KR100214102B1 - Process for preparation of n-alkyl-beta-hydroxyethylsulfon aniline derivative - Google Patents
Process for preparation of n-alkyl-beta-hydroxyethylsulfon aniline derivative Download PDFInfo
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- KR100214102B1 KR100214102B1 KR1019970003601A KR19970003601A KR100214102B1 KR 100214102 B1 KR100214102 B1 KR 100214102B1 KR 1019970003601 A KR1019970003601 A KR 1019970003601A KR 19970003601 A KR19970003601 A KR 19970003601A KR 100214102 B1 KR100214102 B1 KR 100214102B1
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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
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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
Abstract
본 발명은 N-알킬-β-히드록시 에틸 설폰 아닐린 유도체의 제조 방법에 관한 것이다.The present invention relates to a process for the preparation of N-alkyl-β-hydroxy ethyl sulfone aniline derivatives.
본 발명은 알데히드 또는 케톤류와 β-(히드록시 에틸 설폰)니트로 벤젠 또는 β-(히드록시 에틸 설폰) 아닐린을 알콜 또는 케톤 용매하에서 주기율표의 귀금속 Ⅷ족에 속하는 촉매와 더불어 조촉매를 사용하여 일정 온도 및 일정 압력 하에서 반응시킴으로써 N-알킬-β-히드록시 에틸 설폰 아닐린 유도체의 제조시, 촉매의 선택도와 활성을 극대화시켜 반응시간을 단축시키고, 제조된 N-알킬-β-히드록시 에틸 설폰 아닐린 유도체의 순도를 향상시키는 효과가 있다.The present invention utilizes aldehydes or ketones and β- (hydroxy ethyl sulfone) nitrobenzene or β- (hydroxy ethyl sulfone) aniline in co-catalysts in combination with catalysts belonging to the precious metals Group of the Periodic Table in alcohol or ketone solvents. And N-alkyl-β-hydroxy ethyl sulfone aniline derivatives by reacting under a constant pressure, maximizing the selectivity and activity of the catalyst to shorten the reaction time, and the prepared N-alkyl-β-hydroxy ethyl sulfone aniline derivatives It has the effect of improving the purity.
Description
본 발명은 반응성 제조 염료의 원료로 사용되는 N-알킬-β-히드록시 에틸 설폰 아닐린 유도체의 제조 방법에 관한 것이다.The present invention relates to a process for the preparation of N-alkyl-β-hydroxy ethyl sulfone aniline derivatives used as raw materials for reactive preparation dyes.
종래의 N-알킬-β-히드록시 에틸 설폰 아닐린 유도체의 제조 방법으로는, 알데히드 또는 케톤류와 β-(히드록시 에틸 설폰)니트로 벤젠 또는 β-(히드록시 에틸 설폰) 아닐린을 알콜용매하에서 주기율표의 귀금속 Ⅷ족에 속하는 촉매를 사용하여 수소 첨가 알킬화 반응을 시켜 제조하는 방법이 가장 일반적인 방법이나, 이러한 방법에 따라 반응시킬 경우 반응이 완료되기 까지는 3 내지 10시간 정도의 긴 반응시간이 소요되고 생성물의 순도가 낮은 문제점이 있었다.Conventional methods for producing N-alkyl-β-hydroxy ethyl sulfone aniline derivatives include aldehydes or ketones and β- (hydroxy ethyl sulfone) nitrobenzene or β- (hydroxy ethyl sulfone) aniline in an alcohol solvent. Hydrogenated alkylation using a catalyst belonging to the noble metal group is the most common method, but when reacting according to this method, it takes a long reaction time of about 3 to 10 hours to complete the reaction. There was a problem of low purity.
