1-(1-Methylbenzimidazol-2-yl)-1,2-diphenylethanol | 187336-09-0

• 分子结构分类: 有机化合物 - 苯丙烷和聚酮 - 二苯乙烯类
• 英文名称: 1-(1-Methylbenzimidazol-2-yl)-1,2-diphenylethanol
• CAS: 187336-09-0
• 化学式: C₂₂H₂₀N₂O
• 分子量: 328.414
• InChiKey: KDIJXQMJOGAGQN-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.1
• 重原子数：
  25
• 可旋转键数：
  4
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.14
• 拓扑面积：
  38
• 氢给体数：
  1
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  1-(1-Methylbenzimidazol-2-yl)-1,2-diphenylethanol 在 potassium cyanide 作用下， 以 N,N-二甲基甲酰胺 为溶剂， 以45%的产率得到二苯基乙酮
  参考文献：
  名称：

  Carbon-Carbon Bond Cleavage of a-Hydroxybenzylheteroarenes to Ketones and Heteroarenes by Catalytic Action of Cyanide Ion Based on Retro-Benzoin Condensation

  摘要：

  Treatment of 4-(alpha-benzyl-alpha-hydroxybenzyl)quinazoline (2a) with potassium cyanide in DMF resulted in carbon-carbon bond cleavage to give benzyl phenyl ketone (3a) and quinazoline (4). Similar results were obtained with other 4-(alpha-hydroxybenzyl)quinazolines (2b-f and 7a). This reaction proceeds through retrobenzoin condensation. This condensation also proceeded in pyrazolopyrimidine (9a) triazolopyrimidine (10a), quinoxaline (11a), and benzimidazole (12a), and the imidazolium salt (16) was an effective catalyst.

  DOI：

  10.3987/com-96-7618
• 作为产物：
  描述：

  (1-methyl-1H-benzo[d]imidazol-2-yl)(phenyl)methanol 在 sodium hydride 作用下， 以 N,N-二甲基甲酰胺 为溶剂， 反应 3.0h， 生成 1-(1-Methylbenzimidazol-2-yl)-1,2-diphenylethanol
  参考文献：
  名称：

  A New Method of Synthesizing Deoxybenzoins from 1,3-Dimethyl-2-(.ALPHA.-benzyloxybenzyl)imidazolium and 1,3-Dimethyl-2-(.ALPHA.-benzyloxybenzyl)benzimidazolium Iodides Based on Wittig-Type Rearrangement.

  摘要：

  对1, 3-二甲基-2-(α-苄氧苄基)苯并咪唑铵碘化物1进行碱性处理后，得到中等产率的去氧苄酮2。氢化钠（NaH）、碳酸钾（K2CO3）和碳酸铯（Cs2CO3）在此反应中是有效的碱。去氧苄酮2是通过苄基的重排，随后排出1, 3-二甲基苯并咪唑铵烯体（A）而生成的。该重排过程类似于维廷重排。对1, 3-二甲基-2-(α-苄氧苄基)-咪唑铵碘化物4进行类似处理时，去氧苄酮2也以良好的产率形成。然而，具有噻唑铵基团5a和吡啶铵基团6a的季铵盐未能产生去氧苄酮（2a）。

  DOI：

  10.1248/cpb.45.1235

文献信息

• Carbon-Carbon Bond Cleavage of .ALPHA.-Hydroxybenzylheteroarenes Catalyzed by Cyanide Ion: Retro-Benzoin Condensation Affords Ketones and Heteroarenes and Benzyl Migration Affords Benzylheteroarenes and Arenecarbaldehydes.
  作者：Yumiko SUZUKI、Yuki TAKEMURA、Ken-ichi IWAMOTO、Takeo HIGASHINO、AKira MIYASHITA

  DOI：10.1248/cpb.46.199

  日期：——

  4-(α-Benzyl-α-hydroxybenzyl)quinazoline (4a) underwent retro-benzoin condensation catalyzed by cyanide ion to give deoxybenzoin (2a) and quinazoline (5a). Similarly, several nitrogen-containing heteroarenes (4, 9, 12, 16-19) having an α-hydroxybenzyl group at the α-position of the nitrogen underwent retro-benzoin type condensation to afford ketones (2) and heteroarenes (5). However, similar reaction of pyrazolopyrimidines (13, 14, 15) having an α-benzyl-α-hydroxybenzyl group resulted in benzyl migration, giving benzylpyrazolopyrimidines (8) and arenecarbaldehydes (3). Tetrabutylammonium cyanide (11, Bu4NCN) was a more effective cyanide ion donor than KCN (10). The retro-benzoin condensation was applied to the synthesis of 2-substituted quinazolines (38) from 2-chloro-4-aroylquinazolines (34), using the aroyl group as a protecting and electron-withdrawing group.

