WO1998028285A1 - Method for producing 2-chloro-5-aminomethylthiazole from 2-chloro-5-methylthiazole via 2-chloro-5-chloromethylthiazole - Google Patents
Method for producing 2-chloro-5-aminomethylthiazole from 2-chloro-5-methylthiazole via 2-chloro-5-chloromethylthiazole Download PDFInfo
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- WO1998028285A1 WO1998028285A1 PCT/EP1997/006843 EP9706843W WO9828285A1 WO 1998028285 A1 WO1998028285 A1 WO 1998028285A1 EP 9706843 W EP9706843 W EP 9706843W WO 9828285 A1 WO9828285 A1 WO 9828285A1
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- chloro
- aminomethylthiazole
- methylthiazole
- radical
- chloromethylthiazole
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- 0 *c([s]1)cnc1Cl Chemical compound *c([s]1)cnc1Cl 0.000 description 1
- RTEUDRWHKUPKJB-UHFFFAOYSA-N Cc([s]1)cnc1Cl Chemical compound Cc([s]1)cnc1Cl RTEUDRWHKUPKJB-UHFFFAOYSA-N 0.000 description 1
- VRMUIVKEHJSADG-UHFFFAOYSA-N ClCc([s]1)cnc1Cl Chemical compound ClCc([s]1)cnc1Cl VRMUIVKEHJSADG-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D277/00—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings
- C07D277/02—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings not condensed with other rings
- C07D277/20—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
- C07D277/32—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings not condensed with other rings having two or three 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
Definitions
- the present invention relates to a process for the preparation of 2-chloro-5-aminomethylthiazole.
- a process for the preparation of 2-chloro-5-aminomethylthiazole was found, which is characterized in that in a first stage 2-chloro-5-methylthiazole with a radical chlorinating agent in the presence of a radical generator and in the presence of a radical halogenating agent Diluent halogenated up to a conversion of 40 to 70 wt .-% and then added to the resulting reaction mixture with ammonia or aqueous ammonia solution in a second stage and the 2-chloro-5-aminomethylthiazole isolated in a conventional manner.
- the reaction can be represented by the following formula:
- Radical chlorinating agents are preferably N-chlorosuccinimide, 1,3-dichloro-5,5-dimethylhydantoin and trichloroisocyanuric acid.
- the chlorinating agents are used in an amount of 0.5 to 1.3 equivalents of chlorine, based on the thiazole. The approximately equivalent amount of chlorinating agent is preferred.
- the radical generator is used in an amount of 0.01 to 1 equivalent, based on the chlorinating agent. An amount of 0.001 to 0.1 equivalent is preferred.
- diluents which are stable against free radical halogenation: halogenated aromatic or aliphatic hydrocarbons such as e.g. Chlorobenzene, carbon tetrachloride, 1,2-dichloroethane, decachlorobutane and nitrobenzene or acetonitrile.
- halogenated aromatic or aliphatic hydrocarbons such as e.g. Chlorobenzene, carbon tetrachloride, 1,2-dichloroethane, decachlorobutane and nitrobenzene or acetonitrile.
- the reaction is carried out at elevated temperature, preferably from room temperature to 150 ° C., particularly preferably at the boiling point of the diluent.
- the reaction is carried out at normal pressure. But you can also with increased
- the halogenation reaction is carried out until a yield of 2-chloro-5-chloromethylthiazole of 40 to 70% by weight, preferably 50 to 60% by weight, is reached. The reaction is then stopped and the second stage of the reaction is initiated.
- the crude product can also be mixed with aqueous concentrated ammonia solution. It is also possible to add ammonia or ammonia solution to the reaction mixture from the halogenation without first removing the solvent.
- the reaction with ammonia takes place at temperatures from -40 ° C to 150 ° C. You can work at normal pressure but also at elevated pressure. If you work with liquid ammonia, the reaction is preferably carried out in an autoclave at the vapor pressure of the ammonia.
