KR950003423B1 - Process for the preparation of bittering agent - Google Patents
Process for the preparation of bittering agent Download PDFInfo
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- KR950003423B1 KR950003423B1 KR1019910025471A KR910025471A KR950003423B1 KR 950003423 B1 KR950003423 B1 KR 950003423B1 KR 1019910025471 A KR1019910025471 A KR 1019910025471A KR 910025471 A KR910025471 A KR 910025471A KR 950003423 B1 KR950003423 B1 KR 950003423B1
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- dimethylacetanilide
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- C07C237/00—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by amino groups
- C07C237/50—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by amino groups having the nitrogen atom of at least one of the carboxamide groups quaternised
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Abstract
Description
본 발명은 고미제의 제조방법에 관한 것으로서, 더욱 상세하게는 공업용 유기용매나 공업용 화학제품을 사람이나 동물이 먹었을 경우 즉시 토할 수 있도록 매우 쓴 맛을 내게 해주는 w-디알킬아미노-2,6-디메틸아세트아닐리드 4급유기염을 짧은 시간내에 고수율로 제조하는 방법에 관한 것이다.The present invention relates to a method for preparing a bitter agent, and more particularly, w-dialkylamino-2,6-dimethyl, which gives a very bitter taste so that an organic organic solvent or an industrial chemical may be immediately thrown up when a human or an animal eats it. A method for preparing acetanilide quaternary organic salt in high yield in a short time.
이미 잘 알려져 있듯이 공업용 에탄올이나 메탄올을 사람 또는 동물이 우연히 마셨을 경우 치명적인 영향을 주게 된다. 따라서, 이러한 공업용 유기용매나 공업용 화학제품에 일반 물리적, 화학적에는 영향을 주지 않고 사람이나 동물이 먹지 못하도록 변성제를 첨가하는 것이 매우 바람직하다.As is already well known, human or animal accidental drinking of industrial ethanol or methanol has a fatal effect. Therefore, it is highly desirable to add a denaturant to such industrial organic solvents and industrial chemicals so as not to be eaten by humans or animals without affecting general physical and chemical effects.
이처럼 물리적, 화학적 물성 변화없이 단지 쓴맛을 내주는 화합물을 고미제(Bittering agent)라 하는데, 일반적으로 알려진 고미제로는 쿠아신(Quassin), 쿠에브라초(Quebracho), 퀴닌(Quinine), 퀴닌하이드로클로라이드(Quinine Hydrochloride), 퀴닌설페이트(Quinine Sulfate), 수크로오스 옥타아세테이트(Sucrose Octa Acetate), 수크로오스 벤조에이트(Sucrose Benzoate), 나링인(Naringin), 브루신(Brucine), 브루신 설페이트(Brucine Sulfate), 리모닌(Limonin), 겐티안바이올렛(Gentian Violet), 아가산(Agaric acid), 카페인(Caffeine)등이 있으나, 이들 물질은 대부분 천연물에서 추출해야 하기 때문에 공급에 차질을 빚을 수 있고, 그중에서도 리모닌, 겐티안바이올렛, 아가산, 카페인 등은 고미효과가 작기 때문에 효과적이지 못하다.Bittering agent is a compound that gives only a bitter taste without changing physical and chemical properties. Commonly known bitters include quassin, quebracho, quinine, and quinine hydrochloride. Quinine Hydrochloride, Quinine Sulfate, Sucrose Octa Acetate, Sucrose Benzoate, Naringin, Brucine, Brucine Sulfate, Limonine (Limonin), Gentian Violet, Agaric acid, Caffeine, etc., but most of these substances have to be extracted from natural products, which may impede supply, especially limonine, Gentian violet, agamic acid, and caffeine are not effective because of their small bitterness.
