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WO1993020037A1 - Cyclohexenone compound and production thereof - Google Patents

Cyclohexenone compound and production thereof Download PDF

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Publication number
WO1993020037A1
WO1993020037A1 PCT/JP1993/000330 JP9300330W WO9320037A1 WO 1993020037 A1 WO1993020037 A1 WO 1993020037A1 JP 9300330 W JP9300330 W JP 9300330W WO 9320037 A1 WO9320037 A1 WO 9320037A1
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Prior art keywords
compound
general formula
formula
compound represented
lower alkyl
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French (fr)
Japanese (ja)
Inventor
Tsutomu Inoue
Mitsumasa Takata
Keiichi Ishimitsu
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Nippon Soda Co Ltd
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Nippon Soda Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
    • C07C69/74—Esters of carboxylic acids having an esterified carboxyl group bound to a carbon atom of a ring other than a six-membered aromatic ring
    • C07C69/757—Esters of carboxylic acids having an esterified carboxyl group bound to a carbon atom of a ring other than a six-membered aromatic ring having any of the groups OH, O—metal, —CHO, keto, ether, acyloxy, groups, groups, or in the acid moiety

Definitions

  • the present invention relates to a cyclohexenone compound useful as an intermediate for agrochemicals and a method for producing the same.
  • the present invention is a.
  • R 1 , R 2 and R 3 are the same or different and represent a lower alkyl group.
  • R 1 , R 2 , and 3 have the same meanings as described above, and R 4 represents a lower alkyl group. You. Wherein the compound represented by the general formula [I] is reacted in the presence of a zinc compound as a catalyst.
  • the compounds of the present invention as catalysts in their preparation, Z n C ⁇ 2, ⁇ ⁇ ( ⁇ 0 3) 2, ⁇ ⁇ 0, basic zinc carbonate (3 ⁇ ⁇ ( ⁇ ) 2 ⁇ 2 Z n C 0 3) Inorganic zinc compounds such as Zn (CH 3 C 00) 2, zinc benzoate, and zinc powder such as Zn powder (these may be used in combination). It can be obtained in high yields.
  • the amount of the catalyst is 0.01 to 1 mol, preferably 0.1 to 0.3 mol, per 1 mol of the compound of the general formula [II].
  • the reaction temperature is 80 ° C. or higher and up to the boiling point of each solvent.
  • washing with water or acid or alkali treatment is performed for the purpose of removing zinc compounds.
  • the compound of the present invention is useful as an agricultural or pharmaceutical intermediate.
  • Japanese Patent Application No. 3-35869 is disclosed in WO 91/0260
  • Japanese Patent Application It is an intermediate for the herbicides shown in Hei 3—1 9 3 5 9 '5.

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

Abstract

A compound represented by general formula (I), which is useful as an intermediate for producing pesticides and drugs, wherein R?1, R2 and R3¿ may be the same or different from one another and each represents lower alkyl. A process for producing the compound (I) which comprises reacting a compound represented by the formula R4OCH2CH2COCH2OR1 with a compound represented by the formula R2COCH2COOR3 (wherein R?1, R2 and R3¿ are as defined above and R4 represents lower alkyl) in the presence of a zinc compound as the catalyst.

Description

明 細 書 シクロへキセノ ン化合物及びその製造方法  Description Cyclohexenone compound and method for producing the same

技術分野： Technical field:

農医薬の中間体として有用なシクロへキセノ ン化合物及びその製造方法に関す る。 技術背景：  The present invention relates to a cyclohexenone compound useful as an intermediate for agrochemicals and a method for producing the same. Technical background:

本発明化合物の類似化合物として、 J. Chem. So ， Perkin I， 602(1972)に次 の記載がある。  As a similar compound to the compound of the present invention, the following is described in J. Chem. So, Perkin I, 602 (1972).

CH3 COCH2 COO r + CH2 =CHCOCH3 CH 3 COCH 2 COO r + CH 2 = CHCOCH 3

Figure imgf000003_0001
Figure imgf000003_0001

(式中 rは低級アルキル基を示す。 ）  (In the formula, r represents a lower alkyl group.)

