WO2004037766A2 - Process for the preparation of 2,6-dihalo-para-trifluoromethylaniline - Google Patents
Process for the preparation of 2,6-dihalo-para-trifluoromethylaniline Download PDFInfo
- Publication number
- WO2004037766A2 WO2004037766A2 PCT/EP2003/013340 EP0313340W WO2004037766A2 WO 2004037766 A2 WO2004037766 A2 WO 2004037766A2 EP 0313340 W EP0313340 W EP 0313340W WO 2004037766 A2 WO2004037766 A2 WO 2004037766A2
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- para
- trifluoromethylaniline
- process according
- compound
- preparation
- Prior art date
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
- C07C209/68—Preparation of compounds containing amino groups bound to a carbon skeleton from amines, by reactions not involving amino groups, e.g. reduction of unsaturated amines, aromatisation, or substitution of the carbon skeleton
- C07C209/74—Preparation of compounds containing amino groups bound to a carbon skeleton from amines, by reactions not involving amino groups, e.g. reduction of unsaturated amines, aromatisation, or substitution of the carbon skeleton by halogenation, hydrohalogenation, dehalogenation, or dehydrohalogenation
-
- 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
- A01N33/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic nitrogen compounds
- A01N33/02—Amines; Quaternary ammonium compounds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C211/00—Compounds containing amino groups bound to a carbon skeleton
- C07C211/43—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton
- C07C211/44—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton having amino groups bound to only one six-membered aromatic ring
- C07C211/45—Monoamines
- C07C211/46—Aniline
Definitions
- the present invention relates to a novel process for the preparation of a 2,6-dihalo-para-trifluoromethylaniline from para-trifluoromethylaniline.
- Patent Application WO 00/35851 discloses a process for the preparation of a 2,6-dihalo- para-trifluoromethylaniline from a trihalo-para-trifluoromethylbenzene at a temperature of between 130 and 350°C in a preferably polar solvent.
- the use of para- trifluoromethylaniline for the preparation of 2,6-dihalo-para-trifluoromethylaniline does not appear in this patent application.
- Patent Applications FR 2 810 665 and WO 01/64623 disclose a process for the preparation of 2,6-dichloro-para-trifluoromethylaniline by chlorination of precursor anilines in a hydrofluoric acid medium.
- the precursor compound is trifluoromethylphenylcarbamoyl fluoride.
- the use of an other solvent than hydrofluoric acid is not mentioned.
- X represents a halogen atom.
- X can be a chlorine atom, a bromine atom, an iodine atom or a fluorine atom.
- the compound of general formula (I) preferably prepared by virtue of the process according to the present invention is 2,6-dichloro-para- trifluoromethylaniline, which is particularly useful in the synthesis of fipronil, an insecticidal compound of phenylpyrazole type.
- the solvent used during the preparation of the compound of general formula (I) is 2,6-dichloro-para- trifluoromethylaniline, which is particularly useful in the synthesis of fipronil, an insecticidal compound of phenylpyrazole type.
- a preferred polar aprotic solvent can be a chlorinated aromatic solvent, such as monochlorobenzene, or a chlorinated aliphatic solvent, such as dichloroethane. In an entirely preferred way, monochlorobenzene will be chosen as solvent.
- the dihalogen/compound (II) molar ratio is chosen as ranging from 1.9 to 2.5 during the preparation of the 2,6-dihalo-para-trifluoromethylaniline according to the present invention.
- the dihalogen/compound (II) molar ratio is preferably chosen as ranging from 2 to 2.05.
- the temperature of the reaction medium according to the present invention is chosen as ranging from 100 to 300°C.
- the temperature of the reaction medium is preferably chosen as ranging from 100 to 130°C. In an entirely preferred way, the temperature of the reaction medium is chosen as ranging from 105°C to 115°C.
- the process according to the present invention consists in preparing 2,6-dichloro-para-trifluoromethylaniline by simultaneously introducing para-trifluoromethylaniline and Cl 2 into monochlorobenzene in a Cl 2 /para-trifluoromethylaniline molar ratio of between 1.85 and 2.05, at a temperature ranging from 105 to 115°C.
- the process according to the present invention can be carried out according to general techniques known to a person skilled in the art.
- the process according to the present invention can be carried out in a jacketed reactor equipped with a stirring device and surmounted by a reflux condenser maintained at a temperature of less than or equal to -10°C.
