<(trans-2,trans-3-diphenylcyclopropyl)methyl>triphenylphosphonium bromide | 117039-40-4

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: <(trans-2,trans-3-diphenylcyclopropyl)methyl>triphenylphosphonium bromide
• CAS: 117039-40-4
• 化学式: Br*C₃₄H₃₀P
• 分子量: 549.49
• InChiKey: NFQUHJGTWFAHJC-HHUPVFNXSA-M

计算性质

• 辛醇/水分配系数(LogP)：
  4.18
• 重原子数：
  36.0
• 可旋转键数：
  7.0
• 环数：
  6.0
• sp3杂化的碳原子比例：
  0.12
• 拓扑面积：
  0.0
• 氢给体数：
  0.0
• 氢受体数：
  0.0

反应信息

• 作为反应物：
  描述：

  <(trans-2,trans-3-diphenylcyclopropyl)methyl>triphenylphosphonium bromide 、 丙醛 在 sodium acetylide 作用下， 生成 (E)-1-(trans-2,trans-3-diphenylcyclopropyl)butene 、 (Z)-1-(trans-2,trans-3-diphenylcyclopropyl)butene
  参考文献：
  名称：

  Opening of a cyclopropyl ring in (diphenylcyclopropyl)alkenes promoted by electron transfer from potassium 4,4'-di-tert-butylbiphenyl radical anion and x-ray and theoretical calculations of the structure of (Z)-1,2-bis(trans-2,trans-3-diphenylcyclopropyl)ethene

  摘要：

  We have prepared the (diphenylcyclopropyl)alkenes 1a-c and studied their reductions, using potassium 4,4'-di-tert-butylbiphenyl radical anion (DBB.-) as an electron source. Spectra analyses of the reaction products reveal that the double bond of the alkene stayed intact, whereas the cyclopropyl moiety was cleaved to provide alkenes 2a-c. When the reaction was carried out with a simple cyclopropylalkene without phenyl substituents (1e), the starting material was fully recovered. This indicates that the opening of the cyclopropyl ring in the alkenes is promoted by electron transfer from potassium DDB.- onto the phenyl rings attached to the cyclopropyl moiety. Two mechanisms were considered: (1) opening of the cyclopropyl via a cyclopropylcarbinyl to homoallylcarbinyl radical rearrangement (CPCRR) with potassium DBB.- as the le- reductant, with electron transfer to the phenyl rings attached to the cyclopropyl moiety, and (2) 2e- transfer to the phenyl rings and opening of the cyclopropyl moiety via an anionic rearrangement (CPCAR). (Z)-1-(trans-2,trans-3-Diphenylcyclopropyl)butene (1c) was used as a model for AM1 calculations which establish that the isomeric form of the radical anion product with opened cyclopropyl ring (1c.- form 1) is about 7 kcal/mol lower in energy than an isomeric form in which the cyclopropyl ring is closed (1c.- form 2). This suggests that the opening of the cyclopropyl ring is likely to happen through CPCRR rather than CPCAR. The X-ray crystal structure of (Z)-1,2-bis(trans-2,trans-3-diphenylcyclopropyl)ethene (1a) shows the two phenyl rings to be completely out of the cyclopropyl ring plane. The average C-C bond distance for the cyclopropyl moiety in the trans-2,trans-3-diphenylcyclopropyl rings is 1.562 angstrom, which is longer than the average bond distance in unsubstituted cyclopropyl rings. The gas-phase structures as calculated by AM1, PM3, and MNDO molecular orbital methods are all quite similar and agree closely with the X-ray structure. However, MNDO gave more satisfactory results than AM1 and PM3 for bond distances and bond angles and deviated more for torsion angles. The latter is reflected by the relatively large difference in the heat of formations (7 kcal/mol) of the gas-phase fully optimized structure and the X-ray structure.

  DOI：

  10.1021/jo00054a029
• 作为产物：
  描述：

  trans,trans-1-hydroxymethyl-2,3-diphenylcyclopropane 在 三溴化磷 作用下， 以 四氢呋喃 、 二乙二醇二甲醚 为溶剂， 反应 10.0h， 生成 <(trans-2,trans-3-diphenylcyclopropyl)methyl>triphenylphosphonium bromide
  参考文献：
  名称：

  通过细胞色素 P-450 模型进行烯烃环氧化的中间体。2. trans-2,trans-3-diphenylcyclopropyl 取代基在寻找自由基中间体中的应用

  摘要：

  催化复合物：[(F 20 TPP)Fe(III)(Cl)]、[(Cl 8 TPP)Fe(III)(Cl)]等[(Cl 8 TPP)Mn(III)(OH)] . (F 20 TPP=meso-tetrakis-pentafluorophenyl porphyrine, Cl 8 TPP=meso-tetrakis-[dichloro-2,6 phenyl] porphyrine)

  DOI：

  10.1021/ja00230a039

文献信息

• He, Gong-Xin; Bruice, Thomas C., Journal of the American Chemical Society, 1991, vol. 113, # 7, p. 2747 - 2753
  作者：He, Gong-Xin、Bruice, Thomas C.

  DOI：——

  日期：——