WO1993013060A1 - Novel intermediate compound and production thereof - Google Patents
Novel intermediate compound and production thereof Download PDFInfo
- Publication number
- WO1993013060A1 WO1993013060A1 PCT/JP1992/001687 JP9201687W WO9313060A1 WO 1993013060 A1 WO1993013060 A1 WO 1993013060A1 JP 9201687 W JP9201687 W JP 9201687W WO 9313060 A1 WO9313060 A1 WO 9313060A1
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- Prior art keywords
- general formula
- formula
- production
- compound represented
- novel intermediate
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C315/00—Preparation of sulfones; Preparation of sulfoxides
- C07C315/02—Preparation of sulfones; Preparation of sulfoxides by formation of sulfone or sulfoxide groups by oxidation of sulfides, or by formation of sulfone groups by oxidation of sulfoxides
-
- 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
- C07C323/22—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 doubly-bound oxygen atoms bound to the same carbon skeleton
Definitions
- the present invention relates to a novel intermediate compound and a method for producing the same, and a method for producing another intermediate using the intermediate compound. These intermediates are useful as intermediates for agrochemicals.
- An object of the present invention is to provide a novel intermediate compound, a method for producing the same, and a method for producing a substituted benzoic acid using the intermediate.
- the present invention is a.
- This is a method for producing the compound represented by The production method of the present invention is as follows.
- the reaction from the formulas ( ⁇ ) to (I) is a Friedel-Crafts reaction, which is carried out in a solvent such as methylene chloride, chloroform, carbon tetrachloride, dichloroethane, carbon disulfide, and benzene. 2, the presence of S nC ⁇ 4, T i C ⁇ 4, AC 3 , etc. Lewis acids, is carried out at a temperature from 0 ° C to the boiling point of the solvent. Preferably Zn C £ 2.
- the reaction of the formula ( ⁇ ) force is a Ha 10 f 0 rm reaction and an oxidation reaction, and in an inert solvent such as dioxane as a solvent, a halogenating agent and an oxidizing agent such as NaBrO,
- the reaction temperature is from room temperature to the boiling point of the solvent using Na IO, KC ⁇ O, NaC £ 0 aqueous solution, or the like.
- a novel intermediate compound can be obtained in a high yield.
- a substituted benzoic acid can be industrially advantageously obtained.
- This substituted benzoic acid is useful as an intermediate of a herbicide shown in W091 / 0260. Japanese Patent Application No. 3-193595.
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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
A compound represented by general formula (I) which is a novel intermediate for synthesizing a 2-(substituted benzoyl)-1,3-cyclohexanedione compound useful as a herbicide; a process for the production thereof; and a process for the production of an intermediate compound represented by general formula (III) from the compound of formula (I) wherein R1 to R4 may be the same or different from each other and each represents lower alkyl.
Description
新規な中間体化合物及びその製法 技術分野： Novel intermediate compounds and their preparation
新規な中間体化合物及びその製法、 並びに該中間体化合物を用いた別の中間体 の製法に関する。 これら中間体は明農医薬の中間体として有用である。 技術背景： The present invention relates to a novel intermediate compound and a method for producing the same, and a method for producing another intermediate using the intermediate compound. These intermediates are useful as intermediates for agrochemicals. Technical background:
2—置換べンゾィル一 1， 3—シクロへキサ書ンジォン化合物が除草剤どして有 用なことは公知であり、 実に多くの特許が出願されている。 It is known that 2-substituted benzoyl-1,3-cyclohexadione compounds are useful as herbicides and many patents have been filed.
1， 3—シクロへキサンジオン部の改変もさることながら 2位の置換べンゾィ ル部の改変も行われて、 特開昭 6 1— 2 0 7 3 6 9の如く 3つの置換基を有する 安息香酸中間体が報告されている。 In addition to the modification of the 1,3-cyclohexanedione part, the modification of the 2-substituted benzoyl part is also carried out, and as described in JP-A-61-207369, benzo having three substituents Acid intermediates have been reported.
本発明の目的は、 新規な中間体化合物とその製法及び該中間体を用いた置換安 息香酸の製法を提供することである。 発明の開示： An object of the present invention is to provide a novel intermediate compound, a method for producing the same, and a method for producing a substituted benzoic acid using the intermediate. DISCLOSURE OF THE INVENTION:
本発明は The present invention
( 1 ) 一般式 〔 I〕 (1) General formula (I)
(式中 R , 〜R 4 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、
(2)—般式 (I) (Wherein R 1, to R 4 are the same or different and each represents a lower alkyl group.) (2) —General formula (I)
〔π〕(Π)
(式中 R! 〜R3 は前記と同じ意味を示す。 ) (Wherein R! To R 3 are as defined above.)
で表わされる化合物にルイス酸の存在下、 R4 COC^ (式中 R4 は前記と同じ 意味を示す。 ) を反応させることを特徵とする一般式 〔I〕 Wherein R 4 COC ^ (wherein R 4 has the same meaning as described above) is reacted with the compound represented by the general formula [I]
〔I〕 [I]
(式中、 R, 〜R4 は前記と同じ意味を示す。 ) (In the formula, R, to R 4 have the same meaning as described above.)
