrofuryl 2-chloro-5-(2-bromo-4-trifluoromethylphenoxy)benzoate.
EX~PLE 8 Pre~aration of 3-Tetrahydrofuryl 2-Bromo-5-(2-Chloro-4-trifluoromethylphenoxy?benzoate 3-Hydroxytetrahydrofuran (0.04 mole), toluene (50 ml) aDd ; triethylamine ~0.04 mole) are charged into a glass reaction ~essel equipped with a mechanical stirrer and addition funnel. A solution ~ 15 of 2-bromo-5-(2-chloro-4-tri~luoromethylphenoxy)ben~oyl chloride j - ~0.04 mole) in toluene ~20 ml) is slowly added at room temperature ~ith stirring. After the addition is completed stirring is continued for a period of about 8 hours. After this time the reaction mixture is washed with water and dried over anhydrous magnesium sulfate. The dried solution is then stripped of solvent under reduced pressure leaving a residue. This residue is purified by silica gel chromatography using toluene and ethyl acetatel toluene mixture as the eluant to yield the desired product 3-tetra hydrofuryl 2-bromo-5-(2-chloro-4-trifluoromethylphenoxy)ben~o3te.
; 25 EXAMPLE g Pre~aration of 3-Tetrahydrofuryl 2'Cyano-5-t2,4-di-chlorophenoxy benzoate ¦ 3-Hydroxytetrahydrofuran (0.04 mole), toluene (50 ml) and triethylamine (0.04 mole) are charged into a glass reaction vessel _ 7 _ .. .. . . . _ . . _ ... . _ . _ , .. . ... . .. _ . . .
.~ . . .
...... _ . .
! `
. ., .
equipped with a mechanical stirrer and addition fùnnel. A solution of 2-cyano-5-(2,4~dichlorophenoxy)benzoyl chlorid~ (0.04 mole) in - j toluene (20 ml~ is slowly added at room temperature with stirring.
After the addition is completed stirring is continued for a period of about 8 hours. After this time the reaction mixture is washed with water and dried over anhydrous magnesium sulfate. The dried solution is then stripped of solvent under reduced pressure leaving a residue. This residue is purified by silica gel chromatography using toluene and ethyl acetate/toluene mixture as the eluant to 10yield the desired product 3-tetrahydrofuryl 2-cyano-5-~2,4-dichloro-phenoxy~benzoate.
..
EXA~P~E 10 I Preparat.~on of 3-Tet ~hydrofuryl 2-Ethylthio-S _~--- Chloro-4-bromoPhenoxy ben~oate 153-HydroxytetrahydroPuran ~0.04 mole~, toluene ~50 ml) and - ! triethylamine (0.04 mole~ are charged into a glass reaction vessel equipped ~ith a mechanical stirrer and addition funnel. A solution of 2-ethylthio-5-(2-chloro-4-bromophenoxy)benzoyl chloride tO.04 mole`
in toluene (20 ml) is slowly added at room temperature with stirring.
After the addition is completed stirring is continued for a period ._ of about 8 hours. After this time the reaction mixture is washed with water and dried over anhydrous magnesium sulfate. The dried solution is then stripped of solvent under reduced pressure leaving a residue. This residue is purified by silica gel chromatography j 25 using toluene and ethyl acetate/toluene mixture as the eluant to ! yield the desired product 3-tetrahydrofuryl 2-ethylthio-5-(2-~ chloro-4-bromophenoxy)benzoate.
d ¦ EXAMPLE 11 PreParation of 3-Tetrahydropyranyl 2-Nitro-5-~2-chloro-j 304-trifluoromethylPhenoxy benzoate ! 3-Hydroxytetrahydropyran ~0.04 mole), toluene (50 ml) !
.
.. . .. . .. .. ._ , ,~ . ~
, and triethylamine (0.04 mole) are charged into a glass reaction vessel equipped with a mechanical stirrer and addition funnel. A
solution of 2-nitro-5-(2-chloro-4-trifluoromethylphenoxy)benzoyl chloride (0.04 mole) in toluene (20 ml) is slowly added at room temperature with stirring. After the addition is completed stirring is continued for a period of about 8 hours. After this time the reaction mixture is washed with water and dried over anhydrous magnesium sulfate. The dried solution is then stripped of solvent under reduced pressure leaving a residue. This residue is purified 13 by silica gel chromatography using toluene and ethyl acetate/toluene mixture as the eluant to yield the desired product 3 tetrahydro-pyranyl 2-nitro-5-(2-chloro-4-trifluoromethylphenoxy)benzoate.
.
Pre~aration of ~-Tetrahydropyranyl 2-Nitro-5-(2-Chloro- - r:if:luoromethylphenoxy)benzoate 4~Hydroxytetrahydropyran ~0.04 mole), toluene (S0 ml) and triethylamine (0.04 mole) are charged into a glass reaction vessel equipped with a mechanical stirrer and addi-eion funnel. A solution of 2-nitro-5-(2-chloro-4-trifluorometh~lphenoxy)benzoyl chloride (0.04 mole~ in toluene (20 ml) is slowly added at room temperature with stirring. After the addition is completed stirring is continued for a period of about 8 hour~. After this time the reaction mixture is washed with water and dried over anhydro~s magnesium sulfate.
' The dried solution is then stripped of solvent under reduced pressure leaving a residue. This residue is purified by silica gel chromato graphy using toluene and ethyl acetate/,toluene mixture as the eluant to yield the desired product 4-tetrahydropyranyl 2-nitro-
5-(2-chloro-4-trifluoromethylphenoxy)benzoate.
_ g _ .. ... . __ . .. _. . . . . . _ _ . _ _ _ . _ . _ .. _ . . _ _ . _ '--.. , . . ~
c ~'7~ 3 .'i - ' , ' .
¦ . EXA~IPLE 13 Preparation of 3-Tetrahydropyranyl 2-tMethylthio 5-(2-Chloro-4-trlfluoromethylphenoxy benzoate 3-Hydroxytetrahydropyran (0.04 mole), toluene ~50 ml~ and triethylamine ~0.04 mole) are charged into a glass reaction vessel equipped with a mechanical stirrer and addition funnel. A soluti~n of 2-nitro-5 ~2-chloro-4-trifluoromethylphenoxy)benzoyl chloride (0.04 mole) in toluene (20 ml) is slowly added at room temperature with stirring. After the addition is completed stirring is continued for a period of about 8 hours. After this time the reaction mixture is washed with water and dried over anhydrous magnesium sulfate.