反応条件により （a) 又は （b) が合成される。  (A) or (b) is synthesized depending on the reaction conditions.

又、 ビニルケ トンの合成法としては、 Synthetic Communication, 3(3)， 205— 209(1973) に CH3 0 C H2 C H2 C 0 C H2 0 C H 3 に P— トルエンスルホン 酸を作用させて、 CH2 =CHC O CH2 0 C H3 を合成した例が記載されてい るが、 収率は低い。 本発明は、 一般式 R4 0 C H2 CH2 C 0 CH2 OR1 で表される化合物と- 般式 R2 C 0 CH2 C OOR3 で表される化合物より、 工業的に有利に一般式 〔 I〕 で表される化合物 As the method for synthesizing Biniruke tons, Synthetic Communication, 3 (3) , 205- 209 (1973) to be reacted with CH 3 0 CH 2 CH 2 C 0 CH 2 to 0 CH 3 P- toluenesulfonic acid, An example of synthesizing CH 2 = CHC O CH 20 CH 3 is described, but the yield is low. The present invention is generally more industrially advantageous than the compound represented by the general formula R 40 CH 2 CH 2 C 0 CH 2 OR 1 and the compound represented by the general formula R 2 C 0 CH 2 C OOR 3 Compound represented by formula (I)

Figure imgf000004_0001
Figure imgf000004_0001

(式中、 R1 、 R2 、 R3 および R4 は同一または相異なって低級アルキル基を 示す。 ） を提供することである。 発明の開示： (Wherein, R 1 , R 2 , R 3 and R 4 are the same or different and each represent a lower alkyl group.) DISCLOSURE OF THE INVENTION:

本発明は、  The present invention

( 1 ) 一般式 〔 I〕  (1) General formula (I)

Figure imgf000004_0002
Figure imgf000004_0002

(式中、 R1 、 R2 および R3 は同一または栢異なって低級アルキル基を示す。 ） で表される化合物、 (Wherein, R 1 , R 2 and R 3 are the same or different and represent a lower alkyl group.)

( 2 ) 一般式 〔 I I〕  (2) General formula (II)

R4 0 CH2 CH2 C 0 C H2 OR ci n で表される化合物と一般式 〔 I I I〕 A compound represented by R 40 CH 2 CH 2 C 0 CH 2 OR ci n and a general formula (III)

R2 C 0 CH2 C00R3 〔 I I I〕 R 2 C 0 CH 2 C00R 3 (III)

(式中、 R1 、 R2 、 3 は前記と同じ意味を示し、 R4 は低級アルキル基を示 す。 ） で表される化合物とを、 触媒として亜鉛化合物の存在下反応させることを 特徴とする一般式 〔 I〕 (Wherein, R 1 , R 2 , and 3 have the same meanings as described above, and R 4 represents a lower alkyl group. You. Wherein the compound represented by the general formula [I] is reacted in the presence of a zinc compound as a catalyst.

Figure imgf000005_0001
Figure imgf000005_0001

(式中、 R1 、 R2 および R3 は前記と同じ意味を示す。 ） で表される化合物の 製造方法である。 (Wherein, R 1 , R 2 and R 3 have the same meaning as described above.).

本発明化合物は、 その製造法において触媒として、 Z n C ^ 2， Ζ η (Ν03)2 , Ζ η 0， 塩基性炭酸亜鉛 （ 3 Ζ η (ΟΗ)2 · 2 Z n C 03) 等の無機亜鉛化合物、 Z n (C H3C 00) 2, 安息香酸亜鉛等の有機亜鉛化合物、 および Z n末、 など 亜鉛化合物 （これらは混合使用してもよい） を使用することにより 1ポッ トで高 収率で得られる。 The compounds of the present invention, as catalysts in their preparation, Z n C ^ 2, Ζ η (Ν0 3) 2, Ζ η 0, basic zinc carbonate (3 Ζ η (ΟΗ) 2 · 2 Z n C 0 3) Inorganic zinc compounds such as Zn (CH 3 C 00) 2, zinc benzoate, and zinc powder such as Zn powder (these may be used in combination). It can be obtained in high yields.

