CN105949219B - 4‑氨基‑1,2,3‑三氮唑[4,5‑e]呋咱并[3,4‑b]吡嗪‑6‑氧化物 - Google Patents

4‑氨基‑1,2,3‑三氮唑[4,5‑e]呋咱并[3,4‑b]吡嗪‑6‑氧化物 Download PDF

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CN105949219B
CN105949219B CN201610317757.2A CN201610317757A CN105949219B CN 105949219 B CN105949219 B CN 105949219B CN 201610317757 A CN201610317757 A CN 201610317757A CN 105949219 B CN105949219 B CN 105949219B
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furazano
pyrazine
amino
triazoles
oxides
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CN105949219A (zh
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李亚南
舒远杰
王伯周
张生勇
毕福强
霍欢
翟连杰
李祥志
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Xian Modern Chemistry Research Institute
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D498/00—Heterocyclic compounds containing in the condensed system at least one hetero ring having nitrogen and oxygen atoms as the only ring hetero atoms
    • C07D498/12—Heterocyclic compounds containing in the condensed system at least one hetero ring having nitrogen and oxygen atoms as the only ring hetero atoms in which the condensed system contains three hetero rings
    • C07D498/14—Ortho-condensed systems

Abstract

本发明公开了一种4‑氨基‑1,2,3‑三氮唑[4,5‑e]呋咱并[3,4‑b]吡嗪‑6‑氧化物，其结构式如(I)所示：

Description

4-氨基-1,2,3-三氮唑[4,5-e]呋咱并[3,4-b]吡嗪-6-氧化物
技术领域
本发明涉及一种含能材料，具体涉及一种4-氨基-1,2,3-三氮唑[4,5-e]呋咱并[3,4-b]吡嗪-6-氧化物。
背景技术
自1896年呋咱(氧化呋咱)环被发现以来，俄罗斯科学院Zelinsky有机化学研究所Sheremeteev等人开展了大量这方面的研究，已合成了上百种呋咱(氧化呋咱)含能化合物。研究发现：呋咱(氧化呋咱)环本身就是一个爆炸性基团，即便是最简单的取代呋咱(氧化呋咱)，其分子能量也会因呋咱(氧化呋咱)环的存在而增加，并能在特定条件下(如燃烧、爆炸)释放。大量实验结果表明：对于设计含C、H、O、N原子的高能量密度化合物(HEDC)，呋咱和氧化呋咱环是非常有效的结构单元。该类化合物具有氮氧含量高、存在“活性氧”、正的标准生成焓和密度较高等特点，可显著提高推进剂、炸药和发射药的能量和爆炸性能，是当今含能材料领域研究的热点。而呋咱并吡嗪类化合物是近年来发展的一类新型的呋咱含能化合物，这些化合物大多数具有较高的熔点、密度、正生成焓和适当的氧平衡，未来有望应用于推进剂和高能低感炸药领域。