; The dried solution is then stripped of solvent under reduced pressure leaving a residue. This residue is puriEied by silica gel chromatography using toluene and ethyl acetateitoluene rnixture as }S the eluant to yield the desired product 3 tetrahydropyranyl 2-m~thyl-thio-5-~2-chloro-4-trlfluoromethylphenoxy)benzoate.
, EXAMPLE 14 j PreDaration of 2-Tetrahydropyranyl 2-Nitro-5-(2-Chloro-4-trifluoromethylphenoxy ben~oate 2,3-Dihydropyran (20 ml), 2-nitro-5-(2-chloro-4-trifluoro-methylphenoxy)benzoic acid tO.05 mole) and para-toluenesulfonic acid (1 spatula tip) are charged into a glass reaction vessel equipped with a mechan;cal stirrer. The mixture is stirred at room temperature I until the carboxylic acid group as determined by infra-red spectro-scopy is no longer detectable in the mixture. After this time the I mixture is dissolved in methylene chloride washed with dilute !` aqueous sodium carbonate and dried over anhydrous magnesium sulfate I The dried solution is then stripped of solvent and excess dihydro-`I pyran under reduced pressure to yield the desired product ,, 2-tetrahydropyranyl 2-nitro-5-~2-chloro-4-trifluoromethylphenoxy)-, benzoate.
: I -- 10 ,, - . , . ~ l Preparation of 2-Tetrahydrofuryl ?-Nitro-5-(2-Chloro-4-__ tri~luoromethylp enoxy en~oate Dihydrofuran (0.03 mole)~ 2-nitro-5-(2-chloro-4 trifluoro-_ _ 5 methylphenoxy)benzoic acid (0.025 mole) methylene chloride ~25 ml) and ~-toluenesulfonic acid (1 spatula tip) are charged into a glass reaction vessel equipped with a magnetic stirrer. The reaction mixture is stirred at room temperature until the carboxylic acid - group can no longer be detected by IR in the mixture. After this time the reaction mixture is washed with dilute aqueous sodium carbonate and with water. The washed solutiol~ was dried and I stripped of solvent and unreacted starting material to yield the --¦ desired product 2-tetrahydrofuryl 2-nitro-5-(2-chloro 4-trifluoro-_ methylphenoxy)ben~oate.
5.
~or practical use as herbicides the compounds of this invention are generally incorporated into herbicidal compositionR
which comprise an inert carrier and a herbicidally toxic amount of such a compound. Such herbicidal compositions, which can also . J be called formulations, enable the active compound to be applied conveniently to the site of the weed infestation in any desired I quantity. These compositions can be solids such as dusts, granules~
¦ or wettable powders; or they can be liquids such as solutions, ~~~, aerosols or emulsifiable concentrates.
For example, dusts can be prepared by grinding and blending - 25 the active compound with a solid inert carrier such as the talcs, clays, silicas, pyrophyllite, and the like. Granular formulations -.
_ . _ . __ ... .. . . .
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'~
can be prepared by impregnating the compound, usually dissolvcd in a suitable solvent, onto and into granulated carriers such as the attapulgites or the vermiculites, usually of a particle si3e , range of from about 0.3 to l.S mm. Wettable powders, which c~n ¦ 5 be dispersed in water or oil to any desired concerltrat:ion of th~
' active compound, can be prepared by incorporating wetting agentB
- into concentrated dust compositions.
~ In some CaseS the active compounds are sufficiently soluble _ in common organic solvents such as kerosene or xylene so that they can be used directly as solutions in these solvents.
' Frequently, solutions of herbicides can be dispersed under super ¦ atmospheric pressure as aerosols. However, preferred liquid herbicidal compositions are emulsifiable concentrates, which comprise an active compound according to this invention and as the inert carrier, a solvent and an emulsifier. Such emulsifiable concen-trates can be extended with watcr and/or oil to any desired concentration of active compound for application as sprays to the site of the weed infestation. The emulsifiers most ' commonly used in these concentrates are nonionic or mixtures of nonionic with anionic surface-active agents. With the use of some emulsifier systems an inverted emulsion ~water in oil) can be prepared for direct application to weed infestations.
A typical herbicidal composition according to this invention is illustrated by the following example, in which the quantities are in parts by weight.
Preparation of a Dust Product of Example 2 10 Powdered Talc 90 The above ingredients are mixed in a mechanical grinder - 12 ~
.. , .. _ _ -. _, - , ;
c; ~ l blender and are ground until a homogeneous, free-flowing dust of the desired partiele size is obtained. This dust is suitable for direct application to the site of the weed infestation~
The compounds of this invention can be applied as herbicides in any manner recogni7ed by the art. One method for the eontral of weeds comprises contacting the locus of said weeds with a herbicidal composition comprising an inert carrier a~d as an essential active ingredient, in a quantity which is herbicidally toxie to said weeds, a compound of the present invention. The concentration of the new compounds of this invention in the herbicidal compositions will vary greatly with the type of formulation and the purpose for which it is designed, but generally the herbicidal compositions will comprise from about 0.05 to about 95 percent by weight of thc active compounds of this invention. In a preferred embodiment of this invention, the herbicidal compositions will comprise from - about 5 to about 75 percent by weight of the active compound. The eompositions can also comprise such additional substances as other pesticides, sueh as insecticides, nematocides, fungicides, and the like; stabilizers, spreaders, deactivators, adhesives, ~tickers, fertilizers, activators, synergists and the like.
The eompounds of the present invention are also useful when combined with other herbicides and/or defoliants, dessicants, growth inhibitors and the like in the herbicidal compositions heretobefore described. These other materials can comprise from about 5$ to about 95% of the active ingredients in the herbicidal eompositions.