- the halogen necessary for the reaction will be introduced via a dip pipe arriving with stirring.
- the stirrer preferably used will make it possible to provide optimum micromixing of the reactants. This can be carried out by a stirrer of impeller type or by any other stirrer well known to a person skilled in the art.
- hydrochloric acid in the gaseous form is produced.
- the latter is subsequently generally absorbed by a sodium hydroxide trap.
- para-trifluoromethylaniline reacts instantaneously on contact with hydrochloric acid to form para-trifluoromethylaniline hydrochloride, para-trifluoromethylaniline will preferably be fed to the reactor via a dip pipe, in order to avoid blockages.
- the product obtained by virtue of the process according to the present invention (2,6-dihalo-para-trifluoromethylaniline) has a sufficient degree of purity to be reused directly in the synthesis of the pesticidal compounds of phenylpyrazole type. It is generally considered that the degree of purity should be at least 96% in order for the product to be able to be used in the continuation of a preparation process.
- the 2,6-dihalo-para-trifluoromethylaniline obtained can also be isolated, in particular in order to be stored, by distillation of the solvent according to techniques known to a person skilled in the art.
- the reactor is subsequently fed with a 70% solution of para- trifluoromethylaniline in monochlorobenzene at a flow rate of 792 kg/h for 6 h 30 and with Cl 2 at a flow rate of 488 kg/h.
- the temperature is maintained at 110°C by cooling the jacket.
- the monochlorobenzene is distilled off by placing the reactor under gradually increasing vacuum through a distillation column. After removal of the solvent, the 2,6-dichloro-para-trifluoromethylaniline is cooled to 60°C before emptying the reactor to the storage tank.
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Pest Control & Pesticides (AREA)
- Plant Pathology (AREA)
- Health & Medical Sciences (AREA)
- Agronomy & Crop Science (AREA)
- Dentistry (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)
Abstract
Process for the preparation of a compound of general formula (I): in which X represents a halogen atom, by reaction of para-trifluoromethylaniline of formula (II): with a dihalogen x2, the two compounds being introduced simultaneously into a polar aprotic solvent in a dihalogen/compound (II) molar ratio ranging from 1.9 to 2.5 and at a temperature ranging from 100 to 300° C.
Description
Novel process for the preparation of a synthetic intermediate for pesticides
The present invention relates to a novel process for the preparation of a 2,6-dihalo-para-trifluoromethylaniline from para-trifluoromethylaniline.
Numerous studies have already been carried out with the aim of developing processes for the preparation of 2,6-dihalo-para-trifluoromethylanilines. Patent Application WO 00/35851 discloses a process for the preparation of a 2,6-dihalo- para-trifluoromethylaniline from a trihalo-para-trifluoromethylbenzene at a temperature of between 130 and 350°C in a preferably polar solvent. The use of para- trifluoromethylaniline for the preparation of 2,6-dihalo-para-trifluoromethylaniline does not appear in this patent application.
Patent Applications FR 2 810 665 and WO 01/64623 disclose a process for the preparation of 2,6-dichloro-para-trifluoromethylaniline by chlorination of precursor anilines in a hydrofluoric acid medium. The precursor compound is trifluoromethylphenylcarbamoyl fluoride. The use of an other solvent than hydrofluoric acid is not mentioned.
Nevertheless, these processes result in the formation of impurities, such as polycondensates or heavy polychlorinated compounds, which make it impossible to use 2,6-dihalo-para-trifluoromethylaniline in the continuation of the preparation of pesticidal compounds of phenylpyrazole type without subjecting it to a prior purification stage. This purification stage constitutes a major disadvantage when it is a matter of preparing 2,6-dichloro-para-trifluoromethylaniline on an industrial scale, in particular for the production of pesticides of phenylpyrazole type.
It has now been discovered, in an entirely surprising way, that the process for the preparation of 2,6-dihalo-para-trifluoromethylaniline according to the present invention results in a compound which is sufficiently pure to be used directly in the continuation of the process for the production of pesticidal compounds of phenylpyrazole type.
