CA2161219C - Process to prepare p-alkyl- and p-arylsulphonylbenzoic acid derivatives - Google Patents
Process to prepare p-alkyl- and p-arylsulphonylbenzoic acid derivatives Download PDFInfo
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- CA2161219C CA2161219C CA002161219A CA2161219A CA2161219C CA 2161219 C CA2161219 C CA 2161219C CA 002161219 A CA002161219 A CA 002161219A CA 2161219 A CA2161219 A CA 2161219A CA 2161219 C CA2161219 C CA 2161219C
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- 0 *c1ccc(*)cc1 Chemical compound *c1ccc(*)cc1 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C315/00—Preparation of sulfones; Preparation of sulfoxides
- C07C315/04—Preparation of sulfones; Preparation of sulfoxides by reactions not involving the formation of sulfone or sulfoxide groups
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/582—Recycling of unreacted starting or intermediate materials
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
- Physical Or Chemical Processes And Apparatus (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
A process for preparing a compound of formula (I), where R1 is optionally substituted alkyl or phenyl, R2 is COOH, and R3 and R4 are independently selected from hydrogen, halo, haloalkyl, nitro, hydroxy, alkoxy, haloalkoxy or alkoxyalkoxy; which process comprises oxidizing a compound of formula (II), where R1, R3 and R4 ate as defined in relation to formula (I) and R5 is H, halo or C1-4 alkyl with sodium hypochlorite or sodium chlorite in the presence of a catalytic amount of a ruthenium or palladium compound and a phase transfer catalyst in an organic solvent at a pH of 7-11.
Description
PROCESS TO PREPARE P-ALKYL- AND P-ARYLSULPHONYLBENZOIC ACID DERIVATIVES
The present invention relates to the production of sulphonyl benzoic acids by oxidation of sulphonyl alkyl benzene derivatives.
Sulphonyi benzoic acids are useful as intermediates in the preparation of agrochemicals in particular herbicides as described for example in US 4,695,673 and US 4,780,127.
Known methods of producing sulphonyl benzoic acids by oxidation of sulphonyl alkyl benzene derivatives require harsh reaction conditions. In 2 a process is described which requires the use of strongly acid conditions (70% nitric acid) and temperatures of over 170°C. The processes described In WO 90/13537 and EP 505965-A required elevated pressure and a temperature of greater than 120°C. There is therefore a continuing need for a process which can be performed under milder conditions.
According to the present invention there is provided a process for preparing a compound of formula (I), where R1 is optionally substituted alkyl or phenyl, R2 is COOH, and R3 and R4 are independently selected from hydrogen, halo, haloalkyl, vitro, hydroxy, alkoxy, haloalkoxy or alkoxyalkoxy; which process comprises oxidising a compound of formula (II), where R1, R3 and R4 are as defined in relation to formula (I) and R5 is H, halo or C1-4 alkyl with sodium hypochlorite or sodium chlorite in the presence of a catalytic amount of a ruthenium or palladium compound and a phase transfer catalyst in an organic solvent at a pH of 7-11.
As used herein the term "alkyl", refers to straight or branched chains having for example up to 20 carbon atoms. The term "haloalkyl" refers to an alkyl group substituted by at least one halogen such as fluorine and chlorine. Similarly the term "haloaikoxy" refers to an alkoxy group substituted by at least one halogen such as fluorine and chlorine. As used herein the term "halo" refers to fluoro, chloro, bromo and iodo.
Suitable optional substituents for the alkyl and phenyl groups R1 include halogen such as fluorine and chlorine.
Preferably R1 is a C1-6 alkyl group such as methyl or ethyl;
trifluoromethyl or phenyl. Most preferably R1 is methyl.
Suitably R3 and R4 are selected from hydrogen, chloro, vitro, hydroxy, trifluoromethyl or C1-2 alkoxy. Preferably R3 is H. The group R4 is preferably ortho to the group R2. A preferred group R4 is chloro. The WO 94/27959 ' ~ , ~ . i -' PCT/GB94/00934 ~~.6121~ ~ .
group R5 is preferably H or Cl-4 alkyl, most preferably H.
The oxidation may be suitably performed at moderate temperatures of from 0 to 50°C, usually at less than 25°C. The reaction may be continued for extended periods of from 1 to 72 hours until a reasonable yield of desired product is achieved. This will generally be dependent upon the nature of the reactants and catalysts employed.
The reaction is carried out at a pH in the range 7-11, preferably 8-10, even more preferably at a constantly maintained pH of 9 - 9.5 and most preferably at a constant pH of 9.
