EP1131300A2 - Method for producing 5-amino-3-(thio)carbamoylpyrazoles - Google Patents
Method for producing 5-amino-3-(thio)carbamoylpyrazolesInfo
- 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
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- European Patent Office
- Prior art keywords
- formula
- shark
- stands
- chlorine
- amino
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- 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
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- 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).
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Abstract
The invention relates to a novel method for producing 5-amino-3-(thio)carbamoylpyrazoles.
Description
Verfahren zur Herstellung von 5-Amino-3-(thio)carbamoylpyrazo_enProcess for the preparation of 5-amino-3- (thio) carbamoylpyrazo_en
Die vorliegende Erfindung betrifft ein neues Verfahren zur Herstellung von 5- Amino-3-(thio)carbamoylpyrazolen.The present invention relates to a new process for the preparation of 5-amino-3- (thio) carbamoylpyrazoles.
Es ist bekannt, daß man 5-Amino-3-carbamoylpyrazole der Formel (AI )It is known that 5-amino-3-carbamoylpyrazoles of the formula (AI)
(mit Ar = gegebenenfalls substituiertes Phenyl oder Pyridyl; Z = insbesondere Halo- genalkyl und m = 0, 1 oder 2)(with Ar = optionally substituted phenyl or pyridyl; Z = especially halogenoalkyl and m = 0, 1 or 2)
erhält, wenn man Pyrazol-Derivate der Formel (B 1 )obtained when pyrazole derivatives of the formula (B 1)
(mit E = Ester-Gruppierung)(with E = ester grouping)
in üblicher Art und Weise zunächst mit Chloriden der Formel (Cl )in the usual way, first with chlorides of the formula (Cl)
umsetzt und anschließend die so erhaltenen Derivate an der Ester-Gruppierung amidiert, z.B. mittels Ammoniak (vgl. z.B. EP 0 500 209). implemented and then amidated the derivatives thus obtained on the ester grouping, for example by means of ammonia (cf. for example EP 0 500 209).
Ebenfalls bekannt ist, daß man 5-Amino-3-thiocarbamoylpyrazole der Formel (A2)It is also known that 5-amino-3-thiocarbamoylpyrazoles of the formula (A2)
(mit Ar = gegebenenfalls substituiertes Phenyl oder Pyridyl; Z = insbesondere Halo- genalkyl und m = 0, 1 oder 2)(with Ar = optionally substituted phenyl or pyridyl; Z = especially halogenoalkyl and m = 0, 1 or 2)
erhält, wenn man Pyrazol-Derivate der Formel (B2)obtained if pyrazole derivatives of the formula (B2)
in üblicher Art und Weise zunächst mit Chloriden der Formel (C l ) umsetzt und anschließend die so erhaltenen Derivate an der Cyano-Gruppe mittels Schwefelwasserstoff derivatisiert (vgl. z.B. DE-A 1 96 50 197, WO 98/28 279).first reacted in the usual manner with chlorides of the formula (C1) and then the derivatives obtained in this way were derivatized on the cyano group using hydrogen sulfide (cf. e.g. DE-A 1 96 50 197, WO 98/28 279).
Beide Verfahren haben jedoch den Nachteil, daß ausgehend vom fertigen Pyrazol- Ringsystem eine zweistufige Reaktionsfolge erforderlich ist. Hinzu kommt, daß mit dem Einsatz von Schwefelwasserstoff auf ein toxisch nicht unbedenkliches Reagenz zurückgegriffen wird.However, both processes have the disadvantage that, starting from the finished pyrazole ring system, a two-stage reaction sequence is required. In addition, the use of hydrogen sulfide makes use of a toxic, harmless reagent.
