KR0147399B1 - Process for peparing a mixture f 3-dialkylaminomethanesulfonanilides - Google Patents
Process for peparing a mixture f 3-dialkylaminomethanesulfonanilidesInfo
- Publication number
- KR0147399B1 KR0147399B1 KR1019940017650A KR19940017650A KR0147399B1 KR 0147399 B1 KR0147399 B1 KR 0147399B1 KR 1019940017650 A KR1019940017650 A KR 1019940017650A KR 19940017650 A KR19940017650 A KR 19940017650A KR 0147399 B1 KR0147399 B1 KR 0147399B1
- Authority
- KR
- South Korea
- Prior art keywords
- compound
- formula
- reaction
- present
- mixture
- Prior art date
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C303/00—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides
- C07C303/36—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of amides of sulfonic acids
- C07C303/40—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of amides of sulfonic acids by reactions not involving the formation of sulfonamide groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C311/00—Amides of sulfonic acids, i.e. compounds having singly-bound oxygen atoms of sulfo groups replaced by nitrogen atoms, not being part of nitro or nitroso groups
- C07C311/01—Sulfonamides having sulfur atoms of sulfonamide groups bound to acyclic carbon atoms
- C07C311/02—Sulfonamides having sulfur atoms of sulfonamide groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton
- C07C311/08—Sulfonamides having sulfur atoms of sulfonamide groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton having the nitrogen atom of at least one of the sulfonamide groups bound to a carbon atom of a six-membered aromatic ring
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
본 발명은 3-아미노메탄설폰아닐리드를 물 또는 C1-C4 알콜 용매 및 소듐아세테이트 또는 소듐바이카보네이트 등의 염기 존재하에 1 차 알킬화제로 일부 알킬화 반응시키고 계속해서 알킬 그룹이 상이한 2 차 알킬화제로 알킬화 반응을 완료시킴을 특징으로 하여 하기 일반식(Ⅰ)의 3-디알킬아미노메탄설폰아닐리드 혼합물을 제조하는 방법에 관한 것이다.The present invention provides a partial alkylation reaction of 3-aminomethanesulfonanilide with a primary alkylating agent in the presence of water or a C1-C4 alcohol solvent and a base such as sodium acetate or sodium bicarbonate, followed by an alkylation reaction with a secondary alkylating agent having different alkyl groups. Characterizing the completion, it relates to a process for preparing a 3-dialkylaminomethanesulfonanilide mixture of the general formula (I).
Description
본 발명은 분산염료의 중간체로서 유용한 하기 일반식(Ⅰ)의 3-디알킬아미노메탄설폰아닐리드 혼합물의 새로운 제조방법에 관한 것이다.The present invention relates to a new process for the preparation of 3-dialkylaminomethanesulfonanilide mixtures of the general formula (I) below which are useful as intermediates for disperse dyes.
상기식에서,In the above formula,
R1및 R2는 서로 동일하거나 상이하며, C1-C4 알킬을 나타낸다.R 1 and R 2 are the same or different from each other and represent C 1 -C 4 alkyl.
상기 일반식(Ⅰ)의 3-디알킬아미노메탄설폰아닐리드는 공지의 화합물로서 R1및 R2가 서로 동일한 화합물의 제조방법은 대한민국특허 제 44030 호에 자세히 기술되어 있으며, 이와 유사한 화합물, 즉 3-디알킬아미노메탄설폰아닐리드 등의 제조방법은 동독특허공개 제 234,415 호, 일본특허공개 소 59-216,854 호, 일본특허공개 소 60-08,245호, 일본특허공개 소 57-38,755호, 일본특허공개 소 56,135-451 호 등에 기재되어 있다.3-dialkylaminomethanesulfonanilide of the general formula (I) is a known compound and a method for preparing a compound in which R 1 and R 2 are the same is described in detail in Korean Patent No. 44030, and a similar compound, that is, 3 -Dialkylaminomethanesulfonanilide and the like are prepared in East German Patent Publication No. 234,415, Japanese Patent Publication No. 59-216,854, Japanese Patent Publication No. 60-08,245, Japanese Patent Publication No. 57-38,755, and Japanese Patent Publication 56,135-451, and the like.
