EP1131300A2 - Procede de fabrication de 5-amino-3-(thio)carbamoylpyrazoles - Google Patents

Procede de fabrication de 5-amino-3-(thio)carbamoylpyrazoles

Info

Publication number
EP1131300A2
EP1131300A2 EP99955971A EP99955971A EP1131300A2 EP 1131300 A2 EP1131300 A2 EP 1131300A2 EP 99955971 A EP99955971 A EP 99955971A EP 99955971 A EP99955971 A EP 99955971A EP 1131300 A2 EP1131300 A2 EP 1131300A2
Authority
EP
European Patent Office
Prior art keywords
formula
shark
stands
chlorine
amino
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP99955971A
Other languages
German (de)
English (en)
Inventor
Holger Weintritt
Bernd Alig
Reinhard Lantzsch
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Bayer AG
Original Assignee
Bayer AG
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Bayer AG filed Critical Bayer AG
Publication of EP1131300A2 publication Critical patent/EP1131300A2/fr
Withdrawn legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D231/00—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings
    • C07D231/02—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings
    • C07D231/10—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
    • C07D231/14—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole 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
    • C07D231/38—Nitrogen atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D231/00—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings
    • C07D231/02—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings
    • C07D231/10—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
    • C07D231/14—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole 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
    • C07D231/44—Oxygen and nitrogen or sulfur and nitrogen atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
    • C07D401/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings
    • C07D401/04—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings directly linked by a ring-member-to-ring-member bond

