WO1997000250A1 - Procede pour preparer la 3-(3-fluoropropyl)-2-iminothiazoline - Google Patents

Procede pour preparer la 3-(3-fluoropropyl)-2-iminothiazoline Download PDF

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Publication number
WO1997000250A1
WO1997000250A1 PCT/JP1996/001633 JP9601633W WO9700250A1 WO 1997000250 A1 WO1997000250 A1 WO 1997000250A1 JP 9601633 W JP9601633 W JP 9601633W WO 9700250 A1 WO9700250 A1 WO 9700250A1
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WO
WIPO (PCT)
Prior art keywords
fluoropropyl
iminothiazoline
formula
mmol
reaction
Prior art date
Application number
PCT/JP1996/001633
Other languages
English (en)
Japanese (ja)
Inventor
Hideaki Suzuki
Toshio Niki
Yoshiyuki Kusuoka
Toshimasa Hamada
Takashi Mizukoshi
Jun Satow
Original Assignee
Nissan Chemical Industries, 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 Nissan Chemical Industries, Ltd. filed Critical Nissan Chemical Industries, Ltd.
Publication of WO1997000250A1 publication Critical patent/WO1997000250A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C309/00—Sulfonic acids; Halides, esters, or anhydrides thereof
    • C07C309/63—Esters of sulfonic acids
    • C07C309/64—Esters of sulfonic acids having sulfur atoms of esterified sulfo groups bound to acyclic carbon atoms
    • C07C309/65—Esters of sulfonic acids having sulfur atoms of esterified sulfo groups bound to acyclic carbon atoms of a saturated carbon skeleton
    • 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
    • C07D277/38—Nitrogen atoms
    • C07D277/40—Unsubstituted amino or imino radicals