상기 문헌중에서 본 발명의 목적 화합물중 R1및 R2가 서로 동일한 화합물의 제조 방법을 권리로 청구하고 있는 대한민국특허 제 44030 호에서는 하기 구조식(Ⅱ)의 화합물의 출발물질로 하여 방향족 유기용매의 존재하에 액체 유기염기를 사용함으로써 98 내지 99.6% 의 순도와 90 내지 95%의 수율로 목적 화합물을 제조하고 있는데,Korean Patent No. 44030, in which the R 1 and R 2 are claimed as a right method for the preparation of the same compound among the target compounds of the present invention, discloses the presence of an aromatic organic solvent as a starting material of the compound represented by the following formula (II). By using a liquid organic base under the purity of 98 to 99.6% and 90 to 95% yield of the desired compound,
이 발명은 유기용제 및 유기염기를 사용하므로, 경제적인 면에서 사용 원료의 가격이 고가여서 생산단가가 높아지고, 유기용제를 분리해서 폐기 처분해야 하는 번거로움이 있으며, 유기용제 및 유기염기로 인한 냄새가 심하고 화재의 위험이 있는 등 작업환경이 좋지 않은 문제점이 있다.Since the present invention uses organic solvents and organic bases, the cost of raw materials is high in terms of economics, and production costs are high, and there is a hassle to separate and dispose of organic solvents and odors caused by organic solvents and organic bases. There is a problem that the working environment is not good, such as severe and risk of fire.
또한, 본 발명에 따른 목적 화합물의 유사화합물에 대한 제조 방법을 제공하고 있는 기타의 문헌들에는 반응용매로서 물 또는 초산을 사용함으로써 알킬화제인 디에틸설페이트와 구조식(Ⅱ)의 유사화합물을 반응시켜 80 내지 95%의 수율로 일반식(Ⅰ)의 유사화합물을 제조하는 방법이 기술되어 있다.In addition, other documents that provide a preparation method for analogous compounds of the desired compound according to the present invention, by using water or acetic acid as a reaction solvent to react the analogous compound of formula (II) with the alkylating agent diethylsulfate 80 Processes for preparing analogous compounds of formula (I) in yields of from 95% are described.
그러나, 상기의 방법들은 본 발명의 목적 화합물과 동일한 화합물이 아닌 그의 유사화합물을 제조하는 방법에 관한 것일 뿐아니라, 대량 취급시 작업이 용이하지 않고 잔류량이 폐수에 유입되어 환경문제를 야기시키는 등의 단점이 있으며, 특히 동독특허공개 제 234,415 호, 일본특허공개 소 59-216,854 호, 일본특허공개 소 57-38,755호, 일본특허공개 소 56,135-451 호 등에 공지된 제조 방법에서는 반응중에 생성되는 산을 잡아주고 친핵성도를 높여주기 위하여 수산화나트륨과 같은 염기를 사용하는데, 이때 수산화나트륨의 염기도가 너무 높아 설폰아미드기의 질소가 알킬화된 부산물이 생성되어 목적 화합물의 수율이 낮아지므로 바람직하지 못하다.However, the above methods not only relate to a method for preparing a similar compound but the same compound as the target compound of the present invention. There are disadvantages, and in particular, the production methods known from East German Patent Publication No. 234,415, Japanese Patent Publication No. 59-216,854, Japanese Patent Publication No. 57-38,755, Japanese Patent Publication No. 56,135-451, etc. A base such as sodium hydroxide is used to hold and increase the nucleophilicity, which is not preferable because the basicity of sodium hydroxide is so high that the byproduct of the alkylation of nitrogen of the sulfonamide group is generated, which lowers the yield of the target compound.
한편, 상기의 공지 방법에 의해 제조된 일반식(Ⅰ)의 화합물을 중간체로 하여 제조되는 염료는 두 종류 이상의 혼합물로 이루어져야만 제기능을 발휘할 수 있는데, 공지 방법에 의해서는 언제나 R1및 R2가 동일한 한가지 종류의 화합물만이 제조되므로 3-디알킬아미노메탄설폰아닐리드, 3-디프로필아미노메탄설폰아닐리드 등을 개별적으로 합성하고 염료 제조시 혼합해서 사용해야 하는 번거로움이 있으며, 또한 이와 같은 방법을 통해 염료를 제조하게 되면 다단계 공정으로 제조시간이 길어지고 복잡해져, 그 결과 전체적인 제조 수율이 감소되는 단점을 나타내게 된다.On the other hand, the dye prepared by the intermediate of the compound of formula (I) prepared by the above known method can be functional only by consisting of two or more kinds of mixtures, by the known method is always R 1 and R 2 Since only one kind of compound having the same compound is prepared, 3-dialkylaminomethanesulfonanilide, 3-dipropylaminomethanesulfonanilide, and the like have to be synthesized separately and mixed to prepare dyes. When the dye is prepared through the multi-step process, the manufacturing time becomes long and complicated, and as a result, the overall manufacturing yield is reduced.
