3-(diethoxyphosphoryl)acrylonitril | 39492-25-6

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 有机膦酸及其衍生物
• 英文名称: 3-(diethoxyphosphoryl)acrylonitril
• 英文别名: (E)-diethyl 2-cyanovinylphosphonate；Diethyl beta-cyanovinylphosphonate；(E)-3-diethoxyphosphorylprop-2-enenitrile
• CAS: 39492-25-6
• 化学式: C₇H₁₂NO₃P
• 分子量: 189.151
• InChiKey: ODBRSIMTHPKUJD-FNORWQNLSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.1
• 重原子数：
  12
• 可旋转键数：
  5
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.57
• 拓扑面积：
  59.3
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  叠氮苯 、 3-(diethoxyphosphoryl)acrylonitril 以55%的产率得到2-cyano-3-(diethoxyphosphinyl)-1-phenylaziridine
  参考文献：
  名称：

  Khusainova, N. G.; Bredikhina, Z. A.; Ishmaeva, E'. A., Journal of general chemistry of the USSR, 1981, vol. 51, # 3, p. 409 - 411

  摘要：

  DOI：
• 作为产物：
  描述：

  亚磷酸二乙酯 、 2-氯丙烯腈 在 三甲基氯硅烷 、 三乙胺 作用下， 生成 3-(diethoxyphosphoryl)acrylonitril
  参考文献：
  名称：

  A mild and stereoselective synthesis of β-phosphonylacrylates

  摘要：

  The addition of trimethylsilyloxy phosphorus (III) derivatives, generated in situ, to alpha-haloacrylates and acrylonitriles at room temperature provides a mild, general and stereoselective route to beta-phosphonoacrylates. (C) 1997 Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0040-4039(97)10540-8

文献信息

• Regioselective C-Acylation of Vinylphosphorus Compounds Through Electroreduction or Mg-Promoted Reduction
  作者：Makoto Kyoda、Takamichi Yokoyama、Hirofumi Maekawa、Toshinobu Ohno、Ikuzo Nishiguchi

  DOI：10.1055/s-2001-17471

  日期：——

  Either of electroreduction or Mg-promoted electron-transfer reaction of vinylphosphonate derivatives 1-4 in the presence of acid anhydrides 5 a - c or acid chlorides 15 b, c brought about regioselective C-acylation to give the corresponding β-acylphosphonates 3 in good yields. The reaction may be initiated through one-electron transfer from either a cathode or Mg metal to a substrate to give the corresponding anion radical, which is then subjected to electrophilic attack of an acylating agent, followed by the fast second electron-transfer.

  在酸酐5a-c或酰氯15b、c的存在下，乙烯膦酸酯衍生物1-4无论是通过电还原还是Mg促进的电子转移反应，均能选择性地发生C-酰化反应，得到相应的β-酰基膦酸酯3，产率良好。反应可能始于从一个阴极或Mg金属向底物的一次电子转移，生成相应的阴离子自由基，随后遭受酰化剂的亲电攻击，继而迅速进行第二次电子转移。
• Catalytic Hydrocyanation of Activated Terminal Alkynes
  作者：David Tejedor、Samuel Delgado‐Hernández、Lucía Colella、Fernando García‐Tellado

  DOI：10.1002/chem.201903402

  日期：2019.11.27

  electron-withdrawing functionality has been implemented. The catalytic manifold operates under the reactivity generation principle "a good nucleophile generates a strong base", and it uses 1,4-diazabicyclo[2.2.2]octane (DABCO) as the catalyst, activated terminal alkynes as substrates and acetone cyanohydrin as the cyanide source. The acrylonitriles obtained as E,Z mixtures are straightforwardly resolved by simple flash