이러한 기존의 고미제보다 고미효과가 월등히 우수한 w-디알킬아미노-2,6+-디메틸아세트아닐리드 4급유기염을 제조하는 방법이 미국특허 제3,080,327호와 제3,268,577호에 개시되어 있다.Methods for preparing w-dialkylamino-2,6 + -dimethylacetanilide quaternary organic salts that are much better than conventional conventional sweeteners are disclosed in US Pat. Nos. 3,080,327 and 3,268,577.
그러나, 이 방법에서 반응시간이 36시간이나 걸릴뿐만 아니라 생성물이 딱딱한 고체형태로 생기기 때문에 정제할 때 덩어리를 부숴서 사용해야 하는 어려움이 있다.However, in this method, not only does the reaction time take 36 hours, but also the product is formed as a solid solid, which is difficult to use to break up the lumps during purification.
따라서, 본 발명은 짧은 시간내에 쉬운 방법으로 순수한 고미제를 고수율로 제조하는 방법을 제공하는데 그 목적이 있다.It is therefore an object of the present invention to provide a process for producing pure bitumen with a high yield in an easy manner within a short time.
이하, 본 발명을 상세히 설명하면 다음과 같다.Hereinafter, the present invention will be described in detail.
본 발명은 w-디알킬아미노-2,6-디메틸아세트아닐리드부터 w-디알킬아미노-2,6-디메틸아세트아닐리드 4급유기염 고미제를 제조함에 있어서, 다음 구조식(A)의 w-디알킬아미노-2,6-디메틸아세트아닐리드와 다음 구조식(B)의 벤질할라이드를 반응시킬때 톨루엔 또는 벤젠을 용매로 사용하여 다음 구조식(I)로 표시되는 w-디알킬아미노-2,6-디메틸아세트아닐리드 4급유기암모늄 할라이드를 제조하는 것을 특징으로 한다.The present invention is to prepare w-dialkylamino-2,6-dimethylacetanilide to w-dialkylamino-2,6-dimethylacetanilide quaternary organic salt bitumen, and to prepare w-dialkylamino of the following structural formula (A) When reacting -2,6-dimethylacetanilide with benzyl halide of the following structural formula (B), w-dialkylamino-2,6-dimethylacetanilide represented by the following structural formula (I) using toluene or benzene as a solvent It is characterized by preparing a quaternary organic ammonium halide.
상기식들중에서, R1은 벤질기이거나 클로로벤질이고, R2와 R3는 서로 같거나 다른 것으로서, 각각 탄소수 1 내지 4의 알킬기이고, X는 염소 또는 브롬원자이다.In the above formula, R 1 is a benzyl group or chlorobenzyl, R 2 and R 3 are the same as or different from each other, each having an alkyl group having 1 to 4 carbon atoms, X is a chlorine or bromine atom.
이와 같은 본 발명을 더욱 상세히 설명하면 다음과 같다.Referring to the present invention in more detail as follows.
본 발명에서 상기 구조식(I)의 화합물을 제조하는 방법을 반응식으로 나타내면 다음과 같다.In the present invention, a method of preparing the compound of formula (I) is represented by the following scheme.
상기 반응식에서, R1,R2,R3및 X는 상기와 같다.In the above scheme, R 1 , R 2 , R 3 and X are as above.
상기 반응식에서 기존의 방법에서는 상기 구조식(A)(B) 화합물을 넣고 110℃에서 유기용매 없이 36시간을 반응시키면 적갈색의 딱딱한 고체덩어리의 구조식(I) 화합물이 생기고 이를 완전히 가루로 만든 후 이소프로판올과 에틸아세테이트 용매로 재결정하여 순수한 생성물을 얻었다.In the conventional scheme, when the above formula (A) (B) compound is added and reacted for 36 hours without an organic solvent at 110 ° C., a reddish brown solid mass of the structural formula (I) compound is formed and is completely powdered, and then isopropanol and Recrystallization with ethyl acetate solvent gave pure product.