이에 본 발명자들은 이러한 공지 방법들의 단점을 개선하고 보다 효과적인 제조 방법을 개발하기 위하여 연구를 거듭한 결과, 물 또는 C1-C4 알콜용매의 존재하에 소듐아세테이트 또는 소듐바이카보네이트를 염기로 사용하고 구조식(Ⅱ)의 화합물을 서로 상이한 알킬화제와 1 차, 2 차에 걸쳐 반응시켜 본 발명에 따른 목적 화합물을 제조하면 상기의 문제점을 해결할 수 있을 뿐아니라, 공정이 간편하고 생산성이 증가되는 일단계 공정만으로 3-디알킬아미노메탄설폰아닐리드, 3-디프로필아미노메탄설폰아닐리드, 및 3-에틸프로필아미노메탄설폰아닐리드의 혼합물을 제조할 수 있다는 획기적인 사실을 발견하고 본 발명을 완성하게 되었다.Accordingly, the present inventors have conducted research to improve the disadvantages of the known methods and to develop a more effective manufacturing method, using sodium acetate or sodium bicarbonate as a base in the presence of water or a C1-C4 alcohol solvent and the structural formula (II). By reacting the compounds of) with different alkylating agents in the primary and secondary phases to prepare the target compound according to the present invention, the above problems can be solved, and the process is simple and the productivity is increased in only one step. The present invention has been completed by discovering the groundbreaking fact that a mixture of dialkylaminomethanesulfonanilide, 3-dipropylaminomethanesulfonanilide, and 3-ethylpropylaminomethanesulfonanilide can be prepared.
특히, 본 발명의 방법에 따라 생성된 목적 화합물의 혼합물중 3-에틸프로필아미노메탄설폰아닐리드는 염료 제조시 수율을 증가시키는 우수한 물성을 가진 염료 중간체이다.In particular, 3-ethylpropylaminomethanesulfonanilide in the mixture of the desired compounds produced according to the process of the invention is a dye intermediate with excellent physical properties which increases the yield in dye preparation.
본 발명을 더욱 구체적으로 설명하면 다음과 같다.The present invention is explained in more detail as follows.
본 발명은 먼저 구조식(Ⅱ)의 3-아미노메탄설폰아닐리드를 물 또는 C1-C4 알콜 용매에 분산 또는 용해시킨 후, 소듐아세테이트 또는 소듐바이카보네이트 등의 염기 존재하에, 1 차 알킬화제로 일부 알킬화시키고 계속해서 알킬 그룹이 상이한 2차 알킬화제로 알킬화 반응을 완료시켜 목적 화합물인 일반식(Ⅰ)의 화합물의 혼합물을 제조하는 방법을 제공함을 목적으로 한다.The present invention first disperses or dissolves 3-aminomethanesulfonanilide of formula (II) in water or a C1-C4 alcohol solvent, and then partially alkylates with a primary alkylating agent in the presence of a base such as sodium acetate or sodium bicarbonate and continues. It is an object of the present invention to provide a method for preparing a mixture of a compound of general formula (I) which is a target compound by completing an alkylation reaction with a secondary alkylating agent having different alkyl groups.
이때, 출발 물질로 사용되는 구조식(Ⅱ)의 3-아미노메탄설폰아닐리드의 제조방법은 이미 공지되어 있는 것으로서 독일연방공화국 특허공개 제 3,124,009 호 및 제 3,124,010 호, 대한민국특허 제 45641 호, 및 대한민국특허 제 45707 호 등에 자세히 기술되어 있다.At this time, the method for preparing 3-aminomethanesulfonanilide of formula (II), which is used as a starting material, is already known, and the Republic of Germany Patent Publication Nos. 3,124,009 and 3,124,010, Korean Patent No. 45641, and Korean Patent No. 45707 et al.
