KR930006943B1 - Method for producing p-phenylen diamine - Google Patents
Method for producing p-phenylen diamine Download PDFInfo
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- KR930006943B1 KR930006943B1 KR1019900022051A KR900022051A KR930006943B1 KR 930006943 B1 KR930006943 B1 KR 930006943B1 KR 1019900022051 A KR1019900022051 A KR 1019900022051A KR 900022051 A KR900022051 A KR 900022051A KR 930006943 B1 KR930006943 B1 KR 930006943B1
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- phenylene
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- biscarbamic
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C211/00—Compounds containing amino groups bound to a carbon skeleton
- C07C211/43—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton
- C07C211/44—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton having amino groups bound to only one six-membered aromatic ring
- C07C211/49—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton having amino groups bound to only one six-membered aromatic ring having at least two amino groups bound to the carbon skeleton
- C07C211/50—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton having amino groups bound to only one six-membered aromatic ring having at least two amino groups bound to the carbon skeleton with at least two amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton
- C07C211/51—Phenylenediamines
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
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Abstract
내용 없음.No content.
Description
본 발명은 호프만 전위 (Hofmann rearrangement)의 변형된 조건으로서 DMF (디메틸포름아미드)용매에서 NBS (N-브로모숙신아미드)와 메탄올, Hg(OAc)2을 사용하여 테레프탈아마이드를 1, 4-페닐렌 비스-카바민산, 알킬 에스테르로 전위 시킨 후, 1, 4-페닐렌 비스-카바민산, 알킬 에스테르를 금속 촉매하에서 파라 페닐렌 디아민으로 생성시키는 제조방법에 관한 것이다.The present invention relates to terephthalamide 1,4-phenyl using NBS (N-bromosuccinamide), methanol and Hg (OAc) 2 in a DMF (dimethylformamide) solvent as modified conditions of the Hofmann rearrangement. The present invention relates to a process for producing 1,4-phenylene bis-carbamic acid and alkyl esters with para phenylene diamine under a metal catalyst after being transposed to ethylene bis-carbamic acid and alkyl esters.
이 방법은 종래의 기술로 호프만 전위를 시킬 경우 독성이나 조작에서 어려운 할로겐이나 불안정한 하이포할라이트를 사용하는 대신 NBS와 Hg(OAc)2을 사용함으로써 조작이 용이하며 온화한 조건(중성)에서 반응을 시킬 수 있는 장점이 있다.This method is easy to operate by using NBS and Hg (OAc) 2 instead of using halogen or unstable hypohalite, which is difficult to toxic or difficult to operate when Hoffman potential is applied according to the conventional technique, and reacts under mild conditions (neutral). There are advantages to it.
또한, Hg(OAc)2을 회수하여 재사용할 수 있어 경제적으로 1, 4-페닐렌 비스-카바민산 알킬에스테르를 제조할 수 있다. 폴리에스테르 폐기물로 부터 다량으로 얻을 수 있는 테레프탈아마이드를 간단한 반응과 정을 거쳐 그 자체로 유용한 여러가지 1, 4-페닐렌 비스 카바민산의 에스테르를 합성하거나, 이 에스테르로부터 다른 화합물들 (예, 파라페닐렌 디아민)을 얻을 수 있는 파급효과를 고려하여 1990년 발행 Tetrahedron letters[31(11) p.1559]에 수록된 반응조건을 테레프탈아마이드에 적용시켰다.In addition, Hg (OAc) 2 can be recovered and reused to economically produce 1, 4-phenylene bis-carbamic acid alkyl ester. Terephthalamide, which can be obtained in large quantities from polyester waste, is subjected to a simple reaction process to synthesize various esters of 1,4-phenylene biscarbamic acid which are useful on their own, or from other esters (e.g., paraphenyl). In consideration of the ripple effect of lendiamine), the reaction conditions described in Tetrahedron letters [31 (11) p.1559] published in 1990 were applied to terephthalamide.
종래의 방법으로는 일반적인 호프만 반응으로 할로겐과 염기 (혹은 하이포할라이트염, NaOCl)와 알코올을 시약으로 사용하는 방법이 공지되어 있다.As a conventional method, halogen, a base (or hypohalite salt, NaOCl) and an alcohol are known as reagents in a general Hoffman reaction.