Es wurde nun gefunden, daß man 5-Amino-3-(thio)carbamoylpyrazole der Formel (I)
- _> -It has now been found that 5-amino-3- (thio) carbamoylpyrazoles of the formula (I) - _> -
in welcherin which
A für N oder die Gruppierung C-Hal' steht, wobeiA stands for N or the grouping C-Hal ', where
Hai' für Halogen steht,Shark represents halogen,
Hai für Halogen steht,Shark represents halogen,
X für Sauerstoff oder Schwefel steht,X represents oxygen or sulfur,
Y für S, SO oder S02 steht undY stands for S, SO or S0 2 and
R für Halogenalkyl oder Alkyl steht,R represents haloalkyl or alkyl,
in einfacher Art und Weise erhält, wenn man Pyrazol-Derivate der Formel (II)
obtained in a simple manner if pyrazole derivatives of the formula (II)
in welcherin which
A, Hai und X die oben angegebenen Bedeutung haben,A, shark and X have the meaning given above,
mit Halogeniden der Formel (III)with halides of the formula (III)
Ha_"-Y-R (III)Ha _ "- Y-R (III)
in welcherin which
Hai" für Halogen, insbesondere Chlor oder Brom steht undShark "stands for halogen, especially chlorine or bromine, and
R und Y die oben angegebene Bedeutung haben,R and Y have the meaning given above,
gegebenenfalls in Gegenwart eines Verdünnungsmittels und gegebenenfalls in Gegenwart eines Reaktionsmittels umsetzt und gegebenenfallsif appropriate in the presence of a diluent and if appropriate in the presence of a reactant and if appropriate
a) die so erhaltenen Verbindungen der Formel (la) (X = O)
a) the compounds of the formula (Ia) (X = O) thus obtained
in welcherin which
A, Hai, Y und R die oben angegebene Bedeutung haben,A, Hai, Y and R have the meaning given above,
nachträglich mit einem Schwefelungsmittel gegebenenfalls in Gegenwart eines Verdünnungsmittels umsetzt;subsequently reacted with a sulfurizing agent, if appropriate in the presence of a diluent;
oderor
b) die so erhaltenen Verbindungen der Formel (Ib) (Y = S)b) the compounds of the formula (Ib) (Y = S) thus obtained
in welcherin which
A, Hai, X und R die oben angegebene Bedeutung haben,
nachträglich mit einem Oxidationsmittel gegebenenfalls in Gegenwart eines Verdünnungsmittels und gegebenenfalls in Gegenwart eines Katalysators oxidiert.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.
Die erfindungsgemäßen herstellbaren 5-Amino-3-(thio)carbamoylpyrazole sind durch die Formel (I) allgemein definiert. Bevorzugte Substituenten bzw. Bereiche der in den oben und nachstehend erwähnten Formeln aufgeführten Reste werden im folgenden erläutert.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 steht bevorzugt für N oder die Gruppierung C-Hal", wobeiA preferably represents N or the grouping C-Hal ", where
Hai' für Fluor oder Chlor steht.Hai 'represents fluorine or chlorine.
Hai steht bevorzugt für Fluor oder Chlor.Shark is preferably fluorine or chlorine.
X steht bevorzugt für Sauerstoff oder Schwefel.X preferably represents oxygen or sulfur.
Y steht bevorzugt für S, SO oder SO2.Y preferably represents S, SO or SO 2 .
R steht bevorzugt für (Cι-C4)-Halogenalkyl mit 1 bis 9 gleichen oder verschiedenen Halogenatomen aus der Reihe Fluor, Chlor und Brom oder für (C]-C )- Alkyl.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 steht besonders bevorzugt für einen der Reste: -CF-,, -CHF2, -CF2CH,,R particularly preferably represents one of the radicals: -CF- ,, -CHF 2 , -CF 2 CH ,,
-CF2CHF2, -CF,CHFC1, -CH2CF„ -CH,-CF2C1, -CH2-CF,CHF2, -CF2-CFC1-CF„ -C(C1)(CF,)-CF2C1, -C(C1)(CF,)-CI IC1-CF, sowie -CH, und -C2H5.-CF 2 CHF 2 , -CF, CHFC1, -CH 2 CF "-CH, -CF 2 C1, -CH 2 -CF, CHF 2 , -CF 2 -CFC1-CF" -C (C1) (CF,) -CF 2 C1, -C (C1) (CF,) - CI IC1-CF, as well as -CH, and -C 2 H 5 .
Am meisten bevorzugt werden durch das erfindungsgemäße Verfahren Verbindungen der Formeln (IA) oder (IB)
Compounds of the formulas (IA) or (IB) are most preferred by the process according to the invention.
in welchen in which
A, Hai und R die oben angegebene Bedeutung haben, sowie diejenigen Verbindungen, in welchenA, Hai and R have the meaning given above, as well as those compounds in which
A für C-Cl steht,A stands for C-Cl,
Hai für Cl steht undShark stands for Cl and
R für -CF3 steht,R represents -CF 3 ,
hergestellt.manufactured.
