(chloro(4-nitrophenyl)methylene)(1-ethoxyethylidene)-l4-oxidane | 135041-40-6

• 英文名称: (chloro(4-nitrophenyl)methylene)(1-ethoxyethylidene)-l4-oxidane
• CAS: 135041-40-6
• 化学式: C₁₁H₁₂ClNO₄
• 分子量: 257.674
• InChiKey: BDOIZDZSYDMUOS-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  None
• 重原子数：
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• 可旋转键数：
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• 环数：
  None
• sp3杂化的碳原子比例：
  None
• 拓扑面积：
  None
• 氢给体数：
  None
• 氢受体数：
  None

反应信息

• 作为反应物：
  描述：

  (chloro(4-nitrophenyl)methylene)(1-ethoxyethylidene)-l4-oxidane 以 乙酸乙酯 为溶剂， 生成 2-Chloro-3-ethoxy-3-methyl-2-(4-nitro-phenyl)-oxirane
  参考文献：
  名称：

  Spectroscopic detection of an arylchlorocarbene-ethyl acetate carbonyl ylide and subsequent oxirane formation

  摘要：

  Laser flash photolysis of 3-chloro-3-(p-nitrophenyl)diazirine (1) generates the corresponding ground-state singlet carbene (lambda-max = 310 nm), which reacts with ethyl acetate to form a carbonyl ylide of the ester (lambda-max = 490 nm). The absolute rate constant for ylide formation in CH2Cl2 is k = (2.85 +/- 0.17) X 10(6) M-1 s-1. Subsequent cyclization of the ylide to the corresponding oxirane (lambda-max = 350 nm) occurs with a rate constant of 1.26 x 10(6) S-1 (21-degrees-C) in ethyl acetate with Arrhenius activation parameters for oxirane formation of E(act) = 6.68 +/- 0.19 kcal/mol and log A (s-1) = 11.08 +/- 0.15. The carbonyl ylide is also intercepted with the dipolarophile, diethyl fumarate, with a rate constant of (1.04 +/- 0.07) x 10(7) M-1 s-1. Additionally, solvent polarity effects on (p-nitrophenyl)chlorocarbene reactivity and spectroscopic evidence of oxirane formation (lambda-max = 350 nm) from the related acetone ylide of (p-nitrophenyl)chlorocarbene are presented.

  DOI：

  10.1021/ja00017a033
• 作为产物：
  描述：

  亚甲基,氯(4-硝基苯基)- 、 乙酸乙酯 生成 (chloro(4-nitrophenyl)methylene)(1-ethoxyethylidene)-l4-oxidane
  参考文献：
  名称：

  Spectroscopic detection of an arylchlorocarbene-ethyl acetate carbonyl ylide and subsequent oxirane formation

  摘要：

  Laser flash photolysis of 3-chloro-3-(p-nitrophenyl)diazirine (1) generates the corresponding ground-state singlet carbene (lambda-max = 310 nm), which reacts with ethyl acetate to form a carbonyl ylide of the ester (lambda-max = 490 nm). The absolute rate constant for ylide formation in CH2Cl2 is k = (2.85 +/- 0.17) X 10(6) M-1 s-1. Subsequent cyclization of the ylide to the corresponding oxirane (lambda-max = 350 nm) occurs with a rate constant of 1.26 x 10(6) S-1 (21-degrees-C) in ethyl acetate with Arrhenius activation parameters for oxirane formation of E(act) = 6.68 +/- 0.19 kcal/mol and log A (s-1) = 11.08 +/- 0.15. The carbonyl ylide is also intercepted with the dipolarophile, diethyl fumarate, with a rate constant of (1.04 +/- 0.07) x 10(7) M-1 s-1. Additionally, solvent polarity effects on (p-nitrophenyl)chlorocarbene reactivity and spectroscopic evidence of oxirane formation (lambda-max = 350 nm) from the related acetone ylide of (p-nitrophenyl)chlorocarbene are presented.

  DOI：

  10.1021/ja00017a033