CA1064041A - Diphenyl ether amides and s-methyl-n-(4-)4'-chlorophenoxy) phenyl) thiolcarbamate - Google Patents
Diphenyl ether amides and s-methyl-n-(4-)4'-chlorophenoxy) phenyl) thiolcarbamateInfo
- Publication number
- CA1064041A CA1064041A CA257,391A CA257391A CA1064041A CA 1064041 A CA1064041 A CA 1064041A CA 257391 A CA257391 A CA 257391A CA 1064041 A CA1064041 A CA 1064041A
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- Prior art keywords
- chloro
- compound according
- hydrogen
- methyl
- thiomethyl
- Prior art date
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-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D207/00—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom
- C07D207/02—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D207/30—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having two double bonds between ring members or between ring members and non-ring members
- C07D207/34—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having two 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
- C07D207/36—Oxygen or sulfur atoms
- C07D207/40—2,5-Pyrrolidine-diones
- C07D207/404—2,5-Pyrrolidine-diones with only hydrogen atoms or radicals containing only hydrogen and carbon atoms directly attached to other ring carbon atoms, e.g. succinimide
- C07D207/408—Radicals containing only hydrogen and carbon atoms attached to ring carbon atoms
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N37/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids
- A01N37/18—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids containing the group —CO—N<, e.g. carboxylic acid amides or imides; Thio analogues thereof
- A01N37/22—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids containing the group —CO—N<, e.g. carboxylic acid amides or imides; Thio analogues thereof the nitrogen atom being directly attached to an aromatic ring system, e.g. anilides
- A01N37/24—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids containing the group —CO—N<, e.g. carboxylic acid amides or imides; Thio analogues thereof the nitrogen atom being directly attached to an aromatic ring system, e.g. anilides containing at least one oxygen or sulfur atom being directly attached to the same aromatic ring system
-
- 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
- A01N37/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids
- A01N37/18—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids containing the group —CO—N<, e.g. carboxylic acid amides or imides; Thio analogues thereof
- A01N37/32—Cyclic imides of polybasic carboxylic acids or thio analogues 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
- A01N37/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids
- A01N37/44—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids containing at least one carboxylic group or a thio analogue, or a derivative thereof, and a nitrogen atom attached to the same carbon skeleton by a single or double bond, this nitrogen atom not being a member of a derivative or of a thio analogue of a carboxylic group, e.g. amino-carboxylic acids
- A01N37/46—N-acyl derivatives
-
- 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
- A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
- A01N47/08—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having one or more single bonds to nitrogen atoms
- A01N47/10—Carbamic acid derivatives, i.e. containing the group —O—CO—N<; Thio analogues thereof
- A01N47/20—N-Aryl 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
- A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
- A01N47/08—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having one or more single bonds to nitrogen atoms
- A01N47/28—Ureas or thioureas containing the groups >N—CO—N< or >N—CS—N<
- A01N47/34—Ureas or thioureas containing the groups >N—CO—N< or >N—CS—N< containing the groups, e.g. biuret; Thio analogues thereof; Urea-aldehyde condensation products
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C333/00—Derivatives of thiocarbamic acids, i.e. compounds containing any of the groups, the nitrogen atom not being part of nitro or nitroso groups
- C07C333/02—Monothiocarbamic acids; Derivatives thereof
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- Life Sciences & Earth Sciences (AREA)
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Dentistry (AREA)
- Pest Control & Pesticides (AREA)
- Plant Pathology (AREA)
- Health & Medical Sciences (AREA)
- Engineering & Computer Science (AREA)
- Agronomy & Crop Science (AREA)
- General Health & Medical Sciences (AREA)
- Wood Science & Technology (AREA)
- Zoology (AREA)
- Environmental Sciences (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
- Pyrrole Compounds (AREA)
Abstract
Abstract of the Disclosure Compounds having the formula in which X is chloro or methyl; n is zero, one or two: Y is chloro or trifluormethyl; R1 is hydrogen, alkyl, lower alkoxy, lower haloalkyl, thio-lower alkyl, or alkenyl: R2 is hydrogen, lower alkoxy-alkyl or lower alkenoyl; or R1 and R2 taken to-gether is
Description
..D~ 3 Prior Art Cert~in diphenyl ether ureas are known to be usaful ~s herbicides. For example, U,S. P~ten~ 3,119,682, disclo~es cert~in mono- ~nd dia1kyl~mino dipheny:L ether ure~s as sui~ble herb ic ide s .
~y of ~be l~ ~ntion This ~ppl ic~tion rel~tes to movel diphenyl ether ~mides. In p~rticul~r, this ~pplic~'cion relates to novel d~phenyl ether ~mides h~ving the formul~
C-R
Cl,~--~<
: R2 in which X is chloro or me~hyl; n is zero, one or two~ Y is chloro or trifluoromethyl: Rl is hydrogen, ~qlkyl, lower ~lkoxy, lower h~lo~lkyl, thio-l~er alkyl, or ~lkenyl;` R2 ls hydrogerl, lower ~lko~ lkyl c3r lower ~ qnoyl: or Rl ~nd R2 t~ken together is ~C -~H
H~2 ' O
or ~ compound in whi.ch Y i$ ~ydrogen, n is o, Rl iæ th;ome~hyl ~nd R2 1~ hy~rogen.
~-' , .
.'~ ' ~
:'.
~ , ~ ,. .. : . - - .,, ., ., . ~ , , .
.
By the term "alkyl" is meant aliphatic radicals, both straight chain and branched chain, generally those having from 1 to about 10 carbon atoms, preferably from 1 to about 5 carbon atoms, for example, methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, t-butyl, n-amyl, iso-amyl, n-hexyl, heptyl, octyl, nonyl, decyl, etc. By the terms "]Lo~er alkoxy", "thio-lower alkyl", "lower haloalkyl", "lower a:Lkoxy-alkyl", and "lower alkanoyl" are meant such groups containing from 1 to about 4 carbon atoms, for example, methoxy, ethoxy, propoxy, butoxy, thio-methyl, thio-ethyl~ chloromethyl, dichloromethyl, trichloromethyl, trifluoromethyl, methoxymethyl, ethoxyethyl, ethoxymethyl, formyl, acetyl, propionyl, butyryl, isobutyryl, and the like. By the term "alkenyl" is meant an olefinic group having at least one olefinic bond and having from 2 to about 5 carbon atoms, for example, vinyl, allyl, propenyl, butenyl and the like.
The compounds of this invention have been found to be active herbicides, that is, cer-tain members of the class have been found to be herbicidally effective against a wide range of plant species. More particularly, the compounds of `' the present invention are characterized by having little or no pre-emergence herbicidal activity, but having primarily post-emergence herbicidal activity, primarily affecting broad-leaf vegatation. The present compounds have been found to have particular utility in rice cultivation in selectively , affecting the growth of weeds or other undesirable vegetation while leaving rice plants substantially unaffected. This invention also relates to a method of controlling undesirable ! vegetation comprising applying an herbicidally effective amount of a compound as above described to the area or plant locus ~! .
- where control is desired.
.,,.,,~ .
!.
` -3 .
