KR970001473B1 - Method for preparing pyrazole sulfonyl chloride derivatives - Google Patents
Method for preparing pyrazole sulfonyl chloride derivatives Download PDFInfo
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- KR970001473B1 KR970001473B1 KR1019930025836A KR930025836A KR970001473B1 KR 970001473 B1 KR970001473 B1 KR 970001473B1 KR 1019930025836 A KR1019930025836 A KR 1019930025836A KR 930025836 A KR930025836 A KR 930025836A KR 970001473 B1 KR970001473 B1 KR 970001473B1
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Abstract
Description
본 발명은 피라졸 설포닐 우레아계 제초제의 중간체로 유용한 하기 구조식(Ⅰ)로 표시되는 피라졸 설포닐클로라이드 유도체의 제조방법에 관한 것이다.The present invention relates to a process for the preparation of pyrazole sulfonylchloride derivatives represented by the following structural formula (I) which is useful as an intermediate of pyrazole sulfonyl urea herbicides.
상기 식에서, R1는 수소원자, C1-C4알킬기 또는 페닐기이고, R2는 수소원자, C1-C4알킬기, 알릴기 또는 프로파길기이며, R3는 수소원자, 메틸기, 에틸기 또는 페닐기이다.Wherein R 1 is a hydrogen atom, a C 1 -C 4 alkyl group or a phenyl group, R 2 is a hydrogen atom, a C 1 -C 4 alkyl group, an allyl group or a propargyl group, and R 3 is a hydrogen atom, a methyl group, an ethyl group or It is a phenyl group.
상기 구조식(Ⅰ)의 화합물을 합성하는 방법은 예를들어 유럽공개 특허 제87,780호에 알려져 있다. 이 방법에 따르면, 하기 반응도식(A)에 나타낸 바와 같이 구조식(Ⅱ)의 화합물을 염소가스와 반응시켜 목적 화합물인 구조식(Ⅰ)의 피라졸 설포닐클로라이드를 합성하고 있다.Methods of synthesizing the compound of formula (I) are known, for example, from EP 87,780. According to this method, pyrazole sulfonyl chloride of the formula (I) as a target compound is synthesized by reacting the compound of formula (II) with chlorine gas as shown in the following scheme (A).
상기 식에서, R1, R2, R3는 전술한 바와 동일하며, R4는 수소 또는 벤질기이다.In the above formula, R 1 , R 2 , R 3 are the same as described above, and R 4 is hydrogen or benzyl group.
그러나, 상기 방법에서는 인체에 매우 유독한 염소가스를 사용해야 하므로 반응시 특별한 안전장치가 필요할 뿐만 아니라, 염소가스의 반응성이 지나치게 강하여 하기 구조식(Ⅲ)과 같은 부반응물질이 상당히 생성되다는 것이 문제점을 지적되고 있다.However, this method requires the use of very chlorine gas, which is very toxic to the human body, and therefore requires special safety devices. In addition, it is pointed out that the reaction of the chlorine gas is excessively strong, resulting in the generation of side reaction substances such as the following structural formula (III). It is becoming.
상기 식에서, R1, R2및 R3는 전술한 바와 동일하며, X은 수소 또는 C1이다.Wherein R 1 , R 2 and R 3 are the same as described above and X is hydrogen or C 1.
이에 본 발명자들은 목적화합물(Ⅰ)을 보다 안전하고 간단하게 제조할 수 있는 방법에 대하여 연구한 결과, 공지 방법에서의 염소가스 대신에 취급이 간편하고 반응성의 조절이 용이한 염산수용액과 과산화수소수를 사용함으로써 공지의 방법의 문제점들을 해결하고 본 발명을 완성하였다.Therefore, the present inventors have studied the method to prepare the target compound (I) more safely and simply. Instead of the chlorine gas in the known method, the aqueous hydrochloric acid solution and the hydrogen peroxide solution can be easily controlled and the reactivity can be easily controlled. The use solves the problems of known methods and completes the present invention.
따라서, 본 발명은 하기 반응도식(B)에 나타낸 바와 같이 하기 구조식(Ⅳ)의 피라졸디설파이드 유도체를 염산수용액 및 과산화수소수와 반응시킴을 특징으로 하여 하기 구조식(Ⅰ)의 피라졸설포닐클로라이드 유도체를 제조하는 방법을 제공한다.Accordingly, the present invention is characterized by reacting a pyrazole disulfide derivative of the following structural formula (IV) with an aqueous hydrochloric acid solution and hydrogen peroxide solution as shown in the following scheme (B). It provides a method of manufacturing.