Use of combinations of these other herbicides and/or defoliants, dessicants, etc. with the compounds of the present invention provide - herbicidal compositions which are more effective in controlling . ~
weeds and oten provide results unattainable with separate compositions of the individual herbicides. The other he:rbicides, defoliants, dessicants and the plant grow-th inhibitors,~ith - which the compounds o~ this invention can be used in the herbicidal compositions to control weeds, can include chlorophenoxy herbicides such as 2,4-D~ 2,4, 5-T, MCPA, ~CPB, 4~2,4-DB), 2,4-DEB, 4-CPB, 4-CPP, 2,4,5-TB, 2,4,5-TES, 3,~-DA, silvex and the like; carbamate, hPrbicides such as IPC, CIPC, swep, barban, BCPC, CEPC, CPPC, and the like; thiocarbamate and dithiocarbamate herbicides such as DCEC, methan sodium, EPTX, diallate, PEBC, perbulate, vernolate and the like; subs-tituted urea herbicides such as nor~a, siduron, dichlor~l urea, chloroxuron, cycluron, fenuron, monuron, monuron ~CA, diuron, linuron, monolinuron, neburon, buturon, trimeturon and the likc;
i symmetrical tria~ine 9 herbicides such as sim~zine, chloraz;n~
' 15 atraone, desmetryne, norazine, ipazine, prometryn, atrazin~, ¦ trietazine, simetone, prometone, propazine, ametryne, and the like;
chloroacetamide herbicides such as alpha-chloro-N,N-dimethylacetamide, CDEA, CDAA, alpha-chloro-N-isopropylacetamide, 2-chloro-N-isopropyl acetanilide, 4-(chloroacetyl)-morpholine, l-~chloracetyl) piperidine, and the like; chlorinated aliphatic acid herbicides such as TCA, . dalapon, 2,3-dichloropropionic acid, 2,2,3-TPA and the like;
; chlorinated benzoic acid and the phenylacetic acid herbicides such as 2,3,6-TBA, 2,3,5,6-TBA, dicamba, tricamba, amiben, fenac, PBA, ; 2-methoxy-3,6-dichlorophenylacetic acid, 3-methoxy-2,6-dichloro-25 phenylacetic acid, 2-methoxy-3,4,6-trichlorophenylacetic acid, 2,4-dichloro-3-nitrobenzoic acid and the like; and such compounds as aminotriazole, maleic hydrazide, phenyl mercuric acetate, endothal, biuret, technical chlordane, dimethyl 2,3,5,6-tetrachloro-terephthalate, diquat, erbon, DNC, DNBP, dichlorobenil, D~A, diphenamid, dipropalin, triflurallne, solan, dicryl, merphos, DMPA, ._ . ~ ., . . _ . - , - , .
. DS~, MSMA, potassium a~ide, acrolein, benefin, bensulide, AMS, : bromacil, 2-(3,4-dichlorophenyl)-4-methyl-1,2,4-oxadiazolidine, 3,5-dione, bromoxynil, cacodylic acid~ DMA, DPMF, cypro~nid, DCB, 3CPA, dichlone, diphenatril, DMTT, DNAP, EBEP, EXD, HCA, ioxynil, IPX, isocyil, potassium cyanate, NAA, MA~, MCPES, MCPP, MH, --- molinate, NPA, OCH, paraquat, PCP, picloram~ DPA, PCA, pyrichl~r, sesone, terbacil, terbutol, TCBA, brominil, CP-50144, H-176-1, H 732, M-2091, planavin, sodium tetraborate, calcium cyanamid, DEF, ethyl . xanthogen disulfide, sindone, sindone B, propanil and the like.
_ j 10 Such herbicides can also be used in the methods and composition j of this invention in the`form of their salts, csters, amides, and other derivatives whenever applicable to the particu:Lar parent -.:r . compounds.
. Weeds are undesirable plants growing where they are not wanted, - ¦ 15 having no economic value, and interfering with the produc~ion o~
¦ cultivated crops, wi-th the growing of ornamental plants 3 or with ! the welfare of livestock. Many types of weeds are known~ including annuals such as pigweed, lambsquarter, foxtail, crabgrass, wild mustard, field pennycress, ryegrass, goose grass, chickweed, wild ! 20 oats, velvet leaf, purselane, barnyard grass, smartweed, knotweed, t cocklebur, wild buckwheat, kochia, medic corn cockle, ragweed, i~ sowthistle, coffee-weed, croton, cuphea, dodder, fumitorya groundsel~
hemp nettle, knowel, spurge, spurry, emex, jungle rice, pondweed~
dog fennel, carpetweed, morning glory, bedstraw, ducksalad and - .
25 naiad; biennials such as wild carrot, matricaria, ~ild barley, campion, chamomile, burdock, mullein, roundleaved mallow, bull . thistle, hounds-tongue, moth mullein, and purple star thistle;
or perennials such as white cockle, perennial rye-grass, quackgrass . Johnson grass, Canada thistle, hedge bindweed, Bermuda grass, sheep _ . ~
' '.' ? . . ' 3~ ~'7S~
sorrel, curly docX, nutgrass, field chickweed, dandelion, campanula, field bindweed, Russian knapweed, mesquite, toadflax, -yarrow, aster, gromwell, horsetail, ironweed, sesbania, bulrush~
cattail and wintercress.
' 5 Similarly, such weeds can be classified as broadleaf ori grassy weeds. It is economically desirable to control the growth i of such weeds without damaging beneficial plants or livestock.
~t The new compoun~s of this invention are particularly valuable for weed control because they are toxic to many species and groups of weeds while they are relatively nontoxic to many bene~icial plants.
I The axact amount of compound required will depend on a variety of ¦ factors, including the hardiness of the particûlar weed specias, I weather, type of soil, method of application, the kind of benefici~1 j - plants in the same area, and the like. Thus, while the application of up to only abou-t one or two ounces of active compound per acre may be sufficient for good control of a light infestation of weeds growing under adverse conditions, the application of ten pounds or more of active compound per acre may be required for good control of a dense infestation of hardy perennial weeds growing under favorable conditions.
The herbicidal toxicity of the new compounds of this invention can be illustrated by many of the established testing techniques known to the art, such as pre- and pcst-emergenoe testing.