- Example 1 The crude mixture obtained in Example 1 is liquid in an autoclave with 10 ml
- Example 2 The crude mixture obtained in Example 2 is reacted in an autoclave with 30 ml of 65% NH 3 at 70 ° C. and a pressure of 30 bar for 1.5 hours. The mixture was cooled and let down. After degassing in vacuo with aqueous
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Thiazole And Isothizaole Compounds (AREA)
Abstract
Description
VERFAHREN ZUR HERSTELLUNG VON 2-CHLOR-5-AMINOMETHYLTHIAZOL AUSGEHEND VON 2-CHLOR-5-METHYLTHIAZOL ÜBER 2-CHLOR-5-CHLORMETHYLTHIAZOL METHOD FOR PRODUCING 2-CHLORINE-5-AMINOMETHYLTHIAZOL FROM 2-CHLORINE-5-METHYLTHIAZOL FROM 2-CHLORINE-5-CHLOROMETHYLTHIAZOLE
Die vorliegende Erfindung betrifft ein Verfahren zur Herstellung von 2-Chlor-5- aminomethylthiazol.The present invention relates to a process for the preparation of 2-chloro-5-aminomethylthiazole.
Die Herstellung von 2-Chlor-5-aminomethylthiazol durch Umsetzung von 2-Chlor-5- chlormethylthiazol mit Hexamethylentetramin ist bekannt aus JP-A 4 021 674. Bei dieser Reaktion ist es aber erforderlich das intermediär entstehende Hexamethylen- tetraminaddukt zu spalten und die bei der Spaltung entstehenden Nebenprodukte zu entfernen und zu entsorgen.The preparation of 2-chloro-5-aminomethylthiazole by reacting 2-chloro-5-chloromethylthiazole with hexamethylenetetramine is known from JP-A 4 021 674. In this reaction, however, it is necessary to cleave the hexamethylenetetramine adduct formed as an intermediate, and the remove and dispose of by-products of the cleavage.
Es war auch schon bekannt 2-Chlor-5-chlormethylthiazol mit wäßriger Ammoniaklösung umzusetzen (EP-A 446 913). Allerdings sind die dabei erzielten Ausbeuten unbefriedigend.It was also known to react 2-chloro-5-chloromethylthiazole with aqueous ammonia solution (EP-A 446 913). However, the yields achieved are unsatisfactory.
Es wurde ein Verfahren zur Herstellung von 2-Chlor-5-aminomethylthiazol gefunden, das dadurch gekennzeichnet ist, daß man in einer ersten Stufe 2-Chlor-5-methylthiazol mit einem radikalischen Chlorierungsmittel in Gegenwart eines Radikalbildners und in Gegenwart eines gegen radikalische Halogenierungsmittel stabilen Verdünnungs- mittels bis zu einem Umsatz von 40 bis 70 Gew.-% halogeniert und anschließend in einer zweiten Stufe das entstandene Reaktionsgemisch mit Ammoniak oder wäßriger Ammoniaklösung versetzt und das 2-Chlor-5-aminomethylthiazol in üblicher Weise isoliert.A process for the preparation of 2-chloro-5-aminomethylthiazole was found, which is characterized in that in a first stage 2-chloro-5-methylthiazole with a radical chlorinating agent in the presence of a radical generator and in the presence of a radical halogenating agent Diluent halogenated up to a conversion of 40 to 70 wt .-% and then added to the resulting reaction mixture with ammonia or aqueous ammonia solution in a second stage and the 2-chloro-5-aminomethylthiazole isolated in a conventional manner.
Die Reaktion läßt sich durch folgendes Formelschema darstellen:The reaction can be represented by the following formula:
Als radikalische Chlorierungsmittel seien bevorzugt N-Chlorsuccinimid, 1,3-Dichlor- 5,5-dimethylhydantoin und Trichlorisocyanursäure genannt. Die Chlorierungsmittel werden in einer Menge von 0,5 bis 1,3 Äquivalenten Chlor bezogen auf das Thiazol eingesetzt. Bevorzugt ist die in etwa äquivalente Menge Chlorierungsmittel.Radical chlorinating agents are preferably N-chlorosuccinimide, 1,3-dichloro-5,5-dimethylhydantoin and trichloroisocyanuric acid. The chlorinating agents are used in an amount of 0.5 to 1.3 equivalents of chlorine, based on the thiazole. The approximately equivalent amount of chlorinating agent is preferred.
