methyl (E)-2-benzylidene-3-methylbutanoate | 98158-54-4

• 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: methyl (E)-2-benzylidene-3-methylbutanoate
• 英文别名: methyl (2E)-2-benzylidene-3-methylbutanoate
• CAS: 98158-54-4
• 化学式: C₁₃H₁₆O₂
• 分子量: 204.269
• InChiKey: OQIOSOHSUYFXCZ-FMIVXFBMSA-N

物化性质

• 沸点：
  290.8±9.0 °C(Predicted)
• 密度：
  1.020±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.3
• 重原子数：
  15
• 可旋转键数：
  4
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.31
• 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：

  methyl (E)-2-benzylidene-3-methylbutanoate 在 sodium hydroxide 作用下， 以 甲醇 、 水 为溶剂， 反应 21.0h， 生成 (E)-2-benzylidene-3-methylbutanoic acid
  参考文献：
  名称：

  使用手性胺的不对称迈克尔加成反应的新颖实用的不对称合成β2,3-氨基酯

  摘要：

  开发了一种实用的合成具有各种取代基的手性β2，3-氨基酯的方法，其特征在于手性锂酰胺与三取代的（E）-α，β-不饱和酯的不对称迈克尔加成反应。我们发现，高度面选择性质子化发生通过快速加入水以从迈克尔加成反应得到的烯醇化物中间体，得到ñ -保护的β 2,3-氨基酯在中度至良好的产率。通过简便地制备几何纯的三取代（E）-α，β-不饱和酯，这是我们小组最近建立的。通过使用在迈克尔加成物的氨基基团的脱保护Ñ碘代丁二酰亚胺（NIS）β有效地提供2,3-具有各种取代基的氨基酯。

  DOI：

  10.1016/j.tet.2017.02.037
• 作为产物：
  描述：

  异戊酸甲酯 、 苯甲醛 生成 methyl (E)-2-benzylidene-3-methylbutanoate
  参考文献：
  名称：

  The Use of Lewis Acids in Radical Chemistry. Chelation-Controlled Radical Reductions of Substituted α-Bromo-β-alkoxy Esters and Chelation-Controlled Radical Addition Reactions

  摘要：

  The radical reduction of a series of alpha-bromo-beta-alkoxy esters under chelation-controlled conditions is reported. Proceeding with high stereoselectivity in the presence of MgBr2. OEt2, reductions give access to syn, products. Systematic variations in substrate substituents show that these reactions tolerate a wide variety of alkyl functionalities at positions 2 and 3 and are relatively unaffected by the nature of the ester group. Changes to the alkoxy function indicate that a bidentate chelate is involved in the reaction and that an excess of MgBr2. OEt2 is required for optimum selectivity by favoring this species in preference to the anti-selective monodentate or nonchelated pathways. Competition experiments suggest that the monodentate pathway is kinetically favored over the bidentate one. The suppressibility of the reaction by radical chain inhibitors and the need for initiation indicate the intermediacy of radicals. Further support for this mechanism includes both radical addition to alpha,beta-unsaturated esters and reduction of bromides conducted in the presence of a Lewis acid.

  DOI：

  10.1021/jo980636x

文献信息

• Diastereoselectivity in the alkylation and protonation of some β-silyl enolates
  作者：Ian Fleming、John H. M. Hill、David Parker、David Waterson

  DOI：10.1039/c39850000318

  日期：——

  A wide variety of β-silyl enolates are alkylated or protonated with high diastereoselectivity, which appears to be substantially electronic in origin.

