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WO1993013058A1 - Substituted benzoic ester and production thereof - Google Patents

Substituted benzoic ester and production thereof 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
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methyl
reaction
solvent
methoxy
alkyl
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PCT/JP1992/001688
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French (fr)
Japanese (ja)
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Tsutomu Inoue
Katsunori Tanaka
Hiroyuki Adachi
Keiichi Ishimitsu
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Nippon Soda Co., Ltd.
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Publication of WO1993013058A1 publication Critical patent/WO1993013058A1/en

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    • 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]

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  • 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

Compounds represented by general formulae (II), (III) and (IV), and a process for producing the same, wherein R1 represents hydrogen or lower alkyl, and R2 to R4 may be the same or different from one another and each represents lower alkyl.

Description

明 細 書 置換安息香酸エステル及びその製造法 技術分野：  Description Substituted benzoic esters and their production
農医薬中間体として有用な置換安息香酸エステル及びその製造法に関する。 技術背景：  The present invention relates to a substituted benzoic acid ester useful as an agrochemical intermediate and a method for producing the same. Technical background:
3一アルコキシ— 2—アルキル一 4一アルキルチオ安息香酸アルキルは、 例えば 3 一アルコキシ一 2—アルキル一 4一アルキルチオァニリンをサンドマイヤー反応によ り、 ハロゲン化したあとの物質を （1 ) マグネシウム、 炭酸ガスによるグリニャール 反応、 ( 2 ) シアン化銅を用いて二トリルとし、 加水分解、 または （ 3 ) n—ブチル リチウムを用いてリチエイシヨンし、 炭酸ガスを吹き込む方法などにより安息香酸と し、 その核エステル化して得られる。 又、 類似の合成法としては、 U S P 4 , 9 2 5， 9 7 0の記載もある力く、脱水素剤として大変高価な D D Q ( 2 , 3—ジクロロ一 5 , 6—ジシァノベンゾキノン） を当モル使用している。 また、 農薬中間体として極めて 有用な 3—アルコキシ体の記載はない。  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.
本発明は D D Qの代りに容易に入手できる安価な脱水素剤を用いて簡単に高収率に 3一アルコキシ— 2—アルキル一 4一アルキルチオ安息香酸アルキルを提供すること である。 発明の開示：  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. DISCLOSURE OF THE INVENTION:
本発明を下記スキームによつて示す。 0Ra R2 OR; The present invention is illustrated by the following scheme. 0R a R 2 OR ;
Figure imgf000004_0001
Figure imgf000004_0001
R2 0RS R2 ORa
Figure imgf000004_0002
R 2 0R S R 2 ORa
Figure imgf000004_0002
( )新規 ( )新規  () New () New
(式中、 Ri は水素又は低級アルキル基を、 Rz〜R4 は、 各々同一又は異なって、 {g ^アルキル基を示す。 ） (Wherein, Ri a is hydrogen or a lower alkyl group, Rz～R 4 are each the same or different from a {g ^ alkyl group.)
本発明化合物は、 次の方法によつて i することが出来る。  The compound of the present invention can be prepared by the following method.
(I)から （IT)への S¾は、不活性溶媒中、 アルキルメルカブタンを （I) に対 して 2倍モル以±¾0えた後、室温付近で攪拌することによつて行われる。  S¾ 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.