본 발명은 이와 같은 종래의 문제점을 해결하기 위해 창안된 것으로서, 촉매의 선택도와 활성을 극대화시켜 반응시간을 단축시키고, 제조된 N-알킬-β-히드록시 에틸 설폰 아날린 유도체의 순도를 향상시킨 개선된 N-알킬-β-히드록시 에틸 설폰 아닐린 유도체의 제조 방법을 제공하는데 목적이 있다.The present invention was devised to solve such a conventional problem, which maximizes the selectivity and activity of the catalyst to shorten the reaction time, and improves the purity of the prepared N-alkyl-β-hydroxy ethyl sulfone analin derivative. It is an object to provide an improved process for the preparation of N-alkyl-β-hydroxy ethyl sulfone aniline derivatives.
이러한 목적을 달성하기 위한 본 발명의 N-알킬-β-히드록시 에틸 설폰 아닐린 유도체의 제조 방법은, 알데히드 또는 케톤류와 β-(히드록시 에틸 설폰)니트로 벤젠 또는 β-(히드록시 에틸 설폰)아닐린을 알콜 또는 케톤 용매하에서 주기율표의 귀금속 Ⅷ족에 속하는 촉매와 더불어 조촉매를 사용하여 일정 온도 및 일정 압력하에서 반응시킴을 특징으로 한다.The method for producing an N-alkyl-β-hydroxy ethyl sulfone aniline derivative of the present invention for achieving this object is aldehyde or ketones and β- (hydroxy ethyl sulfone) nitrobenzene or β- (hydroxy ethyl sulfone) aniline Is reacted under constant temperature and pressure using a cocatalyst with a catalyst belonging to the precious metal group of the periodic table in an alcohol or ketone solvent.
본 발명은 알데히드 또는 케톤류와 β-(히드록시 에틸 설폰)니트로 벤젠 또는 β-(히드록시 에틸 설폰)아닐린을 알콜 또는 케톤 용매하에서 주기율표의 귀금속 Ⅷ족에 속하는 촉매와 더불어 조촉매를 사용하여 일정 온도 및 일정 압력하에서 반응시킴으로써 N-알킬-β-히드록시 에틸 설폰 아닐린 유도체의 제조하는 것이다.The present invention relates to the use of aldehydes or ketones and β- (hydroxy ethyl sulfone) nitrobenzene or β- (hydroxy ethyl sulfone) aniline in co-catalysts in combination with a catalyst belonging to the precious metal group of the periodic table in an alcohol or ketone solvent. And N-alkyl-β-hydroxy ethyl sulfone aniline derivatives by reacting under constant pressure.
본 발명에서 이용되는 β-(히드록시 에틸 설폰)니트로 벤젠은 하기의 구조식을 가진 화합물이며,Β- (hydroxyethyl sulfone) nitro benzene used in the present invention is a compound having the following structural formula,
β-(히드록시 에틸 설폰) 아닐린은 하기의 구조식을 가진 화합물이다.β- (hydroxy ethyl sulfone) aniline is a compound having the structure
또한, 알데히드와 케톤은 하기의 구조식을 가지는 화합물을 말한다.In addition, aldehyde and ketone refer to a compound having the following structural formula.
(식 중, R1, R2는 H 또는 CNH2N+1의 화학식을 갖는 알킬기임)(Wherein R 1 , R 2 is an alkyl group having the formula of H or C N H 2N + 1 )
β-(히드록시 에틸 설폰)니트로 벤젠 또는 β-(히드록시 에틸 설폰)아닐린과 알데히드 또는 케톤류의 반응물로서의 반응비는 몰수비로 1:1∼1.5가 바람직하다.As for the reaction ratio of (beta)-(hydroxy ethyl sulfone) nitrobenzene or (beta)-(hydroxy ethyl sulfone) aniline, and an aldehyde or ketones, the reaction ratio is preferably 1: 1 to 1.5 in molar ratio.
