1-(2,4,6-Triisopropylphenyl)-3-methyl-2,5-dihydro-1H-phosphole 1-oxide | 191548-33-1

• 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: 1-(2,4,6-Triisopropylphenyl)-3-methyl-2,5-dihydro-1H-phosphole 1-oxide
• 英文别名: 3-Methyl-1-[2,4,6-tri(propan-2-yl)phenyl]-2,5-dihydro-1lambda5-phosphole 1-oxide；3-methyl-1-[2,4,6-tri(propan-2-yl)phenyl]-2,5-dihydro-1λ5-phosphole 1-oxide
• CAS: 191548-33-1
• 化学式: C₂₀H₃₁OP
• 分子量: 318.439
• InChiKey: UIQKWAJLOSRFGZ-UHFFFAOYSA-N

物化性质

• 沸点：
  435.2±45.0 °C(Predicted)
• 密度：
  0.99±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  4.5
• 重原子数：
  22
• 可旋转键数：
  4
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.6
• 拓扑面积：
  17.1
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  1-(2,4,6-Triisopropylphenyl)-3-methyl-2,5-dihydro-1H-phosphole 1-oxide 在 palladium on activated charcoal 氢气 作用下， 以 甲醇 为溶剂， 26.0 ℃ 、999.99 kPa 条件下， 反应 6.0h， 以81%的产率得到3-methyl-1-(2,4,6-triisopropylphenyl-)2,3,4,5-tetrahydro-1H-phosphole 1-oxide
  参考文献：
  名称：

  由1,2- Oxaphosphetes的螺衍生物的合成[2 + 2]环1-（2,4,6-三异丙基）膦氧化物与乙炔二环加成†

  摘要：

  通过将1-（2,4,6-三异丙基苯基）P-杂环的PO基团与二甲基的乙炔部分进行意外的[2 + 2]环加成反应，制得新的杂环家族1,2-氧杂磷的成员乙炔二羧酸盐。新的氧杂磷是起始杂环的螺环衍生物，并显示具有三角双锥体几何形状的磷原子。PM3半经验计算证明了新的反应路径并提出了逐步反应机理。

  DOI：

  10.1016/s0040-4020(00)00401-4
• 作为产物：
  描述：

  2-溴-1,3,5-三异丙苯 在 双氧水 、 magnesium 作用下， 以 四氢呋喃 、 氯仿 为溶剂， 反应 3.0h， 生成 1-(2,4,6-Triisopropylphenyl)-3-methyl-2,5-dihydro-1H-phosphole 1-oxide
  参考文献：
  名称：

  Phospholes with reduced pyramidal character from steric crowding III NMR and X-ray diffraction studies on 1-(2,4,6-tri-isopropylphenyl)-3-methylphosphole

  摘要：

  The 2,4,6-tri-isopropylphenyl substituent was placed on the phosphorus of a phosphole to reduce the pyramidal character. That this was accomplished was revealed by single crystal X-ray diffraction analysis; with respect to the plane of C-2-P-C-5 in the phosphole ring, the ipso carbon of the benzene ring was deflected by only 58.0 degrees, whereas the deflection is 66.9 degrees in the uncrowded 1-benzylphosphole. This proves that the concept of reducing the pyramidal character (with the goal of increasing the electron delocalization) through steric crowding can be realized. In the crystal the two rings are in orthogonal planes, but this relation is not retained in solution; NMR studies show that the two edges of the benzene ring, as well as the 2,6-isopropyl groups, are identical.

  DOI：

  10.1016/s0022-328x(96)06804-0

文献信息

• The Preparation and Anticancer Activity of Some Phosphorus Heterocycles
  作者：Harry R. Hudson、György Keglevich

  DOI：10.1080/10426500801938592

  日期：2008.8.4

  Methods for the preparation of some phosphorus heterocycles are reviewed, together with a preliminary report of their activity in vitro against the NCI 60-cell line panel of human tumour cells. The most active compound, a dimer of 3-methyl-1-(2,4,6-triisopropylphenyl)phosphole oxide, showed GI50 values in the micromolar region against leukaemia cell lines RPMI-8226 and SR, non-small cell lung cancer

