t-butyl β-(p-chlorophenyl)glycidate | 75591-36-5

• 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: t-butyl β-(p-chlorophenyl)glycidate
• 英文别名: (E/Z)-t-butyl 3-(4-chloro)phenylglycidate；2-(4-Chlorophenyl)glycidic acid, tert-butyl ester；tert-butyl 3-(4-chlorophenyl)oxirane-2-carboxylate
• CAS: 75591-36-5
• 化学式: C₁₃H₁₅ClO₃
• 分子量: 254.713
• InChiKey: YSQUJVZXRJWWRR-UHFFFAOYSA-N

物化性质

• 沸点：
  319.5±42.0 °C(Predicted)
• 密度：
  1.226±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.9
• 重原子数：
  17
• 可旋转键数：
  4
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.46
• 拓扑面积：
  38.8
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  t-butyl β-(p-chlorophenyl)glycidate 在 sodium hydroxide 、 苄基三乙基氯化铵 作用下， 以 二氯甲烷 为溶剂， 生成 Sodium; (2S,3R)-3-(4-chloro-phenyl)-oxirane-2-carboxylate 、 tert-butyl (Z)-3-(4-chlorophenyl)-oxirane-2-carboxylate
  参考文献：
  名称：

  Convenient synthesis of t-butyl Z-3-substituted glycidates under conditions of phase-transfer catalysis

  摘要：

  Reactions of mixtures of t-butyl E- and Z-3-substituted glycidates 1a-h with 50% aq. sodium hydroxide and a catalyst, benzyltriethylammonium chloride, TEBAC in dichloromethane (phase-transfer catalysis, PTC led to preferential hydrolysis of the E-isomers to afford pure (90-98%) t-butyl Z-3-substituted glycidates 1a-i in good yields; PTC cleavage of glycidates additionally substituted at C-2, 1g or C-3, 1h,i suggests that an aryl group in the Z isomers hampers attack of HO- on the carbonyl carbon atom. As described in the literature, the diastereoselective PTC synthesis of Z-3-substituted glycidates and glycidonitriles consists of fast hydrolysis of E isomers present in mixtures with Z ones. (C) 2003 Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0040-4039(03)00234-x
• 作为产物：
  描述：

  氯乙酸叔丁酯 、 4-氯苯甲醛 在 氢化钾 作用下， 以 叔丁醇 为溶剂， 以80%的产率得到t-butyl β-(p-chlorophenyl)glycidate
  参考文献：
  名称：

  Bansal, R. K.; Sethi, K.; Bachelor, F. W., Indian Journal of Chemistry - Section B Organic and Medicinal Chemistry, 1980, vol. 19, # 6, p. 515 - 517

  摘要：

  DOI：

文献信息

• Effect of Phase-Transfer Catalyst on Stereochemistry of<i>tert</i>-Butyl-3-aryl(alkyl)-Substituted Glycidates
  作者：Anna Kowalkowska、Andrzej Jończyk

  DOI：10.1021/op1000379

  日期：2010.5.21

  Darzen’s condensation of tert-butyl-chloroacetate with aromatic, α,β-unsaturated, and aliphatic aldehydes in the presence of sodium hydroxide, afforded tert-butyl-glycidates, with trans/cis ratios 2.38−7.75. When TBAB was added as catalyst, the ratio reversed to cis/trans 1.67−4.52. Rate constants of halohydrin anion formations, their cyclization, and hydrolysis of diastereoisomers of glycidates as

  在氢氧化钠的存在下，叔丁基氯乙酸酯与芳族，α，β-不饱和脂族醛和脂肪族醛的Darzen缩合反应，得到缩水甘油酸叔丁酯，反式/顺式比为2.38-7.75。当添加TBAB作为催化剂时，该比例反转为顺式/反式1.67-4.52。卤代醇阴离子形成的速率常数，它们的环化，缩水甘油酯的非对映异构体的水解以及卤代醇阴离子的相应构象异构体的结构被认为可以解释这些结果。
• Bansal, R. K.; Sethi, K.; Bachelor, F. W., Indian Journal of Chemistry - Section B Organic and Medicinal Chemistry, 1980, vol. <B> 19, # 6, p. 515 - 517
  作者：Bansal, R. K.、Sethi, K.、Bachelor, F. W.

  DOI：——

  日期：——
• Convenient synthesis of t-butyl Z-3-substituted glycidates under conditions of phase-transfer catalysis
  作者：Andrzej Jonczyk、Tomasz Zomerfeld

  DOI：10.1016/s0040-4039(03)00234-x

  日期：2003.3

  Reactions of mixtures of t-butyl E- and Z-3-substituted glycidates 1a-h with 50% aq. sodium hydroxide and a catalyst, benzyltriethylammonium chloride, TEBAC in dichloromethane (phase-transfer catalysis, PTC led to preferential hydrolysis of the E-isomers to afford pure (90-98%) t-butyl Z-3-substituted glycidates 1a-i in good yields; PTC cleavage of glycidates additionally substituted at C-2, 1g or C-3, 1h,i suggests that an aryl group in the Z isomers hampers attack of HO- on the carbonyl carbon atom. As described in the literature, the diastereoselective PTC synthesis of Z-3-substituted glycidates and glycidonitriles consists of fast hydrolysis of E isomers present in mixtures with Z ones. (C) 2003 Elsevier Science Ltd. All rights reserved.