1,3,3-trinitroazetidine | 97645-24-4

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 氮杂环丁烷
• 英文名称: 1,3,3-trinitroazetidine
• 英文别名: TNAZ
• CAS: 97645-24-4
• 化学式: C₃H₄N₄O₆
• 分子量: 192.088
• InChiKey: ZCRYIJDAHIGPDQ-UHFFFAOYSA-N

物化性质

• 熔点：
  100-101°
• 密度：
  1.84 g/cm3

计算性质

• 辛醇/水分配系数(LogP)：
  0.1
• 重原子数：
  13
• 可旋转键数：
  0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  141
• 氢给体数：
  0
• 氢受体数：
  7

反应信息

• 作为反应物：
  描述：

  1,3,3-trinitroazetidine 生成 nitroacetaldehyde 、 二氧化碳
  参考文献：
  名称：

  1,3,3-三硝基氮杂环丁烷在气相、溶液和熔体中的热分解

  摘要：

  摘要 1,3,3-三硝基氮杂环丁烷（TNAZ）是在3-肟基-1-（对甲苯磺酰基）氮杂环丁烷与硝酸反应中通过中间体赝硝基转化而成的。通过测压法、体积法、热重法、红外光谱法和质谱法研究了 TNAZ 在气相、熔体和间二硝基苯溶液中在宽浓度范围 (5-80%) 中的热分解。在 170 至 220°C 温度范围内的气相中，热分解按照一级动力学定律进行，活化能为 40.5 kcal mol-1，指前因子为 1015.0 s-1。主要的气态反应产物是 N2、NO、NO2、CO2、H2O 和硝基乙醛，并形成微量的 CO 和 HCN。该过程的速率决定步骤是 TNAZ 分子中 N-NO2 键的均裂裂解。在 170–210 °C 的熔体中，热分解以明显的自加速进行，在转化率为 53.9–67.4% 时观察到最大反应速率。固体分解产物加速反应。液相中TNAZ分解的自催化最有可能是由于TNAZ热分解形成的1-亚硝基-3

  DOI：

  10.1007/s11172-009-0277-y
• 作为产物：
  描述：

  1,3-dinitro-3-(hydroxymethyl)azetidine 在 sodium hydroxide 、 dipotassium peroxodisulfate 、 potassium hexacyanoferrate(III) 、 sodium nitrite 作用下， 反应 48.0h， 以20%的产率得到1,3,3-trinitroazetidine
  参考文献：
  名称：

  A Novel Approach to the Synthesis of 1,3,3-trinitroazetidine

  摘要：

  DOI：

  10.1021/jo00120a049

文献信息

• Synthesis of 1,3,3-trinitroazetidine
  作者：Theodore Axenrod、Clara Watnick、Hamid Yazdekhasti、Paritosh R. Dave

  DOI：10.1016/s0040-4039(00)61673-8

  日期：1993.10

  sulfonate) on treatment with LiH undergoes ring closure to the correponding azetidine which is readily converted to N-tosyl-3-azetidinone oxime. By oxidative nitrolysis the latter affords 1,3,3-trinitroazetidine.

  用LiH处理的3-（对甲苯磺酰胺基）丙烷-2-醇-1-（对甲苯磺酸）的叔丁基二甲基甲硅烷基醚闭环成相应的氮杂环丁烷，后者容易转化为N-甲苯磺酰基-3-氮杂环丁酮肟。通过氧化氮解，后者得到1,3,3-三硝基氮杂环丁烷。
• Synthesis of heterocyclic geminal nitro azides
  作者：D. V. Katorov、G. F. Rudakov、V. F. Zhilin

  DOI：10.1007/s11172-009-0323-9

  日期：2009.11

  The oxidative azidation reactions of C-nitro-substituted saturated heterocyclic compounds, viz., the nitro derivatives of oxetane, azetidine, 1,3-dioxane, tetrahydro-1,3-oxazine, and hexahydropyrimidine, were investigated. A novel representatives of the geminal nitro azides were prepared and their physicochemical properties were studied. The process of the formation of the geminal dinitro compounds

  研究了C-硝基取代的饱和杂环化合物的氧化叠氮化反应，即氧杂环丁烷、氮杂环丁烷、1,3-二恶烷、四氢-1,3-恶嗪和六氢嘧啶的硝基衍生物。制备了一种新型的孪生硝基叠氮化物的代表物并研究了它们的理化性质。分析了氧化叠氮化形成孪生二硝基化合物的过程。
• Synthesis of 3,3-dinitroazetidine
  申请人：The United States of America as represented by the United States

