4-Methylene-2-(tricyclo<3.3.1.1^3,7>decylidene)tricyclo<3.3.1.1^3,7>decane | 159087-60-2

• 分子结构分类: 有机化合物 - 有机卤素化合物 - 有机氯化物
• 英文名称: 4-Methylene-2-(tricyclo<3.3.1.1^3,7>decylidene)tricyclo<3.3.1.1^3,7>decane
• CAS: 159087-60-2
• 化学式: C₂₁H₂₈
• 分子量: 280.453
• InChiKey: NMBBLHPPABRQEW-MRCUWXFGSA-N

物化性质

• 沸点：
  390.7±12.0 °C(predicted)
• 密度：
  1.10±0.1 g/cm3(Temp: 20 °C; Press: 760 Torr)(predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  5.36
• 重原子数：
  21.0
• 可旋转键数：
  0.0
• 环数：
  8.0
• sp3杂化的碳原子比例：
  0.81
• 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：

  4-Methylene-2-(tricyclo<3.3.1.1^3,7>decylidene)tricyclo<3.3.1.1^3,7>decane 在 sodium hydroxide 、 硼烷 、 双氧水 作用下， 生成 (1R*,4R*)-4-(Hydroxymethyl)-2-(tricyclo<3.3.1.1^3,7>decylidene)tricyclo<3.3.1.1^3,7>decane 、 (1R*,4S*)-4-(Hydroxymethyl)-2-(tricyclo<3.3.1.1^3,7>decylidene)tricyclo<3.3.1.1^3,7>decane
  参考文献：
  名称：

  Stereochemistry of the Electrophilic Homoallylic Chlorination Reaction of Sterically Congested Alkenes with Benzenesulfenyl Chloride: The Structure of the Phenylthiiranium Ion Intermediate

  摘要：

  A methyl-substituted derivative (4) of the sterically congested alkene adamanylideneadamantane (Ad=Ad; 2) has been synthesized. Upon reaction with PhSCl, 4 shows a remarkable selectivity; only two of the remaining 15 homoallylic positions undergo reaction to give chlorinated products. The phenylthiiranium ion of the parent alkene Ad=Ad has been prepared and characterized by single-crystal X-ray diffraction and H-1 and C-13 NMR spectroscopy as its triflate salt (1d). Crystal data for [(C10H14)(2)S(C6H5)][SO3CF3]: triclinic, space group P (1) over bar; Z = 4; a = 10.983(3) Angstrom; b = 14.988- (3) Angstrom; c = 16.059(6) Angstrom; alpha = 95.60(2)degrees; beta = 93.39(2)degrees; gamma = 108.98(2)degrees; V = 2476 Angstrom(3); T = 216 K; R(F) = 0.052 for 4840 data (I-o greater than or equal to 2.5 sigma(I-o)) and 633 variables. The dimensions of the thiiranium (SC2) rings are S-C range 1.909(3)-1.937(3) Angstrom; (C-C) = 1.500 Angstrom; (C-S-C) = 46.1 degrees; C-C-S range 66.3(2)-67.9(2)degrees. The crystallographically independent cations display similarly asymmetric dispositions of the phenyl group: C-S-C-ipso are 108.5(2)degrees, 116.7(2)degrees, and 112.9(2)degrees, 117.6(2)degrees respectively; S-C-ipso = 1.789(3) Angstrom in both cases. In both cations the plane of the phenyl ring is approximately orthogonal to the plane of the thiiranium ring but nearly coplanar with one of the ring S-C bonds.

  DOI：

  10.1021/jo00102a042
• 作为产物：
  描述：

  (1R*,2R*)-2-Chloro-4-(tricyclo<3.3.1.1^3,7>decylidene)tricyclo<3.3.1.1^3,7>decane 在 sodium dichromate 、 硫酸 、 silver(l) oxide 、 锌 作用下， 以 四氢呋喃 、 乙醚 、 二氯甲烷 、 水 为溶剂， 反应 9.0h， 生成 4-Methylene-2-(tricyclo<3.3.1.1^3,7>decylidene)tricyclo<3.3.1.1^3,7>decane
  参考文献：
  名称：

  Stereochemistry of the Electrophilic Homoallylic Chlorination Reaction of Sterically Congested Alkenes with Benzenesulfenyl Chloride: The Structure of the Phenylthiiranium Ion Intermediate

  摘要：

  A methyl-substituted derivative (4) of the sterically congested alkene adamanylideneadamantane (Ad=Ad; 2) has been synthesized. Upon reaction with PhSCl, 4 shows a remarkable selectivity; only two of the remaining 15 homoallylic positions undergo reaction to give chlorinated products. The phenylthiiranium ion of the parent alkene Ad=Ad has been prepared and characterized by single-crystal X-ray diffraction and H-1 and C-13 NMR spectroscopy as its triflate salt (1d). Crystal data for [(C10H14)(2)S(C6H5)][SO3CF3]: triclinic, space group P (1) over bar; Z = 4; a = 10.983(3) Angstrom; b = 14.988- (3) Angstrom; c = 16.059(6) Angstrom; alpha = 95.60(2)degrees; beta = 93.39(2)degrees; gamma = 108.98(2)degrees; V = 2476 Angstrom(3); T = 216 K; R(F) = 0.052 for 4840 data (I-o greater than or equal to 2.5 sigma(I-o)) and 633 variables. The dimensions of the thiiranium (SC2) rings are S-C range 1.909(3)-1.937(3) Angstrom; (C-C) = 1.500 Angstrom; (C-S-C) = 46.1 degrees; C-C-S range 66.3(2)-67.9(2)degrees. The crystallographically independent cations display similarly asymmetric dispositions of the phenyl group: C-S-C-ipso are 108.5(2)degrees, 116.7(2)degrees, and 112.9(2)degrees, 117.6(2)degrees respectively; S-C-ipso = 1.789(3) Angstrom in both cases. In both cations the plane of the phenyl ring is approximately orthogonal to the plane of the thiiranium ring but nearly coplanar with one of the ring S-C bonds.

  DOI：

  10.1021/jo00102a042