KR940009935B1 - N-benzoyl-c-thiophenoxyimidoyl chloride derivatives and manufacturing method thereof - Google Patents
N-benzoyl-c-thiophenoxyimidoyl chloride derivatives and manufacturing method thereof Download PDFInfo
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Abstract
Description
본 발명은 의약 및 농약 중간체로서 유용하게 이용되는 신규한 일반식(Ⅰ)의 N-벤조일-C-티오펜옥시이미도일 클로라이드 유도체 및 그 제조방법에 관한 것이다.The present invention relates to a novel general formula (I) N-benzoyl-C-thiophenoxyimidoyl chloride derivatives useful as medicinal and agrochemical intermediates and methods for their preparation.
식중, X는 염소, 수소원자 또는 니트로기를 나타내고, Y는 수소, 염소, 알킬, 알콕시 또는 니트로기를 나타낸다.Wherein X represents a chlorine, hydrogen atom or nitro group, and Y represents hydrogen, chlorine, alkyl, alkoxy or nitro group.
일반식(Ⅰ)으로 표시되는 화합물중에 X가 염소이고 Y가 수소인 화합물은 공지된 물질이지만, 그 외의 화합물들은 현재까지 공지되지 아니한 신규한 화합물들이다.Among the compounds represented by the general formula (I), X is chlorine and Y is hydrogen, but other compounds are novel compounds which are not known to date.
저날 오브 케미칼 소사이어티, 퍼킨 2, 1046-51, 1975에는 일반식(Ⅰ)에서 X가 염소이고 Y가 수소인 N-(4-클로로벤조일)-C-티오펜옥시이미도일 클로라이드와 그 제조방법이 공개되었다. 전기한 문헌에 의하면 N-(4-클로로벤조일)-이미도일디클로라이드 1당량과 티오펜올 1당량을 건조된 벤젠에 용해시킨 다음 생성된 용액에 트리에틸아민 1당량이 용해된 벤젠 용액을 서서히 적가하여 반응 생성물을 얻고 생성된 조생성물을 고진공하에서 저온 증류하여 정제된 N-(4-클로로벤조일)-C-티오펜옥시이미도일 클로라이드를 제조하도록 되었다. 그러나 전기한 문헌에는 X가 염소이고 Y가 수소인 N-벤조일-C-티오펜옥시이미도일 클로라이드 유도체와 그 제조방법만이 공개되었을뿐 X가 Y가 다른 기로 된 화합물이나 그들의 제조방법에 대하여는 언급되어 있지 않고 있다. 특히 전기한 문헌에 의하면 생성물의 수율은 40% 정도로 나타나고 있다.Journal of Chemical Society, Perkin 2, 1046-51, 1975 discloses N- (4-chlorobenzoyl) -C-thiophenoxyimidoyl chloride in which X is chlorine and Y is hydrogen in formula (I) Was released. According to the above documents, one equivalent of N- (4-chlorobenzoyl) -imidoyldichloride and one equivalent of thiophenol are dissolved in dried benzene, and then a benzene solution in which one equivalent of triethylamine is dissolved is slowly added dropwise to the resulting solution. The reaction product was obtained and the resulting crude product was subjected to low temperature distillation under high vacuum to prepare purified N- (4-chlorobenzoyl) -C-thiophenoxyimidoyl chloride. However, the above-mentioned literature only discloses N-benzoyl-C-thiophenoxyimidoyl chloride derivatives in which X is chlorine and Y is hydrogen, and a method of preparing the same, and mentions compounds in which X is a group in which Y is different or a method of preparing them. It is not done. In particular, the above-mentioned literature shows that the yield of the product is about 40%.
본 발명자는 전기한 공지의 X가 염소이고 Y가 수소인 전기한 공지의 화합물과 X가 염소 또는 수소이고 Y가 수소, 염소, 알킬 또는 니트로기인 신규 화합물을 개발하기 위하여 연구하는 과정에서 전기한 공지 방법을 이용하면 반응 부생물이 다량 생성되어 수율이 저하될뿐아니라 일부의 신규 물질들을 융점과 비점이 높아서 고진공하에서도 저온 증류에 의한 정제가 곤란하고 고온 증류시에는 생성물이 분해되어 수율이 현저히 저하되어 산업적으로 이용할 수 없음을 알게 되었다.The inventors of the present invention disclose the aforementioned known compounds in which X is chlorine and Y is hydrogen, and the known compounds described in the course of research to develop new compounds in which X is chlorine or hydrogen and Y is hydrogen, chlorine, alkyl or nitro group. By using the method, a large amount of reaction by-products are generated, which lowers the yield, and some new materials have high melting point and boiling point, making it difficult to purify by low temperature distillation even under high vacuum. It became known that it was not industrially available.