Überraschenderweise werden bei der erfindungsgemäßen Umsetzung der Pyrazol- Derivate der Formel (II) mit Halogeniden der Formel (III) die Verbindungen der
Formel (I) in hoher Selektivität erhalten - die zu erwartende Konkurrenzreaktion der Halogenide an der H2N-CO(S)-Gruppierung ist nicht zu beobachten (vgl. hierzu z.B. Liebigs Ann. 727 (1969), 22; J. Org. Chem. USSR (Engl. Trans.) \967. 963; J. Chem. Soc. 1953, 549; Tetrahedron 50 (1994), 5083 und US 24 76 655).Surprisingly, in the reaction according to the invention of the pyrazole derivatives of the formula (II) with halides of the formula (III), the compounds of Formula (I) obtained with high selectivity - the expected competitive reaction of the halides on the H 2 N-CO (S) group cannot be observed (cf., for example, Liebigs Ann. 727 (1969), 22; J. Org. Chem. USSR (Engl. Trans.) \ 967.963; J. Chem. Soc. 1953, 549; Tetrahedron 50 (1994), 5083 and US 24 76 655).
Die erfindungsgemäße Umsetzung hat den Vorteil, daß die erfindungsgemäßen Verbindungen, ausgehend vom fertigen Pyrazol-Ringsystem in einer einfachen einstufigen Reaktion erhalten werden können. Außerdem wird zur Herstellung der Thioamid-Derivate kein Schwefelwasserstoff benötigt.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.
Verwendet man beispielsweise 5-Amino-3-carbamoyl-l-(2,6-dichlor-4-trifluor- methylphenyl)pyrazol und Trifluormethylsulfinylchlorid als Ausgangsstoffe und anschließend Phosphorpentasulfid als Schwefelungsmittel, so kann der Reaktionsablauf des erfindungsgemäßen Verfahrens und der Anschlußvariante (a) durch das folgende Formelschema skizziert werden:If, for example, 5-amino-3-carbamoyl-l- (2,6-dichloro-4-trifluoromethylphenyl) pyrazole and trifluoromethylsulfinyl chloride are used as starting materials and then phosphorus pentasulfide as a sulfurizing agent, the course of the reaction of the process according to the invention and of connection variant (a) can be outlined by the following formula:
Anschluß ariante (a)Connection ariante (a)
Die beim erfindungsgemäßen Verfahren als Ausgangsstoffe zu verwendendenThose to be used as starting materials in the process according to the invention
Pyrazol-Derivate sind teilweise bekannt (vgl. z.B. DE 1 96 50 197 und EP 0 500 209) bzw. in allgemein bekannter Art und Weise erhältlich.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.
Noch nicht bekannt und ebenfalls Gegenstand dieser Anmeldung sind die Pyrazol- Derivate der Formel (Ha)Not yet known and also the subject of this application are the pyrazole derivatives of the formula (Ha)
in welcher in which
Flal und Hai' die oben angegebene Bedeutung haben.
Die Pyrazol-Derivate der Formel (Ila) werden erhalten, indem man entsprechende 3-Cyano-pyrazol-derivate in bekannter Art und Weise an der Cyano-Gruppe deriva- tisiert (vgl. z.B. EP 0 295 1 17 oder die Herstellungsbeispiele).Flal and Hai 'have the meaning given above. 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).
Die außerdem beim erfindungsgemäßen Verfahren als Ausgangsstoffe zu verwendenden Halogenide der Formel (III) sind allgemein bekannte Verbindungen der organischen Chemie.The 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.
Als Verdünnungsmittel zur Durchführung des erfindungsgemäßen Verfahrens kom- men inerte organische Lösungsmittel infrage. Hierzu gehören insbesondere aliphati- sche, alicyclische oder aromatische, gegebenenfalls halogenierte Kohlenwasserstoffe, wie beispielsweise Benzin, Benzol, Toluol, Xylol, Chlorbenzol, Petrolether, Hexan, Cyclohexan, Dichlormethan, Chloroform, Tetrachlorkohlenstoff; Ether, wie Diethyl- ether, Dioxan, Tetrahydrofuran oder Ethylenglykoldimethyl- oder -diethylether, Ketone wie Aceton oder Butanon, Nitrile, wie Acetonitril oder Propionitril; Amide, wie Dimethylformamid, Dimethylacetamid, N-Methylformanilid, N-Methylpyrroli- don oder Hexamethylphosphorsäuretriamid, Ester, wie Essigsäureethylester, Sulfoxide, wie Dimethylsulfoxid oder Säuren, wie beispielsweise Essigsäure.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, such as dimethyl sulfoxide or acids, such as, for example, acetic acid.
Das erfindungsgemäße Verfahren kann gegebenenfalls in Gegenwart eines Reaktionshilfsmittels durchgeführt werden. Als solche kommen übliche anorganische oder organische Basen, ferner Hydrochloride, Tosylate und Mesylate von primären, sekundären oder tertiären Aminen sowie Salzsäure infrage.The process according to the invention can optionally be carried out in the presence of 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.