식중, X는 할로겐, 바람직하게는 염소 또는 브롬이다. 이 반응의 경우 독성이 강한 염소 가스나 휘발성이 있는 브롬, 또는 불안정한 하이포할라이트 등을 사용해야하는 단점이 있다. 따라서, 본 발명자들은 이러한 문제점들을 해결하기 위하여 꾸준히 연구를 행한 결과, 조작이 용이하며, 온화한 조건하에서 테레프탈아미드로 부터 파라페닐렌 비스 카바믹산 알킬에스테르를 제조한후, 연속적으로 파라페닐렌 디아민을 제조하였으며, 또한 본 발명자들은 파라페닐렌 비스 카바믹산 알킬에스테르를 경제적으로 제조하기 위하여 아세트산 수은을 회수할 수 있는 방법을 발견하여 본 발명을 완성하게 되었다.Wherein X is halogen, preferably chlorine or bromine. This reaction has the disadvantage of using toxic chlorine gas, volatile bromine, or unstable hypohalite. Therefore, the present inventors have steadily researched to solve these problems, and as a result, it is easy to operate, and after the preparation of the paraphenylene bis carbamic acid alkyl ester from terephthalamide under mild conditions, the paraphenylene diamine is continuously produced. In addition, the present inventors have found a method for recovering mercury acetate to economically prepare paraphenylene biscarbamic acid alkyl ester, thereby completing the present invention.
본 발명의 목적은 PET등의 제조시 부산물로서 생기는 폴리에스테르 부산물을 암모놀리시스 (Am-monolysis)시켜서 다량으로 얻을 수 있는 테레프탈아미드를 이용하여 산업적으로 유용한 물질을 얻어내고자 하는 시도의 일환으로써 발명을 수행하였다.An object of the present invention is to attempt to obtain an industrially useful material by using a terephthalamide obtained by am-monolysis of polyester by-products produced as by-products in the production of PET. Was performed.
본 실험과정을 시행함으로써 얻을 수 있는 파라페닐렌 비스 카바민산의 알킬 에스테르는 그 자체로서 제초제나 살충제의 효력이 알려짐), 이 물질을 금속 촉매 (예 : Pd)하에서 수소첨가반응을 시키거나, 가수분해 반응을 시킴으로써, 아라미드 (Aramid), 아조다이 (Azo dye), 산화방지제등의 원료로 쓰이는 파라페닐렌다이아민을 얻기위한 목적으로 본 연구를 수행하였다.Alkyl esters of paraphenylene biscarbamic acid, which can be obtained by conducting this experiment, are known to be effective as herbicides or insecticides, or they can be hydrogenated under metal catalysts (eg Pd), or By conducting the decomposition reaction, this study was carried out for the purpose of obtaining paraphenylenediamine which is used as a raw material of aramid, azo dye, antioxidant and the like.
본 발명을 좀 더 상세히 설명하면 다음과 같다.The present invention is described in more detail as follows.
테레프탈아미드와 Hg(OAc)2(2,4당량)을 DMF에 열을 가하여 용해시킨다. 알코올 (약 60당량)과 건조된 DMF에 용해시킨 NBS(2.6당량)을 넣고 40-60℃에서 교반시킨다. 상기의 공정은 질소 대기 상태에서 시행한다. 반응 완료후 혼합물을 에틸아세테이트로 희석시킨 후 물, 5% 염산, 포화탄산수소나트륨으로 순차적으로 2회씩 세척한다. 유기층을 황산마그네슘으로 탈수시킨 후 용매를 제거하고 컬럼(실리카겔)을 통하여 생성물을 정제한다.Terephthalamide and Hg (OAc) 2 (2,4 equivalents) are dissolved by heating in DMF. Add alcohol (about 60 equivalents) and NBS (2.6 equivalents) dissolved in dried DMF and stir at 40-60 ° C. The process is carried out in a nitrogen atmosphere. After completion of the reaction, the mixture was diluted with ethyl acetate and washed twice with water, 5% hydrochloric acid, and saturated sodium bicarbonate. The organic layer is dehydrated with magnesium sulfate, the solvent is removed and the product is purified through column (silica gel).
이 반응 조건은 종래의 호프만 전위 반응 조건에 비하여 조작이 용이하여 온화한 조건(중성)하에서 수행되는 장점이 있으며, 정량적인 반응의 진행과 높은 수득율을 보여준다.This reaction condition has the advantage of being operated under mild conditions (neutral) because it is easier to operate than the conventional Hoffman potential reaction conditions, and shows the progress of quantitative reaction and high yield.
다음의 실시예로서 본 발명을 더욱 상세히 설명하고자 한다.The present invention will be described in more detail with reference to the following examples.
