WO2002079177A1 - Procede de preparation de (4-phenylthiazol-2-yl)alkanitrile - Google Patents

Procede de preparation de (4-phenylthiazol-2-yl)alkanitrile Download PDF

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Publication number
WO2002079177A1
WO2002079177A1 PCT/JP2002/003056 JP0203056W WO02079177A1 WO 2002079177 A1 WO2002079177 A1 WO 2002079177A1 JP 0203056 W JP0203056 W JP 0203056W WO 02079177 A1 WO02079177 A1 WO 02079177A1
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WIPO (PCT)
Prior art keywords
formula
group
compound represented
sodium
producing
Prior art date
Application number
PCT/JP2002/003056
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English (en)
Japanese (ja)
Inventor
Tomio Yagihara
Tetsushi Ookuchi
Tatsumi Suzuki
Original Assignee
Nippon Soda Co.,Ltd.
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 Nippon Soda Co.,Ltd. filed Critical Nippon Soda Co.,Ltd.
Priority to JP2002577804A priority Critical patent/JPWO2002079177A1/ja
Publication of WO2002079177A1 publication Critical patent/WO2002079177A1/fr

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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
    • C07D277/22—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

Definitions

  • the present invention relates to a method for producing thiazolylalkanenitrile, which is useful as an intermediate for producing pesticides, medicaments, etc., particularly as an intermediate for producing insecticides and acaricides.
  • R represents an alkyl group or the like, n represents 0 or an integer of 1 to 5, and X represents a halogen atom.
  • the method described in this document is hardly an industrial method in that light is blocked and potassium amide is used. Further, no reaction example of 2-halogenothiazole substituted at the 4-position with a nitrile compound is described. Furthermore, when the present inventors applied the method described in this document to 2-halogenothiazole substituted at the 4-position, the yield was low.
  • An object of the present invention is to provide a method for industrially advantageously producing a thiazolylalkanenitrile having a substituent at the 4-position, which is useful as an intermediate for producing agrochemicals, particularly insecticides and acaricides.
  • the present inventors have developed a thiazolyl alcohol having a substituent at the 4-position without using industrially unfavorable raw materials such as cyanothioacetamide and potassium amide.
  • the production method which can obtain nnitrile in high yield was studied diligently.
  • the desired thiazolyl alkane having a substituent at the 4-position is obtained by reacting the 4-position substituted 218-logenothiazole with a nitrile compound in the presence of an inexpensive base. They have found that nitriles can be produced with good yield, and have completed the present invention.
  • R i represents a halogen atom, C i 6 alkyl group, alkoxy group or a phenyl group which may have a substituent
  • n represents an integer of 0 or 15
  • X represents a halogen atom.
  • Equation (3) characterized by reacting in the presence of
  • the present invention comprises reacting a 2-octylogenothiazole conjugate represented by the formula (1) with a nitrile compound represented by the formula (2) in the presence of a base (hereinafter referred to as “the present invention”). It is also called “reaction.”)
  • halogen atom such as fluorine, chlorine, bromine, iodine, etc .
  • Examples of the substituent of the Fuweniru group fluorine, chlorine, bromine, halogen atom such as iodine; methylation, Echiru, n- propyl, isopropyl, n- heptyl, C i _ 6 Al Kill group such t one-butyl group; chloromethyl, triflumizole Ruo Russia methyl, tri furfur O Roe chill, Pentafuruoro Echiru C 6 haloalkyl groups such as; main butoxy, an alkoxy group such as ethoxy group; and the like.
  • the phenyl group may have a plurality of the same or different substituents.
  • n 0 or an integer of 1 to 5, and when n is 2 or more, the Rs may be the same or different.
  • X represents a halogen atom such as fluorine, chlorine, bromine and iodine.
  • R 2 and R 3 are each independently a 7j elementary atom; C ⁇ alkyl such as methyl, ethyl, n-propyl, isopropyl, n-butyl, and t-butyl group; Represents a phenyl group which may have a group or a substituent.
  • Examples of the substituent of the Fuweniru group fluorine, chlorine, bromine, halogen atom such as iodine; methylation, Echiru, n- propyl, isopropyl, n- heptyl, C 6 Al Kill group such t one-butyl group; chloromethyl , triflumizole Ruo Russia methyl, tri furfur O Roe chill, C WINCH 6 haloalkyl group such Pentafuruoro Echiru group; main butoxy, etc. ethoxy (:. Bok 6 alkoxy group; and the like also the Fuweniru groups are the same Alternatively, it may have a plurality of different substituents.
  • the amount of the compound represented by the formula (2) is usually 0.5 to 5 mol, preferably 1 to 3 mol, per 1 mol of the compound represented by the formula (1). is there.
  • Examples of the base used in this reaction include lithium amides such as lithium amide, lithium diisopropyl amide, and lithium hexamethyldisilazide; sodium amide, sodium dimethylamide, and sodium diisopropylamide.
  • Sodium amides such as sodium hexamethyldisilazide
  • potassium amides such as potassium amide, potassium dimethylamide, potassium diisopropylamide, and potassium hexamethyldisilazide
  • Organic lithium compounds such as lithium and t-butyl lithium
  • organic sodium compounds such as n-butyl sodium, sec-butyl sodium and t-butyl sodium
  • Organic bases such as octane (DABCO), 1,4-diazabicyclo [5,4,0] pend-7-
  • sodium amides use of sodium amides is preferable, and sodium amide is more preferable because it is available at a low cost and gives a high yield.
  • the amount of the base to be used is generally in the range of 1 to 100 parts by weight, preferably 20 to 70 parts by weight, based on 100 parts by weight of the compound represented by the formula (1).
  • a compound represented by the formula (1) and a compound represented by the formula (2) are mixed in a solvent.
  • a solvent a compound represented by the formula (1) is added to a solution of the compound represented by the formula (2) and a base dissolved in an appropriate solvent from the viewpoint of performing the reaction efficiently. Stirring is preferred.
  • solvent examples include liquid ammonia; methylamine, ethylamine, ⁇ -propylamine, isopropylamine, ⁇ -butylamine, sec-butylamine, t-butylamine, benzylamine, aniline, dimethylamine.
  • Alkylamine solvents such as ethylene, getylamine, di-n-propylamine, diisopropylamine, di-n-butylamine, triethylamine and diisopropylethylamine; ethylenediamine, trimethylenediamine, tetramethylenediamine, dimethylenetriamine, trimethylene Polyamine-based solvents such as tetramine and triethylenetetramine; nitrogen-containing heterocyclic compounds such as pyridine, 2,6-dimethylpyridine, piperidine, piperazine, and morpholine; methyl alcohol, ethyl alcohol Alcohol solvents such as coal, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, sec-butyl alcohol, and t-butyl alcohol; ethyl ether, di-n-propyl ether, diisopropyl ether, ethylene glycol dimethyl ether, Ether solvents such as tetrahydrofuran (THF
  • the reaction is carried out in the presence of a compound having two or more oxygen atoms or nitrogen atoms in the molecule.
  • a compound having two or more oxygen atoms or nitrogen atoms in the molecule include glycols such as polyethylene glycol; crown ethers such as crown ether and azacrown ether;
  • the reaction temperature varies depending on the solvent used, but when liquid ammonia is not used, the reaction is usually ⁇ 70 ° C. to 50 ° C. When liquid ammonia is used, the reaction is usually ⁇ 70 ° C. It is in the range of 50 ° C.
  • nD22.5 1. 5234 Reference example: Production of 2- [4- (2,6-difluorophenyl) 1-1 (1,3-thiazol-2-yl)] ethanenitrile
  • (4-phenylthiazol-2-yl) alkanenitrile which is useful as an intermediate for producing agrochemicals, particularly insecticides and acaricides, is industrially advantageous. Can be manufactured.
  • (4-1 phenylthiazole-2-yl) alkanenitrile can be produced easily at low cost and with good yield without using cyanothioacetamide and potassium amide.
  • the present invention does not necessarily require the use of liquid ammonia as a solvent. Therefore, when liquid ammonia is not used, there is no need to maintain the reaction system at a low temperature, which is advantageous in terms of production cost.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Thiazole And Isothizaole Compounds (AREA)

