1,1-Diphenyl-1,3-dimethyl-4-(methoxycarbonyl)-2-aza-1λ⁵-phosphabuta-1,3-diene | 152975-97-8

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 脂肪酰基
• 英文名称: 1,1-Diphenyl-1,3-dimethyl-4-(methoxycarbonyl)-2-aza-1λ⁵-phosphabuta-1,3-diene
• 英文别名: methyl (E)-3-[[methyl(diphenyl)-lambda5-phosphanylidene]amino]but-2-enoate；methyl (E)-3-[[methyl(diphenyl)-λ5-phosphanylidene]amino]but-2-enoate
• CAS: 152975-97-8
• 化学式: C₁₈H₂₀NO₂P
• 分子量: 313.336
• InChiKey: BBZDQSHQTKTSOB-CCEZHUSRSA-N

物化性质

• 沸点：
  433.0±47.0 °C(predicted)
• 密度：
  1.07±0.1 g/cm3(Temp: 20 °C; Press: 760 Torr)(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：
  5
• 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：

  1,1-Diphenyl-1,3-dimethyl-4-(methoxycarbonyl)-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 77.0h， 生成 2-Methyl-5-oxo-5,6-dihydro-benzo[h][1,6]naphthyridine-3-carboxylic acid methyl ester
  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)-3-azido-but-2-enoic acid methyl ester 、 二苯基甲氧基膦 以 二氯甲烷 为溶剂， 反应 2.0h， 以91%的产率得到1,1-Diphenyl-1,3-dimethyl-4-(methoxycarbonyl)-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

• 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 and Reactivity of Electron-Poor 2-Azadienes. [4 + 2] Cycloaddition Reactions with Alkenes and Enamines
  作者：Francisco Palacios、Itziar Perez de Heredia、Gloria Rubiales

  DOI：10.1021/jo00113a017

  日期：1995.4

  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.
• Reaction of <i>N</i>-Vinylic Phosphazenes Derived from β-Amino Acids with Aldehydes. Azadiene-Mediated Synthesis of Dihydropyridines, Pyridines, and Polycyclic Nitrogen Derivatives
  作者：Francisco Palacios、Esther Herrán、Gloria Rubiales

  DOI：10.1021/jo9902650

  日期：1999.8.1

  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.