본 발명에서 사용할 수 있는 알킬화제로는 알킬할라이드, 디알킬설페이트, 알킬메탄설포네이트, 알킬 p-톨루엔설포네이트 등의 화합물을 들 수 있는데, 알킬 그룹의 탄소수는 1 내지 4 이며, 알킬할라이드에서 할라이드는 염소, 브롬, 요오도인 것이 바람직하다.Examples of the alkylating agent that can be used in the present invention include compounds such as alkyl halide, dialkyl sulfate, alkylmethanesulfonate, alkyl p-toluenesulfonate, and the alkyl group has 1 to 4 carbon atoms. Preference is given to chlorine, bromine and iodo.
이와 같은 알킬화제를 사용하여 본 발명에서 목적하는 3-디알킬아미노메탄설폰아닐리드 혼합물을 제조하기 위해서는 서로 다른 알킬 그룹을 함유하는 알킬화제와 1, 2 차에 걸쳐 반응시키는 것이 필요하다. 이때 1 차 알킬화제로는 다른 알킬화제에 비해 반응성이 좀 떨어지는 알킬할라이드를 사용하고 2 차 알킬화제로는 그 이외의 반응성이 큰 화합물을 사용하며, 통상 구조식(Ⅱ)의 화합물을 기준으로 할 때 알킬화제의 사용량은 1 차 알킬화제 및 2 차 알킬화제를 각각 0.2 내지 3 당량배 사용하는 것이 적당한데, 단 1, 2 차 알킬화제의 총량은 2 당량배 이상이 되어야 한다. 즉, 본 발명에서는 1 차로 알킬할라이드를 0.2 내지 3 당량배 가하고 70 내지 75℃ 로 승온한 후, 고성능 액체크로마토그래피로 분석하여 구조식(Ⅱ)의 화합물이 40% 미만 존재할 때 냉각시켜 반응을 정지시키고, 2 차로 디알킬설페이트, 알킬메탄설포네이트, 알킬 p-톨루엔설포네이트 중에서 선택된 알킬화제를 0.2 내지 3 당량배 서서히 적가하고 70 내지 120℃ 로 승온하여 반응을 완료시킴으로써 혼합물중 서로 알킬 그룹이 상이한 화합물들의 조성비가 일정한 범위내로 들어오게끔 조절할 수 있으며, 생성된 세종류의 일반식(Ⅰ)의 화합물은 각가 8에서 80% 범위에 들어온다.In order to prepare the 3-dialkylaminomethanesulfonanilide mixture desired in the present invention using such an alkylating agent, it is necessary to react first and secondly with alkylating agents containing different alkyl groups. In this case, an alkyl halide having less reactivity than other alkylating agents is used as the primary alkylating agent, and other highly reactive compounds are used as the secondary alkylating agent, and the amount of alkylating agent is generally used based on the compound of formula (II). It is appropriate to use 0.2 to 3 equivalents of the primary and secondary alkylating agents, respectively, provided that the total amount of the primary and secondary alkylating agents is at least 2 equivalents. That is, in the present invention, 0.2 to 3 equivalents of the alkyl halide is first added, and the temperature is increased to 70 to 75 ° C., and then analyzed by high performance liquid chromatography to stop the reaction by cooling when less than 40% of the compound of formula (II) is present. Secondly, an alkylating agent selected from dialkylsulfate, alkylmethanesulfonate, and alkyl p-toluenesulfonate is slowly added dropwise into an amount of 0.2 to 3 equivalents and the temperature is raised to 70 to 120 ° C. to complete the reaction, thereby reducing the The composition ratio can be adjusted to fall within a certain range, and the three kinds of compounds of the general formula (I) are in the range of 8 to 80%.
또한, 구조식(Ⅱ)의 화합물을 기준으로 할 때 염기는 1 내지 4.5 당량배 사용하고, 용매는 1 내지 10 중량배 사용하는 것이 바람직하며, 반응의 진행 정도를 고성능 액체크로마토그래피로 분석하여 구조식(Ⅱ)의 화합물이 0 에서 1% 이하로 존재하는 경우 반응이 완료되었음을 확인한다.Further, based on the compound of formula (II), it is preferable to use 1 to 4.5 equivalent times of the base, 1 to 10 times the weight of the solvent, and analyze the progress of the reaction by high performance liquid chromatography. When the compound of II) is present at 0 to 1% or less, confirm that the reaction is complete.
