KR20040013368A - manufacturing method of tetrachloro benzidine - Google Patents
manufacturing method of tetrachloro benzidine Download PDFInfo
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- KR20040013368A KR20040013368A KR1020020046253A KR20020046253A KR20040013368A KR 20040013368 A KR20040013368 A KR 20040013368A KR 1020020046253 A KR1020020046253 A KR 1020020046253A KR 20020046253 A KR20020046253 A KR 20020046253A KR 20040013368 A KR20040013368 A KR 20040013368A
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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
- C07C209/30—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of nitrogen-to-oxygen or nitrogen-to-nitrogen bonds
- C07C209/32—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of nitrogen-to-oxygen or nitrogen-to-nitrogen bonds by reduction of nitro groups
- C07C209/36—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of nitrogen-to-oxygen or nitrogen-to-nitrogen bonds by reduction of nitro groups by reduction of nitro groups bound to carbon atoms of six-membered aromatic rings in presence of hydrogen-containing gases and a catalyst
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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
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Abstract
Description
본 발명은 2,5-디클로 니트로벤젠(2,5-Dichloro nitrobenzene ; 이하 DCNB라 한다.)을 출발물질로 하여 테트라클로로벤지딘(Tetrachloro benzidine ; 이하 TCB라 한다.)을 제조하는 방법에 관한 것이다The present invention relates to a method for preparing tetrachloro benzidine (hereinafter referred to as TCB) using 2,5-dichloro nitrobenzene (hereinafter referred to as DCNB) as a starting material.
구체적으로는 DCNB를 귀금속촉매와 환원보조제 존재하의 수소분위기 중에서 테트라클로로아족시벤젠 (tetrachloroazoxybenzene)과 테트라클로로아조벤젠(tetrachloroazobenzene)을 거쳐 테트라클로로하이드라조벤젠 (tetrachlorohydrazobenzene)으로 환원시키고 이를 황산을 이용하여 벤지딘 전위(benzidine rearrangement)시켜 TCB를 제조하는 방법에 관한 것이다.Specifically, DCNB is reduced to tetrachlorohydrazobenzene via tetrachloroazoxybenzene and tetrachloroazobenzene in a hydrogen atmosphere in the presence of a noble metal catalyst and a reducing aid, and is converted to benzidine potential using sulfuric acid. (benzidine rearrangement) to produce a TCB.
DCNB를 출발물질로 하는 TCB 제조공정을 화학반응식으로 표기하면 아래와 같다.The TCB manufacturing process using DCNB as a starting material is described as chemical reaction.
TCB는 커플링(Coupling)제와 커플링시켜 벤지딘 옐로우 81 (benzidine yellow 81)이나 벤지딘 옐로우 113과 같은 유기 안료를 제조하는데 유용하게 사용되는 물질이다.TCB is a material which is usefully used to prepare organic pigments such as benzidine yellow 81 or benzidine yellow 113 by coupling with a coupling agent.
4.4'-디아미노비페닐(4.4'-diaminobiphenyl)을 일명 벤지딘이라고 하는데 디클로로벤지딘(dichloro benzidine)과 같은 벤지딘 화합물은 아세토 아세트 아닐리드와 같은 아민류나 또는 페놀류의 커플링 성분과 커플링 시켜 벤지딘 옐로우, 벤지딘 오렌지와 같은 아조계 염료 및 안료를 제조하는데 유용하게 사용되고 있다.4.4'-diaminobiphenyl is called benzidine, and benzidine compounds such as dichloro benzidine can be combined with amines such as aceto acetanilide or phenols to form a benzidine yellow or benzidine. It is usefully used to prepare azo dyes and pigments such as oranges.
디클로벤지딘이 유용한 황색 안료의 중간체 이기는 하나 비교적 불안정한 화합물이어서 분해시 인체에 유해한 벤지딘계 화합물을 생성시키므로 최근 일부국가에서는 발암성 물질로 지정되어 생산에 제약을 받고 있다. 따라서 최근에는 디클로벤지딘 보다 안정성이 우수하고 소량 사용으로도 우수한 색상을 나타내는 테트라클로로벤지딘의 사용을 선호하고 있는 추세에 있다.Although diclobenzidine is an intermediate of useful yellow pigments, it is a relatively unstable compound, which generates benzidine-based compounds that are harmful to humans when degraded. Therefore, in recent years, there has been a trend to favor the use of tetrachlorobenzidine, which is more stable than diclobenzidine and exhibits excellent color even with a small amount of use.