触媒の量としては、 一般式 〔 I I〕 の化合物 1モルに対し、 0. 0 1〜 1モル、' 好ましくは 0. 1 ~0.3モルである。  The amount of the catalyst is 0.01 to 1 mol, preferably 0.1 to 0.3 mol, per 1 mol of the compound of the general formula [II].

溶媒としては、 ベンゼン、 トルエン、 キシレン、 メシチレン等が用いられ、 反 応温度は 8 0 °C以上それぞれの溶媒の沸点までである。  As the solvent, benzene, toluene, xylene, mesitylene, or the like is used, and the reaction temperature is 80 ° C. or higher and up to the boiling point of each solvent.

後処理は亜鉛化合物を除去する目的で、 水洗または酸、 アルカ リ処理を行う。  In the post-treatment, washing with water or acid or alkali treatment is performed for the purpose of removing zinc compounds.

発明を実施するための最良の形態： BEST MODE FOR CARRYING OUT THE INVENTION

次に実施例を挙げて、 本発明を具体的に説明する。  Next, the present invention will be specifically described with reference to examples.

実施例 1 Example 1

2—メ トキシ一 4ーメ トキシカルボニル一 3—メチルー 2—シクロへキセン一 1一オン CH3OCH2CH2COCH2O CH3 + CH3C 0 C H2C 00 CH3 2-Methoxy-1-4-Methoxycarbonyl-3-Methyl-2-cyclohexene-11-one CH 3 OCH 2 CH 2 COCH 2 O CH 3 + CH 3 C 0 CH 2 C 00 CH 3

Figure imgf000006_0001
トルエン 8 0 ml中に 1 , 4—ジメ トキシ一 2—ブタノ ン 12.8 g、 ァセ ト酢酸メ チル 1 5 g、 Z n C ^ 2 2.3 gを仕込み、 2 4時間還流を行なった。 反応終了後 酢酸ェチル 1 0 Omlを加え、 さらに 1 0%塩酸処理、 水洗、 乾燥後、 溶媒を留去 し、 得られたオイル状物をカラムクロマトダラフィ一により分離精製することに より目的物 14.5 gを得た。 n D 27=1. 9 0 2
Figure imgf000006_0001
In 80 ml of toluene, 12.8 g of 1,4-dimethoxy-1-butanone, 15 g of methyl acetate acetate, and 2.3 g of ZnC ^ 2 were charged and refluxed for 24 hours. After completion of the reaction, 10 Oml of ethyl acetate was added, the mixture was further treated with 10% hydrochloric acid, washed with water, and dried.The solvent was distilled off, and the obtained oily substance was separated and purified by column chromatography to obtain the target compound. 14.5 g were obtained. n D 27 = 1. 9 0 2

実施例 2 Example 2

上記 Z n C 2 を 3 Z n (OH) 2 · 2 Z n C 03 に代える以外は同一な操作 を行ない、 目的物 13.7 gを得た。 Except for replacing the Z n C 2 to 3 Z n (OH) 2 · 2 Z n C 0 3 performs a same operation to obtain the desired compound 13.7 g.

実施例 3 Example 3

2—メ トキシ一 4—メ トキシカルボ二ルー 3—メチル一 2—シク口へキセン一 1一オン  2-Methoxy 1 4-Methoxycarbonyl 2-Methyl 2-hexene 1-one

