4-(Ethoxycarbonyl)-1,1-diphenyl-1-methyl-2-aza-1λ⁵-phosphabuta-1,3-diene | 152975-95-6

• 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: 4-(Ethoxycarbonyl)-1,1-diphenyl-1-methyl-2-aza-1λ⁵-phosphabuta-1,3-diene
• 英文别名: ethyl (E)-3-[[methyl(diphenyl)-lambda5-phosphanylidene]amino]prop-2-enoate；ethyl (E)-3-[[methyl(diphenyl)-λ5-phosphanylidene]amino]prop-2-enoate
• CAS: 152975-95-6
• 化学式: C₁₈H₂₀NO₂P
• 分子量: 313.336
• InChiKey: QFGZJGGNUAMTAC-CCEZHUSRSA-N

物化性质

• 沸点：
  433.9±47.0 °C(Predicted)
• 密度：
  1.07±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.7
• 重原子数：
  22
• 可旋转键数：
  6
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.17
• 拓扑面积：
  38.7
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  4-(Ethoxycarbonyl)-1,1-diphenyl-1-methyl-2-aza-1λ⁵-phosphabuta-1,3-diene 在 铁粉 、 溶剂黄146 作用下， 以 氯仿 、 水 、 丙酮 为溶剂， 反应 55.0h， 生成 3-(ethoxycarbonyl)-benzo[h][1,6]naphthyridin-5-one
  参考文献：
  名称：

  Reaction of N-Vinylic Phosphazenes Derived from β-Amino Acids with Aldehydes. Azadiene-Mediated Synthesis of Dihydropyridines, Pyridines, and Polycyclic Nitrogen Derivatives

  摘要：

  Enamino phosphonium salts 2 are obtained by 1,2-addition of hydrogen chloride to N-vinylic phosphazenes 1 derived from triphenylphosphine. Aza-Wittig reaction of phosphazenes 1 derived from triphenylphosphine and 6 derived from diphenylmethylphosphine with aldehydes 3 leads to the formation of 2-azadienes 7. Reaction of azadienes 7 with enamines affords dihydropyridines 9 and 11, pyridines 12, and bicyclic nitrogen heterocycles 15-18 in a regioselective fashion, while heterodiene 20 reacts in the same way with pyrrolidinocyclohexanone giving 1-azaphenanthrene compound 21. Reaction of enamino phosphonium salts 2 with aldehydes 3 gives symmetrical dihydropyridines 5.

  DOI：

  10.1021/jo9902650
• 作为产物：
  描述：

  E-ethyl 3-azidoacrylate 、 二苯基甲氧基膦 以 二氯甲烷 为溶剂， 反应 2.0h， 以93%的产率得到4-(Ethoxycarbonyl)-1,1-diphenyl-1-methyl-2-aza-1λ⁵-phosphabuta-1,3-diene
  参考文献：
  名称：

  Synthesis and Reactivity of Electron-Poor 2-Azadienes. [4 + 2] Cycloaddition Reactions with Alkenes and Enamines

  摘要：

  Electron deficient 2-azadienes derived from beta-amino acids 3 are obtained by aza-Wittig reaction of N-vinylic phosphazenes 4 with carbonyl compounds. Inverse electron demand Diels-Alder reaction of azadienes 3 with trans-cyclooctene 7 and cis,trans-cyclooctadiene 8 leads to the formation of trans-cycloalkanotetrahydropyridines 10. Heterodienes 3 also react with enamines 13, 14, and 18 affording pyridine derivatives 16, 17, and 20 in a regioselective fashion. Norbornadiene 11, a less strained olefin than cycloalkenes 7 and 8, requires the presence of lithium perchlorate as catalyst in a nonaqueous solvent like ether, to give cycloadducts 12.

