3-Nitro-2-(trinitromethyl)-1,3-diazacyclohept-1-ene | 140657-65-4

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 二氮卓类
• 英文名称: 3-Nitro-2-(trinitromethyl)-1,3-diazacyclohept-1-ene
• 英文别名: 1-Nitro-2-(trinitromethyl)-4,5,6,7-tetrahydro-1,3-diazepine
• CAS: 140657-65-4
• 化学式: C₆H₈N₆O₈
• 分子量: 292.165
• InChiKey: MKABQRKNRJHORZ-UHFFFAOYSA-N

物化性质

• 沸点：
  348.6±52.0 °C(Predicted)
• 密度：
  2.04±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  0.3
• 重原子数：
  20
• 可旋转键数：
  1
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.83
• 拓扑面积：
  199
• 氢给体数：
  0
• 氢受体数：
  9

反应信息

• 作为反应物：
  描述：

  3-Nitro-2-(trinitromethyl)-1,3-diazacyclohept-1-ene 在 盐酸 、 18-冠醚-6 、 potassium iodide 作用下， 以 四氢呋喃 、 水 为溶剂， 反应 16.25h， 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：

  2-(dinitromethylene)-1,3-diazacycloheptane 在 硝酸 、 三氟乙酸酐 作用下， 以 二氯甲烷 为溶剂， 反应 1.0h， 以57%的产率得到3-Nitro-2-(trinitromethyl)-1,3-diazacyclohept-1-ene
  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