KR890002400B1 - Process for the preparation of aromatic amine sulfone compounds - Google Patents
Process for the preparation of aromatic amine sulfone compounds Download PDFInfo
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- KR890002400B1 KR890002400B1 KR1019860003680A KR860003680A KR890002400B1 KR 890002400 B1 KR890002400 B1 KR 890002400B1 KR 1019860003680 A KR1019860003680 A KR 1019860003680A KR 860003680 A KR860003680 A KR 860003680A KR 890002400 B1 KR890002400 B1 KR 890002400B1
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- acetylamino
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C315/00—Preparation of sulfones; Preparation of sulfoxides
- C07C315/04—Preparation of sulfones; Preparation of sulfoxides by reactions not involving the formation of sulfone or sulfoxide groups
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C317/00—Sulfones; Sulfoxides
- C07C317/26—Sulfones; Sulfoxides having sulfone or sulfoxide groups and nitrogen atoms, not being part of nitro or nitroso groups, bound to the same carbon skeleton
- C07C317/32—Sulfones; Sulfoxides having sulfone or sulfoxide groups and nitrogen atoms, not being part of nitro or nitroso groups, bound to the same carbon skeleton with sulfone or sulfoxide groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton
- C07C317/34—Sulfones; Sulfoxides having sulfone or sulfoxide groups and nitrogen atoms, not being part of nitro or nitroso groups, bound to the same carbon skeleton with sulfone or sulfoxide groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton having sulfone or sulfoxide groups and amino groups bound to carbon atoms of six-membered aromatic rings being part of the same non-condensed ring or of a condensed ring system containing that ring
- C07C317/36—Sulfones; Sulfoxides having sulfone or sulfoxide groups and nitrogen atoms, not being part of nitro or nitroso groups, bound to the same carbon skeleton with sulfone or sulfoxide groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton having sulfone or sulfoxide groups and amino groups bound to carbon atoms of six-membered aromatic rings being part of the same non-condensed ring or of a condensed ring system containing that ring with the nitrogen atoms of the amino groups bound to hydrogen atoms or to carbon atoms
Abstract
Description
본 발명은 방향족 아민 술폰화합물의 제조방법에 관한 것이다. 더욱 구체적으로, 본 발명은 다음 구조식(Ⅱ)의 화합물을 1-1.5몰비의 황산으로 가수분해 및 에스테르화 시켜서 다음 구조식(Ⅰ)의 화합물을 제조하는 방법에 관한것이다.The present invention relates to a method for producing an aromatic amine sulfone compound. More specifically, the present invention relates to a method for preparing a compound of formula (I) by hydrolyzing and esterifying a compound of formula (II) with 1-1.5 molar ratio of sulfuric acid.
상기식에서 A는 방향족 화합물의 잔기이고, B는 수소 또는 산에 의해 가수분해 되는 기이고, n은 1-2의 정수를 나타낸다.Wherein A is a residue of an aromatic compound, B is a group hydrolyzed by hydrogen or an acid, and n represents an integer of 1-2.
일반식(Ⅱ)의 화합물을 일반식(Ⅰ)의 화합물로 변형시키는 방법은 일반적으로 다단계의 복잡한 조작을 필요로 하고, 또한 수율이 좋게 목적을 얻기 위하여 대량의 황산을 사용하였다.The method of transforming a compound of formula (II) to a compound of formula (I) generally requires complicated operation in multiple stages, and a large amount of sulfuric acid was used to obtain a good yield.
