7-氨基-6-硝基苯并二氧化呋咱的合成研究

Synthesis of 7-Amino-6-nitrobenzodifuroxan

以3，5-二氯苯胺为原料经过4步反应合成了7-氨基-6-硝基苯并二氧化呋咱（ANBDF）。在四氢呋喃溶剂中-3，5-二氯苯胺与氯乙酰氯反应得到3，5-二氯-N-氯乙酰基苯胺（Ⅰ），收率97．7％；（Ⅰ）在室温下于浓硫酸（98％）-发烟硝酸（98％）中硝化2h，得到3，5-二氯-2，4，6-三硝基-N-氯乙酰苯胺（Ⅱ），收率92．3％。（Ⅱ）在冰乙酸中，与NaN，反应，不经分离直接在110℃下进行热解脱氮得到7-氯乙酰氨基-6-硝基苯并二氧化呋咱（Ⅲ），收率82．5％。（Ⅲ）碱性水解得到目标化合物7-氨基-6-硝基苯并二氧化呋咱（Ⅳ），熔点204～205℃，收率66％。讨论了关键反应的影响因素，并通过红外光谱、核磁共振、质谱及元素分析确定了目标化合物及其中间体的结构。

7-Amino-6-nitrobenzodifuroxan （ANBDF） was prepared through a four-step reaction process using 3, 5-dichloroaniline as starting material.3,5-dichloro-N-chloroacetaniline （ Ⅰ） was prepared in 97.7% yield by the reaction of chloro-acetic chloride with 3,5-dichloroaniline in the media of THF. Nitration of the compound （ Ⅰ ） with a mixture of fuming nitric acid （98%） and concentrated sulphuric acid （98%） at room temperature for 2 h gave 3,5-dichloro-2,4,6- trinitro-N-chloroacetaniline （Ⅱ） in 92.3% yield. 7-Chloroacetamide-6-nitrobenzodifuroxan （Ⅲ） was obtanined in 82.5% yield from （ Ⅱ ） and sodium azide in acetic acid through denitrogenization at 110 ℃. The title compound （Ⅳ） was prepared by hydrolyzing of （Ⅲ） in basic media with a yield of 66% .The melting point of Ⅳ is 204 ～ 205℃.The factors affecting the key reactions were discussed. The structures of 7-amino-6-nitrobenzodifuroxan and its three intermediates have all been determined by IR,^1H NMR, MS and elemental analysis.