Die Reaktionstemperaturen können bei der Durchführung des erfindungsgemäßenThe reaction temperatures can be carried out when carrying out the process according to the invention
Verfahrens in einem größeren Bereich variiert werden. Im allgemeinen arbeitet man bei Temperaturen zwischen -20°C und +120°C, vorzugsweise bei Temperaturen zwischen 0°C und +50°C.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.
Zur Durchführung des erfindungsgemäßen Verfahrens setzt man pro Mol an Pyrazol-To carry out the process according to the invention, per mole of pyrazole
Derivat der Formel (II) im allgemeinen 1 ,0 bis 2.5 Mol, vorzugsweise 1 ,0 bis 1 ,5
Mol an Halogenid der Formel (III) und gegebenenfalls 1,0 bis 2,5 Mol, vorzugsweise 1 ,0 bis 1 ,5 Mol an Reaktionshilfsmittel ein. Die Reaktionsführung, Aufarbeitung und Isolierung der Reaktionsprodukte erfolgt nach allgemein üblichen Verfahren.Derivative of formula (II) in general 1.0 to 2.5 mol, preferably 1.0 to 1.5 Mol of halide of the formula (III) and optionally 1.0 to 2.5 mol, preferably 1.0 to 1.5 mol of reaction auxiliaries. The reaction, working up and isolation of the reaction products is carried out according to generally customary methods.
Als Verdünnungsmittel kommen bei der Durchführung der erfindungsgemäßenSuitable diluents for carrying out the inventive
Anschlußvariante (a) vorzugsweise inerte organische Lösungsmittel, insbesondere Kohlenwasserstoffe, wie Toluol, Xylol, Tetralin, Hexan oder Cyclohexan,oder Ether. wie Tetrahydrofuran, infrage.Connection variant (a) preferably inert organic solvents, in particular hydrocarbons, such as toluene, xylene, tetralin, hexane or cyclohexane, or ether. like tetrahydrofuran.
Die Reaktionstemperaturen können bei der Durchführung der erfindungsgemäßenThe reaction temperatures can be carried out when carrying out the inventive
Anschlußvariante (a) in einem größeren Bereich variiert werden. Im allgemeinen arbeitet man bei Temperaturen zwischen 0°C und 200°C, bevorzugt zwischen 20°C und 150°C.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.
Bei der Durchführung der erfindungsgemäßen Anschlußvariante (a) setzt man proWhen carrying out the connection variant (a) according to the invention, per
Mol Verbindung der Formel (Ia) im allgemeinen zwischen 1 und 3 Mol, vorzugsweise zwischen 1 und 2 Mol Schwefelungsmittel ein. Die Aufarbeitung erfolgt nach üblichen Methoden.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.
Als Oxidationsmittel zur Durchführung der erfindungsgemäßen Anschlußvariante (b) kommen alle üblichen zur Schwefeloxidation verwendbaren Oxidationsmittel infrage. Insbesondere geeignet sind Wasserstoffperoxid, organische Persäuren, wie beispielsweise Peressigsäure, m-Chlorperbenzoesäure, p-Nitroperbenzoesäure oder Luftsauerstoff.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.
Als Verdünnungsmittel zur Durchführung der erfindungsgemäßen Anschlußvariante (b) kommen ebenfalls inerte organische Lösungsmittel infrage. Vorzugsweise verwendet man Kohlenwasserstoffe, wie Benzin, Benzol, Toluol, Hexan oder Petrolether; chlorierte Kohlenwasserstoffe, wie Dichlormethan, 1 ,2-Dichlorethan. Chloroform, Tetrachlorkohlenstoff oder Chlorbenzol; Ether, wie Diethylether, Dioxan oder Tetrahydrofuran; Carbonsäuren, wie Essigsäure oder Propionsäure. oder
dipolare aprotische Lösungsmittel, wie Acetonitril, Aceton, Essigsäureethylester oder Dimethylformamid.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.
Die erfindungsgemäße Anschlußvariante (b) kann gegebenenfalls in Gegenwart eines Säurebindemittels durchgeführt werden. Als solche kommen alle üblicherweise verwendbaren organischen und anorganischen Säurebindemittel infrage. Vorzugsweise verwendet man Erdalkali- oder Alkalimetallhydroxide, -acetate oder -carbonate, wie beispielsweise Calciumhydroxid, Natriumhydroxid, Natriumacetat oder Natriumcarbonat.The connection variant (b) according to the invention can, if appropriate, be carried out in the presence of 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.