예를들면, 일본 특공소 42-16617호에서는 4-아세틸아미노페닐-β-히드록시에틸술폰을 진한황산 또는 진한황산과 유기용매의 혼합물을 이용하여 가수분해하는 동시에 황산 에스테르화하는 방법이 기재되어있다. 그러나, 이 방법은 다량의 발연황산을 첨가하며, 그 결과 얻어진(4-아미노페닐-β-술페이트 에틸술폰이 다량의 진한 황산용액 또는 발연 황산용액으로 얻어져서 과잉황산의 처리에 필요한 알카리제의)비용 및 이것에 의해 발생하는 황산염의 분리 문제등이 있어서 대단히 번잡하고 공업적 이용에 어려움이 있었다.For example, Japanese Unexamined Patent Application No. 42-16617 describes a method for hydrolyzing and simultaneously esterifying 4-acetylaminophenyl-β-hydroxyethylsulfone using concentrated sulfuric acid or a mixture of concentrated sulfuric acid and an organic solvent. have. However, this method adds a large amount of fuming sulfuric acid, and the resultant (4-aminophenyl-β-sulfate ethylsulfone is obtained in a large amount of concentrated sulfuric acid solution or fuming sulfuric acid solution to obtain an alkaline agent necessary for treatment of excess sulfuric acid. The cost and the problem of separation of sulphate generated by it are very complicated and difficult to use industrially.
일본 특공소 45-27096호에서는 아세틸아미노아릴-β-술페이트 에틸술폰을 50%이하의 황산수용액, 45℃에서 가수 분해하여 아미노아릴-β-술페이트 에틸술폰을 제조하고 있으나, 아세틸아미노기의 가수분해와 동시에 β-술페이트 에틸술폰기중의 황산에스테르의 가수분해가 발생하여서 수율이 저하되는 결점이 있다.JP-A-45-27096 manufactures aminoaryl-β-sulfate ethylsulfone by hydrolyzing acetylaminoaryl-β-sulfate ethylsulfone at 50% or less in aqueous sulfuric acid solution at 45 ° C. Simultaneously with the decomposition, hydrolysis of the sulfate ester in the β-sulfate ethyl sulfone group occurs, resulting in a decrease in yield.
일본 특개소 56-142256호는 일반식(Ⅱ) {B-NH-A (SO2CH2CH2OH)N}의 화합물에 술파민산 혹은 클로로술폰산 혹은 이것과 황산의 혼합물을 β-히드록시 에틸술포닐기 1개에 대하여 1-3몰비로 황화시키고, 이 에스테르화제에 탄화수소계의 유기용매를 병용하는 방법을 사용하고 있다. 그러나, 이 방법도 다량의 유기용매와 에스테르화제의 사용이 불가피하여서 반응물로부터 용매와 에스테르화제를 제거하는 다단계가 필요한 공업상 낮은 경제성과 공해발생이 있는 단점이 있다.Japanese Patent Application Laid-Open No. 56-142256 discloses β-hydroxyethyl as a compound of formula (II) {B-NH-A (SO 2 CH 2 CH 2 OH) N } with sulfamic acid or chlorosulfonic acid or a mixture of this and sulfuric acid. A sulfonyl group is sulfided at a molar ratio of 1 to 3 by molar ratio, and a method of using a hydrocarbon-based organic solvent in combination with this esterification agent is used. However, this method also has a disadvantage in that it is inevitable to use a large amount of organic solvents and esterification agents, which requires industrially low economical efficiency and pollution, which requires multiple steps to remove solvents and esterification agents from the reactants.
그외에 일본 특개소 57-7463에서도 상기 일본 특개소 56-142256과 유사한 양의 진한 황산과 유기용매를 사용하는 것을 공개하고 있으나 역시 낮은 경제성과 황산폐수발생이 필연적이었다.In addition, Japanese Patent Application Laid-Open No. 57-7463 discloses the use of a concentrated sulfuric acid and an organic solvent similar to the Japanese Patent Application Laid-Open No. 56-142256, but also low economical efficiency and sulfuric acid wastewater generation were inevitable.
본 발명에서는 이와같은 종래의 단점들을 개선하고자 폐수발생이 전무하며 결정석출단계와 여가단계가 필요없는 공업제조상 유리한 방법을 개발하였다.In the present invention, in order to improve the above disadvantages, there is no waste water generation and developed an advantageous method for industrial manufacturing that does not require a crystal precipitation step and a leisure step.