. ~ .. ..
L$~
An herbicide as used herein, means a compound which controls or modifies the growth of plan-ts. By the term "herbi-cidally effective amount" is meant an amoun-t of compound which causes a modifying effect upon the growth of plants. By "plants" is meant germinant seeds, emerging seedling, and established vegetation, including the roots and above-ground portions. Such modifying effects include all deviations from natural development, for example, killing, retardation, de-foliation, desiccation, regulation, stunting, -tillering, stimulation, leaf burn, dwarfing, and the like.
In general, the compounds of the present invention are prepared by reacting a phenoxy aniline having the formula Cl~ O--~HR 2 with an acyl chloride, alkyl chloroformate (when Rl is lower alkoxy~ or alkyl chlorothiolformate (when Rl is thio-lower alkyl) having the formula Rl-~-Cl to produce the desired com-pound. X, Rl, R2 and n are as defined above. The reaction is conducted in the presence of a hydrogen chloride acceptor such as a trialkyl amine or pyridine, or in the presence of sodium hydride, thus also producing, respectively, an amine hydro-chloride or sodium chloride plus hydrogen. The 2,2-dimethyl-sunninimides (compounds in which Rl and R2 taken together is ' .
C-CH
~ 2 :'~
~3'~
are prepared by reacting a phenoxy aniline having the formula ` Cl ~ ~ O ~ NH2 Xn Y
with 2,2-dimethylsuccinic acid in an acid medium, generally at a temperature of about 140C or higher. The following are illustrative examples of preparation of representative com-pounds o the invention.
Example 1 3-chloro-4(4'-chlorophenoxy) propionanilide (Compound 1 herein below) , S.l g (0~020 mole~ 3-chloro-4-(4'-chlorophenoxy) ani-line were mixed with 3.0 ml pyridine, 50 ml chloroform, and 2.1 ml (0.025 mole) propionyl chloride. The addition of the pro-pionyl chloride caused the temperature of the mixture to rise from room temperature to 45C. The mixture was allowed to stand overnight, then washed with 100 ml water, 50 ml of lN
hydrochloric acid an~ 50 ml of saturated sodium bicarbona-te.
It was then dried over sodium sulfate and evaporated in vacuo ., -~ to give an oil which was crystallized from ether to give 4.5 g of a solid, m.p. 125-127C.
Example 2 3-chloro-4(3l-4'-dichlorophenoxy) propionanilide (Compound 5 .~ .
herein below) `: ~
37.4 g (0.13 mole) 3-chloro-4-(3'-4'-dichlorophenoxy) ~' aniline were mixed with 21 ml (0.13 mole) triethylamine and 150 ml methylene chloride. To the mixture were added 13.0 g (12.2 ml, 0.14 mole) propionyl chloride. I'he reaction became exo-~ .
thermic and an ice bath was used to stabilize temperature at about 25-30C. Ater all the components were added, the mixture was stirred for 1 hour and 20 minutes, washed with 150 ml .
water, 100 ml of lN hydrochloric acid, and 100 ml of saturated sodium bicarbonate solution and dried over magnesium sulfate.
The dried product was filtered, and solvents were stripped off.
Amber crystals were obtained which were washed with n-pentane, vacuum filtered and dried in a vacuum oven at 80C. There were obtained 42.65 g of crystals, m.p. 116-118C.
Example 3 S-methyl-N-[3-chloro-4-(3',4'-dichlorophelloxy)-phenyl]-thiolcar-bamate (Compound 7 herein below) The following were mixed together in a flask equipped with an electric stirrer: 37.4 g (0.13 mole) 3-chloro-4(3',4'-dichlorophenoxy)-aniline, 21 ml (0.15 mole) tr.iethylamine, and - 150 ml acetone. To the mixtu.re were added dropwise 12.1 ml ~ (0.14 mole) methyl chlorothiolformate. An ice bath was uti-lized to maintain the temperature at between 25 and 30C. The mixture was stirred for 3 hours with addition of 200 ml chloro-. form. The product was washed with 150 ml water, lO0 ml of lN
hydrochloric acid and lO0 ml saturated sodium bicarbonate solu-tion and dried with magnesium sulfate. The solvents were re-moved by rotary evaporation. A thick oil was formed which was ; re-crystallized from heptane, vacuum filtered and washed with .. n-pentane and dried at 80C in a vacuum oven. There were ob-tained 41.8 g of a solid, m.p. 103-120C.
Example ~
-- .
: N[4-(3',4'-dichlorophenoxy)-3~chlorophenyl]-propionimide (Com-pound 39 herein below) 6.9 g of Compound 5~ prepared in accordance wi.th : Example 2 above, (0.02 mole) were mixed with 50 ml dry tetra~
hydrofuran. There was added 0.58 g sodium hydride. The system was maintained under argon during this time, with electric ~ .
: stirrin~:. After efEervescence ceased, 1.7 ml (0.02 mole) pro~
pionyl chloride was added and the mixture stirred for l-1/2 hours. 200 ml of chloroform were then added, the mixture - ~ .
:! ' ' ' ' ' ' ' ' ' ' ' ~
washed with water, dried over magnesium sulfate and solvents were removed by rotary stripping. There were obtained 7.9 g of an oil, nD ~ 1.5732.
Example 5 S-methyl-N-[4-(4'-chlorophenoxy~phenyl] thiolcarbamate (Com-:;
pound 48 herein below) The ~ollowing were mixed, in the order stated: 4.6 g (0.021 mole) 4-(4-chlorophenoxy)-aniline~ 50 ml chloroform, 3 ml pyridine and 2.2 ml (0.025 mole) methyl chlorothiolEormate.
The reaction was isothermic on addition of the chlorothiolfor-mate. The reaction mixtur~ was let stand for 2 hours, then washed with 50 ml of water, 25 ml lN HCl, and a saturated NaHCO3 solution, dried over MgSO4 and evaporated in vacuo.
The residue was washed with n-pentane. There resulted 5.7 g of product, m.p. 101-103C.
The following Table I lists ccmpounds representative of the invention TABLE I
Cl ~ O - ~ N f Compound m.p.30 Number X y Rl R2 or nD
1 ___ Cl C2H5 H 125-127C
~y of ~be l~ ~ntion This ~ppl ic~tion rel~tes to movel diphenyl ether ~mides. In p~rticul~r, this ~pplic~'cion relates to novel d~phenyl ether ~mides h~ving the formul~
C-R
Cl,~--~<
: R2 in which X is chloro or me~hyl; n is zero, one or two~ Y is chloro or trifluoromethyl: Rl is hydrogen, ~qlkyl, lower ~lkoxy, lower h~lo~lkyl, thio-l~er alkyl, or ~lkenyl;` R2 ls hydrogerl, lower ~lko~ lkyl c3r lower ~ qnoyl: or Rl ~nd R2 t~ken together is ~C -~H
H~2 ' O
or ~ compound in whi.ch Y i$ ~ydrogen, n is o, Rl iæ th;ome~hyl ~nd R2 1~ hy~rogen.
~-' , .
.'~ ' ~
:'.
~ , ~ ,. .. : . - - .,, ., ., . ~ , , .
