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WO1993013058A1 - Ester benzoique substitue et production de ce compose - Google Patents

Ester benzoique substitue et production de ce compose Download PDF

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Publication number
WO1993013058A1
WO1993013058A1 PCT/JP1992/001688 JP9201688W WO9313058A1 WO 1993013058 A1 WO1993013058 A1 WO 1993013058A1 JP 9201688 W JP9201688 W JP 9201688W WO 9313058 A1 WO9313058 A1 WO 9313058A1
Authority
WO
WIPO (PCT)
Prior art keywords
methyl
reaction
solvent
methoxy
alkyl
Prior art date
Application number
PCT/JP1992/001688
Other languages
English (en)
Japanese (ja)
Inventor
Tsutomu Inoue
Katsunori Tanaka
Hiroyuki Adachi
Keiichi Ishimitsu
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.
Publication of WO1993013058A1 publication Critical patent/WO1993013058A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C323/00—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups
    • C07C323/50—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and carboxyl groups bound to the same carbon skeleton
    • C07C323/62—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and carboxyl groups bound to the same carbon skeleton having the sulfur atom of at least one of the thio groups bound to a carbon atom of a six-membered aromatic ring of the carbon skeleton
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C323/00—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups
    • C07C323/50—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and carboxyl groups bound to the same carbon skeleton
    • C07C323/61—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and carboxyl groups bound to the same carbon skeleton having the sulfur atom of at least one of the thio groups bound to a carbon atom of a ring other than a six-membered aromatic ring of the carbon skeleton
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2601/00—Systems containing only non-condensed rings
    • C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
    • C07C2601/16—Systems containing only non-condensed rings with a six-membered ring the ring being unsaturated

Definitions

  • the present invention relates to a substituted benzoic acid ester useful as an agrochemical intermediate and a method for producing the same.
  • Alkyl-3-alkoxy-2-alkyl-14-alkylthiobenzoates can be obtained, for example, by subjecting a substance obtained by halogenating 31-alkoxy-1-alkyl-14-alkylthioaniline to a (1) magnesium, Grignard reaction with carbon dioxide gas, (2) nitrile with copper cyanide, hydrolysis or (3) lithiation with n-butyllithium, benzoic acid by blowing carbon dioxide gas, etc. Obtained by esterification.
  • a similar synthetic method is described in USP 4,925,970, which is a powerful and very expensive DDQ (2,3-dichloro-1,5,6-dicyanobenzoquinone) as a dehydrogenating agent. Is used in equimolar. There is no description of a 3-alkoxy compound that is extremely useful as an intermediate for pesticides.
  • An object of the present invention is to provide an alkyl 3-alkoxy-2-alkyl-14-alkylthiobenzoate easily and in high yield by using a readily available inexpensive dehydrogenating agent instead of DDQ.
  • the present invention is illustrated by the following scheme. 0R a R 2 OR ;
  • Ri a is hydrogen or a lower alkyl group
  • Rz ⁇ R 4 are each the same or different from a ⁇ g ⁇ alkyl group.
  • the compound of the present invention can be prepared by the following method.
  • S3 ⁇ 4 from (I) to (IT) is carried out by adding alkyl mercaptan in an inert solvent at least twice the molar amount of (I) and then stirring the mixture at around room temperature.
  • hydrocarbon solvents such as benzene, toluene and hexane, alcoholic solvents such as methanol and ethanol, and mixtures thereof are used.
  • a catalyst an inorganic acid such as hydrogen chloride or sulfuric acid, or a Lewis acid such as kffi-lead or titanium tetrachloride is used.
  • ⁇ From CD to or) is performed by heating in an inert solvent.
  • the inert solvent include mesitylene, benzene, toluene, and xylene, and the reaction is performed by heating at the boiling point of the solvent.
  • reaction from (IE) to (IV) 3 ⁇ 4E and from (IE) to (IV) must be carried out by (1) chlorine, bromine, etc., (2) io, or (3) heating. It is performed by
  • (1) is triethylamine, DB which is equimolar to chlorine, bromine etc.
  • the reaction is carried out using an inorganic or organic base such as U at a reaction temperature of from 20 ° C to room temperature.
  • the inert solvent include methylene chloride, chloroform, carbon tetrachloride, ether, THF, and acetonitrile.
  • the reaction is carried out using a catalytic amount of zeolite in an inert solvent or without using a solvent.
  • a high boiling point solvent such as mesitylene, benzene, toluene and xylene is used, and the reaction is carried out at a reaction temperature up to the boiling point of the solvent.
  • the reaction is performed without using a solvent, the reaction is performed at a reaction temperature from 100 ° C to the raw material power ⁇ a temperature at which no decomposition occurs.
  • Heating is performed in an inert solvent or without using a solvent.
  • a high boiling point solvent such as mesitylene, benzene, toluene, or xylene is used at a reaction temperature up to the boiling point of the solvent.
  • reaction When the reaction is carried out without using a solvent, the reaction is carried out at a reaction temperature from 100 ° C to a raw material strength ⁇ a temperature at which no decomposition occurs.
  • the desired product can be obtained by performing ordinary post-treatment.
  • the synthesized compound was identified by NMR, IR, MASS and the like. BEST MODE FOR CARRYING OUT THE INVENTION
  • OCH ; CH ; OCH Add 10 g of methyl hexoxycarboxylate and 1.0 g of paratoluenesulfonic acid to the solution at 20 ° C. In the following, 9.5 g of methyl mercaptan was blown in over 3 hours, and left overnight at room temperature. After the reaction is completed, the reaction solution is placed in ice water, extracted with methylene chloride, washed with water, magnesium sulfate, and then the solvent is distilled off. The resulting oily substance is purified and separated by column chromatography to obtain the desired product. 11.9 g were obtained.
  • Alkyl-3-alkoxy1-2-alkyl-14-alkylthiobenzoates can be obtained inexpensively and easily in high yield.
  • This alkyl 3-alkoxy1-2-alkyl-14-alkylthiobenzoate is dissolved in an appropriate organic solvent such as alcohol or THF, and treated in an aqueous alkaline solution such as caustic soda at 0 to room temperature to the reflux temperature of the solvent.
  • an oxidizing agent such as NaC 107]

