1-(2,4,6-tri-tert-butylphenyl)-3-methyl-3-phospholene 1-oxide | 190438-03-0

• 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: 1-(2,4,6-tri-tert-butylphenyl)-3-methyl-3-phospholene 1-oxide
• 英文别名: 3-methyl-1-(2,4,6-tritert-butylphenyl)-2,5-dihydro-1λ5-phosphole 1-oxide
• CAS: 190438-03-0
• 化学式: C₂₃H₃₇OP
• 分子量: 360.52
• InChiKey: DJXUJQZYDVGBAY-UHFFFAOYSA-N

物化性质

• 沸点：
  438.2±45.0 °C(Predicted)
• 密度：
  0.97±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  6.53
• 重原子数：
  25.0
• 可旋转键数：
  1.0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.65
• 拓扑面积：
  17.07
• 氢给体数：
  0.0
• 氢受体数：
  1.0

反应信息

• 作为反应物：
  描述：

  1-(2,4,6-tri-tert-butylphenyl)-3-methyl-3-phospholene 1-oxide 在 苄基三乙基氯化铵 作用下， 以 氯仿 为溶剂， 反应 169.0h， 生成 4-chloro-1-(2,6-di-tert-butyl-phenyl)-5-methyl-2H-phosphinine 1-oxide
  参考文献：
  名称：

  磷原子上具有空间要求取代基的六元P-杂环的合成

  摘要：

  1-(2,4,6-三烷基苯基)2,5-二氢-1H-磷氧化物 (1) 通过 6,6-二氯-3-磷杂双环 [3.1.0] 己烷 (2) 的环扩大提供了双1,2-二氢膦氧化物 (3) 的键合异构体。异构 1-(二叔丁基甲苯基)-1,2-二氢膦氧化物 (3a) 的催化氢化得到氧化膦 (4) 的非对映异构体，而 1-(三异丙基苯基) 异构体 (5) 的非对映异构体导致主要是由环收缩形成的磷烷氧化物 (6)。© 2001 John Wiley & Sons, Inc. 杂原子化学 12:528–533, 2001

  DOI：

  10.1002/hc.1080
• 作为产物：
  描述：

  1-溴-2,4,6-三叔丁基苯 在 正丁基锂 、 双氧水 作用下， 以 四氢呋喃 、 正己烷 、 氯仿 、 水 为溶剂， 反应 3.0h， 生成 1-(2,4,6-tri-tert-butylphenyl)-3-methyl-3-phospholene 1-oxide
  参考文献：
  名称：

  1-(2,4,6-Tri-tert-butylphenyl)-3-methylphosphole:  A Phosphole with a Significantly Flattened Phosphorus Pyramid Having Pronounced Characteristics of Aromaticity

  摘要：

  Single-crystal X-ray analysis of 1-(2,4,6-tri-tert-butylphenyl)-3-methylphosphole synthesized to test the effect of the strongly sterically demanding P-substituent on the geometry of the molecule, revealed that the phosphorus pyramid was drastically flattened; the normal out of plane angle of 65 degrees (formed between the P-substituent and the ring C-2-P-C-5 plane) was reduced to 45.9 degrees. Consistent with strong electron delocalization, the C-3-C-4 bond length was dramatically shortened relative to that for other phospholes, and the Bird index of aromaticity was 56.5, almost the equivalent of that in pyrrole (59). The phosphole ring, normally resisitant to electrophilic substitutions, underwent reaction with acetyl chloride-aluminum chloride, consistent with considerable cyclic electron delocalization.

  DOI：

  10.1021/ja970463d

文献信息

• 1-(2,4,6-Tri-<i>tert</i>-butylphenyl)-3-methylphosphole:  A Phosphole with a Significantly Flattened Phosphorus Pyramid Having Pronounced Characteristics of Aromaticity
  作者：György Keglevich、Zsolt Böcskei、György Miklós Keserü、Kálmán Újszászy、Louis D. Quin

  DOI：10.1021/ja970463d

  日期：1997.6.1

  Single-crystal X-ray analysis of 1-(2,4,6-tri-tert-butylphenyl)-3-methylphosphole synthesized to test the effect of the strongly sterically demanding P-substituent on the geometry of the molecule, revealed that the phosphorus pyramid was drastically flattened; the normal out of plane angle of 65 degrees (formed between the P-substituent and the ring C-2-P-C-5 plane) was reduced to 45.9 degrees. Consistent with strong electron delocalization, the C-3-C-4 bond length was dramatically shortened relative to that for other phospholes, and the Bird index of aromaticity was 56.5, almost the equivalent of that in pyrrole (59). The phosphole ring, normally resisitant to electrophilic substitutions, underwent reaction with acetyl chloride-aluminum chloride, consistent with considerable cyclic electron delocalization.
• The synthesis of six-membered P-heterocycles with sterically demanding substituent on the phosphorus atom
  作者：György Keglevich、Henrietta Forintos、Melinda Sipos、András Dobó、Krisztina Ludányi、Károly Vékey、Antal Tungler、László Tőke

  DOI：10.1002/hc.1080

  日期：——

  The ring enlargement of 1-(2,4,6-trialkylphenyl)2,5-dihydro-1H-phosphole oxides (1) via 6,6-dichloro-3-Phosphabicyclo[3.1.0]hexanes (2) afforded the double-bond isomers of 1,2-dihydrophosphinine oxides (3). Catalytic hydrogenation of the isomeric 1-(di-tert-butyltolyl)-1,2-dihydrophosphinine oxides (3a) gave the diastereomers of phosphinane oxide (4), while that of the 1-(tri-isopropylphenyl) isomers

  1-(2,4,6-三烷基苯基)2,5-二氢-1H-磷氧化物 (1) 通过 6,6-二氯-3-磷杂双环 [3.1.0] 己烷 (2) 的环扩大提供了双1,2-二氢膦氧化物 (3) 的键合异构体。异构 1-(二叔丁基甲苯基)-1,2-二氢膦氧化物 (3a) 的催化氢化得到氧化膦 (4) 的非对映异构体，而 1-(三异丙基苯基) 异构体 (5) 的非对映异构体导致主要是由环收缩形成的磷烷氧化物 (6)。© 2001 John Wiley & Sons, Inc. 杂原子化学 12:528–533, 2001