예를 들어, 니켈, 팔라듐, 플레티늄 등 주기율표의 귀금속 Ⅷ족에 속하는 원소가 활성화시킨 니켈 등이 바람직하다. 촉매로 사용되는 귀금속 Ⅷ족에 속하는 원소는 β-(히드록시 에틸 설폰)니트로 벤젠 또는 β-(히드록시 에틸 설폰)아닐린 중량의 1.5∼3%를 사용하는 것이 바람직하다.For example, nickel activated by an element belonging to the noble metal group of the periodic table such as nickel, palladium, platinum and the like is preferable. The element belonging to the noble metal Group VIII to be used as the catalyst is preferably 1.5 to 3% by weight of β- (hydroxy ethyl sulfone) nitrobenzene or β- (hydroxy ethyl sulfone) aniline.
활성탄 또는 인산 등이 조촉매로 사용되며 β-(히드록시 에틸 설폰)니트로 벤젠 또는 β-(히드록시 에틸 설폰)아닐린 중량의 0.001∼3%를 사용하는 것이 바람직하다.Activated carbon or phosphoric acid is used as a promoter and it is preferable to use 0.001 to 3% of the weight of β- (hydroxy ethyl sulfone) nitrobenzene or β- (hydroxy ethyl sulfone) aniline.
본 발명에서 상기 구조식 Ⅲ의 알데히드 또는 케톤과 β-(히드록시 에틸 설폰)니트로 벤젠 또는 β-(히드록시 에틸 설폰)아닐린을 알콜 용매를 사용하지 않고 반응물인 상기 구조식 Ⅲ의 알데히드 또는 케톤을 용매로 사용하여 니켈, 팔라듐, 플레티늄 등 주기율표의 귀금속 Ⅷ족에 속하는 촉매와 활성탄 또는 인산등 조촉매를 함께 사용하여 일정 온도 및 일정 압력 하에서 반응시킴으로써 N-알킬-β-히드록시 에틸 설폰 아닐린 유도체를 제조하는 경우에는 반응속도 및 생성물의 순도를 더욱 향상시킬 수 있다.In the present invention, the aldehyde or ketone of the structural formula III and the β- (hydroxy ethyl sulfone) nitrobenzene or the β- (hydroxy ethyl sulfone) aniline are reactants without using an alcohol solvent. N-alkyl-β-hydroxyethyl sulfone aniline derivatives are prepared by reacting under a certain temperature and pressure using a catalyst belonging to a precious metal group of the periodic table such as nickel, palladium, platinum, and the like and a cocatalyst such as activated carbon or phosphoric acid. In this case, the reaction rate and the purity of the product can be further improved.
이하 본 발명을 하기의 실시예를 통해 구체적으로 설명하고자 하나, 이는 본 발명의 실시예에 불과할 뿐 본 발명이 이에 한정되는 것은 아니다.Hereinafter, the present invention will be described in detail with reference to the following examples, which are only examples of the present invention, but the present invention is not limited thereto.
[실시예 1]Example 1
3-β-(히드록시 에틸 설폰)아닐린 70g, 메탄올 200g, 5%의 Pd/C(탄소상의 팔라듐 촉매) 1.56g, 조촉매로서 인산 0.03∼0.05g, 아세트 알데히드 17.6g을 반응기내에 넣은 후 반응기를 밀폐하고 공기를 질소로 치환하였다.70 g of 3-β- (hydroxy ethyl sulfone) aniline, 200 g of methanol, 1.56 g of 5% Pd / C (carbon-based palladium catalyst), 0.03 to 0.05 g of phosphoric acid as a promoter, and 17.6 g of acetaldehyde were added to the reactor, followed by Was sealed and air was replaced with nitrogen.
80∼95℃의 온도, 30~40㎏/㎠의 압력으로 40분동안 환원 알킬화 반응을 진행시켰다. 촉매 여과후 용매를 감압 증류하여 3-β-(히드록시 에틸 설폰)-N-에틸 아닐린을 수득하였으며 전환율은 100%였다.The reduction alkylation reaction was performed for 40 minutes at the temperature of 80-95 degreeC and the pressure of 30-40 kg / cm <2>. After filtration of the catalyst, the solvent was distilled off under reduced pressure to obtain 3-β- (hydroxy ethyl sulfone) -N-ethyl aniline and the conversion was 100%.
