GB2253625A - Intermediate compounds for use in the production of herbicides - Google Patents
Intermediate compounds for use in the production of herbicides Download PDFInfo
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- GB2253625A GB2253625A GB9209798A GB9209798A GB2253625A GB 2253625 A GB2253625 A GB 2253625A GB 9209798 A GB9209798 A GB 9209798A GB 9209798 A GB9209798 A GB 9209798A GB 2253625 A GB2253625 A GB 2253625A
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- mole
- methyl
- triazolin
- reaction mixture
- chloro
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- 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
- A01N43/64—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with three nitrogen atoms as the only ring hetero atoms
- A01N43/647—Triazoles; Hydrogenated triazoles
- A01N43/653—1,2,4-Triazoles; Hydrogenated 1,2,4-triazoles
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D249/00—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms
- C07D249/02—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms not condensed with other rings
- C07D249/08—1,2,4-Triazoles; Hydrogenated 1,2,4-triazoles
- C07D249/10—1,2,4-Triazoles; Hydrogenated 1,2,4-triazoles 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
- C07D249/12—Oxygen or sulfur atoms
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- 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)
- Heterocyclic Carbon Compounds Containing A Hetero Ring Having Nitrogen And Oxygen As The Only Ring Hetero Atoms (AREA)
Abstract
Novel compounds have the formula <IMAGE> They are used as intermediate compounds in the production of herbicides. <IMAGE>
Description
INTERMEDIATE COMPOUNDS FOR USE IN THE PRODUCTION OF HERBICIDES
The present invention is concerned with intermediate compounds for use in the production of herbicides. The herbicides in question form part of the invention claims in the specification of our copending
Application No. 2 230 261, from which the present application is divided.The herbicides claimed in the said copending application have the general formula
in which
X is Br, C1, F, alkyl or haloalkyl;
Y is Br, Cl, F, methyl, haloalkyl, difluoromethoxy, nitro, or a radical of the formula R80CH2-, R8SCH2-, R8SOCH2- or R8SO2CH2- where R8 is C13 alkyl, C2-5 5 alkenyl, C35 alkynyl, phenyl, or substituted phenyl;
R3 is hydrogen, halogen, alkyl, haloalkyl, cyanoalkyl, arylalkyl, alkoxyalkyl, alkylthio, alkylsulfinyl, alkylsulfonyl, alkylthioalkyl, alkylsulfinylalkyl or alkylsulfonylalkyl;;
R2 is alkyl, C15 alkoxy, haloalkyl, C25 alkenyl, C35 alkynyl, cyanoalkyl, thiocyanoalkyl, or a group of the formula (C1-5 alkylene)
Y'-R5, where Y' is -O-, -S-, -SO- or -SO2- and R5 is alkyl, C25 alkenyl or C35 alkynyl;
R is alkyl, dialkylamino, carboxymethyl, hydroxy, haloalkyl, or aryl, provided that X and R are not both alkyl;
R1 is hydrogen, a salt-forming group, alkyl, benzyl, haloalkyl, dichlorobenzyl, alkoxy, SO2R, alkynyl. alkenyl, a group of the formula -alkylene-SO2R or alkoxymethyl; or R and Rt together form an alkylene group.
The compounds of the present invention have the formula
They can be converted to certain of the said herbicidal compounds by methods described and claimed in the said copending application.
The compounds of the present invention can be prepared as follows.
Example 1
Synthesis of 1- (5-amino-4-chloro-2-fluorophenyl) -3-methyl- 4-difluoromethyl- fl 21 , 2, 4-triazolin-5-one Step A 2-Fluoroacetanilide
To a stirred solution of 100 g (0.9 mole) of 2-fluoroaniline in 200 ml of water was added 105 ml (1.1 moles) of acetic anhydride. Upon completion of addition the reaction mixture was filtered to collect a solid. The solid was dried to yield 105 g of 2-fluoroacetanilide; m.p.
74-76"C. The reaction was repeated several times.
Step B 4-Chloro-2-fluoroacetanilide
To a stirred solution of 180.0 g (1.17 moles) of 2-fluoroacetanilide in 210 ml of p-dioxane was slowly added dropwise 173.4 g (9.29 moles) of sulfuryl chloride. Upon completion of addition the reaction mixture was stirred at ambient temperature for 16 hours.
