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WO1994024099A1 - Procede pour la production de benzene trisubstitue, et intermediaire - Google Patents

Procede pour la production de benzene trisubstitue, et intermediaire Download PDF

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Publication number
WO1994024099A1
WO1994024099A1 PCT/JP1994/000636 JP9400636W WO9424099A1 WO 1994024099 A1 WO1994024099 A1 WO 1994024099A1 JP 9400636 W JP9400636 W JP 9400636W WO 9424099 A1 WO9424099 A1 WO 9424099A1
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WO
WIPO (PCT)
Prior art keywords
formula
compound represented
same meaning
producing
mixture
Prior art date
Application number
PCT/JP1994/000636
Other languages
English (en)
Japanese (ja)
Inventor
Tsutomu Inoue
Mitsumasa Takada
Tatsumi Suzuki
Kenji Saito
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 WO1994024099A1 publication Critical patent/WO1994024099A1/fr

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Classifications

    • 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
    • C07C323/00—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups
    • C07C323/10—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 singly-bound oxygen atoms bound to the same carbon skeleton
    • C07C323/17—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 singly-bound oxygen atoms 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 an industrially advantageous production method and an intermediate of a cyclohexane derivative useful as an agrochemical intermediate.
  • the o-form and the p-form are obtained as a mixture during the synthesis of the o-nitoral body, so that this is not an essential improvement.
  • the present invention relates to the formula [I], which has been difficult to produce industrially until now.
  • R 1 represents a C 1 -C 6 alkyl group, a C 1 -C 6 alkoxy C 1 -C 6 alkyl group or a phenyl group which may have a substituent
  • R 2 represents a C 1 -C 6 6 represents an alkyl group or a furyl group which may have a substituent. It is an object of the present invention to provide an inexpensive and easy method for producing the compound represented by the formula:
  • R 1 represents a C 1 -C 6 alkyl group, a C 1 -C 6 alkoxy C 1 -C 6 alkyl group or a phenyl group which may have a substituent
  • R 2 represents a C 1 -C 6 6 represents an alkyl group or a phenyl group which may have a substituent.
  • R 3 represents a C 1 -C 6 alkyl group.
  • Step b adding hydrogen peroxide to a mixture of the compound represented by the formula [III] and the catalyst to cause a reaction
  • Step c A compound represented by the formula [IV] is converted to a compound represented by the formula [V]
  • R ′ has the same meaning as described above. Is added to a heated mixture of the compound of the formula
  • Step d converting the compound represented by the formula [VI] into a compound represented by the formula [VII]:
  • Step e Aromatizing the compound represented by the formula [VIII],
  • R 3 represents the same meaning as described above.
  • an adduct [lXa] and (or IXb)
  • the compound represented by the formula [ ⁇ ] is 2 to 5 equivalents, preferably 3 to 4 equivalents of formalin
  • the catalyst is a cyclic amine such as piperazine or morpholine, or a tertiary amine such as triethylamine. And the like.
  • the reaction is carried out at a temperature of 0 to 40 ° C, preferably 10 to 20 ° C.
  • the reaction time is usually 2 to 18 hours.
  • the compound represented by the formula [III] is obtained by heating the adduct ([IXa] and / or [IXb]) in an acid.
  • an acid a mineral acid such as hydrochloric acid or sulfuric acid is preferable, the concentration is 15 to 40%, and the reaction time is usually 3 to 18 hours.
  • Hydrogen peroxide is added to an alkaline solution of the compound represented by the formula [III].
  • the alkaline solution of the compound represented by the formula [III] is prepared by adding a 1N concentration of an alkaline solution to a lower alcohol solution of 5 to 10 times the volume of the compound represented by the formula [III] at a low temperature. Adjust by doing.
  • the alkaline metal include sodium hydroxide and alkaline metal hydroxides such as hydroxylated aluminum, and alkali metal carbonates such as sodium carbonate and carbonated alkaline.
  • Hydrogen peroxide is added in a solution of 5 to 90%, preferably 10 to 30%, in an amount of 1.2 to 2.2 equivalents at 0 to 20 ° C, preferably 3 to 10 ° C.
  • R 1 represents the same meaning as described above.
  • the lower alcohol is 5 to 30 times the volume of the compound represented by the formula (IV), and the alcohol is an inorganic base such as sodium hydroxide or hydroxide, or an organic base such as DBU. .
  • the addition temperature is 60.
  • the boiling point of C to the solvent is preferred.
  • a compound represented by the formula [VI] is reacted with a compound represented by the formula [VII] in a solvent.
  • Solvents include alcoholic solvents such as methanol and ethanol, and chlorinated solvents such as methylene chloride and chloroform, and have 5 to 20 times the capacity.
  • the alkanethiol represented by the formula [VII] is used in an amount of 3 to 5 equivalents.
  • the catalyst include acids such as paratoluenesulfonic acid, sulfuric acid, and boron trifluoride ether complex, and are used in an amount of 0.01 to 0.05 equivalent.
  • the reaction temperature may be room temperature.
  • [VIII] can be converted to [I] by the following method.
  • [I] can be obtained by adding dicyanodichlorbenzoquinone (DDQ) or chloranil to [VIII] and heating.
  • DDQ or chloranil is preferably 1.5 equivalents of [VIII]
  • the solvent is chloroform, carbon tetrachloride, benzene, toluene, xylene, etc.
  • the reaction temperature is preferably from 60 ° to the boiling point of the solvent.
  • DMSO dimethyl sulfoxide
  • the volume of DMSO is 1 to 3 equivalents, the volume of DMSO is 1 to 3 times, and the temperature for adding [VIII] is preferably 130 to 170, particularly preferably 140 to 150.
  • halogenating agent examples include chlorine, bromine, thionyl chloride, N-chlorosuccinimide, N-bromosuccinimide and the like. These halogenating agents are desirably used in a molar amount of 1 to 2 times the ketal.
  • solvent an inert solvent such as methylene chloride, chloroform, carbon tetrachloride, and hexane is preferable.
  • the reaction temperature is from 140 ° C. to room temperature, preferably from 120 to 110 ° C .; and the reaction time is from 15 minutes to 3 hours.
  • the desired product can be obtained by performing ordinary post-treatment.
  • the synthesized compound was determined from NMR, IR, MASS and the like. BEST MODE FOR CARRYING OUT THE INVENTION
  • Example 4 The yield through Example 1, Example 2, and Example 3 was 65% based on formalin.
  • Example 4 The yield through Example 1, Example 2, and Example 3 was 65% based on formalin.
  • step b an aqueous solution of sodium hydroxide is added to a mixture of xenon and hydrogen peroxide disclosed in Japanese Patent Application Laid-Open No. 60-123439.
  • the yield is low (65%)
  • hydrogen peroxide is charged from the beginning, it is not suitable for mass synthesis (including industrialization) from the viewpoint of safety. is there.
  • the method of the present invention is safe, easy to control the generation of heat, and greatly improves the yield.
  • step c there is a method of heating and refluxing a mixture of 3-methyl-2-cyclohexenone, an alcohol, and a hydration power lyme disclosed in Berichte. 148 (1933). is there.
  • this method it was difficult to control the reaction, yield fluctuation occurred, and the yield was low (approximately 50%) according to additional tests.
  • the desired product could be obtained stably in a high yield (80% or more).
  • the compound represented by the formula [1] which has been difficult to produce industrially, can be easily produced at low cost.
  • the compound represented by the formula [I] obtained in the present invention can be prepared, for example, by the method described in W093130306.