Suitable organic solvents include halogenated alkanes and arenes such as dichloromethane, chloroform, ethylene dichloride, chlorobenzene, dichlorobenzene; alkanes and cyloalkanes such as hexane and cyclohexane or esters such as ethyl acetate and isopropyl acetate.
The selection of a suitable phase transfer catalyst can be determined by routine procedures well known to the skilled chemist. Known phase transfer catalysts include tetralkyl artunonium halides and phosphonium salts. Preferred catalysts are tetralkyl ammonium halides, especially tetrabutyl ammonium chloride. The phase transfer catalyst is generally used at 1-10 mol%.
The oxidation catalyst comprising a ruthenium or palladium compound may be for example ruthenium chloride, RuCl2(PPh3)3, ruthenium dioxide supported on an inert carrier such as silica or titania or palladium on carbon. A preferred oxidation catalyst is ruthenium chloride. The amount of ruthenium or palladium catalyst should be sufficient to catalyse the reaction in a reasonable timescale. This will depend upon many factors including the catalyst selected, the nature of the compounds of formula (II) and other reaction conditions. In general 0.01 mol% to 5 moi% of ruthenium or palladium catalyst is suitable.
The reaction may be performed as a batch process or as a continuous process.
Unreacted starting materials may be re-cycled, optionally with the , addition of further oxidation catalyst and phase transfer catalyst.
Further starting material may be added to the recycled liquors.
The invention will now be illustrated by reference to the following Example.
WO 94/27959 ~ ~. 61219 PCT/GB94/00934 2-chloro-4-methylsulphonyltoluene (20.478, 0.1 moles); tetrabutyl ammonium chloride (1.468, 0.0053 moles), ruthenium chloride trihydrate (0.238, 0.0011 moles washed into the reactor with water) and 1,2-dichloroethane (55.48, 0.57 moles) were charged into a 500m1 round bottom flask.
Sodium hypochlorite (119.128, 1.6 moles) was pumped into the reaction flask over a 1 hour period (pH adjusted automatically to pH 9 using 20%
sulphuric acid 2 minutes into addition) then maintained at pH 9 automatically using 10% sodium hydroxide for a further hour.
The reaction was agitated at 570 r.p.m. and the temperature controlled at <25°C throughout.
The reaction mass was diluted with water to dissolve any precipitated sodium salt of the product, the phases separated and the aqueous phase filtered through a bed of clarcel flo filter aid to remove the ruthenium catalyst. The aqueous phase was acidified with 20% sulphuric acid and the precipitated product filtered off, washed with water and dried to yield 2-chloro-4-methylsulphonylbenzoic acid, (15.278, yield 51.5%), m.p.
189°C.
2-Chloro-4-methylsulphonyl toluene (14.28), tetrabutylammonium chloride (1.5998), and ruthenium trichloride (0.6028) were charged to a 200m1 jacketed reaction flask fitted with condenser, thermometer and pH
probe. Ethyl acetate (30.78) was charged to the materials and the contents of the reactor agitated to dissolve the solids present. Sodium hypochlorite (12% active chlorine content) (9.58) was charged to the reactor and the pH of the mixture adjusted to pH 9 + 0.2 with sulphuric acid and sodium hydroxide liquors as required. More sodium hypochlorite (1848) was then charged slowly to the reactor the pH being maintained at 9 to 9.5 by the addition of sodium hydroxide as required, the temperature was allowed to rise to 25 to 28°C during this time, controlled if necessary with water on the reactor jacket. When all of the hypochlorite was charged the reaction mass was left stirring for 6 hours at room temperature, the a reactor was tested with starch iodide to ensure some hypochlorite was present and if necessary a drop or two of hypochlorite was added. The agitation was stopped and the lower aqueous phase was separated off.
The lower aqueous phase was then agitated and heated to 50°C then ~~.6~219 acidified to pH 2 with hydrochloric acid to precipitate the 2-chloro-4-methylsulphonylbenzoic acid product. The reaction mixture was cooled to room temperature and the product was filtered off and washed with water.
The organic phase was re-cycled and an additional ethyl acetate and d ruthenium trichloride charge (10% of the amounts used in the first reaction) introduced into the reaction vessel.
The reaction was then repeated with a further 193.58 of sodium hypochlorite.
After four re-cycles the yield of 2-chloro-4-methylsulphonylbenzoic acid was 89%.
