1-(N,N-Dimethylamino)-3-methyl-1,5-hexadiene

• 分子结构分类: 有机化合物 - 有机氮化合物
• 英文名称: 1-(N,N-Dimethylamino)-3-methyl-1,5-hexadiene
• 英文别名: (1E)-N,N,3-trimethylhexa-1,5-dien-1-amine
• 化学式: C₉H₁₇N
• 分子量: 139.241
• InChiKey: ABMIMWPSAKBESX-BQYQJAHWSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.5
• 重原子数：
  10
• 可旋转键数：
  4
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.56
• 拓扑面积：
  3.2
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为产物：
  描述：

  Ethyl 2-(N,N-dimethylamino)-4-pentenoate 在 正丁基锂 、 二异丁基氢化铝 作用下， 以 四氢呋喃 、 正己烷 为溶剂， 反应 17.25h， 生成 1-(N,N-Dimethylamino)-3-methyl-1,5-hexadiene
  参考文献：
  名称：

  Use of Hine's D Values To Predict the Position of the Equilibrium in the Cope Rearrangement of Multiply Substituted 1,5-Dienes

  摘要：

  A series of 1,5-dienes (1a-f) were employed to test whether Hine's D values can predict the position of equilibrium in Cope rearrangements. In the cases of the substituent pairs [OCH3, H], [OCH3, CH3], [N(CH3)(2), H], [N(CH3)(2), CH3], and [N(CH3)(2), OCH3], equilibrium constants calculated with Hine's D values gave reasonable agreement with those obtained experimentally. Dienes 1g-i were prepared to test whether reduction of the pi-donating character of a nitrogen substituent (carbamoyl vs dimethylamino) would change the directing ability of the nitrogen group. The aggregate order of directing ability was N(CH3)(2) > OCH3 > EtO(2)CN(CH3) > CH3 > A. Diene 15a, with a more complicated substitution pattern (OCH3 and CH3 versus CH3 and H) not directly amenable to analysis with D values, can be considered to reduce to the case of [OCH3, H]. The experimental K-eq obtained agreed with that expected for the [OCH3, H] pair. Dienes 15c and 16b, designed to test the pairs [CH3, SPh] and [OCH3, SPh], respectively, decomposed under the gas phase conditions of the rearrangement. Attempts to effect rearrangement with Pd(II) catalysis failed.

  DOI：

  10.1021/jo00128a019

文献信息

• Use of Hine's D Values To Predict the Position of the Equilibrium in the Cope Rearrangement of Multiply Substituted 1,5-Dienes
  作者：James P. Hagen、Kemberly D. Lewis、Scott W. Lovell、Paolo Rossi、Ayse Z. Tezcan

  DOI：10.1021/jo00128a019

  日期：1995.11

  A series of 1,5-dienes (1a-f) were employed to test whether Hine's D values can predict the position of equilibrium in Cope rearrangements. In the cases of the substituent pairs [OCH3, H], [OCH3, CH3], [N(CH3)(2), H], [N(CH3)(2), CH3], and [N(CH3)(2), OCH3], equilibrium constants calculated with Hine's D values gave reasonable agreement with those obtained experimentally. Dienes 1g-i were prepared to test whether reduction of the pi-donating character of a nitrogen substituent (carbamoyl vs dimethylamino) would change the directing ability of the nitrogen group. The aggregate order of directing ability was N(CH3)(2) > OCH3 > EtO(2)CN(CH3) > CH3 > A. Diene 15a, with a more complicated substitution pattern (OCH3 and CH3 versus CH3 and H) not directly amenable to analysis with D values, can be considered to reduce to the case of [OCH3, H]. The experimental K-eq obtained agreed with that expected for the [OCH3, H] pair. Dienes 15c and 16b, designed to test the pairs [CH3, SPh] and [OCH3, SPh], respectively, decomposed under the gas phase conditions of the rearrangement. Attempts to effect rearrangement with Pd(II) catalysis failed.