2-(dinitromethylene)-1,3-diazacycloheptane | 137143-84-1

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 二氮杂卓
• 英文名称: 2-(dinitromethylene)-1,3-diazacycloheptane
• 英文别名: 2-(Dinitromethylene)-1,3-diazepan；2-(dinitromethylidene)-1,3-diazepane
• CAS: 137143-84-1
• 化学式: C₆H₁₀N₄O₄
• 分子量: 202.17
• InChiKey: BKOSWOSVZAVQII-UHFFFAOYSA-N

物化性质

• 沸点：
  287.5±40.0 °C(Predicted)
• 密度：
  1.341±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1
• 重原子数：
  14
• 可旋转键数：
  0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.67
• 拓扑面积：
  116
• 氢给体数：
  2
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  2-(dinitromethylene)-1,3-diazacycloheptane 在 盐酸 、 18-冠醚-6 、 硝酸 、 三氟乙酸酐 、 potassium iodide 作用下， 以 四氢呋喃 、 二氯甲烷 、 水 为溶剂， 反应 17.25h， 生成 2-(Dinitromethylene)-1-nitro-1,3-diazacycloheptane
  参考文献：
  名称：

  Nitration of 1,1-diamino-2,2-dinitroethylenes

  摘要：

  The nitration of 1,1-diamino-2,2-dinitroethylenes, obtained by the reaction of amines with 1,1-diiododinitroethylene, was studied. Reaction of 2-(dinitromethylene)-1,3-diazacyclopentane (la) with nitric acid and trifluoroacetic anhydride in methylene chloride gave 3-nitro-2-(trinitromethyl)-1,3-diazacyclopent-1-ene (3a) in high yield. Analogous products 3b-3d were obtained from 2-(dinitromethylene)-1,3-diazacyclohexane (1b), 2-(dinitromethylene)-1,3-diazacycloheptane (1c), and 3,9-bis(dinitromethylene)-2,4,8,10-tetraazaspiro[5.5]undecane (1d). Nitration of 1a with nitric acid in sulfuric acid gave the corresponding nitrosamine 2a. Reductive denitrations of the trinitromethyl compounds 3a, 3b, and 3c with potassium iodide gave salts of the corresponding dinitromethyl compounds 4a, 4b, and 4c. Bromination and chlorination of 4a afforded 2-(bromodinitromethyl)-3-nitro-1,3-diazacyclopentent-1-ene (5) and 2-(chlorodinitromethyl)-3-nitro-1,3-diazacyclopent-1-ene (6), respectively. Acidification of the salts 4a, 4b, and 4c gave 2-(dinitromethylene)-1-nitro-1,3-diazacyclopentane (7a), 2-(dinitromethylene)-1-nitro-1,3-diazacyclohexane (7b), and 2-(dinitromethylene)-1-nitro-1,3-diazacycloheptane (7c), respectively. The nitration of 7a gave 3a. Nitrations of the diamino mononitro olefins, 2-(nitromethylene)-1, 3-diazacyclopentane (8a) and 2-(nitromethylene)-1,3-diazacyclohexane (8b), gave 3a and 3b. The structures of 3a, 3d, 7a, 7b, and 7c were obtained by X-ray crystallography. Olefin twist angles for 7a-7c, as high as 74.5-degrees, are rationalized on the bases of ring geometry and hydrogen bonding.

  DOI：

  10.1021/jo00037a015
• 作为产物：
  描述：

  1,1-diiodo-2,2-dinitroethylene 、 四亚甲基二胺 以 甲醇 、 水 为溶剂， 反应 2.0h， 生成 2-(dinitromethylene)-1,3-diazacycloheptane
  参考文献：
  名称：

  1,1-二氨基-2,2-二硝基乙烯总是两性离子。

  摘要：

  四碘乙烯（7）的硝化反应生成1,1-二碘-2,2-二硝基乙烯（8）。后者与烷基胺9或烷基二胺11反应，分别得到相应的无环1，1-二氨基-2，2-二硝基乙烯10或它们的环状类似物12。根据液态和固态（13）C和（15）N NMR数据，x射线分析和从头算计算，我们建议标题化合物始终为两性离子，C（A）-C（N ）键不是真正的双键。

  DOI：

  10.1002/mrc.3861

文献信息

• Thermal Behaviors of 2-(Dinitromethylene)-1,3-diazacycloheptane (DNDH)
  作者：Lei Lü、Kangzhen Xu、Gang Wang、Jinan Luo、Jirong Song、Bozhou Wang、Fengqi Zhao

  DOI：10.1002/cjoc.201180283

  日期：2011.8

  the reaction of 1,1‐diamino‐2,2‐dinitroethylene (FOX‐7) with 1,4‐diaminoethane in NMP. Thermal decomposition behavior of DNDH was studied under the non‐isothermal conditions with DSC method, and presents only one intensely exothermic decomposition process. The kinetic equation of the decomposition reaction is dα/dT=1033.88×3α2/3exp(−3.353×105/RT)/β. The critical temperature of thermal explosion is 215