상기 식에서, R1, R2및 R3는 전술한 바와 동일하다. 이하, 본 발명의 제조방법을 상세히 설명한다.Wherein R 1 , R 2 and R 3 are the same as described above. Hereinafter, the manufacturing method of the present invention will be described in detail.
본 발명에 따른 반응은 출발물질을 별도의 용매에 녹여 반응시키거나, 용매없이 바로 염산용액에 용해시켜 수행할 수 있다. 용매를 사용하는 경우는 n-헥산과 같은 알칸류, 디클로로메탄과 같은 할로겐화 알칸류 또는 톨루엔등의 유기용매를 사용하는 것이 바람직하다.The reaction according to the present invention may be carried out by dissolving the starting material in a separate solvent or by directly dissolving it in a hydrochloric acid solution without a solvent. When using a solvent, it is preferable to use organic solvents, such as alkanes, such as n-hexane, halogenated alkanes, such as dichloromethane, and toluene.
본 발명의 반응에서, 염산수용액 및 과산화수소는 출발물질(Ⅳ)에 대하여 각각 1.0당량 이상이면 특별한 제한없이 사용할 수 있으나, 부반응 생성물을 최대한 억제하고 반응시간을 줄임과 동시에 반응 효율적인 측면에서 볼때, 각각 6.0 내지 8.0 당량을 사용하는 것이 바람직하다.In the reaction of the present invention, the aqueous hydrochloric acid solution and hydrogen peroxide can be used without particular limitation as long as they are each 1.0 equivalent or more based on the starting material (IV), but in view of suppressing side reaction products as much as possible and reducing the reaction time, the reaction efficiency is 6.0, respectively. Preference is given to using from 8.0 equivalents.
또한, 본 발명에 따른 반응은 반응기 내부온도가 20℃ 이하일 경우에는 반응시간이 길어지며, 반대로 50℃이상의 온도에서 목적 화합물인 구조식(Ⅰ)의 화합물이 가수분해되어 수율이 감소될 수 있으므로 반응기 내부 온도를 30~50℃, 보다 바람직하게는 35~45℃의 범위를 유지하도록 반응물질 투입 등에 주의하여야 하는 것이 좋다.In addition, the reaction according to the present invention has a long reaction time when the temperature inside the reactor is 20 ℃ or less, on the contrary, since the compound of formula (I), which is the target compound, may be hydrolyzed at a temperature of 50 ° C. or higher, the yield may be reduced. Attention should be paid to the addition of reactants to maintain the temperature in the range of 30 to 50 ° C, more preferably 35 to 45 ° C.
본 발명의 출발물질인 구조식(Ⅳ)의 화합물은, 본 발명자들에 의한 대한민국 특허출원 제92-24734호에 기재된 방법을 용융하여, 하기 반응도식(C)와 같이 구조식(Ⅴ)의 디티오카르바제이트 유도체를 염기와 반응시킨 후 통상적인 방법에 따라 산화시켜 제조할 수 있다.The compound of formula (IV), which is the starting material of the present invention, is melted by the method described in Korean Patent Application No. 92-24734 by the present inventors, and the dithiocar of formula (V) is represented by the following Reaction Scheme (C). It may be prepared by reacting a bazate derivative with a base and then oxidizing it according to a conventional method.
상기 식에서, R1, R2및 R3는 전술한 바와 동일하고, R은 C1-C4알킬기, C2-C4알케닐기, 아릴알킬기(바람직하게는 벤질기) 또는 알킬기(바람직하게는 페닐기)를 나타낸다.Wherein R 1 , R 2 and R 3 are the same as described above and R is a C 1 -C 4 alkyl group, a C 2 -C 4 alkenyl group, an arylalkyl group (preferably benzyl group) or an alkyl group (preferably Phenyl group).
이하, 본 발명을 실시에에 의거 보다 구체적으로 설명하지만, 본 발명의 기술적 범위가 이들 실시예로 제한되는 것은 아니다.Hereinafter, although an Example demonstrates this invention more concretely, the technical scope of this invention is not restrict | limited to these Examples.