언급한 바와같이 일반식(Ⅱ)화합물을 제조한 후 이 화합물을 다량의 황산 혹은 유기용매 혼합물에 용해시켜서 고온으로 가열하므로서 가수분해와 에스테르화가 진행되었으며, 이어서 생성된 치환페닐-β-술페이토 에틸술폰을 빙냉수에 넣고 40℃전후의 온도에서 통상 8-10시간 동안 교반한 후 분리하면 습한 케이크모양의 생성물이 수득된다. 이때에 반응용매가 다량 배출되며 또한 습한 목적물을 다시 건조하여야 하는 새로운 공정이 필요하므로 공업적인 면에서 크게 불리한 점으로 지적되고 있으며, 더구나 다량의 산폐수는 심각한 공해물질로 취급되고 있는 것이다.As mentioned above, after the preparation of the compound of formula (II), the compound was dissolved in a large amount of sulfuric acid or an organic solvent mixture and heated to a high temperature, followed by hydrolysis and esterification. Ethyl sulfone was added to ice-cold water and stirred at a temperature of about 40 ° C. for 8-10 hours, followed by separation to obtain a wet cake-like product. At this time, a large amount of the reaction solvent is discharged and a new process for re-drying the wet object is required, which is pointed out as an industrial disadvantage. Furthermore, a large amount of acid wastewater is treated as a serious pollutant.
본 발명은 생성된 페닐-β-히드록시에틸술폰을 몰비로 1.0-1.5인 진한 황산에 첨가하고 반응온도를 80°-100℃로 하여서 로터리 베이커내에서 1-2시간 균질혼합하며 반응시키고, 이어서 130°-150℃로 온도를 상승시킨 후 3-5시간 동안 2차 반응시키면 산폐수의 방출이 전무하며 생성물이 고순도와 고수율로 수득되었다.In the present invention, the resulting phenyl-β-hydroxyethylsulfone is added to concentrated sulfuric acid having a molar ratio of 1.0-1.5, and the reaction temperature is 80 ° -100 ° C, followed by homogeneous mixing for 1-2 hours in a rotary baker, followed by reaction. After the temperature was raised to 130 ° -150 ° C. and the second reaction was performed for 3-5 hours, there was no release of acid wastewater and the product was obtained in high purity and high yield.
그 결과 산폐수 발생을 위한 부차적인 설비와 공정이 필요없게 되며 생성물의 수율도 크게 향상되는 놀라운 결과를 얻었다.The result is a surprising result, which eliminates the need for additional equipment and processes for generating wastewater and greatly improves the yield of the product.
본 발명에서 원료물질로 사용될 수 있는 일반식(Ⅱ)의 화합물은 다음과 같다.Compounds of general formula (II) which can be used as raw materials in the present invention are as follows.
4- (아미노 혹은 아세틸아미노)페닐-β-히드록시 에틸술폰, 2-메톡시-5-(아미노 혹은 아세틸아미노)페닐-β-히드록시 에틸술폰 2-메틸-4-(아미노 혹은 아세틸아미노)-5-메톡시페닐-β-히드록시 에틸술폰, 3-(아미노-혹은 아세틸아미노)-4-메톡시페닐-β-히드록시 에틸술폰 3-아미노페닐-β-히드록시 에틸술폰, 4-(아미노 혹은 아세틸아미노)-2,5-디메톡시페닐-β-히드록시 에틸 술폰, 5-(아미노 혹은 아세틸아미노)-2.4-디메톡시페닐-β-히드록시 에틸 술폰, 3-클로로-4-(아미노 혹은 아세틸아미노)페닐-β-히드록시에틸술폰, 3-(아미노 혹은 아세틸아미노)-4-클로로페닐-β-히드록시에틸 술폰, 2-메틸-5-(아미노 혹은 아세틸아미노)페닐-β-히드록시에틸 술폰, 3-카르복시-4-(아미노 혹은 아세틸아미노)페닐-β-히드록시페닐술폰 3-히드록시-4-(아미노 혹은 아세틸아미노)페닐-β-히드록시페닐술폰 3-아미노-4-술포페닐-β-히드록시에틸 술폰, 2-(아미노 혹은 아세틸아미노)페닐-β-히드록시에틸 술폰 등의 무수물을 