WO2002076962A1 - Procede de production de 3-oxo-2-(2-thiazolyl)propanenitrile et intermediaire - Google Patents

Procede de production de 3-oxo-2-(2-thiazolyl)propanenitrile et intermediaire Download PDF

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Publication number
WO2002076962A1
WO2002076962A1 PCT/JP2002/002703 JP0202703W WO02076962A1 WO 2002076962 A1 WO2002076962 A1 WO 2002076962A1 JP 0202703 W JP0202703 W JP 0202703W WO 02076962 A1 WO02076962 A1 WO 02076962A1
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ome
group
formula
compound represented
halogen atom
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PCT/JP2002/002703
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English (en)
Japanese (ja)
Inventor
Tomio Yagihara
Tatsumi Suzuki
Original Assignee
Nippon Soda Co.,Ltd.
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Application filed by Nippon Soda Co.,Ltd. filed Critical Nippon Soda Co.,Ltd.
Priority to JP2002576222A priority Critical patent/JPWO2002076962A1/ja
Publication of WO2002076962A1 publication Critical patent/WO2002076962A1/fr

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    • 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
    • C07D277/22—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 only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms
    • C07D277/30—Radicals substituted by carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C319/00—Preparation of thiols, sulfides, hydropolysulfides or polysulfides
    • C07C319/14—Preparation of thiols, sulfides, hydropolysulfides or polysulfides of sulfides
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C319/00—Preparation of thiols, sulfides, hydropolysulfides or polysulfides
    • C07C319/14—Preparation of thiols, sulfides, hydropolysulfides or polysulfides of sulfides
    • C07C319/20—Preparation of thiols, sulfides, hydropolysulfides or polysulfides of sulfides by reactions not involving the formation of sulfide groups