[실시예 1]Example 1
202mg 테레프탈아미드와 954mg Hg(OAc)2을 12ml DMF에 용해시킨 후 2.37g의 메탄올과 6ml 건조 DMF에 용해된 576mg의 NBS을 넣고 상온에서 13시간 교반시킨후 온도를 40-60℃ 정도로 올려 2시간 더 교반시킨다. n-헥산 : 에틸아세테이트=1 : 1의 전개용매를 사용하여 반응 진행을 박층크로마토크라피상으로 확인하고 (생성물의 Rf=0.5), 500ml의 에틸아세테이트로 반응혼합물을 희석시킨다. 50ml의 물, 5% 염산, 포화탄산수소나트륨으로 순서대로 2회씩 세척한후 황산마그네슘으로 유기층을 탈수시킨다. 유기 용매를 제거한 후 n-헥산 : 에틸아세테이트=3 : 1 전개용매를 사용하여 실리카겔 컬럼 크로마토그라피로 정제하여 아래의 NMR 자료를 갖는 1, 4-페닐렌 비스 카바민산, 메틸에스테르를 얻는다.After dissolving 202mg terephthalamide and 954mg Hg (OAc) 2 in 12ml DMF, 37mg of methanol and 576mg of NBS dissolved in 6ml dry DMF were added and stirred at room temperature for 13 hours, and the temperature was raised to 40-60 ℃ for 2 hours. Stir further. The reaction progress was confirmed by thin layer chromatography using a developing solvent of n-hexane: ethyl acetate = 1: 1 (Rf = 0.5 of the product), and the reaction mixture was diluted with 500 ml of ethyl acetate. After washing twice with 50 ml of water, 5% hydrochloric acid and saturated sodium bicarbonate in that order, the organic layer was dehydrated with magnesium sulfate. The organic solvent was removed and purified by silica gel column chromatography using n-hexane: ethyl acetate = 3: 1 developing solvent to obtain 1, 4-phenylene biscarbamic acid and methyl ester having the following NMR data.
수득율 : 90%Yield: 90%
NMR 자료 (60MHz in CDCl3)NMR Data (60MHz in CDCl 3 )
3.76ppm : singlet 6H (2, -CH3)3.76ppm: singlet 6H (2, -CH 3 )
6.50ppm : broad singlet 2H (2, -NH)6.50ppm: broad singlet 2H (2, -NH)
7.28ppm : doublet 4H (4, -CH)7.28ppm: doublet 4H (4, -CH)
이와 같이 제조된 1, 4-페닐렌 비스 카바민산, 메틸에스테르 100mg을 Pd 촉매하에서 20ml 33% HBr의 빙초산에 용해시킨 후, 상온에서 교반하여 이산화탄소의 발생이 멈추면 건조시킨 후 에틸에테르에 녹여 물, 포화 탄산수소나트륨 용액, 포화 염화나트륨 용액으로 세척한 후 용매를 제거하여 아래의 NMR 자료를 갖는 파라페닐렌 디아민을 얻는다.100 mg of 1,4-phenylene biscarbamic acid and methyl ester prepared as described above were dissolved in 20 ml of 33% HBr glacial acetic acid under Pd catalyst, stirred at room temperature, dried when carbon dioxide ceased to occur, and dried in ethyl ether. After washing with saturated sodium bicarbonate solution and saturated sodium chloride solution, the solvent is removed to obtain paraphenylene diamine having the following NMR data.
수득율 : 80%Yield: 80%
NMR 자료 (60MHz in CDCl3)NMR Data (60MHz in CDCl 3 )
3.26ppm : broad singlet 4H3.26ppm: broad singlet 4H
6.58ppm : singlet 4H6.58ppm: singlet 4H
1, 4-페닐렌 비스 카바민산, 메틸에스테르를 제조할때 세척에 사용된 물, 5% 염산, 포화탄산수소나트륨용액, 수용액층에 탄산나트륨을 용해시켜 HgOㆍHgCO3의 침전물이 생성된다. 이 침전물을 여과하여 20% 수용성 아세트산 용액에서 70℃로 가열하여 환류시켜 Hg (OAc)2을 회수한다.In preparing 1,4-phenylene biscarbamic acid and methyl ester, a precipitate of HgO.HgCO 3 is formed by dissolving sodium carbonate in the water used for washing, 5% hydrochloric acid, saturated sodium hydrogen carbonate solution and aqueous solution layer. The precipitate was filtered and heated to reflux at 70 ° C. in a 20% aqueous acetic acid solution to recover Hg (OAc) 2 .
[실시예 2]Example 2
실시예 1에서 파라페닐렌디아민을 제조할 때 사용된 촉매를 Pd 대신에 Ni을 사용한 것을 제외하고는 동일하게 실시하였고, 아래의 NMR 자료룰 갖는 파라페닐렌디아민을 얻는다.The catalyst used in the preparation of paraphenylenediamine in Example 1 was carried out in the same manner except that Ni was used instead of Pd, thereby obtaining paraphenylenediamine having the following NMR data.
수율 : 82%Yield: 82%
NMR 자료 (60MHz in CDCl3)NMR Data (60MHz in CDCl 3 )
3.26ppm : broad singlet 4H3.26ppm: broad singlet 4H
6.59ppm : singlet 4H6.59ppm: singlet 4H
Claims (4)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
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| KR1019900022051A KR930006943B1 (en) | 1990-12-27 | 1990-12-27 | Method for producing p-phenylen diamine |
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| Application Number | Priority Date | Filing Date | Title |
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| KR1019900022051A KR930006943B1 (en) | 1990-12-27 | 1990-12-27 | Method for producing p-phenylen diamine |
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| Publication Number | Publication Date |
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| KR920012006A KR920012006A (en) | 1992-07-25 |
| KR930006943B1 true KR930006943B1 (en) | 1993-07-24 |
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