  综述了一些磷杂环化合物的制备方法，并对其体外对抗人类肿瘤细胞 NCI 60 细胞系面板的活性进行了初步报告。活性最强的化合物是 3-甲基-1-（2,4,6-三异丙基苯基）氧化磷的二聚体，在微摩尔区域显示出针对白血病细胞系 RPMI-8226 和 SR、非小细胞肺癌的 GI50 值。 NCI-H460)、结肠癌 (COLO 205) 和黑色素瘤 (SK-Mel-5 和 UACC-62)。
• Efficient Synthesis of Cyclic β-Oxophosphoranes by Microwave-Assisted Reaction of Cyclic Phosphine Oxides and Dialkyl Acetylenedicarboxylates
  作者：György Keglevich、Eszter Dudás、Melinda Sipos、Dóra Lengyel、Krisztina Ludányi

  DOI：10.1055/s-2006-926395

  日期：2006.4

  The inverse Wittig-type reaction of a series of 2,4,6-trialkylphenyl cyclic phosphine oxides 3, 5, 7, 9, 11, 13, 15, 18 and 20 and dialkyl acetylenedicarboxylate giving β-oxophosphoranes 4, 6, 8, 10, 12, 14, 16, 19 and 21, respectively, can be accomplished in a convenient way under microwave conditions. At 150 °C, the MW-assisted reaction is more efficient and becomes 50-fold faster as compared to the thermal transformation. A further advantage is that the 2,5-dihydrophosphole moiety of the 2,4,6-triisopropylphenyl derivative 3 does not undergo double-bond rearrangement and that the 2,4,6-trimethylphenyl substrates 11 and 13, otherwise inactive in the reaction under discussion, could also be converted to β-oxophosphoranes 12 and 14. A series of new products 4Bb, 12, 14, 16b, 19 and 21 have been made available.

  在微波条件下，一系列 2,4,6-三烷基苯基环状氧化膦 3、5、7、9、11、13、15、18 和 20 与乙炔二甲酸二烷基酯的逆维蒂希型反应可以方便地进行，并分别生成δ-氧膦 4、6、8、10、12、14、16、19 和 21。在 150 °C 的温度下，微波辅助反应的效率更高，比热转化快 50 倍。另一个优点是，2,4,6-三异丙基苯基衍生物 3 中的 2,5-二氢磷孔分子不会发生双键重排，而且 2,4,6-三甲基苯基底物 11 和 13 也可以转化为 δ-氧代磷烷 12 和 14。一系列新产品 4Bb、12、14、16b、19 和 21 已经问世。
• Unexpected [2 + 2] cycloaddition between the PO group of P-(2,4,6-triisopropylphenyl) P-heterocycles and dimethyl acetylenedicarboxylate
  作者：György Keglevich、Henrietta Forintos、Áron Szöllõsy、László Tõke

  DOI：10.1039/a904422a

  日期：——

  The reaction of 1-(2,4,6-triisopropylphenyl)-1,2-dihydrophosphinine 1-oxide 1d with dimethyl acetylenedicarboxylate (DMAD) affords, surprisingly, oxaphosphetene 3 instead of the expected Diels–Alder cycloadduct; the unusual reactivity of the trialkylphenylphosphine oxides towards DMAD seems to be of general value.

  1-(2,4,6-三异丙基苯基)-1,2-二氢膦 1-氧化物 1d 与乙酰二羧酸二甲酯 (DMAD) 反应，出人意料地生成了氧磷苯 3，而不是预期的 Diels-Alder 环加载产物；三烷基苯基膦氧化物对 DMAD 的不寻常反应性似乎具有普遍价值。
• Keglevich, Gyoergy; Forintos, Henrietta; Ujvari, Aniko, Journal of Chemical Research, 2005, # 4, p. 215 - 217
  作者：Keglevich, Gyoergy、Forintos, Henrietta、Ujvari, Aniko、Ludanyi, Krisztina、Bitter, Istvan、Toeke, Laszlo

  DOI：——

  日期：——
• Keglevich, Gyoergy; Keseru, Gyoergy Miklos; Forintos, Henrietta, Journal of the Chemical Society. Perkin transactions I, 1999, # 13, p. 1801 - 1805
  作者：Keglevich, Gyoergy、Keseru, Gyoergy Miklos、Forintos, Henrietta、Szoellosy, Aron、Ludanyi, Krisztina、Toke, Laszlo

  DOI：——

  日期：——