Definitions

  • the present invention relates to a method for producing 3-oxo-l2- (2-thiazolyl) propanenitrile, which is useful as an intermediate for producing agricultural chemicals and the like, particularly an intermediate for producing an acrylonitrile derivative which is an active ingredient of insecticides and acaricides.
  • Background technology :
  • Y ′ and Z ′ each represent an alkyl group or the like, and m ′ and ⁇ ′ each represent 0 or an integer of 1 to 5). It is useful as an intermediate material for insecticides described in 74 and the like, and is a compound that is expected to have physiological activities such as agricultural chemicals and pharmaceuticals by itself.
  • cyanothioacetamide ( ⁇ ) is reacted with phenacyl halide (m) to obtain cyanomethylthiazane.
  • the target compound (I) can be obtained in a relatively high yield.
  • the cyanothioacetamide (II) used as a reaction raw material is expensive and disadvantageous for industrial mass production. It is.
  • An object of the present invention is to provide a production method capable of industrially producing 3-oxo-1- (2-thiazolyl) propane nitrile in an industrially advantageous manner.
  • the present inventors have diligently studied a production method capable of obtaining 3-oxo-1- (2-thiazolyl) propane nitrile in high yield without using expensive cyanothioacetamide, and as a result, (2)
  • Z is a nitro group, Shiano group, a halogen atom, Ji alkyl group, Ji Le 6 Haroaruki group, an alkoxy group, which may have an optionally substituted Fuweniru group or a substituted group
  • n represents 0 or an integer of 1 to 5
  • Y represents a halogen atom, a C x - 6 alkyl group, a C i- 6 alkoxy group or a substituent which may have a substituent.
  • m represents 0 or an integer of 1 to 5
  • R represents a hydrogen atom, an ⁇ alkyl group or a metal atom.
  • the present invention provides a method for producing a compound represented by the above formula (1), wherein ammonia is allowed to act on the compound represented by the above formula (2).
  • the present invention secondly provides a compound represented by the above formula (3).
  • the present invention provides a method for producing a compound represented by the formula (2), comprising reacting a compound represented by the formula (3) with a compound represented by the formula (4).
  • a fourth aspect of the present invention is a step of obtaining a compound represented by the formula (2) by reacting a compound represented by the formula (4) with a compound represented by the formula (3);
  • a method for producing a compound represented by the above formula (1) comprising a step of reacting the obtained compound represented by the formula (2) with ammonia.
  • a first aspect of the present invention is a method for producing a compound represented by the formula (1), wherein ammonia is allowed to act on the compound represented by the formula (2).
  • ⁇ represents a nitro group; a cyano group; a halogen atom such as fluorine, chlorine, bromine, or iodine; methyl, ethyl, ⁇ -propyl, isopropyl, ⁇ -butyl, sec-butyl, isobutyl, t-heptyl, n- pentyl, CI_ 6 alkyl cyclohexyl, etc., to n-; chloromethyl, Furuoromechiru, Promo methyl, dichloromethyl, Jifuruoromechiru, di promo, trichloromethyl, triflumizole Ruo Russia, tribromomethyl, Ci- 6 haloalkyl groups such as trichloroethyl, tolufluoroethyl, and pentafluoroethyl; C such as methoxy, ethoxy, n_propoxy, isopropoxy, n-butoxy
  • substituent of the phenyl group and the phenyl group include halogen atoms such as fluorine, chlorine, bromine, and iodine; methyl, ethyl, n-propyl, isopropyl, n-butyl, and t_butyl. And c- 6 alkyl groups; chloromethyl, trifluoromethyl, trifluorofluoryl, pentafluoroethyl and the like; 6 haloalkyl groups; methoxy, ethoxy and the like d-6 alkoxy groups; and the like. Further, the phenyl group and the phenoxy group may have the same or different plural substituents.
  • n 0 or an integer of 1 to 5.
  • R represents a hydrogen atom; an alkyl group such as methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isoptyl, t-butyl, n-pentyl, n-hexyl; or a metal atom.
  • the metal atom include: alkali metal atoms such as lithium, potassium, and sodium; alkaline earth metals such as magnesium and potassium; transition metals such as copper, zinc, iron, cobalt, nickel, and manganese; and aluminum and tin. Typical metals; and the like, with preference given to alkali metals.
  • Y is a halogen atom such as fluorine, chlorine, bromine and iodine; C such as methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, t-butyl, n-pentyl and n-hexyl 6 alkyl group; ( 6 alkoxy group such as methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, sec-butoxy, isobutoxy, t-butoxy, etc .; or a phenyl group optionally having a substituent.
  • C such as methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, t-butyl, n-pentyl and n-hexyl 6 alkyl group
  • 6 alkoxy group such as methoxy
  • substituent of the phenyl group examples include halogen atoms such as fluorine, chlorine, bromine and iodine; ( 6 alkyl groups such as methyl, ethyl, n-propyl, isopropyl, n-butyl and t-butyl; chloromethyl, trifluoromethyl)
  • halogen atoms such as fluorine, chlorine, bromine and iodine
  • 6 alkyl groups such as methyl, ethyl, n-propyl, isopropyl, n-butyl and t-butyl; chloromethyl, trifluoromethyl
  • a Ci-e haloalkyl group such as chloromethyl, trifluoroethyl and pentafluoroethyl
  • a C-i-s alkoxy group such as methoxy and ethoxy
  • It may have a plurality of different substituents.
  • m represents 0 or an integer of 1 to 5.
  • a method of reacting ammonia with the compound represented by the formula (2) any method can be used in which the compound represented by the formula (1) can be obtained by reacting the compound represented by the formula (2) with ammonia. There are no particular restrictions. For example, a method of blowing ammonia gas into a solution of the compound represented by the formula (2) with stirring, a method of adding aqueous ammonia to a solution of the compound represented by the formula (2), and the like can be given.
  • Examples of the solvent used in the reaction include water; alcohol solvents such as methanol, ethanol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, isobutyl alcohol, and t-butyl alcohol; getyl ether, tetrahydrofuran, Ether solvents such as 1,2-dimethoxyethane and dioxane; nitrile solvents such as acetonitrile and benzonitrile; and aromatic hydrocarbon solvents such as benzene, toluene and xylene. These solvents can be used alone or in combination of two or more. Among these, in the present invention, the use of alcoholic solvents such as methanol and ethanol is preferred.
  • the amount of the solvent to be used is generally in the range of 1 to 100 ml, preferably 3 to 2 Oml, per 1 g of the compound represented by the formula (2).
  • the reaction proceeds smoothly in the range of 0 to 50 ° C, preferably 10 to 20 ° C.
  • the desired compound represented by the above formula (1) can be obtained by performing ordinary post-treatment.
  • the resulting tautomer represented by the formula (1) may have, for example, the following tautomers. These are all included in the present invention.
  • the compound represented by the formula (2) can be produced by reacting a compound represented by the formula (3) with a compound represented by the formula (4).
  • X represents a halogen atom such as fluorine, chlorine, bromine and iodine.
  • the compound represented by the formula (3) is reacted with the compound represented by the formula (4).
  • the method is not particularly limited as long as it can obtain the compound represented by the formula (2).
  • a compound represented by the formula (4) is added at a predetermined reaction temperature to a solution of the compound represented by the formula (3) dissolved in an appropriate solvent. After dropping, a method of stirring at a predetermined temperature for a predetermined time is preferable.
  • the amount of the compound represented by the formula (4) to be used is generally in the range of 0.5 to 5 mol, preferably 1 to 3 mol, per 1 mol of the compound represented by the formula (3).
  • the solvent to be used examples include water; alcohol solvents such as methanol, ethanol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, isobutyl alcohol, and t-butyl alcohol; getyl ether, tetrahydrofuran, Ether solvents such as 1,2 dimethyloxetane and dioxane; nitrile solvents such as acetonitrile and benzonitrile; and aromatic hydrocarbon solvents such as benzene, toluene and xylene; I can do it. These solvents can be used alone or in combination of two or more. Among these, in the present invention, use of acetonitrile is preferred.
  • the amount of the solvent to be used is generally 1-100 ml, preferably 10-40 ml, per 1 g of the compound represented by the formula (3).
  • the reaction proceeds smoothly in the range of usually 0 to 50 ° C, preferably 5 to 15 ° C, and is completed usually in several minutes to 10 hours, preferably in 1 to 5 hours.
  • the compound represented by the formula (1) is represented by the formula (2) by reacting the compound represented by the formula (3) with the compound represented by the formula (4).
  • the compound can also be produced by reacting ammonia without isolation after obtaining the compound. That is, a reaction between the compound represented by the formula (3) and the compound represented by the formula (4), and after the reaction, a series of operations for reacting ammonia with the compound represented by the formula (2) in the reaction solution.
  • the compound represented by the formula (1) can be obtained simply and efficiently by performing the reaction continuously.
  • the conjugated compound represented by the formula (1) produced as described above is reacted with an acid halide to form a more stable agricultural chemical active compound represented by the formula (5).
  • the acrylonitrile derivative represented can be derived.
  • 3-oxo-1- (2-thiazolyl) is useful as an intermediate for producing agricultural chemicals and the like, particularly as an intermediate for producing an acrylonitrile derivative which is an active ingredient of insecticides and acaricides.
  • Propane nitrile can be produced industrially advantageously.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