The procedure of Example 2 was repeated using dichloroethane as solvent in place of ethyl acetate. The yield of 2-chloro-4-methylsulphonylbenzoic acid was 88.6%.
The present invention relates to the production of sulphonyl benzoic acids by oxidation of sulphonyl alkyl benzene derivatives.
Sulphonyi benzoic acids are useful as intermediates in the preparation of agrochemicals in particular herbicides as described for example in US 4,695,673 and US 4,780,127.
Known methods of producing sulphonyl benzoic acids by oxidation of sulphonyl alkyl benzene derivatives require harsh reaction conditions. In 2 a process is described which requires the use of strongly acid conditions (70% nitric acid) and temperatures of over 170°C. The processes described In WO 90/13537 and EP 505965-A required elevated pressure and a temperature of greater than 120°C. There is therefore a continuing need for a process which can be performed under milder conditions.
According to the present invention there is provided a process for preparing a compound of formula (I), where R1 is optionally substituted alkyl or phenyl, R2 is COOH, and R3 and R4 are independently selected from hydrogen, halo, haloalkyl, vitro, hydroxy, alkoxy, haloalkoxy or alkoxyalkoxy; which process comprises oxidising a compound of formula (II), where R1, R3 and R4 are as defined in relation to formula (I) and R5 is H, halo or C1-4 alkyl with sodium hypochlorite or sodium chlorite in the presence of a catalytic amount of a ruthenium or palladium compound and a phase transfer catalyst in an organic solvent at a pH of 7-11.
As used herein the term "alkyl", refers to straight or branched chains having for example up to 20 carbon atoms. The term "haloalkyl" refers to an alkyl group substituted by at least one halogen such as fluorine and chlorine. Similarly the term "haloaikoxy" refers to an alkoxy group substituted by at least one halogen such as fluorine and chlorine. As used herein the term "halo" refers to fluoro, chloro, bromo and iodo.
Suitable optional substituents for the alkyl and phenyl groups R1 include halogen such as fluorine and chlorine.
Preferably R1 is a C1-6 alkyl group such as methyl or ethyl;
trifluoromethyl or phenyl. Most preferably R1 is methyl.
Suitably R3 and R4 are selected from hydrogen, chloro, vitro, hydroxy, trifluoromethyl or C1-2 alkoxy. Preferably R3 is H. The group R4 is preferably ortho to the group R2. A preferred group R4 is chloro. The WO 94/27959 ' ~ , ~ . i -' PCT/GB94/00934 ~~.6121~ ~ .
group R5 is preferably H or Cl-4 alkyl, most preferably H.
The oxidation may be suitably performed at moderate temperatures of from 0 to 50°C, usually at less than 25°C. The reaction may be continued for extended periods of from 1 to 72 hours until a reasonable yield of desired product is achieved. This will generally be dependent upon the nature of the reactants and catalysts employed.
The reaction is carried out at a pH in the range 7-11, preferably 8-10, even more preferably at a constantly maintained pH of 9 - 9.5 and most preferably at a constant pH of 9.
Suitable organic solvents include halogenated alkanes and arenes such as dichloromethane, chloroform, ethylene dichloride, chlorobenzene, dichlorobenzene; alkanes and cyloalkanes such as hexane and cyclohexane or esters such as ethyl acetate and isopropyl acetate.
The selection of a suitable phase transfer catalyst can be determined by routine procedures well known to the skilled chemist. Known phase transfer catalysts include tetralkyl artunonium halides and phosphonium salts. Preferred catalysts are tetralkyl ammonium halides, especially tetrabutyl ammonium chloride. The phase transfer catalyst is generally used at 1-10 mol%.
The oxidation catalyst comprising a ruthenium or palladium compound may be for example ruthenium chloride, RuCl2(PPh3)3, ruthenium dioxide supported on an inert carrier such as silica or titania or palladium on carbon. A preferred oxidation catalyst is ruthenium chloride. The amount of ruthenium or palladium catalyst should be sufficient to catalyse the reaction in a reasonable timescale. This will depend upon many factors including the catalyst selected, the nature of the compounds of formula (II) and other reaction conditions. In general 0.01 mol% to 5 moi% of ruthenium or palladium catalyst is suitable.
The reaction may be performed as a batch process or as a continuous process.
Unreacted starting materials may be re-cycled, optionally with the , addition of further oxidation catalyst and phase transfer catalyst.
Further starting material may be added to the recycled liquors.
The invention will now be illustrated by reference to the following Example.