그러나, 본 발명은 상기 반응식에서 보다 빠른 시간내에 간단한 방법으로 고순도의 구조식(I) 화합물을 고수율로 얻는 방법으로서, 상기 구조식(A),(B) 화합물을 반응시킬때 벤젠이나 톨루엔을 구조식(A) 화합물 1mmol당 0.1~0.5ml 가한 다음 80~110℃에서 환류시키면 적갈색의 액체가 생기기 시작하고 약 10시간이 지나면 교반이 힘들 정도의 매우 점도가 높은 끈적끈적한 액체가 생성된다.However, the present invention is a method of obtaining a high-purity structural formula (I) compound in a high yield in a simple manner within a short time in the reaction scheme, when benzene or toluene is reacted when reacting the structural formula (A), (B) A) 0.1 ~ 0.5ml per 1mmol of compound is added and refluxed at 80 ~ 110 ℃. A reddish brown liquid begins to form, and after about 10 hours, a very viscous and sticky liquid is produced.
여기서 상기 벤젠이나 톨루엔을 0.5ml보다 많이 첨가하면 반응시간이 길어지는 (48시간 이상)문제가 있고, 0.1ml미만을 첨가하면 반응물이 굳어져 재결정이 어려운 문제가 발생한다.In this case, when the benzene or toluene is added more than 0.5 ml, the reaction time becomes long (over 48 hours), and when less than 0.1 ml is added, the reactant becomes hard and recrystallization becomes difficult.
이와 같이 생성된 끈끈한 액체에 과량의 벤젠이나 톨루엔을 110℃에서 넣고 교반하면 침전물이 생기게 되고, 온도를 상온으로 내린 후 여과지로 여과하면 w-디알킬아미노-2,6-디메틸아세트아닐리드 4급유기염을 90% 이상의 수율로 얻을 수 있고, 이 생성물을 이소프로판올과 에틸아세테이트 또는 석유에테르의 혼합액을 최소한의 양으로 끓는 액에 녹인 후 냉각시키면 순수한 생성물을 80% 이상의 수율로 얻을 수 있다.In the sticky liquid thus produced, excess benzene or toluene was added at 110 ° C. and stirred to form a precipitate. When the temperature was lowered to room temperature and filtered through a filter paper, w-dialkylamino-2,6-dimethylacetanilide quaternary organic salt was added. It can be obtained in a yield of 90% or more, the product is isopropanol and ethyl acetate or a mixture of petroleum ether is dissolved in a boiling liquid in a minimum amount and cooled to obtain a pure product in a yield of 80% or more.
이와 같이 본 발명에 의하면 고미제로 유용한 w-디알킬아미노-2,6-디메틸아세트아닐리드의 4급유기염을 고순도, 고수율로 얻을 수 있는 장점이 있다.As described above, according to the present invention, quaternary organic salts of w-dialkylamino-2,6-dimethylacetanilide, which are useful as a delicacy agent, can be obtained with high purity and high yield.
이하, 본 발명을 실시예를 통하여 더욱 상세히 설명하겠는바, 실시예에 의해 본 발명이 한정되는 것은 아니다.Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited by Examples.
[실시예 1]Example 1
200ml 2구 플라스크에 w-디에틸아미노-2,6-디메틸아세트아닐리드 5.9g(25mmol)과 벤젠 10ml를 넣고 오일중탕에서 80℃로 유지시킨 후 벤질클로라이드 3.36g(26.5mmol)을 첨가한다.In a 200 ml two-necked flask, 5.9 g (25 mmol) of w-diethylamino-2,6-dimethylacetanilide and 10 ml of benzene were added and maintained at 80 ° C. in an oil bath. Then, 3.36 g (26.5 mmol) of benzyl chloride was added.