CH3OCH2CH2CO CH2O CH3 + C H 3 C 0 C H 2 C 00 C H 3 CH 3 OCH 2 CH 2 CO CH 2 O CH3 + CH 3 C 0 CH 2 C 00 CH 3

Figure imgf000006_0002
キシレン 24 ^に 1， 4ージメ トキシ一 2—ブタノ ン 6. 3 7 k g、 ァセ ト酢酸 メチル 7. 2 0 k g. ZnC i 2 1. 4 k g. Z n(OA c)2 - 2 H201. 2 k を仕込み、 7時間還流を行った。 反応終了後酢酸ェチル 3 ^を加え、 さらに 1 0 %塩酸処理、 水洗、 乾^後、 溶媒を留去し、 得られたオイル状物 1 2. 3 k gを 蒸留し、 目的物 6. 2 k g ( 1 3 2 ~ 1 3 6 ノ 3 mmH g) を得た。 産業上の利用可能性：
Figure imgf000006_0002
1 in xylene 24 ^, 4 Jime butoxy one 2-butanol down 6. 3 7 kg, § Seto acetate 7. 2 0 k g ZnC i 2 1. 4 k g Z n (OA c) 2 -.. 2 H 2 01. 2 k was charged and refluxed for 7 hours. After the reaction was completed, ethyl acetate 3 ^ was added, and the mixture was further treated with 10% hydrochloric acid, washed with water, dried, and the solvent was distilled off. Distillation gave the desired product (6.2 kg, 1332 to 1336 mm 3 mmHg). Industrial applicability:

本発明の化合物は、 農医薬中間体として有用であり、 例えば、 特願平 3— 3 5 6 8 2 9に開示された工程を経れば、 WO 9 1 / 0 0 2 6 0、 特願平 3— 1 9 3 5 9 '5に示された除草剤の中間体となる。  The compound of the present invention is useful as an agricultural or pharmaceutical intermediate. For example, if the compound disclosed in Japanese Patent Application No. 3-35869 is disclosed in WO 91/0260, Japanese Patent Application It is an intermediate for the herbicides shown in Hei 3—1 9 3 5 9 '5.

Claims

1. 一般式 〔 I〕 1. General formula [I] R 0 0 〔I〕R 0 0 [I]
Figure imgf000008_0001
Figure imgf000008_0001
 請  Contract (式中、 R1 、 R2 および R3 は同一または相異なって低級アルキル基を示す。 ） で表される化合物。 (Wherein, R 1 , R 2 and R 3 are the same or different and each represents a lower alkyl group.) の  of 2. 一般式 〔I I〕 2. General formula [II] R4 0 CH2 CH2 C 0 CH2 OR Π I〕 で表される化合物と一般式 〔I I I〕 R 40 CH 2 CH 2 C 0 CH 2 OR Π I] and the general formula (III) R2 C 0 CH2 COOR c I I n R 2 C 0 CH 2 COOR c II n (式中、 R1 、 R2 、 R3 は前記と同じ意味を示し、 R4 は低級アルキル基を示 す。 ） で表される化合物とを、 触媒として亜鉛化合物の存在下反応させることを 特徵とする一般式 〔I〕 (Wherein, R 1 , R 2 , and R 3 have the same meanings as described above, and R 4 represents a lower alkyl group.) A compound represented by the formula: is reacted in the presence of a zinc compound as a catalyst. Special formula [I]
Figure imgf000008_0002
Figure imgf000008_0002
 (式中、 R1 、 R2 および R3 は前記と同じ意味を示す。 ） で表される化合物の 製造方法。 (Wherein, R 1 , R 2 and R 3 have the same meanings as described above.).
PCT/JP1993/000330 1992-03-27 1993-03-22 Cyclohexenone compound and production thereof Ceased WO1993020037A1 (en)

Applications Claiming Priority (2)

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JP4/101836 1992-03-27
JP10183692 1992-03-27

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH021422A (en) * 1988-02-01 1990-01-05 Sandoz Ag Improvements related to organic compounds
US4925970A (en) * 1988-12-22 1990-05-15 Brown Richard W Process for producing cyclohexadiene thioether
JPH03255047A (en) * 1989-07-04 1991-11-13 Nippon Soda Co Ltd Substituted bicycloheptadione derivative, its preparation and herbicide

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH021422A (en) * 1988-02-01 1990-01-05 Sandoz Ag Improvements related to organic compounds
US4925970A (en) * 1988-12-22 1990-05-15 Brown Richard W Process for producing cyclohexadiene thioether
JPH03255047A (en) * 1989-07-04 1991-11-13 Nippon Soda Co Ltd Substituted bicycloheptadione derivative, its preparation and herbicide

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