间氨基苯酚和 3-（二丁基氨基）苯酚的实用、无废水合成,Organic Preparations and Procedures International

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间氨基苯酚和 3-（二丁基氨基）苯酚的实用、无废水合成
Organic Preparations and Procedures International ( IF 1.2 ) Pub Date : 2020-04-27 , DOI: 10.1080/00304948.2020.1743117
Yongjun Mao ₁ , Long Zhang ₁ , Wenxin Chen ₁ , Pengfei Wu ₁ , Lehao Bu ₁ , Jingli Xu ₁

Affiliation

作为重要的有机化工和医药中间体，间氨基苯酚（1，图1）广泛应用于农药、医药、印染等行业。例如，它可以用作除草剂（苯丙胺）、杀菌剂（美普尼）和镇痛剂（曲马多）的原料。主要用于生产3-(二丁氨基)苯酚(2，图1)、3-(二乙氨基)苯酚(3，图1)、2-苯胺基-3-甲基-6等功能性染料及染料中间体-（二丁氨基）荧烷（ODB-2、4、图1）和罗丹明B，全球年产量超过2000吨。间氨基苯酚(1)和3-(二丁基氨基)苯酚(2)的基本工业合成路线如Scheme 1所示。硝基苯在0 60 C下用发烟硫酸处理得到3-硝基苯磺酸(5)> 90% 的收率，然后用铁粉在盐酸中还原，以 95% 的产率得到 3-氨基苯磺酸 (6)。在350 380°C下将化合物6分离并与NaOH（10 12mol当量）混合以获得产物1，然后将其通过真空蒸馏纯化，分离产率为80%。该工艺的主要缺陷是处理大量的废酸、废碱、铁泥。此外，碱熔过程的高温增加了生产成本，并具有重要的安全后果。化合物1可通过间苯二胺(7)在20%硫酸中在200 220℃和2.0 2.5MPa条件下水解得到。反应选择性不高，产生大量间苯二酚，使产物1难以分离纯化。1的分离收率仅为10 15%，根据我们自己的实验结果。此外，由于强酸和高温条件，需要使用特殊设备。化合物1也可以通过将间苯二酚（8）与氨在二甲苯和二氧化硅氧化铝催化剂（沸石或粘土）中在220℃下混合5小时以82％的产率（由HPLC监测）合成，而1的分离产率没有更多超过 40%。这种方法的问题是催化剂容易形成副产物，导致失活和失去潜在的回收利用。该方法8的转化率不高，导致1的分离纯化困难。化合物1也可以通过将间苯二酚（8）与氨在二甲苯和二氧化硅氧化铝催化剂（沸石或粘土）中在220℃下混合5小时以82％的产率（由HPLC监测）合成，而1的分离产率没有更多超过 40%。这种方法的问题是催化剂容易形成副产物，导致失活和失去潜在的回收利用。该方法8的转化率不高，导致1的分离纯化困难。化合物1也可以通过将间苯二酚（8）与氨在二甲苯和二氧化硅氧化铝催化剂（沸石或粘土）中在220℃下混合5小时以82％的产率（由HPLC监测）合成，而1的分离产率没有更多超过 40%。这种方法的问题是催化剂容易形成副产物，导致失活和失去潜在的回收利用。该方法8的转化率不高，导致1的分离纯化困难。

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A Practical, Wastewater-free Synthesis of m-Aminophenol and 3-(Dibutylamino)phenol

As an important organic chemical and pharmaceutical intermediate, m-aminophenol (1, Figure 1) is widely used in the pesticide, medicinal, printing and dyeing industries. As examples, it can be used as the starting material for herbicides (phenmedipham), sterilizing agents (mepronil), and analgesics (tramadol). It is mainly used in the production of functional dyes and dye intermediates such as 3-(dibutylamino)phenol (2, Figure 1), 3-(diethylamino)phenol (3, Figure 1), 2-anilino-3-methyl-6-(dibutylamino)fluoran (ODB-2, 4, Figure 1) and rhodamine B, with a global annual yield of more than 2000 tons. The fundamental industrial synthesis routes of m-aminophenol (1) and 3-(dibutylamino)phenol (2) are depicted in Scheme 1. Nitrobenzene is treated with fuming sulfuric acid at 0 60 C to give 3-nitrobenzenesulfonic acid (5) in >90% yield, which is then reduced by iron powder in hydrochloric acid to give 3-aminobenzenesulfonic acid (6) in 95% yield. Compound 6 is isolated and mixed with NaOH (10 12mol eq.) at 350 380 C to obtain product 1, which is then purified by vacuum distillation in 80% isolated yield. The main defect of this process is dealing with large quantities of waste acid, waste alkali, and iron mud. In addition, the high temperature of the alkali fusion process increases the cost of production, and has important safety consequences. Compound 1 can be obtained by hydrolysis of m-phenylenediamine (7) in 20% sulfuric acid at 200 220 C and 2.0 2.5MPa. The selectivity of the reaction is not high and a substantial amount of resorcinol is produced, which makes it difficult to separate and purify product 1. The isolated yield of 1 is only 10 15%, based on our own experiment results. Furthermore, special equipment needs to be used as a result of the strong acid and high temperature conditions. Compound 1 can also be synthesized by mixing resorcinol (8) with ammonia in xylene and silica alumina catalyst (zeolites or clays) at 220 C for 5 h in 82% yield (monitored by HPLC), while the isolated yield of 1 is no more than 40%. The problem with this method is that the catalyst is prone to form by-products, resulting in inactivation and loss of potential recycling. The conversion rate of 8 in this method is not high, leading to difficulties of separation and purification of 1.

更新日期：2020-04-27

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