溶媒としては、 ベンゼン、 トルエン、 へキサンなどの炭化水素系、 メタノール、 ェ タノ一ルなどのアルコーノレ系溶媒あるいは、 これらの混合物が用いられる。 触媒とし ては、塩化水素、硫酸などの無機酸、塩ィ kffi鉛、 四塩化チタンなどのルイス酸が用い られる力 S¾には、パラトルエンスルホン酸力く用いられる。  As the solvent, hydrocarbon solvents such as benzene, toluene and hexane, alcoholic solvents such as methanol and ethanol, and mixtures thereof are used. As 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.
CDから or)への^;は、 不活性溶媒中、 加熱することにより行われる。 不活 性溶媒としては、 メシチレン、 ベンゼン、 トルエン、 キシレンなどであり、反応は、 溶媒の沸点で加熱、することにより行われる。  ^ From CD to or) is performed by heating in an inert solvent. Examples of the inert solvent include mesitylene, benzene, toluene, and xylene, and the reaction is performed by heating at the boiling point of the solvent.
(IE)から （IV)への ¾E及び（IE)から （IV)への反応は、 (1)塩素、臭素等、 (2) ィォゥ、 （3)加熱のいずれかの方法により脱水素することにより行われる。  The reaction from (IE) to (IV) ¾E and from (IE) to (IV) must be carried out by (1) chlorine, bromine, etc., (2) io, or (3) heating. It is performed by
( 1 ) は不活性溶媒中、 igffiする塩素、 臭素等と等モルの卜リェチルァミン、 D B U等の無機又は有機の塩基を使用し、 一 20°C〜室温までの反応温度で行われる。 不活性溶媒としては、 塩化メチレン、 クロ口ホルム、 四塩化炭素、 エーテル、 TH F、 ァセトニトリノレ等力用いられる。 ，(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. Examples of the inert solvent include methylene chloride, chloroform, carbon tetrachloride, ether, THF, and acetonitrile. ,
(2)不活性溶媒中又は溶媒を用いずに、触媒量のィォゥを用いて行われる。 不活性溶媒としては、 メシチレン、 ベンゼン、 トルエン、 キシレン等の高沸点溶媒 を用 、て溶媒の沸点までの反応温度で行われる。 (2) The reaction is carried out using a catalytic amount of zeolite in an inert solvent or without using a solvent. As the inert 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.
溶媒を用いずに行う場合は 100°Cから原料力 <分解しない温度までの反応温度で行 われる。  When 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.
( 3 )不活性溶媒中又は溶媒を用いずに、加熱することにより行われる。 不活性溶 媒としては、 メシチレン、 ベンゼン、 トルエン、 キシレン等の高沸点溶媒を用いて溶 媒の沸点までの反応温度で行われる。  (3) Heating is performed in an inert solvent or without using a solvent. As the inert 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.
溶媒を用いずに行う場合は、 100°Cから原料力〈分解しない温度までの反応温度で 行われる。  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.
反応終了後は、通常の後処理を行なうことにより目的物を得ることができる。 合成した化合物は、 NMR、 I R、 MASS等より同定した。 発明を実施するための最良の形態：  After completion of the reaction, 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
次に実施例を挙げて、 本発明を更に具体的に説明する。  Next, the present invention will be described more specifically with reference to examples.
実施例 1 Example 1
メチル 2—メチルー 3—メ トキシ一 4, 4一ビスメチルチオ一 2—シクロへキセ ンカルボキシレー卜  Methyl 2-methyl-3-methoxy-1,4-bismethylthio-1-cyclohexenecarboxylate
OCH; CH; OCH
Figure imgf000005_0001
エタノール 6 Omi中にメチル 4一ォキソ一3—メ トキシー 2—メチルー 2—シク 口へキセンカルボキシレ一ト 1 0 gとパラトルエンスルホン酸 1. 0 gを加え、 この溶 液に 2 0 °C以下でメチルメルカプタン 9. 5 gを 3時間をかけ吹き込み、 さらに一夜、 室温で放置した。 反応終了^ 5応液を氷水に入れ、 塩化メチレン抽出、 水洗、 硫酸マ グネシゥム «の後、 溶媒を留去し、 得られたオイル状物をカラムクロマトグラフ ィ一により精製分離することにより目的物 1 1. 9 gを得た。 OCH ; CH ; OCH
Figure imgf000005_0001
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.
nD 27· ° 1. 5 4 4 2 n D 27 ° 1.5 4 4 2
実施例 2 Example 2