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)

Abstract

Composés représentés par les formules générales (II), (III) et (IV), et procédé de production de ces composés. Dans les formules, R1 représente hydrogène ou alkyle inférieur, et R2 à R4 peuvent être identiques ou différents l'un de l'autre et représentent chacun alkyle inférieur.
PCT/JP1992/001688 1991-12-26 1992-12-24 Ester benzoique substitue et production de ce compose WO1993013058A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP3/356829 1991-12-26
JP3356829A JPH05178818A (ja) 1991-12-26 1991-12-26 置換安息香酸エステル及びその製造法

Publications (1)

Publication Number Publication Date
WO1993013058A1 true WO1993013058A1 (fr) 1993-07-08

Family

ID=18450984

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP1992/001688 WO1993013058A1 (fr) 1991-12-26 1992-12-24 Ester benzoique substitue et production de ce compose

Country Status (2)

Country Link
JP (1) JPH05178818A (fr)
WO (1) WO1993013058A1 (fr)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1994024099A1 (fr) * 1993-04-19 1994-10-27 Nippon Soda Co., Ltd. Procede pour la production de benzene trisubstitue, et intermediaire

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS63122673A (ja) * 1986-11-10 1988-05-26 Nissan Chem Ind Ltd ピラゾ−ル誘誉体および除草剤
JPH0245448A (ja) * 1988-08-05 1990-02-15 Nissan Chem Ind Ltd 安息香酸類の製法
US4990648A (en) * 1988-12-22 1991-02-05 Ici Americas Inc. Process for producing an alkylthiobenzoate
US5110979A (en) * 1991-01-15 1992-05-05 Imperial Chemical Industries Plc Trisubstituted benzoic acid intermediates

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS63122673A (ja) * 1986-11-10 1988-05-26 Nissan Chem Ind Ltd ピラゾ−ル誘誉体および除草剤
JPH0245448A (ja) * 1988-08-05 1990-02-15 Nissan Chem Ind Ltd 安息香酸類の製法
US4990648A (en) * 1988-12-22 1991-02-05 Ici Americas Inc. Process for producing an alkylthiobenzoate
US5110979A (en) * 1991-01-15 1992-05-05 Imperial Chemical Industries Plc Trisubstituted benzoic acid intermediates

Also Published As

Publication number Publication date
JPH05178818A (ja) 1993-07-20

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