본 발명의 목적은 전술한 종래 방법에서 나타나는 수율저하의 문제점을 해결하기 위한 것이다.SUMMARY OF THE INVENTION An object of the present invention is to solve the problem of yield reduction in the aforementioned conventional method.
본 발명의 또다른 목적은 X가 염소 또는 수소원자를 나타내고 Y가 수소, 염소, 알킬 또는 니트로기를 나타내는 일반식(Ⅰ)의 화합물중 X가 염소이고 Y가 수소인 화합물을 제외한 신규의 N-벤조일-4-티오펜옥시이미도일 클로라이드를 제공하는 것이다.Another object of the present invention is a novel N-benzoyl except for a compound of formula (I) wherein X is chlorine or a hydrogen atom and Y is hydrogen, chlorine, alkyl or a nitro group except X is chlorine and Y is hydrogen. To provide 4-thiophenoxyimidoyl chloride.
본 발명자 등의 연구 결과에 의하면 N-벤조일카르보이미도일 디클로라이드와 트리에틸아민 및 티오펜올의 반응순서를 공지 방법과 달리하여 티오펜올과 트리에틸아민을 미리 벤젠에 용해시키고 이를 N-벤조일카르보이미도일 디틀로라이드의 벤젠 용액에 가하여 반응시키므로서 반응 부생물의 생성이 억제되어 수율이 향상되고 또한 정제시에는 진공증류에 의하여 벤젠을 제거한 다음 유기 용매에서의 재결정화 방법을 이용하면 종래 방법보다 수율이 월등히 향상되고 융점과 비점이 높은 물질의 정제도 가능함을 알게 되어 본 발명을 완성하게 된 것이다.According to the research results of the present inventors, the reaction order of N-benzoylcarbodiimidoyl dichloride, triethylamine and thiophenol is different from the known method, and thiophenol and triethylamine are previously dissolved in benzene, and the N- By adding to the benzene solution of benzoylcarbodiidoyl ditride and reacting to suppress the formation of reaction by-products, the yield is improved, and when purification, benzene is removed by vacuum distillation and then recrystallization in an organic solvent is used. The present invention has been completed by recognizing that the yield is much improved and that the melting point and the boiling point are higher than those of the conventional method.
본 발명의 신규한 N-벤조일-C-티오펜옥시이미도일 클로라이드 유도체는 전술한 일반식(Ⅰ)에서 X가 염소이고 Y가 수소가 아니라는 전제하에 X가 염소 또는 수소를 나타내고 Y가 수소, 염소, 알킬 또는 니트로기를 나타내는 화합물이다.The novel N-benzoyl-C-thiophenoxyimidoyl chloride derivatives of the present invention represent X in the formula (I), X being chlorine and Y is not hydrogen, and X is chlorine or hydrogen and Y is hydrogen, chlorine , Alkyl or nitro group.
본 발명에 있어서 Y로 표시되는 알킬기로는 탄소수 4개 이하의 알킬기가 적당한바, 예를들면 메틸, 에틸, N-프로필, i-프로필, N-부틸, Sec-부틸, t-부틸기등이며, Y로 표시되는 알콕시기로는 4개 이하의 탄소원자를 갖는 알콕시기, 예를들면 메톡시, 에콕시, n-프로폭시, t-부톡시기등이 있다.As the alkyl group represented by Y in the present invention, an alkyl group having 4 or less carbon atoms is suitable, for example, methyl, ethyl, N-propyl, i-propyl, N-butyl, Sec-butyl, t-butyl group, etc. And an alkoxy group represented by Y include an alkoxy group having 4 or less carbon atoms, for example, a methoxy, epoxy, n-propoxy, t-butoxy group and the like.
본 발명의 일반식(Ⅰ)로 표시되는 화합물로는 다음과 같은 것이 있다.Examples of the compound represented by the general formula (I) of the present invention include the following.
