isopropylidenemalonic acid chloride | 323577-42-0

• 分子结构分类: 有机化合物 - 有机卤素化合物 - 酰卤
• 英文名称: isopropylidenemalonic acid chloride
• 英文别名: 2-Propan-2-ylidenepropanedioyl dichloride
• CAS: 323577-42-0
• 化学式: C₆H₆Cl₂O₂
• 分子量: 181.018
• InChiKey: WDIFZZFQZWEGJM-UHFFFAOYSA-N

物化性质

• 沸点：
  258.5±23.0 °C(Predicted)
• 密度：
  1.313±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.9
• 重原子数：
  10
• 可旋转键数：
  2
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.33
• 拓扑面积：
  34.1
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  叔丁基过氧化氢 、 isopropylidenemalonic acid chloride 在 吡啶 作用下， 以 正戊烷 为溶剂， 反应 72.0h， 以32.8%的产率得到isopropylidenemalonate di-t-butylperester
  参考文献：
  名称：

  Photochemical Generation and Matrix-Isolation Detection of Dimethylvinylidene

  摘要：

  We report the spectroscopic characterization of dimethylvinylidene, (CH3)(2)C=C:, generated within an argon matrix at 14 K from a bisperoxyester precursor. The carbene was identified by comparison of the experimental IR spectrum with vibrational frequencies computed at the B3LYP/6-31G(d) level. Chemical trapping of the carbene within a 9% CO/Ar matrix to form dimethylpropadienone supports this analysis. Additional products produced during photolysis were identified by comparison to the appropriate computed vibrational frequencies. The potential energy surface of dimethylvinylidene and its intramolecular rearrangement products, 2-butyne and methylcyclopropene, were also investigated computationally at the B3LYP/6-31G(d) level. A spin-state analysis of this carbene using a variety of computational methods (CCSD(T), B3LYP, MP2) indicates the singlet state is more stable than the triplet by similar to 45 kcal mol(-1). We anticipate the bisperoxyester precursor used here will be a convenient and general way for initiating future studies of alkylvinylidenes under matrix-isolation conditions.

  DOI：

  10.1021/jo001464i
• 作为产物：
  描述：

  isopropylidenemalonic acid 在 氯化亚砜 作用下， 以79.7%的产率得到isopropylidenemalonic acid chloride
  参考文献：
  名称：

  Photochemical Generation and Matrix-Isolation Detection of Dimethylvinylidene

  摘要：

  We report the spectroscopic characterization of dimethylvinylidene, (CH3)(2)C=C:, generated within an argon matrix at 14 K from a bisperoxyester precursor. The carbene was identified by comparison of the experimental IR spectrum with vibrational frequencies computed at the B3LYP/6-31G(d) level. Chemical trapping of the carbene within a 9% CO/Ar matrix to form dimethylpropadienone supports this analysis. Additional products produced during photolysis were identified by comparison to the appropriate computed vibrational frequencies. The potential energy surface of dimethylvinylidene and its intramolecular rearrangement products, 2-butyne and methylcyclopropene, were also investigated computationally at the B3LYP/6-31G(d) level. A spin-state analysis of this carbene using a variety of computational methods (CCSD(T), B3LYP, MP2) indicates the singlet state is more stable than the triplet by similar to 45 kcal mol(-1). We anticipate the bisperoxyester precursor used here will be a convenient and general way for initiating future studies of alkylvinylidenes under matrix-isolation conditions.

  DOI：

  10.1021/jo001464i