五唑钠简便合成方法

A Simple Synthesis Method of Sodium Pentazolate

为了简便合成五唑钠,采用环化/C—N切断“一锅法”合成了五唑钠,并对其合成方法和条件进行了研究。采用红外、核磁、质谱或离子色谱等对氯化重氮盐4a、四氟硼酸重氮盐4b及五唑钠进行了表征分析。结果表明:采用环化/C—N切断“一锅法”可简便地合成五唑钠;以氯化重氮盐4a合成五唑钠的适宜反应条件为:NaHCO3与2,6-二甲基-4-氨基苯酚(1)的摩尔比为0.6∶1,环化温度-45℃,环化时间2 h,C—N切断反应温度-35℃,C—N切断反应时间24 h,m-CPBA与化合物4a的摩尔比为3∶1;以四氟硼酸重氮盐4b合成五唑钠的适宜反应条件为:NaHCO3与化合物4b的摩尔比为0.3∶1,环化温度-45℃,环化时间7 h,C—N切断反应温度-35℃,C—N切断反应时间24 h,m-CPBA与化合物4b的摩尔比为4∶1;采用乙醇提取法可简便分离得到五唑钠,纯度达98.87%(面积归一法)。

In order to easily synthesize sodium pentazolate, the synthesis method and conditions of sodium pentazolate were studied. Diazoniums 4a-b and sodium pentazolate were characterized by infrared(IR), nuclear magnetic resonance(NMR), mass spectrometry(ESI-MS), or ion chromatography(IC). Results show that sodium pentazolate can be easily synthesized via the cyclization/C—N cleavage one-pot method;the appropriate reaction conditions for the synthesis of sodium pentazolates from diazonium chloride 4a are as follows: the molar ratio of NaHCO3to 2,6-dimethyl-4-aminophenol is 0.6, the cyclization temperature is -45 ℃, the cyclization time is 2 h, the C—N cleavage temperature is -35 ℃, the C—N cleavage reaction time is 24 h, and the molar ratio of m-CPBA to 2,6-dimethyl-4-aminophenol is 3∶1;the suitable reaction conditions for synthesizing sodium pentazolate from diazonium tetrafluoroborate 4b are as follows: the molar ratio of NaHCO3to diazonium tetrafluoroborate is 0.3, the cyclization temperature is -45 ℃, the cyclization time is 7 h, the C—N cleavage temperature is -35 ℃, the C—N cleavage reaction time is 24 h, and the molar ratio of m-CPBA to diazonium tetrafluoroborate is 4∶1;sodium pentazolate can be easily isolated by ethanol extraction, of which the purity is up to 98.87%(area normalization).