HPLC(고압 액체 크로마토그래피)분석 결과, 수득한 3-β-(히드록시 에틸 설폰)-N-에틸 아닐린의 순도는 91%이상이었다.HPLC (high pressure liquid chromatography) analysis showed that the obtained 3-β- (hydroxy ethyl sulfone) -N-ethyl aniline had a purity of 91% or more.
[실시예 2]Example 2
3-β-(히드록시 에틸 설폰)니트로벤젠 70g, 메탄올 200g, 5%의 Pd/C(탄소상의 팔라듐 촉매) 1.56g, 조촉매로서 활성탄 1.56g, 아세트 알데히드 17.4g을 반응기 내에 넣은 후 반응기를 밀폐하고 공기를 질소로 치환하였다.70 g of 3-β- (hydroxy ethyl sulfone) nitrobenzene, 200 g of methanol, 1.56 g of 5% Pd / C (palladium catalyst on carbon), 1.56 g of activated carbon as cocatalyst, 17.4 g of acetaldehyde were added to the reactor and then the reactor was It was sealed and air was replaced with nitrogen.
초기 수소압력은 5-15㎏/㎠, 온도는 80℃ 이하로 반응을 30분간 진행시킨 후 압력을 30∼40㎏/㎠, 온도는 80∼95℃로 올려 40분동안 환원 알킬화 반응을 진행시켰다. 촉매 여과후 용매를 감압 증류하여 3-β-(히드록시 에틸 설폰)-N-에틸 아닐린을 수득하였으며, 총 반응시간은 70분이 소요되었고, 전환율은 100%였다.The initial hydrogen pressure was 5-15 kg / cm 2, the temperature was lowered to 80 ° C. for 30 minutes, and then the pressure was raised to 30-40 kg / cm 2 and the temperature was increased to 80 to 95 ° C. for 40 minutes. . After filtration of the catalyst, the solvent was distilled off under reduced pressure to obtain 3-β- (hydroxy ethyl sulfone) -N-ethyl aniline. The total reaction time was 70 minutes and the conversion was 100%.
HPLC(고압 액테 크로마토그래피)분석 결과, 수득한 3-β-(히드록시 에틸 설폰)-N-에틸 아닐린의 순도는 91% 이상이었다.HPLC (high pressure act chromatography) analysis showed that the obtained 3-β- (hydroxy ethyl sulfone) -N-ethyl aniline had a purity of 91% or more.
[실시예 3]Example 3
3-β-(히드록시 에틸 설폰)아닐린 70g, 메탄올 200g. 5%의 Pd/C(탄소상의 팔라듐 촉매) 1.56g, 조촉매로서 활성탄 0.03∼0.05g, 아세트 알데히드 17.4g을 반응기 내에 넣은 후 반응기를 밀폐하고 공기를 질소로 치환하였다.70 g of 3-β- (hydroxy ethyl sulfone) aniline, 200 g of methanol. 1.56 g of 5% Pd / C (carbon-based palladium catalyst), 0.03 to 0.05 g of activated carbon and 17.4 g of acetaldehyde were put into the reactor, and the reactor was sealed and air was replaced with nitrogen.
초기 수소압력은 5∼15㎏/㎠, 온도는 80℃ 이하로 반응을 20분간 진행시킨 후 압력을 30∼40㎏/㎠, 온도는 80∼95℃로 올려 50분동안 환원 알킬화 반응을 진행시켰다. 촉매 여과후 용매를 감압 증류하여 3-β-(히드록시 에틸 설폰)-N-에틸 아닐린을 수득하였으며 전환율은 100%였다.The initial hydrogen pressure was 5-15 kg / cm 2 and the temperature was 80 ° C. or less for 20 minutes, and then the pressure was raised to 30-40 kg / cm 2 and the temperature was 80-95 ° C. for 50 minutes. . After filtration of the catalyst, the solvent was distilled off under reduced pressure to obtain 3-β- (hydroxy ethyl sulfone) -N-ethyl aniline and the conversion was 100%.