이상 설명한 바와 같은 본 발명에 의하여 혼합 제조된 일반식(Ⅰ)의 화합물로 목적하는 염료를 제조하면 기존의 방법으로 합성하여 염료 제조시 혼합 사용하는 방법보다 수율이 5 내지 15% 증가하는 장점을 가지고 있으며, 본 발명에서 염기로 사용되는 소듐아세테이트 및 소듐바이카보네이트는 반응성이 온화하여 부산물이 생성되지 않으므로 목적 화합물의 제조 수율을 높일 수 있는 장점이 있다.When the desired dye is prepared from the compound of formula (I) mixed and prepared according to the present invention as described above, the yield is increased by 5 to 15% compared to the method of mixing and synthesizing by a conventional method. In addition, the sodium acetate and sodium bicarbonate used as a base in the present invention has the advantage that the by-products are not generated because the reactivity is mild to increase the production yield of the target compound.
이하, 본 발명을 실시예에 좀더 구체적으로 설명한다. 그러나, 본 발명이 하기 실시예에만 한정되는 것은 아니다.Hereinafter, the present invention will be described in more detail with reference to Examples. However, the present invention is not limited only to the following examples.
[실시예 1]Example 1
3-디알킬아미노메탄설폰아닐리드, 3-에틸프로필아미노메탄설폰아닐리드, 3-디프로필아미노메탄설폰아닐리드의 제조Preparation of 3-dialkylaminomethanesulfonanilide, 3-ethylpropylaminomethanesulfonanilide, 3-dipropylaminomethanesulfonanilide
3-아미노메탄설폰아닐리드 18.6g을 프로판올 30g에 분산시키고, 여기에 소듐아세테이트 20g 및 프로필브로마이드 16.40g을 가하고 70내지 75℃로 승온하여 동온도에서 2 내지 3 시간동안 교반시켰다. 고성능 액체크로마토그래피로 확인하여 3-아미노메탄설폰아닐리드가 30% 미만 존재하면 40℃로 냉각시키고, 디에틸설페이트 38.34g을 2 내지 3 시간동안 적가한 다음, 80 내지 90℃로 승온하여 반응을 완결시켰다(수율: 98%, 순도: 3-디에틸아미노메탄설폰아닐리드 25%, 3-에틸프로필아미노메탄설폰아닐리드 59%, 3-디프로필아미노메탄설폰아닐리드 15%). 분석은 아세트니트릴 70% 및 물 30%의 혼합액을 전개용매로 하는 C-18μ-Bondapak 로 분리하고 254㎚에서 측정함으로써 수행하였다.18.6 g of 3-aminomethanesulfonanilide was dispersed in 30 g of propanol, and 20 g of sodium acetate and 16.40 g of propyl bromide were added thereto, and the temperature was raised to 70 to 75 ° C. and stirred for 2 to 3 hours at the same temperature. When high-performance liquid chromatography confirmed that less than 30% of 3-aminomethanesulfonanilide was cooled to 40 ° C, 38.34 g of diethylsulfate was added dropwise for 2 to 3 hours, and then heated to 80 to 90 ° C to complete the reaction. (Yield: 98%, Purity: 3-diethylaminomethanesulfonanilide 25%, 3-ethylpropylaminomethanesulfonanilide 59%, 3-dipropylaminomethanesulfonanilide 15%). The analysis was carried out by separating a mixed solution of 70% acetonitrile and 30% water with C-18μ-Bondapak as a developing solvent and measuring at 254 nm.