WO 94/27959 ~ ~. 61219 PCT/GB94/00934 2-chloro-4-methylsulphonyltoluene (20.478, 0.1 moles); tetrabutyl ammonium chloride (1.468, 0.0053 moles), ruthenium chloride trihydrate (0.238, 0.0011 moles washed into the reactor with water) and 1,2-dichloroethane (55.48, 0.57 moles) were charged into a 500m1 round bottom flask.
Sodium hypochlorite (119.128, 1.6 moles) was pumped into the reaction flask over a 1 hour period (pH adjusted automatically to pH 9 using 20%
sulphuric acid 2 minutes into addition) then maintained at pH 9 automatically using 10% sodium hydroxide for a further hour.
The reaction was agitated at 570 r.p.m. and the temperature controlled at <25°C throughout.
The reaction mass was diluted with water to dissolve any precipitated sodium salt of the product, the phases separated and the aqueous phase filtered through a bed of clarcel flo filter aid to remove the ruthenium catalyst. The aqueous phase was acidified with 20% sulphuric acid and the precipitated product filtered off, washed with water and dried to yield 2-chloro-4-methylsulphonylbenzoic acid, (15.278, yield 51.5%), m.p.
189°C.
2-Chloro-4-methylsulphonyl toluene (14.28), tetrabutylammonium chloride (1.5998), and ruthenium trichloride (0.6028) were charged to a 200m1 jacketed reaction flask fitted with condenser, thermometer and pH
probe. Ethyl acetate (30.78) was charged to the materials and the contents of the reactor agitated to dissolve the solids present. Sodium hypochlorite (12% active chlorine content) (9.58) was charged to the reactor and the pH of the mixture adjusted to pH 9 + 0.2 with sulphuric acid and sodium hydroxide liquors as required. More sodium hypochlorite (1848) was then charged slowly to the reactor the pH being maintained at 9 to 9.5 by the addition of sodium hydroxide as required, the temperature was allowed to rise to 25 to 28°C during this time, controlled if necessary with water on the reactor jacket. When all of the hypochlorite was charged the reaction mass was left stirring for 6 hours at room temperature, the a reactor was tested with starch iodide to ensure some hypochlorite was present and if necessary a drop or two of hypochlorite was added. The agitation was stopped and the lower aqueous phase was separated off.
The lower aqueous phase was then agitated and heated to 50°C then ~~.6~219 acidified to pH 2 with hydrochloric acid to precipitate the 2-chloro-4-methylsulphonylbenzoic acid product. The reaction mixture was cooled to room temperature and the product was filtered off and washed with water.
The organic phase was re-cycled and an additional ethyl acetate and d ruthenium trichloride charge (10% of the amounts used in the first reaction) introduced into the reaction vessel.
The reaction was then repeated with a further 193.58 of sodium hypochlorite.
After four re-cycles the yield of 2-chloro-4-methylsulphonylbenzoic acid was 89%.
The procedure of Example 2 was repeated using dichloroethane as solvent in place of ethyl acetate. The yield of 2-chloro-4-methylsulphonylbenzoic acid was 88.6%.
CHEMICAL FORMUT--AF
(IN DESCRIPTION) R
R3 ~R~ ~ I ) SO~R
4 (II) R
SO,R
(IN DESCRIPTION) R
R3 ~R~ ~ I ) SO~R
4 (II) R
SO,R
Claims (10)
1. A process for preparing a compound of formula (I), where R1 is optionally substituted alkyl or phenyl, R2 is COOH, and R3 and R4 are independently selected from hydrogen, halo, haloalkyl, nitro, hydroxy, alkoxy, haloalkoxy and alkoxyalkoxy; which process comprises oxidising a compound of formula (II) where R1, R3 and R4 are as defined in relation to formula (I) and R5 is H, halo or C1-4 alkyl with sodium hypochlorite or sodium chlorite in the presence of a catalytic amount of a ruthenium or palladium compound and a phase transfer catalyst in an organic solvent at a pH
of 7-11.
of 7-11.
2. A process according to claim 1, wherein the reaction is performed at 0-50°C.
3. A process according to claim 2, wherein the reaction is carried out at 0-25°C.
4. A process according to any one of claims 1 to 3, wherein the reaction is performed at a constantly maintained pH of 9 - 9.5.
5. A process according to any one of claims 1 to 4, wherein the ruthenium or palladium compound is ruthenium trichloride.
6. A process according to to any one of claims 1 to 5, wherein the phase transfer catalyst is tetrabutylammonium chloride.
