P,P-bis(diisopropylamino)-4-phenyl-1,3,2λ(5)-diazaphosphete | 153656-77-0

• 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: P,P-bis(diisopropylamino)-4-phenyl-1,3,2λ(5)-diazaphosphete
• 英文别名: 4-phenyl-2-N,2-N,2-N',2-N'-tetra(propan-2-yl)-1,3-diaza-2lambda5-phosphacyclobuta-1,3-diene-2,2-diamine；4-phenyl-2-N,2-N,2-N',2-N'-tetra(propan-2-yl)-1,3-diaza-2λ5-phosphacyclobuta-1,3-diene-2,2-diamine
• CAS: 153656-77-0
• 化学式: C₁₉H₃₃N₄P
• 分子量: 348.472
• InChiKey: SDQBUDZXDZJMIM-UHFFFAOYSA-N

物化性质

• 沸点：
  413.0±28.0 °C(Predicted)
• 密度：
  1.06±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  5.4
• 重原子数：
  24
• 可旋转键数：
  7
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.63
• 拓扑面积：
  31.2
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  硼烷四氢呋喃络合物 、 P,P-bis(diisopropylamino)-4-phenyl-1,3,2λ(5)-diazaphosphete 以 甲苯 为溶剂， 以90%的产率得到P,P-bis(diisopropylamino)-4-phenyl-1,3,2λ(5)-diazaphosphete, bis(BH3) adduct
  参考文献：
  名称：

  X-ray Crystal Structure, ab Initio Calculations, and Reactivity of 1,3,2λ⁵-Diazaphosphetes:  A New Type of 4-π-Electron 4-Membered Heterocycle

  摘要：

  The structure of P,P-bis(diisopropylamino)-4-phenyl-1,3,2 lambda(5)-diazaphosphete , 1a, has been determined by a single-crystal X-ray diffraction study (C19H33N4P, monoclinic system, space group P2(1), a = 9.482(1) Angstrom, b = 11.374(3) Angstrom, c = 9.668(2) Angstrom, beta = 97.16(1)degrees, Z = 2). According to quantum chemical calculations at an RHF level of optimization utilizing the 6-31g(d,p) basis set, 1a has a zwitterionic structure with the negative charge delocalized on the NCN allylic fragment and the positive charge localized at the phosphorus. Heterocycle 1a reacts with water and benzaldehyde affording N-phosphoranylbenzamidine 3 (95% yield) and the expected aza-Wittig adduct 4 (85% yield), respectively. Addition of 1 equiv of methyl trifluoromethanesulfonate and of 2 equiv of BH3 . THF to la affords cyclic phosphonium salt 5 (94% yield) and the bis(borane) adduct 6a (90% yield), respectively. Dimethyl acetylenedicarboxylate slowly reacts with 1a giving rise to 1,3,4 lambda(5)-diazaphosphinine, 9, in 70% yield. The X-ray crystal structures of products 2, 3, and 6a are reported (2: C26H38N5P, monoclinic system, space group C2/c, a = 16.337(8) Angstrom, b = 19.810(2) Angstrom, c = 8.800(2) Angstrom, beta = 117.68(2)degrees, Z = 4. 3: C19H35N4OP, orthorhombic system, space group P2(1)2(1)2(1), a = 9.090(1) Angstrom, b = 12.955(2) Angstrom, c = 17.860(3) Angstrom, Z = 4. 6a: C19H39B2N4P, orthorhombic system, space group P2(1)2(1)2(1), a = 10.340(1) Angstrom, b = 13.247(1) Angstrom, c = 16.996(1) Angstrom, Z = 4).

  DOI：

  10.1021/ic951474f
• 作为产物：
  描述：

  bis(diisopropylamino)(trimethylstannyl)phosphine 、 3-bromo-3-phenyl-3H-diazirine 以 二氯甲烷 为溶剂， 反应 20.0h， 以26%的产率得到P,P-bis(diisopropylamino)-4-phenyl-1,3,2λ(5)-diazaphosphete
  参考文献：
  名称：

  重新审视 Halodiazirines 与亲核试剂的交换反应机制。中性、单或双阳离子 4−16 元磷杂环化合物的合成

  摘要：

  三甲基-、二苯基甲基-、三苯基-、二苯基噻吩基-和双（二甲氨基）（异丙基硫代）膦与溴苯基二氮嗪 (1) 反应，在 83− 中生成阳离子 N,N'-双（膦）加合物 2a-c、7 和 8 95% 的收率。根据所使用的实验条件，将 1,2-双（二苯基膦基）乙烷添加到 1 会导致双阳离子 14 和单阳离子七元杂环 3（产率 90%）和 4（产率 60%）或阳离子 N,N' -双（二膦）加合物 5（产率 86%）；类似地，当使用二苯基（异丙基硫代）膦时，会发生竞争反应，导致阳离子五元杂环 9（产率 34%）和/或 N,N'-双（二膦）加合物 10（产率 65%）。1,3-双（二苯基膦基）丙烷也与 1 反应，得到双阳离子 16 元杂环 6（75% 产率）。

