KR19990027761A - Method for preparing ο- (carboalkoxy) phenylmethanesulfonyl chloride derivative - Google Patents
Method for preparing ο- (carboalkoxy) phenylmethanesulfonyl chloride derivative Download PDFInfo
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- KR19990027761A KR19990027761A KR1019970050282A KR19970050282A KR19990027761A KR 19990027761 A KR19990027761 A KR 19990027761A KR 1019970050282 A KR1019970050282 A KR 1019970050282A KR 19970050282 A KR19970050282 A KR 19970050282A KR 19990027761 A KR19990027761 A KR 19990027761A
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- C07C303/00—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides
- C07C303/02—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of sulfonic acids or halides thereof
- C07C303/22—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of sulfonic acids or halides thereof from sulfonic acids, by reactions not involving the formation of sulfo or halosulfonyl groups; from sulfonic halides by reactions not involving the formation of halosulfonyl groups
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- C07C309/79—Halides of sulfonic acids having halosulfonyl groups bound to acyclic carbon atoms
- C07C309/81—Halides of sulfonic acids having halosulfonyl groups bound to acyclic carbon atoms of an unsaturated carbon skeleton
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- C07C309/00—Sulfonic acids; Halides, esters, or anhydrides thereof
- C07C309/78—Halides of sulfonic acids
- C07C309/79—Halides of sulfonic acids having halosulfonyl groups bound to acyclic carbon atoms
- C07C309/82—Halides of sulfonic acids having halosulfonyl groups bound to acyclic carbon atoms of a carbon skeleton substituted by singly-bound oxygen atoms
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Abstract
본 발명은o-(카르보알콕시)페닐메탄술포닐 클로라이드 유도체의 제조방법에 관한 것으로서, 더욱 상세하게는o-(클로로메틸)벤조산 에스테르로부터 중간체 화합물으로서o-(카르보알콕시)페닐메탄티오술폰산염을 합성한 다음, 염소화반응시켜 술포닐우레아 제초제 합성에 중요한 화합물인 다음 화학식 1로 표시되는o-(카르보알콕시)페닐메탄술포닐 클로라이드 유도체를 제조하는 새로운 방법에 관한 것이다.The present invention o - (carboalkoxy) phenyl methanesulfonyl relates to a production method of the chloride derivative, and more particularly, o- (chloromethyl) o- as an intermediate compound from the acid esters (carboalkoxy) phenyl methane thio acid The present invention relates to a new method for preparing o- (carboalkoxy) phenylmethanesulfonyl chloride derivative represented by the following Chemical Formula 1, which is an important compound for synthesizing sulfonylurea herbicides by synthesizing salts.
상기 화학식 1에서 : R1은 수소원자, 할로겐원자, 니트로기, C1∼ C4의 알킬기 또는 C1∼ C4의 할로알킬기를 나타내고; R2는 C1∼ C6의 알킬기 또는 C3∼ C6의 사이클로알킬기를 나타낸다.In formula (1): R 1 represents a hydrogen atom, a halogen atom, a nitro group, a C 1 to C 4 alkyl group or a C 1 to C 4 haloalkyl group; R 2 represents a cycloalkyl group of C 1 ~ C 6 alkyl group or a C 3 ~ C 6 a.
Description
본 발명은o-(카르보알콕시)페닐메탄술포닐 클로라이드 유도체의 제조방법에 관한 것으로서, 더욱 상세하게는o-(클로로메틸)벤조산 에스테르로부터 중간체 화합물으로서o-(카르보알콕시)페닐메탄티오술폰산염을 합성한 다음, 염소화반응시켜 술포닐우레아 제초제 합성에 중요한 화합물인 다음 화학식 1로 표시되는o-(카르보알콕시)페닐메탄술포닐 클로라이드 유도체를 제조하는 새로운 방법에 관한 것이다.The present invention o - (carboalkoxy) phenyl methanesulfonyl relates to a production method of the chloride derivative, and more particularly, o- (chloromethyl) o- as an intermediate compound from the acid esters (carboalkoxy) phenyl methane thio acid The present invention relates to a new method for preparing o- (carboalkoxy) phenylmethanesulfonyl chloride derivative represented by the following Chemical Formula 1, which is an important compound for synthesizing sulfonylurea herbicides by synthesizing salts.
화학식 1Formula 1
상기 화학식 1에서 : R1은 수소원자, 할로겐원자, 니트로기, C1∼ C4의 알킬기 또는 C1∼ C4의 할로알킬기를 나타내고; R2는 C1∼ C6의 알킬기 또는 C3∼ C6의 사이클로알킬기를 나타낸다.In formula (1): R 1 represents a hydrogen atom, a halogen atom, a nitro group, a C 1 to C 4 alkyl group or a C 1 to C 4 haloalkyl group; R 2 represents a cycloalkyl group of C 1 ~ C 6 alkyl group or a C 3 ~ C 6 a.