Die erfindungsgemäße Anschlußvariante (b) kann gegebenenfalls in Gegenwart eines geeigneten Katalysators durchgeführt werden. Als solche kommen alle üblicherweise für derartige Schwefeloxidationen gebräuchlichen Metallsalz-Katalysatoren infrage. Beispielhaft genannt sei in diesem Zusammenhang Ammoniummolybdat und Natriumwolframat.If appropriate, the connection variant (b) according to the invention can be carried out in the presence of a suitable catalyst. All metal salt catalysts customarily used for such sulfur oxidations are suitable as such. Examples include ammonium molybdate and sodium tungstate.
Die Reaktionstemperaturen können bei der Durchführung der erfindungsgemäßen Anschlußvariante (b) in einem größeren Bereich variiert werden. Im allgemeinen arbeitet man bei Temperaturen zwischen -20°C und +70°C, vorzugsweise bei Temperaturen zwischen 0°C und +50°C.The 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.
Zur Durchführung der erfindungsgemäßen Anschlußvariante (b) setzt man pro Mol an Verbindung der Formel (Ib) im allgemeinen 0,8 bis 1,2 Mol, vorzugsweise äquimolare Mengen Oxidationsmittel ein, wenn man die Oxidation des Schwefels auf der Sulfoxidstufe unterbrechen will. Zur Oxidation zum Sulfon setzt man proTo carry out the connection variant (b) according to the invention, 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. For the oxidation to the sulfone one sets pro
Mol an Verbindung der Formel (Ib) im allgemeinen 1 ,8 bis 3,0 Mol, vorzugsweise doppelt molare Mengen an Oxidationsmittel ein. Die Reaktionsdurchführung, Aufarbeitung und Isolierung der Endprodukte erfolgt nach üblichen Verfahren.
Die nach dem erfindungsgemäßen Verfahren herzustellenden 5-Amino-3- (thio)carbamoylpyrazole der Formel (I) sind biologisch aktive Verbindungen, beispielsweise Insektizide (vgl. z.B. DE 1 96 50 197 und WO 98/28 279).
Mol of compound of formula (Ib) in general 1.8 to 3.0 mol, preferably double molar amounts of oxidizing agent. The reaction, working up and isolation of the end products is carried out according to customary methods. 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).
HerstellungsbeispieleManufacturing examples
Beispiel 1example 1
5-Amino-3-carbamoyl- 1 -(2,6-dichlor-4-trifluormethylphenyl)pyrazol ( 1 ,0 g. 5-amino-3-carbamoyl-1 - (2,6-dichloro-4-trifluoromethylphenyl) pyrazole (1.0 g.
3,0 mmol) [Bsp. (II-l)] und Pyridinium-p-toluolsulfonat (1 ,1 g, 4,5 mmol) in Toluol (6 ml) werden mit Trifluormethylsulfinylchlorid (0,6 g, 3,9 mmol) versetzt. Man erhitzt für 18 Stunden auf 50°C, kühlt die Reaktionsmischung ab, gibt Wasser (20 ml) hinzu und extrahiert gründlich mit Ethylacetat. Die vereinigten organischen Extrakte werden mit Na2CO3 (aq.) und Wasser gewaschen, anschließend mit3.0 mmol) [Ex. (II-1)] and pyridinium p-toluenesulfonate (1.1 g, 4.5 mmol) in toluene (6 ml) are mixed with trifluoromethylsulfinyl chloride (0.6 g, 3.9 mmol). The mixture is heated at 50 ° C. for 18 hours, cooled, the reaction mixture is added, water (20 ml) is added and the mixture is extracted thoroughly with ethyl acetate. The combined organic extracts are washed with Na 2 CO 3 (aq.) And water, then with
Kieselgel/Aktivkohle/MgS04 versetzt und filtriert. Man engt das Filtrat vollständig ein, trocknet den Rückstand im Vakuum und erhält 5-Amino-3-carbamoyl-l-(2,6- dichlor-4-trifluormethylphenyl)-4-trifluormethylsulfιnylpyrazol (1,2 g, GC: 93,2 %, 81,9 % der Theorie) als hellbeigen Feststoff.
Silica gel / activated carbon / MgS0 4 added and filtered. The filtrate is concentrated completely, the residue is dried in vacuo and 5-amino-3-carbamoyl-l- (2,6-dichloro-4-trifluoromethylphenyl) -4-trifluoromethylsulfionylpyrazole (1.2 g, GC: 93.2 %, 81.9% of theory) as a light beige solid.
