cis-α-Methylcinnamic acid dimethylamide | 32180-41-9

• 分子结构分类: 有机化合物 - 苯丙烷和聚酮 - 肉桂酸及其衍生物
• 英文名称: cis-α-Methylcinnamic acid dimethylamide
• 英文别名: (Z)-N,N,2-trimethyl-3-phenylacrylamide；(Z)-N,N,2-trimethyl-3-phenylprop-2-enamide
• CAS: 32180-41-9
• 化学式: C₁₂H₁₅NO
• 分子量: 189.257
• InChiKey: DBPUUFLWAAYBLB-KTKRTIGZSA-N

物化性质

• 沸点：
  340.7±21.0 °C(Predicted)
• 密度：
  1.027±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.2
• 重原子数：
  14
• 可旋转键数：
  2
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.25
• 拓扑面积：
  20.3
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  cis-α-Methylcinnamic acid dimethylamide 以 二氯甲烷 为溶剂， 生成 (E)-N,N,2-trimethyl-3-phenylacrylamide
  参考文献：
  名称：

  Lewis-acid catalysis of photochemical reactions. 9. Structure and photoisomerization of (E)- and (Z)-cinnamamides and their Lewis acid complexes

  摘要：

  The spectroscopic properties and photoisomerization reactions of several (E)- and (Z)-cinnamamides have been investigated in the absence and presence of the strong Lewis acid BF3. The (E)-cinnamamides are essentially planar and exist predominantly in the enone s-cis conformation, except in the case of the alpha-methyl tertiary amide which adopts the s-trans conformation in order to minimize nonbonded repulsion. The (Z)-cinnamamides exist predominantly in the highly nonplanar s-trans conformation. This unusual conformational preference is attributed to intramolecular charge transfer from the aromatic to amide functionality. Photoisomerization efficiencies are dependent upon N-alkylation, aromatic substitution, alpha-alkylation, solvent, and excitation wavelength. These effects are attributed to the existence of two lowest energy pi,pi* singlet states (one reactive and one nonreactive) whose relative energies are dependent upon substitution. The cinnamamides from 1:1 complexes with BF3 with equilibrium constants > 10(3). Complexation alters both the electronic structure and photochemical behavior of the cinnamamides. Quantitative E --> Z isomerization has been observed for the BF3 complexes of two tertiary amides.

  DOI：

  10.1021/jo00002a015
• 作为产物：
  描述：

  3-苯基-2-甲基丙-2-烯酸 在 正丁基锂 、 草酰氯 、 copper diacetate 、 R-(+)-1,1'-联萘-2,2'-双二苯膦 、 N,N-二甲基甲酰胺 作用下， 以 四氢呋喃 、 正己烷 、 二氯甲烷 、 乙酸乙酯 为溶剂， 反应 22.0h， 生成 cis-α-Methylcinnamic acid dimethylamide
  参考文献：
  名称：

  铜对极化烯烃的催化热力学异构化。

  摘要：

  报道了Cu（OAc）2 / rac -BINAP配合物在蓝光下催化α-和β-取代肉桂酸酯衍生物的反热力学异构化。恶唑烷酮模板的使用有利于铜催化剂与底物的络合，允许在简单而稳定的反应条件下以良好至优异的比率进行催化形成的生色团的E → Z异构化。还研究了基于生色团的瞬时形成的该过程的机理。

  DOI：

  10.1021/acs.orglett.0c02894

文献信息

• Kinetic asymmetric protonation as a stereochemistry determining step in theMichael addition of acetic acid derivatives to ?-substituted cinnamic acid derivatives
  作者：L. Viteva、L. Gorrichon

  DOI：10.1007/bf00811020

  日期：——

  The reaction between acetic acid derivatives and alpha-substituted cinnamic acid derivatives has been studied in THF and THF:HMPT (80:20) as an alternative pathway of the Michael addition of phenylacetic and cinnamic acid derivatives. The regioselectivity observed is found to depend on the acceptor functional group and its geometry but not on the solvent used. The diastereoselectivity of the conjugate addition results from kinetic protonation of diastereotopic enolates (1,2-asymmetric induction). It varies from low in the presence of HMPT to considerable or even high in pure THF. The favoured anti or syn configuration in THF depends on the nature of the enolate. The results obtained are rationalized in terms of protonation via transition structures different in type (open us. chelated) and geometry.
• Copper-Photocatalyzed <i>Contra</i>-Thermodynamic Isomerization of Polarized Alkenes
  作者：Thibaud Brégent、Jean-Philippe Bouillon、Thomas Poisson

  DOI：10.1021/acs.orglett.0c02894

  日期：2020.10.2

  The contra-thermodynamic isomerization of α- and β-substituted cinnamate derivatives catalyzed by the Cu(OAc)2/rac-BINAP complex under blue light irradiation is reported. The use of an oxazolidinone template, which favored the complexation of the copper catalyst to the substrate, allowed the E → Z isomerization of the catalytically formed chromophore under simple and robust reaction conditions in good

  报道了Cu（OAc）2 / rac -BINAP配合物在蓝光下催化α-和β-取代肉桂酸酯衍生物的反热力学异构化。恶唑烷酮模板的使用有利于铜催化剂与底物的络合，允许在简单而稳定的反应条件下以良好至优异的比率进行催化形成的生色团的E → Z异构化。还研究了基于生色团的瞬时形成的该过程的机理。
• Lewis-acid catalysis of photochemical reactions. 9. Structure and photoisomerization of (E)- and (Z)-cinnamamides and their Lewis acid complexes
  作者：Frederick D. Lewis、Jeffrey E. Elbert、Alana L. Upthagrove、Paul D. Hale

  DOI：10.1021/jo00002a015

  日期：1991.1

  The spectroscopic properties and photoisomerization reactions of several (E)- and (Z)-cinnamamides have been investigated in the absence and presence of the strong Lewis acid BF3. The (E)-cinnamamides are essentially planar and exist predominantly in the enone s-cis conformation, except in the case of the alpha-methyl tertiary amide which adopts the s-trans conformation in order to minimize nonbonded repulsion. The (Z)-cinnamamides exist predominantly in the highly nonplanar s-trans conformation. This unusual conformational preference is attributed to intramolecular charge transfer from the aromatic to amide functionality. Photoisomerization efficiencies are dependent upon N-alkylation, aromatic substitution, alpha-alkylation, solvent, and excitation wavelength. These effects are attributed to the existence of two lowest energy pi,pi* singlet states (one reactive and one nonreactive) whose relative energies are dependent upon substitution. The cinnamamides from 1:1 complexes with BF3 with equilibrium constants > 10(3). Complexation alters both the electronic structure and photochemical behavior of the cinnamamides. Quantitative E --> Z isomerization has been observed for the BF3 complexes of two tertiary amides.