メチル 3—メ トキシー 2—メチルー 4ーメチルチオ一 1. 3—シクロへキサジェ ンカルボキシレート  Methyl 3-methoxy-2-methyl-4-methylthio-1-1.3-cyclohexagenecarboxylate
Figure imgf000006_0001
メシチレン 2 5ml中にメチル 2—メチルー 3—メ 卜キシー 4 , 4—ビスメチルチ ォ一 2—シクロへキセンカルボキシレー卜 1 0 gを加え、 1 8時間還流した。 SiS終 了後、 溶媒を留去し、 得られたオイノレ伏物をカラムクロマトグラフィーにより精製分 離することにより目的物 6. 6 gを得た。
Figure imgf000006_0001
To 25 ml of mesitylene was added 10 g of methyl 2-methyl-3-methoxy-4,4-bismethylthio-1-cyclohexenecarboxylate, and the mixture was refluxed for 18 hours. After the completion of SiS, the solvent was distilled off, and the obtained oily residue was purified and separated by column chromatography to obtain 6.6 g of the desired product.
nD 28 1. 5 7 6 1 n D 28 1.5 7 6 1
実施例 3 Example 3
3—メトキシー 2ーメチルー 4—メチルチオ安息香酸メチル  3-methoxy-2-methyl-4-methyl thiobenzoate
CH5 O C H; C Ha O CH5 C Ha
Figure imgf000006_0002
塩ィ匕メチレン 5 Oml中にメチル 3—メ トキシ一 2—メチルー 4—メチルチオ一 1， 3—シクロへキサジェンカルボキシレート 7. 8 gと トリエチルアミン 1 4 gを加え、 0 °Cで塩素 9. 7 gを 2時間にわたり吹込み、 さらに 3時間攪拌を続けた。 反応終了後、 反応液を氷水に入れ、 塩化メチレン抽出、 水洗、 硫酸マグネシウム乾燥の後、 溶媒を 留去し、得られたオイル状物をカラムクロマトグラフィーにより精製分離することに より目的物 5. 8 gを得た。 CH 5 OCH ; CH a O CH 5 C Ha
Figure imgf000006_0002
To 5 ml of methylene chloride, add 7.8 g of methyl 3-methoxy-1-methyl-4-methylthio-1,3-cyclohexadienecarboxylate and 14 g of triethylamine, and add chlorine 9. 7 g was blown in for 2 hours and stirring was continued for another 3 hours. After completion of the reaction, the reaction solution is put in ice water, extracted with methylene chloride, washed with water, dried over magnesium sulfate, the solvent is distilled off, and the obtained oily substance is purified and separated by column chromatography to obtain the desired product 5. 8 g were obtained.
27. 5  27. 5
nD 1. 57 1 1 n D 1.57 1 1
実施例 4 Example 4
3—メ トキシ一 2—メチルー 4ーメチルチオ安息香酸メチル  3-Methoxy-1-methyl-4-methylthiobenzoate
;
Figure imgf000007_0001
塩ィ匕メチレン 1 0 Oml中にメチル 2—メチルー 3—メ トキシー 4, 4一ビスメチル チォー 2—シクロへキセンカルボキシレート 6. 9 gとトリエチルアミン 22 gを方□え、 0 °Cで臭素 32 gを 1時間で滴下し、 さらに 3時間攪拌を続けた。反応終了後、 反応 液を氷水に入れ、塩ィ匕メチレン抽出、 水洗、 硫酸マグネシウム乾燥の後、 溶媒を留去 し、 得られたオイル状物をカラムクロマトグラフィーにより精製分離することにより 目的物 4. 1 gを得た。 ;
Figure imgf000007_0001
Methylene chloride Methylene 2-methyl-3-methoxy-4,4-bismethylthio-2-cyclohexenecarboxylate (6.9 g) and triethylamine (22 g) in 10 Oml Was added dropwise over 1 hour, and stirring was continued for another 3 hours. After completion of the reaction, the reaction solution is poured into ice water, extracted with methylene chloride, washed with water, and dried over magnesium sulfate. The solvent is distilled off, and the resulting oil is purified and separated by column chromatography to obtain the desired product. 1 g was obtained.
nD 27- 5 1. 57 1 1 n D 27 - 5 1. 57 1 1
実施例 5 Example 5
3—メ トキシー 2—メチルー 4ーメチルチオ安息香酸メチル  3-Methoxy 2-methyl-4-methylthiobenzoate
OCH OCH; OCH OCH;
SCH;
Figure imgf000007_0002