.
By the term "alkyl" is meant aliphatic radicals, both straight chain and branched chain, generally those having from 1 to about 10 carbon atoms, preferably from 1 to about 5 carbon atoms, for example, methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, t-butyl, n-amyl, iso-amyl, n-hexyl, heptyl, octyl, nonyl, decyl, etc. By the terms "]Lo~er alkoxy", "thio-lower alkyl", "lower haloalkyl", "lower a:Lkoxy-alkyl", and "lower alkanoyl" are meant such groups containing from 1 to about 4 carbon atoms, for example, methoxy, ethoxy, propoxy, butoxy, thio-methyl, thio-ethyl~ chloromethyl, dichloromethyl, trichloromethyl, trifluoromethyl, methoxymethyl, ethoxyethyl, ethoxymethyl, formyl, acetyl, propionyl, butyryl, isobutyryl, and the like. By the term "alkenyl" is meant an olefinic group having at least one olefinic bond and having from 2 to about 5 carbon atoms, for example, vinyl, allyl, propenyl, butenyl and the like.
The compounds of this invention have been found to be active herbicides, that is, cer-tain members of the class have been found to be herbicidally effective against a wide range of plant species. More particularly, the compounds of `' the present invention are characterized by having little or no pre-emergence herbicidal activity, but having primarily post-emergence herbicidal activity, primarily affecting broad-leaf vegatation. The present compounds have been found to have particular utility in rice cultivation in selectively , affecting the growth of weeds or other undesirable vegetation while leaving rice plants substantially unaffected. This invention also relates to a method of controlling undesirable ! vegetation comprising applying an herbicidally effective amount of a compound as above described to the area or plant locus ~! .
- where control is desired.
.,,.,,~ .
!.
` -3 .
. ~ .. ..
L$~
An herbicide as used herein, means a compound which controls or modifies the growth of plan-ts. By the term "herbi-cidally effective amount" is meant an amoun-t of compound which causes a modifying effect upon the growth of plants. By "plants" is meant germinant seeds, emerging seedling, and established vegetation, including the roots and above-ground portions. Such modifying effects include all deviations from natural development, for example, killing, retardation, de-foliation, desiccation, regulation, stunting, -tillering, stimulation, leaf burn, dwarfing, and the like.
In general, the compounds of the present invention are prepared by reacting a phenoxy aniline having the formula Cl~ O--~HR 2 with an acyl chloride, alkyl chloroformate (when Rl is lower alkoxy~ or alkyl chlorothiolformate (when Rl is thio-lower alkyl) having the formula Rl-~-Cl to produce the desired com-pound. X, Rl, R2 and n are as defined above. The reaction is conducted in the presence of a hydrogen chloride acceptor such as a trialkyl amine or pyridine, or in the presence of sodium hydride, thus also producing, respectively, an amine hydro-chloride or sodium chloride plus hydrogen. The 2,2-dimethyl-sunninimides (compounds in which Rl and R2 taken together is ' .
C-CH
~ 2 :'~
~3'~
are prepared by reacting a phenoxy aniline having the formula ` Cl ~ ~ O ~ NH2 Xn Y
with 2,2-dimethylsuccinic acid in an acid medium, generally at a temperature of about 140C or higher. The following are illustrative examples of preparation of representative com-pounds o the invention.
Example 1 3-chloro-4(4'-chlorophenoxy) propionanilide (Compound 1 herein below) , S.l g (0~020 mole~ 3-chloro-4-(4'-chlorophenoxy) ani-line were mixed with 3.0 ml pyridine, 50 ml chloroform, and 2.1 ml (0.025 mole) propionyl chloride. The addition of the pro-pionyl chloride caused the temperature of the mixture to rise from room temperature to 45C. The mixture was allowed to stand overnight, then washed with 100 ml water, 50 ml of lN
hydrochloric acid an~ 50 ml of saturated sodium bicarbona-te.
It was then dried over sodium sulfate and evaporated in vacuo ., -~ to give an oil which was crystallized from ether to give 4.5 g of a solid, m.p. 125-127C.
Example 2 3-chloro-4(3l-4'-dichlorophenoxy) propionanilide (Compound 5 .~ .
herein below) `: ~
37.4 g (0.13 mole) 3-chloro-4-(3'-4'-dichlorophenoxy) ~' aniline were mixed with 21 ml (0.13 mole) triethylamine and 150 ml methylene chloride. To the mixture were added 13.0 g (12.2 ml, 0.14 mole) propionyl chloride. I'he reaction became exo-~ .
thermic and an ice bath was used to stabilize temperature at about 25-30C. Ater all the components were added, the mixture was stirred for 1 hour and 20 minutes, washed with 150 ml .
water, 100 ml of lN hydrochloric acid, and 100 ml of saturated sodium bicarbonate solution and dried over magnesium sulfate.
The dried product was filtered, and solvents were stripped off.
Amber crystals were obtained which were washed with n-pentane, vacuum filtered and dried in a vacuum oven at 80C. There were obtained 42.65 g of crystals, m.p. 116-118C.
Example 3 S-methyl-N-[3-chloro-4-(3',4'-dichlorophelloxy)-phenyl]-thiolcar-bamate (Compound 7 herein below) The following were mixed together in a flask equipped with an electric stirrer: 37.4 g (0.13 mole) 3-chloro-4(3',4'-dichlorophenoxy)-aniline, 21 ml (0.15 mole) tr.iethylamine, and - 150 ml acetone. To the mixtu.re were added dropwise 12.1 ml ~ (0.14 mole) methyl chlorothiolformate. An ice bath was uti-lized to maintain the temperature at between 25 and 30C. The mixture was stirred for 3 hours with addition of 200 ml chloro-. form. The product was washed with 150 ml water, lO0 ml of lN
hydrochloric acid and lO0 ml saturated sodium bicarbonate solu-tion and dried with magnesium sulfate. The solvents were re-moved by rotary evaporation. A thick oil was formed which was ; re-crystallized from heptane, vacuum filtered and washed with .. n-pentane and dried at 80C in a vacuum oven. There were ob-tained 41.8 g of a solid, m.p. 103-120C.
Example ~
-- .
: N[4-(3',4'-dichlorophenoxy)-3~chlorophenyl]-propionimide (Com-pound 39 herein below) 6.9 g of Compound 5~ prepared in accordance wi.th : Example 2 above, (0.02 mole) were mixed with 50 ml dry tetra~
hydrofuran. There was added 0.58 g sodium hydride. The system was maintained under argon during this time, with electric ~ .
: stirrin~:. After efEervescence ceased, 1.7 ml (0.02 mole) pro~
pionyl chloride was added and the mixture stirred for l-1/2 hours. 200 ml of chloroform were then added, the mixture - ~ .
:! ' ' ' ' ' ' ' ' ' ' ' ~
washed with water, dried over magnesium sulfate and solvents were removed by rotary stripping. There were obtained 7.9 g of an oil, nD ~ 1.5732.
