cyclopropylchlorodiazirine | 4222-24-6

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 异戊烯醇脂质
• 英文名称: cyclopropylchlorodiazirine
• 英文别名: 3-Chloro-3-cyclopropyldiazirine；3-Cyclopropyl-3-chlor-diazirin
• CAS: 4222-24-6
• 化学式: C₄H₅ClN₂
• 分子量: 116.55
• InChiKey: GGAPUNPHRKYFBJ-UHFFFAOYSA-N

物化性质

• 沸点：
  115.5±50.0 °C(Predicted)
• 密度：
  1.83±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.6
• 重原子数：
  7
• 可旋转键数：
  1
• 环数：
  2.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  24.7
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  cyclopropylchlorodiazirine 以 异辛烷 为溶剂， 生成 cyclopropylchlorocarbene
  参考文献：
  名称：

  通过直接观察卡宾在激光闪光光谱中测量的环丙基氯卡宾重排的能垒

  摘要：

  DOI：

  10.1021/j100358a007
• 作为产物：
  描述：

  环丙甲脒盐酸盐 在 lithium chloride 、 sodium hypochlorite 、 sodium chloride 作用下， 以 二甲基亚砜 为溶剂， 反应 0.83h， 生成 cyclopropylchlorodiazirine
  参考文献：
  名称：

  通过 σ → p 吸收跟踪“隐形”烷基氯卡宾：动力学和溶剂相互作用

  摘要：

  与文献中的含义相反，烷基氯卡宾 (RCCl) 的 sigma --> p 吸收很容易通过激光闪光光解在环境温度下在溶液中使用 UV-vis 检测获得。实例包括 RCCl，其中 R = 甲基、苄基、叔丁基、1-金刚烷基和环丙基。这些吸收允许直接监测卡宾反应和卡宾-溶剂复合物的形成。“游离”和复合的 MeCCl 和 PhCH2CCl 的反应动力学直接与四甲基乙烯和 1-己烯跟踪。苯甲醚和 1,3-二甲氧基苯提供了特别有效的络合，它们调节了分子间卡宾加成的速率。介绍了计算研究，这有助于理解卡宾吸收光谱和溶剂配合物的性质。

  DOI：

  10.1021/ja071799i

文献信息

• Cyclopropyl/phenylcyclopropenyl cations: studies in stabilization
  作者：Robert A. Moss、Shilan. Shen、Karsten. Krogh-Jespersen、Joseph A. Potenza、Harvey J. Schugar、Ramesh C. Munjal

  DOI：10.1021/ja00261a022

  日期：1986.1

  Etude des structures cristallines des composes Cy 3 C 3 SbF 6 et Cy 2 PhC 3 BF 4 . Calcul d'orbitale moleculaire rationalisant la stabilite relative de ces cations

  晶体结构练习曲由Cy 3 C 3 SbF 6 和Cy 2 PhC 3 BF 4 组成。计算轨道分子合理性的稳定相对下降
• Kinetic and Spectroscopic Properties of Carbene−Diazirine Ylides
  作者：Roland Bonneau、Michael T. H. Liu

  DOI：10.1021/jp993711w

  日期：2000.5.1

  The formation of a metastable carbene−diazirine ylide (CDY), characterized by an UV absorption spectrum in the range of 270−290 nm and yielding azine by rearrangement, is shown to be a general process in the photolysis of diazirines. However, the yield of formation and the lifetime of CDY greatly depend on the system considered. The decreasing value of the rate constant of the reaction, carbene + diazirine

  亚稳态卡宾-二氮丙啶叶立德 (CDY) 的形成，其特征在于 270-290 nm 范围内的紫外吸收光谱并通过重排产生吖嗪，被证明是二氮丙啶光解的一般过程。然而，形成的产量和 CDY 的寿命很大程度上取决于所考虑的系统。对于单线态二烷基卡宾，卡宾 + 二氮丙啶 → CDY 的反应速率常数从 ∼109 M-1 s-1 递减，Ad: (金刚亚基) 和 BCN: (bicyclo[3.3.1]non-9-ylidene )，对于苄基氯卡宾，到 ~108 M-1 s-1，对于环丙基和苯基氯卡宾，到 ~106 M-1 s-1，反映了这些卡宾的反应性降低。这些叶立德的寿命取决于它们重排成吖嗪的活化能垒值，Ea ≈ 15.5 kcal/mol，对于二烷基卡宾，≈11。烷基氯卡宾为 5 kcal/mol，苯基氯卡宾为 <10 kcal/mol。这种 Ea 的降低与从 C 开始时对嗪的强烈稳定性有关...
• The tricyclopropylcyclopropenium ion
  作者：Koichi Komatsu、Isao Tomioka、Kunio Okamoto