A subject-matter of the present invention is thus a process for the preparation of a compound of general formula (I):
in which X represents a halogen atom, by reaction of para-trifluoromethylaniline of formula (II):
with a dihalogen X2, the two compounds being introduced simultaneously into a polar aprotic solvent at a temperature ranging from 100 to 300°C and at a dihalogen compound (II) molar ratio ranging from 1.9 to 2.5.
In the context of the present invention, X represents a halogen atom. X can be a chlorine atom, a bromine atom, an iodine atom or a fluorine atom.
The compound of general formula (I) preferably prepared by virtue of the process according to the present invention is 2,6-dichloro-para- trifluoromethylaniline, which is particularly useful in the synthesis of fipronil, an insecticidal compound of phenylpyrazole type.
The solvent used during the preparation of the compound of general formula
(I) according to the present invention is a polar aprotic solvent. A preferred polar aprotic solvent can be a chlorinated aromatic solvent, such as monochlorobenzene, or a chlorinated aliphatic solvent, such as dichloroethane. In an entirely preferred way, monochlorobenzene will be chosen as solvent.
The dihalogen/compound (II) molar ratio is chosen as ranging from 1.9 to 2.5 during the preparation of the 2,6-dihalo-para-trifluoromethylaniline according to the present invention. The dihalogen/compound (II) molar ratio is preferably chosen as ranging from 2 to 2.05.
The temperature of the reaction medium according to the present invention is chosen as ranging from 100 to 300°C. The temperature of the reaction medium is preferably chosen as ranging from 100 to 130°C. In an entirely preferred way, the temperature of the reaction medium is chosen as ranging from 105°C to 115°C.
In an entirely preferred way, the process according to the present invention consists in preparing 2,6-dichloro-para-trifluoromethylaniline by simultaneously introducing para-trifluoromethylaniline and Cl2 into monochlorobenzene in a Cl2/para-trifluoromethylaniline molar ratio of between 1.85 and 2.05, at a temperature ranging from 105 to 115°C.
The process according to the present invention can be carried out according to general techniques known to a person skilled in the art. Thus, the process according to the present invention can be carried out in a jacketed reactor equipped with a stirring device and surmounted by a reflux condenser maintained at a temperature of less than or equal to -10°C. The halogen necessary for the reaction will be introduced via a dip pipe arriving with stirring. The stirrer preferably used will make it possible to provide optimum micromixing of the reactants. This can be carried out by a stirrer of impeller type or by any other stirrer well known to a person skilled in the art.
During the reaction according to the present invention, hydrochloric acid in the gaseous form is produced. The latter is subsequently generally absorbed by a sodium hydroxide trap. As para-trifluoromethylaniline reacts instantaneously on contact with hydrochloric acid to form para-trifluoromethylaniline hydrochloride,
para-trifluoromethylaniline will preferably be fed to the reactor via a dip pipe, in order to avoid blockages.
During the introduction of the reactants, a marked tendency to foam is sometimes observed. This can generally be avoided by reducing the flow rate for the introduction of the reactants. Nevertheless, in order to avoid the accumulation of foam, the latter should be taken up by the liquid. One answer is therefore generally to increase the stirring rate.
The product obtained by virtue of the process according to the present invention (2,6-dihalo-para-trifluoromethylaniline) has a sufficient degree of purity to be reused directly in the synthesis of the pesticidal compounds of phenylpyrazole type. It is generally considered that the degree of purity should be at least 96% in order for the product to be able to be used in the continuation of a preparation process.
The 2,6-dihalo-para-trifluoromethylaniline obtained can also be isolated, in particular in order to be stored, by distillation of the solvent according to techniques known to a person skilled in the art.
The example of the preparation of compounds which follows is mentioned with the aim of illustrating the invention but should on no account be regarded as limiting the latter.
Preparation of 98% 2.6-dichloro-para-trifluoromethyIaniline
12 140 kg of pure monochlorobenzene are charged to a 20 m jacketed reactor rendered inert with nitrogen. The solvent heel is subsequently brought to 110°C by heating the jacket.
The reactor is subsequently fed with a 70% solution of para- trifluoromethylaniline in monochlorobenzene at a flow rate of 792 kg/h for 6 h 30 and with Cl2 at a flow rate of 488 kg/h. The temperature is maintained at 110°C by cooling the jacket.
Once feeding is complete, the residual content of para-trifluoromethylaniline or of monochloro derivative is monitored. If one of these compounds remains, it is then advisable to adjust the amount of chlorine in order to consume the residual product.