HLPC(고압 액체 크로마토그래피)분석 결과, 수득한 3-β-(히드록시 에틸 설폰)-N-에틸 아닐린의 순도는 90% 이상이었다.As a result of HLPC (high pressure liquid chromatography) analysis, the purity of the obtained 3-β- (hydroxy ethyl sulfone) -N-ethyl aniline was 90% or more.
[실시예 4]Example 4
3-β-(히드록시 에틸 설폰)아닐린 70g, 메탄올 200g, 5%의 Pd/C(탄소상의 팔라듐 촉매) 1.56g, 조촉매로서 활성탄 1.56g, 아세트 알데히드 17.4g을 반응기 내에 넣은 후 반응기를 밀폐하고 공기를 질소로 치환하였다.70 g of 3-β- (hydroxy ethyl sulfone) aniline, 200 g of methanol, 1.56 g of 5% Pd / C (palladium catalyst on carbon), 1.56 g of activated carbon as cocatalyst, 17.4 g of acetaldehyde in the reactor, and then the reactor was sealed. And air was replaced with nitrogen.
80∼95℃의 온도, 30∼40㎏/㎠의 압력으로 40분동안 환원 알킬화 반응을 진행시켰다. 촉매 여과후 용매를 감압 증류하여 3-β-(히드록시 에틸 설폰)-N-에틸 아닐린을 수득하였으며 전환율은 100%였다.The reduction alkylation reaction was performed for 40 minutes at the temperature of 80-95 degreeC and the pressure of 30-40 kg / cm <2>. After filtration of the catalyst, the solvent was distilled off under reduced pressure to obtain 3-β- (hydroxy ethyl sulfone) -N-ethyl aniline and the conversion was 100%.
HPLC(고압 액테 크로마토그래피)분석 결과, 수득한 3-β-(히드록시 에틸 설폰)-N-에틸 아닐린의 순도는 91% 이상이었다.HPLC (high pressure act chromatography) analysis showed that the obtained 3-β- (hydroxy ethyl sulfone) -N-ethyl aniline had a purity of 91% or more.
[실시예 5]Example 5
3-β-(히드록시 에틸 설폰)니트로벤젠 70g, 아세톤 200g, 3%의 Pt/C(탄소상의 플래티늄 촉매) 1.56g, 조촉매로서 인산 0.03∼0.05g을 반응기내에 넣은 후 반응기를 밀폐하고 공기를 질소로 치환하였다.70 g of 3-β- (hydroxy ethyl sulfone) nitrobenzene, 200 g of acetone, 1.56 g of 3% Pt / C (platinum catalyst on carbon), 0.03 to 0.05 g of phosphoric acid as a promoter, the reactor was sealed and air Was replaced with nitrogen.
초기 수소압력은 5∼15㎏/㎠, 온도는 80℃ 이하로 반응을 30분간 진행시킨 후 압력을 30∼40㎏/㎠, 온도는 150℃로 올려 60분동안 환원 알킬화 반응을 진행시켰다. 촉매 여과후 용매를 감압 증류하여 3-β-(히드록시 에틸 설폰)-N-이소프로필 벤젠을 수득하였으며, 총반응시간은 90분이 소요되었고, 전환율은 100%였다.The initial hydrogen pressure was 5 to 15 kg / cm 2, the temperature was 80 ° C. or less for 30 minutes, and then the pressure was raised to 30 to 40 kg / cm 2 and the temperature was 150 ° C. for 60 minutes. After filtration of the catalyst, the solvent was distilled off under reduced pressure to obtain 3-β- (hydroxy ethyl sulfone) -N-isopropyl benzene. The total reaction time was 90 minutes and the conversion was 100%.
HPLC(고압 액테 크로마토그래피)분석 결과, 수득한 3-β-(히드록시 에틸 설폰)-N-이소프로필 벤젠의 순도는 95% 이상이었다.HPLC (high pressure actochromatography) analysis showed that the obtained 3-β- (hydroxy ethyl sulfone) -N-isopropyl benzene was 95% or more in purity.