종래 테트라클로로벤지딘을 제조하는 방법으로서 2, 2',5, 5'-테트라클로로아족시벤젠을 황화수소 나트륨(NaSH)과 반응시켜 테트라 클로로하이드라조벤젠을 제조하는 방법이 알려져 있다.(USP 4075195호)Conventionally, as a method for producing tetrachlorobenzidine, a method for producing tetrachlorohydrolazobenzene by reacting 2, 2 ', 5, and 5'-tetrachloroaoxy benzene with sodium hydrogen sulfide (NaSH) is known. (USP 4075195) )
상기의 방법에서는 2, 2', 5, 5'- 테트라클로로아족시벤젠의 환원제로서는 NaSH를, 환원보조제로서는 Na2S2O3를 사용하여 얻어지는 테트라클로로하이드라조벤젠의 침전물을 알카리성분이 남아 있지 않을때까지 수세하여주어야 하며 환원수율이 75%정도로 낮다.In the above method, the alkali component does not remain in the precipitate of tetrachlorohydrazobenzene obtained by using NaSH as a reducing agent of 2, 2 ', 5, 5'-tetrachloroaoxy benzene and Na 2 S 2 O 3 as a reducing aid. It should be washed until it is not and the reduction yield is low as 75%.
상기 방법에서는 반응 출발 물질로서 비교적 고가의 테트라클로로아족시벤젠을 사용한다는 점이외에도 환원제로서 무기약품을 사용하므로서 반응생성물이 다량의 불순물을 함유하게 되므로 이를 수세제거 하여야 하는 불편이 있으며 반응수율도 낮다는 문제가 있다.In the above method, besides using relatively expensive tetrachloroaoxy benzene as a starting material for the reaction, since the reaction product contains a large amount of impurities by using an inorganic chemical as a reducing agent, it is inconvenient to remove water washing, and the reaction yield is low. there is a problem.
본 발명의 목적은 비교적 저가인 DCNB를 원료로하여 높은 수율로 고순도의 TCHB를 제조하는 방법과 황산을 사용하여 벤지딘 전위를 실시하므로서 용미한 정제공정으로 고순도의 테트라클로로벤젠(TBC)을 제조하는 방법을 제공하는데 있다. 본 발명자 들은 DCNB를 귀금속촉매와 환원보조제의 존재하의 수소분위기중에서 테트라클로로아족시벤젠을 거쳐 테트라클로로아조벤젠 및 테트라클로로 하이드라조벤젠으로 환원되는 과정에서 수소압을 조정한 2단계 반응을 연속적으로 진행시켜 테트라클로로하이드라조벤젠을 얻고 이를 황산을 이용한 벤지딘 전위반응시켜 고순도의TCB를 높은 수율로 얻을수 있음을 확인하여 본 발명을 완성하게되었다.An object of the present invention is to prepare a high-purity TCHB with a high yield from a relatively low-cost DCNB as a raw material and to produce a high-purity tetrachlorobenzene (TBC) in a mild purification process by carrying out benzidine potential using sulfuric acid. To provide. The present inventors continuously proceeded a two-step reaction in which hydrogen pressure was adjusted in the process of reducing DCNB to tetrachloroazobenzene and tetrachloro hydrazobenzene through tetrachloroaoxybenzene in a hydrogen atmosphere in the presence of a noble metal catalyst and a reducing aid. The present invention was completed by confirming that tetrachlorohydrazobenzene was obtained and benzidine potential reaction using sulfuric acid to obtain high purity TCB in high yield.
본 발명은 DCNB을 백금을 활성탄에 담지시켜서된 pt/C 촉매와 2,3-디클로로 1,4-나프타 퀴논을 환원 보조제로하는 수소분위기 중에서 테트라클로로아족시벤젠, 테트라클로로아조벤젠을 거쳐 테트라클로로하이드라조벤젠으로 환원시키고 이를 벤지딘 전위시켜 TCB를 제조하는 방법에 관한 것이다.The present invention provides tetrachlorohydride via tetrachloroaoxybenzene and tetrachloroazobenzene in a hydrogen atmosphere in which DCNB is a pt / C catalyst supported by platinum on activated carbon and 2,3-dichloro 1,4-naphthaquinone as a reducing aid. The present invention relates to a method for preparing TCB by reducing with lazobenzene and converting it to benzidine.
종래의 TCHB 제조방법으로서는 2, 2', 5, 5' 테트라 클로로 아족시벤젠을 출발물질로하고 환원제로서 NaHS(Sodium HydroSulfide)를, 환원보조제로서는 Na2S2O3를 사용하여 메탄올 용매 중에서 환원반응시켜 얻은 반응혼합물을 PH 9에서 환류(Reflex)시킨후 2~5℃로 냉각하고 여과하여 침전물을 얻고 이침전물을 알카리가 남아 있지 않을때 까지 수세 건조시켜 2, 2', 5, 5' TCHB를 제조하는 방법이 알려져 있다.(USP 4,075 198호)In the conventional TCHB production method, 2, 2 ', 5, 5' tetrachloro azoxybenzene is used as a starting material, NaHS (Sodium HydroSulfide) as a reducing agent, and Na 2 S 2 O 3 as a reducing aid are reduced in methanol solvent. The reaction mixture obtained by the reaction was refluxed at PH 9, cooled to 2-5 ° C., filtered to obtain a precipitate, and the precipitate was washed with water until no alkali remained, followed by 2, 2 ', 5, 5' TCHB. Processes for the preparation of these are known (USP 4,075 198).