At the end of the reaction, the monochlorobenzene is distilled off by placing the reactor under gradually increasing vacuum through a distillation column. After removal of the solvent, the 2,6-dichloro-para-trifluoromethylaniline is cooled to 60°C before emptying the reactor to the storage tank.
The product obtained according to the process described above was analysed. The results given in the table below correspond to the mean of the analytical results which are obtained for the product over a period of one year:
These results thus show that the 2,6-dichloro-para-trifluoromethylaniline obtained by the process according to the present invention is pure to greater than 98%, that the reaction yield is very good, since only 0.05% of reactant (p-TFMA) remains, and that only 0.09% of the monochloro-para-trifluoromethylaniline has not been converted to 2,6-dichloro-para-trifluoromethylaniline.
Claims
Process for the preparation of a compound of general formula (I):
in which X represents a halogen atom, by reaction of para-trifluoromethylaniline of formula (II):
with a dihalogen X2, the two compounds being introduced simultaneously into a polar aprotic solvent in a dihalogen/compound (II) molar ratio ranging from 1.9 to 2.5 and at a temperature ranging from 100 to 300°C.
2. Process according to Claim 1, characterised in that the compound of formula (I) is 2,6-dichloro-para-trifluoromethylaniline.
3. Process according to Claim 1 or 2, characterised in that the solvent used is a chlorinated aliphatic solvent.
4. Process according to Claim 3, characterised in that the solvent used is dichloroethane.
5. Process according to Claim 1 or 2, characterised in that the solvent used is a chlorinated aromatic solvent.
6. Process according to Claim 5, characterised in that the solvent used is monochlorobenzene.
7. Process according to any one of Claims 1 to 6, characterised in that the reactants are introduced in a dihalogen/compound (II) molar ratio ranging from 2 to 2.05.
8. Process according to any one of Claims 1 to 7, characterised in that the temperature of the reaction medium is chosen as ranging from 100 to 130°C.
9. Process according to Claim 8, characterised in that the temperature of the reaction medium is chosen as ranging from 105 to 115°C.
10. Process according to Claim 2, characterized in that the reactants are introduced into monochlorobenzene in a dichlorine/compound (II) molar ratio ranging from 1.85 to 2.05, at a temperature ranging from 105 to 115°C.
Priority Applications (13)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2004546031A JP4511359B2 (en) | 2002-10-25 | 2003-10-24 | A novel method for preparing synthetic intermediates for pesticides |
| UAA200504880A UA79998C2 (en) | 2002-10-25 | 2003-10-24 | Process for the preparation of a synthetic intermediate for pesticides |
| CA002503188A CA2503188A1 (en) | 2002-10-25 | 2003-10-24 | Process for the preparation of a synthetic intermediate for pesticides |
| US10/532,160 US7553993B2 (en) | 2002-10-25 | 2003-10-24 | Process for the preparation of 2,6-dihalo-para-trifluoromethylaniline |
| MXPA05004234A MXPA05004234A (en) | 2002-10-25 | 2003-10-24 | Process for the preparation of 2,6-dihalo-para-trifluoromethylaniline. |
| EP03780071A EP1558560B1 (en) | 2002-10-25 | 2003-10-24 | Process for the preparation of 2,6-dihalo-para-trifluoromethylaniline |
| DK03780071T DK1558560T3 (en) | 2002-10-25 | 2003-10-24 | Process for the preparation of 2,6-dihalo-para-trifluoromethylaniline |