3-β-(히드록시 에틸 설폰)니트로 벤젠 70g, 아세톤 200g, 3%의 Pt/C(탄소상의 플래티늄 촉매) 1.56g, 조촉매로서 활성탄 1.56g을 반응기내에 넣은 후 반응기를 밀폐하고 공기를 질소로 치환하였다.70 g of 3-β- (hydroxy ethyl sulfone) nitrobenzene, 200 g of acetone, 1.56 g of 3% Pt / C (platinum catalyst on carbon), 1.56 g of activated carbon as a promoter were placed in the reactor, and the reactor was sealed and air was Substituted by
초기 수소압력은 5∼15㎏/㎠, 온도는 80℃ 이하로 반응을 30분간 진행시킨 후 수소압력을 30∼40㎏/㎠, 온도는 150℃로 올려 40분동안 환원 알킬화 반응을 진행시켰다. 촉매 여과후 용매를 감압 증류하여 3-β-(히드록시 에틸 설폰)-N-이소프로필 벤젠을 수득하였으며, 총반응시간은 80분이 소요되었고, 전환율은 100%였다.The initial hydrogen pressure was 5 to 15 kg / cm 2, the temperature was lowered to 80 ° C. for 30 minutes, and then the hydrogen pressure was raised to 30 to 40 kg / cm 2 and the temperature was raised to 150 ° C. for 40 minutes. After filtration of the catalyst, the solvent was distilled off under reduced pressure to obtain 3-β- (hydroxy ethyl sulfone) -N-isopropyl benzene. The total reaction time was 80 minutes and the conversion was 100%.
HPLC(고압 액테 크로마토그래피)분석 결과, 수득한 3-β-(히드록시 에틸 설폰)-N-이소프로필 벤젠의 순도는 95% 이상이었다.HPLC (high pressure actochromatography) analysis showed that the obtained 3-β- (hydroxy ethyl sulfone) -N-isopropyl benzene was 95% or more in purity.
N-알킬-β-히드록시 에틸 설폰 아닐린 유도체 제조시 조촉매를 사용하지 않는 종래의 방법과 조촉매를 사용하는 본원 발명의 제조방법의 소요시간 및 수율 등을 비교하기 위하여 하기의 비교 실험을 실시하였다.The following comparative experiments were carried out to compare the time required and the yield of the conventional method using no cocatalyst in the preparation of N-alkyl-β-hydroxyethyl sulfone aniline derivatives and the preparation method of the present invention using the cocatalyst. It was.
[비교예 1]Comparative Example 1
3-β-(히드록시 에틸 설폰)니트로 벤젠 70g, 메탄올 200g, 5%의 Pd/C(탄소상의 팔라듐 촉매) 1.56g, 아세트 알데히드 17.4g을 반응기내에 넣은 후 반응기를 밀폐하고 공기를 질소로 치환한다.70 g of 3-β- (hydroxy ethyl sulfone) nitrobenzene, 200 g of methanol, 1.56 g of 5% Pd / C (carbon-based palladium catalyst) and 17.4 g of acetaldehyde were placed in the reactor, and the reactor was sealed and air was replaced with nitrogen. do.