Example 5 S-methyl-N-[4-(4'-chlorophenoxy~phenyl] thiolcarbamate (Com-:;
pound 48 herein below) The ~ollowing were mixed, in the order stated: 4.6 g (0.021 mole) 4-(4-chlorophenoxy)-aniline~ 50 ml chloroform, 3 ml pyridine and 2.2 ml (0.025 mole) methyl chlorothiolEormate.
The reaction was isothermic on addition of the chlorothiolfor-mate. The reaction mixtur~ was let stand for 2 hours, then washed with 50 ml of water, 25 ml lN HCl, and a saturated NaHCO3 solution, dried over MgSO4 and evaporated in vacuo.
The residue was washed with n-pentane. There resulted 5.7 g of product, m.p. 101-103C.
The following Table I lists ccmpounds representative of the invention TABLE I
Cl ~ O - ~ N f Compound m.p.30 Number X y Rl R2 or nD
1 ___ Cl C2H5 H 125-127C
2 --- Cl SCH3 H 133-135C
3 --- Cl CC13 H 82-83C
{ 4 3,5-CH3 Cl OCH3 H 67-69C
3-Cl Cl C2H5 H 110-112C
6 3-Cl Cl OCH3 HThick oil :
~ 7 3-Cl Cl SOE13 HThick oil :, 8 3-Cl Cl CH3 H129 131C
Cl C3H7 9 3-Cl C1 -CH C H H68-70C
3-Cl CF3 SCH3 HnD ~ 1.5590 11 3-Cl CF3 C2H5 H110-112C
12 3-Cl CF3 OCH3 HLow melting solid 13 3-Cl CF3 -C-C3H7 H102-104C
: CH3 14 3-Cl CF3 -CH-C3H H 88-90C
3-CH3 Cl SCH3 H114-118C
16 2-CH3 Cl SCH3 HSticky solid 17 3-CH3 Cl OCH3 HSticky solid :
18 2-CH3 Cl C2H5 H117-119C
19 3-CH3 Cl C2H5 H115-117C
CH
.
Hl 3 21 3-CH3 Cl ~CH-C3H7 H 65-67C
: CH3 ., 22 2-CH3 Cl -CH-C3H7 H68-70C
23 3-CH3 Cl -C-C3H7 H114-118C
: CH3 'J ~ 24 2-CH3 Cl OCH3 HSticky semi-solid :l 25 2~CH3 Cl 2 5 H103-106C
26 3-CH3 Cl 2 5 H115-120C
:j:
~, 27 2-CH3 C1 CH3C=CH2 HSticky semi-solid ;~
.' 30 28 3-C1 C1 SC2H5 H104-105C . ~:
;!~ 29 3-C1 C1 t-C4Hg H 160-165C ~
': :
, -8- ~ :~
~, "
?
3-Cl Cl CH3 H 111-116C
31 3-Cl Cl CH3C=CII H 85-94C
32 3-Cl Cl -CH=CH2 H 68-82C
33 3-Cl Cl -CH-C H H 87-90C
34 3-Cl Cl C2H5 -~12-0-C2H5 I~D - 1.5758 ~3 2-Cl Cl -CH-C H H 108-110C
36 2-Cl Cl C2H5 H 125-127C
37 2-Cl Cl SCH3 H 120--121C
38 2-Cl Cl OCH3 H Thick oil O ..
39 3-Cl C1 C2H5 -C-C2H5 nD ~ 1.5732 O
2-Cl Cl C2~I5 -C-C2H5 nD ~ 1.5871 C~13 1 41 2-Cl Cl 3 7 C C2 5 nD 1.5457 -~
42 2-Cl Cl SCH3 2 5 Thick oil O
,. 11 43 3~Cl C1 SCH3 -C-C2H5 75C
fH3 44 3-Cl Cl -f-CH3 111-114C
3 Cl Cl H H 134C
,~ 46 3-C1 Cl 3 ~2~C2H5 ~ -1~5958 47 2-Cl Cl -C-CH3 ]20C
-C~CEI
. 1l 2 O
I 48 ---- H SCH3 H 1.0:1.-:L03C
.
g_ ..
~. . . - - .
;~3~
Herbicidal Screening Tests The representative compol~ds in the foregoing Table I were tested as herbicides in the following manner:
A. Pre-emergence ~Ierbicide Scrleening Test: Usiny an analytical balance, 20 mg o~ the compound to be tested is weighed out on a piece of glassine weighing paper. The paper and compound are placed in a 30 ml wide-mouth bottle and 3 ml of acetone containing 1~ Tween 20 ~ is added to dissolve the compound. If the material is not soluble in acetone, another solvent such as water, alcohol or dimethylformamide (DMF) is used instead. When DMF is used, only 0.5 ml or less is used to dissolve the compound and then another solvent is used to make the volume up to ml. The 3 ml of solution is sprayed uniformly on the soil contained in a small Styrofoam flat one day after planting weed seeds in the flat or soil. A No. 152 DeVilbiss atomizer is used to apply the spray using compressed air at a pressure of 5 lb/sq. inch.
On the day preceding treatment, the Styrofoam flat, which is 7 inches long, 5 inches wide and 2.75 inches deep ~ 20 is filled to a depth of 2 inches with loamy sand 50il. Seeds ; of seven different weed species are planted in individual ; rows using one specie per row across the width of the flat.
The seeds are covered with soil so that they are plan~ed at a depth of 0.5 inch. The seeds used are hairy crabgrass (Digitaria sanguinalis), yellow foxtail (Setaria glauca), .. ~ , watergrass (Echinochloa crus~alli), red oat (Avena Sativa) redroot pigweed (~maranthus retroflexus)) Indian mustard (Brassica juncea), and curly dock (Rumex crispus). Ample seeds are planted to give about 20 to 50 seedlings per row af~er emergence, depending on -the size of the plants.
;'~
,` , ~'. "
A~ter treatment, the flats are placed in the green-house at a temperature of 70 -to 85F and watered by sprinkling.
Two weeks after treatmen-t, the degree of injury or control is determined by comparison with untreated check plants of the same age. The injury rating from 0 to 100% is recorded for each species as percent control with 0% representing no in-jury and 100% representing complete kill.
B. Post-emergence Herbicide Screening Test: Seeds o~ six plant species, including hairy crabgrass, watergrass, red oat, mustard, curly dock and pinto beans (Phaseolus vul-garis) are planted in the Styrofoam flats as described above for pre-emergence screening. The flats are placed in the greenhouse at 70 to 85F and watered daily with a sprinkler.
About 10 to 14 days after planting when the primary leaves of the bean plants are almost ~ully expanded and the first trifoliate leaves are just starting to form, the plants are . spraved. The spray is prepared by weighing out 20 mg of the : test compound, dissolving it in 5 ml of acetone containing 1% Tween 20 ~ and then addin~ 5 ml of water. The solution ; 20 is sprayed on the foliage using a No. 152 DeVilbiss atomizer at an air pressure of 5 lb/sq inch.
The results of these tests are shown in Table II.
