3-(2-溴苯基)-2-氰基丙-2-烯酸甲酯 | 196512-60-4

• 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
• 中文名称: 3-(2-溴苯基)-2-氰基丙-2-烯酸甲酯
• 英文名称: methyl 2-(2-bromobenzylidene)-2-cyanoacetate
• 英文别名: (E)-methyl-3-(2-bromophenyl)-2-cyanoacrylate；Methyl 2-cyano-3-(2-bromophenyl)acrylate；methyl (E)-3-(2-bromophenyl)-2-cyanoprop-2-enoate
• CAS: 196512-60-4；109460-96-0
• 化学式: C₁₁H₈BrNO₂
• 分子量: 266.094
• InChiKey: SSKFRKHFQPOMDS-RMKNXTFCSA-N

物化性质

• 密度：
  1.5735 (rough estimate)

计算性质

• 辛醇/水分配系数(LogP)：
  2.8
• 重原子数：
  15
• 可旋转键数：
  3
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.09
• 拓扑面积：
  50.1
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  3-(2-溴苯基)-2-氰基丙-2-烯酸甲酯 在 C₂₆H₃₆N₄O₂ 、 双氧水 作用下， 以 水 、 甲苯 为溶剂， 反应 72.0h， 以93%的产率得到C₁₁H₈BrNO₃
  参考文献：
  名称：

  手性脲催化α，β-不饱和酯的对映选择性环氧化

  摘要：

  的高度不对称环氧化反式- α氰基α，β不饱和酯已经通过使用描述金鸡纳生物碱类尿素和H 2 ö 2作为有机催化剂和氧化剂，得到含以良好产率氰基手性缩水甘油酸酯衍生物（高达95％）具有出色的对映选择性（高达97％ee）。还提出了一个合理的过渡状态。

  DOI：

  10.1016/j.tetlet.2021.152909
• 作为产物：
  描述：

  邻溴苯甲醛 、 氰乙酸甲酯 在 C₉H₂₀NO₂⁽¹⁺⁾*C₂H₃O₂^(1-) 作用下， 以 水 为溶剂， 反应 20.0h， 以88%的产率得到3-(2-溴苯基)-2-氰基丙-2-烯酸甲酯
  参考文献：
  名称：

  Nmp-based ionic liquids: Recyclable catalysts for both hetero-Michael addition and Knoevenagel condensation in water

  摘要：

  A series of novel N-methyl piperidine (Nmp)-based ionic liquids with 1,2-propanediol group are synthesized and used as catalysts for both hetero-Michael addition of alpha,beta-unsaturated amides and Knoevenagel condensation at room temperature in water; and all the examined substrates could be transformed into corresponding products in good to excellent yields. Meanwhile IL-catalyzed hetero-Michael addition of alpha,beta-unsaturated amides in water has not been reported in the previous literatures. Additionally, the catalyst is recyclable for the two reactions. This finding provides a green catalyst for both hetero-Michael addition of alpha,beta-unsaturated amides and Knoevenagel condensation in water.

  DOI：

  10.1080/00397911.2018.1434544

文献信息

• Michael Monoaddition of Nitromethane on Gem-Diactivated Alkenes in Dry Media Coupled with Microwave Irradiation
  作者：David Michaud、Françoise Texier-Boullet、Jack Hamelin

  DOI：10.1016/s0040-4039(97)10035-1

  日期：1997.10

  Nitromethane reacts readily and selectively with a variety of electrophilic alkenes activated by cyano, ester or amide group to give the corresponding Michael monoadduct within a few minutes, in good yields over alumina without solvent and under focused microwaves. © 1997 Elsevier Science Ltd.