온도는 110℃로 올린 후 냉각기를 이용해 10시간 환류한 후, 빠른 속도로 교반하면서 60ml의 벤젠을 넣어주면 용액이 침전화된다. 이를 상온까지 냉각시킨 후 여과지를 이용해 여과하고, 침전물을 석유에테르와 n-헥산으로 차례로 씻어주면 초기생성물 8.1g을 얻을 수 있다.The temperature was raised to 110 ° C, refluxed for 10 hours using a cooler, and 60 ml of benzene was added with rapid stirring to precipitate the solution. After cooling to room temperature, the filter was filtered using a filter paper, and the precipitate was washed with petroleum ether and n-hexane in order to obtain 8.1 g of an initial product.
이를 끓는 이소프로판올 최소량으로 놓이고 약 5배의 석유에테르에 혼합시키면 생성물이 재결정화되고 0℃까지 냉각시키면 순수한 w-디에틸아미노-2,6-디메틸아세트아닐리드 벤질클로라이드(mp 175~177℃) 7.5g(수율 : 83.5%)을 얻을 수 있다.Place it in a minimum amount of boiling isopropanol and mix with about 5 times petroleum ether to recrystallize the product and cool to 0 ° C pure w-diethylamino-2,6-dimethylacetanilide benzylchloride (mp 175-177 ° C) 7.5 g (yield: 83.5%) is obtained.
[실시예 2]Example 2
100ml 플라스크에 10ml 에탄올(순도 99%이상)과 수산화나트륨 0.4g을 넣고 용해시킨 후, 다른 플라스크에 10ml 에탄올에 리도카인 벤질클로라이드 3.6g(10mmol)을 녹여 앞의 용액에 첨가한다. 약 2시간 교반후 생성된 NaCl을 여과지로 제거한 후, 벤조익산 1.22g(10mmol)을 에탄올 10ml에 녹여 여과된 액에 넣고 상온에서 3시간 교반한다.10 ml ethanol (more than 99% purity) and 0.4 g of sodium hydroxide are dissolved in a 100 ml flask, and 3.6 g (10 mmol) of lidocaine benzyl chloride is dissolved in 10 ml ethanol and added to the previous solution. After stirring for about 2 hours to remove the NaCl produced by the filter paper, 1.22g (10mmol) of benzoic acid is dissolved in 10ml of ethanol and put into the filtered solution and stirred for 3 hours at room temperature.
그리고 나서 에탄올을 증발시키면 초기생성물 4.1g을 얻을 수 있고 이를 이소프로판올과 에틸아세테이트 혼합액으로 재결정하면 순수한 리도카인 벤질벤조에이트(mp 160~161℃) 3.7g(수율 : 82.2%)을 얻게 된다.Then, by evaporating ethanol, 4.1g of the initial product can be obtained, and recrystallized with a mixture of isopropanol and ethyl acetate to obtain 3.7g (yield: 82.2%) of pure lidocaine benzylbenzoate (mp 160 ~ 161 ° C).
[실시예 3]Example 3
100ml 2구-플라스크에 w-디에칠아미노-2,6-디메칠아세트아닐리드 2.34g(10mmol)을 톨루엔 5ml와 넣고 오일 중탕에서 80℃로 유지시킨 후, p-클로로 벤질클로라이드 1.61g(10mmol)을 첨가한다.2.34 g (10 mmol) of w-dimethylamino-2,6-dimethylacetanilide was added to a 100 ml two-necked flask with 5 ml of toluene, and maintained at 80 ° C. in an oil bath, followed by 1.61 g (10 mmol) of p-chlorobenzyl chloride. Add.
온도를 110℃로 올린 후 10시간 환류시키고, 교반하면서 톨루엔 30ml을 넣어주면 생성물이 침전으로 떨어진다. 이를 여과하여 이소프로판올과 10배의 에칠 아세테이트 혼합액으로 재결정하면 순수한 w-디메칠아미노-2,6-디메칠아세트아닐리드 p-클로로 벤질클로라이드(mp 180℃), 3.36g(85.1%)을 얻을 수 있다.The temperature was raised to 110 ° C. and refluxed for 10 hours, and 30 ml of toluene was added while stirring, and the product fell into the precipitate. This was filtered and recrystallized from isopropanol and 10-fold ethyl acetate mixture to obtain 3.36 g (85.1%) of pure w-dimethylamino-2,6-dimethylacetanilide p-chlorobenzylchloride (mp 180 ° C). .
