((mesityl(methyl)phosphaneyl)diphenylmethyl)lithium | 501418-47-9

• 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: ((mesityl(methyl)phosphaneyl)diphenylmethyl)lithium
• CAS: 501418-47-9
• 化学式: C₂₃H₂₄LiP
• 分子量: 338.358
• InChiKey: MMVGUASHCQVXCQ-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.42
• 重原子数：
  25.0
• 可旋转键数：
  4.0
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.22
• 拓扑面积：
  0.0
• 氢给体数：
  0.0
• 氢受体数：
  0.0

反应信息

• 作为反应物：
  描述：

  ((mesityl(methyl)phosphaneyl)diphenylmethyl)lithium 在 双氧水 作用下， 生成 benzhydryl(mesityl)(methyl)phosphane oxide
  参考文献：
  名称：

  A nucleophilic reaction of a phosphaalkene: the methylation of mesityldiphenylmethylenephosphine

  摘要：

  DOI：

  10.1016/s0040-4039(00)87254-8
• 作为产物：
  描述：

  bis(trimethylsilyl)mesitylphosphine 在 氢氧化钾 作用下， 以 四氢呋喃 为溶剂， 反应 1.0h， 生成 ((mesityl(methyl)phosphaneyl)diphenylmethyl)lithium
  参考文献：
  名称：

  The Addition Polymerization of a PC Bond:  A Route to New Phosphine Polymers

  摘要：

  Addition polymerization, the most general method of preparation for organic polymers, has successfully been extended to P=C bonds. The polymerization of a phosphaalkene has been initiated by thermolysis or with alkyllithium reagents. The unprecedented poly(methylenephosphine)s are easily oxidized using oxygen or sulfur to give air stable macromolecules. A molecular weight (M(w)) of 35000 g/mol for the poly(methylenephosphine sulfude) was estimated by light-scattering GPC.

  DOI：

  10.1021/ja029120s

文献信息

• Molecular studies of the initiation and termination steps of the anionic polymerization of P=C bonds
  作者：Bronwyn H Gillon、Kevin JT Noonan、Bastian Feldscher、Jennifer M Wissenz、Zhi Ming Kam、Tom Hsieh、Justin J Kingsley、Joshua I Bates、Derek P Gates

  DOI：10.1139/v07-121

  日期：2007.12.1

  The initiation and termination steps of the anionic polymerization of P=C bonds have been modeled. The initiation step was investigated through the stoichiometric reaction of MesP=CPh₂ (1) with RLi (R = Me or n-Bu). In each case, the addition was highly regioselective with the formal attack of R^– at phosphorus to give the carbanion Li[Mes(R)P–CPh₂] (3a, R = Me; 3b, R = n-Bu). To simulate the termination step in the anionic polymerization of 1, carbanions 3a and 3b were quenched in situ with various electrophiles. Through these reactions, several new tertiary phosphines have been prepared, namely, Mes(Me)P–CPh₂H (4a), Mes(n-Bu)P–CPh₂H (4b), Mes(Me)P–CPh₂Me (6a), Mes(Me)P–CPh₂–P(NEt₂)₂ (7a), Mes(Me)P–CPh₂–SiMe₂H (8a), and Mes(Me)P–CPh₂–SiMe₃ (9a). In addition, compounds 4a, 7a, 8a, and 9a were characterized by X-ray crystallography. Most of the metrical parameters are typical of tertiary phosphines; however, the P–CPh₂H bonds were elongated in all cases reflecting the considerable steric bulk surrounding this bond. Unexpectedly, an unusually large ³¹P–³¹P coupling constant (²J_PP > 200 Hz) was observed for 7a both in solution and the solid state. This observation may be rationalized by a through space P···P interaction. This rationale is further supported by the short P···P distance [P(1)—P(2) = 2.966(1) Å; cf. Σ r_vdw = 3.7 Å] and a small P–C–P bond angle for 7a [P(1)–C(11)–P(1) = 99.17(9)°].Key words: phosphaalkenes, phosphorus polymers, phosphines, anionic polymerization.

  对 P=C 键阴离子聚合反应的起始和终止步骤进行了建模。我们通过 MesP=CPh2 (1) 与 RLi（R = Me 或 n-Bu）的化学反应研究了起始步骤。在每种情况下，加成反应都具有高度的区域选择性，R- 在磷上发生形式攻击，生成碳阴离子 Li[Mes(R)P-CPh2] （3a，R = Me；3b，R = n-Bu）。为了模拟 1 阴离子聚合反应中的终止步骤，用各种亲电体原位淬灭了碳阴离子 3a 和 3b。通过这些反应，制备出了几种新的叔膦，即 Mes(Me)P-CPh2H (4a)、Mes(n-Bu)P-CPh2H (4b)、Mes(Me)P-CPh2Me (6a)、Mes(Me)P-CPh2-P(NEt2)2 (7a)、Mes(Me)P-CPh2-SiMe2H (8a) 和 Mes(Me)P-CPh2-SiMe3 (9a)。此外，化合物 4a、7a、8a 和 9a 还通过 X 射线晶体学进行了表征。大多数计量参数都是典型的叔膦化合物；然而，P-CPh2H 键在所有情况下都被拉长，反映出围绕该键的立体体积很大。意外的是，7a 在溶液和固态中都观察到了异常大的 31P-31P 耦合常数（2JPP > 200 Hz）。这一观察结果可以通过空间 P-P 相互作用得到合理解释。7a 的 P-P 间距较短 [P(1)-P(2) = 2.966(1) Å; cf. Σ rvdw = 3.7 Å]，P-C-P 键角较小 [P(1)-C(11)-P(1) = 99.17(9)°] 也进一步证实了这一观点。
• Analysis of the products of the anionic oligomerisation of a phosphaalkene using MALDI-TOF mass spectrometryElectronic supplementary information (ESI) available: experimental procedures and an additional figure. See http://www.rsc.org/suppdata/cc/b4/b406160h/
  作者：Bronwyn H. Gillon、Derek P. Gates

  DOI：10.1039/b406160h

  日期：——

  The first use of MALDI-TOF MS in the study of the products of RLi (R = Me, Bu) initiated oligomerisation of PC bonds is reported. These studies may be considered as models for analogous polymerisation reactions. The detected linear products with R–P and C–H end-groups are consistent with a chain growth mechanism similar to that known for olefins. Interestingly, the results suggest that backbiting may compete with chain growth.

  报告首次将 MALDI-TOF MS 用于研究 RLi（R = Me，Bu）引发的 PC 键低聚产物。这些研究可被视为类似聚合反应的模型。检测到的带有 R-P 和 C-H 端基的线性产物与烯烃的已知链增长机制相一致。有趣的是，研究结果表明，反向配位可能会与链增长发生竞争。