  DOI：10.1016/s0040-4039(00)77747-1

  日期：1980.1
• Precise control of the formation of a covalent and an ionic bond in carbocation-carbanion combination reactions
  作者：Kenichi Takeuchi、Toshikazu Kitagawa、Atsushi Miyabo、Hideshi Hori、Koichi Komatsu

  DOI：10.1021/jo00073a047

  日期：1993.10

  The electronic effect on the selectivity of covalent or ionic bond formation was examined for the reaction of Kuhn's anion 1- (C67H39-; tris(7H-dibenzo[c,g]fluorenylidenemethyl)methide ion) and 1-aryl-2,3-dicyclopropylcyclopropenylium ions. The carbocation stability was progressively changed by varying the substituent on the phenyl ring, while the steric effect was kept essentially unchanged. The cations having the p-chlorophenyl (2a+), phenyl (2b+), m-methylphenyl (2c+), or m,m'-dimethylphenyl (2d+) group gave a covalent product, whereas a carbocation-carbanion salt was obtained from the cations having the p-methylphenyl (2e+) or p-methoxyphenyl (2f+) group. The reduction potentials E(red) of the cations, as determined by cyclic voltammetry, showed that the formation of the covalent or ionic product is switched by a small difference in stability (less-than-or-equal-to 0.4 kcal/mol) between 2d+ and 2e+. In chloroform, the salts 1-2e+ and 1-2f+ were transformed into covalent forms 1-2e and 1-2f, which can exist only in solution. When 1-(2a-d) and 1-2e,f+ were dissolved in DMSO, equilibrium between a covalent compound and ions was established. A plot of the free energy of heterolysis DELTAG(het)-degrees for 1-(2a-f) against the E(red) of the corresponding cations 2a-f+ showed that DELTAG(het)-degrees decreases as the cation is more stabilized. The heterolysis in DMSO was shown to be enhanced by ca. 13 kcal/mol both by the steric congestion in the covalent molecules and the stabilization of the cyclopropenylium ions by solvation.
• Kinetics of alkylhalocarbene rearrangements: modulation by fluorine substituents
  作者：Robert A. Moss、Guo Jie Ho、Weiguo Liu

  DOI：10.1021/ja00029a025

  日期：1992.1

  Rate constants were measured by laser flash photolytic methods for hydrogen and carbon 1,2-migrations in four different alkylchlorocarbenes and in the analogous alkylfluorocarbenes. The carbenes, products, and rate constants (s-1) were as follows: phenoxymethylchlorocarbene to (Z)- and (E)-1-chloro-2-phenoxyethene (Z/E approximately 4/1), k = 3.6 x 10(7); phenoxymethylfluorocarbene to (Z)-1-fluoro-2-phenoxyethene (Z/E > 10/1), k = 1.3 x 10(7); neopentylchlorocarbene to (Z)- and (E)-1-tert-butyl-2-chloroethene (Z/E = 1/12), k = 1.4 x 10(7); neopentylfluorocarbene to (Z)- and (E)-1-tert-butyl-2-fluoroethene (Z/E = 1/2.5), k = 2.6 X 10(6); cyclobutylchlorocarbene to 1-chlorocyclopentene (C migration) and chloromethylenecyclobutane (H migration), k(c) = 4.6 X 10(7), k(H) = 2.1 X 10(7); cyclobutylfluorocarbene to 1-fluorocyclopentene (C migration) and fluoromethylenecyclobutane (H migration), k(c) = 1.8 x 10(6), k(H) = 5.3 x 10(5); cyclopropylchlorocarbene to 1-chlorocyclobutene, k = 9 x 10(5); cyclopropylfluorocarbene to 1-fluorocyclobutene, k = 1.4 x 10(5). Activation energies for several of these processes were in the range of 2-4 kcal/mol, with A approximately 10(8)-10(9) s-1.