| SI200331493T SI1558560T1 (en) | 2002-10-25 | 2003-10-24 | Process for the preparation of 2,6-dihalo-para-trifluoromethylaniline |
| EA200500688A EA008062B1 (en) | 2002-10-25 | 2003-10-24 | Novel process for the preparation of a synthetic intermediate for pesticides |
| DE60325631T DE60325631D1 (en) | 2002-10-25 | 2003-10-24 | PROCESS FOR THE PREPARATION OF 2,6-DIHALO-PARA-TRIFLUOROMETHYLANILINE |
| AU2003288184A AU2003288184B2 (en) | 2002-10-25 | 2003-10-24 | Process for the preparation of 2,6-dihalo-para-trifluoromethylaniline |
| BRPI0315671-0A BR0315671B1 (en) | 2002-10-25 | 2003-10-24 | PROCESS FOR PREPARING A COMPOUND |
| IL168096A IL168096A (en) | 2002-10-25 | 2005-04-18 | Process for the preparation of synthetic intermediate for pesticides |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FR0213392 | 2002-10-25 | ||
| FR0213392A FR2846325B1 (en) | 2002-10-25 | 2002-10-25 | NOVEL PROCESS FOR PREPARING A PESTICIDE SYNTHESIS INTERMEDIARY |
Publications (3)
| Publication Number | Publication Date |
|---|---|
| WO2004037766A2 true WO2004037766A2 (en) | 2004-05-06 |
| WO2004037766A3 WO2004037766A3 (en) | 2004-08-26 |
| WO2004037766A8 WO2004037766A8 (en) | 2005-03-17 |
Family
ID=32088287
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PCT/EP2003/013340 WO2004037766A2 (en) | 2002-10-25 | 2003-10-24 | Process for the preparation of 2,6-dihalo-para-trifluoromethylaniline |
Country Status (23)
| Country | Link |
|---|---|
| US (1) | US7553993B2 (en) |
| EP (1) | EP1558560B1 (en) |
| JP (1) | JP4511359B2 (en) |
| KR (1) | KR20050055780A (en) |
| CN (1) | CN100519510C (en) |
| AT (1) | ATE419230T1 (en) |
| AU (1) | AU2003288184B2 (en) |
| BR (1) | BR0315671B1 (en) |
| CA (1) | CA2503188A1 (en) |
| DE (1) | DE60325631D1 (en) |
| DK (1) | DK1558560T3 (en) |
| EA (1) | EA008062B1 (en) |
| ES (1) | ES2316840T3 (en) |
| FR (1) | FR2846325B1 (en) |
| IL (1) | IL168096A (en) |
| MX (1) | MXPA05004234A (en) |
| PL (1) | PL207084B1 (en) |
| PT (1) | PT1558560E (en) |
| SI (1) | SI1558560T1 (en) |
| TW (1) | TWI295154B (en) |
| UA (1) | UA79998C2 (en) |
| WO (1) | WO2004037766A2 (en) |
| ZA (1) | ZA200504203B (en) |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2846325B1 (en) * | 2002-10-25 | 2006-09-08 | Bayer Cropscience Sa | NOVEL PROCESS FOR PREPARING A PESTICIDE SYNTHESIS INTERMEDIARY |
| US7846399B2 (en) * | 2004-03-23 | 2010-12-07 | W.R. Grace & Co.-Conn. | System and process for injecting catalyst and/or additives into a fluidized catalytic cracking unit |
| CN103408437A (en) * | 2013-08-30 | 2013-11-27 | 江苏丰华化学工业有限公司 | Method for preparing 2,6-dichloro-4-trifluoromethyl phenylamine |
| KR102229374B1 (en) * | 2013-10-10 | 2021-03-17 | 바이엘 크롭사이언스 악티엔게젤샤프트 | Process for preparing 4-[[(benzoyl)amino]sulphonyl]benzoyl chlorides and preparation of acylsulphamoylbenzamides |
| WO2015125155A1 (en) | 2014-02-19 | 2015-08-27 | Srf Limited | Process for the preparation of 2,6-dihalo-para-trifluoromethyl- anilines as intermediates of pyrazoles |
| CN103910639A (en) * | 2014-03-13 | 2014-07-09 | 凯美泰克（天津）化工科技有限公司 | A method of preparing 2,6-dichloro-4-trifluoromethyl phenylamine |
| CN104072379B (en) * | 2014-06-10 | 2018-03-20 | 台州海辰药业有限公司 | A kind of preparation method of 2,6 dichloro-4,4 5-trifluoromethylaniline |
| TWI699351B (en) * | 2015-04-08 | 2020-07-21 | 德商拜耳作物科學公司 | Process for preparing acylsulfamoylbenzamides |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2001064623A1 (en) * | 2000-03-01 | 2001-09-07 | Rhodia Chimie | Chlorination of an aniline in ortho in a hydrofluoric medium |