상기 화학식 1로 표시되는o-(카르보알콕시)페닐메탄술포닐 클로라이드 유도체는 술포닐우레아 제초제를 합성하는 중요한 원료물질로서 이미 공지되어 있다[독일특허공개 제3,927,788호; 미국특허 제4,420,325호 등].The o- (carboalkoxy) phenylmethanesulfonyl chloride derivative represented by Chemical Formula 1 is already known as an important raw material for synthesizing sulfonylurea herbicides [German Patent Publication No. 3,927,788; U.S. Patent 4,420,325 and the like.
또한, 상기 화학식 1로 표시되는o-(카르보알콕시)페닐메탄술포닐 클로라이드 유도체를 합성하는 종래의 방법이 미국특허 제4,420,325호와 중국문헌 Hauxue Shijie 31 211(1990)(CA 114 101, 765)에 게시되어 있으며, 이의 제조과정을 간략히 나타내면 다음 반응식 1과 같다.In addition, conventional methods for synthesizing o- (carboalkoxy) phenylmethanesulfonyl chloride derivative represented by Chemical Formula 1 are disclosed in US Pat. No. 4,420,325 and Chinese literature Hauxue Shijie 31 211 (1990) (CA 114 101, 765). It is published in, and briefly shows the manufacturing process of the following scheme 1.
상기 반응식 1에 따른 종래 제조방법에서는o-(클로로메틸)벤조산 메틸 에스테르와 티오우레아를 반응시켜 이소티오우로늄염 중간체를 합성하고, 이러한 중간체 화합물을 염소화 반응시켜 목적으로 하는 페닐메탄술포닐 클로라이드를 제조한다. 그러나, 이소티오우로늄염 중간체 합성을 위해 사용되는 티오우레아가 강한 발암성 물질이기 때문에 이 방법을 공업적 대량 생산에 적용하기에는 어려움이 많다.In the conventional preparation method according to Scheme 1, the o- (chloromethyl) benzoic acid methyl ester is reacted with thiourea to synthesize isothiouronium salt intermediate, and the intermediate compound is chlorinated to prepare phenylmethanesulfonyl chloride. do. However, it is difficult to apply this method to industrial mass production because thiourea, which is used for the synthesis of isothiouronium salt intermediates, is a strong carcinogenic substance.
본 발명은o-(클로로메틸)벤조산 에스테르를 출발물질로 하고, 발암 유발의 위험성이 강한 티오우레아를 사용하는 대신에 독성이 적은 티오술폰산염을 사용하여o-(카르보알콕시)페닐메탄티오술폰산염을 중간체로서 합성하고, 중간체 화합물을 염소화 반응시켜 목적으로 하는 상기 화학식 1로 표시되는o-(카르보알콕시)페닐메탄술포닐 클로라이드 유도체를 안전하게 수득하는 방법을 제공하는데 그 목적이 있다.The invention o- (chloromethyl) benzoic acid ester as a starting material, instead of using the less toxic thio acid salts used in this strong thiourea risk of cancer caused o- (carboalkoxy) phenyl methane thio acid It is an object of the present invention to provide a method for synthesizing salts as intermediates and chlorinating intermediate compounds to safely obtain o- (carboalkoxy) phenylmethanesulfonyl chloride derivatives represented by the above formula (1).
본 발명은 다음 화학식 2로 표시되는o-(클로로메틸)벤조산 에스테르로부터 다음 화학식 1로 표시되는o-(카르보알콕시)페닐메탄술포닐 클로라이드 유도체를 제조하는 방법에 있어서,A process for producing a (carboalkoxy) phenyl methane sulfonyl chloride derivative, - the present invention has the following o represented by the formula (1) from o- (chloromethyl) benzoic acid ester represented by the following formula (2)
다음 화학식 2로 표시되는o-(클로로메틸)벤조산 에스테르와 다음 화학식 3으로 표시되는 티오술폰산염을 반응시켜 다음 화학식 4로 표시되는o-(카르보알콕시)페닐메탄티오술폰산염을 합성하고, 그리고Reacting o- (chloromethyl) benzoic acid ester represented by the following formula (2) with thiosulfonate represented by the following formula (3) to synthesize o- (carboalkoxy) phenylmethanethiosulfonate represented by the following formula (4), and
상기 화학식 4로 표시되는 중간체 화합물을 염소화반응시켜 다음 화학식 1로 표시되는o-(카르보알콕시)페닐메탄술포닐 클로라이드 유도체를 제조하는 방법을 그 특징으로 한다.It is characterized by a method of producing an o- (carboalkoxy) phenylmethanesulfonyl chloride derivative represented by the following Chemical Formula 1 by chlorination reaction of the intermediate compound represented by Chemical Formula 4.