  硝基甲烷可在几分钟内与氰基，酯或酰胺基团活化的各种亲电烯烃轻松且选择性地反应，生成相应的迈克尔单加合物，在无溶剂的情况下和在聚焦微波下，氧化铝的收率很高。©1997爱思唯尔科学有限公司。
• MIMIRC Reactions of nitromethane with electrophilic alkenes in solvent-free reactions under microwave irradiation
  作者：David Michaud、Jack Hamelin、Françoise Texier-Boullet、Loı̈c Toupet

  DOI：10.1016/s0040-4020(02)00568-9

  日期：2002.7

  at C-3) are obtained from the reaction of nitromethane 1 with electrophilic alkenes 2a–i RCH=C(CN)(Y) with Y=CO2R′, CN, CONH2 in a solvent-free reaction catalyzed by piperidine at room temperature or under focused microwave irradiation after a few min. The mechanism involves a double Michael addition followed by intramolecular ring closure (MIMIRC reaction). The reaction is diastereoselective (two diastereoisomers

  从硝基甲烷1与亲电烯烃2a – i RCH = C（CN）（Y）与Y = CO 2 R的反应中获得新的高度官能化的环己烯3a – h或4a – i（在C-3处脱甲氧基羰基化或脱酰胺后）′，CN，CONH 2在室温下或经过几分钟的聚焦微波辐射下，由哌啶催化的无溶剂反应中的反应。该机制包括两次迈克尔加成，随后分子内闭环（MIMIRC反应）。该反应是非对映选择性的（仅两个非对映异构体）。在某些情况下，未环化的中间体已被分离出来。化学计量的哌啶可促进3的脱甲氧基羰基化。当Y为酰胺基时，观察到化学脱酰胺的第一个例子。
• New route to functionalized cyclohexenes from nitromethane and electrophilic alkenes without solvent under focused microwave irradiation
  作者：David Michaud、Sahar Abdallah-El Ayoubi、Marie-Joëlle Dozias、Loïc Toupet、Françoise Texier-Boullet、Jack Hamelin

  DOI：10.1039/a704241h

  日期：——

  Nitromethane reacts via a diastereoselective double Michael addition with electrophilic alkenes activated by cyano and methoxycarbonyl groups [XC 6 H 4 CHC(CN)CO 2 Me] in the presence of catalytic amounts of piperidine under solvent-free conditions coupled with focused microwave irradiation to afford new, highly functionalized cyclohexenes; no cyclopropane formation is observed.

  在无溶剂条件和聚焦微波辐照下，硝基甲烷在催化量哌啶的存在下，通过非对映选择性双迈克尔加成反应，与由氰基和甲氧羰基活化的亲电烯[XC 6 H 4 CHC(CN)CO 2 Me]发生反应，生成新的、高度官能化的环己烯；没有观察到环丙烷的形成。
• COPOLYMER AND OPTICAL FILM USING SAME
  申请人：Tosoh Corporation

  公开号：EP3553097A1

  公开（公告）日：2019-10-16

  Provided are a novel copolymer which is expected to form an optical film that has excellent retardation characteristics such as high retardation even in a thin film and an optical film using the same. A copolymer comprising a residue unit A represented by the general formula (1) and a residue unit B represented by the general formula (2): wherein R1 and R2 each independently represent hydrogen (provided that the case where R1 and R2 are both hydrogen is eliminated), a cyano group, an ester group (-C(=O)OX1), an amide group (-C(=O)N(X2)(X3)), or an acyl group (-C(=O)X4) (where X1 to X3 each independently represent a linear alkyl group having 1 to 12 carbon atoms, a branched alkyl group having 1 to 12 carbon atoms, or a cyclic alkyl group having 3 to 6 carbon atoms, and X4 represents a linear alkyl group having 1 to 12 carbon atoms, a branched alkyl group having 1 to 12 carbon atoms, or a cyclic group having 3 to 14 carbon atoms); R3 to R7 each independently represent hydrogen, a linear alkyl group having 1 to 12 carbon atoms, a branched alkyl group having 1 to 12 carbon atoms, a cyclic group having 3 to 14 carbon atoms, a halogen, a hydroxy group, a carboxy group, a nitro group, a cyano group, an alkoxy group (-OX5), an ester group (-C(=O)OX6), an amide group (-C(=O)N(X7)(X8)), an acyl group (-C(=O)X9), an amino group (-N(X10)(X11)), or a sulfonic acid group (-SOOX12) (where X5 to X8 each independently represent a linear alkyl group having 1 to 12 carbon atoms, a branched alkyl group having 1 to 12 carbon atoms, or a cyclic alkyl group having 3 to 6 carbon atoms, X9 to X12 each independently represent hydrogen, a linear alkyl group having 1 to 12 carbon atoms, a branched alkyl group having 1 to 12 carbon atoms, or a cyclic alkyl group having 3 to 6 carbon atoms); and adjacent substituents among R3 to R7 may form a fused ring structure each other, wherein R8 represents an m-membered heterocyclic residue containing one or more heteroatoms or a 5-membered or 6-membered ring residue containing no heteroatom (provided that, when R8 is a 6-membered ring residue containing no heteroatom, at least one of R3 to R7 in the general formula (1) represents a hydroxy group), and m represents an integer of 5 to 10; and the m-membered heterocyclic residue, the 5-membered ring residue, and the 6-membered ring residue may form a fused ring structure.