[실시예 2]Example 2
3-디에틸아미노메탄설폰아닐리드, 3-에틸부틸아미노메탄설폰아닐리드, 3-디부틸아미노메탄설폰아닐리드의 제조Preparation of 3-diethylaminomethanesulfonanilide, 3-ethylbutylaminomethanesulfonanilide, 3-dibutylaminomethanesulfonanilide
3-아미노메탄설폰아닐리드 18.6g을 프로판올 30g에 분산시키고, 여기에 소듐아세테이트 20g 및 부틸브로마이드 18.30g을 가하고 85 내지 95℃로 승온하여 동온도에서 2 내지 3 시간동안 교반시켰다. 고성능 액체크로마토그래피로 확인하여 3-아미노메탄설폰아닐리드가 30% 미만 존재하면 40℃로 냉각시키고, 디에틸설페이트 38.34g을 2 내지 3 시간동안 적가한 다음, 80 내지 90℃로 승온하여 반응을 완결시켰다(수율: 97.5%, 순도: 3-디에틸아미노메탄설폰아닐리드 28%, 3-에틸부틸아미노메탄설폰아닐리드 63%, 3-디부틸아미노메탄설폰아닐리드 8%), 분석은 실시예 1에 기술되어 있는 방법과 동일하게 실시하였다.18.6 g of 3-aminomethanesulfonanilide was dispersed in 30 g of propanol, and 20 g of sodium acetate and 18.30 g of butyl bromide were added thereto, and the temperature was raised to 85 to 95 ° C and stirred for 2 to 3 hours at the same temperature. When high-performance liquid chromatography confirmed that less than 30% of 3-aminomethanesulfonanilide was cooled to 40 ° C, 38.34 g of diethylsulfate was added dropwise for 2 to 3 hours, and then heated to 80 to 90 ° C to complete the reaction. (Yield: 97.5%, Purity: 3-diethylaminomethanesulfonanilide 28%, 3-ethylbutylaminomethanesulfonanilide 63%, 3-dibutylaminomethanesulfonanilide 8%), analysis as described in Example 1 It carried out similarly to the method shown.
[실시예 3]Example 3
3-디에틸아미노메탄설폰아닐리드, 3-에틸프로필아미노메탄설폰아닐리드, 3-디프로필아미노메탄설폰아닐리드의 제조Preparation of 3-diethylaminomethanesulfonanilide, 3-ethylpropylaminomethanesulfonanilide, 3-dipropylaminomethanesulfonanilide
3-아미노메탄설폰아닐리드 18.6g을 물 70g에 분산시키고, 여기에 소듐바이카보네이트 35g 및 프로필브로마이드 16.40g을 가하고 70 내지 75℃로 승온하여 동온도에서 2 내지 3 시간동안 교반시켰다. 고성능 액체크로마토그래피로 확인하여 3-아미노메탄설폰아닐리드가 30% 미만 존재하면 40℃로 냉각시키고, 디에틸설페이트 40g을 2 내지 3 시간동안 적가한 다음, 60 내지 65℃에서 2 내지 4 시간동안 반응을 진행시키고, 다시 85 내지 90℃로 승온하여 반응을 완결시켰다(수율: 98%, 순도: 3-디에틸아미노메탄설폰아닐리드 26%, 3-에틸프로필아미노메탄설폰아닐리드 54%, 3-디프로필아미노메탄설폰아닐리드 19%). 분석은 실시예 1에 기술되어 있는 방법과 동일하게 실시하였다.18.6 g of 3-aminomethanesulfonanilide was dispersed in 70 g of water, and 35 g of sodium bicarbonate and 16.40 g of propyl bromide were added thereto, and the temperature was raised to 70 to 75 ° C and stirred for 2 to 3 hours at the same temperature. When confirmed by high performance liquid chromatography, when 3-aminomethanesulfonanilide is present in less than 30%, it is cooled to 40 ° C, and 40g of diethylsulfate is added dropwise for 2 to 3 hours, followed by reaction for 2 to 4 hours at 60 to 65 ° C. The reaction was completed, and the reaction was completed by raising the temperature to 85 to 90 ° C (yield: 98%, purity: 3-diethylaminomethanesulfonanilide 26%, 3-ethylpropylaminomethanesulfonanilide 54%, 3-dipropyl). Aminomethanesulfonanilide 19%). The analysis was carried out in the same manner as described in Example 1.