The herbicidal activity of the compounds of this invention was demonstrated by experiments carried out for the pre-emergence control of a variety of weeds. In these experiments small plastic 3 ~--greenhouse pots filled with dry soil were seeded with th~ variou~
weed seeds. Twenty-four hours or less after the seeding, the pot~
were sprayed with water until the 50il was wet and the test compounds formulated as aqueous emulsions of acetone solutions containing ~ -5 emulsifiers were sprayed at the indicated concentrations on the surface of the soil.
After spraying~ the soil containers were placed in the green-house and provided with supplementary heat as required and daily or more frequent watering. The plants were maintained under these conditions for a period of from 15 to 21 days, at which time the condition of the plants and the degree oP injury to the plants was rated on a scale of from 0 to 10, as follows: 0 = no injury, 19 2 - slight injury, 3, 4 ~ moderate injury, 5, 6 = moderately severe injury, 7, 8, ~ - severe injury, 10 = death and NE indicated not emerged. The effectiveness of these compounds is demonstrated by the following date set out in Tables I and II. Numbers with decimal places are the result of averaglng two or more ratings obtained from replicate experiments.
The herbicidal activity of the compounds of this invention was also demonstrated by experiments carried out for the post-emergence control of a variety of weeds. In these experiments the compounds to be tested were formulated as aqueous emulsions and sprayed at the indicated dosage on the foliage of the various weed species that have attained a prescribed size. After spraying, the plants were placed in a greenhouse and watered daily or more frequently. Water was not applied to the foliage of the treated plants. The severity of the injury was determined 10 to 15 days after treatment and was rated on the scale of from 0 to 10 heretobefore described. The effectiveness of these compounds is demonstrated by the following data set forth in Tables III and IV. ~alues with decimal places again are the result of averaging of replicate experimentsO
. _ . _. . . _ . .
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E~ L ~ I rl O ¦
C -1 I u~ rl O O C rl I ~ o 3 N ~ ~ O O l ~ O O ~ ~-1 i _ rl rl u ¦ rl l v ~ I r L o -l o o L r' O O O ~a r 3 ~ 0 0 0 SL ~1 r~ rl rl ~_ O O n o .
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al ~ ~ rlrl r~t 2; Z r~ r~ ~n o o ~ l ~ L~l ~ 1- ~ i ,~9~
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TABLE II ' Post-Emer~ence Scre~n .
Compound Product of ~xample 2 _INJURY ]~ATIN~ _ .
WEED SPECIES#~ACRE 1 ¦ .5 .25 .125 _ _.
BDWD 10 10 10 lD
MNGY 10 10 10 10 .
YLFX 10 lD 10 3 SPGT 10 10 10 lo SUBT 10 10 ,10 10 ALFA 10 . 10 10 14 WRCHIoCN 10 _10 1 1 _ _ _ _ ___ . '.
Abbreviations For Weeds WMSD = Wild Mustard CBGS = Crabgrass BDWD = Bindweed SPGT = Sprangletop PIGW = Pigweed CTGS = Cheatgrass JMWD = Jimsonweed SUBT = Sugarbeet VTLF = Velvetleaf COTN = Cotton MNGY = Morningglory SOYB = Soybean YLFX = Yellow Foxtail PTBN = Pintobean BNGS = Barnyardgrass hLFA = Alfalfa JNGS = Johnson~rass SORG = Sorgum QKGS - Quickgrass WHT = Whsat WOAT = Wild Oat .
.,
_ g _ .. ... . __ . .. _. . . . . . _ _ . _ _ _ . _ . _ .. _ . . _ _ . _ '--.. , . . ~
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¦ . EXA~IPLE 13 Preparation of 3-Tetrahydropyranyl 2-tMethylthio 5-(2-Chloro-4-trlfluoromethylphenoxy benzoate 3-Hydroxytetrahydropyran (0.04 mole), toluene ~50 ml~ and triethylamine ~0.04 mole) are charged into a glass reaction vessel equipped with a mechanical stirrer and addition funnel. A soluti~n of 2-nitro-5 ~2-chloro-4-trifluoromethylphenoxy)benzoyl chloride (0.04 mole) in toluene (20 ml) is slowly added at room temperature with stirring. After the addition is completed stirring is continued for a period of about 8 hours. After this time the reaction mixture is washed with water and dried over anhydrous magnesium sulfate.
; The dried solution is then stripped of solvent under reduced pressure leaving a residue. This residue is puriEied by silica gel chromatography using toluene and ethyl acetateitoluene rnixture as }S the eluant to yield the desired product 3 tetrahydropyranyl 2-m~thyl-thio-5-~2-chloro-4-trlfluoromethylphenoxy)benzoate.
, EXAMPLE 14 j PreDaration of 2-Tetrahydropyranyl 2-Nitro-5-(2-Chloro-4-trifluoromethylphenoxy ben~oate 2,3-Dihydropyran (20 ml), 2-nitro-5-(2-chloro-4-trifluoro-methylphenoxy)benzoic acid tO.05 mole) and para-toluenesulfonic acid (1 spatula tip) are charged into a glass reaction vessel equipped with a mechan;cal stirrer. The mixture is stirred at room temperature I until the carboxylic acid group as determined by infra-red spectro-scopy is no longer detectable in the mixture. After this time the I mixture is dissolved in methylene chloride washed with dilute !` aqueous sodium carbonate and dried over anhydrous magnesium sulfate I The dried solution is then stripped of solvent and excess dihydro-`I pyran under reduced pressure to yield the desired product ,, 2-tetrahydropyranyl 2-nitro-5-~2-chloro-4-trifluoromethylphenoxy)-, benzoate.
: I -- 10 ,, - . , . ~ l Preparation of 2-Tetrahydrofuryl ?-Nitro-5-(2-Chloro-4-__ tri~luoromethylp enoxy en~oate Dihydrofuran (0.03 mole)~ 2-nitro-5-(2-chloro-4 trifluoro-_ _ 5 methylphenoxy)benzoic acid (0.025 mole) methylene chloride ~25 ml) and ~-toluenesulfonic acid (1 spatula tip) are charged into a glass reaction vessel equipped with a magnetic stirrer. The reaction mixture is stirred at room temperature until the carboxylic acid - group can no longer be detected by IR in the mixture. After this time the reaction mixture is washed with dilute aqueous sodium carbonate and with water. The washed solutiol~ was dried and I stripped of solvent and unreacted starting material to yield the --¦ desired product 2-tetrahydrofuryl 2-nitro-5-(2-chloro 4-trifluoro-_ methylphenoxy)ben~oate.
