2,2,3,3-tetradeuterio(methylidene)cyclopropane | 159837-96-4

• 分子结构分类: 有机化合物 - 碳氢化合物 - 不饱和烃
• 英文名称: 2,2,3,3-tetradeuterio(methylidene)cyclopropane
• 英文别名: 2.2.3.3-Tetradeuteriomethylencyclopropan；tetradeuterio-methylene-cyclopropane；Tetradeuterio(methylidene)cyclo propane；1,1,2,2-tetradeuterio-3-methylidenecyclopropane
• CAS: 159837-96-4
• 化学式: C₄H₆
• 分子量: 58.0599
• InChiKey: XSGHLZBESSREDT-RRVWJQJTSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1
• 重原子数：
  4
• 可旋转键数：
  0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.5
• 拓扑面积：
  0
• 氢给体数：
  0
• 氢受体数：
  0

反应信息

• 作为反应物：
  描述：

  二氧化碳 、 2,2,3,3-tetradeuterio(methylidene)cyclopropane 在 2,2,6,6-四甲基哌啶 、 正丁基锂 、 potassium tert-butylate 作用下， 以 四氢呋喃 、 正己烷 为溶剂， 反应 12.42h， 以0.95 g的产率得到1,3,3-trideuterio-2-methylidenecyclopropanecarboxylic acid
  参考文献：
  名称：

  摘要：

  N-(1,3,3-Trideuterio-2-methylidenecyclopropyl)-N-nitrosourea was synthesized and its decomposition on treatment with K2CO3 in the presence of acrylonitrile and ethyl acrylate or on treatment with MeONa in the absence of unsaturated substrates was studied. The rate of decomposition of the nitrosourea is much lower than that of the nondeuterated analog. The use of acrylates for trapping the intermediate 3,3-dideuterio-1-diazo-2-methylidenecyclopropane results in the corresponding 2'-methylidenespiro[4,5-dihydropyrazole-5,1'-cyclopropanes] containing two deuterium atoms in the cyclopropane fragment. The resulting dihydropyrazoles are isomerized almost entirely over a period of 1-3 days to give a mixture (similar to1 : 1) of isopropenylpyrazoles in which both deuterium atoms occur either in the methyl or in the methylidene groups of the isopropenyl substituent. A possible mechanism of this transformation is considered.

  DOI：

  10.1023/a:1023910923663
• 作为产物：
  描述：

  亚甲基环丙烷 在 氘代二甲亚砜 、 potassium hydride 作用下， 反应 4.0h， 生成 2,2,3,3-tetradeuterio(methylidene)cyclopropane
  参考文献：
  名称：

  摘要：

  N-(1,3,3-Trideuterio-2-methylidenecyclopropyl)-N-nitrosourea was synthesized and its decomposition on treatment with K2CO3 in the presence of acrylonitrile and ethyl acrylate or on treatment with MeONa in the absence of unsaturated substrates was studied. The rate of decomposition of the nitrosourea is much lower than that of the nondeuterated analog. The use of acrylates for trapping the intermediate 3,3-dideuterio-1-diazo-2-methylidenecyclopropane results in the corresponding 2'-methylidenespiro[4,5-dihydropyrazole-5,1'-cyclopropanes] containing two deuterium atoms in the cyclopropane fragment. The resulting dihydropyrazoles are isomerized almost entirely over a period of 1-3 days to give a mixture (similar to1 : 1) of isopropenylpyrazoles in which both deuterium atoms occur either in the methyl or in the methylidene groups of the isopropenyl substituent. A possible mechanism of this transformation is considered.

  DOI：

  10.1023/a:1023910923663

文献信息

• Evidence for diazenyl allyl diradicals in the thermolysis of 4-alkylidene-1-pyrazolines
  作者：Robert J. Crawford、Moon Ho Chang

  DOI：10.1016/0040-4020(82)80164-6

  日期：1982.1

  e breaks preferentially to the syn bond. It is suggested that the product determining step involves an intramolecular radical displacement of nitrogen, as well as an electrocyclic rotation of the allylic methylene groups of the diazenyl allyl diradical, to generate the cyclopropane ring concerted with the loss of nitrogen. The position of deuterium in the methylmethylenecyclopropane can best be rationalized

  次级氘动力学同位素效应表明CN键反向Me基团上4-亚乙基-1-吡唑啉场所优先于顺式键。建议产物确定步骤涉及氮的分子内自由基置换，以及二氮烯基烯丙基二自由基的烯丙基亚甲基的电环旋转，以产生与氮损失协同作用的环丙烷环。氘在甲基亚甲基环丙烷中的位置可以通过后面的步骤来最好地合理化。
• Chang, Moon Ho; Crawford, Robert J., Canadian Journal of Chemistry, 1981, vol. 59, p. 2556 - 2568
  作者：Chang, Moon Ho、Crawford, Robert J.

  DOI：——

  日期：——