α-methylbenzyl anion | 13822-53-2

• 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: α-methylbenzyl anion
• 英文别名: 1-phenyl-ethanide；ethylbenzene
• CAS: 13822-53-2
• 化学式: C₈H₉
• 分子量: 105.159
• InChiKey: MOBCEBITJHCPMO-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.1
• 重原子数：
  8
• 可旋转键数：
  1
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.12
• 拓扑面积：
  0
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  六羰基钨 、 α-methylbenzyl anion 以 gas 为溶剂， 以0%的产率得到
  参考文献：
  名称：

  氢化物在气相中转移至过渡金属羰基化合物。阴离子甲酰基配合物的形成和相对稳定性

  摘要：

  摘要Fe（CO）5，Cr（CO）6，Mo（CO）6和W（CO）6（HA（M（CO）n）= D [（CO）n-MCOH- ]）是根据气相中的双分子氢化物转移反应估算的。氢化物转移到羰基金属上产生相应的阴离子甲酰基络合物，氢化物亲和力包围实验建立HA（Fe（CO）5）= 56±4 kcal mol -1和HA（Cr（CO）6）= HA（Mo（CO ）6）= HA（W（CO）6）= 44±4 kcal mol -1。金属甲酰基阴离子的气相形成热和金属-碳键强度来自氢化物结合能。金属羰基化合物的氢化物亲和力排序与它们对溶液中亲核加成反应的相对反应性平行，并且与它们的CO拉伸力常数的相对大小（k co）相关。

  DOI：

  10.1016/s0277-5387(00)81786-6
• 作为产物：
  描述：

  螺[2.5]辛-5,7-二烯 在 methanolate 作用下， 生成 α-methylbenzyl anion
  参考文献：
  名称：

  On the generation and characterization of the spiro[2,5]octadienyl anion in the gas phase

  摘要：

  AbstractThree routes have been explored in both a high‐pressure chemical ionization (CI) source and a low‐pressure Fourier transform ion cyclotron resonance (FT‐ICR) cell to generate the spiro[2,5]octadienyl anion in the gas phase: (i) proton abstraction from spiro[2,5]octa‐4,6‐diene; (ii) expulsion of trimethysilyl fluoride by phenyl ring participation following fluoride anion attack upon the silicon centre of 2‐phenylethyl trimethylsilane; and (iii) collisionally induced dissociation (CID) of the carboxylate anion of 3‐phenylpropanoic acid via carbon dioxide loss. From comparison of the CID spectra of various reference [C8H9]− ions with those of the [C8H9]− ions which could be generated via the routes (i) and (iii) in the CI source it can be concluded that only the third route yields a [C8H9]−ion whose CID spectrum is not inconsistent with the one expected for the spiro[2,5]octadienyl anion. In the FT‐ICR cell [C8H9]− ions are generated along all three routes; their structures have been identified by specific ion‐molecule reactions and appear to be different. Route (i) yields an α‐methyl benzyl anion, probably due to isomerization within the ion‐molecule complex formed. An ortho‐ethylphenyl anion is formed along route (ii), presumably due to an intramolecular ortho proton abstraction in the generated trimethylsilyl fluoride solvated 2‐phenylethyl primary carbanion. The [C8H9]− ion formed along route (iii) shows reactions similar to those of the 1,1‐dimethylcyclohexadienyl anion which is structurally related to the spiro[2,5]octadienyl anion. Furthermore, the [C8H9]− ion generated via route (iii) reacts with hexafluorobenzene under expulsion of only one hydrogen fluoride molecule which contains exclusively one of the original phenyl ring hydrogen atoms. On the basis of all these observations it is therefore quite likely that the spiro[2,5]octadienyl anion is formed by collisionally induced decarboxylation of the 3‐phenylpropanoic acid carboxylate anion and can be a long‐lived and stable species in the gas phase.