  DOI：

  10.1021/jo00113a017

文献信息

• Regioselective synthesis of pyridines and dihydropyridines derived from β-amino acids and aminophosphonates by reaction of N-vinylic phosphazenes with α,β-unsaturated ketones
  作者：Francisco Palacios、Esther Herrán、Gloria Rubiales、Concepción Alonso

  DOI：10.1016/j.tet.2007.03.146

  日期：2007.6

  Reaction of N-vinylic phosphazenes with α,β-unsaturated ketones leads to the formation of pyridines derived from β-amino acids in a regioselective fashion. The use of functionalized enones derived from α-acylstyryl-carboxylates or -phosphonates affords biologically active asymmetrical and symmetrical dihydropyridines substituted with carboxylate or phosphonate groups including nitrendipine, felodipine

  的反应Ñ与α-vinylic磷腈，β不饱和酮导致吡啶的形成从β氨基酸在一个区域选择性的方式得到。使用衍生自α-酰基苯乙烯基-羧酸酯或-膦酸酯的官能化烯酮提供了被羧酸酯或膦酸酯基团取代的生物活性不对称和对称二氢吡啶，包括硝苯地平，非洛地平，MRS 1097和依诺地平类似物。
• Aza-Wittig reaction of N-vinylic phosphazenes with carbonyl compounds. Azadiene-mediated synthesis of dihydropyridines and pyridines
  作者：Francisco Palacios、Gloria Rubiales

  DOI：10.1016/0040-4039(96)01352-4

  日期：1996.8

  diphenylmethylphosphine 4 with carbonyl compounds leads to the formation of 2-azadienes derived from β-aminoacids 5. Dimerization of 2-azadienes 5c,d and reaction of compounds 5 with phosphazene 4 or enemine 6 affords substituted dihydropyridines 7 and 8. Aza-Wittig reaction of phosphazenes 4 with α,β-unsaturated aldehydes gives 3-azatrienes 12, which are easily converted into pyridines 13.

  衍生自二苯基甲基膦4的N-乙烯基磷腈与羰基化合物的Aza-Wittig反应导致衍生自β-氨基酸5的2-氮杂二烯形成。2-氮杂二烯5c，d的二聚和化合物5与磷腈4或亚胺6的反应，得到取代的二氢吡啶7和8。磷腈4与α，β-不饱和醛的Aza-Wittig反应产生3-氮杂三酮12，该氮杂三氮烯12易于转化为吡啶13。
• Preparation and reactivity of electron-poor 2-azadienes. Diels-Alder reaction with trans-cyclooctene.
  作者：Francisco Palacios、Itziar Perez de Heredia、Gloria Rubiales

  DOI：10.1016/s0040-4039(00)79357-9

  日期：1993.7

  Di-, tri- and tetra- substituted 2-azadienes 3 underbar with electron withdrawing groups have been obtained by Aza-Wittig reaction of N-vinylic phosphazenes with carbonyl compounds. The Diels-Alder reaction of 3 underbar with trans-cyclooctene has also been explored.
• Synthesis of N-Functionalized Carbodiimides, Hydantoins, 1,3-Diazetidines, and Imidazolidine Derivatives from N-Vinylic Phosphazenes Derived from b-Amino Acids
  作者：Francisco Palacios、Marta Legido、Itziar Pérez de Heredia、José María Ezpeleta、Gloria Rubiales

  DOI：10.3987/com-01-9264

  日期：——

  Synthesis of N-vinylic carbodiimides through Aza-Wittig reaction of N-vinylic phosphazenes with isocyanates is reported. These heterocumulenes are used for the preparation of unsymmetrical ureas and nitrogen heterocycles such as hydantoins, 1,3-diazetidines, imidazolidinones, and bis-imidazolidinone azines.
• Regioselective cycloaddition of 3-azatrienes with enamines. Synthesis of pyridines derived from β-aminoacids
  作者：Francisco Palacios、Esther Herrán、Concepción Alonso、Gloria Rubiales

  DOI：10.1016/j.tet.2006.05.073

  日期：2006.8

  Aza-Wittig reaction of N-vinylic phosphazenes with alpha,beta-unsaturated aldehydes leads to the formation of 3-azatrienes through a [2+2]-cycloaddition-cycloreversion process. Subsequent, regioselective [4+2]-cycloaddition of 3-azatrienes with pyrrolidinocycloalkanone affords bicyclic dihydropyridines and pyridines in a regioselective fashion. 2-Heterodiene moiety of azatriene is involved in the formation of the six-membered ring skeleton of pyridine derivatives. (c) 2006 Elsevier Ltd. All rights reserved.