상기의 방법은 비교적 고가의 테트라 클로로아족시벤젠을 출발물질로 한다는 점이외에도 무기약품을 환원제 및 환원 보조제로 사용하므로서 반응 생성물중에 다량의 불순물이 함유되게되어 수세, 정제 하여야하는 불편이 있으며 환원반응수율도 75% 정도로 낮다는 문제가 있다.In addition to the use of relatively expensive tetrachloroaoxy benzene as a starting material, the above-mentioned method uses inorganic chemicals as a reducing agent and a reducing aid, so that a large amount of impurities are contained in the reaction product. There is also a problem that is as low as 75%.
본 발명은 비교적 저가인 DCNB를 출발물질로 하고 수소분위기중에서 환원반응을 실시하므로서 반응생성물중에 불순물 함량이 낮으며 환원반응 수율도 80~85%인 고수율이고, 순도 99% 이상인 고순도의 TCHB를 제조하고 이를 벤지딘 전위시켜 TCB를 제조하는 방법에 관한 것이다.In the present invention, a relatively inexpensive DCNB is used as a starting material and a reduction reaction is performed in a hydrogen atmosphere, thereby producing a high purity TCHB having a low impurity content in the reaction product, a yield of 80-85% reduction, and a purity of 99% or more. And it relates to a method for preparing TCB by benzidine translocation.
이하 실시예를 들어 본 발명을 구체적으로 설명한다.The present invention will be described in detail with reference to the following Examples.
실시예Example
고압반응기에 2.5-디클로로 니트로벤젠 156g과 톨루엔 188㎖을 투입한다.Into the high pressure reactor, 156 g of 2.5-dichloro nitrobenzene and 188 ml of toluene were added.
여기에 30% NaOH 79g, 2.3-디클로로 1.4-나프타퀴논 2g, 분산제로서 소디움 도데실 벤젠 설포네이트 2g, 환원촉매로서 pt/C 0.8g, 물 79g을 투입한다. 원료투입후 반응기 내부의 공기를 질소로 제거한 후 진공펌프를 이용하여 반응기 내부를 진공상태로 유지시킨다.79 g of 30% NaOH, 2 g of 2.3-dichloro 1.4-naphthaquinone, 2 g of sodium dodecyl benzene sulfonate as a dispersant, 0.8 g of pt / C and 79 g of water as a reducing catalyst were added thereto. After inputting raw materials, the inside of the reactor is removed with nitrogen, and the inside of the reactor is maintained in a vacuum state using a vacuum pump.
반응기온도를 상승시키면서 반응기 내부로 수소압 1~4kg/㎠를 유지 하면서 수소를 주입한다.While increasing the reactor temperature, hydrogen is injected into the reactor while maintaining the hydrogen pressure of 1 ~ 4kg / ㎠.
70~90℃에서 20~40분 반응시킨후 다시 수소압 6~10㎏/㎠로 상승시켜 30~40분간 반응시켜 환원반응을 완료시킨다. 상기의 2단계 환원반응을 연속적으로 진행시킨다.After 20-40 minutes of reaction at 70-90 ° C, the hydrogen pressure is increased to 6-10kg / ㎠ and reacted for 30-40 minutes to complete the reduction reaction. The two-stage reduction reaction is carried out continuously.
상기 환원반응에서 얻은 반응물을 60~70℃로 유지하면서 여과하여 pt/C를 회수하고, 여액중의 톨루엔을 환류시켜 회수하면 TCHB 120g을 침전물로 얻게된다.The reaction product obtained in the reduction reaction is filtered while maintaining at 60-70 ° C. to recover pt / C, and toluene in the filtrate is recovered by reflux to obtain 120 g of TCHB as a precipitate.
여기서 얻은 TCNB를 황산 54g(55-65%)을 사용하여 고온에서 벤지딘 전위를 실시하면 조(Crude) TCB를 얻게되며, 알콜을 이용 정제과정을 거치면 고순도의 TCB를 얻게된다. 최종 TCB 수율은 68%이었다.The TCNB obtained here was subjected to benzidine potential using 54 g of sulfuric acid (55-65%) at high temperature to obtain Crude TCB, and to obtain high purity TCB through purification with alcohol. Final TCB yield was 68%.
본 발명의 방법은 비교적 저가의 원료를 출발물질로 하여 높은 수율로 고순도의 TCB를 얻을수 있는 효과가 있다.The method of the present invention has the effect of obtaining a high purity TCB with a high yield using a relatively low cost raw material as a starting material.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100711310B1 (en) * | 2002-10-15 | 2007-04-27 | 주식회사 협화화학 | Process for the preparation of benzidine compound |
| CN115650860A (en) * | 2022-10-31 | 2023-01-31 | 常州市阳光药业有限公司 | Synthesis method of 2,2', 5' -tetrachlorobenzidine |
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2002
- 2002-08-06 KR KR1020020046253A patent/KR20040013368A/en not_active Application Discontinuation
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100711310B1 (en) * | 2002-10-15 | 2007-04-27 | 주식회사 협화화학 | Process for the preparation of benzidine compound |
| CN115650860A (en) * | 2022-10-31 | 2023-01-31 | 常州市阳光药业有限公司 | Synthesis method of 2,2', 5' -tetrachlorobenzidine |
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