[비교예 1]Comparative Example 1
200ml 2구 플라스크에 w-디에칠아미노-2,6-디메칠아세트아닐리드 5.9g(25mmol)과 벤질 클로라이드 3.36g(26.5mmol)을 넣고 오일 중탕에서 110℃로 36시간 반응시킨다. 생성된 딱딱한 고체 덩어리를 가루로 분쇄한 후, 에칠아세테이트로 1시간 동안 환류시키고 여과하면 초기 생성물이 얻어지고 이를 끓는 이소프로판올과 10배의 에칠아세테이트 최소량에 녹여 재결정하면 순수한 w-디에칠아미노-2,6-디메칠아세트아닐리드 벤질클로라이드 6.7g(75%)을 얻을 수 있다.Into a 200 ml two-necked flask, 5.9 g (25 mmol) of w-dimethylamino-2,6-dimethylacetanilide and 3.36 g (26.5 mmol) of benzyl chloride were added and reacted at 110 ° C. in an oil bath for 36 hours. The resulting solid solid mass was pulverized into powder, and then refluxed with ethyl acetate for 1 hour and filtered to give an initial product, which was dissolved in boiling isopropanol and 10 times the amount of ethyl acetate and recrystallized to obtain pure w-dimethylamino-2, 6.7 g (75%) of 6-dimethylacetanilide benzylchloride can be obtained.
[비교예 2]Comparative Example 2
200ml 2구 플라스크에 w-디에칠아미노-2,6-디메칠아세트아닐리드 5.9g(25mmol)과 o-클로로벤질클로라이드 4.0g(25mmol)을 toluene 25ml에 넣고 110℃에서 10시간 환류시킨 후, 생성물을 침전화시켜 얻어진 초기 생성물을 이소프로판올과 에칠아세테이트 5배 혼합액으로 재결정하면 순수한 w-디에칠아미노-2,6-디메칠아세트아닐리드 o-클로로 벤질클로라이드(mp 186℃~188℃) 0.5g(5.1%)을 얻을 수 있다.Into a 200 ml two-necked flask, 5.9 g (25 mmol) of w-dimethylamino-2,6-dimethylacetanilide and 4.0 g (25 mmol) of o-chlorobenzyl chloride were added to 25 ml of toluene and refluxed at 110 ° C. for 10 hours. The initial product obtained by precipitation was recrystallized from a 5-fold mixture of isopropanol and ethyl acetate, and pure w-dimethylamino-2,6-dimethylacetanilide o-chloro benzyl chloride (mp 186 ° C-188 ° C) 0.5 g (5.1 %) Can be obtained.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR1019910025471A KR950003423B1 (en) | 1991-12-30 | 1991-12-30 | Process for the preparation of bittering agent |
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| Application Number | Priority Date | Filing Date | Title |
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| KR1019910025471A KR950003423B1 (en) | 1991-12-30 | 1991-12-30 | Process for the preparation of bittering agent |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| KR930012688A KR930012688A (en) | 1993-07-21 |
| KR950003423B1 true KR950003423B1 (en) | 1995-04-12 |
Family
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| KR1019910025471A KR950003423B1 (en) | 1991-12-30 | 1991-12-30 | Process for the preparation of bittering agent |
Country Status (1)
| Country | Link |
|---|---|
| KR (1) | KR950003423B1 (en) |
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1991
- 1991-12-30 KR KR1019910025471A patent/KR950003423B1/en not_active IP Right Cessation
Also Published As
| Publication number | Publication date |
|---|---|
| KR930012688A (en) | 1993-07-21 |
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