の製法、 Manufacturing method,
(3) —般式 〔I〕 (3) —General formula [I]
〔I〕[I]
(式中 〜R4 は前記と同じ意味を示す。 ) (Wherein, -R 4 has the same meaning as described above.)
で表わされる化合物にハロゲン化剤と酸化剤を作用させることを特徵とする一般 式 〔m〕 Wherein a halogenating agent and an oxidizing agent act on the compound represented by the general formula (m)
〔 〕[]
(式中 R, 〜R3 は前記と同じ意味を示す。 ） (In the formula, R, to R 3 have the same meanings as described above.)
で表わされる化合物の製法である。
本発明の製法は次の通りである。 This is a method for producing the compound represented by The production method of the present invention is as follows.
式 〔Π〕 から式 〔I〕 の反応は、 F r i e d e l— C r a f t s反応であって、 塩化メチレン、 クロ口ホルム、 四塩化炭素、 ジクロロェタン、 二硫化炭素、 ニト 口ベンゼン等の溶媒中、 ZnC ^2 、 S nC ^4 、 T i C^4 、 A C 3 等の ルイス酸の存在下、 温度は 0°Cから溶媒の沸点までで行われる。 好ましくは Zn C £ 2 である。 The reaction from the formulas (Π) to (I) is a Friedel-Crafts reaction, which is carried out in a solvent such as methylene chloride, chloroform, carbon tetrachloride, dichloroethane, carbon disulfide, and benzene. 2, the presence of S nC ^ 4, T i C ^ 4, AC 3 , etc. Lewis acids, is carried out at a temperature from 0 ° C to the boiling point of the solvent. Preferably Zn C £ 2.
式 〔Π〕 力、ら式 〔ΠΙ〕 の反応は、 Ha 1 0 f 0 rm反応及び酸化反応であって、 溶媒としてジォキサン等の不活性溶媒中、 ハロゲン化剤及び酸化剤として例えば NaB rO、 Na I O、 KC ^O、 N a C £ 0水溶液等を用い、 反応温度は室温 から溶媒の沸点までで行われる。 発明を実施するための最良の形態： The reaction of the formula (Π) force, the reaction of the formula (で あ) is a Ha 10 f 0 rm reaction and an oxidation reaction, and in an inert solvent such as dioxane as a solvent, a halogenating agent and an oxidizing agent such as NaBrO, The reaction temperature is from room temperature to the boiling point of the solvent using Na IO, KC ^ O, NaC £ 0 aqueous solution, or the like. 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 3—メ トキシー 2—メチル一 4—メチルチオァセトフエノン Example 13 3-Methoxy-2-methyl-4-methylthioacetophenone
塩化メチレン 3 Omlに室温で 2—メ トキシー 3—メチルチオトルエン 5. 0 g、 塩化亜鉛 6. 1 g 塩化ァセチル 3. 5 gの順に加え、 一夜攪拌した。 反応終了 後、 反応液を氷水に入れ、 塩化メチレンで抽出、 水洗、 乾燥の後、 反応液を濃縮、 得られたォィル状物質を力ラムクロマトグラフィーにより分離精製することによ り目的物 4. 1 gを得た。 5.0 g of 2-methoxy-3-methylthiotoluene, 6.1 g of zinc chloride and 3.5 g of acetyl chloride were added in order to 3 Oml of methylene chloride at room temperature, and the mixture was stirred overnight. After the completion of the reaction, the reaction solution is put into ice water, extracted with methylene chloride, washed with water, dried, concentrated, and the reaction mixture is concentrated. 1 g was obtained.
nD 23- 5 ： 1. 5 8 9 1
実施例 2 3—メ トキシ一 2—メチルー 4—メチルスルホニル安息香酸 n D 23 - 5: 1. 5 8 9 1 Example 2 3-Methoxy-1-methyl-4-methylsulfonylbenzoic acid
ジォキサン 25mlに 3—メトキシ」 2—メチルー 4—メチルチオァセ卜フヱノ ン 5. 9 gを加え、 70°Cで 5%NaC ΟτΚ溶液 1 0 4 gを 3 0分間にわたり 滴下し、 3時間反応した。 反応終了後、 エーテル洗浄、 水層を濃塩酸で酸性化、 酢酸ェチル抽出、 水洗、 乾燥後、 溶媒を留去し得られたオイル状物質をカラムク 口マトグラフィ一により分離精製することにより目的物 4. 5 gを得た。 To 25 ml of dioxane was added 5.9 g of 3-methoxy "2-methyl-4-methylthioacetophenone, and at 70 ° C, 104 g of a 5% NaC {τ} solution was added dropwise over 30 minutes and reacted for 3 hours. After completion of the reaction, the target compound 4 was obtained by washing with ether, acidifying the aqueous layer with concentrated hydrochloric acid, extracting with ethyl acetate, washing with water, and drying.The solvent was distilled off and the resulting oily substance was separated and purified by column chromatography. .5 g were obtained.