Als Radikalbildner seien genannt Diazylperoxide und Azobisalkylnitrile, bevorzugt Azobisisobutyronitril (= ®Profor N), Azobiscyclohexylcarbodinitril, Peroxide wie z.B. Laurylperoxid und Dibenzoylperoxid. Der Radikalbildner wird in einer Menge von 0,01 bis 1 Äquivalent, bezogen auf das Chlorierungsmittel eingesetzt. Bevorzugt ist eine Menge von 0,001 bis 0,1 Äquivalent.Diazyl peroxides and azobisalkyl nitriles, preferably azobisisobutyronitrile (= ®Profor N), azobiscyclohexylcarbodinitrile, peroxides such as e.g. Lauryl peroxide and dibenzoyl peroxide. The radical generator is used in an amount of 0.01 to 1 equivalent, based on the chlorinating agent. An amount of 0.001 to 0.1 equivalent is preferred.
Als Verdünnungsmittel die gegen radikalische Halogenierung stabil sind seien genannt: halogenierte aromatische oder aliphatische Kohlenwasserstoffe wie z.B. Chlorbenzol, Tetrachlorkohlenstoff, 1,2-Dichlorethan, Decachlorbutan sowie Nitro- benzol oder Acetonitril.The following may be mentioned as diluents which are stable against free radical halogenation: halogenated aromatic or aliphatic hydrocarbons such as e.g. Chlorobenzene, carbon tetrachloride, 1,2-dichloroethane, decachlorobutane and nitrobenzene or acetonitrile.
Die Reaktion wird bei erhöhter Temperatur bevorzugt von Raumtemperatur bis 150°C, besonders bevorzugt bei der Siedetemperatur des Verdünnungsmittels durchgeführt.The reaction is carried out at elevated temperature, preferably from room temperature to 150 ° C., particularly preferably at the boiling point of the diluent.
Die Reaktion wird bei Normaldruck durchgeführt. Man kann aber auch bei erhöhtemThe reaction is carried out at normal pressure. But you can also with increased
Druck von 1 bis 10 bar arbeiten.Work pressure from 1 to 10 bar.
Die Halogenierungsreaktion wird solange durchgeführt, bis eine Ausbeute an 2-Chlor- 5-chlormethylthiazol von 40 bis 70 Gew.-%, bevorzugt von 50 bis 60 Gew.-%, erreicht ist. Dann wird die Reaktion abgebrochen und die zweite Stufe der Reaktion eingeleitet.The halogenation reaction is carried out until a yield of 2-chloro-5-chloromethylthiazole of 40 to 70% by weight, preferably 50 to 60% by weight, is reached. The reaction is then stopped and the second stage of the reaction is initiated.
Es war überraschend, daß die Halogenierung von 2-Chlor-5-methylthiazol in der Seitenkette ohne Probleme erfolgt. So konnte mit elementarem Chlor oder Sul- furylchlorid keine gezielte Seitenkettenhalogenierung erzielt werden. Es war auch überraschend, daß das gewünschte Produkt ohne weitere Aufreinigung weiter umgesetzt werden konnte. So war aus J. Am. Chem. Soc. 67 S. 400 (1945) bekannt, daß z.B. 4-Chlormethyl-2-methylthiazol rasch verharzt. Auch vom gewünschten 5- Chlormethyl-thiazolderivat hätte man ähnliche Verharzungsreaktionen und somit Vereinigungen und Ausbeuteminderungen erwarten können.It was surprising that the halogenation of 2-chloro-5-methylthiazole in the side chain takes place without problems. In this way, no targeted side chain halogenation could be achieved with elemental chlorine or sulphuryl chloride. It was also surprising that the desired product could be reacted further without further purification. From J. Am. Chem. Soc. 67 p. 400 (1945) known, that, for example, 4-chloromethyl-2-methylthiazole resinifies quickly. Similar resinification reactions and thus associations and reductions in yield could also have been expected from the desired 5-chloromethyl-thiazole derivative.