A solid was collected by filtration, washed with water, and dried to yield 155 g of 4-chloro-2-fluoroacetanilide; m.p. 147-1480C.
Step C 4-Chloro-2-fluoraniline
To a stirred solution of 155 g (0.83 mole) of 4-chloro-2fluoroacetanilide in 400 ml of ethanol was added dropwise a solution of 72.0 g (1.8 moles) of sodium hydroxide in 100 ml of water. Upon completion of addition the reaction mixture was heated under reflux for three hours. The reaction mixture was cooled to ambient temperature and extracted with diethyl ether. The combined extracts were concentrated under reduced pressure to a residual oil. The oil was distilled under reduced pressure to yield 81.0 g of 4-chloro-2fluoroaniline; b.p. 83-85/12 mm. The reaction was repeated several times.
Step D Pyruvic acid 4-chloro-2-fluorophenylhydrazone
Under a nitrogen atmosphere, a stirred solution of 20.0 g (0.137 mole) of 4-chloro-2-fluoroaniline in 162 ml of concentrated hydrochloric acid was cooled to -9 C and a solution of 9.5 g (0.137 mole) of sodium nitrite in 50 ml of water was added dropwise at a rate to maintain the reaction mixture temperature at -9UC. The complete addition required 30 minutes. The reaction mixture was stirred for an additional one hour at -9 C to OOC, then a solution of 68.1 g (0.30 mole) of stannous chloride in 68 ml of concentrated hydrochloric acid was added dropwise at a rate to maintain the reaction mixture temperature at -9 C to 00C. The complete addition required 40 minutes.The reaction mixture was stirred at -9 C to OOC for an additional 30 minutes, and was then allowed to warm to ambient temperature, at which it was stirred for two hours. 110 ml of water was added to the reaction mixture, and then a solution of 12.2 g (0.137 mole) of pyruvic acid in 125 ml of water was added dropwise during five minutes. Upon completion of addition the reaction mixture was stirred for an additional 30 minutes, then filtered to collect a solid. The solid was washed with water and dried to give 27.7 g of pyruvic acid 4-chloro-2-fluorophenylhydrazone; m.p. 162-1620C. The reaction was repeated several times.
Step E Synthesis of 1- (4-chloro-2-fluorophenyl) -3-methyl-n 2- 1,2,4-triazolin-5-one as an intermediate
To a stirred suspension of 25.4 g (0.110 mole) of pyruvic acid 4chloro-2-fluorophenylhydrazone in 200 ml of toluene was added 11.1 g (0.11 mole) of triethylamine. The reaction mixture became homogeneous and 30.3 g (0.11 mole) of diphenylphosphoryl azide was added. Upon completion of addition the reaction mixture was heated to reflux where it was stirred for two hours. The reaction mixture was cooled to ambient temperature and extracted with 300 ml of aqueous 1N sodium hydroxide. The extract was neutralized with concentrated hydrochloric acid, and a solid precipitate collected by filtration.The solid was washed with water and dried to yield 21.1 g of 1-(4-chloro-2 fluorophenyl)-3-methyl-A2-1,2,'t-triazolin-5-one; m.p. 189-191 C. The reaction was repeated several times.
Step F 1- (4-chloro-2-fluorophenyl) -3-methyl-4-difluoromethyl- h2- 1,2,4-triazolin-5-one
A stirred solution of 27.4 g (0.12 mole) of 1-(4-chloro-2 fluorophenyl)-3-methyl-A 2-1,2,4-triazolin-5-one, 13.5 g (0.24 mole) of powdered potassium hydroxide, and 3.9 g (0.012 mole) of tetrabutylammonium bromide in 500 ml of tetrahydrofuran was cooled in an ice bath, and chlorodifluoromethane was bubbled into the reaction mixture. The ice bath was removed and bubbling of chlorodifluoromethane continued until condensation of it was observed on a solid-CO2 condenser attached to the reaction vessel. Upon completion of addition the reaction mixture was stirred at ambient temperature for 16 hours.An additional 6.7 g (0.12 mole) of powdered potassium hydroxide was added to the reaction mixture and it was again saturated with chlorodifluoromethane. The reaction mixture was stirred for two hours, then diluted with water. The mixture was extracted with diethyl ether and the combined extracts washed with water. The organic layer was dried with sodium sulphate and filtered. The filtrate was concentrated under reduced pressure to a residue. The residue was dissolved in methylene chloride and passed through a pad of silica gel.