~; Compounds 1-4 and 48 were tested at 20 lbs/acre; the remaining .~ compounds were tested at 8 lbs~acre. The values given ~or compounds 1-4 and 48 relate ko percent control for seven plant species tested pre-emergence and six p]ant species tested post-emergence; with respect to pre-emergence, a value of 21 indicates 70 to 100% control; with respect to post-emergence, a value of 18 indicates 70 to 100% controlO The values given . 30 :
:` -11-,' , L~
for ~pounds 5-A7 indicate an average of control for seven plant species in pre-emergence tests and six plant species in post-emergence tests, with respect to 100% control.
C. Post-flood - Post-emergence Application to Paddy Rice: Plastic tubs, 10 x 7.5 x 5.75 inches were filled to a depth of 2 inches with 8 pounds of a loamy sand soil pre-treated with 50 ppm Captan 50W and 18. 18. 18 fertilizer.
~; One pint of the soil was removed, the remaining soil was leveled and seven rows were impressed across the width of the flat. Three dayflower (Commelina diffusa) cuttings 3 to 4 inches long, six yellow nutsedge tubers (~y~ esculen-tus), and seeds of annual morning-glory (Ipomoea purpurea), curly dock (Rumex crispus), sesbania (Sesbania spp.) and rice (Oryza sativa) were planted in separate rows. The pint of soil was used to cover 0.5 inches deep the seeds, tubers and part of the cuttings. The planted soil was placed in ~ a greenhouse-and irrigated by sprinkling as needed to keep -~ the soil moist. Three days ater the initial seeding an-other row was impressed 0.5 inches deep across the width of the flat and seeds of watergrass (Echinochlow crusgalli) ,,;, were planted and covered by pinching together the soil on either side of the seeder row. Seven to ten days after the original seeding, the soil was flooded with 2 inches oE
water. At floodlng time the grass species were in two leaf stage 1 to 2 inches high, the nutsedge was 1 inch high, the cuxly dock was in thecotyledon stage about 1 inch high, , ~
`~ the other broadleaf species were 2 to 3 inches high the ~ ~
;.'` ':
the day 1Ower was rooted with little new growth. Test com ` pounds were applied by pipetting into the flood water a ' .
,~
.~ .
.
stock solution of test compound dissolved in 20 ml of acetone containing 1% Tween 20 at a level proportiona-te to 2 lb/acre of the test compound. The water level in the tubs was main-tained by adding water as needed. Three weeks after ap-plication the species were rated visual]y as percent control Erom 0 to 100~, where 0% represents no injury and 100%
represents complete kill when compared to the untreated check.
; The rice was substantially unaffected. The percent control was based on the total injury to the other plants.
The results of this test are given in Table II
under the heading "Post-flood - Rice" in terms of percent control of species other than rice, with respect to 100 control.
TABLE II
., :
.1 CompoundPre-Emergence Post-EmergencePost-flood -Number_ Control Control Rice
{ 4 3,5-CH3 Cl OCH3 H 67-69C
3-Cl Cl C2H5 H 110-112C
6 3-Cl Cl OCH3 HThick oil :
~ 7 3-Cl Cl SOE13 HThick oil :, 8 3-Cl Cl CH3 H129 131C
Cl C3H7 9 3-Cl C1 -CH C H H68-70C
3-Cl CF3 SCH3 HnD ~ 1.5590 11 3-Cl CF3 C2H5 H110-112C
12 3-Cl CF3 OCH3 HLow melting solid 13 3-Cl CF3 -C-C3H7 H102-104C
: CH3 14 3-Cl CF3 -CH-C3H H 88-90C
3-CH3 Cl SCH3 H114-118C
16 2-CH3 Cl SCH3 HSticky solid 17 3-CH3 Cl OCH3 HSticky solid :
18 2-CH3 Cl C2H5 H117-119C
19 3-CH3 Cl C2H5 H115-117C
CH
.
Hl 3 21 3-CH3 Cl ~CH-C3H7 H 65-67C
: CH3 ., 22 2-CH3 Cl -CH-C3H7 H68-70C
23 3-CH3 Cl -C-C3H7 H114-118C
: CH3 'J ~ 24 2-CH3 Cl OCH3 HSticky semi-solid :l 25 2~CH3 Cl 2 5 H103-106C
26 3-CH3 Cl 2 5 H115-120C
:j:
~, 27 2-CH3 C1 CH3C=CH2 HSticky semi-solid ;~
.' 30 28 3-C1 C1 SC2H5 H104-105C . ~:
;!~ 29 3-C1 C1 t-C4Hg H 160-165C ~
': :
, -8- ~ :~
~, "
?
3-Cl Cl CH3 H 111-116C
31 3-Cl Cl CH3C=CII H 85-94C
32 3-Cl Cl -CH=CH2 H 68-82C
33 3-Cl Cl -CH-C H H 87-90C
34 3-Cl Cl C2H5 -~12-0-C2H5 I~D - 1.5758 ~3 2-Cl Cl -CH-C H H 108-110C
36 2-Cl Cl C2H5 H 125-127C
37 2-Cl Cl SCH3 H 120--121C
38 2-Cl Cl OCH3 H Thick oil O ..
39 3-Cl C1 C2H5 -C-C2H5 nD ~ 1.5732 O
2-Cl Cl C2~I5 -C-C2H5 nD ~ 1.5871 C~13 1 41 2-Cl Cl 3 7 C C2 5 nD 1.5457 -~
42 2-Cl Cl SCH3 2 5 Thick oil O
,. 11 43 3~Cl C1 SCH3 -C-C2H5 75C
fH3 44 3-Cl Cl -f-CH3 111-114C
3 Cl Cl H H 134C
,~ 46 3-C1 Cl 3 ~2~C2H5 ~ -1~5958 47 2-Cl Cl -C-CH3 ]20C
-C~CEI
. 1l 2 O
I 48 ---- H SCH3 H 1.0:1.-:L03C
.
g_ ..
~. . . - - .
;~3~
Herbicidal Screening Tests The representative compol~ds in the foregoing Table I were tested as herbicides in the following manner:
A. Pre-emergence ~Ierbicide Scrleening Test: Usiny an analytical balance, 20 mg o~ the compound to be tested is weighed out on a piece of glassine weighing paper. The paper and compound are placed in a 30 ml wide-mouth bottle and 3 ml of acetone containing 1~ Tween 20 ~ is added to dissolve the compound. If the material is not soluble in acetone, another solvent such as water, alcohol or dimethylformamide (DMF) is used instead. When DMF is used, only 0.5 ml or less is used to dissolve the compound and then another solvent is used to make the volume up to ml. The 3 ml of solution is sprayed uniformly on the soil contained in a small Styrofoam flat one day after planting weed seeds in the flat or soil. A No. 152 DeVilbiss atomizer is used to apply the spray using compressed air at a pressure of 5 lb/sq. inch.
On the day preceding treatment, the Styrofoam flat, which is 7 inches long, 5 inches wide and 2.75 inches deep ~ 20 is filled to a depth of 2 inches with loamy sand 50il. Seeds ; of seven different weed species are planted in individual ; rows using one specie per row across the width of the flat.
The seeds are covered with soil so that they are plan~ed at a depth of 0.5 inch. The seeds used are hairy crabgrass (Digitaria sanguinalis), yellow foxtail (Setaria glauca), .. ~ , watergrass (Echinochloa crus~alli), red oat (Avena Sativa) redroot pigweed (~maranthus retroflexus)) Indian mustard (Brassica juncea), and curly dock (Rumex crispus). Ample seeds are planted to give about 20 to 50 seedlings per row af~er emergence, depending on -the size of the plants.
