isopropylidenemalonate di-t-butylperester | 1025928-21-5

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 羧酸及其衍生物
• 英文名称: isopropylidenemalonate di-t-butylperester
• 英文别名: 1,3-Bis(1,1-dimethylethyl) 2-(1-methylethylidene)propanediperoxoate；ditert-butyl 2-propan-2-ylidenepropanediperoxoate
• CAS: 1025928-21-5
• 化学式: C₁₄H₂₄O₆
• 分子量: 288.341
• InChiKey: XXYDYYFRYJCRHU-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.7
• 重原子数：
  20
• 可旋转键数：
  8
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.71
• 拓扑面积：
  71.1
• 氢给体数：
  0
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  isopropylidenemalonate di-t-butylperester 以 various solvent(s) 为溶剂， 生成 二甲基乙烯酮 、 二甲基亚乙烯基 、 isopropylideneketene 、 3-Propan-2-ylideneoxiran-2-one
  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 吡啶 、 氯化亚砜 作用下， 以 正戊烷 为溶剂， 反应 72.0h， 生成 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

文献信息

• Photochemical Generation and Matrix-Isolation Detection of Dimethylvinylidene
  作者：Sasha C. Reed、Gregory J. Capitosti、Zhendong Zhu、David A. Modarelli

  DOI：10.1021/jo001464i

  日期：2001.1.1

  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.