mp. 1 50〜 1 52 °C 産業上の利用可能性： ^ mp. 1 50 ~ 1 52 ° C Industrial availability: ^
新規な中間体化合物が高収率で得られ、 この中間体を用レ、て置換安息香酸が工 業的に有利に得られる。 この置換安息香酸は W09 1 /0 0 2 6 0. 特願平 3— 1 9 3 59 5に示される除草剤の中間体として有用である。
A novel intermediate compound can be obtained in a high yield. By using this intermediate, a substituted benzoic acid can be industrially advantageously obtained. This substituted benzoic acid is useful as an intermediate of a herbicide shown in W091 / 0260. Japanese Patent Application No. 3-193595.
Claims
1. 一般式 〔I〕 1. General formula [I]
R4 〔I〕R 4 [I]
請 Contract
(式中、 R, 〜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。 の (Wherein, R and R 4 are the same or different and each represents a lower alkyl group.) of
2, —般式 〔Π〕 2, —general formula [Π]
〔Π〕[Π]
(式中 〜R3 は前記と同じ意味を示す。 ） (Wherein, -R 3 has the same meaning as described above.)
で表わされる化合物にルイス酸の存在下、 R4 COC^ (式中 R4 は前記と同じ 意味を示す。 ） を反応させることを特徴とする一般式 〔I〕 Wherein R 4 COC ^ (wherein R 4 has the same meaning as described above) is reacted with the compound represented by the general formula [I]
〔I〕[I]
(式中 R, 〜R4 は前記と同じ意味を示す。 ） (In the formula, R, to R 4 have the same meanings as described above.)
の製法。
3· —般式 [13 Recipe. 3—General formula [13
R4 〔I〕R 4 [I]
(式中 R, 〜R4 は前記と同じ意味を示す。 ) (In the formula, R, to R 4 have the same meaning as described above.)
で表わされる化合物にノ、ロゲン化剤と酸化剤を作用させることを特徵とする一般 式 〕 A general formula characterized by reacting a compound represented by
〔ΠΓ〕[ΠΓ]
(式中 〜R3 は前記と同じ意味を示す。 ) (Wherein, -R 3 has the same meaning as described above.)
で表わされる化合物の製法。
A method for producing a compound represented by the formula:
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3/356447 | 1991-12-25 | ||
| JP35644791A JPH05170730A (en) | 1991-12-25 | 1991-12-25 | New intermediate compound and its production |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| WO1993013060A1 true WO1993013060A1 (en) | 1993-07-08 |
Family
ID=18449057
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PCT/JP1992/001687 WO1993013060A1 (en) | 1991-12-25 | 1992-12-24 | Novel intermediate compound and production thereof |
Country Status (2)
| Country | Link |
|---|---|
| JP (1) | JPH05170730A (en) |
| WO (1) | WO1993013060A1 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1997028122A3 (en) * | 1996-02-01 | 1997-10-02 | Rhone Poulenc Agrochimie | Process for preparing diketone compounds |
| EP2546240A1 (en) | 2005-12-15 | 2013-01-16 | Ishihara Sangyo Kaisha, Ltd. | Benzoylpyrazole compounds and herbicides containing them |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS61207369A (en) * | 1985-03-07 | 1986-09-13 | ストウフアー ケミカル カンパニー | Benzoic acid intermediate having three substituents |
-
1991
- 1991-12-25 JP JP35644791A patent/JPH05170730A/en active Pending
-
1992
- 1992-12-24 WO PCT/JP1992/001687 patent/WO1993013060A1/en active Application Filing
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS61207369A (en) * | 1985-03-07 | 1986-09-13 | ストウフアー ケミカル カンパニー | Benzoic acid intermediate having three substituents |
Non-Patent Citations (1)
| Title |
|---|
| By SANDRO CARO, "Method for Synthesizing Organic Compounds by Functional Group (I)", 25 March 1976, Hirokawa Shoten (Tokyo), p. 183. * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1997028122A3 (en) * | 1996-02-01 | 1997-10-02 | Rhone Poulenc Agrochimie | Process for preparing diketone compounds |
| US6235942B1 (en) | 1996-02-01 | 2001-05-22 | Rhone-Poulenc Agrochimie | Process for preparing diketone compounds |
| US6525225B2 (en) | 1996-02-01 | 2003-02-25 | Rhone Poulenc Agrochimie | Process for preparing diketone compounds and precursors thereto |
| US6696613B2 (en) | 1996-02-01 | 2004-02-24 | Rhone Poulenc Agrochimie | Process for preparing diketone compounds and precursors thereto |
| EP2546240A1 (en) | 2005-12-15 | 2013-01-16 | Ishihara Sangyo Kaisha, Ltd. | Benzoylpyrazole compounds and herbicides containing them |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH05170730A (en) | 1993-07-09 |
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