(E)-isopropyl cinnamate | 60512-85-8

• 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: (E)-isopropyl cinnamate
• 英文别名: isopropyl cinnamate；isopropyl trans-cinnamate；isopropyl (E)-cinnamate；i-propyl cinnamate；propan-2-yl (E)-3-phenylprop-2-enoate
• CAS: 60512-85-8
• 化学式: C₁₂H₁₄O₂
• 分子量: 190.242
• InChiKey: RGACABDFLVLVCT-CMDGGOBGSA-N

物化性质

• 沸点：
  269°C (estimate)
• 密度：
  1.0320
• 物理描述：
  Colourless viscous liquid, balsamic, sweet and dry amber type odour
• 溶解度：
  insoluble in water; soluble in oils
• 折光率：
  1.541-1.548
• 保留指数：
  1485

计算性质

• 辛醇/水分配系数(LogP)：
  3.4
• 重原子数：
  14
• 可旋转键数：
  4
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.25
• 拓扑面积：
  26.3
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  (E)-isopropyl cinnamate 在 sodium tetrahydroborate 作用下， 以 二乙二醇二甲醚 为溶剂， 反应 5.0h， 以2%的产率得到3-苯基丙-2-烯-1-醇
  参考文献：
  名称：

  Reductions of Carboxylic Acids and Esters with NaBH₄ in Diglyme at 162°C

  摘要：

  Aromatic esters, including the extremely sterically hindered ester: t-amyl 2-chlorobenzoate, are readily reduced to the corresponding benzyl alcohols in high yield with NaBH4 in refluxing diglyme (162 degreesC). In sharp contrast, aliphatic esters usually gave only low yields of alcohols. Instead, diglyme fragmentation products are formed which undergo transesterification reactions, producing complex product mixtures including products such as RCOOCH2CH2OCH3. The mechanism of this process involves sodium borohydride-induced S(N)2 cleavage of diglyme (hydride attack) at high temperatures. However, when the extremely electron rich, 3,4,5-trimethoxybenzoic acid is treated with NaBH4/diglyme at 162 degreesC (with or without an equivalent of LiCl), no 3,4,5-trimethyoxybenzyl alcohol is formed. The electron rich and hindered ester, t-amyl-3,4,5-trimethoxybenzoate, also does not reduce under these conditions (with or without LiCl). However, both methyl and isopropyl 3,4,5-trimethoxybenzoate esters were converted into 3,4,5-trimethyoxybenzyl alcohol in good yields in NaBH4/diglyme/LiCl at 162 degreesC. These reductions did not occur unless LiCl was present, illustrating the electron releasing effect of the three methoxy functions which reduce the carbonyl group's reactivity.

  DOI：

  10.1081/scc-120018935
• 作为产物：
  描述：

  iso-propyl 2-(benzo[d]thiazol-2-ylsulfonyl)acetate 在 titanium(IV) isopropylate 、 偶氮二异丁腈 、 三(三甲基硅基)硅烷 作用下， 以 乙腈 、 苯 为溶剂， 反应 13.5h， 生成 (E)-isopropyl cinnamate
  参考文献：
  名称：

  三取代高活化苯并[d]噻唑-2-基砜的烯烃是有机合成中的基础。

  摘要：

  在本文中，我们报告了高度亲电子的1,1-失活烯烃的形成，它们作为新型合成构件的使用以及它们向结构多样的分子支架的转化。分别被BT-磺酰基和羰基或腈取代的1,1-失活烯烃的合成由不寻常的Ti（OPr i）4组成介导的Knoevenagel型缩合反应，收率好至极好。产生的烯烃可以高度立体选择性的方式和高收率进一步转化为各种多官能化杂环和无环分子支架。总体而言，从（主要是）市售醛开始，分两到四个步骤获得所得结构。另外，在制备的结构中BT-磺酰基的存在允许进一步的化学选择性官能化/合成后转化以提供结构上多样化的最终化合物。

  DOI：

  10.1021/acs.joc.0c00571

文献信息

• Primary Amides. A General Nitrogen Source for Catalytic Asymmetric Aminohydroxylation of Olefins
  作者：Zachary P. Demko、Michael Bartsch、K. Barry Sharpless

  DOI：10.1021/ol000098m

  日期：2000.7.1

  N-Bromo,N-lithio salts of primary carboxamides have been shown to be efficient nitrogen sources for catalytic asymmetric aminohydroxylation of olefins, behaving much like the parent N-bromoacetamide in these reactions. alpha-Chloro-N-bromoacetamide is a particularly interesting nitrogen source, as it is functionalized for further reaction, including easy deprotection by treatment with thiourea.

