4-methoxycarbonyl-1-methyl-1,4-dihydropyridine anion enolate | 36907-10-5

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 吡啶及其衍生物
• 英文名称: 4-methoxycarbonyl-1-methyl-1,4-dihydropyridine anion enolate
• 英文别名: 1,4-dihydro-4-methoxycarbonyl-1-methylpyridine anion；1,4-dihydro-4-methoxycarbonyl-1-methylpyridine；1-Methyl-4-carbomethoxypyridinyl
• CAS: 36907-10-5
• 化学式: C₈H₁₀NO₂
• 分子量: 152.173
• InChiKey: JPSPOJOUFWHEDK-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.71
• 重原子数：
  11.0
• 可旋转键数：
  1.0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.25
• 拓扑面积：
  29.54
• 氢给体数：
  0.0
• 氢受体数：
  3.0

反应信息

• 作为反应物：
  描述：

  1-溴-2,2-二甲基丙烷 、 4-methoxycarbonyl-1-methyl-1,4-dihydropyridine anion enolate 在 四丁基碘化铵 作用下， 以 N,N-二甲基甲酰胺 为溶剂， 以85%的产率得到1,4-dihydro-4-methoxycarbonyl-1-methyl-4-neopentylpyridine
  参考文献：
  名称：

  Lund, Torben; Lund, Henning, Acta chemica Scandinavica. Series B: Organic chemistry and biochemistry, 1986, vol. 40, # 6, p. 470 - 485

  摘要：

  DOI：
• 作为产物：
  描述：

  4-methoxycarbonyl-1-methylpyridinium perchlorate 在 2e^(1-) 作用下， 生成 4-methoxycarbonyl-1-methyl-1,4-dihydropyridine anion enolate
  参考文献：
  名称：

  Daasbjerg, Kim; Pedersen, Steen U.; Lund, Henning, Acta Chemica Scandinavica, 1989, vol. 43, # 9, p. 876 - 881

  摘要：

  DOI：

文献信息

• Correlation between inner-sphere stabilization and stereochemistry for the aliphatic nucleophilic substitution.
  作者：Torben Lund

  DOI：10.1016/s0040-4039(00)74281-x

  日期：1991.3

  The stereochemistry of the nucleophilic reaction of the enolate anion of 1,4-dihydro-4-methoxycarbonyl-1-methylpyridine (1−) with cis and trans-2-bromomethoxycyclohexane was investigated and correlated with the inner-sphere stabilization of the reactions calculated from the ratio kSUB/kET, where kSUB is the rate of substitution and kET the expected rate of electron transfer.

  1,4-二氢-4-甲氧基羰基-1-甲基吡啶（的烯醇阴离子的亲核反应的立体化学1 - ）与顺式和反式-2- bromomethoxycyclohexane进行了研究，并用计算出的反应的内球稳定化相关从比率k SUB / k ET，其中k SUB是取代率，k ET是预期的电子转移率。
• Lund, Torben; Lund, Henning, Acta chemica Scandinavica. Series B: Organic chemistry and biochemistry, 1988, vol. 42, # 5, p. 269 - 279
  作者：Lund, Torben、Lund, Henning

  DOI：——

  日期：——
• Complete Inversion of Configuration in Aliphatic Nucleophilic Substitution Reactions with Small Inner-Sphere Stabilization.
  作者：Torben Lund、Karin Bay Jacobsen、Carsten Christophersen、Per Halfdan Nielsen、Yngve Stenstrøm、Ruo-Hua Zhang、Kurt V. Mikkelsen、Alexander Senning

  DOI：10.3891/acta.chem.scand.52-0778

  日期：——

  The stereochemistry of the nucleophilic reaction of the enolate anion of 1,4-dihydro-4-methoxycarbonyl-1-methylpyridine (1(-)) with (R)-(-)- and (S)-(+)-2-bromobutane has been investigated and correlated with the inner-sphere stabilization of the reactions calculated from the ratio k(SUB)/k(ET), where k(SUB) is the rate of substitution and k(ET) the expected rate of electron transfer. It was shown that 1(-) reacts with 2-bromobutane with nearly complete inversion of configuration (99.7%). A complete shift in stereochemistry of the nucleophilic reactions of 1(-) with alkyl halides from racemization to complete inversion is induced by a small increase in the inner-sphere stabilization of the transition state from 0 to 3 kcal mol(-1). The results in this work suggest that the S(N)2 inversion process in general is extremely sensitive towards inner-sphere stabilization.