Definitions

  • the present invention relates to a new process for the preparation of 5-amino-3- (thio) carbamoylpyrazoles.
  • A stands for N or the grouping C-Hal ', where
  • X represents oxygen or sulfur
  • Y stands for S, SO or S0 2 and
  • R represents haloalkyl or alkyl
  • A, Hai, X and R have the meaning given above, subsequently oxidized with an oxidizing agent, optionally in the presence of a diluent and optionally in the presence of a catalyst.
  • Formula (I) provides a general definition of the 5-amino-3- (thio) carbamoylpyrazoles which can be prepared according to the invention. Preferred substituents or ranges of the radicals listed in the formulas mentioned above and below are explained below.
  • A preferably represents N or the grouping C-Hal ", where
  • Shark is preferably fluorine or chlorine.
  • X preferably represents oxygen or sulfur.
  • Y preferably represents S, SO or SO 2 .
  • R preferably represents (-C-C 4 ) haloalkyl having 1 to 9 identical or different halogen atoms from the series fluorine, chlorine and bromine or for (C ] -C) - alkyl.
  • R particularly preferably represents one of the radicals: -CF- ,, -CHF 2 , -CF 2 CH ,,
  • R represents -CF 3
  • the reaction according to the invention has the advantage that the compounds according to the invention can be obtained in a simple one-step reaction starting from the finished pyrazole ring system. In addition, no hydrogen sulfide is required to produce the thioamide derivatives.
  • Pyrazole derivatives are known in some cases (cf. e.g. DE 1 96 50 197 and EP 0 500 209) or are obtainable in a generally known manner.
  • the pyrazole derivatives of the formula (Ila) are obtained by derivatizing corresponding 3-cyano-pyrazole derivatives in a known manner on the cyano group (cf., for example, EP 0 295 1 17 or the preparation examples).
  • halides of the formula (III) which are also to be used as starting materials in the process according to the invention are generally known compounds of organic chemistry.
  • Inert organic solvents are suitable as diluents for carrying out the process according to the invention.
  • These include in particular aliphatic, alicyclic or aromatic, optionally halogenated hydrocarbons, such as, for example, gasoline, benzene, toluene, xylene, chlorobenzene, petroleum ether, hexane, cyclohexane, dichloromethane, chloroform, carbon tetrachloride; Ethers such as diethyl ether, dioxane, tetrahydrofuran or ethylene glycol dimethyl or diethyl ether, ketones such as acetone or butanone, nitriles such as acetonitrile or propionitrile; Amides, such as dimethylformamide, dimethylacetamide, N-methylformanilide, N-methylpyrrolidone or hexamethylphosphoric triamide, esters, such as ethyl acetate, sulfoxides
  • the process according to the invention can optionally be carried out in the presence of a reaction auxiliary.
  • a reaction auxiliary Common inorganic or organic bases, furthermore hydrochlorides, tosylates and mesylates of primary, secondary or tertiary amines and hydrochloric acid are suitable as such.
  • reaction temperatures can be carried out when carrying out the process according to the invention.
  • Process can be varied over a wide range. In general, temperatures between -20 ° C and + 120 ° C, preferably at temperatures between 0 ° C and + 50 ° C.
  • Connection variant (a) preferably inert organic solvents, in particular hydrocarbons, such as toluene, xylene, tetralin, hexane or cyclohexane, or ether. like tetrahydrofuran.
  • hydrocarbons such as toluene, xylene, tetralin, hexane or cyclohexane, or ether. like tetrahydrofuran.
  • reaction temperatures can be carried out when carrying out the inventive reaction temperatures.
  • Connection variant (a) can be varied over a wide range. In general, temperatures between 0 ° C and 200 ° C, preferably between 20 ° C and 150 ° C.
  • Mol of compound of formula (Ia) generally between 1 and 3 mol, preferably between 1 and 2 mol of sulfurizing agent.
  • the processing takes place according to usual methods.
  • Suitable oxidizing agents for carrying out the connection variant (b) according to the invention are all customary oxidizing agents which can be used for sulfur oxidation. Hydrogen peroxide, organic peracids such as peracetic acid, m-chloroperbenzoic acid, p-nitroperbenzoic acid or atmospheric oxygen are particularly suitable.
  • Inert organic solvents are also suitable as diluents for carrying out the connection variant (b) according to the invention.
  • Hydrocarbons such as gasoline, benzene, toluene, hexane or petroleum ether, are preferably used; chlorinated hydrocarbons, such as dichloromethane, 1, 2-dichloroethane. Chloroform, carbon tetrachloride or chlorobenzene; Ethers such as diethyl ether, dioxane or tetrahydrofuran; Carboxylic acids such as acetic acid or propionic acid. or dipolar aprotic solvents such as acetonitrile, acetone, ethyl acetate or dimethylformamide.
  • connection variant (b) according to the invention can, if appropriate, be carried out in the presence of an acid binder.
  • an acid binder As such, all commonly used organic and inorganic acid binders come into question. Alkaline earth or alkali metal hydroxides, acetates or carbonates, such as calcium hydroxide, sodium hydroxide, sodium acetate or sodium carbonate, are preferably used.
  • connection variant (b) according to the invention can be carried out in the presence of a suitable catalyst.
  • a suitable catalyst All metal salt catalysts customarily used for such sulfur oxidations are suitable as such. Examples include ammonium molybdate and sodium tungstate.
  • reaction temperatures can be varied over a wide range when carrying out the connection variant (b) according to the invention. In general, temperatures between -20 ° C and + 70 ° C, preferably at temperatures between 0 ° C and + 50 ° C.
  • connection variant (b) 0.8 to 1.2 mol, preferably equimolar amounts, of oxidizing agent are generally used per mole of compound of the formula (Ib) if one wishes to interrupt the oxidation of the sulfur at the sulfoxide stage.
  • oxidizing agent 0.8 to 1.2 mol, preferably equimolar amounts, of oxidizing agent are generally used per mole of compound of the formula (Ib) if one wishes to interrupt the oxidation of the sulfur at the sulfoxide stage.
  • the 5-amino-3- (thio) carbamoylpyrazoles of the formula (I) to be prepared by the process according to the invention are biologically active compounds, for example insecticides (cf., for example, DE 1 96 50 197 and WO 98/28 279).