Herstellung des AusgangsproduktesManufacture of the starting product
5-Amino-3-cyano-l-(2,6-dichlor-4-trifluormethylphenyl)pyrazol (6,4 g, 0.02 mol) werden in Dioxan (145 mlVWasser (120 ml) gelöst. Nach Zugabe von K .CO-, (12,0 g, 0,09 mol) versetzt man bei 0°C tropfenweise mit 30 %-H2O2 (27.5 ml, 0,27 mol), rührt 2 Stunden bei Raumtemperatur, gießt die Reaktionslösung in Wasser (500 ml) und extrahiert mehrmals mit Ethylacetat. Die vereinigten organischen Extrakte werden mit Na2HSO, (aq.) gewaschen, über Na2SO4 getrocknet, das Lösungsmittel wird abdestilliert und der Rückstand im Vakuum getrocknet.5-Amino-3-cyano-1- (2,6-dichloro-4-trifluoromethylphenyl) pyrazole (6.4 g, 0.02 mol) are dissolved in dioxane (145 ml of water (120 ml). After adding K .CO- , (12.0 g, 0.09 mol) is added dropwise at 0 ° C with 30% -H 2 O 2 (27.5 ml, 0.27 mol), stirred for 2 hours at room temperature, the reaction solution is poured into water (500 ml) and extracted several times with ethyl acetate, the combined organic extracts are washed with Na 2 HSO, (aq.), dried over Na 2 SO 4 , the solvent is distilled off and the residue is dried in vacuo.
Man erhält 5-Amino-3-carbamoyl-l-(2,6-dichlor-4-trifluormethylphenyl)pyrazol (5,6 g, HPLC: 98,3 %, 81,2 % der Theorie) als gelben Feststoff.
5-Amino-3-carbamoyl-1- (2,6-dichloro-4-trifluoromethylphenyl) pyrazole (5.6 g, HPLC: 98.3%, 81.2% of theory) is obtained as a yellow solid.
Beispiel 2Example 2
P4S,0 (0,38 g. 0,85 mmol) und Na2CO, (0,09 g, 0,85 mmol) werden in THF (20 ml) suspendiert und bei Raumtemperatur gerührt bis sich eine gelbe Lösung ausbildet (ca. 30 Minuten). Man gibt 5-Amino-3-carbamoyl-l -(2,6-dichlor-4-trifluormethyl- phenyl)-4-tri_luormethylsulfinylpyrazol (0,3 g, 0,65 mmol) [Bsp. 1] hinzu, rührt 24 Stunden bei Raumtemperatur, gießt die Reaktionsmischung in Wasser, extrahiert mit Ethylacetat, wäscht den organischen Extrakt mit NaHCO3 (ges.), trocknet überP 4 S, 0 (0.38 g. 0.85 mmol) and Na 2 CO, (0.09 g, 0.85 mmol) are suspended in THF (20 ml) and stirred at room temperature until a yellow solution forms (about 30 minutes). 5-Amino-3-carbamoyl-1 - (2,6-dichloro-4-trifluoromethylphenyl) -4-tri_luoromethylsulfinylpyrazol (0.3 g, 0.65 mmol) [Ex. 1], stirred for 24 hours at room temperature, poured the reaction mixture into water, extracted with ethyl acetate, washed the organic extract with NaHCO 3 (sat.), Dried over
Na2SO4 und erhält 5-Amino-l-(2,6-dichlor-4-trifluormethylphenyl)-3-thiocarbamoyl- 4-(tri_luormethyl-sulfinyl)pyrazol nach Abdestillieren des Lösungsmittels.
Na 2 SO 4 and receives 5-amino-1- (2,6-dichloro-4-trifluoromethylphenyl) -3-thiocarbamoyl- 4- (tri_luoromethyl-sulfinyl) pyrazole after distilling off the solvent.
Claims
Patentansprücheclaims
1. Verfahren zum Herstellen von 5-Amino-3-(thio)carbamoylpyrazolen der1. Process for the preparation of 5-amino-3- (thio) carbamoylpyrazoles of
Formel (I)Formula (I)
in welcherin which
A für N oder die Gruppierung C-Hal' steht, wobeiA stands for N or the grouping C-Hal ', where
Hai' für Halogen steht,Shark represents halogen,
Hai für Halogen steht,Shark represents halogen,
X für Sauerstoff oder Schwefel steht,X represents oxygen or sulfur,
Y für S, SO oder SO2 steht undY stands for S, SO or SO 2 and
R für Halogenalkyl oder Alkyl steht,R represents haloalkyl or alkyl,
dadurch gekennzeichnet, daß man Pyrazol-Derivate der Formel (II)
characterized in that pyrazole derivatives of the formula (II)
in welcherin which
A, Hai und X die oben angegebenen Bedeutung haben,A, shark and X have the meaning given above,
mit Halogeniden der Formel (III)with halides of the formula (III)
Hal"-Y-R (III)Hal "-Y-R (III)
in welcherin which
Hai" für Halogen, insbesondere Chlor oder Brom steht undShark "stands for halogen, especially chlorine or bromine, and
R und Y die oben angegebene Bedeutung haben,R and Y have the meaning given above,
gegebenenfalls in Gegenwart eines Verdünnungsmittels und gegebenenfalls in Gegenwart eines Reaktionsmittels umsetzt.if appropriate in the presence of a diluent and if appropriate in the presence of a reactant.