The eluate was concentrated under reduced pressure to a residual solid.
The solid was recrystallized from mixtures of methylene chloride and heptane to yield 9.5 g of 1-(4-chloro-2-fluorophenyl)-3-methyl-4- difluoromethyl- 02-1,2,4- tetrazolin-5-one as a solid. The reaction was repeated several times.
Step G 1-(4-chloro-2-fluoro-5-nitrophenyl)-3-methyl-4- difluoromethyl- A2-1 , 2, 't-triazolin-5-one To a stirred solution of 6.1 g (0.022 mole) of 1-(4-chloro-2 fluorophenyl) -3-methyl-4-difluoromethyl- A 2-1,2, 4-triazolin-5-one in 9 ml of concentrated sulphuric acid was slowly added 1.96 ml of 70% nitric acid, while the temperature of the reaction mixture was maintained at 250C. Upon completion of the addition, the reaction mixture was stirred at 25 C for 30 minutes, then poured into ice water.
The resultant solid was collected by filtration. The solid was dissolved in methylene chloride and passed through a pad of silica gel.
The eluate was subjected to column chromatography on silica gel.
Elution was completed using 1:1 petroleum ether:methylene chloride.
The appropriate fractions were combined and concentrated under reduced pressure to yield 3.0 g of 1-('t-chloro-2-fluoro-5-nitrophenyl)-3- methyl-4-difluoromethyl- a2-1,2, 4-triazolin-5-one; m.p. 102-1040C. The reaction was repeated several times.
Step H 1-(4-amino-4-chloro-2-fluoro-phenyl)-3-methyl-4- difluoromethyl- n 2-1 ,2, 4-triazolin-5-one To a stirred solution of 4.0 g (0.012 mole) of 1-(4-chloro-2 fluoro-5-nitrophenyl ) -3-methyl-4-difluoromethyl- 2-1,2,4-triazolin-5- one in 50 ml of acetic acid and 20 ml of water was added portionwise 4.0 g (0.072 mole) of powdered iron at a rate to maintain the reaction mixture temperature below 350C. Upon completion of addition the reaction mixture stirred at 25-300C for two hours. The reaction mixture was diluted with diethyl ether with stirring, and was then filtered through diatomaceous earth. The stirred filtrate was made basic with aqueous 10% sodium bicarbonate solution and solid potassium carbonate.
The organic layer was separated, washed with three portions of water, and then dried with sodium sulphate. The mixture was filtered and the filtrate concentrated under reduced pressure to a residue. The residue was purified by column chromatography on silica gel using methylene chloride:acetone as an eluent. The appropriate fractions were combined and concentrated under reduced pressure to yield 3.1 g of 1-(5-amino-4- chloro-2-fluorophenyl) -3-methyl-'t-difluoromethyl-A2-1 ,2,'t-triazolin-5- one; m.p. 128-1290C. The nmr and the ir spectra were consistent with the proposed structure. The reaction was repeated several times.
EXAMPLE 2
Synthesis of 1-(5-amino-2,4-dichlorophenyl)-3-methyl-4- difluoromethyl- 2~1, 2, 't-triazolin-5-one Step A Pyruvic acid 2,4-dichlorophenylhydrazone
To a stirred solution of 16.2 g (0.07 mole) of commercially available 2,4-dichlorophenylhydrazine hydrochloride in 100 ml of ethanol was added in one portion 9.2 g (0.11 mole) of pyruvic acid in 100 ml of water. The reaction mixture was stirred for 10 minutes and the resultant solid collected by filtration to yield when dried 13.5 g of pyruvic acid 2,4-dichlorophenylhydrazone, m.p. 193-194"C. The reaction was repeated several times.
Step B 1-(2,4-Dichlorophenyl)-3-methyl-n -1, 2,4-triazolin-5-one
This compound was prepared in a manner analogous to that of
Example 1, Step E using 13.6 g (0.054 mole) of pyruvic acid 2,4dichlorophenylhydrazone, 14.9 g (0.054 mole) of diphenylphosphoryl azide, and 5.5 g (0.054 mole) of triethylamine in 100 ml of toluene.