이용한다.4- (amino or acetylamino) phenyl-β-hydroxy ethylsulfone, 2-methoxy-5- (amino or acetylamino) phenyl-β-hydroxy ethylsulfone 2-methyl-4- (amino or acetylamino) -5-methoxyphenyl-β-hydroxy ethylsulfone, 3- (amino- or acetylamino) -4-methoxyphenyl-β-hydroxy ethylsulfone 3-aminophenyl-β-hydroxy ethylsulfone, 4- (Amino or acetylamino) -2,5-dimethoxyphenyl-β-hydroxy ethyl sulfone, 5- (amino or acetylamino) -2.4-dimethoxyphenyl-β-hydroxy ethyl sulfone, 3-chloro-4- (Amino or acetylamino) phenyl-β-hydroxyethylsulfone, 3- (amino or acetylamino) -4-chlorophenyl-β-hydroxyethyl sulfone, 2-methyl-5- (amino or acetylamino) phenyl- β-hydroxyethyl sulfone, 3-carboxy-4- (amino or acetylamino) phenyl-β-hydroxyphenylsulfone 3-hydroxy-4- (amino or acetylamino) phenyl-β-hydroxy Anhydrides such as hydroxyphenyl sulfone 3-amino-4-sulfophenyl-β-hydroxyethyl sulfone and 2- (amino or acetylamino) phenyl-β-hydroxyethyl sulfone are used.
본 발명에서 황산에스테르화제로서 진한 황산을 사용하며, 일체의 유기용매 혹은 다른 산류의 병용은 불필요하다.Concentrated sulfuric acid is used as the sulfate esterification agent in the present invention, and any organic solvent or combination of other acids is unnecessary.
이 황산의 사용량은 일반식(Ⅱ)의 화합물내의 β-히드록시에틸 술폰기 1개에 대하여 1-1.5몰비로 하여 첨가하며 발연황산의 경우에는 1-1.3몰비로도 충분히 반응이 완결된다.The amount of sulfuric acid used is added in a 1-1.5 molar ratio to one β-hydroxyethyl sulfone group in the compound of formula (II). In the case of fuming sulfuric acid, the reaction is sufficiently completed even at 1-1.3 molar ratio.
반응온도는 80°-150℃가 적당하며, 1단계에서 80°-100℃로 하고 2단계에서는 130°-150℃로 하여서 반응시키는 것이 적당하다.The reaction temperature is suitably 80 ° -150 ° C., and the reaction temperature is preferably 80 ° -100 ° C. in the first step and 130 ° -150 ° C. in the second step.
본 발명에서 이용하는 반응장치는 통상의 온도제어장치가 부착된 히분식 또는 연속식의 조, 솥, 건조기에서 행하며, 종래의 방법과 달리 황에스테르화제의 전처리가 전혀 필요없다.The reaction apparatus used in the present invention is carried out in a heat-type or continuous tank, a pot, and a dryer equipped with a conventional temperature control device. Unlike the conventional method, no pretreatment of the sulfur esterification agent is required.
이하 본 발명의 실시예를 구체적으로 설명한다.Hereinafter, embodiments of the present invention will be described in detail.
[실시예 1]Example 1
아세타닐리드 술포클로라이드 46.6부를 Na2SO3법에 의하여 환원하고, 이 환원액을 환산첨가로 산성화하여 석출시킨 후 여과하면 아세타닐리드술핀산 44.27부가 얻어진다.46.6 parts of acetanylide sulfochloride are reduced by the Na 2 SO 3 method, and the reduced solution is acidified by addition and precipitated to precipitate 44.27 parts of acetanilide sulfinic acid by filtration.