화학식 2Formula 2
화학식 3Formula 3
화학식 4Formula 4
화학식 1Formula 1
상기 화학식들에서, R1및 R2는 각각 상기에서 정의한 바와 같고; M은 알칼리금속원자를 나타낸다.In the above formulas, R 1 and R 2 are each as defined above; M represents an alkali metal atom.
이와같은 본 발명을 더욱 상세히 설명하면 다음과 같다.Referring to the present invention in more detail as follows.
본 발명은 미국특허 제4,420,325호 등에서 사용하고 있는 인체에 유해한 티 오우레아의 사용을 배제하여 제조공정상의 안정성을 도모하고, 또한 중간체 (o-카르보알콕시)페닐메탄티오술폰산염의 제조공정 및 염소화 반응이 온화한 반응조건하에서 수행되어 부생성물이 거의 생성되지 않아 높은 제조 수율로 목적물을 얻을 수 있다.The present invention is U.S. Patent No. 4,420,325 to eliminate the use of hazardous thioureido LEA in the human body that are used in number the manufacturing process and promote the top of the stability, and the intermediate (o - carboalkoxy) methane thio acid salt production process and Chlorination It is carried out under these mild reaction conditions to produce little by-products so that the desired product can be obtained with high production yield.
본 발명에 따른 상기 화학식 1로 표시되는o-(카르보알콕시)페닐메탄술포닐 클로라이드 유도체의 제조과정을 보다 간략히 나타내면 다음 반응식 1과 같다.The preparation process of o- (carboalkoxy) phenylmethanesulfonyl chloride derivative represented by Chemical Formula 1 according to the present invention will be briefly shown in Scheme 1 below.
반응식 1Scheme 1
상기 반응식 1에서, R1, R2및 M은 각각 상기에서 정의한 바와 같다.In Scheme 1, R 1 , R 2 and M are as defined above, respectively.
본 발명에서 출발물질로 사용하는 상기 화학식 2로 표시되는o-(클로로메틸)벤조산 에스테르는 공지 화합물로서 공지 제조방법에 의해 쉽게 제조하여 사용할 수 있다[미국특허 제4,689,425호].The o- (chloromethyl) benzoic acid ester represented by Formula 2 used as a starting material in the present invention can be easily prepared and used by a known production method as a known compound [US Patent No. 4,689,425].
본 발명에서는 특징적으로 상기 화학식 2로 표시되는o-(클로로메틸)벤조산 에스테르와 화학식 3으로 표시되는 티오술폰산염을 반응시켜 화학식 4로 표시되는o-(카르보알콕시)페닐메탄티오술폰산염을 중간체 화합물으로서 제조하는 바, 이 반응은 30 ~ 90℃, 바람직하기로는 40 ∼ 60℃의 온도범위에서 수행한다. 그리고, 화학식 3으로 표시되는 티오술폰산염은 상기 화학식 2로 표시되는 화합물에 대하여 몰비로 1.0 ∼ 2.0 당량, 바람직하기로는 1.0 ∼ 1.2 당량 사용한다.In the present invention, the intermediate of the o- (carboalkoxy) phenylmethanethiosulfonate represented by the formula (4) by characteristically reacting the o- (chloromethyl) benzoic acid ester represented by the formula (2) with the thiosulfonate represented by the formula (3) Prepared as a compound, the reaction is carried out in a temperature range of 30 ~ 90 ℃, preferably 40 ~ 60 ℃. The thiosulfonate represented by the general formula (3) is used in the molar ratio of 1.0 to 2.0 equivalents, preferably 1.0 to 1.2 equivalents, relative to the compound represented by the general formula (2).