초기 수소압력은 5∼15㎏/㎠, 온도는 80℃ 이하로 반응을 30분간 진행시킨 후 수소압력을 30∼40㎏/㎠, 온도는 85∼95℃로 올려 2시간 30분동안 환원 알킬화 반응을 진행시켰다. 촉매 여과후 용매를 감압 증류하여 3-β-(히드록시 에틸 설폰)-N-에틸 아닐린을 수득하였으며, 총반응시간은 3시간이 소요되었고, 전환율은 100%였다. 80∼95℃의 온도, 30∼40㎏/㎠의 압력으로 40분동안 환원 알킬화 반응을 진행시켰다. 촉매 여과후 용매를 감압 증류하여 3-β-(히드록시 에틸 설폰)-N-에틸 아닐린의 순도는 87% 이상이었다.The initial hydrogen pressure was 5-15 kg / cm 2, the temperature was 80 ° C. or lower for 30 minutes, and then the hydrogen pressure was raised to 30-40 kg / cm 2 and the temperature was 85-95 ° C. for 2 hours 30 minutes. Proceeded. After filtration of the catalyst, the solvent was distilled under reduced pressure to obtain 3-β- (hydroxy ethyl sulfone) -N-ethyl aniline, and the total reaction time was 3 hours and the conversion was 100%. The reduction alkylation reaction was performed for 40 minutes at the temperature of 80-95 degreeC and the pressure of 30-40 kg / cm <2>. The solvent was distilled off under reduced pressure after filtration of the catalyst, and the purity of 3-β- (hydroxy ethyl sulfone) -N-ethyl aniline was 87% or more.
[비교예 2]Comparative Example 2
3-β-(히드록시 에틸 설폰)니트로 벤젠 70g, 메탄올 200g, 3%의 Pt/C(탄소상의 플래티늄 촉매) 1.56g, 아세톤 26.7g을 반응기내에 넣은 후 반응기를 밀폐하고 공기를 질소로 치환하였다.70 g of 3-β- (hydroxy ethyl sulfone) nitrobenzene, 200 g of methanol, 1.56 g of 3% Pt / C (platinum catalyst on carbon) and 26.7 g of acetone were placed in the reactor, and the reactor was sealed and air was replaced with nitrogen. .
초기 수소압력은 5∼15㎏/㎠, 온도는 80℃ 이하로 반응을 30분간 진행시킨 후 수소압력을 30∼40㎏/㎠, 온도는 150℃로 올려 4시간 30분동안 환원 알킬화 반응을 진행시켰다. 촉매 여과후 용매를 감압 증류하여 3-β-(히드록시 에틸 설폰)-N-이소프로필 아닐린을 수득하였으며, 총반응시간은 5시간이 소요되었고, 전환율은 98%였다.The initial hydrogen pressure was 5-15 kg / cm 2, the temperature was 80 ° C. or lower for 30 minutes, and then the hydrogen pressure was raised to 30-40 kg / cm 2 and the temperature was 150 ° C. for 4 hours 30 minutes. I was. After filtration of the catalyst, the solvent was distilled off under reduced pressure to obtain 3-β- (hydroxy ethyl sulfone) -N-isopropyl aniline. The total reaction time was 5 hours and the conversion was 98%.
HPLC(고압 액체 크로마토그래피)분석 결과, 수득한 3-β-(히드록시 에틸 설폰)-N-이소프로필 아닐린의 순도는 90∼95%였다.HPLC (high pressure liquid chromatography) analysis showed that the obtained 3-β- (hydroxy ethyl sulfone) -N-isopropyl aniline had a purity of 90 to 95%.
이상에서 상세히 설명한 바와 같은 본 발명은 알데히드 또는 케톤류와 β-(히드록시 에틸 설폰)니트로 벤젠 또는 β-(히드록시 에틸 설폰)아닐린을 알콜 또는 케톤 용매 하에서 주기율표의 귀금속 Ⅷ족에 속하는 촉매와 더불어 조촉매를 사용하여 일정 온도 및 일정 압력하에서 반응시킴으로써 N-일킬-β-히드록시 에틸 설폰 아닐린 유도체 제조시, 반응시간을 현저하게 단축시키고 생성물의 순도 및 수율을 향상시킬 수 있는 효과가 있다.As described in detail above, the present invention provides crude aldehyde or ketones and β- (hydroxy ethyl sulfone) nitrobenzene or β- (hydroxy ethyl sulfone) aniline together with a catalyst belonging to the precious metal group of the periodic table under an alcohol or ketone solvent. By using a catalyst to react at a constant temperature and a constant pressure in the production of N-yl-yl-β-hydroxy ethyl sulfon aniline derivative, there is an effect that can significantly shorten the reaction time and improve the purity and yield of the product.
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