The yield of 1-(2,'t-dichlorophenyl)-3-methyl-A2-1,2,'t-triazolin-5-one was 13.0 g; m.p. 174-1750C. The reaction was repeated several times.
Step C 1- (2,4-Dichlorophenyl ) -3-methyl-4-difluoromethyl- 42-1,2,4- triazolin-5-one
This compound was prepared in a manner analogous to that of
Example 1, Step F using 16.0 g (0.065 mole) of 1-(2,'t-dichlorophenyl)- 3-methyl- n 2-1 , 2 , 4-triazolin-5-one , chlorodifluoromethane, 7.3 g (0.13 mole) of potassium hydroxide and 10.5 g (0.03 mole) of tetrabutylammonium bromide in 150 ml of tetrahydrofuran. The yield of 1-(2, 4-dichlorophenyl) -3-methyl-4-difluoromethyl-P2-l ,2,4-triazolin-5- one was 4.1 g; m.p. 108-1100C. The reaction was repeated several times.
Step D 1-(2,4-Dichloro-5-nitrophenyl)-3-methyl-4-difluoromethyl 2-1,2,4- 4-triazolin-5-one This compound was prepared in the manner of Example 1, Step G using 4.0 g (0.013 mole) of 1-(2,4-dichlorophenyl)-3-methyl-4 difluoromethyl- b2-1,2,4-triazolin-5-one and 1.2 ml (0.015 mole) of 70% nitric acid in 20 ml of concentrated sulphuric acid. The yield of 1 (2,4-dichloro-5-nitrophenyl)-3-methyl-4-difluoromethyl-Li2~1,2,4- triazolin-5-one was 3.0 g; m.p. 95-970C. The reaction was repeated several times.
Step E 1-(5-Amino-2,4-dichlorophenyl)-3-methyl-4-difluoromethyl- A2-1 ,2,'t-triazolin-5-one This compound was prepared in a manner analogous to that of
Example 1, Step H using 2.5 g (0.007 mole) of 1-(2,4-dichloro-5- nitrophenyl)-3-methyl-4-difluoromethyl-iS2- 1,2,4-triazolin-5-one and 2.5 g (0.045 mole) of powdered iron in 6 ml of water and 60 ml of water. The yield of 1-(5-amino-2,4-dichlorophenyl)-3-methyl-4- difluoromethyl-n2-l,2,4-triazolin-5-one was 2.0 g; m.p. 133-1350C. The reaction was repeated several times.
Claims (4)
1. A compound of formula
2. A compound of formula
3. A method for preparing a compound as claimed in Claim 1 substantially as hereinbefore described in Example 2.
4. A method for preparing a compound as claimed in Claim 2 substantially as hereinbefore described in Example 1.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US33283589A | 1989-04-03 | 1989-04-03 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| GB9209798D0 GB9209798D0 (en) | 1992-06-24 |
| GB2253625A true GB2253625A (en) | 1992-09-16 |
Family
ID=23300062
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| GB9209798A Withdrawn GB2253625A (en) | 1989-04-03 | 1992-05-07 | Intermediate compounds for use in the production of herbicides |
Country Status (1)
| Country | Link |
|---|---|
| GB (1) | GB2253625A (en) |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1987003782A1 (en) * | 1985-12-20 | 1987-07-02 | Fmc Corporation | Herbicidal aryl triazolinones |
-
1992
- 1992-05-07 GB GB9209798A patent/GB2253625A/en not_active Withdrawn
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1987003782A1 (en) * | 1985-12-20 | 1987-07-02 | Fmc Corporation | Herbicidal aryl triazolinones |
| US4818275A (en) * | 1985-12-20 | 1989-04-04 | Fmc Corporation | Herbicidal aryl triazolinones |
Also Published As
| Publication number | Publication date |
|---|---|
| GB9209798D0 (en) | 1992-06-24 |
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| Date | Code | Title | Description |
|---|---|---|---|
| WAP | Application withdrawn, taken to be withdrawn or refused ** after publication under section 16(1) |