2-(2-Chlorophenyl)-2,4-dimethyl[1-13C]pentan-3-ol | 484001-20-9

• 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: 2-(2-Chlorophenyl)-2,4-dimethyl[1-13C]pentan-3-ol
• 英文别名: 2-(2-chlorophenyl)-2,4-dimethyl(313C)pentan-3-ol
• CAS: 484001-20-9
• 化学式: C₁₃H₁₉ClO
• 分子量: 227.735
• InChiKey: JGEHVMDYSFORNW-HNHCFKFXSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.4
• 重原子数：
  15
• 可旋转键数：
  3
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.54
• 拓扑面积：
  20.2
• 氢给体数：
  1
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  2-(2-Chlorophenyl)-2,4-dimethyl[1-13C]pentan-3-ol 在 硫酸 作用下， 反应 0.5h， 以12%的产率得到4-chloro-1,1,3,3-tetramethyl-2H-indene
  参考文献：
  名称：

  Über Umlagerungen bei der Cyclialkylierung von Arylpentanolen zu 2,3-Dihydro-1H-inden-Derivaten, 5. Mitteilung

  摘要：

  The mechanism proposed in [1] to explain the surprising result of the cyclialkylation of 4-(2-chlorophenyl)-2,4-dimethylpentan-2-ol (3, R = Me), which gives not only the 'normal' product, i.e., the 4-chloro-2,3-dihydro-1,1,3,3-tetramethyl- (4), but also the isomer trans-4-chloro-2,3-dihydro-1,1,2,3-tetramethyl-1H-inden (5), could be differentiated in two sections (cf. Scheme 2): the first from 3 to the intermediary ion IIareversible arrowIIb, and the second from the latter ions to the final product 5. For the first section, a sufficiently satisfactory explanation has been given in [1]; the second section has received important support from the mechanisms of the cyclialkylation of 2,4-dimethyl-2-phenylpentan-3-ol (6), the precursor of II'a, the ion IIa without the o-Cl substituent (cf. Schemes 2, 3 and 5 and [4]). The present communication gives an explanation of the influence of the o-Cl substituent: a mechanism is proposed for the very complex cyclialkylation of 2-(2-chlorophenyl)-2,4-dimethylpentan-3-ol (11; cf Scheme 9). Both mechanism may be considered as definitive. It is very surprising that, by the cyclialkylation of the compounds 1, 3, 8, 11, 15, and 17, only compound 1 gives the 'normal' product; the cyclialkylation of all other phenylpentanols follows complex pathways including Et, i-Pr, and Ph migrations, which could not be expected. In addition, it has been established that the transformation of 21 to 22 (cf Scheme 12) and that of 23 to 24 (cf Scheme 13) occur through two consecutive 1,2- and not through a single 1,3-hydride migration or through an elimination-addition process (cf Scheme 13). It can be assumed that the transformation of ion IV (the 2-(2-chlorophenyl)-3,4-dimethylpent-2-ylium ion) to the ion V (the 4-(2-chlorophenyl)-3,4-dimethylpent-2-ylium ion (both shown in Scheme 9 as D-isomers) occurs through the same pathway.

  DOI：

  10.1002/1522-2675(200207)85:7<2089::aid-hlca2089>3.0.co;2-0
• 作为产物：
  描述：

  2-(2-Chlorophenyl)-2-methyl[1-13C]propannitril 在 lithium aluminium tetrahydride 、 乙酸乙酯 作用下， 以 乙醚 、 正戊烷 为溶剂， 反应 2.0h， 生成 2-(2-Chlorophenyl)-2,4-dimethyl[1-13C]pentan-3-ol
  参考文献：
  名称：

  Über Umlagerungen bei der Cyclialkylierung von Arylpentanolen zu 2,3-Dihydro-1H-inden-Derivaten, 5. Mitteilung

