CN105820131B - 二(3‑硝基‑1,2,4‑三唑‑5‑基)甲二醇化合物 - Google Patents

二(3‑硝基‑1,2,4‑三唑‑5‑基)甲二醇化合物 Download PDF

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CN105820131B
CN105820131B CN201610317796.2A CN201610317796A CN105820131B CN 105820131 B CN105820131 B CN 105820131B CN 201610317796 A CN201610317796 A CN 201610317796A CN 105820131 B CN105820131 B CN 105820131B
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triazole
methylene
nitro
methylene glycol
base
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CN105820131A (zh
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黄晓川
郭涛
王子俊
刘敏
邱少君
秦明娜
唐望
张彦
石强
李洪丽
吕英迪
姚冰洁
郑晓东
陈志强
姜俊
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Xian Modern Chemistry Research Institute
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D249/00—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms
    • C07D249/02—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms not condensed with other rings
    • C07D249/08—1,2,4-Triazoles; Hydrogenated 1,2,4-triazoles
    • C07D249/10—1,2,4-Triazoles; Hydrogenated 1,2,4-triazoles with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D249/14—Nitrogen atoms
    • C—CHEMISTRY; METALLURGY
    • C06—EXPLOSIVES; MATCHES
    • C06B—EXPLOSIVES OR THERMIC COMPOSITIONS; MANUFACTURE THEREOF; USE OF SINGLE SUBSTANCES AS EXPLOSIVES
    • C06B25/00—Compositions containing a nitrated organic compound
    • C06B25/34—Compositions containing a nitrated organic compound the compound being a nitrated acyclic, alicyclic or heterocyclic amine