Verfahren gemäß Anspruch 1 , dadurch gekennzeichnet, daß man die Verbindungen der Formel (Ia) (X = O)
Process according to Claim 1, characterized in that the compounds of the formula (Ia) (X = O)
in welcherin which
A, Hai, Y und R die in Anspruch 1 angegebene Bedeutung haben,A, Hai, Y and R have the meaning given in Claim 1,
nachträglich mit einem Schwefelungsmittel gegebenenfalls in Gegenwart eines Verdünnungsmittels umsetzt.subsequently reacted with a sulfurizing agent, if appropriate in the presence of a diluent.
Verfahren gemäß Anspruch 1, dadurch gekennzeichnet, daß man die Verbindungen der Formel (Ib) (Y = S)Process according to Claim 1, characterized in that the compounds of the formula (Ib) (Y = S)
in welcherin which
A, Hai, X und R die im Anspruch 1 angegebene Bedeutung haben.
nachträglich mit einem Oxidationsmittel gegebenenfalls in Gegenwart eines Verdünnungsmittels und gegebenenfalls in Gegenwart eines Katalysators oxidiert.A, shark, X and R have the meaning given in claim 1. subsequently oxidized with an oxidizing agent, optionally in the presence of a diluent and optionally in the presence of a catalyst.
4. Verfahren gemäß einem der Ansprüche 1 bis 3, dadurch gekennzeichnet, daß4. The method according to any one of claims 1 to 3, characterized in that
A für N oder die Gruppierung C-Hal' steht, wobeiA stands for N or the grouping C-Hal ', where
Hai' für Fluor oder Chlor steht,Shark represents fluorine or chlorine,
Hai für Fluor oder Chlor steht, undShark stands for fluorine or chlorine, and
R für (C]-C4)-Halogenalkyl mit 1 bis 9 gleichen oder verschiedenenR represents (C ] -C 4 ) haloalkyl with 1 to 9 identical or different
Halogenatomen aus der Reihe Fluor, Chlor und Brom oder für (CrC4)- Alkyl steht.Halogen atoms from the series fluorine, chlorine and bromine or for (C r C 4 ) alkyl.
5. Verfahren gemäß einem der Ansprüche 1 bis 4, dadurch gekennzeichnet, daß5. The method according to any one of claims 1 to 4, characterized in that
R für einen der folgenden Reste steht: -CF3, -CHF2, -CF2CH3, -CF2CHF2, -CF2CHFC1, -CH2CF3, -CH2-CF2C1, -CH2-CF2CHF2,R represents one of the following radicals: -CF 3 , -CHF 2 , -CF 2 CH 3 , -CF 2 CHF 2 , -CF 2 CHFC1, -CH 2 CF 3 , -CH 2 -CF 2 C1, -CH 2 -CF 2 CHF 2 ,
-CF2-CFC1-CF3, -C(C1)(CF3)-CF2C1, -C(C1)(CF3)-CHC1-CF3, -CH3, -C2H5.
-CF 2 -CFC1-CF 3 , -C (C1) (CF 3 ) -CF 2 C1, -C (C1) (CF 3 ) -CHC1-CF 3 , -CH 3 , -C 2 H 5 .
Verbindungen der Formel (Ila)Compounds of the formula (Ila)
in welcher in which
Hai und Hai' für Halogen, insbesondere für Fluor oder Chlor steht.
Shark and shark 'represents halogen, in particular fluorine or chlorine.