L'invention concerne un procédé pour produire un 3-oxo-2-(2-thiazolyl)propanenitrile, utile comme intermédiaire pour des produits chimiques agricoles, des médicaments, etc., en particulier comme intermédiaire pour un dérivé d'acrylonitrile qui est un ingrédient actif pour des insecticides ou des acaricides. L'invention concerne notamment un nouveau composé représenté par la formule (2), un procédé de production de ce composé (2), consistant à faire réagir un composé représenté par la formule (3) avec un composé représenté par la formule (4), ainsi qu'un procédé de production d'un composé représenté par la formule (1), consistant à faire agir de l'ammoniac sur le composé (2). Dans les formules mentionnées, Z est un groupe nitro, cyano, etc., Y est un groupe halogéno, alkyl C1-6, etc., R est un atome d'hydrogène, un groupe alkyl C1-6, etc., X est un groupe halogéno et n et m sont indépendamment un nombre entier compris entre 0 et 5.)(4) (3) → (2) (2) → (1).
PCT/JP2002/002703 2001-03-23 2002-03-20 Procede de production de 3-oxo-2-(2-thiazolyl)propanenitrile et intermediaire WO2002076962A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP2002576222A JPWO2002076962A1 (ja) 2001-03-23 2002-03-20 ３−オキソ−２−（２−チアゾリル）プロパンニトリルの製造方法および中間体

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2001-84214 2001-03-23
JP2001084214 2001-03-23

Publications (1)

Publication Number Publication Date
WO2002076962A1 true WO2002076962A1 (fr) 2002-10-03

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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5382584A (en) * 1992-07-31 1995-01-17 Bristol-Myers Squibb Company Adenosine re-uptake inhibiting derivatives of diphenyl oxazoles, thiazoles and imidazoles
WO2000017174A1 (fr) * 1998-09-17 2000-03-30 Nippon Soda Co., Ltd. Thiazolylcinnamonitriles et agents antiparasitaires

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5382584A (en) * 1992-07-31 1995-01-17 Bristol-Myers Squibb Company Adenosine re-uptake inhibiting derivatives of diphenyl oxazoles, thiazoles and imidazoles
WO2000017174A1 (fr) * 1998-09-17 2000-03-30 Nippon Soda Co., Ltd. Thiazolylcinnamonitriles et agents antiparasitaires

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
HIRAI KENTARO ET AL.: "Studies on heterocycles cation systems. XI. Synthesis of 2-disubstituted-amino-4-arylthiazol-5-ylalkanoic acids", CHEM. PHARM. BULL., vol. 25, no. 9, 1971, pages 2282 - 2299, XP002192713 *

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