V.Thottempudi等人《1,2,3-Triazolo[4,5,-e]furazano[3,4,-b]pyrazine 6-Oxide—A Fused Heterocycle with a Roving Hydrogen Forms a New Class ofInsensitive Energetic Materials》，Chem.Eur.J.,2014,20,542–548公开了1,2,3-三氮唑[4,5-e]呋咱并[3,4-b]吡嗪-6-氧化物的结构及性能数据，该化合物结构如下所示：
该化合物密度为1.85g/cm3，氮含量为54.75％，计算爆速为8532m/s，爆压为32.4GPa，生成热为597kJ/mol。但是该化合物生成热较小、能量较低。
发明内容
本发明所要解决的技术问题是克服背景技术的不足和缺陷，提供一种生成热较大、能量较高的4-氨基-1,2,3-三氮唑[4,5-e]呋咱并[3,4-b]吡嗪-6-氧化物。
本发明的4-氨基-1,2,3-三氮唑[4,5-e]呋咱并[3,4-b]吡嗪-6-氧化物的合成路线如下：
以1,2,3-三氮唑[4,5-e]呋咱并[3,4-b]吡嗪-6-氧化物为原料，首先与四乙基羟胺的甲醇溶液反应生成1,2,3-三氮唑[4,5-e]呋咱并[3,4-b]吡嗪-6-氧化物四乙基铵盐，再与2,4,6-三甲基苯磺酰羟胺(MSH)反应生成4-氨基-1,2,3-三氮唑[4,5-e]呋咱并[3,4-b]吡嗪-6-氧化物。
本发明的4-氨基-1,2,3-三氮唑[4,5-e]呋咱并[3,4-b]吡嗪-6-氧化物，其结构式如(I)所示：
本发明的4-氨基-1,2,3-三氮唑[4,5-e]呋咱并[3,4-b]吡嗪-6-氧化物的合成方法，包括以下步骤：
(1)1,2,3-三氮唑[4,5-e]呋咱并[3,4-b]吡嗪-6-氧化物四乙基铵盐的合成
冰水浴搅拌下，依次将1,2,3-三氮唑[4,5-e]呋咱并[3,4-b]吡嗪-6-氧化物、甲醇加入到烧瓶中，滴加四乙基羟胺甲醇溶液，加完后升温至20℃～25℃反应1h，反应液冷却至10℃～15℃，过滤、甲醇洗、干燥得1,2,3-三氮唑[4,5-e]呋咱并[3,4-b]吡嗪-6-氧化物四乙基铵盐；其中1,2,3-三氮唑[4,5-e]呋咱并[3,4-b]吡嗪-6-氧化物与四乙基羟胺的摩尔比为1:1～1.5。
(2)4-氨基-1,2,3-三氮唑[4,5-e]呋咱并[3,4-b]吡嗪-6-氧化物的合成
室温搅拌下，将2,4,6-三甲基苯磺酰羟胺加入到无水乙腈中，搅拌溶解，分批加入1,2,3-三氮唑[4,5-e]呋咱并[3,4-b]吡嗪-6-氧化物四乙基铵盐，加完后在20℃～25℃反应4h～10h，蒸除溶剂，加入蒸馏水搅拌，过滤、滤饼经水洗、干燥得4-氨基-1,2,3-三氮唑[4,5-e]呋咱并[3,4-b]吡嗪-6-氧化物；其中1,2,3-三氮唑[4,5-e]呋咱并[3,4-b]吡嗪-6-氧化物四乙基铵盐与2,4,6-三甲基苯磺酰羟胺的摩尔比为1:1～2。
本发明的优点：
本发明的4-氨基-1,2,3-三氮唑[4,5-e]呋咱并[3,4-b]吡嗪-6-氧化物计算生成热较大，其生成热为705kJ/mol，对比文件的1,2,3-三氮唑[4,5-e]呋咱并[3,4-b]吡嗪-6-氧化物的计算生成热为592kJ/mol；本发明的4-氨基-1,2,3-三氮唑[4,5-e]呋咱并[3,4-b]吡嗪-6-氧化物能量较高，其计算爆速为8743m/s，爆压为34.6GPa，对比文件的1,2,3-三氮唑[4,5-e]呋咱并[3,4-b]吡嗪-6-氧化物的计算爆速为8532m/s，爆压为32.4GPa。
具体实施方式
以下结合实施例对本发明作进一步详细说明。
实施例1
(1)1,2,3-三氮唑[4,5-e]呋咱并[3,4-b]吡嗪-6-氧化物四乙基铵盐的合成
冰水浴搅拌下，依次将0.54g(3mmol)1,2,3-三氮唑[4,5-e]呋咱并[3,4-b]吡嗪-6-氧化物、10.0mL甲醇加入到烧瓶中，滴加1.76g(3mmol)质量百分比为25％的四乙基羟胺甲醇溶液，加完后升温至20℃～25℃反应1h，反应液冷却至10℃～15℃，过滤、甲醇洗、干燥得1,2,3-三氮唑[4,5-e]呋咱并[3,4-b]吡嗪-6-氧化物四乙基铵盐0.88g，收率为95.2％。
结构鉴定：
红外光谱：IR(KBr,cm-1),υ：2996,2951,1592,1495,1438,1391,1331,1300,1172,1043,990,885,873,782,738,718
