3-Methoxy-1,2,3-tri-tert-butylcyclopropene | 150668-50-1

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 3-Methoxy-1,2,3-tri-tert-butylcyclopropene
• 英文别名: 1,2,3-tri-t-butyl-3-methoxycyclopropene；1,2,3-tritert-butyl-3-methoxycyclopropene
• CAS: 150668-50-1
• 化学式: C₁₆H₃₀O
• 分子量: 238.414
• InChiKey: BXAKHCBCQUJNOZ-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.5
• 重原子数：
  17
• 可旋转键数：
  4
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.88
• 拓扑面积：
  9.2
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为产物：
  描述：

  sodium methylate 、 Tri-tert-butylcyclopropenylium perchlorate 生成 3-Methoxy-1,2,3-tri-tert-butylcyclopropene
  参考文献：
  名称：

  控制烃盐或共价烃形成的阳离子稳定性差异很小

  摘要：

  空间上可比的阳离子 3-(p-甲基苯基)- 和 3-苯基-1,2-二环丙基环丙烯离子与高度稳定的库恩阴离子 (C67H39-) 的反应分别产生烃盐和共价烃，表明轻微的阳离子稳定性的差异区分了两种产物的形成。

  DOI：

  10.1246/cl.1992.683

文献信息

• Precise control of the formation of a covalent and an ionic bond in carbocation-carbanion combination reactions
  作者：Kenichi Takeuchi、Toshikazu Kitagawa、Atsushi Miyabo、Hideshi Hori、Koichi Komatsu

  DOI：10.1021/jo00073a047

  日期：1993.10

  The electronic effect on the selectivity of covalent or ionic bond formation was examined for the reaction of Kuhn's anion 1- (C67H39-; tris(7H-dibenzo[c,g]fluorenylidenemethyl)methide ion) and 1-aryl-2,3-dicyclopropylcyclopropenylium ions. The carbocation stability was progressively changed by varying the substituent on the phenyl ring, while the steric effect was kept essentially unchanged. The cations having the p-chlorophenyl (2a+), phenyl (2b+), m-methylphenyl (2c+), or m,m'-dimethylphenyl (2d+) group gave a covalent product, whereas a carbocation-carbanion salt was obtained from the cations having the p-methylphenyl (2e+) or p-methoxyphenyl (2f+) group. The reduction potentials E(red) of the cations, as determined by cyclic voltammetry, showed that the formation of the covalent or ionic product is switched by a small difference in stability (less-than-or-equal-to 0.4 kcal/mol) between 2d+ and 2e+. In chloroform, the salts 1-2e+ and 1-2f+ were transformed into covalent forms 1-2e and 1-2f, which can exist only in solution. When 1-(2a-d) and 1-2e,f+ were dissolved in DMSO, equilibrium between a covalent compound and ions was established. A plot of the free energy of heterolysis DELTAG(het)-degrees for 1-(2a-f) against the E(red) of the corresponding cations 2a-f+ showed that DELTAG(het)-degrees decreases as the cation is more stabilized. The heterolysis in DMSO was shown to be enhanced by ca. 13 kcal/mol both by the steric congestion in the covalent molecules and the stabilization of the cyclopropenylium ions by solvation.