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE19853560 | 1998-11-20 | ||
DE19853560A DE19853560A1 (en) | 1998-11-20 | 1998-11-20 | Single-stage preparation of 4-substituted pyrazole compounds useful e.g. as insecticides, from new or known 4-unsubstituted compound and halide |
PCT/EP1999/008642 WO2000031043A2 (en) | 1998-11-20 | 1999-11-10 | Method for producing 5-amino-3-(thio)carbamoylpyrazoles |
Publications (1)
Publication Number | Publication Date |
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EP1131300A2 true EP1131300A2 (en) | 2001-09-12 |
Family
ID=7888443
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
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EP99955971A Withdrawn EP1131300A2 (en) | 1998-11-20 | 1999-11-10 | Method for producing 5-amino-3-(thio)carbamoylpyrazoles |
Country Status (10)
Country | Link |
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EP (1) | EP1131300A2 (en) |
JP (1) | JP2002530382A (en) |
KR (1) | KR20010085955A (en) |
CN (1) | CN1326446A (en) |
AU (1) | AU1270400A (en) |
DE (1) | DE19853560A1 (en) |
HK (1) | HK1041002A1 (en) |
IL (1) | IL142643A0 (en) |
WO (1) | WO2000031043A2 (en) |
ZA (1) | ZA200103144B (en) |
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US7262214B2 (en) | 2003-02-26 | 2007-08-28 | Merial Limited | 1-N-arylpyrazole derivatives in prevention of arthropod-borne and mosquito-borne diseases |
BRPI0414081A (en) * | 2003-09-04 | 2006-10-24 | Bayer Cropscience Sa | pesticides |
AU2007316718B2 (en) | 2006-11-10 | 2013-03-28 | Basf Se | Process for the sulfinylation of a pyrazole derivative |
EA018047B1 (en) | 2006-11-10 | 2013-05-30 | Басф Се | Process for the sulfinylation of a pyrazole derivative |
DE102006061538A1 (en) | 2006-12-27 | 2008-07-03 | Bayer Healthcare Ag | Agent for controlling parasites on animals comprises an N-phenylpyrazole, a pyrethroid, an aliphatic cyclic carbonate and an aliphatic polyether |
DE102006061537A1 (en) | 2006-12-27 | 2008-07-03 | Bayer Healthcare Ag | Agent for controlling parasites on animals comprises an N-phenylpyrazole, an aliphatic cyclic carbonate and an aliphatic polyether |
EP2349987B1 (en) | 2008-10-02 | 2012-11-14 | Basf Se | Method for producing and purifying trifluoromethanesulfinic acid |
BR112013033914A2 (en) | 2011-06-30 | 2016-11-22 | Hansen Ab Gmbh | agent for the control of parasites in animals and use of an agent |
JO3626B1 (en) | 2012-02-23 | 2020-08-27 | Merial Inc | Topical compositions comprising fipronil and permethrin and methods of use |
AU2020243450A1 (en) * | 2019-03-19 | 2021-11-04 | Gharda Chemicals Limited | A process for synthesis of Fipronil |
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NO179282C (en) * | 1991-01-18 | 1996-09-11 | Rhone Poulenc Agrochimie | New 1- (2-pyridyl) pyrazole compounds for control of insect pests |
DE19650197A1 (en) * | 1996-12-04 | 1998-06-10 | Bayer Ag | 3-thiocarbamoylpyrazole derivatives |
JP2001506665A (en) * | 1996-12-24 | 2001-05-22 | ローヌ−プーラン・アグロ | 1-Aryl and pyridyl pyrazole derivatives as pesticides |
-
1998
- 1998-11-20 DE DE19853560A patent/DE19853560A1/en not_active Withdrawn
-
1999
- 1999-11-10 AU AU12704/00A patent/AU1270400A/en not_active Abandoned
- 1999-11-10 KR KR1020017005158A patent/KR20010085955A/en not_active Application Discontinuation
- 1999-11-10 CN CN99813520A patent/CN1326446A/en active Pending
- 1999-11-10 JP JP2000583871A patent/JP2002530382A/en active Pending
- 1999-11-10 IL IL14264399A patent/IL142643A0/en unknown
- 1999-11-10 EP EP99955971A patent/EP1131300A2/en not_active Withdrawn
- 1999-11-10 WO PCT/EP1999/008642 patent/WO2000031043A2/en not_active Application Discontinuation
-
2001
- 2001-04-18 ZA ZA2001/03144A patent/ZA200103144B/en unknown
-
2002
- 2002-04-18 HK HK02102935.2A patent/HK1041002A1/en unknown
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DE19853560A1 (en) | 2000-05-25 |
WO2000031043A2 (en) | 2000-06-02 |
HK1041002A1 (en) | 2002-06-28 |
IL142643A0 (en) | 2002-03-10 |
KR20010085955A (en) | 2001-09-07 |
JP2002530382A (en) | 2002-09-17 |
AU1270400A (en) | 2000-06-13 |
WO2000031043A3 (en) | 2000-11-09 |
ZA200103144B (en) | 2002-06-26 |
CN1326446A (en) | 2001-12-12 |
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