Der Verlauf der Halogenierung wird durch fortlaufende gaschromatische Untersuchung der Reaktionsmischung kontrolliert. Nach Erreichen der gewünschten Ausbeute an 2-Chlor-5-chlormethylthiazol wird das Reaktionsgemisch durch Destillation vom Lösungsmittel befreit. Das so erhaltene Rohprodukt wird ohne weitere Aufreini- gung mit Ammoniak, gegebenenfalls in Gegenwart eines inerten Lösungsmittels wie z.B. Ether. Besonders bevorzugt ist die Umsetzung mit 65 % NH (Rest H2O) beiThe course of the halogenation is checked by continuous gas-chromatic examination of the reaction mixture. After the desired yield of 2-chloro-5-chloromethylthiazole has been reached, the reaction mixture is freed from the solvent by distillation. The crude product obtained in this way is purified without further purification with ammonia, if appropriate in the presence of an inert solvent such as ether. The reaction with 65% NH (rest H 2 O) is particularly preferred
Temperaturen von 20 bis 150°C und erhöhtem Druck von 2 - 100 bar. Der Molquotient 2-Chlor-5-chlormethylthiazol:NH3 beträgt 1 : 10-60. Die Reaktionszeit liegt zwischen 0,5 und 6 Stunden.Temperatures from 20 to 150 ° C and increased pressure from 2 - 100 bar. The molar quotient 2-chloro-5-chloromethylthiazole: NH 3 is 1: 10-60. The response time is between 0.5 and 6 hours.
Das Rohprodukt kann auch mit wäßriger konzentrierter Ammoniaklösung versetzt werden. Es ist auch möglich die Reaktionsmischung aus der Halogenierung ohne vorherige Entfernung des Lösungsmittels mit Ammoniak oder Ammoniaklösung zu versetzen.The crude product can also be mixed with aqueous concentrated ammonia solution. It is also possible to add ammonia or ammonia solution to the reaction mixture from the halogenation without first removing the solvent.
Die Umsetzung mit Ammoniak erfolgt bei Temperaturen von -40°C bis 150°C. Es kann bei Normaldruck aber auch bei erhöhtem Druck gearbeitet werden. Arbeitet man mit flüssigem Ammoniak, wird die Umsetzung bevorzugt im Autoklaven beim Dampfdruck des Ammoniak durchgeführt.The reaction with ammonia takes place at temperatures from -40 ° C to 150 ° C. You can work at normal pressure but also at elevated pressure. If you work with liquid ammonia, the reaction is preferably carried out in an autoclave at the vapor pressure of the ammonia.
Nach beendeter Reaktion wird überschlüssiges Ammoniak entfernt, z.B. durchWhen the reaction is complete, excess ammonia is removed, e.g. by
Destillation oder durch Neutralisation mit einer wäßrigen Säure z.B. Salzsäure.Distillation or by neutralization with an aqueous acid e.g. Hydrochloric acid.