  伯羧酰胺的N-溴，N-硫代盐已被证明是烯烃催化不对称氨基羟基化的有效氮源，其行为与母体N-溴代乙酰胺非常相似。α-氯-N-溴乙酰胺是一种特别令人感兴趣的氮源，因为它被官能化用于进一步反应，包括通过硫脲处理而易于脱保护。
• Novel multi-dentate phosphines for Pd-catalyzed alkoxycarbonylation of alkynes promoted by H2O additive
  作者：Da Yang、Lei Liu、Dong-Liang Wang、Yong Lu、Xiao-Li Zhao、Ye Liu

  DOI：10.1016/j.jcat.2019.01.031

  日期：2019.3

  A series of novel multi (bi-/tri-/tetra-)-dentate phosphines with good robustness against water and oxygen were synthesized and fully characterized. It was found that the developed ionic tri-dentate phosphine (L2′) enabled Pd-catalyzed alkoxycarbonylation of alkynes most efficiently while H2O was used as an additive instead of acid. As for L2′, its unique steric configuration with two types of potential

  合成并充分表征了一系列新颖的多（双-/三-/四-）齿状膦，其对水和氧具有良好的耐受性。发现开发的离子型三齿膦（L2'）能够最有效地Pd催化炔烃的烷氧基羰基化，同时使用H 2 O代替酸作为添加剂。至于L2'，其独特的空间构型以及两种潜在的PP螯合模式（P⋯P距离分别为4.31Å和4.36Å）到Pd中心使得相应的Pd催化剂具有高活性和良好的炔烃羰基羰基化稳定性。的原位FT-IR分析也证实了钯-H活性物质的形成和稳定性大大用的存在促进L2'和H 2 O添加剂。此外，作为离子化膦，固定在[Bmim] NTf 2的RTIL中的基于L2'的PdCl 2（MeCN）2系统可以循环使用7次，而不会造成明显的活性损失或金属浸出。
• NHC-catalyzed C–O or C–N bond formation: efficient approaches to α,β-unsaturated esters and amides
  作者：Bo Zhang、Peng Feng、Yuxin Cui、Ning Jiao

  DOI：10.1039/c2cc32862c

  日期：——

  Simple and efficient NHC-catalyzed transformations of bromoenal or α,β-dibromoenal into α,β-unsaturated esters or amides with high stereoselectivity through C–O or C–N bond formation have been demonstrated. The NHC-catalyzed processes occur under mild conditions. The ready availability of the starting materials, avoidance of external oxidants and the usefulness of the products all make the strategy attractive.

  简单高效的NHC催化转化，通过C-O或C-N键形成，将溴代烯酸或α,β-二溴代烯酸高立体选择性地转化为α,β-不饱和酯或酰胺。NHC催化的过程在温和条件下进行。起始原料易于获得，避免使用外部氧化剂，以及产品的实用价值，都使这一策略具有吸引力。
• Tandem Oxidation Processes: The Direct Conversion of Activated Alcohols into Esters and Amides
  作者：Richard J. Taylor、Jonathan S. Foot、Hisashi Kanno、Gerard M. Giblin

  DOI：10.1055/s-2002-32951

  日期：——

  The direct conversion of primary alcohols into methyl esters and amides using manganese dioxide and sodium cyanide with methanol or the appropriate amine is reported. These transformations, which proceed via an in situ four step, double oxidation sequence, have been applied to a range of benzylic, heterocyclic, allylic and propargylic alcohols.

  据报道，使用二氧化锰和氰化钠与甲醇或适当的胺将伯醇直接转化为甲酯和酰胺。这些通过原位四步双氧化序列进行的转化已应用于一系列苄醇、杂环醇、烯丙醇和炔丙醇。
• Photoinduced Oxidative Alkoxycarbonylation of Alkenes with Alkyl Formates
  作者：Wan-Ying Tang、Ling Chen、Ming Zheng、Le-Wu Zhan、Jing Hou、Bin-Dong Li

  DOI：10.1021/acs.orglett.1c01096

  日期：2021.5.21

  A photoinduced oxidative alkoxycarbonylation of alkenes initiated by intermolecular addition of alkoxycarbonyl radicals has been demonstrated. Employing alkyl formates as alkoxycarbonyl radical sources, a range of α,β-unsaturated esters were obtained with good regioselectivity and E selectivity under ambient conditions.

  已经证明了通过分子间加成烷氧基羰基引发的烯烃的光诱导氧化烷氧基羰基化。利用烷基甲酸酯作为烷氧羰基自由基源，在环境条件下获得了一系列具有良好区域选择性和E选择性的α，β-不饱和酯。

表征谱图