3-(Benzotriazol-1-yl)-3-ethoxy-2-phenylpent-4-en-2-ol | 172846-87-6

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 苯并三唑类
• 英文名称: 3-(Benzotriazol-1-yl)-3-ethoxy-2-phenylpent-4-en-2-ol
• 英文别名: 3-(1H-benzotriazol-1-yl)-3-ethoxy-2-phenylpent-4-en-2-ol
• CAS: 172846-87-6
• 化学式: C₁₉H₂₁N₃O₂
• 分子量: 323.395
• InChiKey: FHMIODANJATMLK-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.1
• 重原子数：
  24
• 可旋转键数：
  6
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.26
• 拓扑面积：
  60.2
• 氢给体数：
  1
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  3-(Benzotriazol-1-yl)-3-ethoxy-2-phenylpent-4-en-2-ol 在 盐酸 作用下， 以 四氢呋喃 为溶剂， 反应 34.0h， 生成 2-hydroxy-2-phenylhexan-3-one
  参考文献：
  名称：

  Novel Routes to Enol Ethers, Unsymmetrical Ketones, .alpha.-Bromoalkyl Ketones, 1,4-Diketones, 2-Ethoxy-2-cyclopentenones, and .alpha.-Keto Enamines

  摘要：

  Highly regioselective S(N)2' reactions of adducts 6 (readily prepared by reactions of halides with the allyl anion 12 of 11) with Grignard reagents gave enol ethers 13, which were converted (in one-pot reactions from 11) into ketones 14 and alpha-bromoalkyl ketones 15 in good yields. The monoprotected 1,4-diketone derivative 16 (prepared by Michael addition of the allyl anion 12 with methyl vinyl ketone) was converted both into 1,4-diketones 18 and into protected gamma-hydroxyalkyl ketone 20 by selective Grignard reactions, which could be directed either to the carbonyl, or the protected propenoyl, or to both functionalities. The allyl anion 12 with alpha-substituted acetic esters gave alpha-acylated adducts 24, which underwent in situ unfavored endo-trig cyclization upon treatment with NaH and secondary amines, to give 2-ethoxy-2-cyclopentenones 27 and 28 and alpha-keto enamines 25 in good yield. The mechanism for the cyclization is discussed.

  DOI：

  10.1021/jo00128a037
• 作为产物：
  描述：

  苯乙酮 、 1-(1-乙氧基-2-丙烯-1-基)-1H-苯并三唑 在 正丁基锂 作用下， 以 四氢呋喃 为溶剂， 以55%的产率得到3-(Benzotriazol-1-yl)-3-ethoxy-2-phenylpent-4-en-2-ol
  参考文献：
  名称：

  A Novel Heterocycle-Stabilized Allylic Anion Route to Cyclopropanes, 1-Ethoxy-1-vinylethylene Oxides, 1-Hydroxyalkyl 2-Methoxyethyl Ketones, 1-Hydroxyalkyl Vinyl Ketones, .beta.-Ethoxy-.beta.-vinylalkyl Alcohols, .gamma.-Lactones, and .beta.,.gamma.-Unsaturated Carboxylic Acids

  摘要：

  Treatment of N-(alpha-ethoxyallyl)benzotriazole (8) with butyllithium followed by alpha,beta-unsaturated esters at -78 degrees C formed the 1,1-adducts 11 which underwent internal displacement of the benzotriazolyl group at 20 degrees C to give cyclopropanecarboxylic esters 14 and 15. In the presence of ZnBr2, addition of anion 13 to cyclic and methyl ketones gave 1-ethoxy-1-vinylethylene oxides 25 in good yields. Epoxides 25 were subsequently converted to 1-hydroxyalkyl 2-methoxyethyl ketones 24, 1-hydroxyalkyl vinyl ketones 26, and beta-ethoxy-beta-vinylalkyl alcohols 27. Treatment of anion 13 with aromatic ketones or sterically hindered aliphatic ketones produced gamma-alkylated adducts 31 which were hydrolyzed to beta,gamma-unsaturated carboxylic acids 32 (R(1), R(2) = aromatic) or gamma-lactones 33 (R(1), R(2) = aliphatic).

  DOI：

  10.1021/jo00128a036

文献信息

• Novel Routes to Enol Ethers, Unsymmetrical Ketones, .alpha.-Bromoalkyl Ketones, 1,4-Diketones, 2-Ethoxy-2-cyclopentenones, and .alpha.-Keto Enamines
  作者：Alan R. Katritzky、Guifen Zhang、Jinlong Jiang

  DOI：10.1021/jo00128a037

  日期：1995.11

  Highly regioselective S(N)2' reactions of adducts 6 (readily prepared by reactions of halides with the allyl anion 12 of 11) with Grignard reagents gave enol ethers 13, which were converted (in one-pot reactions from 11) into ketones 14 and alpha-bromoalkyl ketones 15 in good yields. The monoprotected 1,4-diketone derivative 16 (prepared by Michael addition of the allyl anion 12 with methyl vinyl ketone) was converted both into 1,4-diketones 18 and into protected gamma-hydroxyalkyl ketone 20 by selective Grignard reactions, which could be directed either to the carbonyl, or the protected propenoyl, or to both functionalities. The allyl anion 12 with alpha-substituted acetic esters gave alpha-acylated adducts 24, which underwent in situ unfavored endo-trig cyclization upon treatment with NaH and secondary amines, to give 2-ethoxy-2-cyclopentenones 27 and 28 and alpha-keto enamines 25 in good yield. The mechanism for the cyclization is discussed.
• A Novel Heterocycle-Stabilized Allylic Anion Route to Cyclopropanes, 1-Ethoxy-1-vinylethylene Oxides, 1-Hydroxyalkyl 2-Methoxyethyl Ketones, 1-Hydroxyalkyl Vinyl Ketones, .beta.-Ethoxy-.beta.-vinylalkyl Alcohols, .gamma.-Lactones, and .beta.,.gamma.-Unsaturated Carboxylic Acids
  作者：Alan R. Katritzky、Jinlong Jiang

  DOI：10.1021/jo00128a036

  日期：1995.11

  Treatment of N-(alpha-ethoxyallyl)benzotriazole (8) with butyllithium followed by alpha,beta-unsaturated esters at -78 degrees C formed the 1,1-adducts 11 which underwent internal displacement of the benzotriazolyl group at 20 degrees C to give cyclopropanecarboxylic esters 14 and 15. In the presence of ZnBr2, addition of anion 13 to cyclic and methyl ketones gave 1-ethoxy-1-vinylethylene oxides 25 in good yields. Epoxides 25 were subsequently converted to 1-hydroxyalkyl 2-methoxyethyl ketones 24, 1-hydroxyalkyl vinyl ketones 26, and beta-ethoxy-beta-vinylalkyl alcohols 27. Treatment of anion 13 with aromatic ketones or sterically hindered aliphatic ketones produced gamma-alkylated adducts 31 which were hydrolyzed to beta,gamma-unsaturated carboxylic acids 32 (R(1), R(2) = aromatic) or gamma-lactones 33 (R(1), R(2) = aliphatic).