  本发明提供了一种新型共聚物，该共聚物可望形成一种光学薄膜，该光学薄膜具有优异的延缓特性，例如即使在薄膜中也具有高延缓性，本发明还提供了使用该共聚物的光学薄膜。 由通式（1）表示的残留单元 A 和通式（2）表示的残留单元 B 组成的共聚物： 其中 R1 和 R2 各自独立地代表氢（前提是排除 R1 和 R2 都是氢的情况）、氰基、酯基（-C(＝O)OX1）、酰胺基（-C(＝O)N(X2)(X3)）或酰基（-C(＝O)X4）（其中 X1 至 X3 各自独立地代表具有 1 至 12 个碳原子的直链烷基、具有 1 至 12 个碳原子的支链烷基或具有 3 至 6 个碳原子的环状烷基，而 X4 代表具有 1 至 12 个碳原子的直链烷基、具有 1 至 12 个碳原子的支链烷基或具有 3 至 14 个碳原子的环状基团）；R3 至 R7 各自独立地代表氢、具有 1 至 12 个碳原子的直链烷基、具有 1 至 12 个碳原子的支链烷基、具有 3 至 14 个碳原子的环基、卤素羟基、羧基、硝基、氰基、烷氧基 (-OX5)、酯基 (-C(=O)OX6)、酰胺基 (-C(=O)N(X7)(X8))、酰基 (-C(=O)X9)、氨基 (-N(X10)(X11))、或磺酸基（-SOOX12）（其中 X5 至 X8 各自独立地代表具有 1 至 12 个碳原子的直链烷基、具有 1 至 12 个碳原子的支链烷基或具有 3 至 6 个碳原子的环状烷基，X9 至 X12 各自独立地代表氢、具有 1 至 12 个碳原子的直链烷基、具有 1 至 12 个碳原子的支链烷基或具有 3 至 6 个碳原子的环状烷基）；R3 至 R7 中的相邻取代基可相互形成融合环结构、 其中 R8 代表含有一个或多个杂原子的 m 元杂环残基或不含杂原子的 5 元或 6 元环残基（条件是，当 R8 是不含杂原子的 6 元环残基时，通式（1）中 R3 至 R7 中至少有一个代表羟基），且 m 代表 5 至 10 的整数；且 m 元杂环残基、5 元环残基和 6 元环残基可形成融合环结构。
• Copolymer and optical film using same
  申请人：TOSOH CORPORATION

  公开号：US11225540B2

  公开（公告）日：2022-01-18

  A novel copolymer suitable for an optical film which is excellent in optical characteristics and has high retardation even in a thin film state, and an optical film containing the same are provided. A copolymer excellent in optical characteristics and easy to form a composite with a different polymer, and an optical film composed of the same are also provided.

  本发明提供了一种适用于光学薄膜的新型共聚物，这种共聚物具有优异的光学特性，即使在薄膜状态下也具有较高的延缓性，本发明还提供了一种含有这种共聚物的光学薄膜。此外，还提供了一种光学特性优异且易于与其他聚合物形成复合材料的共聚物，以及由其构成的光学薄膜。