  4-(α-苄基-α-羟基苄基)喹唑啉(4a)在氰离子催化下经历逆苯偶姻缩合反应，生成脱氧苯偶姻(2a)和喹唑啉(5a)。同样，多个含氮杂环芳烃(4, 9, 12, 16-19)在其氮原子的α位上具有α-羟基苄基的结构，也经历逆苯偶姻型缩合反应，生成了酮(2)和杂环芳烃(5)。然而，具有α-苄基-α-羟基苄基结构的吡唑嘧啶(13, 14, 15)在类似的反应中引发了苄基迁移，生成了苄基吡唑嘧啶(8)和芳烃羰醛(3)。四丁基铵氰(11, Bu4NCN)比KCN(10)更有效地作为氰离子的供体。逆苯偶姻缩合反应被应用于从2-氯-4-芳酰基喹唑啉(34)合成2-取代喹唑啉(38)，使用芳酰基作为保护和电子 withdrawing 基团。
• Carbon-Carbon Bond Cleavage of a-Hydroxybenzylheteroarenes to Ketones and Heteroarenes by Catalytic Action of Cyanide Ion Based on Retro-Benzoin Condensation
  作者：Akira Miyashita、Yumiko Suzuki、Yuki Takemura、Ken-ichi Iwamoto、Takeo Higashino

  DOI：10.3987/com-96-7618

  日期：——

  Treatment of 4-(alpha-benzyl-alpha-hydroxybenzyl)quinazoline (2a) with potassium cyanide in DMF resulted in carbon-carbon bond cleavage to give benzyl phenyl ketone (3a) and quinazoline (4). Similar results were obtained with other 4-(alpha-hydroxybenzyl)quinazolines (2b-f and 7a). This reaction proceeds through retrobenzoin condensation. This condensation also proceeded in pyrazolopyrimidine (9a) triazolopyrimidine (10a), quinoxaline (11a), and benzimidazole (12a), and the imidazolium salt (16) was an effective catalyst.
• A New Method of Synthesizing Deoxybenzoins from 1,3-Dimethyl-2-(.ALPHA.-benzyloxybenzyl)imidazolium and 1,3-Dimethyl-2-(.ALPHA.-benzyloxybenzyl)benzimidazolium Iodides Based on Wittig-Type Rearrangement.
  作者：Akira MIYASHITA、Yoshiyuki MATSUOKA、Yumiko SUZUKI、Ken-ichi IWAMOTO、Takeo HIGASHINO

  DOI：10.1248/cpb.45.1235

  日期：——

  The treatment of 1, 3-dimethyl-2-(α-benzyloxybenxyl)benzimidazolium iodides 1 with a base gave deoxybenzoins 2 in moderate yields. Sodium hydride (NaH), potassium carbonate (K2CO3), and cesium carbonate (Cs2CO3) were effective bases in this reaction. Deoxybenzoins 2 were produced through rearrangement of the benzyl group followed by expulsion of the 1, 3-dimethylbenzimidazolium ylide (A). The rearrangement proceeds in a way similar to Witting rearrangement. Deoxybenzoins 2 were also formed in good yields from 1, 3-dimethyl-2-(α-benzyloxybenxyl)-imidazolium iodides 4 upon similar treatment. However, the quaternary salts having a thiazolium moiety 5a and a pyridinium moiety 6a failed to produce deoxybenzoin (2a).

  对1, 3-二甲基-2-(α-苄氧苄基)苯并咪唑铵碘化物1进行碱性处理后，得到中等产率的去氧苄酮2。氢化钠（NaH）、碳酸钾（K2CO3）和碳酸铯（Cs2CO3）在此反应中是有效的碱。去氧苄酮2是通过苄基的重排，随后排出1, 3-二甲基苯并咪唑铵烯体（A）而生成的。该重排过程类似于维廷重排。对1, 3-二甲基-2-(α-苄氧苄基)-咪唑铵碘化物4进行类似处理时，去氧苄酮2也以良好的产率形成。然而，具有噻唑铵基团5a和吡啶铵基团6a的季铵盐未能产生去氧苄酮（2a）。