그리고나서, 상기 화학식 4로 표시되는o-(카르보알콕시)페닐메탄티오술폰산염을 염소화반응시켜 본 발명에서 목적으로 하는 화학식 1로 표시되는o-(카르보알콕시)페닐메탄술포닐 클로라이드 유도체를 제조한다. 염소화반응시 염소화제로는 염소가스(Cl2)를 사용하거나 또는N-클로로숙신이미드 등의 염소화 시약을 사용하는 통상의 염소화 방법에 의하며, 염소화반응은 0 ∼ 20℃ 온도범위내에서 수행된다. 특히 바람직하기로는 염소가스(Cl2)를 사용하여 5 ∼ 10℃에서 염소화반응을 수행하는 것이다. 염소(Cl)의 양은 몰비로 3 당량이 사용되나 과량을 사용해도 무방하다. 그리고, 염소화반응 용매로는 물 또는 초산을 사용하는 것이 바람직하며, 이를 병용하여 사용해도 좋다.Then, o- (carboalkoxy) phenyl methane thio acid represented by the present invention in a chlorination salt by the following general formula (1) for the purpose o represented by Formula 4-a (carboalkoxy) phenyl methane sulfonyl chloride derivative Manufacture. In the chlorination reaction, a chlorination agent is used by a conventional chlorination method using chlorine gas (Cl 2 ) or a chlorination reagent such as N -chlorosuccinimide, and the chlorination reaction is performed within a temperature range of 0 to 20 ° C. Especially preferably, the chlorination reaction is performed at 5 to 10 ° C. using chlorine gas (Cl 2 ). The amount of chlorine (Cl) is used in a molar ratio of 3 equivalents, but an excess may be used. In addition, it is preferable to use water or acetic acid as a chlorination reaction solvent, and you may use it together.
상기 염소화반응이 종료된 후에는 남은 염소가스를 제거하고 반응기에 물을 넣어 반응액을 희석시킨 후 생성된 고체생성물을 여과하면 화학식 1로 표시되는 원하는 목적물을 얻을 수 있다.After the chlorination is completed, the remaining chlorine gas is removed, water is added to the reactor to dilute the reaction solution, and the produced solid product is filtered to obtain a desired target represented by Chemical Formula 1.
이하 본 발명을 다음의 실시예에 의거하여 더욱 상세히 설명하는 바, 본 발명이 실시예에 한정되는 것은 아니다. 또한, 다음의 실시예에서는 몇몇 특징적인 화합물만의 제조방법을 기재하였지만, 본 발명에 포함되는 유도체들은 통상의 당업자는 다음의 실시예에 의해 합성이 가능하다.Hereinafter, the present invention will be described in more detail with reference to the following examples, but the present invention is not limited to the examples. In addition, the following examples describe a method for preparing only some characteristic compounds, but derivatives included in the present invention can be synthesized by those skilled in the art by the following examples.
실시예 1 :Example 1: o-o- (카르보메톡시)페닐메탄술포닐 클로라이드의 합성Synthesis of (carbomethoxy) phenylmethanesulfonyl chloride
o-(클로로메틸)벤조산 메틸 에스테르 20g에 물 50㎖와 티오술폰산 나트륨염 수화물(Na2S2O3·5H2O) 29.5g을 가하여 50 ∼ 55℃에서 5시간 교반하였다. 여기에 초산 300㎖를 가하고 내부온도를 5 ∼ 10℃로 유지하면서 3시간에 걸쳐 과량의 염소가스를 주입하였다. 그리고 동일온도에서 1시간 더 교반하였다. 과량의 염소가스는 질소가스를 불어 넣어 제거하고, 얼음물 300㎖를 넣고 30분간 교반하였다. 생성된 고체를 여과하고 찬물로 세척하여 건조하면 목적화합물 22.4g(수율 83%)이 흰색 고체로 얻어진다. To 20 g of o- (chloromethyl) benzoic acid methyl ester, 50 ml of water and 29.5 g of sodium thiosulfonic acid sodium hydrate (Na 2 S 2 O 3 .5H 2 O) were added, followed by stirring at 50 to 55 ° C for 5 hours. 300 ml of acetic acid was added thereto, and excess chlorine gas was injected over 3 hours while maintaining the internal temperature at 5 to 10 ° C. And it stirred for 1 hour at the same temperature. Excess chlorine gas was removed by blowing nitrogen gas, 300 ml of ice water was added and stirred for 30 minutes. The resulting solid was filtered, washed with cold water and dried to give 22.4 g (yield 83%) of the title compound as a white solid.
녹는점: 85 ∼ 86℃Melting Point: 85 ～ 86 ℃
1H-NMR(CDCl3) : δ3.95(s, 3H), 5.67(s, 2H), 7.51∼7.68(m, 3H), 8.07∼8.16(m, 1H) 1 H-NMR (CDCl 3 ): δ 3.95 (s, 3H), 5.67 (s, 2H), 7.51 to 7.68 (m, 3H), 8.07 to 8.16 (m, 1H)
실시예 2 :Example 2: o-o- (카르보에톡시)페닐메탄술포닐 클로라이드의 합성Synthesis of (Carboethoxy) phenylmethanesulfonyl chloride
상기 실시예 1과 동일한 제조과정을 수행하되, 다만o-(클로로메틸)벤조산 메틸 에스테르 대신에o-(클로로메틸)벤조산 에틸에스테르 20g을 사용하여 목적화합물 21.5g(수율 81%)을 흰색 고체로 얻었다.But performing the same manufacturing process as in Example 1, but the o- (chloromethyl) benzoic acid methyl ester instead of o- (chloromethyl) benzoic acid ethyl ester The desired compound 20g 21.5g (yield 81%) as a white solid using the Got it.