5.
~or practical use as herbicides the compounds of this invention are generally incorporated into herbicidal compositionR
which comprise an inert carrier and a herbicidally toxic amount of such a compound. Such herbicidal compositions, which can also . J be called formulations, enable the active compound to be applied conveniently to the site of the weed infestation in any desired I quantity. These compositions can be solids such as dusts, granules~
¦ or wettable powders; or they can be liquids such as solutions, ~~~, aerosols or emulsifiable concentrates.
For example, dusts can be prepared by grinding and blending - 25 the active compound with a solid inert carrier such as the talcs, clays, silicas, pyrophyllite, and the like. Granular formulations -.
_ . _ . __ ... .. . . .
, , cj c~;
'~
can be prepared by impregnating the compound, usually dissolvcd in a suitable solvent, onto and into granulated carriers such as the attapulgites or the vermiculites, usually of a particle si3e , range of from about 0.3 to l.S mm. Wettable powders, which c~n ¦ 5 be dispersed in water or oil to any desired concerltrat:ion of th~
' active compound, can be prepared by incorporating wetting agentB
- into concentrated dust compositions.
~ In some CaseS the active compounds are sufficiently soluble _ in common organic solvents such as kerosene or xylene so that they can be used directly as solutions in these solvents.
' Frequently, solutions of herbicides can be dispersed under super ¦ atmospheric pressure as aerosols. However, preferred liquid herbicidal compositions are emulsifiable concentrates, which comprise an active compound according to this invention and as the inert carrier, a solvent and an emulsifier. Such emulsifiable concen-trates can be extended with watcr and/or oil to any desired concentration of active compound for application as sprays to the site of the weed infestation. The emulsifiers most ' commonly used in these concentrates are nonionic or mixtures of nonionic with anionic surface-active agents. With the use of some emulsifier systems an inverted emulsion ~water in oil) can be prepared for direct application to weed infestations.
A typical herbicidal composition according to this invention is illustrated by the following example, in which the quantities are in parts by weight.
Preparation of a Dust Product of Example 2 10 Powdered Talc 90 The above ingredients are mixed in a mechanical grinder - 12 ~
.. , .. _ _ -. _, - , ;
c; ~ l blender and are ground until a homogeneous, free-flowing dust of the desired partiele size is obtained. This dust is suitable for direct application to the site of the weed infestation~
The compounds of this invention can be applied as herbicides in any manner recogni7ed by the art. One method for the eontral of weeds comprises contacting the locus of said weeds with a herbicidal composition comprising an inert carrier a~d as an essential active ingredient, in a quantity which is herbicidally toxie to said weeds, a compound of the present invention. The concentration of the new compounds of this invention in the herbicidal compositions will vary greatly with the type of formulation and the purpose for which it is designed, but generally the herbicidal compositions will comprise from about 0.05 to about 95 percent by weight of thc active compounds of this invention. In a preferred embodiment of this invention, the herbicidal compositions will comprise from - about 5 to about 75 percent by weight of the active compound. The eompositions can also comprise such additional substances as other pesticides, sueh as insecticides, nematocides, fungicides, and the like; stabilizers, spreaders, deactivators, adhesives, ~tickers, fertilizers, activators, synergists and the like.
The eompounds of the present invention are also useful when combined with other herbicides and/or defoliants, dessicants, growth inhibitors and the like in the herbicidal compositions heretobefore described. These other materials can comprise from about 5$ to about 95% of the active ingredients in the herbicidal eompositions.
Use of combinations of these other herbicides and/or defoliants, dessicants, etc. with the compounds of the present invention provide - herbicidal compositions which are more effective in controlling . ~
weeds and oten provide results unattainable with separate compositions of the individual herbicides. The other he:rbicides, defoliants, dessicants and the plant grow-th inhibitors,~ith - which the compounds o~ this invention can be used in the herbicidal compositions to control weeds, can include chlorophenoxy herbicides such as 2,4-D~ 2,4, 5-T, MCPA, ~CPB, 4~2,4-DB), 2,4-DEB, 4-CPB, 4-CPP, 2,4,5-TB, 2,4,5-TES, 3,~-DA, silvex and the like; carbamate, hPrbicides such as IPC, CIPC, swep, barban, BCPC, CEPC, CPPC, and the like; thiocarbamate and dithiocarbamate herbicides such as DCEC, methan sodium, EPTX, diallate, PEBC, perbulate, vernolate and the like; subs-tituted urea herbicides such as nor~a, siduron, dichlor~l urea, chloroxuron, cycluron, fenuron, monuron, monuron ~CA, diuron, linuron, monolinuron, neburon, buturon, trimeturon and the likc;
i symmetrical tria~ine 9 herbicides such as sim~zine, chloraz;n~
' 15 atraone, desmetryne, norazine, ipazine, prometryn, atrazin~, ¦ trietazine, simetone, prometone, propazine, ametryne, and the like;
chloroacetamide herbicides such as alpha-chloro-N,N-dimethylacetamide, CDEA, CDAA, alpha-chloro-N-isopropylacetamide, 2-chloro-N-isopropyl acetanilide, 4-(chloroacetyl)-morpholine, l-~chloracetyl) piperidine, and the like; chlorinated aliphatic acid herbicides such as TCA, . dalapon, 2,3-dichloropropionic acid, 2,2,3-TPA and the like;
; chlorinated benzoic acid and the phenylacetic acid herbicides such as 2,3,6-TBA, 2,3,5,6-TBA, dicamba, tricamba, amiben, fenac, PBA, ; 2-methoxy-3,6-dichlorophenylacetic acid, 3-methoxy-2,6-dichloro-25 phenylacetic acid, 2-methoxy-3,4,6-trichlorophenylacetic acid, 2,4-dichloro-3-nitrobenzoic acid and the like; and such compounds as aminotriazole, maleic hydrazide, phenyl mercuric acetate, endothal, biuret, technical chlordane, dimethyl 2,3,5,6-tetrachloro-terephthalate, diquat, erbon, DNC, DNBP, dichlorobenil, D~A, diphenamid, dipropalin, triflurallne, solan, dicryl, merphos, DMPA, ._ . ~ ., . . _ . - , - , .