Abstract

Procédé servant à préparer thiazolylalkanitrile utile en tant qu'intermédiaire de substances chimiques agricoles ou médicales, particulièrement en tant qu'intermédiaire d'insecticides ou d'acaricides, ce qui consiste à effectuer la réaction d'un composé de 2-halogénothiazole représenté par la formule (I) avec un composé de nitrile représenté par la formule (II) en présence d'une base. Dans ces formules, R1 représente halogéno, alkyle C1-6, n est un entier de 0 à 5 ; X représente halogéno ; R2 et R3 représentent indépendamment chacun hydrogène, alkyle C1-6.
PCT/JP2002/003056 2001-03-29 2002-03-28 Procede de preparation de (4-phenylthiazol-2-yl)alkanitrile WO2002079177A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP2002577804A JPWO2002079177A1 (ja) 2001-03-29 2002-03-28 （４−フェニルチアゾール−２−イル）アルカンニトリルの製造方法

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2001097145 2001-03-29
JP2001-97145 2001-03-29

Publications (1)

Publication Number Publication Date
WO2002079177A1 true WO2002079177A1 (fr) 2002-10-10

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JP (1) JPWO2002079177A1 (fr)
WO (1) WO2002079177A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2007500724A (ja) * 2003-07-30 2007-01-18 アボット・ラボラトリーズ 置換されたチアゾールの製造方法

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4725606A (en) * 1984-07-25 1988-02-16 Merck & Co., Inc. 2-benzyl-4-(4-pyridyl)thiazoles and derivatives thereof as immunoregulants and compositions

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4725606A (en) * 1984-07-25 1988-02-16 Merck & Co., Inc. 2-benzyl-4-(4-pyridyl)thiazoles and derivatives thereof as immunoregulants and compositions

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
HACQUES V. METZGER: "Thiazole and its derivatives", 1979, JOHN WILEY & SONS, USA, XP002953104 *
YAMANAKA HIROSHI ET AL.: "On the reactivity of halo-1,3-azoles and related compounds toward aromatic SN2 substitution", HETEROCYCLES, vol. 31, no. 6, 1990, pages 1115 - 1127, XP002953103 *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2007500724A (ja) * 2003-07-30 2007-01-18 アボット・ラボラトリーズ 置換されたチアゾールの製造方法

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