  通过NMP中的1,1-二氨基-2-2,2-二硝基乙烯（FOX-7）与1,4-二氨基乙烷的反应制得2-（二硝基亚甲基）-1,3-二氮杂环庚烷（DNDH）。在非等温条件下，采用DSC方法研究了DNDH的热分解行为，仅显示了一个强烈的放热分解过程。分解反应的动力学方程为：d α / d Ť = 10 33.88 ×3 α 2/3 EXP（-3.353×10 5 / RT）/ β。热爆炸的临界温度为215.97°C。用micro-DSC法和理论计算方法研究了DNDH的比热容，摩尔热容为215.40 J·mol -1 ·K-1在298.15K。绝热爆炸时间经计算为92.07 s。DNDH具有与FOX-7相同的热稳定性。
• Synthesis and reactions of 1,1-diiododinitroethylene
  作者：Kurt Baum、Sean S. Bigelow、Nguyen Nghi Van、Thomas G. Archibald、Richard Gilardi、Judith L. Flippen-Anderson、Clifford George

  DOI：10.1021/jo00027a042

  日期：1992.1

  The nitration of tetraiodoethylene gave 1,1-diiododinitroethylene (1). X-ray crystallography showed that one of the two nitro groups is perpendicular to the ethylene plane. Simple amines (dimethylamine, propylamine, aniline) reacted with 1 to give 1,1-diamino-2,2-dinitroethylene derivatives; diamines (o-phenylenediamine, ethylenediamine, 1,3-diaminopropane, 1,4-diaminobutane) gave the corresponding cyclic products, and a tetramine [(tetrakis(aminomethyl)methane] gave the analogous spiro derivative. Ammonia gave only ammonium cyanodinitromethide, whereas phenol gave 1,1-dinitro-2,2,2-triphenoxyethane. The reaction of 1 with potassium nitrite gave the dipotassium salt of tetranitroethane. X-ray crystallography of the 1,1-diamino-2,2-dinitroethylenes showed twisted olefins, some with twist angles greater than any previously reported for twisted ethylenes, with concomitant bond-distance distortions.
• Nitration of 1,1-diamino-2,2-dinitroethylenes
  作者：Kurt Baum、Nguyen Nghi Van、Richard Gilardi、Judith L. Flippen-Anderson、Clifford George

  DOI：10.1021/jo00037a015

  日期：1992.5

  The nitration of 1,1-diamino-2,2-dinitroethylenes, obtained by the reaction of amines with 1,1-diiododinitroethylene, was studied. Reaction of 2-(dinitromethylene)-1,3-diazacyclopentane (la) with nitric acid and trifluoroacetic anhydride in methylene chloride gave 3-nitro-2-(trinitromethyl)-1,3-diazacyclopent-1-ene (3a) in high yield. Analogous products 3b-3d were obtained from 2-(dinitromethylene)-1,3-diazacyclohexane (1b), 2-(dinitromethylene)-1,3-diazacycloheptane (1c), and 3,9-bis(dinitromethylene)-2,4,8,10-tetraazaspiro[5.5]undecane (1d). Nitration of 1a with nitric acid in sulfuric acid gave the corresponding nitrosamine 2a. Reductive denitrations of the trinitromethyl compounds 3a, 3b, and 3c with potassium iodide gave salts of the corresponding dinitromethyl compounds 4a, 4b, and 4c. Bromination and chlorination of 4a afforded 2-(bromodinitromethyl)-3-nitro-1,3-diazacyclopentent-1-ene (5) and 2-(chlorodinitromethyl)-3-nitro-1,3-diazacyclopent-1-ene (6), respectively. Acidification of the salts 4a, 4b, and 4c gave 2-(dinitromethylene)-1-nitro-1,3-diazacyclopentane (7a), 2-(dinitromethylene)-1-nitro-1,3-diazacyclohexane (7b), and 2-(dinitromethylene)-1-nitro-1,3-diazacycloheptane (7c), respectively. The nitration of 7a gave 3a. Nitrations of the diamino mononitro olefins, 2-(nitromethylene)-1, 3-diazacyclopentane (8a) and 2-(nitromethylene)-1,3-diazacyclohexane (8b), gave 3a and 3b. The structures of 3a, 3d, 7a, 7b, and 7c were obtained by X-ray crystallography. Olefin twist angles for 7a-7c, as high as 74.5-degrees, are rationalized on the bases of ring geometry and hydrogen bonding.
• 1,1-Diamino-2,2-dinitroethylenes are always zwitterions
  作者：Pessia Gilinsky-Sharon、Hugo E. Gottlieb、David E. Rajsfus、Keren Keinan-Adamsky、Vered Marks、Pinchas Aped、Aryeh A. Frimer

  DOI：10.1002/mrc.3861

  日期：2012.10

  or alkyldiamines 11 to give the corresponding acyclic 1,1-diamino-2,2-dinitroethylenes 10 or their cyclic analogs 12, respectively. On the basis of liquid and solid-state (13)C and (15)N NMR data, x-ray analysis and ab initio calculations, we suggest that the title compounds are always zwitterionic and that the C(A)-C(N) bond is not a true double bond.

  四碘乙烯（7）的硝化反应生成1,1-二碘-2,2-二硝基乙烯（8）。后者与烷基胺9或烷基二胺11反应，分别得到相应的无环1，1-二氨基-2，2-二硝基乙烯10或它们的环状类似物12。根据液态和固态（13）C和（15）N NMR数据，x射线分析和从头算计算，我们建议标题化合物始终为两性离子，C（A）-C（N ）键不是真正的双键。