  DOI：

  10.1021/ja9532143

文献信息

• Evidence for Imidoylnitrene Intermediates in the Reaction of Bromophenyldiazirine with Phosphines: First Ring-Expansion Reaction of a Diazirine
  作者：Gilles Alcaraz、Antoine Baceiredo、Martin Nieger、Guy Bertrand

  DOI：10.1021/ja00084a072

  日期：1994.3
• Mechanism of the Exchange Reaction of Halodiazirines with Nucleophiles Revisited. Synthesis of Neutral, Mono- or Dicationic 4−16-Membered Phosphorus Heterocycles
  作者：Gilles Alcaraz、Valérie Piquet、Antoine Baceiredo、Françoise Dahan、Wolfgang W. Schoeller、Guy Bertrand

  DOI：10.1021/ja9532143

  日期：1996.1.1

  monocationic seven-membered heterocycles 3 (90% yield) and 4 (60% yield) or cationic N,N‘-bis(diphosphine) adduct 5 (86% yield); similarly, when diphenyl(isopropylthio)phosphine is used, competitive reactions occur, leading to cationic five-membered heterocycle 9 (34% yield) and/or N,N‘-Bis(diphosphine) adduct 10 (65% yield). 1,3-bis(diphenylphosphino)propane also reacts with 1, affording dicationic 16-membered

  三甲基-、二苯基甲基-、三苯基-、二苯基噻吩基-和双（二甲氨基）（异丙基硫代）膦与溴苯基二氮嗪 (1) 反应，在 83− 中生成阳离子 N,N'-双（膦）加合物 2a-c、7 和 8 95% 的收率。根据所使用的实验条件，将 1,2-双（二苯基膦基）乙烷添加到 1 会导致双阳离子 14 和单阳离子七元杂环 3（产率 90%）和 4（产率 60%）或阳离子 N,N' -双（二膦）加合物 5（产率 86%）；类似地，当使用二苯基（异丙基硫代）膦时，会发生竞争反应，导致阳离子五元杂环 9（产率 34%）和/或 N,N'-双（二膦）加合物 10（产率 65%）。1,3-双（二苯基膦基）丙烷也与 1 反应，得到双阳离子 16 元杂环 6（75% 产率）。
• X-ray Crystal Structure, ab Initio Calculations, and Reactivity of 1,3,2λ⁵-Diazaphosphetes:  A New Type of 4-π-Electron 4-Membered Heterocycle
  作者：Gilles Alcaraz、Antoine Baceiredo、Martin Nieger、Wolfgang W. Schoeller、Guy Bertrand

  DOI：10.1021/ic951474f

  日期：1996.1.1

  The structure of P,P-bis(diisopropylamino)-4-phenyl-1,3,2 lambda(5)-diazaphosphete , 1a, has been determined by a single-crystal X-ray diffraction study (C19H33N4P, monoclinic system, space group P2(1), a = 9.482(1) Angstrom, b = 11.374(3) Angstrom, c = 9.668(2) Angstrom, beta = 97.16(1)degrees, Z = 2). According to quantum chemical calculations at an RHF level of optimization utilizing the 6-31g(d,p) basis set, 1a has a zwitterionic structure with the negative charge delocalized on the NCN allylic fragment and the positive charge localized at the phosphorus. Heterocycle 1a reacts with water and benzaldehyde affording N-phosphoranylbenzamidine 3 (95% yield) and the expected aza-Wittig adduct 4 (85% yield), respectively. Addition of 1 equiv of methyl trifluoromethanesulfonate and of 2 equiv of BH3 . THF to la affords cyclic phosphonium salt 5 (94% yield) and the bis(borane) adduct 6a (90% yield), respectively. Dimethyl acetylenedicarboxylate slowly reacts with 1a giving rise to 1,3,4 lambda(5)-diazaphosphinine, 9, in 70% yield. The X-ray crystal structures of products 2, 3, and 6a are reported (2: C26H38N5P, monoclinic system, space group C2/c, a = 16.337(8) Angstrom, b = 19.810(2) Angstrom, c = 8.800(2) Angstrom, beta = 117.68(2)degrees, Z = 4. 3: C19H35N4OP, orthorhombic system, space group P2(1)2(1)2(1), a = 9.090(1) Angstrom, b = 12.955(2) Angstrom, c = 17.860(3) Angstrom, Z = 4. 6a: C19H39B2N4P, orthorhombic system, space group P2(1)2(1)2(1), a = 10.340(1) Angstrom, b = 13.247(1) Angstrom, c = 16.996(1) Angstrom, Z = 4).