核磁光谱：1HNMR(DMSO-d6,500MHz),δ:1.165～1.201(t,12H,4CH3),3.209～3.224(t,8H,4CH2)；13CNMR(DMSO-d6,125MHz),δ:7.549,51.91,153.39,159.41
元素分析：分子式C12H20N8O2
理论值：C 46.74,H 6.54,N 36.34
实测值：C 46.78,H 6.50,N 36.30。
上述结构鉴定数据证实得到物质确实是1,2,3-三氮唑[4,5-e]呋咱并[3,4-b]吡嗪-6-氧化物四乙基铵盐。
(2)4-氨基-1,2,3-三氮唑[4,5-e]呋咱并[3,4-b]吡嗪-6-氧化物的合成
室温搅拌下，将0.56g(2.6mmol)2,4,6-三甲基苯磺酰羟胺加入到15.0mL无水乙腈中，搅拌溶解，分批加入0.62g(2mmol)1,2,3-三氮唑[4,5-e]呋咱并[3,4-b]吡嗪-6-氧化物四乙基铵盐，加完后在20℃～25℃反应7h，蒸除溶剂，加入6.0mL蒸馏水搅拌，过滤、滤饼经水洗、干燥得4-氨基-1,2,3-三氮唑[4,5-e]呋咱并[3,4-b]吡嗪-6-氧化物0.30g，收率为77.3％。
结构鉴定：
红外光谱：IR(KBr,cm-1),υ：3201,3067,1625,1603,1513,1486,1439,1391,1334,1297,1222,1172,1084,1044,989,833,782,737,719,678
核磁光谱：1HNMR(DMSO-d6,500MHz),δ:6.735(s,2H,NH2)；13CNMR(DMSO-d6,125MHz),δ:130.27,136.34
元素分析：分子式C4H2N8O2
理论值：C 24.75,H 1.04,N 57.73
实测值：C 24.79,H 1.10,N 57.65。
上述结构鉴定数据证实得到物质确实是4-氨基-1,2,3-三氮唑[4,5-e]呋咱并[3,4-b]吡嗪-6-氧化物。
本发明4-氨基-1,2,3-三氮唑[4,5-e]呋咱并[3,4-b]吡嗪-6-氧化物的性能
(1)物化性能
外观：黄褐色固体
溶解度：易溶于二甲基亚砜、N,N-二甲基甲酰胺、乙腈、甲醇等，微溶于水、乙醚、石油醚密度：1.82g/cm3Gaussian 09程序B3LYP方法(2)爆轰性能
本发明的4-氨基-1,2,3-三氮唑[4,5-e]呋咱并[3,4-b]吡嗪-6-氧化物的用途
本发明的4-氨基-1,2,3-三氮唑[4,5-e]呋咱并[3,4-b]吡嗪-6-氧化物具有生成热较大、能量较高等特点，可以应用于混合炸药、推进剂等领域。

Claims (1)

1.一种4-氨基-1,2,3-三氮唑[4,5-e]呋咱并[3,4-b]吡嗪-6-氧化物，其结构式如(I)所示：
CN201610317757.2A 2016-05-13 2016-05-13 4‑氨基‑1,2,3‑三氮唑[4,5‑e]呋咱并[3,4‑b]吡嗪‑6‑氧化物 Expired - Fee Related CN105949219B (zh)

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Non-Patent Citations (3)

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Title
1,2,3-Triazolo[4,5,-e]furazano[3,4,-b]pyrazine 6-Oxide—A Fused Heterocycle with a Roving Hydrogen Forms a New Class of Insensitive Energetic Materials;Venugopal Thottempudi，等;《Chem. Eur. J.》;20141231;第20卷;摘要，第543页化合物5 *
两种呋咱并［3，4-b］四唑并［1，2-d］吡嗪化合物的合成、晶体结构及热性能;刘宁，等;《含能材料》;20150228;第23卷(第1期);13-17页 *
双呋咱并吡嗪衍生物的合成、表征及性能;刘宁，等;《含能材料》;20140831;第22卷(第4期);473-477页 *

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