. DS~, MSMA, potassium a~ide, acrolein, benefin, bensulide, AMS, : bromacil, 2-(3,4-dichlorophenyl)-4-methyl-1,2,4-oxadiazolidine, 3,5-dione, bromoxynil, cacodylic acid~ DMA, DPMF, cypro~nid, DCB, 3CPA, dichlone, diphenatril, DMTT, DNAP, EBEP, EXD, HCA, ioxynil, IPX, isocyil, potassium cyanate, NAA, MA~, MCPES, MCPP, MH, --- molinate, NPA, OCH, paraquat, PCP, picloram~ DPA, PCA, pyrichl~r, sesone, terbacil, terbutol, TCBA, brominil, CP-50144, H-176-1, H 732, M-2091, planavin, sodium tetraborate, calcium cyanamid, DEF, ethyl . xanthogen disulfide, sindone, sindone B, propanil and the like.
_ j 10 Such herbicides can also be used in the methods and composition j of this invention in the`form of their salts, csters, amides, and other derivatives whenever applicable to the particu:Lar parent -.:r . compounds.
. Weeds are undesirable plants growing where they are not wanted, - ¦ 15 having no economic value, and interfering with the produc~ion o~
¦ cultivated crops, wi-th the growing of ornamental plants 3 or with ! the welfare of livestock. Many types of weeds are known~ including annuals such as pigweed, lambsquarter, foxtail, crabgrass, wild mustard, field pennycress, ryegrass, goose grass, chickweed, wild ! 20 oats, velvet leaf, purselane, barnyard grass, smartweed, knotweed, t cocklebur, wild buckwheat, kochia, medic corn cockle, ragweed, i~ sowthistle, coffee-weed, croton, cuphea, dodder, fumitorya groundsel~
hemp nettle, knowel, spurge, spurry, emex, jungle rice, pondweed~
dog fennel, carpetweed, morning glory, bedstraw, ducksalad and - .
25 naiad; biennials such as wild carrot, matricaria, ~ild barley, campion, chamomile, burdock, mullein, roundleaved mallow, bull . thistle, hounds-tongue, moth mullein, and purple star thistle;
or perennials such as white cockle, perennial rye-grass, quackgrass . Johnson grass, Canada thistle, hedge bindweed, Bermuda grass, sheep _ . ~
' '.' ? . . ' 3~ ~'7S~
sorrel, curly docX, nutgrass, field chickweed, dandelion, campanula, field bindweed, Russian knapweed, mesquite, toadflax, -yarrow, aster, gromwell, horsetail, ironweed, sesbania, bulrush~
cattail and wintercress.
' 5 Similarly, such weeds can be classified as broadleaf ori grassy weeds. It is economically desirable to control the growth i of such weeds without damaging beneficial plants or livestock.
~t The new compoun~s of this invention are particularly valuable for weed control because they are toxic to many species and groups of weeds while they are relatively nontoxic to many bene~icial plants.
I The axact amount of compound required will depend on a variety of ¦ factors, including the hardiness of the particûlar weed specias, I weather, type of soil, method of application, the kind of benefici~1 j - plants in the same area, and the like. Thus, while the application of up to only abou-t one or two ounces of active compound per acre may be sufficient for good control of a light infestation of weeds growing under adverse conditions, the application of ten pounds or more of active compound per acre may be required for good control of a dense infestation of hardy perennial weeds growing under favorable conditions.
The herbicidal toxicity of the new compounds of this invention can be illustrated by many of the established testing techniques known to the art, such as pre- and pcst-emergenoe testing.
The herbicidal activity of the compounds of this invention was demonstrated by experiments carried out for the pre-emergence control of a variety of weeds. In these experiments small plastic 3 ~--greenhouse pots filled with dry soil were seeded with th~ variou~
weed seeds. Twenty-four hours or less after the seeding, the pot~
were sprayed with water until the 50il was wet and the test compounds formulated as aqueous emulsions of acetone solutions containing ~ -5 emulsifiers were sprayed at the indicated concentrations on the surface of the soil.
After spraying~ the soil containers were placed in the green-house and provided with supplementary heat as required and daily or more frequent watering. The plants were maintained under these conditions for a period of from 15 to 21 days, at which time the condition of the plants and the degree oP injury to the plants was rated on a scale of from 0 to 10, as follows: 0 = no injury, 19 2 - slight injury, 3, 4 ~ moderate injury, 5, 6 = moderately severe injury, 7, 8, ~ - severe injury, 10 = death and NE indicated not emerged. The effectiveness of these compounds is demonstrated by the following date set out in Tables I and II. Numbers with decimal places are the result of averaglng two or more ratings obtained from replicate experiments.
The herbicidal activity of the compounds of this invention was also demonstrated by experiments carried out for the post-emergence control of a variety of weeds. In these experiments the compounds to be tested were formulated as aqueous emulsions and sprayed at the indicated dosage on the foliage of the various weed species that have attained a prescribed size. After spraying, the plants were placed in a greenhouse and watered daily or more frequently. Water was not applied to the foliage of the treated plants. The severity of the injury was determined 10 to 15 days after treatment and was rated on the scale of from 0 to 10 heretobefore described. The effectiveness of these compounds is demonstrated by the following data set forth in Tables III and IV. ~alues with decimal places again are the result of averaging of replicate experimentsO
. _ . _. . . _ . .
. --_ . . . . .
;, : ._ .
_. _.. . . . _ .. .. . .. . . . . .
E~ L ~ I rl O ¦
C -1 I u~ rl O O C rl I ~ o 3 N ~ ~ O O l ~ O O ~ ~-1 i _ rl rl u ¦ rl l v ~ I r L o -l o o L r' O O O ~a r 3 ~ 0 0 0 SL ~1 r~ rl rl ~_ O O n o .
o o ~_ . ~I rl .