7. A process according to any one of claims 1 to 6, wherein R1 is CH3.
8. A process according to any one of claims 1 to 7, wherein R5 is H.
9. A process according to any one of claims 1 to 8, wherein R3 is H and R4 is ortho to the group R2.
10. A process according to any one of claims 1 to 9, wherein the compound of formula (I) is 2-chloro-4-methylsulphonylbenzoic acid.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB939310699A GB9310699D0 (en) | 1993-05-24 | 1993-05-24 | Chemical process |
| GB9310699.5 | 1993-05-24 | ||
| PCT/GB1994/000934 WO1994027959A1 (en) | 1993-05-24 | 1994-04-29 | Process to prepare p-alkyl- and p-arylsulphonylbenzoic acid derivatives |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CA2161219A1 CA2161219A1 (en) | 1994-12-08 |
| CA2161219C true CA2161219C (en) | 2005-12-06 |
Family
ID=10736044
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002161219A Expired - Fee Related CA2161219C (en) | 1993-05-24 | 1994-04-29 | Process to prepare p-alkyl- and p-arylsulphonylbenzoic acid derivatives |
Country Status (15)
| Country | Link |
|---|---|
| US (1) | US5783729A (en) |
| EP (1) | EP0700379B1 (en) |
| JP (1) | JP3556222B2 (en) |
| KR (1) | KR100344013B1 (en) |
| CN (1) | CN1037265C (en) |
| AT (1) | ATE161827T1 (en) |
| AU (1) | AU6578294A (en) |
| CA (1) | CA2161219C (en) |
| DE (1) | DE69407783T2 (en) |
| ES (1) | ES2110745T3 (en) |
| GB (2) | GB9310699D0 (en) |
| HU (1) | HU218710B (en) |
| IL (1) | IL109560A (en) |
| TW (1) | TW275061B (en) |
| WO (1) | WO1994027959A1 (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5565608A (en) * | 1995-06-07 | 1996-10-15 | Zeneca Limited | Process for the preparation of 2-(substituted)-4-sulfobenzoic acid |
| US5659074A (en) * | 1995-06-12 | 1997-08-19 | Zeneca Limited | Herbicide intermediates |
| DE19735879A1 (en) * | 1997-08-19 | 1999-02-25 | Hoechst Schering Agrevo Gmbh | Process for the preparation of 2-carboxy-5-nitro-benzenesulfonic acid and its salts by oxidation |
| US20010020110A1 (en) * | 2000-02-02 | 2001-09-06 | Tetsuya Shintaku | Production methods of alpha, alpha, alpha-trifluoromethylphenyl-substituted benzoic acid and intermediate therefor |
| JP4576802B2 (en) * | 2003-05-14 | 2010-11-10 | 三菱瓦斯化学株式会社 | Method for producing adamantanols |
| US7749672B2 (en) * | 2006-12-21 | 2010-07-06 | Xerox Corporation | Polyester toner compositions |
Family Cites Families (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3504022A (en) * | 1966-11-14 | 1970-03-31 | Phillips Petroleum Co | Oxidation of aralkyl compounds |
| US3812159A (en) * | 1969-02-13 | 1974-05-21 | Trw Inc | Polybasic aromatic carboxylic acids,esters and anhydrides |
| US3692828A (en) * | 1970-05-01 | 1972-09-19 | Gulf Research Development Co | Process for preparing phenyl sulfone carboxylic acids |
| BE793689A (en) * | 1972-07-19 | 1973-05-02 | Renfag Sa | PROCESS FOR PREPARING 2-ALCOXY-5-ALCOYSULFONYLBENZOIC ACIDS |
| US4780127A (en) * | 1982-03-25 | 1988-10-25 | Stauffer Chemical Company | Certain 2-(substituted benzoyl)-1,3-cyclohexanediones and their use as herbicides |
| US4503245A (en) * | 1983-08-02 | 1985-03-05 | Rhone-Poulenc, Inc. | Solvent and catalyst recovery and recycle in the manufacture of phenoxybenzoic acid derivatives |
| US4695673A (en) * | 1985-11-20 | 1987-09-22 | Stauffer Chemical Company | Process for the production of acylated 1,3-dicarbonyl compounds |
