Phloroglucinol → Trinitrophloroglucinol

Participants

Reaction Steps

One method of synthesizing TATB from phloroglucinol is described in GB 2355715. Phloroglucinol, also known as 1,3,5-trihydroxybenzene, is nitrated using sodium nitrite and nitric acid, forming trinitrophloroglucinol (“TNPG”), which is also known as 1,3,5-trihydroxy-2,4,6-trinitrobenzene. The nitric acid is added sequentially or in multiple additions. When cooled, a solid is produced, which is filtered, washed with 3 M hydrochloric acid (“HCl”), and dried, yielding a solid product that is a monohydrate of TNPG. The monohydrate of TNPG is a free-flowing solid. The TNPG is alkoxylated using a trialkyl orthoformate, such as trimethyl orthoformate, forming 1,3,5-trimethoxy-2,4,6-trinitrobenzene. Methanol and methyl formate are also formed and are removed by distillation. The solution of 1,3,5-trimethoxy-2,4,6-trinitrobenzene is concentrated, yielding 1,3,5-trimethoxy-2,4,6-trinitrobenzene as a solid, which is recrystallized from ethanol. The purified 1,3,5-trimethoxy-2,4,6-trinitrobenzene is then aminated using liquid ammonia or gaseous ammonia, filtered, washed with N-methylpyrrolidinone and methanol, and dried, yielding crystals of the TATB. To conduct the amination reaction, a solution of the 1,3,5-trimethoxy-2,4,6-trinitrobenzene is cooled to −10° C. and ammonia gas is introduced. If liquid ammonia is used, the animation reaction is conducted at room temperature and a pressure of 8-9 bar, or at atmospheric pressure and −33° C. If gaseous ammonia is used, the animation reaction is conducted at atmospheric pressure or at a pressure of 8-9 bar. At higher temperatures, the method is described as being less energy efficient. The TATB synthesis utilizes multiple drying and isolation acts to produce solid products of TNPG, TETNB, and TATB.

Provenance & Evidence