Überschüssiges Lösungsmittel wird abdestilliert und die entstandene Mischung aus 2- Chlor-5-aminomethylthiazol und 2-Chlor-5-methylthiazol wird in üblicher Weise, z.B. über Chromatographie, Destillation oder Abtrennung des Amins durch Salzbildung getrennt. Beispiel 1Excess solvent is distilled off and the resulting mixture of 2-chloro-5-aminomethylthiazole and 2-chloro-5-methylthiazole is separated in a customary manner, for example by chromatography, distillation or removal of the amine by salt formation. example 1
2 g (0,015 mol) 2-Chlor-5-methylthiazol in 15 ml Tetrachlorkohlenstoff werden mit 2,4 g (0,019 mol) N-Chlorsuccinimid und 200 mg Azobisisobutyronitril (AiBN) und für 6 Stunden auf Rückfluß erhitzt. Nach dem Abkühlen versetzt man mit 50 ml CH2Cl2, filtriert, wäscht zweimal mit Wasser. Nach dem Trocknen und dem Abziehen des Lösungsmittels im Vakuum erhält man eine gelblich gefärbte Flüssigkeit, welche mit Feststoff durchsetzt ist. Der Umsatz beträgt nach GC 50,5 %, kernchlorierte und mehrfach chlorierte Verbindungen treten in einer Konzentration von <2 % auf.2 g (0.015 mol) of 2-chloro-5-methylthiazole in 15 ml of carbon tetrachloride are heated with 2.4 g (0.019 mol) of N-chlorosuccinimide and 200 mg of azobisisobutyronitrile (AiBN) and refluxed for 6 hours. After cooling, 50 ml of CH 2 Cl2 are added, the mixture is filtered and washed twice with water. After drying and stripping off the solvent in vacuo, a yellowish liquid is obtained, which is permeated with solid. According to GC, the conversion is 50.5%, core chlorinated and multi-chlorinated compounds occur in a concentration of <2%.
Beispiel 2Example 2
1,5 g (0,011 mol) 2-Chlor-5-methylthiazol in 10 ml Tetrachlorkohlenstoff werden mit 1,7 g l,3-Dichlor-5,5-dimethylhydantoin und 150 mg AiBN 6 h auf Raumtemperatur erhitzt. Nach analoger Aufarbeitung erhält man ein Rohprodukt, welches zu 48,5 % aus 2-Chlor-5-chlormethylthiazol besteht.1.5 g (0.011 mol) of 2-chloro-5-methylthiazole in 10 ml of carbon tetrachloride are heated to room temperature with 1.7 g of l, 3-dichloro-5,5-dimethylhydantoin and 150 mg of AiBN for 6 hours. After working up analogously, a crude product is obtained which consists of 48.5% 2-chloro-5-chloromethylthiazole.
Beispiel 3Example 3
Das in Beispiel 1 erhaltene Rohgemisch wird in einem Autoklav mit 10 ml flüssigemThe crude mixture obtained in Example 1 is liquid in an autoclave with 10 ml
NH3 und 50 ml tert.-Amyl-methylether umgesetzt. Man läßt auf Raumtemperatur kommen und rührt weitere 16 h bei Raumtemperatur nach. Nach dem Abdampfen des Lösungsmittels und überschüssigen Ammoniaks versetzt man mit 50 ml 5 % HC1, extrahiert dreimal mit CH2Cl2, stellt die wäßrige Phase mit konz. NaOH auf pH 7 und extrahiert dann erneut. Nach der Extraktion wird mit konz. NaOH auf pH 11-12 gestellt und das Produkt durch erneute Extraktion erhalten. Man isoliert 1,18 g an 5- Aminomethyl-2-chlorthiazol mit einem Gehalt von 95,3 % nach GC. Beispiel 4NH 3 and 50 ml of tert-amyl methyl ether implemented. The mixture is allowed to come to room temperature and stirred for a further 16 h at room temperature. After evaporation of the solvent and excess ammonia, 50 ml of 5% HCl are added, the mixture is extracted three times with CH 2 Cl 2 and the aqueous phase is concentrated. NaOH to pH 7 and then extracted again. After extraction with conc. NaOH adjusted to pH 11-12 and the product obtained by further extraction. 1.18 g of 5-aminomethyl-2-chlorothiazole with a content of 95.3% are isolated by GC. Example 4
Das in Beispiel 2 erhaltene Rohgemisch wird in einem Autoklav mit 30 ml 65-%iger NH3 bei 70°C und einem Druck von 30 bar 1,5 Stunden umgesetzt. Der Ansatz wurde abgekühlt und entspannt. Nach dem Entgasen im Vakuum wird mit wäßrigenThe crude mixture obtained in Example 2 is reacted in an autoclave with 30 ml of 65% NH 3 at 70 ° C. and a pressure of 30 bar for 1.5 hours. The mixture was cooled and let down. After degassing in vacuo with aqueous
HC1 (5 %) und 10 ml H2O ein pH-Wert von 7 eingestellt. Nach wie in Beispiel 3 beschriebener Aufarbeitung isoliert man 0,74 g des gewünschten Produkts. HC1 (5%) and 10 ml H 2 O set a pH of 7. After working up as described in Example 3, 0.74 g of the desired product is isolated.
