α-Methylenebenzyl formate | 84553-32-2

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: α-Methylenebenzyl formate
• 英文别名: alpha-Formoxystyrene；1-phenylethenyl formate
• CAS: 84553-32-2
• 化学式: C₉H₈O₂
• 分子量: 148.161
• InChiKey: YBGKMOKBFUCCPP-UHFFFAOYSA-N

物化性质

• 沸点：
  40 °C(Press: 0.1 Torr)
• 密度：
  1.066±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.3
• 重原子数：
  11
• 可旋转键数：
  3
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.0
• 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：

  α-Methylenebenzyl formate 在 硫酸 作用下， 生成 苯乙酮 、 甲乙酐
  参考文献：
  名称：

  Reaction de l'acide perchlorique sur les phenylacetylenes substitues. Mise en evidence d'un mecanisme ionique et radicalaire

  摘要：

  DOI：

  10.1016/s0040-4039(00)87647-9
• 作为产物：
  描述：

  聚合甲醛 、 苯乙炔 反应 14.0h， 以20%的产率得到α-Methylenebenzyl formate
  参考文献：
  名称：

  Montheard, Jean-Pierre; Camps, Marcel; Chatzopoulos, Michel, Bulletin de la Societe Chimique de France, 1984, vol. 2, # 3-4, p. 109 - 116

  摘要：

  DOI：

文献信息

• 1‐Arylvinyl formats: A New CO Source and Ketone Source in Carbonylative Synthesis of Chalcone Derivatives
  作者：Xinxin Qi、Ming Lai、Min‐Jie Zhu、Jin‐Bao Peng、Jun Ying、Xiao‐Feng Wu

  DOI：10.1002/cctc.201900011

  日期：2019.11.7

  1‐Arylvinyl formates as a kind of new CO surrogate have been explored for the first time. Most of the known CO precursors usually produce undesired residuals, which have to be removed. In this strategy, after CO release, the in situ generated acetophenones from 1‐arylvinyl formates can be successfully applied as a good ketone source in the synthesis of chalcones with benzaldehydes via a palladium‐catalyzed

  首次探索了1-芳基乙烯基甲酸酯作为一种新的CO替代物。大多数已知的CO前体通常会产生不希望有的残留物，必须将其除去。在该策略中，释放出CO后，由1-芳基乙烯基甲酸酯原位生成的苯乙酮可通过钯催化的还原羰基化反应成功地用作苯甲醛与查耳酮合成的良好酮源。在温和条件下，以令人满意的产率获得了各种查耳酮，并具有良好的底物相容性。
• Control over C–O and C–C bond formation: ruthenium catalyzed regiospecific addition of carboxylic acid to alkyne and stereoselective dimerization of alkyne
  作者：Jyotsna Tripathy、Manish Bhattacharjee

  DOI：10.1016/j.tetlet.2009.06.039

  日期：2009.8

  A cationic ruthenium(II) complex, [Ru(PPh3)2(CH3CN)3Cl][BPh4] (1), has been found to be an effective catalyst for stereoselective dimerization of alkynes in the presence of a base, and for regiospecific addition of carboxylic acids to alkynes in presence of the Lewis acid, BF3·Et2O.

  发现阳离子钌（II）配合物[Ru（PPh 3）2（CH 3 CN）3 Cl] [BPh 4 ]（1）是在碱存在下炔烃立体选择性二聚的有效催化剂。 ，以及在路易斯酸BF 3 ·Et 2 O的存在下将羧酸区域特异性地添加到炔烃中。
• A new heterogeneous hybrid ruthenium catalyst being an eco-friendly option for the production of polymers and organic intermediates
  作者：Bob De Clercq、Fr??d??ric Lefebvre、Francis Verpoort

  DOI：10.1039/b202872g

  日期：2002.8.22

  We succeeded in synthesising and characterising a new heterogeneous hybrid ruthenium catalyst that exhibits excellent stability, reusability and leaching characteristics. The host–guest interaction is studied by XRD, XRF, ICP/MS, BET, FT-Raman and solid state NMR analysis. Moreover, we tested this catalytic system in ring-closing metathesis (RCM), ring-opening metathesis polymerization (ROMP), Kharasch addition, atom transfer radical polymerization (ATRP) and vinylation reactions. The results obtained from these tests show that for ROMP, RCM, Kharasch addition and vinylation reactions the heterogeneous catalyst possesses important advantages in comparison with its homogeneous analogue.

  我们成功合成并表征了一种新型的异质混合钌催化剂，该催化剂表现出优良的稳定性、可重复使用性和浸出特性。通过XRD、XRF、ICP/MS、BET、FT-Raman和固态NMR分析研究了宿主–客体相互作用。此外，我们在环闭合交叉反应（RCM）、环打开交叉聚合（ROMP）、卡拉什加成、原子转移自由基聚合（ATRP）和乙烯化反应中测试了该催化系统。测试结果表明，在ROMP、RCM、卡拉什加成和乙烯化反应中，该异质催化剂相比其均相类似物具有重要优势。
• Ring-closing metathesis, Kharasch addition and enol ester synthesis catalysed by a novel class of ruthenium(II) complexes
  作者：Bob De Clercq、Francis Verpoort

  DOI：10.1016/s0040-4039(01)01952-9

  日期：2001.12

  addition of carbon tetrachloride across olefins with high yields which markedly depended on the catalyst and the substrate used. In addition, ring-closing metathesis of some representative diolefins was carried out. The best catalytic system III is able to form tri- and tetrasubstituted double bond products. Finally, dependent of the catalytic system and the reaction conditions used, these systems can catalyse

  钌席夫碱配合物I – III以高收率介导了四氯化碳在烯烃中的Kharasch加成反应，这明显取决于所用的催化剂和底物。另外，进行了一些代表性二烯烃的闭环易位。最佳的催化体系III能够形成三取代和四取代的双键产物。最后，取决于所使用的催化体系和反应条件，这些体系可以以优异的产率催化烯醇酯或烯炔的立体选择形成。
• Selective Dimerisation and Addition of Carboxylic Acids to Terminal Alkynes, Catalysed by Thermolysed Grubbs’ Catalyst: A Novel Synthesis of Enynes and Vinyl Esters
  作者：Karen Melis、Tom Opstal、Francis Verpoort

  DOI：10.1002/1099-0690(200211)2002:22<3779::aid-ejoc3779>3.0.co;2-j

  日期：2002.11

  triple bonds of terminal alkynes was carried out at 110 °C in the presence of the thermolysed RuII-alkylidene [Cl2(PCy3)2Ru=CHPh]. The transformation of phenylacetylene is strongly pKa-dependent, the preference switching from vinylation to dimerisation at increasing pKa values. Aliphatic alkynes only give rise to vinylation adducts, with a regioselectivity for Markovnikov addition. (© Wiley-VCH Verlag

  在热解的 RuII-亚烷基 [Cl2(PCy3)2Ru=CHPh] 存在下，末端炔烃的三键转化在 110°C 下进行。苯乙炔的转化强烈依赖于 pKa，随着 pKa 值的增加，偏好从乙烯基化转变为二聚化。脂肪族炔烃只产生乙烯基化加合物，对马尔科夫尼科夫加成具有区域选择性。(© Wiley-VCH Verlag GmbH, 69451 Weinheim, Germany, 2002)