녹는점: 63 ∼ 64℃Melting Point: 63∼64 ℃
1H-NMR(CDCl3) : δ1.4(t, 3H,J=8Hz), 4.4(q, 2H,J=8Hz), 5.66(s, 2H), 7.51∼ 7.68(m, 3H), 8.07∼8.15(m, 1H) 1 H-NMR (CDCl 3 ): δ 1.4 (t, 3H, J = 8 Hz), 4.4 (q, 2H, J = 8 Hz), 5.66 (s, 2H), 7.51 to 7.68 (m, 3H), 8.07 -8.15 (m, 1 H)
실시예 3 :Example 3: o-o- (2-클로로에톡시카르보닐)페닐메탄술포닐 클로라이드 합성(2-Chloroethoxycarbonyl) phenylmethanesulfonyl chloride synthesis
상기 실시예 1과 동일한 제조과정을 수행하되, 다만o-(클로로메틸)벤조산 메틸 에스테르 대신에o-(클로로메틸)벤조산 2-클로로에틸에스테르 20g을 사용하여 목적화합물 20.5g(수율 80%)을 흰색 고체로 얻었다.But performing the same manufacturing process as Example 1, but the o- (chloromethyl) benzoic acid methyl ester instead of o- (chloromethyl) benzoic acid 2-chloro-ethyl ester using a 20g The desired compound 20.5g (80% yield) in Obtained as a white solid.
녹는점: 66 ∼ 67℃Melting Point: 66 ～ 67 ℃
1H-NMR(CDCl3) : δ3.83(t, 2H,J=5.5Hz), 4.59(t, 2H,J=5.5Hz), 5.4(s, 2H), 7.52∼7.68(m, 3H), 8.15(d, 1H,J=8Hz) 1 H-NMR (CDCl 3 ): δ3.83 (t, 2H, J = 5.5 Hz), 4.59 (t, 2H, J = 5.5 Hz), 5.4 (s, 2H), 7.52 to 7.68 (m, 3H) , 8.15 (d, 1H, J = 8 Hz)
본 발명에 따른 제조방법은 독성이 적은 반응물질을 사용하고 온화한 반응조건하에서 안전하게 수행되므로 상기 화학식 1로 표시되는o-(카르보알콕시)페닐메탄술포닐 클로라이드 유도체의 공업적인 생산에 유용하다.The preparation method according to the present invention is useful for the industrial production of o- (carboalkoxy) phenylmethanesulfonyl chloride derivatives represented by the formula (1) because it uses less toxic reactants and is safely carried out under mild reaction conditions.
Claims (5)
Priority Applications (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR1019970050282A KR100245015B1 (en) | 1997-09-30 | 1997-09-30 | Process for preparation of o-(carboxy)phenylmethanesulfonyl chloride derivatives |
| CN98809695A CN1120149C (en) | 1997-09-30 | 1998-09-30 | Process for preparing i(O)-(carboalkoxy) phenylmethanesulfonyl chloride derivatives |
| PCT/KR1998/000302 WO1999016743A1 (en) | 1997-09-30 | 1998-09-30 | A PROCESS FOR PREPARING o-(CARBOALKOXY) PHENYLMETHANESULFONYL CHLORIDE DERIVATIVES |
| JP2000513829A JP3433319B2 (en) | 1997-09-30 | 1998-09-30 | Method for producing o- (carboalkoxy) phenylmethanesulfonyl derivative |
| US09/509,440 US6222060B1 (en) | 1997-09-30 | 2000-03-28 | Process for preparing o-(carboalkoxy)phenylmethanesulfonyl chloride derivatives |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR1019970050282A KR100245015B1 (en) | 1997-09-30 | 1997-09-30 | Process for preparation of o-(carboxy)phenylmethanesulfonyl chloride derivatives |
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| KR19990027761A true KR19990027761A (en) | 1999-04-15 |
| KR100245015B1 KR100245015B1 (en) | 2000-03-02 |
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| KR1019970050282A KR100245015B1 (en) | 1997-09-30 | 1997-09-30 | Process for preparation of o-(carboxy)phenylmethanesulfonyl chloride derivatives |
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| Country | Link |
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