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Plural Heterocyclic Compounds (AREA)
  • Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)

Abstract

L'invention concerne un nouveau procédé permettant de fabriquer des 5-amino-3-(thio)carbamoylpyrazoles.
EP99955971A 1998-11-20 1999-11-10 Procede de fabrication de 5-amino-3-(thio)carbamoylpyrazoles Withdrawn EP1131300A2 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE19853560A DE19853560A1 (de) 1998-11-20 1998-11-20 Verfahren zur Herstellung von 5-Amino-3-(thio)carbamoylpyrazolen
DE19853560 1998-11-20
PCT/EP1999/008642 WO2000031043A2 (fr) 1998-11-20 1999-11-10 Procede de fabrication de 5-amino-3-(thio)carbamoylpyrazoles

Publications (1)

Publication Number Publication Date
EP1131300A2 true EP1131300A2 (fr) 2001-09-12

Family

ID=7888443

Family Applications (1)

Application Number Title Priority Date Filing Date
EP99955971A Withdrawn EP1131300A2 (fr) 1998-11-20 1999-11-10 Procede de fabrication de 5-amino-3-(thio)carbamoylpyrazoles

Country Status (10)

Country Link
EP (1) EP1131300A2 (fr)
JP (1) JP2002530382A (fr)
KR (1) KR20010085955A (fr)
CN (1) CN1326446A (fr)
AU (1) AU1270400A (fr)
DE (1) DE19853560A1 (fr)
HK (1) HK1041002A1 (fr)
IL (1) IL142643A0 (fr)
WO (1) WO2000031043A2 (fr)
ZA (1) ZA200103144B (fr)

Families Citing this family (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7262214B2 (en) 2003-02-26 2007-08-28 Merial Limited 1-N-arylpyrazole derivatives in prevention of arthropod-borne and mosquito-borne diseases
AU2004270341B9 (en) * 2003-09-04 2011-06-30 Boehringer Ingelheim Animal Health USA Inc. Pesticides
MX2009004262A (es) 2006-11-10 2009-05-05 Basf Se Proceso para la sulfinilacion de un derivado de pirazol.
KR20090083454A (ko) 2006-11-10 2009-08-03 바스프 에스이 피라졸 유도체의 술피닐화 방법
DE102006061537A1 (de) 2006-12-27 2008-07-03 Bayer Healthcare Ag Mittel zur Bekämpfung von Parasiten an Tieren
DE102006061538A1 (de) 2006-12-27 2008-07-03 Bayer Healthcare Ag Kombinationsprodukt zur Bekämpfung von Parasiten an Tieren
EA019071B1 (ru) 2008-10-02 2013-12-30 Мериал Лимитед Способ получения и очистки трифторметансульфиновой кислоты
AU2012278286B2 (en) 2011-06-30 2016-01-21 Hansen-Ab Gmbh Agents for the control of parasites on animals
JO3626B1 (ar) 2012-02-23 2020-08-27 Merial Inc تركيبات موضعية تحتوي على فيبرونيل و بيرميثرين و طرق استخدامها
EP3941907A4 (fr) * 2019-03-19 2023-01-04 Gharda Chemicals Limited Procédé de synthèse de fipronil

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
NO179282C (no) * 1991-01-18 1996-09-11 Rhone Poulenc Agrochimie Nye 1-(2-pyridyl)pyrazolforbindelser til kontroll av skadeinsekter
DE19650197A1 (de) * 1996-12-04 1998-06-10 Bayer Ag 3-Thiocarbamoylpyrazol-Derivate
IL130537A (en) * 1996-12-24 2004-08-31 Bayer Cropscience Sa 1 - Arylpirazoles, pesticide preparations containing them, process for their preparation and methods for pest control

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO0031043A2 *

Also Published As

Publication number Publication date
CN1326446A (zh) 2001-12-12
HK1041002A1 (zh) 2002-06-28
WO2000031043A2 (fr) 2000-06-02
WO2000031043A3 (fr) 2000-11-09
JP2002530382A (ja) 2002-09-17
KR20010085955A (ko) 2001-09-07
IL142643A0 (en) 2002-03-10
ZA200103144B (en) 2002-06-26
DE19853560A1 (de) 2000-05-25
AU1270400A (en) 2000-06-13

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