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

Abstract

L'invention se rapporte à un procédé pour produire un composé représenté par la formule générale [I] selon les étapes ci-dessus, ainsi qu'à un intermédiaire représenté par la formule générale [VIII], où R1 représente alkyle C¿1?-C6 pouvant être substitué par alcoxy C1-C6 ou phényle éventuellement substitué; R?2¿ représente alkyle C¿1?-C6 ou phényle éventuellement substitué; et R?3¿ représente alkyle C¿1?-C6.
PCT/JP1994/000636 1993-04-19 1994-04-18 Procede pour la production de benzene trisubstitue, et intermediaire WO1994024099A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP11530293 1993-04-19
JP5/115302 1993-04-19

Publications (1)

Publication Number Publication Date
WO1994024099A1 true WO1994024099A1 (fr) 1994-10-27

Family

ID=14659273

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP1994/000636 WO1994024099A1 (fr) 1993-04-19 1994-04-18 Procede pour la production de benzene trisubstitue, et intermediaire

Country Status (1)

Country Link
WO (1) WO1994024099A1 (fr)

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH021422A (ja) * 1988-02-01 1990-01-05 Sandoz Ag 有機化合物に関する改良
JPH05178818A (ja) * 1991-12-26 1993-07-20 Nippon Soda Co Ltd 置換安息香酸エステル及びその製造法

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH021422A (ja) * 1988-02-01 1990-01-05 Sandoz Ag 有機化合物に関する改良
JPH05178818A (ja) * 1991-12-26 1993-07-20 Nippon Soda Co Ltd 置換安息香酸エステル及びその製造法

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