  各种各样的β-甲硅烷基烯醇化物以高非对映选择性被烷基化或质子化，这似乎基本上是电子起源的。
• The diastereoselectivity of electrophilic attack on trigonal carbon adjacent to a stereogenic centre: diastereoselective alkylation and protonation of open-chain enolates having a stereogenic centre carrying a silyl group at the ? position
  作者：Roger A. N. C. Crump、Ian Fleming、John H. M. Hill、David Parker、N. Laxma Reddy、David Waterson

  DOI：10.1039/p19920003277

  日期：——

  The alkylation and protonation of enolates having a β-silyl group, prepared by conjugate addition of a silyl-cuprate reagent to enone systems, are almost always highly diastereoselective in the sense 3 in a wide variety of reactions. The effects of varying the type of enolate (Scheme 1) and its geometry, the size of the medium-sized group R1 on the stereogenic centre (Scheme 3), the nature of the alkylating

  通过将甲硅烷基-铜酸酯试剂共轭加到烯酮体系中制备的具有β-甲硅烷基的烯醇酸酯的烷基化和质子化在各种反应中在意义3上几乎总是非对映选择性的。改变烯醇化物类型（方案1）及其几何形状，中型基团R 1在立体中心的大小（方案3），烷基化剂R 3 X或质子源的性质（方案4）的影响），以及取代基R 4和R 5的大小报告了甲硅烷基基团上的化学式（方案6）。在创建某些四元中心时，立体选择性也很高（方案7）。因为可以将苯基二甲基甲硅烷基基团转化为羟基，同时保留在β碳原子上的立体化学，所以该反应允许立体控制合成β-羟基羰基化合物。作为合成方法的主要限制是，当基团R 3时，非对映选择性低，甚至偶而逆转。亲核中心上的甲基比甲基大得多。有一些不确定的证据表明某些立体声控制源可能是电子的，而不仅仅是空间的。无论电子控制的程度如何，β-甲硅烷基基团都是对双键进行亲电攻击的有效控制元素，因为它的电子和空间效应可能朝同一方向
• A Facile and Convenient Synthesis of Trisubstituted (<i>E</i>)-α,β-Unsaturated Esters by Tandem Acetylation-E1cB Reaction
  作者：Minoru Ozeki、Ayumi Hachino、Takashi Shigeta、Aya Niki、Natsuko Kobayashi、Hideki Mizutani、Akihiro Nakamura、Ayano Horie、Kenji Arimitsu、Tetsuya Kajimoto、Shinzo Hosoi、Hiroki Iwasaki、Naoto Kojima、Masayuki Yamashita、Ikuo Kawasaki

  DOI：10.1248/cpb.c18-00666

  日期：2019.1.1

  A facile and convenient synthesis of trisubstituted (E)-α,β-unsaturated esters was developed by improving our previously established method. The new method circumvented the separation of the intermediates, which have an activating group of the hydroxyl group in β-hydroxy esters, furnishing α,β-unsaturated esters in shorter steps than the previous method: an acetylation of β-hydroxy group and subsequent

  通过改进我们先前建立的方法，开发了一种简便易行的三取代（E）-α，β-不饱和酯的合成方法。新方法规避了中间体的分离，该中间体在β-羟基酯中具有羟基的活化基团，与以前的方法相比，可在更短的步骤中提供α，β-不饱和酯：β-羟基的乙酰化和随后的E1cB反应一齐进行。另外，该新方法不仅可以将底物的非对映异构体混合物用于E1cB反应，而且具有广泛的底物范围，这将使得能够合成各种三取代的（E）-α，β-不饱和酯。
• FLEMING, I.;HILL, J. H. M.;PARKER, D.;WATERSON, D., J. CHEM. SOC. CHEM. COMMUN., 1985, N 6, 318-321
  作者：FLEMING, I.、HILL, J. H. M.、PARKER, D.、WATERSON, D.

  DOI：——

  日期：——
• Composition With Tight Capsules Containing a Sunscreen Agent
  申请人：Poschalko Alexander

  公开号：US20080199526A1

  公开（公告）日：2008-08-21

  The present invention provides a topical composition comprising a first sunscreen agent which is encapsulated and a second sunscreen agent which is different from the first sunscreen agent, characterized in that the first sunscreen agent is encapsulated in microcapsules having an average particle size D(v, 0.5) from 3 μm to 8 μm. The encapsulated sunscreen agent is preferably a cinnamic ester derivative.