[비교예 1]Comparative Example 1
공지의 방법에 의하여 제조된 3-디에틸아미노메탄설폰아닐리드 24.20g을 2,6-디브로모-4-메틸아닐린 26.50g과 통상적인 방법으로 디아조, 커플링하여 49.20g의 3-메탄설폰아미도-4-(2',6'-디브로모-4'-메틸페닐아조)-N,N-디에틸아닐린을 수득하고 계속하여 이를 N,N-디메틸포름아미드 중에서 Zn(CN)211.20g 및 CuCN 0.9g을 사용하여 시안화하여 3-메탄설폰아미도-4-(2',6'-디시아노-4'-메틸페닐아조)-N,N-디에틸아닐린 염료를 31.46g (수율: 80%) 수득하였다. 또한 공지 방법에 의하여 제조된 3-디프로필아미노메탄설폰아닐리드 27g을 2,6-디브로모-4-메틸아닐린 26.50g과 통상적인 방법으로 디아조, 커플링하여 51.87g의 3-메탄설폰아미노-4-(2',6'-디브로모-4'-메틸페닐아조)-N,N-디프로필아닐린을 수득하고, 이를 N,N-디메틸포름아미드 중에서 Zn(CN)211.20g 및 CuCN 0.9g을 사용하여 시안화하여 3-메탄설폰아미도-4-(2',6'-디시아노-4'-메틸페닐아조)-N,N-디프로필아닐린 염료를 30.23g (수율: 72%) 수득하였다.24.20 g of 3-diethylaminomethanesulfonanilide prepared by a known method was combined with 26.50 g of 2,6-dibromo-4-methylaniline in a diazo by a conventional method to couple 49.20 g of 3-methanesulfone Amido-4- (2 ', 6'-dibromo-4'-methylphenylazo) -N, N-diethylaniline was obtained, followed by Zn (CN) 2 11.20 in N, N-dimethylformamide. 31.46 g of 3-methanesulfonamido-4- (2 ', 6'-dicyano-4'-methylphenylazo) -N, N-diethylaniline dye, cyanated using 0.9 g and CuCN (yield: 80%) was obtained. In addition, 27.3-g of 3-dipropylaminomethanesulfonanilide prepared by a known method was combined with 26.50 g of 2,6-dibromo-4-methylaniline and diazo in a conventional manner to couple 51.87g of 3-methanesulfonamino 4- (2 ', 6'-dibromo-4'-methylphenylazo) -N, N-dipropylaniline was obtained, which was 11.20 g of Zn (CN) 2 and CuCN in N, N-dimethylformamide. Cyanation using 0.9 g gives 30.23 g of 3-methanesulfonamido-4- (2 ', 6'-dicyano-4'-methylphenylazo) -N, N-dipropylaniline dye (yield: 72%) Obtained.
상기의 염료를 75%와 25%의 비율로 혼합하여 목적하는 염료 화합물을 제조하였다(평균수율: 78%).The dye was mixed at a ratio of 75% and 25% to prepare a desired dye compound (average yield: 78%).
[비교예 2]Comparative Example 2
실시예 1에 의하여 제조된 3-디에틸아미노메탄설폰아닐리드, 3-에틸프로필아미노메탄설폰아닐리드, 3-디프로필아미노메탄설폰아닐리드의 혼합물 25.46g을 2,6-디브로모-4-메틸아닐린 26.50g과 통상적인 방법으로 디아조, 커플링하여 3 종류의 혼합염료 중간체를 50.40g 수득하고, 계속하여 이를 N,N-디메틸포름아미드 중에서 Zn(CN)211.20g 및 CuCN 0.9g을 사용하여 시안화하여 3-메탄설폰아미도-4-(2',6'-디시아노-4'-메틸페닐아조)-N,N-디에틸아닐린, 3-메탄설폰아미도-4-(2',6'-디시아노-4'-메틸페닐아조)-N-에틸-N-프로필아닐린, 3-메탄설폰아미도-4-(2',6'-디시아노-4'-메틸페닐아조)-N,N-디프로필아닐린 혼합 염료를 36.40g (평균수율: 90%) 수득하였다.25.46 g of a mixture of 3-diethylaminomethanesulfonanilide, 3-ethylpropylaminomethanesulfonanilide and 3-dipropylaminomethanesulfonanilide prepared according to Example 1 was added to 2,6-dibromo-4-methylaniline. Diazo and coupling with 26.50 g in a conventional manner yielded 50.40 g of three mixed dye intermediates, which were subsequently obtained using 11.20 g of Zn (CN) 2 and 0.9 g of CuCN in N, N-dimethylformamide. Cyanated to 3-Methanesulfonamido-4- (2 ', 6'-dicyano-4'-methylphenylazo) -N, N-diethylaniline, 3-methanesulfonamido-4- (2', 6 '-Dicyano-4'-methylphenylazo) -N-ethyl-N-propylaniline, 3-methanesulfonamido-4- (2', 6'-dicyano-4'-methylphenylazo) -N, N 36.40 g (average yield: 90%) of dipropylaniline mixed dye were obtained.