1) X=C1, Y=H(공지화합물)1) X = C1, Y = H (known compound)
N-(4-클로로벤조일)-C-(티오펜옥시)이미도일클로라이드N- (4-chlorobenzoyl) -C- (thiophenoxy) imidoylchloride
2) X=C1, Y=CH3 2) X = C1, Y = CH 3
N-(4-클로로벤조일)-C-(4-메틸티오펜옥시)이미도일클로라이드N- (4-chlorobenzoyl) -C- (4-methylthiophenoxy) imidoylchloride
3) X=C1, Y=C13) X = C1, Y = C1
N-(4-클로로벤조일)-C-(4-클로로티오펜옥시)이미도일클로라이드N- (4-chlorobenzoyl) -C- (4-chlorothiophenoxy) imidoylchloride
4) X=C1, Y=NO2 4) X = C1, Y = NO 2
N-(4-클로로벤조일)-C-(4-니트로티오펜옥시)이미도일클로라이드N- (4-chlorobenzoyl) -C- (4-nitrothiophenoxy) imidoylchloride
5) X=C1, Y=-C(CH3)3 5) X = C1, Y = -C (CH 3 ) 3
N-(4-클로로벤조일)-C-(4-t-부틸티오펜옥시)이미도일클로라이드N- (4-chlorobenzoyl) -C- (4-t-butylthiophenoxy) imidoylchloride
6) X=C1, Y=O(CH3)6) X = C1, Y = O (CH 3 )
N-(4-클로로벤조일)-C-(4-메톡시티오펜옥시)이미도일클로라이드N- (4-chlorobenzoyl) -C- (4-methoxythiophenoxy) imidoylchloride
7) X=H, Y=H7) X = H, Y = H
N-벤조일-C-(티오펜옥시)이미도일클로라이드N-benzoyl-C- (thiophenoxy) imidoylchloride
8) X=H, Y=CH3 8) X = H, Y = CH 3
N-벤조일-C-(4-메틸티오펜옥시)이미도일클로라이드N-benzoyl-C- (4-methylthiophenoxy) imidoylchloride
9) X=H, Y=C19) X = H, Y = C1
N-벤조일-C-(4-클로로티오펜옥시)이미도일클로라이드N-benzoyl-C- (4-chlorothiophenoxy) imidoylchloride
10) X=H, Y=NO2 10) X = H, Y = NO 2
N-벤조일-C-(4-니트로티오펜옥시)이미도일클로라이드N-benzoyl-C- (4-nitrothiophenoxy) imidoylchloride
11) X=H, Y=O(CH3)11) X = H, Y = O (CH 3 )
N-벤조일-C-(4-메톡시티오펜옥시)이미도일클로라이드N-benzoyl-C- (4-methoxythiophenoxy) imidoylchloride
12) X=NO2, Y=CH3 12) X = NO 2 , Y = CH 3
N-(4-니트로벤조일)-C-(4-메틸티오펜옥시)이미도일클로라이드N- (4-nitrobenzoyl) -C- (4-methylthiophenoxy) imidoylchloride
전술한 일반식(Ⅰ)의 화합물을 제조하는 본 발명의 방법은 티오펜을 유도체와 트리에틸아민을 무수 벤젠에 용해시키고 생성된 용액을 N-벤조일카르보이미도일디클로라이드가 용해된 벤젠 용액에 적가하여 반응시킨 다음 부생물로 생성되는 트리에틸아민하이드로클로라이드를 여과 제거하고 벤젠을 증류제거한 후 유기용매에서 재결정화시키는 방법으로 구성된다.In the method of the present invention for preparing the compound of general formula (I) described above, thiophene is dissolved in a derivative and triethylamine in anhydrous benzene, and the resulting solution is added dropwise to a benzene solution in which N-benzoylcarboimidoyldichloride is dissolved. After the reaction, the triethylamine hydrochloride produced as a by-product is filtered off, benzene is distilled off, and then recrystallized from an organic solvent.
본 발명에서 재결정에 사용되는 유기용매로는 클로로포름/펜탄, 벤젠, 디옥산등이 사용된다.As the organic solvent used for recrystallization in the present invention, chloroform / pentane, benzene, dioxane and the like are used.
본 발명의 방법에서는 수분이 반응계에는 존재하지 않아야 하므로 반응시 공기중의 수분이 침투되지 아니하는 밀폐용기에서 반응시켜야 한다.In the method of the present invention, the moisture should not be present in the reaction system, so the reaction should be carried out in a closed container which does not penetrate moisture in the air.
본 발명의 방밥은 당량 반응이므로 반응 물질은 동일한 몰비로 사용한다.Since Bangbab of the present invention is an equivalent reaction, the reactants are used in the same molar ratio.