  公开号：US05395945A1

  公开（公告）日：1995-03-07

  The compound, 3,3-dinitroazetidine, and a process of preparing 3,3-dinitroazetidine including reacting a mixture of 1-tertiary-butyl-3,3-dinitroazetidine and benzyl chloroformate to form 1-(benzyloxycarbonyl)-3,3-dinitroazetidine, reacting the 1-(benzyloxycarbonyl)-3,3-dinitroazetidine and trifluoromethanesulfonic acid to form 3,3-dinitroazetidinium trifluoromethanesulfonate, and neutralizing the 3,3-dinitroazetidinium trifluoromethanesulfonate with a base to form 3,3-dinitroazetidine are provided. Salts of the 3,3-dinitroazetidine and preparation of such salts are also disclosed.

  本发明提供了3,3-二硝基氮杂环丙烷化合物和制备3,3-二硝基氮杂环丙烷的方法，包括将1-叔丁基-3,3-二硝基氮杂环丙烷和苄基氯甲酸酯混合物反应以形成1-(苄氧羰基)-3,3-二硝基氮杂环丙烷，将1-(苄氧羰基)-3,3-二硝基氮杂环丙烷和三氟甲磺酸反应以形成3,3-二硝基氮杂环丙烷三氟甲磺酸盐，然后用碱中和3,3-二硝基氮杂环丙烷三氟甲磺酸盐以形成3,3-二硝基氮杂环丙烷。本发明还公开了3,3-二硝基氮杂环丙烷的盐以及制备这种盐的方法。
• Substitutions on azetidines by acylative dealylation with lewis acid
  申请人：The United States of America as represented by the Secretary of the Army

  公开号：US06121462A1

  公开（公告）日：2000-09-19

  The invention is a process for the modification or substitution of aza suituted azetidines through acylative dealkylation.

  这项发明是通过酰基脱烷基反应对氮杂环戊烷类化合物进行改性或置换的过程。
• Mechanisms of Nitramine Thermolysis
  作者：J. C. Oxley、A. B. Kooh、R. Szekeres、W. Zheng

  DOI：10.1021/j100079a019

  日期：1994.7

  The thermal decomposition of a number of nitramines was studied in dilute solution and in the melt, The nitramines included acyclic mononitramines [dimethylnitramine (DMN), diethylnitramine (DEN), dipropylnitramine (DPN), and diisopropylnitramine (DIPN)], cyclic mononitramines [N-nitropiperidine (NPIP) and N-nitropyrrolidine (NPyr)], cyclic dinitramines [N-dinitropiperazine (pDNP), 1,3-dinitro-1,3-diazacyclopentane (DNI), and 1,3-dinitro-1,3-diazacyclohexane (mDNP)], and 1,3,5-trinitro-1,3,5-triazocyclohexane (RDX), octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine (HMX), hexanitrohexaazaisowurtzitane (HNIW), and 1,3,3-trinitroazetidine (TNAZ). For the acyclic and cyclic mono- and dinitramines, the corresponding nitrosamines were the only or major condensed-phase product. Kinetics and activation parameters were determined for the thermolysis of dilute solutions (0.01-1.0 wt %) over the range 200-300 degrees C. The thermolyses were found to be first-order with the rate constants unaffected by the use of deuterated solvent. As the nitramines became more complex than dimethylnitramine (DMN), the rate of decomposition increased and the product distribution became more complex. As the length of the aliphatic chain increased (DMN < DEN < DPN), the rate of thermolysis increased, yet nitrosamine remained the only observed condensed-phase product. When a secondary carbon was attached to the N-nitramine (DIPN) rather than the primary (DPN), the rate of decomposition increased and a new condensed-phase product was observed. Among the cyclic nitramines, the rate of decomposition increased as the number of NNO2 groups increased (NPIP < pDNP; NPyr < DNI; mDMP < RDX). The position of the nitramine groups affected the decomposition: meta NNO2 groups (mDNP) decomposed faster than para (pDNP). Ring strain decreased stability: mDNP < DNI; HMX < RDX. In complex nitramines, the increase in decomposition rate, the appearance of new products, and the change in the relative importance of nitrosamine and of N-2 and N2O are attributed to new decomposition routes available to them. However, since complex nitramines (e.g. RDX) maintain first-order kinetics and since most have activation energies in the range of 40-50 kcal/mol, it is believed that the triggering mechanism remains N-NO2 homolysis. Intramolecular hydrogen transfer is also considered an important mode of nitramine decomposition.