--~ O O ~ O ~ _ c r I r1 ¦
al ~ ~ rlrl r~t 2; Z r~ r~ ~n o o ~ l ~ L~l ~ 1- ~ i ,~9~
1~ 3 ~ o o o cn E~ _ o o o o ,. ' .i ~ l ~ , ooo~
~ 1-1 ~ O ~) ~ L~Ooo l ~1',' ' . 1:~ ~ ~
'.. ''~ ' .- ' .
,~
TABLE II ' Post-Emer~ence Scre~n .
Compound Product of ~xample 2 _INJURY ]~ATIN~ _ .
WEED SPECIES#~ACRE 1 ¦ .5 .25 .125 _ _.
BDWD 10 10 10 lD
MNGY 10 10 10 10 .
YLFX 10 lD 10 3 SPGT 10 10 10 lo SUBT 10 10 ,10 10 ALFA 10 . 10 10 14 WRCHIoCN 10 _10 1 1 _ _ _ _ ___ . '.
Abbreviations For Weeds WMSD = Wild Mustard CBGS = Crabgrass BDWD = Bindweed SPGT = Sprangletop PIGW = Pigweed CTGS = Cheatgrass JMWD = Jimsonweed SUBT = Sugarbeet VTLF = Velvetleaf COTN = Cotton MNGY = Morningglory SOYB = Soybean YLFX = Yellow Foxtail PTBN = Pintobean BNGS = Barnyardgrass hLFA = Alfalfa JNGS = Johnson~rass SORG = Sorgum QKGS - Quickgrass WHT = Whsat WOAT = Wild Oat .
.,
Claims (19)
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. A compound of general formula:
wherein n represents an integer of 1 or 2; R represents a group selected from -CN, -NO2, halogen and alkylthio; X
represents a group selected from -CF3 and halogen; and Y
represents a group selected from H, -CN, -NO2 and halogen.
wherein n represents an integer of 1 or 2; R represents a group selected from -CN, -NO2, halogen and alkylthio; X
represents a group selected from -CF3 and halogen; and Y
represents a group selected from H, -CN, -NO2 and halogen.
2. A compound as defined in claim 1, wherein R
represents a group selected from C1, Br, -CN, -NO2 and -SCH3;
X represents a group selected from C1, Br and -CF3; and Y
represents a group selected from H, C1, Br, -CN and -NO2.
represents a group selected from C1, Br, -CN, -NO2 and -SCH3;
X represents a group selected from C1, Br and -CF3; and Y
represents a group selected from H, C1, Br, -CN and -NO2.
3. A compound as defined in claim 1, wherein the moiety of general formula:
is selected from the group consisting of 2-nitro-5-(2-chloro-4-trifluoromethylphenoxy)benzoyl, 2-nitro-5-(2-bromo-4-trifluoromethylphenoxy)benzoyl, 2-nitro-5-(,2,4-dichloro-phenoxy)benzoyl, 2-nitro-5-(2-nitro-4-chlorophenoxy)benzoyl, 2-nitro-5-(2-cyano-4-trifluoromethylphenoxy)benzoyl, 2-nitro-5-(4-trifluoromethylphenoxy)benzoyl, 2-methylthio-5-(2-chloro-4-trifluoromethylphenoxy)benzoyl, 2-chloro-5-(2-chloro-4-trifluoromethylphenoxy)benzoyl, 7.-bromo-5-(2-chloro-4-tri-fluoromethylphenoxy)benzoyl, 2-ethylthio-5-(2-chloro-4-trifluoromethylphenoxy)benzoyl, 2-propylthio-5-(2-chloro-4-trifluoromethylphenoxy)benzoyl and 2-cyano-5-(2-chloro-4-trifluoromethylphenoxy)benzoyl.
is selected from the group consisting of 2-nitro-5-(2-chloro-4-trifluoromethylphenoxy)benzoyl, 2-nitro-5-(2-bromo-4-trifluoromethylphenoxy)benzoyl, 2-nitro-5-(,2,4-dichloro-phenoxy)benzoyl, 2-nitro-5-(2-nitro-4-chlorophenoxy)benzoyl, 2-nitro-5-(2-cyano-4-trifluoromethylphenoxy)benzoyl, 2-nitro-5-(4-trifluoromethylphenoxy)benzoyl, 2-methylthio-5-(2-chloro-4-trifluoromethylphenoxy)benzoyl, 2-chloro-5-(2-chloro-4-trifluoromethylphenoxy)benzoyl, 7.-bromo-5-(2-chloro-4-tri-fluoromethylphenoxy)benzoyl, 2-ethylthio-5-(2-chloro-4-trifluoromethylphenoxy)benzoyl, 2-propylthio-5-(2-chloro-4-trifluoromethylphenoxy)benzoyl and 2-cyano-5-(2-chloro-4-trifluoromethylphenoxy)benzoyl.
4. A compound as defined in claim 1, wherein the moiety of general formula:
is selected from the group consisting of 3- oxytetrahydrofuran, 3- oxytetrahydropyran and 4-oxytetrahydropyran.
is selected from the group consisting of 3- oxytetrahydrofuran, 3- oxytetrahydropyran and 4-oxytetrahydropyran.
5. 3- Tetrahydrofuryl 2-nitro-5-(2-chloro-4-trifluoromethylphenoxy)benzoate.
6. 3-Tetrahydrofuryl 2-nitro-5-(2-bromo-4-tri-fluoromethylphenoxy)benzoate.
7. 3-Tetrahydrofuryl 2-nitro-5-(2-nitro-4-tri-fluoromethylphenoxylbenzoate.
8. 3-Tetrahydrofuryl 2-nitro-5-(2-cyano-4-tri-fluoromethylphenoxylbenzoate.
9. 3-Tetrahydrofuryl 2-methylthio-5-(4-trifluoro-methylphenoxylbenzoate.
10. 3-Tetrahydrofuryl 2-chloro-5-(2-bromo-4-trifluoromethylphenoxy)benzoate.
11. 3-Tetrahydrofuryl 2-bromo-5-(2-chloro-4-trifluoromethylphenoxy)benzoate.
12. 3-Tetrahydrofuryl 2-cyano-5-(2,4-dichloro-phenoxy)benzoate.
13. 3-Tetrahydrofuryl 2-ethylthio-5-(2-chloro-4-bromophenoxy)benzoate.