Definitions

  • the present invention relates to a method for producing an intermediate used for producing a fluoropropylthiazoline derivative (described in JP-A-7-242665) useful as a herbicide, and a synthetic intermediate thereof.
  • Prior art of the present invention includes 3- (3-fluoropropyl) -2-iminothiazoline via 3- (3-fluoropropyl) -2-iminothiazoline-hydrobromide described in JP-A-7-242665. There is a synthesis of However, the production method using 1-bromo-3-fluoropropane described in the literature is not always satisfactory as a production method of 3- (3-fluoropropyl) -2-iminothiazoline, It is desirable to expand the freedom of choice and to use an advantageous production method using industrially inexpensive raw materials.
  • U.S. Pat.Nos. 4,237,302 and WO9300336 disclose a method for synthesizing 3-alkyl-2-iminothiazolines using 2-aminothiazole and alkylhalide in Scheme 1 below, which is used in the literature.
  • Alkyl halides are bromide or iodide, and there is no disclosure of alkyl chloride.
  • Those skilled in the art will appreciate that these prior art disclosures suggest that highly reactive alkyl bromides or iodides are suitable for the alkylation reaction of 2-aminothiazole, and that the reaction using alkyl chloride is difficult. The suggestions can be easily analogized.
  • the present inventors have conducted intensive studies on a method for producing a 3-fluoropropylthiazoline derivative (described in JP-A-7-242665) useful as a herbicide. As a result, the following scheme using a less expensive raw material was obtained. The present inventors have found a method for producing 3- (3-fluoropropyl) -2-ylline represented by 1 and Scheme 2, and have completed the present invention.
  • Scheme 1
  • R represents a methyl group, a paratolyl group, or a trifluoromethyl group.
  • the method of Scheme 2 uses a sulfonic acid fluoropropyl ester (4) and a 2-aminothiazole (1) To give 3- (3-fluoropropyl) -2-iminothiazoline-sulfonate (5), and this is further converted to 3- (3-fluoropropyl) -2-iminothiazoline ( 3).
  • 3- (3-fluoropropyl) -2-iminothiazoline which is useful as an intermediate of a highly active herbicide, can be efficiently produced from an industrially inexpensive raw material.
  • BEST MODE FOR CARRYING OUT THE INVENTION The reaction between 2-aminothiazole (1) and 1-chloro-3-fluoropropane (2) in Scheme 1 is 1-chloro-3 to 1 mole of 2-aminothiazole (1).
  • -Fluopropane (2) is used with 0.5 to 3 moles, more preferably from 0.75 to 2.0 moles.
  • the additives include metal halides such as potassium iodide, sodium iodide, potassium bromide, and sodium bromide; Alternatively, a catalyst such as 18-crown-6-ether is added in an amount of 2.0 mole equivalents based on the amount of the catalyst to 1-kokuguchi-3-fluoropropane (2). These additives may be used alone or as a mixture.
  • metal halides such as potassium bromide and sodium bromide can be used by further adding chloroethers such as 18-crown-6-ether.
  • the reaction temperature is a force that can be arbitrarily selected from the range of -30 ° C to 150 ° C, and is preferably in the range of 0 ° C to 100 ° C.
  • Solvents used in this reaction include solvents inert to this reaction, for example, aromatic hydrocarbons such as benzene, toluene and xylene, halogenated aromatic hydrocarbons such as benzene and dichlorobenzene, dichloromethane, and chloroform.
  • aromatic hydrocarbons such as benzene, toluene and xylene
  • halogenated aromatic hydrocarbons such as benzene and dichlorobenzene, dichloromethane, and chloroform.
  • Halogenated hydrocarbons such as form, ethylene dichloride and carbon tetrachloride, ethers such as ethyl ether, isopropyl ether, dioxane, and tetrahydrofuran; alcohols such as methanol, ethanol, normal propyl alcohol, and isopropyl alcohol; Nitriles such as acetonitrile and propionitrile; amides such as dimethylformamide, dimethylacetamide, N-methylpyrrolidone and hexamethylphosphoric acid trimid; 1,3-dimethyl-2-imidazolidinone; 3-dimethyl-1,3-diazacyclohexyl Cyclic ureas such as san-2-one, sulfoxides such as dimethyl sulfoxide, sulfones such as sulfolane, ketones such as acetone and methyl ethyl ketone, esters such as ethyl acetate, petroleum ether
  • the base examples include inorganic bases such as potassium carbonate, sodium carbonate, potassium hydroxide, sodium hydroxide, potassium hydrogen carbonate, and sodium hydrogen carbonate; organic bases such as triethylamine, pyridine, and DBU; sodium methoxide; Metal alkoxides such as methoxide; and metal hydrides such as sodium hydride.
  • inorganic bases and organic bases are used.
  • the reaction temperature is a force that can be arbitrarily selected from the range of -30 ° C to 100 ° C, preferably the range of -20 ° C to 40 ° C.
  • Solvents for this reaction include solvents inert to this reaction, for example, alcohols such as methanol, ethanol, normal propyl alcohol, and isopropyl alcohol, dimethylformamide, dimethylacetamide, N-methylpyrrolidone, and hexamethylphosphine.
  • solvents inert to this reaction for example, alcohols such as methanol, ethanol, normal propyl alcohol, and isopropyl alcohol, dimethylformamide, dimethylacetamide, N-methylpyrrolidone, and hexamethylphosphine.
  • solvents inert to this reaction for example, alcohols such as methanol, ethanol, normal propyl alcohol, and isopropyl alcohol, dimethylformamide, dimethylacetamide, N-methylpyrrolidone, and hexamethylphosphine.
  • amides such as acid triamide, aromatic hydrocarbons such as benzene, toluene, and xylene
  • ethers such as
  • 3- (3-fluoropropyl) -2-iminothiazoline (3) can be obtained by performing a usual treatment.
  • the structure can be confirmed by IR, NMR, MS spectrum and the like.
  • the desired 3- (3-fluoropropyl) -2-iminothiazoline (3) is obtained by reacting the intermediate (6) with a base without isolation and purification. It is also possible.
  • the reaction of 2-aminothiazole (1) with sulfonic acid fluoropropyl ester (4) in Scheme 2 is based on 1 mole of 2-aminothiazole (1)
  • the reaction is carried out using 0.5 to 3.0 moles of the pillester (4), more preferably 0.75 to 2.0 moles.
  • the reaction temperature is a force that can be arbitrarily selected from the range of -30 ° C to 150 ° C, and is preferably in the range of O'C to 100 ° C.
  • Solvents used in this reaction include solvents inert to this reaction, for example, aromatic hydrocarbons such as benzene, toluene and xylene, halogenated aromatic hydrocarbons such as benzene and dichlorobenzene, dichloromethane, and chloroform.
  • aromatic hydrocarbons such as benzene, toluene and xylene
  • halogenated aromatic hydrocarbons such as benzene and dichlorobenzene, dichloromethane, and chloroform.
  • Halogenated hydrocarbons such as form, ethylene dichloride and carbon tetrachloride, ethers such as ethyl ether, isopropyl ether, dioxane and tetrahydrofuran, alcohols such as methanol, ethanol, normal propyl alcohol and isopropyl alcohol; Nitriles such as acetonitrile and propionitrile; amides such as dimethylformamide, dimethylacetamide, N-methylpyrrolidone and hexamethylphosphoric acid triamide; 1,3-dimethyl-2-imidazolidinone; 3-dimethyl-1,3-diazacyclo Cyclic ureas such as xan-2-one; sulfoxides such as dimethyl sulfoxide; sulfones such as sulfolane; ketones such as acetone and methyl ethyl ketone; esters such as ethyl acetate; petroleum ether; petroleum benzine ,
  • the compound (5) of the present invention can be obtained by performing ordinary post-treatment.
  • the reaction of 3- (3-fluoropropyl) -2-iminothiazoline-sulfonate (5) with a base is based on 1 mol of 3- (3-fluoropropyl) -2-iminothiazoline'sulfonate (5)
  • the reaction is carried out using 0.5 to 3.0 moles of base. It is preferably carried out in the range of 0.9 to 1.2 molar amount.
  • the base examples include inorganic bases such as potassium carbonate, sodium carbonate, potassium hydroxide, sodium hydroxide, potassium hydrogen carbonate, and sodium hydrogen carbonate; organic bases such as triethylamine, pyridine, and DBU; sodium methoxide; Metal alkoxides such as methoxide; and metal hydrides such as sodium hydride. Preferred are inorganic bases and organic bases.
  • the reaction temperature can be arbitrarily selected from the range of -30 ° C to 100 ° C, but is preferably in the range of -20 ° C to 40 ° C.
  • Solvents for this reaction include solvents inert to this reaction, for example, alcohols such as methanol, ethanol, normal propyl alcohol, and isopropyl alcohol, dimethylformamide, dimethylacetamide, N-methylpyrrolidone, and hexamethylphosphoric triamide. And the like, aromatic hydrocarbons such as benzene, toluene, and xylene; ethers such as ethyl ether, isopropyl ether, dioxane, and tetrahydrofuran; and water solvents.
  • alcohols such as methanol, ethanol, normal propyl alcohol, and isopropyl alcohol
  • dimethylformamide dimethylacetamide
  • N-methylpyrrolidone N-methylpyrrolidone
  • hexamethylphosphoric triamide hexamethylphosphoric triamide.
  • aromatic hydrocarbons such as benzene, toluene, and xylene
  • ethers such as eth
  • 3-Fluoropropyl trifluoromethanesulfonate used in this reaction is also a novel compound.
  • the intermediate sulfonic acid 3-fluoromethyl propyl ester (4) used in this reaction can be produced by a method known from the literature or a method used per se.
  • Known techniques include U.S. Pat. No. 5,035,740, U.S. Pat. No. 4,913,724, Journal-of'Medical 'Chemistry GJ.Med.Chem) 35, 2221 (1992), Journal of Ob. Chemical 'Society' (J.Chem.Soc.) 2574 (1957), Angew.Chem. (98), 264 (1986), Hemitsche Berichte (Chem.Ber.) 126, 779 (1993), Tetrahedron Le. 21, 21, 2991 (1980).