;'~
,` , ~'. "
A~ter treatment, the flats are placed in the green-house at a temperature of 70 -to 85F and watered by sprinkling.
Two weeks after treatmen-t, the degree of injury or control is determined by comparison with untreated check plants of the same age. The injury rating from 0 to 100% is recorded for each species as percent control with 0% representing no in-jury and 100% representing complete kill.
B. Post-emergence Herbicide Screening Test: Seeds o~ six plant species, including hairy crabgrass, watergrass, red oat, mustard, curly dock and pinto beans (Phaseolus vul-garis) are planted in the Styrofoam flats as described above for pre-emergence screening. The flats are placed in the greenhouse at 70 to 85F and watered daily with a sprinkler.
About 10 to 14 days after planting when the primary leaves of the bean plants are almost ~ully expanded and the first trifoliate leaves are just starting to form, the plants are . spraved. The spray is prepared by weighing out 20 mg of the : test compound, dissolving it in 5 ml of acetone containing 1% Tween 20 ~ and then addin~ 5 ml of water. The solution ; 20 is sprayed on the foliage using a No. 152 DeVilbiss atomizer at an air pressure of 5 lb/sq inch.
The results of these tests are shown in Table II.
~; Compounds 1-4 and 48 were tested at 20 lbs/acre; the remaining .~ compounds were tested at 8 lbs~acre. The values given ~or compounds 1-4 and 48 relate ko percent control for seven plant species tested pre-emergence and six p]ant species tested post-emergence; with respect to pre-emergence, a value of 21 indicates 70 to 100% control; with respect to post-emergence, a value of 18 indicates 70 to 100% controlO The values given . 30 :
:` -11-,' , L~
for ~pounds 5-A7 indicate an average of control for seven plant species in pre-emergence tests and six plant species in post-emergence tests, with respect to 100% control.
C. Post-flood - Post-emergence Application to Paddy Rice: Plastic tubs, 10 x 7.5 x 5.75 inches were filled to a depth of 2 inches with 8 pounds of a loamy sand soil pre-treated with 50 ppm Captan 50W and 18. 18. 18 fertilizer.
~; One pint of the soil was removed, the remaining soil was leveled and seven rows were impressed across the width of the flat. Three dayflower (Commelina diffusa) cuttings 3 to 4 inches long, six yellow nutsedge tubers (~y~ esculen-tus), and seeds of annual morning-glory (Ipomoea purpurea), curly dock (Rumex crispus), sesbania (Sesbania spp.) and rice (Oryza sativa) were planted in separate rows. The pint of soil was used to cover 0.5 inches deep the seeds, tubers and part of the cuttings. The planted soil was placed in ~ a greenhouse-and irrigated by sprinkling as needed to keep -~ the soil moist. Three days ater the initial seeding an-other row was impressed 0.5 inches deep across the width of the flat and seeds of watergrass (Echinochlow crusgalli) ,,;, were planted and covered by pinching together the soil on either side of the seeder row. Seven to ten days after the original seeding, the soil was flooded with 2 inches oE
water. At floodlng time the grass species were in two leaf stage 1 to 2 inches high, the nutsedge was 1 inch high, the cuxly dock was in thecotyledon stage about 1 inch high, , ~
`~ the other broadleaf species were 2 to 3 inches high the ~ ~
;.'` ':
the day 1Ower was rooted with little new growth. Test com ` pounds were applied by pipetting into the flood water a ' .
,~
.~ .
.
stock solution of test compound dissolved in 20 ml of acetone containing 1% Tween 20 at a level proportiona-te to 2 lb/acre of the test compound. The water level in the tubs was main-tained by adding water as needed. Three weeks after ap-plication the species were rated visual]y as percent control Erom 0 to 100~, where 0% represents no injury and 100%
represents complete kill when compared to the untreated check.
; The rice was substantially unaffected. The percent control was based on the total injury to the other plants.
The results of this test are given in Table II
under the heading "Post-flood - Rice" in terms of percent control of species other than rice, with respect to 100 control.
TABLE II
., :
.1 CompoundPre-Emergence Post-EmergencePost-flood -Number_ Control Control Rice
4 7 15 ~3 ~ 6 0 71 67 .~ 7 11 72 75 0 7~ 65 , .
'~
~ -13-,' . .
Compound Pre-Ernergence Post~Emergence Po~t-100d Number Control __Control _ Rice 1~ 19 60 63 13 0 () 28 ~ 8 37 52 60 ~ 30 50 ~2 0 58 60 ~5 ~ 25 54 ~6 0 0 40 27 û Sl 58 ;~ 28 0 52 ~7 29 0 ~ 67 ~ 72 ~7 32 0 7~ 6 7 ~ 33 10 8~ 80 `~ 34 0 8~ 67 , 36 29 70 8 37 0 9~ 8 .~
38 0 84 ~-39 ~ 99 57 ~: -14 . - -Compound Pre-Emergence Post-Emergence Post-flood -Number Control Control Rice . . . ~
~1 'I 99 100 4~ 0 80 69 43 0 77 7~1 44 0 18 ~2 ~7 0 27 ---In practice, the compounds are formula-ted with an inert carrier, utilizing methods well-known -to those skilled -~
in the art, thereby making them suitable for application as dusts, sprays, or drenches and the like, in the form and manner required. The mixtures can be dispersed in water with the aid of a wetting agent or -they can be employed in organic liquid compQsitions, oil and water, water in oil emulsions, with or without the addition of wetting, dispersing 20 or emulsifying agents. An herbicidally effec-tive amount depends upon the nature of -the seeds or plants -to be control-led and the rate of application varies from 0O5 -to approxi-mately 50 pounds per acre.
The compositions of the present invention are mos-t advantageously applied at the post-emergen , post-flood stage, . .l .
for example by spraying from either aircraft or with hand-held or other ground level sprayers. Incorporation of the compounds into the flood water is most advan-tageously performed when the rice is at a height of several inches above the water; if ap-plied too early the compound~ could cause injury to very young rice plants; i~ appliPd much later the compounds would llO-t be as effective against fully grown weed species.
.
'~
~ -13-,' . .
Compound Pre-Ernergence Post~Emergence Po~t-100d Number Control __Control _ Rice 1~ 19 60 63 13 0 () 28 ~ 8 37 52 60 ~ 30 50 ~2 0 58 60 ~5 ~ 25 54 ~6 0 0 40 27 û Sl 58 ;~ 28 0 52 ~7 29 0 ~ 67 ~ 72 ~7 32 0 7~ 6 7 ~ 33 10 8~ 80 `~ 34 0 8~ 67 , 36 29 70 8 37 0 9~ 8 .~
38 0 84 ~-39 ~ 99 57 ~: -14 . - -Compound Pre-Emergence Post-Emergence Post-flood -Number Control Control Rice . . . ~
~1 'I 99 100 4~ 0 80 69 43 0 77 7~1 44 0 18 ~2 ~7 0 27 ---In practice, the compounds are formula-ted with an inert carrier, utilizing methods well-known -to those skilled -~
in the art, thereby making them suitable for application as dusts, sprays, or drenches and the like, in the form and manner required. The mixtures can be dispersed in water with the aid of a wetting agent or -they can be employed in organic liquid compQsitions, oil and water, water in oil emulsions, with or without the addition of wetting, dispersing 20 or emulsifying agents. An herbicidally effec-tive amount depends upon the nature of -the seeds or plants -to be control-led and the rate of application varies from 0O5 -to approxi-mately 50 pounds per acre.