  DOI：

  10.1002/oms.1210240807
• 作为试剂：
  描述：

  二甲基二硫 在 α-methylbenzyl anion 作用下， 26.9 ℃ 、40.0 Pa 条件下， 生成 methanethiolate 、
  参考文献：
  名称：

  Dimethyl disulfide: anion-molecule reactions in the gas phase at 300 K

  摘要：

  DOI：

  10.1021/ja00186a005

文献信息

• Hydride transfer to transition-metal carbonyls in the gas phase. The heat of formation of (CO)4FeCHO-
  作者：Kelley R. Lane、Larry Sallans、Robert R. Squires

  DOI：10.1021/om00121a042

  日期：1985.2
• On the generation and characterization of the spiro[2,5]octadienyl anion in the gas phase
  作者：Wilfrid P. M. Maas、Peter A. Van Veelen、Nico M. M. Nibbering

  DOI：10.1002/oms.1210240807

  日期：1989.8

  AbstractThree routes have been explored in both a high‐pressure chemical ionization (CI) source and a low‐pressure Fourier transform ion cyclotron resonance (FT‐ICR) cell to generate the spiro[2,5]octadienyl anion in the gas phase: (i) proton abstraction from spiro[2,5]octa‐4,6‐diene; (ii) expulsion of trimethysilyl fluoride by phenyl ring participation following fluoride anion attack upon the silicon centre of 2‐phenylethyl trimethylsilane; and (iii) collisionally induced dissociation (CID) of the carboxylate anion of 3‐phenylpropanoic acid via carbon dioxide loss. From comparison of the CID spectra of various reference [C8H9]− ions with those of the [C8H9]− ions which could be generated via the routes (i) and (iii) in the CI source it can be concluded that only the third route yields a [C8H9]−ion whose CID spectrum is not inconsistent with the one expected for the spiro[2,5]octadienyl anion. In the FT‐ICR cell [C8H9]− ions are generated along all three routes; their structures have been identified by specific ion‐molecule reactions and appear to be different. Route (i) yields an α‐methyl benzyl anion, probably due to isomerization within the ion‐molecule complex formed. An ortho‐ethylphenyl anion is formed along route (ii), presumably due to an intramolecular ortho proton abstraction in the generated trimethylsilyl fluoride solvated 2‐phenylethyl primary carbanion. The [C8H9]− ion formed along route (iii) shows reactions similar to those of the 1,1‐dimethylcyclohexadienyl anion which is structurally related to the spiro[2,5]octadienyl anion. Furthermore, the [C8H9]− ion generated via route (iii) reacts with hexafluorobenzene under expulsion of only one hydrogen fluoride molecule which contains exclusively one of the original phenyl ring hydrogen atoms. On the basis of all these observations it is therefore quite likely that the spiro[2,5]octadienyl anion is formed by collisionally induced decarboxylation of the 3‐phenylpropanoic acid carboxylate anion and can be a long‐lived and stable species in the gas phase.
• Hydride transfer to transition-metal carbonyls in the gas phase. Formation and relative stabilities of anionic formyl complexes
  作者：Kelley R. Lane、Robert R. Squires

  DOI：10.1016/s0277-5387(00)81786-6

  日期：1988.1

  of Fe(CO) 5 , Cr(CO) 6 , Mo(CO) 6 and W(CO) 6 ( HA (M(CO) n ) = D[(CO) n − MCOH − ]) have been estimated from bimolecular hydride transfer reactions in the gas phase. Hydride transfer to the metal carbonyls yields the corresponding anionic formyl complexes and the hydride affinity bracketing experiments establish HA (Fe(CO) 5 ) = 56±4 kcal mol −1 and HA (Cr(CO) 6 ) = HA (Mo(CO) 6 ) = HA (W(CO) 6 )

  摘要Fe（CO）5，Cr（CO）6，Mo（CO）6和W（CO）6（HA（M（CO）n）= D [（CO）n-MCOH- ]）是根据气相中的双分子氢化物转移反应估算的。氢化物转移到羰基金属上产生相应的阴离子甲酰基络合物，氢化物亲和力包围实验建立HA（Fe（CO）5）= 56±4 kcal mol -1和HA（Cr（CO）6）= HA（Mo（CO ）6）= HA（W（CO）6）= 44±4 kcal mol -1。金属甲酰基阴离子的气相形成热和金属-碳键强度来自氢化物结合能。金属羰基化合物的氢化物亲和力排序与它们对溶液中亲核加成反应的相对反应性平行，并且与它们的CO拉伸力常数的相对大小（k co）相关。