2,3-二羟甲基-2,3-二硝基-1,4-丁二醇四硝酸酯的合成、晶体结构及性能研究

Synthesis,Crystal structure and Properties of 2,3-Bis(hydroxymethyl)-2,3-dinitro-1,4-butanediol Tetranitrate

以硝基甲烷为起始原料,经缩合、环化、氧化耦合、脱缩酮及硝化等5步反应合成了2,3-二羟甲基-2,3-二硝基-1,4-丁二醇四硝酸酯(BHDBT),总收率为36.1%,并采用核磁共振谱、红外光谱以及元素分析等进行了结构表征.用浓盐酸代替氯化氢气体,改进了关键中间体2,3-二羟甲基-2,3-二硝基-1,4-丁二醇(BHDB)的合成方法,并确定最佳反应条件为:n(浓盐酸)∶n(BDND)=1.1∶1,反应温度55℃,时间4 h,收率为94.8%.首次发现了BHDB和BHDBT的亚甲基质子具有磁不等价性,并从理论上分析其产生的原因.培养了BHDBT单晶,四元衍射晶体结构解析表明:BHDBT属于单斜晶系,空间群P2(1)/n,晶胞参数:a=0.81944(11)nm,b=2.3365(3)nm,c=0.85838(11)nm,α=90°,β=113.501(2)°,γ=90°,V=1.5072(3)nm3,Z=4,Dc=1.852 g cm-3,μ=0.189 mm-1,F(000)=856.BHDBT熔点为86.37℃,分解峰温度为185.79℃(DSC),摩擦感度为100%(3.92 MPa,90°),特性落高H50为10.0 cm(5 kg).

Starting from nitromethane,2,3-bis（hydroxymethyl）-2,3-dinitro-1,4-butanediol tetranitrate（BHDBT） was synthesized by the condensation,cyclization,oxidative dimerization,deketalization and nitration in total yield of 36.1%.The structures of BHDBT and its intermediates were characterized by means of 1H NMR,13C NMR,FT-IR and elemental analysis.The synthetic process for 2,3-bis（hydroxymethyl）-2,3-dinitro-1,4-butanediol（BHDB） was improved by using concentrated hydrochloric acid instead of HCl gas.It was found that the optimum conditions for the synthesis of BHDB were as follows： the molar ratio of concen-trated hydrochloric acid to BDND is 1.1∶1,the reaction temperature is 55 ℃,the reaction time is 4 h,and the yield is up to 94.8%.It was experimentally first found that the protons in BHDB and BHDBT are mag-netic nonequivalent.The crystal structure of BHDBT was determined by X-ray single crystal diffractometer.It was shown that the crystal is monoclinic and P2（1）/n space group with unit cell dimensions of a=0.81944（11） nm,b=2.3365（3） nm,c=0.85838（11） nm,α=90°,β=113.501（2）°,γ=90°,V=1.5072（3） nm3,Z=4,Dc=1.852 g？cm-3,μ=0.189 mm-1,F（000）=856.Furthermore,the thermal decomposition per-formance of BHDBT was tested by DSC and TG,and its sensitive properties such as friction sensitivity and impact sensitivity were also investigated.The results showed that the melting point and decomposition peak of BHDBT,which can be used for castable explosive componets and high energy plasticizer for the propel-lants,are 86.37 and 185.79 ℃,respectively.The friction sensitivity and impact sensitivity（H50） of BHDBT are 100%（3.92 MPa,90°） and 10.0 cm（5 kg）,respectively.