제조예Production Example
4-에톡시-1-메틸-5-피라졸디설파이드의 합성Synthesis of 4-ethoxy-1-methyl-5-pyrazoledisulfide
무수에탄올 250㎖에 메틸 3-[2',2'-(디에톡시)카보닐)에틸리덴]2-메틸디티오카르바제이트 30.6g과 소디움 에톡사이드 8g을 넣고 질소 대기하에서 가열하여 10시간 정도 환류시킨다. 반응이 완료되면 에탄올을 증류하여 제거한 다음, 여기에 물 200㎖와 메틸렌디클로라이드 500㎖를 가한 후 98% 황산으로 pH를 약 8정도로 조절하여 층분리하다. 수층을 취하여 pH를 2로 맞추고 생성물을 메틸렌디클로라이드 500㎖로 추출한다. 계속하여 메틸렌디클로라이드 층에 38% 과산화수소 5.0g을 첨가하여 실온에서 3시간 교반하여 반응을 완료시킨다. 반응혼합물을 충분리하여 유기층을 무수 마그네슘설페이트로 건조시킨 다음, 용매를 감압증류하여 제거하면 갈색고체의 표제화합물 16.8g(수율 91%, 순도 98%)을 얻는다.To 250 ml of anhydrous ethanol, 30.6 g of methyl 3- [2 ', 2'-(diethoxy) carbonyl) ethylidene] 2-methyldithiocarbazate and 8 g of sodium ethoxide were added and heated under a nitrogen atmosphere for 10 hours. Reflux to degree. After the reaction was completed, ethanol was distilled off, and 200 mL of water and 500 mL of methylene dichloride were added thereto, and the layers were separated by adjusting the pH to about 8 with 98% sulfuric acid. The aqueous layer is taken, the pH is adjusted to 2 and the product is extracted with 500 ml of methylenedichloride. Subsequently, 5.0 g of 38% hydrogen peroxide was added to the methylene dichloride layer and stirred at room temperature for 3 hours to complete the reaction. Sufficient reaction mixture was dried over anhydrous magnesium sulfate, and then the solvent was distilled off under reduced pressure to obtain 16.8 g of a brown solid title compound (yield 91%, purity 98%).
실시예 1Example 1
4-에톡시카보닐-1-메틸피라졸-5-설포닐클로라이드의 합성Synthesis of 4-ethoxycarbonyl-1-methylpyrazole-5-sulfonylchloride
4-에톡시카보닐-1-메틸-5-피라졸설파이드 370g과 디클로로메탄 390g 및 35% 염산수용액 834g을 플라스크에 넣고 실온에서 교반시켜 출발물질을 용해시킨 후 36% 과산화수소 560g을 2시간에 걸쳐 천천히 적가한다. 이때 반응기 내부온도는 40℃ 정도로 유지시킨다. 과산화수소 적가가 완료된 후 동온도를 유지하면서 30분정도 더 교반하여 반응을 완결시키고 실온으로 냉각한 후 유기층을 분리한다. 분리된 유기층을 무수 마그네슘설페이트로 건조시키고 용매를 제거하여 노란색 액상의 표제화합물 476g(수율 94%)을 얻었다(기체 크로마토그래피 순도 94%).370 g of 4-ethoxycarbonyl-1-methyl-5-pyrazolesulfide, 390 g of dichloromethane and 834 g of 35% aqueous hydrochloric acid were added to the flask, and the mixture was stirred at room temperature to dissolve the starting material. Then, 560 g of 36% hydrogen peroxide was added over 2 hours. Add slowly At this time, the temperature inside the reactor is maintained at about 40 ℃. After completion of the dropwise addition of hydrogen peroxide, the mixture was stirred for 30 minutes while maintaining the same temperature to complete the reaction, cooled to room temperature, and the organic layer was separated. The separated organic layer was dried over anhydrous magnesium sulfate and the solvent was removed to obtain 476 g (yield 94%) of the title compound as a yellow liquid (gas chromatography purity 94%).
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| KR1019930025836A KR970001473B1 (en) | 1993-03-05 | 1993-11-30 | Method for preparing pyrazole sulfonyl chloride derivatives |
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| KR93-3308 | 1993-03-05 | ||
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| KR1019930025836A KR970001473B1 (en) | 1993-03-05 | 1993-11-30 | Method for preparing pyrazole sulfonyl chloride derivatives |
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