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Plural Heterocyclic Compounds (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)

Abstract

L'invention concerne un procédé pour préparer la 3-(3-fluoropropyl)-2-iminothiazoline suivant le schéma réactionnel (1) (dans lequel X représente halogéno) ou le schéma réactionnel (2) (dans lequel R représente méthyle, p-toluyle ou un trifluorométhyle), ainsi que les intermédiaires utilisés dans ce procédé.
PCT/JP1996/001633 1995-06-15 1996-06-14 Procede pour preparer la 3-(3-fluoropropyl)-2-iminothiazoline WO1997000250A1 (fr)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
JP7/149020 1995-06-15
JP14902095 1995-06-15
JP17989295 1995-07-17
JP7/179892 1995-07-17

Publications (1)

Publication Number Publication Date
WO1997000250A1 true WO1997000250A1 (fr) 1997-01-03

Family

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Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP1996/001633 WO1997000250A1 (fr) 1995-06-15 1996-06-14 Procede pour preparer la 3-(3-fluoropropyl)-2-iminothiazoline

Country Status (1)

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WO (1) WO1997000250A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114057546A (zh) * 2021-05-07 2022-02-18 安徽伟祥新材料有限公司 一种3-氟-1-丙醇的制备方法

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4237302A (en) * 1978-09-29 1980-12-02 Gulf Oil Corporation Dichloroacetylimino herbicide antagonists as plant protection agents
WO1993000336A1 (fr) * 1991-06-28 1993-01-07 Nissan Chemical Industries Ltd. Derive d'iminosulfonyluree et herbicide
JPH07242665A (ja) * 1994-01-11 1995-09-19 Nissan Chem Ind Ltd フルオロプロピルチアゾリン誘導体及び除草剤

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4237302A (en) * 1978-09-29 1980-12-02 Gulf Oil Corporation Dichloroacetylimino herbicide antagonists as plant protection agents
WO1993000336A1 (fr) * 1991-06-28 1993-01-07 Nissan Chemical Industries Ltd. Derive d'iminosulfonyluree et herbicide
JPH07242665A (ja) * 1994-01-11 1995-09-19 Nissan Chem Ind Ltd フルオロプロピルチアゾリン誘導体及び除草剤

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114057546A (zh) * 2021-05-07 2022-02-18 安徽伟祥新材料有限公司 一种3-氟-1-丙醇的制备方法

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