Claims
Priority Applications (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP52829998A JP2001506659A (en) | 1996-12-20 | 1997-12-08 | Method for producing 2-chloro-5-aminomethylthiazole |
| IL13009297A IL130092A0 (en) | 1996-12-20 | 1997-12-08 | Method for producing 2-chloro-5-aminomethylthiazole from 2-chloro-5-methylthiazole via 2-chloro-5-chloromethylthiazole |
| EP97953756A EP0946530A1 (en) | 1996-12-20 | 1997-12-08 | Method for producing 2-chloro-5-aminomethylthiazole from 2-chloro-5-methylthiazole via 2-chloro-5-chloromethylthiazole |
| AU57549/98A AU5754998A (en) | 1996-12-20 | 1997-12-08 | Method for producing 2-chloro-5-aminomethylthiazole from 2-chloro-5-methylthiazole via 2-chloro-5-chloromethylthiazole |
| BR9713589-5A BR9713589A (en) | 1996-12-20 | 1997-12-08 | Process for the preparation of 2-chloro-5-aminomethylthiazole starting from 2-chloro-5-methylthiazole and passing through 2-chloro-5-chloromethylthiazole |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19653586.7 | 1996-12-20 | ||
| DE19653586A DE19653586A1 (en) | 1996-12-20 | 1996-12-20 | Process for the preparation of 2-chloro-5-aminomethylthiazole |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| WO1998028285A1 true WO1998028285A1 (en) | 1998-07-02 |
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ID=7815722
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PCT/EP1997/006843 Ceased WO1998028285A1 (en) | 1996-12-20 | 1997-12-08 | Method for producing 2-chloro-5-aminomethylthiazole from 2-chloro-5-methylthiazole via 2-chloro-5-chloromethylthiazole |
Country Status (8)
| Country | Link |
|---|---|
| EP (1) | EP0946530A1 (en) |
| JP (1) | JP2001506659A (en) |
| KR (1) | KR20000069058A (en) |
| AU (1) | AU5754998A (en) |
| BR (1) | BR9713589A (en) |
| DE (1) | DE19653586A1 (en) |
| IL (1) | IL130092A0 (en) |
| WO (1) | WO1998028285A1 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2011118832A1 (en) * | 2010-03-24 | 2011-09-29 | 住友化学株式会社 | Manufacturing method for 5-(aminomethyl)-2-chlorothiazole |
| CN114014821A (en) * | 2021-11-22 | 2022-02-08 | 江苏中旗科技股份有限公司 | Preparation method of clothianidin |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE19908447A1 (en) | 1999-02-26 | 2000-08-31 | Bayer Ag | Process for the preparation of 2-chloro-5-chloromethylthiazole |
| DE10061083A1 (en) * | 2000-12-08 | 2002-06-13 | Bayer Ag | Bis (2-chloro-thiazolyl-5-methyl) amine and its salts and process for working up 5-aminomethyl-2-chloro-thiazole and bis (2-chloro-thiazole-5-methyl) amine containing reaction mixtures |
Citations (7)
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|---|---|---|---|---|
| GB1067097A (en) * | 1961-06-16 | 1967-05-03 | Merck & Co Inc | Chloroalkyl thiazoles |
| EP0391205A1 (en) * | 1989-04-07 | 1990-10-10 | Bayer Ag | Process for the preparation of 2-chloro-5-aminomethyl-pyridine |
| EP0446913A1 (en) * | 1990-03-16 | 1991-09-18 | Takeda Chemical Industries, Ltd. | Process for the preparation of chlorothiazole derivatives |
| JPH03223252A (en) * | 1989-12-27 | 1991-10-02 | Nippon Soda Co Ltd | Production of substituted methylamine compound |
| JPH05286936A (en) * | 1992-04-06 | 1993-11-02 | Takeda Chem Ind Ltd | Production of formamide derivative and new formamide derivative |