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Abstract

本发明公开了一种二(3‑硝基‑1,2,4‑三唑‑5‑基)甲二醇化合物，其结构式如下：

Description

二(3-硝基-1,2,4-三唑-5-基)甲二醇化合物
技术领域
本发明涉及一种桥亚甲基-1,2,4-三唑类化合物，尤其涉及一种二(3-硝基-1,2,4-三唑-5-基)甲二醇化合物，属于含能材料领域。
背景技术
桥亚甲基-1,2,4-三唑结构以其具有高密度、高氮含量和高生成焓等特点，而作为含能化合物的基本结构单元。近年来，研究人员将桥亚甲基-1,2,4-三唑结构单元与其他含能基团结合设计合成出了一系列含能化合物，基本都表现出高能量密度的特点。例如《5,5'-Dinitrimino-3,3'-methylene-1H-1,2,4-bistriazole-a Metal Free PrimaryExplosive Combining Excellent Thermal Stability and High Performance》，CentralEuropean Journal of Energetic Materials，2011，8(4)：261-278公开了一种具有桥亚甲基-1,2,4-三唑结构的含能化合物——5,5′-二硝胺基-3,3′-亚甲基-联-1,2,4-三唑，其晶体密度为1.86g·cm-3，理论爆速为8511m·s-1，理论爆压为30.9GPa，爆轰性能与RDX相当，其结构式如下：
然而该含能化合物的氧平衡(CO2，％)仅为-53.3％，存在氧平衡水平较低的不足。
发明内容
本发明要解决的技术问题是针对现有技术的不足和缺陷，提供一种具有较高氧平衡水平的二(3-硝基-1,2,4-三唑-5-基)甲二醇化合物。
本发明提供的二(3-硝基-1,2,4-三唑-5-基)甲二醇化合物，其结构式如下：
本发明的二(3-硝基-1,2,4-三唑-5-基)甲二醇化合物合成路线如下：
本发明的二(3-硝基-1,2,4-三唑-5-基)甲二醇化合物合成方法，包括以下步骤：
1)反应瓶中加入3,3′-二氨基-5,5′-亚甲基-联-1,2,4-三唑和硫酸(质量百分比20％)，5℃下，滴加亚硝酸钠的水溶液，滴加完毕后，25℃反应2h，过滤得到3,3′-二硝基-5,5′-亚甲基-联-1,2,4-三唑；其中3,3′-二氨基-5,5′-亚甲基-联-1,2,4-三唑、硫酸以及亚硝酸钠的摩尔比为1:4.6:3。
2)搅拌下，将3,3′-二硝基-5,5′-亚甲基-联-1,2,4-三唑溶解于浓硫酸中，滴加浓硝酸，常温下反应2h后，将反应液倒入至碎冰中，用二氯甲烷萃取得到二氯甲烷萃取液，将少量冰醋酸加入至二氯甲烷萃取液中，搅拌2h后，经水洗，蒸干二氯甲烷得到二(3-硝基-1,2,4-三唑-5-基)甲二醇化合物；其中3,3′-二硝基-5,5′-亚甲基-联-1,2,4-三唑、浓硫酸、浓硝酸、二氯甲烷以及冰醋酸的摩尔比为1:40:40:176:6。
本发明的优点：本发明化合物氧平衡水平(CO2)较高，为-35.3％，对比文献中化合物的氧平衡水平-53.3％。
具体实施方式
化合物结构鉴定所使用仪器：NEXUS870型傅里叶变换红外光谱仪，美国热电尼高力公司；AV 500型(500MHz)超导核磁共振仪，瑞士BRUKER公司；VARIO EL 3型元素分析仪，德国EXEMENTAR公司。
实施例1 二(3-硝基-1,2,4-三唑-5-基)甲二醇的合成
1)在带有机械搅拌、温度计及冷凝管的100ml反应瓶中依次加入硫酸(20％)20ml和3,3′-二氨基-5,5′-亚甲基-联-1,2,4-三唑1.8g(10mmol)，搅拌至完全溶解；5℃下，滴加含亚硝酸钠2.0g(30mmol)的水溶液，滴加完毕后，25℃反应2h，过滤得到3,3′-二硝基-5,5′-亚甲基-联-1,2,4-三唑2.2g，收率91.7％。
2)100ml反应瓶，依次加入20ml浓硫酸和3,3′-二硝基-5,5′-亚甲基-联-1,2,4-三唑2.2g(9mmol)，磁力搅拌下使3,3′-二硝基-5,5′-亚甲基-联-1,2,4-三唑完全溶解于浓硫酸中；2℃条件下，滴加15ml浓硝酸，滴加完毕后，升至25℃，反应2h后，将反应液倒入至碎冰中，使用二氯甲烷100ml萃取得到黄色的二氯甲烷萃取液。
3)25℃下，250ml反应瓶中依次加入二氯甲烷萃取液100ml和冰醋酸3ml，搅拌2h后，经水洗，蒸干二氯甲烷得到二(3-硝基-1,2,4-三唑-5-基)甲二醇1.6g，收率58.8％。
结构鉴定：
3,3′-二硝基-5,5′-亚甲基-联-1,2,4-三唑
元素分析：
分子式：C5H4N8O4
理论值：C 25.01，H 1.68，N 46.66；
实测值：C 24.98，H 1.62，N 46.78。
红外(KBr,cm-1)：3423，3163，3039，2998，2869，2150，1705，1576，1552，1489，1442，1401，1388，1305，1206，1162，1071，922，843，809，767，672，652，457。
1H核磁(DMSO-d6，ppm)：δ4.608(s，2H)，δ15.355(br，2H)。
13C核磁(DMSO-d6，ppm)：24.708，153.341，170.346。
二(3-硝基-1,2,4-三唑-5-基)甲二醇
元素分析：
分子式：C5H4N8O6
理论值：C 22.07，H 1.48，N 41.18；
实测值：C 21.98，H 1.43，N 41.25。
红外(KBr,cm-1)：3539，3361，3067，2978，2759，1957，1641，1574，1553，1485，1463，1427，1385，1308，1131，1114，1064，1004，897，840，786，765，707，659，568，474。
1H核磁(DMSO-d6，ppm)：δ4.322(br，2H)，δ8.725(br，2H)。
13C核磁(DMSO-d6，ppm)：88.475，159.043，162.824。
上述分析数据证实按该合成方法得到的物质确实是二(3-硝基-1,2,4-三唑-5-基)甲二醇。
本发明中所使用的氧平衡(CO2)计算公式为：(c－2a－b/2)/Mw，含能化合物的化学通式为CaHbNcOd，Mw为化合物的分子量；计算得到本发明化合物二(3-硝基-1,2,4-三唑-5-基)甲二醇氧平衡水平(CO2)为-35.3％。

Claims (1)

1.一种二(3-硝基-1,2,4-三唑-5-基)甲二醇化合物，其结构式如下：
CN201610317796.2A 2016-05-13 2016-05-13 二(3‑硝基‑1,2,4‑三唑‑5‑基)甲二醇化合物 Expired - Fee Related CN105820131B (zh)

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