メシチレン 2 Omlにメチル 3—メ 卜キシー 2—メチルー 4ーメチルチオ一 1, 3 —シクロへキサジェンカルボキシレー卜 15 gとィォゥ 1.7 gを加え、 18時間還流 した。 Μίδ終了後、 液を氷水に入れエーテル抽出、 5%NaHC03 洗、 硫酸マ グネシウム^^後、溶媒を留去し、得られたオイル状物をカラムクロマトグラフィー により精製分離することにより目的物 9.2 gを得た。 SCH;
Figure imgf000007_0002
To 20 ml of mesitylene, 15 g of methyl 3-methoxy-2-methyl-4-methylthio-1,3-cyclohexadienecarboxylate and 1.7 g of iodomethane were added, and the mixture was refluxed for 18 hours. After Μίδ completion, ether extract put the liquid into ice water, 5% NaHCO 3 wash, the desired product 9.2 by after magnesium sulfate ^^, the solvent was distilled off, the resulting oily matter is purified and separated by column chromatography g was obtained.
nD 27- 5 1. 5711 n D 27 - 5 1. 5711
雄例 6 Male example 6
3—メトキシー 2—メチルー 4ーメチルチオ安息香酸メチル  3-Methoxy-2-methyl-4-methylthiobenzoate
Figure imgf000008_0001
メチル 2—メチルー 3—メトキシー 4, 4一ビスメチルチオ一 2—シクロへキセ ンカルボキシレート 28 gに硫黄 3.2 gを加え、 180°Cで 3時間保った。 反^;終了 後、反応液を氷水に入 エーテル抽出、 5%NaHC03 洗、硫酸マグネシゥム乾 燥後、溶媒を留去し、得られたオイノレ状物をカラムクロマトグラフィーにより精製分 離することにより目的物 12.6 gを得た。
Figure imgf000008_0001
3.2 g of sulfur was added to 28 g of methyl 2-methyl-3-methoxy-4,4-bismethylthio-12-cyclohexenecarboxylate, and the mixture was kept at 180 ° C. for 3 hours. Anti ^; after the end of input ether extract the reaction mixture into ice water, 5% NaHCO 3 wash, sulfate Maguneshiumu dry燥後, the solvent was evaporated, and the resulting Oinore like product by purification fraction separated by column chromatography 12.6 g of the desired product was obtained.
nD Ζ7·3 1. 5711 n D Ζ7 · 3 1. 5711
3—メトキシー 2—メチルー 4ーメチルチオ安息香酸メチル 3-Methoxy-2-methyl-4-methylthiobenzoate
CHs OCHs OCH£ CHs OCHs OCH £
CH3 O CH£
Figure imgf000008_0002
メチル 3—メ 卜キシー 2—メチル一4—メチルチオ一 1, 3—シクロへキサジェン カルボキシレー卜 3 0 gを窒素雰囲気下 2 5 0°Cで 3時間保った。 反応終了後、 反応 液を'减圧蒸留 （ 1 2 8〜 1 3 3 °C/ 1 mmHg)することにより目的物 1 6 gを得た。 nD 27- 5 1. 57 1 1 産業上の利用可能性： CH 3 O CH £
Figure imgf000008_0002
30 g of methyl 3-methoxy-2-methyl-1-methylthio-1,3-cyclohexadiene carboxylate was kept at 250 ° C. for 3 hours under a nitrogen atmosphere. After completion of the reaction, the reaction solution was subjected to low pressure distillation (128 to 133 ° C / 1 mmHg) to obtain 16 g of the desired product. n D 27 - 5 1. availability on the 57 1 1 industry:
3一アルコキシ一 2—アルキル一 4—アルキルチオ安息香酸アルキルが安価で簡単 に高収率に得ることができる。 この 3—アルコキシ一 2—アルキル一 4一アルキルチ ォ安息香酸アルキルを、 アルコール、 THF等の適当な有機溶媒に溶かし苛性ソーダ 等のアル力リ水溶液中 0て〜室温〜溶媒の還流温度で処理することにより、 3—アル コキシ一 2—アルキル一 4一アルキルチオ安息香酸とし、 これをジォキサン等の不活 性溶媒中 Na C 107]<溶液等の酸化剤で酸化することにより 3—アルコキシ一 2—ァ ルキルー 4一アルキルスルホニル安息香酸とすれば、 これは、 WO 9 1Z00 260、 特願平 3— 1 93595に示された除草剤の中間体となる。  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. To give 3-alkoxy-12-alkyl-14-alkylthiobenzoic acid, which is oxidized with an oxidizing agent such as NaC 107] <solution in an inert solvent such as dioxane to obtain a 3-alkoxy1-2-carboxylic acid. In the case of luciryl 4-alkylsulfonylbenzoic acid, this is an intermediate of a herbicide shown in WO 91Z00 260, Japanese Patent Application No. 3-193595.