| EP0775700A1 (en) * | 1995-11-22 | 1997-05-28 | Kureha Chemical Industry Co., Ltd. | Process for the replacement of a primary amino group by a chlorine atom and utilization of this process for the preparation of 2-chloro-5-chloromethyl-thiazol |
| WO1997023469A1 (en) * | 1995-12-21 | 1997-07-03 | Novartis Ag | Process for the preparation of 2-chloro-5-chloromethyl-thiazole |
-
1996
- 1996-12-20 DE DE19653586A patent/DE19653586A1/en not_active Withdrawn
-
1997
- 1997-12-08 AU AU57549/98A patent/AU5754998A/en not_active Abandoned
- 1997-12-08 JP JP52829998A patent/JP2001506659A/en active Pending
- 1997-12-08 WO PCT/EP1997/006843 patent/WO1998028285A1/en not_active Ceased
- 1997-12-08 IL IL13009297A patent/IL130092A0/en unknown
- 1997-12-08 EP EP97953756A patent/EP0946530A1/en not_active Withdrawn
- 1997-12-08 BR BR9713589-5A patent/BR9713589A/en not_active Application Discontinuation
- 1997-12-08 KR KR1019997004473A patent/KR20000069058A/en not_active Withdrawn
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|---|---|---|---|---|
| GB1067097A (en) * | 1961-06-16 | 1967-05-03 | Merck & Co Inc | Chloroalkyl thiazoles |
| EP0391205A1 (en) * | 1989-04-07 | 1990-10-10 | Bayer Ag | Process for the preparation of 2-chloro-5-aminomethyl-pyridine |
| JPH03223252A (en) * | 1989-12-27 | 1991-10-02 | Nippon Soda Co Ltd | Production of substituted methylamine compound |
| EP0446913A1 (en) * | 1990-03-16 | 1991-09-18 | Takeda Chemical Industries, Ltd. | Process for the preparation of chlorothiazole derivatives |
| JPH05286936A (en) * | 1992-04-06 | 1993-11-02 | Takeda Chem Ind Ltd | Production of formamide derivative and new formamide derivative |
| EP0775700A1 (en) * | 1995-11-22 | 1997-05-28 | Kureha Chemical Industry Co., Ltd. | Process for the replacement of a primary amino group by a chlorine atom and utilization of this process for the preparation of 2-chloro-5-chloromethyl-thiazol |
| WO1997023469A1 (en) * | 1995-12-21 | 1997-07-03 | Novartis Ag | Process for the preparation of 2-chloro-5-chloromethyl-thiazole |
Non-Patent Citations (2)
| Title |
|---|
| CHEMICAL ABSTRACTS, vol. 116, no. 7, 17 February 1992, Columbus, Ohio, US; abstract no. 59366r, KAKU S. ET AL.: "Preparation of chlorine-containing heterocyclic group-substituted methylamines" page 862; column 2; XP002063442 * |
| CHEMICAL ABSTRACTS, vol. 120, no. 15, 11 April 1994, Columbus, Ohio, US; abstract no. 191511w, UNEME H. & MINAMIDA I.: "Heterocycle-substituted formamide derivatives and their preparation" page 1027; column 2; XP002063443 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2011118832A1 (en) * | 2010-03-24 | 2011-09-29 | 住友化学株式会社 | Manufacturing method for 5-(aminomethyl)-2-chlorothiazole |
| CN114014821A (en) * | 2021-11-22 | 2022-02-08 | 江苏中旗科技股份有限公司 | Preparation method of clothianidin |
Also Published As
| Publication number | Publication date |
|---|---|
| EP0946530A1 (en) | 1999-10-06 |
| DE19653586A1 (en) | 1998-06-25 |
| IL130092A0 (en) | 2000-02-29 |
| BR9713589A (en) | 2000-04-04 |
| JP2001506659A (en) | 2001-05-22 |
| AU5754998A (en) | 1998-07-17 |
| KR20000069058A (en) | 2000-11-25 |
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