2-<3-(2-chloropropenyl)>norbornadiene | 149183-29-9

• 分子结构分类: 有机化合物 - 有机卤素化合物 - 乙烯基卤化物
• 英文名称: 2-<3-(2-chloropropenyl)>norbornadiene
• 英文别名: 2-(2-Chloroprop-2-enyl)bicyclo[2.2.1]hepta-2,5-diene；2-(2-chloroprop-2-enyl)bicyclo[2.2.1]hepta-2,5-diene
• CAS: 149183-29-9
• 化学式: C₁₀H₁₁Cl
• 分子量: 166.65
• InChiKey: RIAOAZYIZQUJRQ-UHFFFAOYSA-N

物化性质

• 沸点：
  215.6±29.0 °C(Predicted)
• 密度：
  1.109±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.1
• 重原子数：
  11
• 可旋转键数：
  2
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.4
• 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：

  乙烯基溴化镁 、 2-<3-(2-chloropropenyl)>norbornadiene 在 bis(triphenylphosphine)nickel(II) chloride 作用下， 以 四氢呋喃 为溶剂， 反应 16.0h， 以70%的产率得到2-<(2-buta-1,3-dienyl)methyl>norbornadiene
  参考文献：
  名称：

  Polymers containing ring-strain energy. 1. New monomers and polymers based on cyclopropane, norbornadiene, and quadricyclane

  摘要：

  The synthesis and polymerization chemistry of 1,1-bis(XCH2)cyclopropane {1, X = OH; 4, X = I} was studied. Treatment of 1 with base in the presence of alpha,omega-dihalides did not produce a polyether. However, treatment of 4 with the bis(alkoxide) derived from hexanediol afforded a polyether of low molecular weight {M(n) = 3000, PD = 3}. A general method for alkylating norbornadiene in the 2-position was developed. Treatment of norbornadiene with tert-BuOK, tetramethylethylenediamine (TMEDA), n-BuLi, and tributylchloroetannane (in that order) afforded 2-(tributylstannyl)norbornadiene in excellent yield. On the other hand, carbon electrophiles {eg. bromobutane, 1,4-dibromobutane, and 2,3-dichloropropene} required the generation of the 2-(lithiocyanocuprate) in order to effect clean alkylation. Treatment of 2-[3-(2-chloropropenyl)]norbornadiene (8a) with RMgX {where R = vinyl and phenyl} in the presence of (dppp)NiCl2 afforded the cross-coupling products 2-(XCH2)-norbornadiene {9, X = 2-buta-1,3-dienyl; 10, X = alpha-styryl; respectively} in high yield. Polymerization of 9 in THF initiated by n-BuLi resulted in an elastomeric polymer (12) [M(n) = 18,000, PD = 1.5]. Photolysis of 12 in the presence of (Ph3P)2CuBr converted the pendant norbornadiene to quadricyclane (13). Heating of the photoisomerized sample to 180-degrees-C caused an exothermic (by DSC) reaction which corresponded to 59% of theory (using the value 26 kcal/mol: quadricyclane --> norbornadiene).

  DOI：

  10.1021/jo00067a055
• 作为产物：
  描述：

  2,3-二氯丙烯 、 2,5-降冰片二烯 生成 2-<3-(2-chloropropenyl)>norbornadiene
  参考文献：
  名称：

  Polymers containing ring-strain energy. 1. New monomers and polymers based on cyclopropane, norbornadiene, and quadricyclane

  摘要：

  The synthesis and polymerization chemistry of 1,1-bis(XCH2)cyclopropane {1, X = OH; 4, X = I} was studied. Treatment of 1 with base in the presence of alpha,omega-dihalides did not produce a polyether. However, treatment of 4 with the bis(alkoxide) derived from hexanediol afforded a polyether of low molecular weight {M(n) = 3000, PD = 3}. A general method for alkylating norbornadiene in the 2-position was developed. Treatment of norbornadiene with tert-BuOK, tetramethylethylenediamine (TMEDA), n-BuLi, and tributylchloroetannane (in that order) afforded 2-(tributylstannyl)norbornadiene in excellent yield. On the other hand, carbon electrophiles {eg. bromobutane, 1,4-dibromobutane, and 2,3-dichloropropene} required the generation of the 2-(lithiocyanocuprate) in order to effect clean alkylation. Treatment of 2-[3-(2-chloropropenyl)]norbornadiene (8a) with RMgX {where R = vinyl and phenyl} in the presence of (dppp)NiCl2 afforded the cross-coupling products 2-(XCH2)-norbornadiene {9, X = 2-buta-1,3-dienyl; 10, X = alpha-styryl; respectively} in high yield. Polymerization of 9 in THF initiated by n-BuLi resulted in an elastomeric polymer (12) [M(n) = 18,000, PD = 1.5]. Photolysis of 12 in the presence of (Ph3P)2CuBr converted the pendant norbornadiene to quadricyclane (13). Heating of the photoisomerized sample to 180-degrees-C caused an exothermic (by DSC) reaction which corresponded to 59% of theory (using the value 26 kcal/mol: quadricyclane --> norbornadiene).

  DOI：

  10.1021/jo00067a055