이 아세타닐리드술핀산 수용액에 히드록시에틸클로라이드 25부를 첨가후 60°-75℃에서 축합반응시켜서 4-아세틸아미노페닐-β-히드록시에틸술폰 42g을 얻었다.25 parts of hydroxyethyl chlorides were added to this acetanilide sulfinic acid aqueous solution, and condensation reaction was carried out at 60 ° -75 ° C to give 42 g of 4-acetylaminophenyl-β-hydroxyethylsulfone.
황산(100%) 10.56부에 4-아세틸아미노페닐-β-히드록시에틸 술폰(99%이상)을 가하여 로터리베이커에서 균질 혼합하여 80°-100℃에서 1시간 동안 반응시키고, 이어서 130°-140℃에서 3-4시간 동안 반응시킨 후 서서히 냉각시키면 1-아미노벤젠-β-술페이토에틸술폰 화합물이 얻어졌다.4-acetylaminophenyl-β-hydroxyethyl sulfone (more than 99%) was added to 10.56 parts of sulfuric acid (100%), homogeneously mixed in a rotary baker and reacted at 80 ° -100 ° C for 1 hour, followed by 130 ° -140 After the reaction at 3 ° C. for 3-4 hours, the mixture was slowly cooled to obtain a 1-aminobenzene-β-sulfatoethylsulfone compound.
수율 99%Yield 99%
[실시예 2]Example 2
황산(100%) 12.74부 중에 상기 실시예 1의 4-아세틸아미노페닐-β-히드록시에틸술폰제조방법과 유사하게 제조된 4-아세틸아미노-2-메틸-5-메톡시페닐-β-히드록시에틸술폰(99%이상) 28.7부를 첨가한 후 로터리 베이커에 넣고 균질혼합하며 90°-100℃에서 1시간동안 반응시키고, 130°-140℃에서 4-5시간 반응시킨 후 냉각시키면 1-아미노-2-메틸-5-메톡시페닐-β-술페이토에틸술폰 34부가 얻어진다.4-acetylamino-2-methyl-5-methoxyphenyl-β-hydroxide prepared in a similar manner to the 4-acetylaminophenyl-β-hydroxyethylsulfone preparation of Example 1 in 12.74 parts of sulfuric acid (100%) Add 28.7 parts of oxyethylsulfone (more than 99%), put it in a rotary baker, homogeneously mix, react for 1 hour at 90 ° -100 ° C, react for 4-5 hours at 130 ° -140 ° C, and cool to 1-amino 34 parts of 2-methyl-5-methoxyphenyl- (beta) -sulfatoethylsulfone are obtained.
수율 98%Yield 98%
[실시예 3]Example 3
상기한 실시예와 동일한 방법으로 다음과 같이 처리하여서 목적물인 치환페닐-β-술페이토에틸술폰을 고순도, 고수율로 얻었다.In the same manner as in the above-described example, the following procedure was performed to obtain a substituted phenyl-β-sulfatoethylsulfone of high purity and high yield.
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| Application Number | Priority Date | Filing Date | Title |
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| KR1019860003680A KR890002400B1 (en) | 1986-05-12 | 1986-05-12 | Process for the preparation of aromatic amine sulfone compounds |
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| KR1019860003680A KR890002400B1 (en) | 1986-05-12 | 1986-05-12 | Process for the preparation of aromatic amine sulfone compounds |
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| KR870011085A KR870011085A (en) | 1987-12-19 |
| KR890002400B1 true KR890002400B1 (en) | 1989-07-03 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| KR1019860003680A KR890002400B1 (en) | 1986-05-12 | 1986-05-12 | Process for the preparation of aromatic amine sulfone compounds |
Country Status (1)
| Country | Link |
|---|---|
| KR (1) | KR890002400B1 (en) |
-
1986
- 1986-05-12 KR KR1019860003680A patent/KR890002400B1/en not_active IP Right Cessation
Also Published As
| Publication number | Publication date |
|---|---|
| KR870011085A (en) | 1987-12-19 |
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