본 발명에 의하면 티오펜올과 트리에틸아민을 무수벤젠에 용해시키고 이를 벤조일이미도일디클로라이드가 용해된 용액에 적가하되 반응계에 수분이 침투되지 않도록 밀폐용기내에서 진행시키므로 부반응이 억제되어 수율이 향상될뿐아니라 정제시 고온증류방법을 사용하지 않고 용매에서 정제하므로 생성물의 분해에 따른 수율의 저하를 방지할 수 있게 된다.According to the present invention, thiophenol and triethylamine are dissolved in anhydrous benzene and added dropwise to a solution in which benzoylimidoyldichloride is dissolved, but in a closed container to prevent moisture from penetrating into the reaction system, side reactions are suppressed to improve yield. In addition, since purification is performed in a solvent without using a high temperature distillation method during purification, it is possible to prevent a decrease in yield due to decomposition of a product.
[실시예 1]Example 1
N-(4-클로로벤조일)-C-(4-메틸티오펜옥시)이미도일클로라이드의 제조Preparation of N- (4-chlorobenzoyl) -C- (4-methylthiophenoxy) imidoylchloride
교반기와 주입펀넬이 착설된 250ml 둥근 플라스크에 벤젠 80ml와 4-클로로벤조일이미도일디클로라이드 5.09g(0.02몰)을 가하고 교반하면서 트리에틸아민 2.02g(0.02몰)과 4-메틸티올 2.49g(0.02몰)이 용해된 무수벤젠용액 80ml을 30분동안에 걸쳐 서서히 적가한다. 이때 공기중의 수분이 반응계에 침투되지 않도록 플라스크는 밀봉한다. 반응이 완결된후 백색침전 상태로 침강된 트리에틸아민하이드로클로라이드를 여과 제거하고 벤젠을 진공 증류시킨 다음 클로로포름/펜탄 혼합액에서 재결정화시켜 백색 침상 결정으로 된 N-(4-클로로벤조일)-C-(4-메틸티오펜옥시)이미도일클로라이드를 얻는다.To a 250 ml round flask equipped with a stirrer and an injection funnel, 80 ml of benzene and 5.09 g (0.02 mol) of 4-chlorobenzoylimidoyldichloride were added, followed by stirring, 2.02 g (0.02 mol) of triethylamine and 2.49 g (0.02 mol) of 4-methylthiol. 80 ml of anhydrous benzene solution dissolved in) is slowly added dropwise over 30 minutes. At this time, the flask is sealed so that moisture in the air does not penetrate the reaction system. After the reaction was completed, triethylamine hydrochloride precipitated in white precipitate was filtered off, benzene was vacuum distilled, and then recrystallized in chloroform / pentane mixture to give N- (4-chlorobenzoyl) -C- as white needle crystal. (4-methylthiophenoxy) imidoylchloride is obtained.
생성물의 수율, 융점, 원소 분석결과는 표 1에 기재하고 PRM 트랙트락 데이터는 표 2에 기재한다.The yield, melting point, and elemental analysis results of the products are shown in Table 1 and the PRM tracktrack data is shown in Table 2.
[실시예 2-12][Example 2-12]
[실시예 1}과 동일한 방법을 이용하된 출발물질인 벤조일이미도일디클로라이드류와 티오펜올류를 달리 사용하여 실시한다. 생성물과 분선결과는 표 1및 표 2에 기재한다.Using the same method as in [Example 1], benzoylimidoyldichloride and thiophenol, which are starting materials, were used differently. The products and the separation results are shown in Table 1 and Table 2.
[표 1] 화합물의 수율, 융점, 원소 분석결과Table 1 Compound Yield, Melting Point, Elemental Analysis
[표 2] 스펙트랄 데이터Table 2 Spectral Data
Claims (3)
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR1019910004337A KR940009935B1 (en) | 1991-03-19 | 1991-03-19 | N-benzoyl-c-thiophenoxyimidoyl chloride derivatives and manufacturing method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR1019910004337A KR940009935B1 (en) | 1991-03-19 | 1991-03-19 | N-benzoyl-c-thiophenoxyimidoyl chloride derivatives and manufacturing method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| KR920018019A KR920018019A (en) | 1992-10-21 |
| KR940009935B1 true KR940009935B1 (en) | 1994-10-19 |
Family
ID=19312234
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| KR1019910004337A KR940009935B1 (en) | 1991-03-19 | 1991-03-19 | N-benzoyl-c-thiophenoxyimidoyl chloride derivatives and manufacturing method thereof |
Country Status (1)
| Country | Link |
|---|---|
| KR (1) | KR940009935B1 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR101068384B1 (en) | 2004-06-28 | 2011-09-28 | 엘지디스플레이 주식회사 | Glass support system and support pin structure |
-
1991
- 1991-03-19 KR KR1019910004337A patent/KR940009935B1/en not_active IP Right Cessation
Also Published As
| Publication number | Publication date |
|---|---|
| KR920018019A (en) | 1992-10-21 |
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