  已经实现了通用的，实用的和可扩展的有机催化氢氰化歧管，以提供具有吸电子功能的β-取代的丙烯腈。催化歧管按照反应活性生成原理“良好的亲核试剂生成强碱”操作，它使用1,4-二氮杂双环[2.2.2]辛烷（DABCO）作为催化剂，活化的末端炔烃作为底物，丙酮氰醇作为催化剂。氰化物来源。通过简单的快速色谱法可直接拆分作为E，Z混合物获得的丙烯腈，以制备量提供纯净的异构体。
• NMR and X-ray diffraction analysis of 3-thioamido-5-phosphono-1-cyclohexene derivatives: Conformational and stereochemical assignments
  作者：Jean-Christophe Monbaliu、Bernard Tinant、Jacqueline Marchand-Brynaert

  DOI：10.1016/j.molstruc.2007.08.018

  日期：2008.5

  efficiency of the oxazolidin-2-thione chiral auxiliary in the facial discrimination of Diels-Alder reactions. The absolute configuration of the 3,4,5-trisubstituted cyclohexene derivatives (3a-c) was established by X-ray diffraction analysis. NMR studies confirmed the relative stereochemistries and showed two possible conformers in solution. (C) 2007 Elsevier B.V. All rights reserved.

  N-(二烯基)-4-(R)-苯基恶唑烷-2-硫酮(1)与1-二乙氧基磷酰基-1-丁烯-3-酮(2a)、3-(二乙氧基磷酰基)丙烯酸甲酯(2b)和3的反应-(dietlioxypliosphoryl)丙烯腈 (2c) 分别提供 [4+2] 环加合物 3a、3b 和 3c，作为单一立体异构体，证实了恶唑烷-2-硫酮手性助剂在 Diels-Alder 反应的面部辨别中的效率。3,4,5-三取代的环己烯衍生物 (3a-c) 的绝对构型是通过 X 射线衍射分析确定的。核磁共振研究证实了相对立体化学，并在溶液中显示了两种可能的构象异构体。(C) 2007 Elsevier BV 版权所有。
• [4+2] Cycloaddition of 1-aminodienes and 2-substituted vinylphosphonates: application to asymmetric synthesis of 3-amino-5-phosphono-1-cyclohexene derivatives
  作者：Raphaël Robiette、Nathalie Defacqz、Jimmy Stofferis、Jacqueline Marchand-Brynaert

  DOI：10.1016/s0040-4020(03)00580-5

  日期：2003.6

  N-Butadienylsuccinimide (1), iso-propyl N-butadienyl-(S)-pyroglutamate (5) and N-butadienyl-(R)-4-phenyloxazolidin-2-one (6) reacted with vinylphosphonates, vicinally-substituted (2) by electronwithdrawing groups (CO2Me, CN, COMe), to furnish [4+2] cycloadducts (3-4,7-10, and 11-14) in moderate to good yields (40-88%). The reactions were highly selective: regioselectivity of 95-100%, endoselectivity of 75-92% and facial selectivity of 80-95%. The major diastereoisomers were fully characterized by H-1 and C-13 NMR spectroscopy. (C) 2003 Elsevier Science Ltd. All rights reserved.
• (R)-4-phenyloxazolidin-2-thione: an efficient chiral auxiliary for [4+2] cycloaddition of 1-aminodiene and activated phosphonodienophiles
  作者：Jean-Christophe Monbaliu、Raphaël Robiette、Daniel Peeters、Jacqueline Marchand-Brynaert

  DOI：10.1016/j.tetlet.2009.01.036

  日期：2009.3

  A theoretical model for the facial selectivity of N-dienyl oxazolidin-2-(thi)one and thiazolidin-2-thione 2a-c is presented. Our analysis provides a clear understanding of factors controlling stereoselectivity in reaction of these dienes, and allows predictions of high diastereoselectivity in the case of oxazolidin-2-thionyl diene (2b). The application of this diene to the synthesis of beta- and gamma-aminophosphonic derivatives is then investigated. Under classical conditions or under microwave activation, the D-A reaction of diene 2b leads to aminophosphonic chirons with high regio- and stereoselectivities. (C) 2009 Elsevier Ltd. All rights reserved.