Claims (6)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR1019940017650A KR0147399B1 (en) | 1994-07-21 | 1994-07-21 | Process for peparing a mixture f 3-dialkylaminomethanesulfonanilides |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR1019940017650A KR0147399B1 (en) | 1994-07-21 | 1994-07-21 | Process for peparing a mixture f 3-dialkylaminomethanesulfonanilides |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| KR960004318A KR960004318A (en) | 1996-02-23 |
| KR0147399B1 true KR0147399B1 (en) | 1998-08-17 |
Family
ID=19388506
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| KR1019940017650A KR0147399B1 (en) | 1994-07-21 | 1994-07-21 | Process for peparing a mixture f 3-dialkylaminomethanesulfonanilides |
Country Status (1)
| Country | Link |
|---|---|
| KR (1) | KR0147399B1 (en) |
-
1994
- 1994-07-21 KR KR1019940017650A patent/KR0147399B1/en not_active IP Right Cessation
Also Published As
| Publication number | Publication date |
|---|---|
| KR960004318A (en) | 1996-02-23 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| KR0147399B1 (en) | Process for peparing a mixture f 3-dialkylaminomethanesulfonanilides | |
| JPH0480898B2 (en) | ||
| IL106669A (en) | Synthesis of bicyclic aromatic sulfonic acids sulfonyl chlorides and sulfonamides | |
| JPH0759671B2 (en) | Method for producing cationic hydrazone dye | |
| KR0143864B1 (en) | Process for preparing 3-dialkylamino-methanesulfonanilide | |
| KR950001685B1 (en) | Process for the preparation of antraquinone derivatives use reactivity dye | |
| JP3287437B2 (en) | Method for producing dioxazine compound | |
| DE2536051C3 (en) | Process for the preparation of anthraquinone dyes | |
| US4943655A (en) | Salt of 5-acetyl-2-alkylbenzenesulfonic acid | |
| US4618721A (en) | Process for the preparation of nitrodiphenyl disulfides | |
| KR970001535B1 (en) | Process for the preparation of n-£3-{(2-cyanoethyl)-2-prophenylamino}-4 substituted phenyl| acetamide | |
| KR0161208B1 (en) | Process for preparing anthraquinone red disperse dye | |
| KR0181635B1 (en) | Process for preparation of 1-thianaphthen-3-one 1,1-dioxide | |
| EP0731089B1 (en) | Aniline derivatives | |
| JPH08245898A (en) | Water-soluble fiber-reactive anthraquinone compound | |
| FR2489317A1 (en) | ||
| JPH04308538A (en) | Halogenation | |
| JPH0676360B2 (en) | Synthesis of 4-alkoxy- and 4-aryloxy-3-acylaminophenyl carbonates | |
| KR920002916B1 (en) | Purification of 2,4-dinitro chrolo benzene | |
| JPH051023A (en) | Production of alkanesulfonanilide derivative | |
| KR0174333B1 (en) | Process for preparing fluoran dye | |
| KR910003636B1 (en) | Process for the preparation of benzophenon oxime compounds | |
| KR970000143B1 (en) | Process for the preparation of 2,5-substituted-n,n-di-2-propenyl-benzeneamine | |
| JPS5929070B2 (en) | 3-Amino-4-carbalkoxybenzoic acid-4'-phenoxyanilide and its production and use method | |
| KR0185127B1 (en) | Process for preparation of n-(2-amino-3,5-dibromobenzoyl)-n'-(alkansulfonyl)hydrazide |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A201 | Request for examination | ||
| E902 | Notification of reason for refusal | ||
| E701 | Decision to grant or registration of patent right | ||
| GRNT | Written decision to grant | ||
| FPAY | Annual fee payment |
Payment date: 20010821 Year of fee payment: 4 |
|
| LAPS | Lapse due to unpaid annual fee |