  摘要：

  The mechanism proposed in [1] to explain the surprising result of the cyclialkylation of 4-(2-chlorophenyl)-2,4-dimethylpentan-2-ol (3, R = Me), which gives not only the 'normal' product, i.e., the 4-chloro-2,3-dihydro-1,1,3,3-tetramethyl- (4), but also the isomer trans-4-chloro-2,3-dihydro-1,1,2,3-tetramethyl-1H-inden (5), could be differentiated in two sections (cf. Scheme 2): the first from 3 to the intermediary ion IIareversible arrowIIb, and the second from the latter ions to the final product 5. For the first section, a sufficiently satisfactory explanation has been given in [1]; the second section has received important support from the mechanisms of the cyclialkylation of 2,4-dimethyl-2-phenylpentan-3-ol (6), the precursor of II'a, the ion IIa without the o-Cl substituent (cf. Schemes 2, 3 and 5 and [4]). The present communication gives an explanation of the influence of the o-Cl substituent: a mechanism is proposed for the very complex cyclialkylation of 2-(2-chlorophenyl)-2,4-dimethylpentan-3-ol (11; cf Scheme 9). Both mechanism may be considered as definitive. It is very surprising that, by the cyclialkylation of the compounds 1, 3, 8, 11, 15, and 17, only compound 1 gives the 'normal' product; the cyclialkylation of all other phenylpentanols follows complex pathways including Et, i-Pr, and Ph migrations, which could not be expected. In addition, it has been established that the transformation of 21 to 22 (cf Scheme 12) and that of 23 to 24 (cf Scheme 13) occur through two consecutive 1,2- and not through a single 1,3-hydride migration or through an elimination-addition process (cf Scheme 13). It can be assumed that the transformation of ion IV (the 2-(2-chlorophenyl)-3,4-dimethylpent-2-ylium ion) to the ion V (the 4-(2-chlorophenyl)-3,4-dimethylpent-2-ylium ion (both shown in Scheme 9 as D-isomers) occurs through the same pathway.

  DOI：

  10.1002/1522-2675(200207)85:7<2089::aid-hlca2089>3.0.co;2-0

文献信息

• Über Umlagerungen bei der Cyclialkylierung von Arylpentanolen zu 2,3-Dihydro-1H-inden-Derivaten, 5. Mitteilung
  作者：Behrouz Fathi、Edgardo Giovannini、Pierre Pasquier

  DOI：10.1002/1522-2675(200207)85:7<2089::aid-hlca2089>3.0.co;2-0

  日期：2002.7

  The mechanism proposed in [1] to explain the surprising result of the cyclialkylation of 4-(2-chlorophenyl)-2,4-dimethylpentan-2-ol (3, R = Me), which gives not only the 'normal' product, i.e., the 4-chloro-2,3-dihydro-1,1,3,3-tetramethyl- (4), but also the isomer trans-4-chloro-2,3-dihydro-1,1,2,3-tetramethyl-1H-inden (5), could be differentiated in two sections (cf. Scheme 2): the first from 3 to the intermediary ion IIareversible arrowIIb, and the second from the latter ions to the final product 5. For the first section, a sufficiently satisfactory explanation has been given in [1]; the second section has received important support from the mechanisms of the cyclialkylation of 2,4-dimethyl-2-phenylpentan-3-ol (6), the precursor of II'a, the ion IIa without the o-Cl substituent (cf. Schemes 2, 3 and 5 and [4]). The present communication gives an explanation of the influence of the o-Cl substituent: a mechanism is proposed for the very complex cyclialkylation of 2-(2-chlorophenyl)-2,4-dimethylpentan-3-ol (11; cf Scheme 9). Both mechanism may be considered as definitive. It is very surprising that, by the cyclialkylation of the compounds 1, 3, 8, 11, 15, and 17, only compound 1 gives the 'normal' product; the cyclialkylation of all other phenylpentanols follows complex pathways including Et, i-Pr, and Ph migrations, which could not be expected. In addition, it has been established that the transformation of 21 to 22 (cf Scheme 12) and that of 23 to 24 (cf Scheme 13) occur through two consecutive 1,2- and not through a single 1,3-hydride migration or through an elimination-addition process (cf Scheme 13). It can be assumed that the transformation of ion IV (the 2-(2-chlorophenyl)-3,4-dimethylpent-2-ylium ion) to the ion V (the 4-(2-chlorophenyl)-3,4-dimethylpent-2-ylium ion (both shown in Scheme 9 as D-isomers) occurs through the same pathway.