The compositions of the present invention are mos-t advantageously applied at the post-emergen , post-flood stage, . .l .
for example by spraying from either aircraft or with hand-held or other ground level sprayers. Incorporation of the compounds into the flood water is most advan-tageously performed when the rice is at a height of several inches above the water; if ap-plied too early the compound~ could cause injury to very young rice plants; i~ appliPd much later the compounds would llO-t be as effective against fully grown weed species.
.
Claims (77)
1. A compound having the formula in which X is chloro or methyl; n is 0, 1 or 2; Y is chloro or trifluoromethyl; R1 is hydrogen, alkyl, lower alkoxy, lower haloalkyl, thio-lower alkyl or alkenyl; R2 is hydrogen, lower alkoxyalkyl or lower alkanoyl; or R1 and R2 taken to-gether is or in which Y is hydrogen, n is 0, R1 is thiomethyl and R2 is hydrogen with the proviso that when Y is trifluoromethyl R, is other than alkyl, alkenyl or haloalkyl.
2. A compound according to Claim 1 in which X is chloro.
3. A compound according to Claim 2 in which X is 3-chloro.
4. A compound according to Claim 2 in which X is 2-chloro.
5. A compound according to Claim 1 in which X is methyl.
6. A compound according to Claim 5 in which X is 3-methyl.
7. A compound according to Claim 5 in which X is 2-methyl.
8. A compound according to Claim 1 in which n is 0.
9. A compound according to Claim 1 in which Y is chloro.
10. A compound according to Claim 1 in which Y is trifluoromethyl.
11. A compound according to Claim 1 in which Y is chloro and X is 3-chloro.
12. A compound according to Claim 1 in which Y is chloro and X is 2-chloro.
13. A compound according to Claim 1 in which R1 is alkyl.
14. A compound according to Claim 13 in which R1 is alkyl having 1 to 6 carbon atoms.
15. A compound according to Claim 13 in which R1 is ethyl.
16. A compound according to Claim 13 in which R1 is 1-methylbutyl.
17. A compound according to Claim 13 in which R1 is 1,1-dimethylbutyl.
18. A compound according to Claim 13 in which R1 is t-hutyl.
19. A compound according to Claim 13 in which R1 is methyl.
20. A compound according to Claim 1 in which R1 is lower alkoxy.
21. A compound according to Claim 20 in which R1 is methoxy.
22. A compound according to Claim 1 in which R1 is lower haloalkyl.
23. A compound according to Claim 1 in which R1 is thio-lower alkyl.
24. A compound according to Claim 23 in which R1 is thio-methyl.
25. A compound according to Claim 23 in which R1 is thio-ethyl.
26. A compound according to Claim 1 in which R1 is alkenyl.
27. A compound according to Claim 26 in which R1 is vinyl.
28. A compound according to Claim 26 in which R1 is isopropenyl.
29. A compound according to Claim 1 in which R2 is hydrogen.
30. A compound according to Claim 1 in which R2 is lower alkanoyl.
31. A compound according to Claim 1 in which R2 is lower alkoxy-alkyl.
32. A compound according to Claim 1 in which R1 and R2 taken together is
33. A compound according to Claim 1 in which n is 0, Y is chloro, R1 is ethyl and R2 is hydrogen.
34. A compound according to Claim 1 in which n is 0, Y is chloro, R1 is thiomethyl and R2 is hydrogen.
35. A compound according to Claim 1 in which n is 0, Y is chloro, R1 is trichloromethyl and R2 is hydrogen.
36. A compound according to Claim 1 in which n is 2, X is 3,5-dimethyl, Y is chloro, R1 is methoxy and R2 is hydrogen.
37. A compound according to Claim 1 in which n is 1, X is 3-chloro, Y is chloro, R1 is ethyl and R2 is hydrogen.
38. A compound according to Claim 1 in which n is 1, X is 3-chloro, Y is chloro, R1 is methoxy and R2 is hydrogen.
39. A compound according to Claim 1 in which n is 1, X is 3-chloro, Y is chloro, R1 is thiomethyl and R2 is hydrogen.
40. A compound according to Claim 1 in which n is 1, X is 3-chloro, Y is chloro, R1 is 1,1-dimethylbutyl and R2 is hydrogen.
41. A compound according to Claim 1 in which n is 1, X is 3-chloro, Y is chloro, R1 is 1-methylbutyl and R2 is hydrogen.
42. A compound according to Claim 1 in which n is 1, X is 3-chloro, Y is trifluoromethyl, R1 is thiomethyl and R2 is hydrogen.
43. A compound according to Claim 1 in which n is 1, X is 3-chloro, Y is trifluoromethyl, R1 is methoxy and R2 is hydrogen.
44. A compound according to Claim 1 in which n is 1, X is 3-methyl, Y is chloro, R1 is thiomethyl and R2 is hydrogen.
45. A compound according to Claim 1 in which n is 1, X is 2-methyl, Y is chloro, R1 is thiomethyl and R2 is hydrogen.
46. A compound according to Claim 1 in which n is 1, X is 3-methyl, Y is chloro, R1 is methoxy and R2 is hydrogen.
47. A compound according to Claim 1 in which n is 1, X is 2-methyl, Y is chloro, R1 is ethyl and R2 is hydrogen.
48. A compound according to Claim 1 in which n is 1, X is 3-methyl, Y is chloro, R1 is ethyl, and R2 is hydro-gen.
49. A compound according to Claim 1 in which n is 1, X is 2-methyl, Y is chloro, R1 is 1,1-dimethylbutyl and R2 is hydrogen.
50. A compound according to Claim 1 in which n is 1, X is 3-methyl, Y is chloro, R1 is 1-methylbutyl and R2 is hydrogen.
51. A compound according to Claim 1 in which n is 1, X is 2-methyl, Y is chloro, R1 is 1-methylbutyl and R2 is hydrogen.
52. A compound according to Claim 1 in which n is 1, X is 3-methyl, Y is chloro, R1 is 1,1-dimethylbutyl and R2 is hydrogen.
