1-chloro-3-methyl-2,5-dihydro-1H-phosphole | 28273-35-0

• 分子结构分类: 有机化合物 - 有机磷化合物 - 烷基卤代膦
• 英文名称: 1-chloro-3-methyl-2,5-dihydro-1H-phosphole
• 英文别名: 1-chloro-3-methyl-3-phospholene；1H-Phosphole, 1-chloro-2,5-dihydro-3-methyl-；1-chloro-3-methyl-2,5-dihydrophosphole
• CAS: 28273-35-0
• 化学式: C₅H₈ClP
• mdl: MFCD02177903
• 分子量: 134.545
• InChiKey: HUMPNEBBCNEZKL-UHFFFAOYSA-N

物化性质

• 沸点：
  140.2±20.0 °C(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  0.9
• 重原子数：
  7
• 可旋转键数：
  0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.6
• 拓扑面积：
  0
• 氢给体数：
  0
• 氢受体数：
  0

反应信息

• 作为反应物：
  描述：

  1-chloro-3-methyl-2,5-dihydro-1H-phosphole 在 碳酸甲丙酯 、 正丁基锂 、 三氯化铝 、 溴 作用下， 以 四氢呋喃 、 正己烷 、 二氯甲烷 、 Petroleum ether 为溶剂， 反应 73.5h， 生成 1-[4-Methyl-1-(2,4,6-tritert-butylphenyl)phosphol-2-yl]ethanone
  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
• 作为产物：
  描述：

  1-chloro-3-methyl-3-phospholene-1-oxide 在 六氯乙硅烷 作用下， 以 苯 为溶剂， 生成 1-chloro-3-methyl-2,5-dihydro-1H-phosphole
  参考文献：
  名称：

  Synthesis and properties of some 1-halophospholenes

  摘要：

  DOI：

  10.1021/jo00808a025

文献信息

• Process
  申请人：The Upjohn Company

  公开号：US04010209A1

  公开（公告）日：1977-03-01

  A process is described for the preparation of phospholene-1-oxides and 1-sulfides having an aliphatic substituent in the 1-position, a double bond at the 2- or 3-positions and, optionally, having additional substituents at one or more of positions 2, 3, 4 or 5. The process comprises the reaction of a 1-(2-chloroalkoxy)-phospholene with the appropriate aliphatic alcohol or thiol optionally in the presence of an alkylation catalyst. Use of an aliphatic alcohol gives rise to a phospholene oxide while use of the corresponding thiol gives rise to a phospholene sulfide. The phospholene-1-oxides and 1-sulfides so obtained are useful as catalysts for the conversion of isocyanates to carbodiimides.

  描述了一种制备磷环-1-氧化物和1-硫化物的过程，其在1位具有脂肪族取代基，在2位或3位有双键，并且在2、3、4或5位置之一或多个位置上可以有额外的取代基。该过程包括将1-(2-氯烷氧基)-磷环与适当的脂肪族醇或硫醇反应，可选地在烷基化催化剂的存在下进行。使用脂肪族醇会产生磷环氧化物，而使用相应的硫醇会产生磷环硫化物。所得的磷环-1-氧化物和1-硫化物可用作将异氰酸酯转化为碳二亚胺的催化剂。
• Phospholes with Reduced Pyramidal Character from Steric Crowding. 1. Synthesis and NMR Characterization of 1-(2,4-Di-<i>tert</i>-butyl-6-methylphenyl)-3-methylphosphole
  作者：Louis D. Quin、György Keglevich、Alexey S. Ionkin、Rajdeep Kalgutkar、Gábor Szalontai

  DOI：10.1021/jo960640d

  日期：1996.1.1

  positioned under the phosphole ring. This conformational prediction was amply confirmed by several chemical shift and coupling effects in the (13)C NMR spectrum. The (1)H NMR spectrum displayed an unusually large four-bond coupling (6 Hz) of (31)P to the m-phenyl proton syn to the lone pair (and none to the anti-meta proton), consistent with the orthogonal conformation. The oxide of the phosphole showed more

  通过对相应的3,4-二溴膦环烷进行脱卤化氢反应，合成了空间拥挤的1-（2,4-二叔丁基-6-甲基苯基）-3-甲基磷脂，以探究空间拥堵会引起某些问题的可能性。磷金字塔的扁平化和电子离域的增加。磷脂是具有（31）P NMRδ1.8的可重结晶的固体。半经验计算表明，棱锥的形状得以保留，但比1-苯基磷光体明显更平。在低能构象中，磷脂和苯环平面近似正交，其中2-叔丁基处于较不拥挤的位置，该位置与磷上的孤对是同位的。6-甲基位于磷脂环的下方。通过（13）C NMR光谱中的几种化学位移和偶联效应充分证实了这种构象预测。（1）H NMR谱图显示（31）P与间苯质子同构到孤对上的异常大的四键耦合（6 Hz），与正交对一致构象。磷脂的氧化物显示出比较少拥挤的磷脂更高的稳定性，并给出了在室温下数小时内可检测到的（31）P NMR信号。氧化物继续产生通常的Diels-Alder二聚体，并且还与N-苯基马来酰亚胺形
• Synthesis and properties of some 1-halophospholenes
  作者：Dale K. Myers、Louis D. Quin

  DOI：10.1021/jo00808a025

  日期：1971.5
• Vizel',A.O. et al., Journal of general chemistry of the USSR, 1973, vol. 43, p. 2128 - 2134
  作者：Vizel',A.O. et al.

  DOI：——

  日期：——
• Phospholes with reduced pyramidal character from steric crowding III NMR and X-ray diffraction studies on 1-(2,4,6-tri-isopropylphenyl)-3-methylphosphole
  作者：György Keglevich、Louis D. Quin、Zsolt Böcskei、György M. Keserü、Rajdeep Kalgutkar、Paul M. Lahti

  DOI：10.1016/s0022-328x(96)06804-0

  日期：1997.4

  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.