14. 3-Tetrahydropyranyl 2-nitro-5-(2-chloro-4-trifluoromethylphenoxy)benzoate.
15. 4-Tetrahydropyranyl 2-nitro-5-(2-chloro-4-trifluoromethylphenoxy)benzoate.
16. 3-Tetrahydropyranyl 2-methylthio-5-(2-chloro-4-trifluoromethylphenoxy)benzoate.
17. 2-Tetrahydropyranyl 2-nitro-5-(2-chloro-4-trifluoromethylphenoxy)benzoate.
18. 2-Tetrahydrofuryl 2-nitro-5-2-chloro-4-trifluoromethylphenoxy)benzoateu.
19. A method of controlling weeds which comprises contacting said weeds or the locus of said weeds with a toxic amount of a herbicidal composition comprising as an active ingredient a compound as defined in claim 1, 2 or 3.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US35169782A | 1982-02-24 | 1982-02-24 | |
| US351,697 | 1982-02-24 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1175849A true CA1175849A (en) | 1984-10-09 |
Family
ID=23381984
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000419935A Expired CA1175849A (en) | 1982-02-24 | 1983-01-20 | Heterocyclic esters of phenoxybenzoic acids |
Country Status (18)
| Country | Link |
|---|---|
| JP (1) | JPS58157778A (en) |
| KR (1) | KR860000133B1 (en) |
| AU (1) | AU556105B2 (en) |
| BE (1) | BE895662A (en) |
| BR (1) | BR8300459A (en) |
| CA (1) | CA1175849A (en) |
| CH (1) | CH653678A5 (en) |
| DE (1) | DE3306339A1 (en) |
| DK (1) | DK82883A (en) |
| ES (1) | ES520010A0 (en) |
| FR (1) | FR2521996B1 (en) |
| GB (1) | GB2115418B (en) |
| IL (1) | IL67513A (en) |
| IN (1) | IN159369B (en) |
| IT (1) | IT1164592B (en) |
| NL (1) | NL8300084A (en) |
| RO (2) | RO88222B (en) |
| ZA (1) | ZA83146B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3762858D1 (en) * | 1986-08-28 | 1990-06-28 | Shell Int Research | Phenylharnstoff-herbicide. |
| CA2018845A1 (en) * | 1989-06-15 | 1990-12-15 | Tetsuo Jikihara | Diphenyl ether derivative, herbicidal composition containing the derivative as active ingredient, and process for producing the derivative |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5951950B2 (en) * | 1979-12-17 | 1984-12-17 | 三井東圧化学株式会社 | Tetrahydrofuran derivative |
| AU6651581A (en) * | 1980-02-01 | 1981-08-06 | Rhone-Poulenc, Inc. | 2-nitro-(substituted phenoxy) benzoyl derivatives as herbicides |
| JPS56113744A (en) * | 1980-02-13 | 1981-09-07 | Nippon Nohyaku Co Ltd | Benzoate derivative, its preparation, and use of said derivative |
-
1982
- 1982-12-17 IN IN924/DEL/82A patent/IN159369B/en unknown
- 1982-12-17 IL IL67513A patent/IL67513A/en unknown
- 1982-12-20 AU AU91665/82A patent/AU556105B2/en not_active Ceased
-
1983
- 1983-01-10 ZA ZA83146A patent/ZA83146B/en unknown
- 1983-01-11 NL NL8300084A patent/NL8300084A/en not_active Application Discontinuation
- 1983-01-19 FR FR8300779A patent/FR2521996B1/en not_active Expired
- 1983-01-20 BE BE0/209940A patent/BE895662A/en not_active IP Right Cessation
- 1983-01-20 CA CA000419935A patent/CA1175849A/en not_active Expired
- 1983-01-20 KR KR1019830000200A patent/KR860000133B1/en not_active IP Right Cessation
- 1983-01-31 BR BR8300459A patent/BR8300459A/en unknown
- 1983-02-11 CH CH793/83A patent/CH653678A5/en not_active IP Right Cessation
- 1983-02-22 RO RO114628A patent/RO88222B/en unknown
- 1983-02-22 RO RO110112A patent/RO85315B/en unknown
- 1983-02-23 DK DK82883A patent/DK82883A/en not_active Application Discontinuation
- 1983-02-23 IT IT47773/83A patent/IT1164592B/en active
- 1983-02-23 ES ES520010A patent/ES520010A0/en active Granted
- 1983-02-23 DE DE19833306339 patent/DE3306339A1/en not_active Withdrawn
- 1983-02-23 JP JP58029202A patent/JPS58157778A/en active Pending
- 1983-02-24 GB GB08305099A patent/GB2115418B/en not_active Expired
Also Published As
| Publication number | Publication date |
|---|---|
| ZA83146B (en) | 1983-10-26 |
| GB2115418B (en) | 1986-05-08 |
| AU9166582A (en) | 1983-09-01 |
| IL67513A (en) | 1986-02-28 |
| GB2115418A (en) | 1983-09-07 |
| RO88222A (en) | 1985-12-30 |
| KR860000133B1 (en) | 1986-02-26 |
| RO88222B (en) | 1985-12-31 |
| DE3306339A1 (en) | 1983-09-22 |
| IT1164592B (en) | 1987-04-15 |
| BR8300459A (en) | 1983-11-01 |
| IN159369B (en) | 1987-05-09 |
| ES8403882A1 (en) | 1984-04-01 |
| RO85315B (en) | 1984-10-30 |
| JPS58157778A (en) | 1983-09-19 |
| KR840003246A (en) | 1984-08-20 |
| ES520010A0 (en) | 1984-04-01 |
| FR2521996B1 (en) | 1986-09-05 |
| DK82883A (en) | 1983-08-25 |
| IT8347773A0 (en) | 1983-02-23 |
| RO85315A (en) | 1984-09-29 |
| DK82883D0 (en) | 1983-02-23 |
| CH653678A5 (en) | 1986-01-15 |
| AU556105B2 (en) | 1986-10-23 |
| NL8300084A (en) | 1983-09-16 |
| BE895662A (en) | 1983-05-16 |
| FR2521996A1 (en) | 1983-08-26 |
| IL67513A0 (en) | 1983-05-15 |
| GB8305099D0 (en) | 1983-03-30 |
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