53. A compound according to Claim 1 in which n is 1, X is 2-methyl, Y is chloro, R1 is methoxy and R2 is hydrogen.
54. A compound according to Claim 1 in which n is 1, X is 2-methyl, Y is chloro, R1 is thioethyl and R2 is hydrogen.
55. A compound according to Claim 1 in which n is 1, X is 3-methyl, Y is chloro, R1 is thioethyl and R2 is hydrogen.
56. A compound according to Claim 1 in which n is 1, X is 2-methyl, Y is chloro, R1 is isopropenyl and R2 is hydrogen.
57. A compound according to Claim 1 in which n is 1, X is 3-chloro, Y is chloro, R1 is thioethyl and R2 is hydrogen.
58. A compound according to Claim 1 in which n is 1, X is 3-chloro, Y is chloro, R1 is t-butyl and R2 is hydrogen.
59. A compound according to Claim 1 in which n is 1, X is 3-chloro, Y is chloro, R1 is methyl, and R2 is hydrogen.
60. A compound according to Claim 1 in which n is 1, X is 3-chloro, Y is chloro, R1 is isopropenyl and R2 is hydrogen.
61. A compound according to Claim 1 in which n is 1, X is 3-chloro, Y is chloro, R1 is vinyl and R2 is hydrogen.
62. A compound according to Claim 1 in which n is 1, X is 3-chloro, Y is chloro, R1 is 1-methylbutyl and R2 is hydrogen.
63. A compound according to Claim 1 in which n is 1, X is 3-chloro, Y is chloro, R1 is ethyl and R2 is ethoxy-methyl.
64. A compound according to Claim 1 in which n is 1, X is 2 chloro, Y is chloro, R1 is 1-methylbutyl and R2 is hydrogen.
65. A compound according to Claim 1 in which n is 1, X is 2-chloro, Y is chloro, R1 is ethyl and R2 is hydrogen.
66. A compound according to Claim 1 in which n is 1, X is 2-chloro, Y is chloro, R1 is thiomethyl and R2 is hydrogen.
67. A compound according to Claim 1 in which n is 1, X is 2-chloro, Y is chloro, R1 is methoxy and R2 is hydro-gen.
68. A compound according to Claim 1 in which n is 1, X is 3-chloro, Y is chloro, R1 is ethyl and R2 is pro-pionyl.
69. A compound according to Claim 1 in which n is 1, X is 2-chloro, Y is chloro, R1 is ethyl and R2 is propionyl.
70. A compound according to Claim 1 in which n is 1, X is 2-chloro, Y is chloro, R1 is 1-methylbutyl and R2 is propionyl.
71. A compound according to Claim 1 in which n is 1, X is 2-chloro, Y is chloro, R1 is thiomethyl and R2 is propionyl.
72. A compound according to Claim 1 in which n is 1, X is 3-chloro, Y is chloro, R1 is thiomethyl and R2 is propionyl.
73. A compound according to Claim 1 in which n is 1, X is 3-chloro, Y is chloro, R1 and R2 taken together is
74. A compound according to claim 1 in which n is 1, X is 3-chloro, Y is chloro, R1 is hydrogen and R2 is hydrogen.
75. A compound according to Claim 1 in which n is 1, X is 3-chloro, Y is chloro, R1 is thiomethyl and R2 is ethoxymethyl.
76. A compound according to Claim 1 in which n is 1, X is 2-chloro, Y is chloro, R1 and R2 taken together is
77. A compound according to Claim 1 in which n is 0, Y is hydrogen, R1 is thiomethyl and R2 is hydrogen.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US05/598,486 US3976470A (en) | 1975-07-23 | 1975-07-23 | Diphenyl ether amides |
| US05/598,485 US3971649A (en) | 1975-07-23 | 1975-07-23 | S-methyl-N-[4-(4'-chlorophenoxy)phenyl] thiolcarbamate |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1064041A true CA1064041A (en) | 1979-10-09 |
Family
ID=27083083
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA257,391A Expired CA1064041A (en) | 1975-07-23 | 1976-07-20 | Diphenyl ether amides and s-methyl-n-(4-)4'-chlorophenoxy) phenyl) thiolcarbamate |
Country Status (16)
| Country | Link |
|---|---|
| JP (1) | JPS5214735A (en) |
| AU (1) | AU500853B2 (en) |
| BG (1) | BG27348A3 (en) |
| BR (1) | BR7604720A (en) |
| CA (1) | CA1064041A (en) |
| DD (1) | DD127666A5 (en) |
| DE (1) | DE2632619A1 (en) |
| EG (1) | EG12038A (en) |
| ES (1) | ES449982A1 (en) |
| FR (1) | FR2318860A1 (en) |
| GB (1) | GB1506092A (en) |
| GR (1) | GR62663B (en) |
| IL (1) | IL50074A (en) |
| NL (1) | NL7608133A (en) |
| PH (1) | PH13979A (en) |
| SU (1) | SU797542A3 (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4336062A (en) * | 1977-09-19 | 1982-06-22 | Stauffer Chemical Company | Herbicidal cyclohexenone derivatives |
| JPS54124074A (en) * | 1978-03-20 | 1979-09-26 | Toshiba Chem Corp | Flame-resistant phenolic resin laminated sheet |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS539688B2 (en) * | 1972-06-09 | 1978-04-07 |
-
1976
- 1976-07-07 AU AU15668/76A patent/AU500853B2/en not_active Expired
- 1976-07-14 GR GR51266A patent/GR62663B/en unknown
- 1976-07-19 FR FR7621944A patent/FR2318860A1/en active Granted
- 1976-07-19 EG EG441/76A patent/EG12038A/en active
- 1976-07-19 DD DD193950A patent/DD127666A5/xx unknown
- 1976-07-20 BR BR7604720A patent/BR7604720A/en unknown
- 1976-07-20 CA CA257,391A patent/CA1064041A/en not_active Expired
- 1976-07-20 DE DE19762632619 patent/DE2632619A1/en not_active Withdrawn
- 1976-07-20 PH PH18708A patent/PH13979A/en unknown
- 1976-07-20 IL IL50074A patent/IL50074A/en unknown
- 1976-07-20 BG BG033794A patent/BG27348A3/en unknown
- 1976-07-21 ES ES449982A patent/ES449982A1/en not_active Expired
- 1976-07-21 JP JP51086077A patent/JPS5214735A/en active Pending
- 1976-07-22 NL NL7608133A patent/NL7608133A/en not_active Application Discontinuation
- 1976-07-22 GB GB30595/76A patent/GB1506092A/en not_active Expired
- 1976-07-23 SU SU762385901A patent/SU797542A3/en active
Also Published As
| Publication number | Publication date |
|---|---|
| EG12038A (en) | 1978-03-29 |
| ES449982A1 (en) | 1977-08-16 |
| AU500853B2 (en) | 1979-06-07 |
| DD127666A5 (en) | 1977-10-05 |
| NL7608133A (en) | 1977-01-25 |
| DE2632619A1 (en) | 1977-02-24 |
| FR2318860A1 (en) | 1977-02-18 |
| GB1506092A (en) | 1978-04-05 |
| GR62663B (en) | 1979-05-17 |
| BG27348A3 (en) | 1979-10-12 |
| IL50074A (en) | 1981-05-20 |
| PH13979A (en) | 1980-11-20 |
| IL50074A0 (en) | 1976-09-30 |
| AU1566876A (en) | 1978-01-12 |
| JPS5214735A (en) | 1977-02-03 |
| SU797542A3 (en) | 1981-01-15 |
| BR7604720A (en) | 1977-08-02 |
| FR2318860B1 (en) | 1980-05-09 |
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