| IL85976A0 (en) * | 1987-07-23 | 1988-09-30 | Gadot Petrochem Ind | Process for the manufacture of derivatives of benzoic acid |
| IL83293A (en) * | 1987-07-23 | 1992-03-29 | Gadot Petrochem Ind | Process for the manufacture of benzoic acid and salts thereof by catalytic oxidation of toluene in the liquid phase in the presence of a phase transfer catalyst |
| JPS6479145A (en) * | 1987-09-19 | 1989-03-24 | New Japan Chem Co Ltd | Purification of diphenylsulfonetetracarboxylic acid |
| JP2739738B2 (en) * | 1987-10-19 | 1998-04-15 | 日産化学工業株式会社 | Substituted benzoyl derivatives and selective herbicides |
| JPH02237978A (en) * | 1988-06-03 | 1990-09-20 | Nissan Chem Ind Ltd | Production of 4-benzoyl-5-hydroxypyrazole |
| JP2734579B2 (en) * | 1988-09-19 | 1998-03-30 | 日産化学工業株式会社 | Method for producing substituted benzoic acid |
| KR900701746A (en) * | 1988-11-25 | 1990-12-04 | 원본미기재 | Method for preparing 2-halo-4-alkylsulfonylbenzoic acid |
| DE3914390A1 (en) * | 1989-04-29 | 1990-11-08 | Hoechst Ag | METHOD FOR THE PRODUCTION OF ALKANSULFONYLBENZOESAEUR |
| ES2065095T3 (en) * | 1991-03-26 | 1995-02-01 | Hoechst Ag | PROCEDURE FOR THE PREPARATION OF ALCANOSULFONILBENZOIC ACIDS. |
-
1993
- 1993-05-24 GB GB939310699A patent/GB9310699D0/en active Pending
-
1994
- 1994-04-28 GB GB9408387A patent/GB9408387D0/en active Pending
- 1994-04-29 ES ES94913748T patent/ES2110745T3/en not_active Expired - Lifetime
- 1994-04-29 WO PCT/GB1994/000934 patent/WO1994027959A1/en not_active Ceased
- 1994-04-29 KR KR1019950704968A patent/KR100344013B1/en not_active Expired - Fee Related
- 1994-04-29 EP EP94913748A patent/EP0700379B1/en not_active Expired - Lifetime
- 1994-04-29 AT AT94913748T patent/ATE161827T1/en active
- 1994-04-29 DE DE69407783T patent/DE69407783T2/en not_active Expired - Lifetime
- 1994-04-29 HU HU9503229A patent/HU218710B/en not_active IP Right Cessation
- 1994-04-29 CA CA002161219A patent/CA2161219C/en not_active Expired - Fee Related
- 1994-04-29 AU AU65782/94A patent/AU6578294A/en not_active Abandoned
- 1994-04-29 CN CN94192182A patent/CN1037265C/en not_active Expired - Fee Related
- 1994-04-29 JP JP52583494A patent/JP3556222B2/en not_active Expired - Fee Related
- 1994-05-04 IL IL10956094A patent/IL109560A/en not_active IP Right Cessation
- 1994-05-10 TW TW083104213A patent/TW275061B/zh not_active IP Right Cessation
-
1996
- 1996-11-18 US US08/751,272 patent/US5783729A/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| TW275061B (en) | 1996-05-01 |
| ATE161827T1 (en) | 1998-01-15 |
| AU6578294A (en) | 1994-12-20 |
| DE69407783D1 (en) | 1998-02-12 |
| EP0700379B1 (en) | 1998-01-07 |
| KR100344013B1 (en) | 2003-03-04 |
| ES2110745T3 (en) | 1998-02-16 |
| CN1124023A (en) | 1996-06-05 |
| IL109560A (en) | 1998-07-15 |
| EP0700379A1 (en) | 1996-03-13 |
| IL109560A0 (en) | 1994-11-28 |
| HU218710B (en) | 2000-11-28 |
| HUT73021A (en) | 1996-06-28 |
| GB9408387D0 (en) | 1994-06-22 |
| DE69407783T2 (en) | 1998-04-16 |
| CA2161219A1 (en) | 1994-12-08 |
| GB9310699D0 (en) | 1993-07-07 |
| JP3556222B2 (en) | 2004-08-18 |
| HU9503229D0 (en) | 1996-01-29 |
| JPH09505025A (en) | 1997-05-20 |
| WO1994027959A1 (en) | 1994-12-08 |
| US5783729A (en) | 1998-07-21 |
| CN1037265C (en) | 1998-02-04 |
| KR960702432A (en) | 1996-04-27 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| EEER | Examination request | ||
| MKLA | Lapsed |
Effective date: 20140429 |