| FR2810665A1 (en) * | 2000-06-21 | 2001-12-28 | Rhodia Chimie Sa | Preparation of aniline having chlorine atom and perhalogenated aliphatic group with fluorine atom, used as intermediates for e.g. pharmaceuticals, by contacting N-aryl carbamoyl fluoride with chlorinating agent in hydrofluoric medium |
| FR2846325A1 (en) * | 2002-10-25 | 2004-04-30 | Bayer Cropscience Sa | NOVEL PROCESS FOR PREPARING A PESTICIDE SYNTHESIS INTERMEDIARY |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0034402B1 (en) * | 1980-02-05 | 1984-08-29 | Imperial Chemical Industries Plc | Method of preparing fluorine-substituted diphenyl ether derivatives and fluorine-substituted halogeno benzene derivatives for use therein |
| FR2787445B1 (en) * | 1998-12-17 | 2001-01-19 | Rhone Poulenc Agrochimie | PROCESS FOR THE PREPARATION OF POLYHALOGENATED PARA-TRIFLUOROMETHYLANILINES |
-
2002
- 2002-10-25 FR FR0213392A patent/FR2846325B1/en not_active Expired - Lifetime
-
2003
- 2003-10-24 KR KR1020057006958A patent/KR20050055780A/en not_active Application Discontinuation
- 2003-10-24 EA EA200500688A patent/EA008062B1/en not_active IP Right Cessation
- 2003-10-24 EP EP03780071A patent/EP1558560B1/en not_active Expired - Lifetime
- 2003-10-24 JP JP2004546031A patent/JP4511359B2/en not_active Expired - Fee Related
- 2003-10-24 MX MXPA05004234A patent/MXPA05004234A/en active IP Right Grant
- 2003-10-24 PT PT03780071T patent/PT1558560E/en unknown
- 2003-10-24 ES ES03780071T patent/ES2316840T3/en not_active Expired - Lifetime
- 2003-10-24 WO PCT/EP2003/013340 patent/WO2004037766A2/en active Application Filing
- 2003-10-24 PL PL375378A patent/PL207084B1/en not_active IP Right Cessation
- 2003-10-24 CA CA002503188A patent/CA2503188A1/en not_active Abandoned
- 2003-10-24 AT AT03780071T patent/ATE419230T1/en active
- 2003-10-24 UA UAA200504880A patent/UA79998C2/en unknown
- 2003-10-24 DE DE60325631T patent/DE60325631D1/en not_active Expired - Lifetime
- 2003-10-24 TW TW092129612A patent/TWI295154B/en not_active IP Right Cessation
- 2003-10-24 CN CNB2003801019166A patent/CN100519510C/en not_active Expired - Lifetime
- 2003-10-24 AU AU2003288184A patent/AU2003288184B2/en not_active Expired
- 2003-10-24 SI SI200331493T patent/SI1558560T1/en unknown
- 2003-10-24 BR BRPI0315671-0A patent/BR0315671B1/en active IP Right Grant
- 2003-10-24 DK DK03780071T patent/DK1558560T3/en active
- 2003-10-24 US US10/532,160 patent/US7553993B2/en not_active Expired - Lifetime
-
2005
- 2005-04-18 IL IL168096A patent/IL168096A/en active IP Right Grant
- 2005-05-24 ZA ZA200504203A patent/ZA200504203B/en unknown
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2001064623A1 (en) * | 2000-03-01 | 2001-09-07 | Rhodia Chimie | Chlorination of an aniline in ortho in a hydrofluoric medium |
| FR2810665A1 (en) * | 2000-06-21 | 2001-12-28 | Rhodia Chimie Sa | Preparation of aniline having chlorine atom and perhalogenated aliphatic group with fluorine atom, used as intermediates for e.g. pharmaceuticals, by contacting N-aryl carbamoyl fluoride with chlorinating agent in hydrofluoric medium |
| FR2846325A1 (en) * | 2002-10-25 | 2004-04-30 | Bayer Cropscience Sa | NOVEL PROCESS FOR PREPARING A PESTICIDE SYNTHESIS INTERMEDIARY |
Non-Patent Citations (1)
| Title |
|---|
| TOBE YOSHITO ET AL: "Novel Self-Assembly of m-Xylylene Type Dithioureas by Head-to-Tail Hydrogen Bonding" JOURNAL OF ORGANIC CHEMISTRY, AMERICAN CHEMICAL SOCIETY. EASTON, US, vol. 63, 1998, pages 7481-7489, XP002243988 ISSN: 0022-3263 * |
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