(Z)-7-Iodo-2-methoxy-2-heptenenitrile | 108945-93-3

• 分子结构分类: 有机化合物 - 有机氮化合物
• 英文名称: (Z)-7-Iodo-2-methoxy-2-heptenenitrile
• 英文别名: 7-iodo-2-methoxy-2-heptenenitrile；2-Heptenenitrile, 7-iodo-2-methoxy-, (Z)-；(Z)-7-iodo-2-methoxyhept-2-enenitrile
• CAS: 108945-93-3
• 化学式: C₈H₁₂INO
• 分子量: 265.094
• InChiKey: MWZWNHHYTYXUQL-YVMONPNESA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.3
• 重原子数：
  11
• 可旋转键数：
  5
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.62
• 拓扑面积：
  33
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  (Z)-7-Iodo-2-methoxy-2-heptenenitrile 在 lithium aluminium tetrahydride 、 碘 作用下， 以 四氢呋喃 为溶剂， 反应 29.0h， 生成 (E)-2-Methoxy-2-heptenenitrile
  参考文献：
  名称：

  Reinvestigation of a criticized mechanistic probe study of metal hydride reductions of alkyl halides

  摘要：

  Published claims that LiAlH4 promotes isomerizations of either 7-iodo-2-methoxy-2-heptenenitrile (1) or 2-methoxy-2-heptenenitrile (2) and the speculations resulting from these claims have led to new studies of reactions of 1 and 2. Highly isomerically enriched samples of 1 and 2 were prepared, and the equilibrium populations of isomers for both 1 and 2 were determined by iodine-mediated equilibrations. Reactions of isomerically enriched samples of 1 and 2 as well as mixtures of isomers with LiAlH4 demonstrated that LiAlH4-induced isomerizations did not occur. Absolute yields of product 2 from reactions of 1 with limited amounts of LiAlH4 did not agree with previously reported results. Reactions of 2 with limited amounts of LiAlH4 resulted in selective destruction of 2 with (Z)-2 reacting faster than (E)-2. On the basis of these facts and the fact that speculations regarding radical intermediates from reactions of 1 with LiAlH4 are inconsistent with known kinetic values for radical reactions, the published criticisms of a study employing 1 as a probe for radical formation in reactions with metal hydrides are found to be without merit.

  DOI：

  10.1021/jo00027a065
• 作为产物：
  描述：

  (E)-7-Iodo-2-methoxy-2-heptenenitrile 在 碘 作用下， 以 四氢呋喃 为溶剂， 反应 50.0h， 生成 (Z)-7-Iodo-2-methoxy-2-heptenenitrile
  参考文献：
  名称：

  Reinvestigation of a criticized mechanistic probe study of metal hydride reductions of alkyl halides

  摘要：

  Published claims that LiAlH4 promotes isomerizations of either 7-iodo-2-methoxy-2-heptenenitrile (1) or 2-methoxy-2-heptenenitrile (2) and the speculations resulting from these claims have led to new studies of reactions of 1 and 2. Highly isomerically enriched samples of 1 and 2 were prepared, and the equilibrium populations of isomers for both 1 and 2 were determined by iodine-mediated equilibrations. Reactions of isomerically enriched samples of 1 and 2 as well as mixtures of isomers with LiAlH4 demonstrated that LiAlH4-induced isomerizations did not occur. Absolute yields of product 2 from reactions of 1 with limited amounts of LiAlH4 did not agree with previously reported results. Reactions of 2 with limited amounts of LiAlH4 resulted in selective destruction of 2 with (Z)-2 reacting faster than (E)-2. On the basis of these facts and the fact that speculations regarding radical intermediates from reactions of 1 with LiAlH4 are inconsistent with known kinetic values for radical reactions, the published criticisms of a study employing 1 as a probe for radical formation in reactions with metal hydrides are found to be without merit.

  DOI：

  10.1021/jo00027a065

文献信息

• ASHBY, E. C.;PHAM, TUNG;MADJDABADI, A. AMROLLAH, J. ORG. CHEM., 53,(1988) N6, C. 6156-6158
  作者：ASHBY, E. C.、PHAM, TUNG、MADJDABADI, A. AMROLLAH

  DOI：——

  日期：——
• PARK, SEUNG-UN;CHUNG, SUNG-KEE;NEWCOMB, MARTIN, J. ORG. CHEM., 52,(1987) N 15, 3275-3278
  作者：PARK, SEUNG-UN、CHUNG, SUNG-KEE、NEWCOMB, MARTIN

  DOI：——

  日期：——
• Reinvestigation of a criticized mechanistic probe study of metal hydride reductions of alkyl halides
  作者：Martin Newcomb、Thomas R. Varick、Seung Yong Choi

  DOI：10.1021/jo00027a065

  日期：1992.1

  Published claims that LiAlH4 promotes isomerizations of either 7-iodo-2-methoxy-2-heptenenitrile (1) or 2-methoxy-2-heptenenitrile (2) and the speculations resulting from these claims have led to new studies of reactions of 1 and 2. Highly isomerically enriched samples of 1 and 2 were prepared, and the equilibrium populations of isomers for both 1 and 2 were determined by iodine-mediated equilibrations. Reactions of isomerically enriched samples of 1 and 2 as well as mixtures of isomers with LiAlH4 demonstrated that LiAlH4-induced isomerizations did not occur. Absolute yields of product 2 from reactions of 1 with limited amounts of LiAlH4 did not agree with previously reported results. Reactions of 2 with limited amounts of LiAlH4 resulted in selective destruction of 2 with (Z)-2 reacting faster than (E)-2. On the basis of these facts and the fact that speculations regarding radical intermediates from reactions of 1 with LiAlH4 are inconsistent with known kinetic values for radical reactions, the published criticisms of a study employing 1 as a probe for radical formation in reactions with metal hydrides are found to be without merit.