Claims

請 求 の 範 囲 The scope of the claims
1 - "^式 (I) 1-"^ formula (I)
R5 ORa
Figure imgf000010_0001
R 5 OR a
Figure imgf000010_0001
(式中、 Ri は水素又は纖アルキル基を、 R2〜R4 は、 各々同一又は異なって、 低級アルキル基を示す。 )で表わされる化合物。 (Wherein, Ri represents a hydrogen or fiber alkyl group, and R 2 to R 4 each represent the same or different and represent a lower alkyl group.)
2. (I)  2. (I)
R2 0R3
Figure imgf000010_0002
で表わされる化合物を K«の存在下、 R4 SH (式中、 R, は前記と同じ意味を 示す。 ) と SiiSさせることを とする一般式 (I) R 2 0R 3
Figure imgf000010_0002
A compound represented by the general formula (I) wherein R 4 SH (where R, has the same meaning as described above) and SiiS in the presence of K
R2 0R2
Figure imgf000010_0003
R 2 0R 2
Figure imgf000010_0003
(式中、 R: 〜R4 は鲴己と同じ意味を示す。 ） で表わされる化合物の製造法。 (Wherein, R: to R 4 have the same meaning as 鲴).
3.一般式（m) 3. General formula (m)
0R;
Figure imgf000011_0001
0R ;
Figure imgf000011_0001
(式中、 R, 〜R4 は前記と同じ意味を示す。 )で表わされる化合物。 (Wherein, R and R 4 have the same meanings as described above.).
4. —般式 (I) 4. —General formula (I)
0R:
Figure imgf000011_0002
0R :
Figure imgf000011_0002
(式中、 R! 〜R4 は前記と同じ意味を示す。 ） で表わされる化合物を脱 R 4 SHす ることを特徴とする一般式（IE) (Wherein, R! To R 4 is. As defined above) formula, wherein de R 4 SH to Rukoto a compound represented by (IE)
Figure imgf000011_0003
Figure imgf000011_0003
(式中、 R, 〜R4 は前記と同じ意味を示す。 ） で表わされる化合物の製造法。 (Wherein, R and R 4 have the same meanings as described above.).
5. —般式 (IV) 5. —General formula (IV)
0R;
Figure imgf000011_0004
0R ;
Figure imgf000011_0004
(式中、 R, ~R4 は前記と同じ意味を示す。 ） で表わされる化合物。 (Wherein, R and R 4 have the same meanings as described above.)
6. ~¾式（m) 6. ~ ¾ formula (m)
( ）()
Figure imgf000012_0001
Figure imgf000012_0001
(式中、 Rt〜R4 は編 Sと同じ意味を示す。 ）で表わされる化合物を脱水素する, とを とする"^式 ( ) (Wherein, R t to R 4 have the same meaning as in Part S.).
R2 OR3
Figure imgf000012_0002
R 2 OR 3
Figure imgf000012_0002
(式中、 R, 〜R4 は前記と同じ意味を示す。 ）で表わされる化合物の 法。 (Wherein, R, to R 4 have the same meanings as described above.).
7. —般式（I) 7. —General formula (I)
R2
Figure imgf000012_0003
R 2
Figure imgf000012_0003
(式中、 Rt〜R4 は前記と同じ意味を示す。 )で表わされる化合物を脱水素する, と专 とする"^式 ( ) (Wherein, R t to R 4 have the same meanings as described above.)
R2 O R3
Figure imgf000012_0004
R 2 OR 3
Figure imgf000012_0004
(式中、 Rt 〜R4 は前記と同じ意味を示す）で表わされる化合物の製造法。 (Wherein, R t to R 4 have the same meanings as described above).
PCT/JP1992/001688 1991-12-26 1992-12-24 Substituted benzoic ester and production thereof WO1993013058A1 (en)

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WO1994024099A1 (en) * 1993-04-19 1994-10-27 Nippon Soda Co., Ltd. Process for producing trisubstituted benzene, and intermediate

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS63122673A (en) * 1986-11-10 1988-05-26 Nissan Chem Ind Ltd Pyrazole derivative and herbicide
JPH0245448A (en) * 1988-08-05 1990-02-15 Nissan Chem Ind Ltd Production of benzoic acids
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 (en) * 1986-11-10 1988-05-26 Nissan Chem Ind Ltd Pyrazole derivative and herbicide
JPH0245448A (en) * 1988-08-05 1990-02-15 Nissan Chem Ind Ltd Production of benzoic acids
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

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