mesityldiphenylmethylenephoshine | 67565-91-7

• 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: mesityldiphenylmethylenephoshine
• 英文别名: mesityl(diphenylmethylene)phosphine；diphenylmethylene(mesityl)phosphine；2,4,6-tri-methylphenyl(diphenylmethylene)phosphine；Phosphine, (diphenylmethylene)(2,4,6-trimethylphenyl)-；benzhydrylidene-(2,4,6-trimethylphenyl)phosphane
• CAS: 67565-91-7
• 化学式: C₂₂H₂₁P
• 分子量: 316.382
• InChiKey: WHYQQRXNLARTFB-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.2
• 重原子数：
  23
• 可旋转键数：
  3
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.14
• 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：

  mesityldiphenylmethylenephoshine 在 sulfur 作用下， 以 苯 为溶剂， 反应 3.0h， 以50%的产率得到二苯基甲烷硫酮
  参考文献：
  名称：

  Oxidation reactions of phosphaalkenes

  摘要：

  DOI：

  10.1021/ja00350a047
• 作为产物：
  描述：

  2-溴-1,3,5-三甲基苯 在 盐酸 、 正丁基锂 、 1,8-二氮杂双环[5.4.0]十一碳-7-烯 作用下， 以 四氢呋喃 、 乙醚 为溶剂， 反应 42.5h， 生成 mesityldiphenylmethylenephoshine
  参考文献：
  名称：

  芳基取代的膦基烯烃的合成与结构

  摘要：

  描述了两个三芳基取代的膦基-烯烃均三甲苯基（二苯基亚甲基）膦（1a）和2，6-二甲基苯基（二苯基亚甲基）膦（1b）的改进合成。在几种变体中，优选的途径从芳基溴化物4开始，其被转化为相应的格氏试剂和与PCl 3转化为芳基膦酰二酰胺7的芳基膦酰胺氯化物9，从而由磷酰胺10生成至膦酰氯11，其经DBU除去HCl，以60-85％的收率得到标题化合物。1a和1b的化学和光谱数据被讨论；它们本质上包含局部的P ＝ C键，并且。主要通过位阻保护来稳定。这些结论是通过简单的模型化合物（HFS-计算证实17，16'，18，19和20）将磷孤对识别为HOMO，将π轨道识别为NHOMO；但是，两个轨道的能量都很接近。此外，计算结果揭示了磷d轨道在键合中的重要性，以及先前从化学证据中得出的P = C键（P为正极）中的极化。最后，表明P = C键与苯基的相互作用不会显着影响键合情况，但是被杂原子取代（氮在碳上取代；20）确实如此。

  DOI：

  10.1016/s0040-4020(01)91106-8

文献信息

• A Lewis acid-mediated synthesis of P-alkyl-substituted phosphaalkenes
  作者：Joshua I. Bates、Brian O. Patrick、Derek P. Gates

  DOI：10.1039/c0nj00188k

  日期：——

  Treating an equimolar mixture of R1P(SiMe3)2 (R1 = tBu, Ad, Mes, Me3Si; Ad = 1-adamantyl, Mes = 2,4,6-trimethylphenyl) and R2C(O)R3 (R2:R3 = tBu:H, Ph:Ph, tBu:tBu, tBu:Ph, tBu:Me) with AlCl3 (1 equiv.) affords the corresponding phosphaalkenes R1PCR2R3 as monitored by 31P NMR spectroscopy. This new method was applied to the multigram synthesis of R1PCR2R3 [1a: R1 = tBu, R2 = tBu, R3 = H; 2a: R1 = Ad, R2 = tBu, R3 = H; 3a: R1 = Mes, R2 = tBu, R3 = H; 3b: R1 = Mes, R2 = R3 = Ph] in good isolated yields (1a: 80%; 2a: 57%; 3a: 63%; 3b: 76%). Previously unknown 2a has been fully characterized. The reactivity of 1a and 2a with group 13 Lewis acids was performed in an effort to probe their reactivity and provide a means to structurally characterize these P-alkyl phosphaalkenes. The X-ray crystal structures of 1a·AlCl3, 1a·GaCl3 and 2a·GaCl3 reveal that the tBu substituents are configured in a trans arrangement and the PC bond lengths are as expected (avg. 1.64 Å).

  使用等摩尔量的R1P(SiMe3)2（R1 = tBu、Ad、Mes、Me3Si；Ad = 1-金刚烷基，Mes = 2,4,6-三甲基苯基）和R2C(O)R3（R2:R3 = tBu:H、Ph:Ph、tBu:tBu、tBu:Ph、tBu:Me）与AlCl3（1当量）处理，通过31P NMR光谱监测，得到了相应的磷杂烯R1PCR2R3。这种方法被用于多克级合成R1PCR2R3 [1a: R1 = tBu, R2 = tBu, R3 = H; 2a: R1 = Ad, R2 = tBu, R3 = H; 3a: R1 = Mes, R2 = tBu, R3 = H; 3b: R1 = Mes, R2 = R3 = Ph]，产率良好（1a: 80%; 2a: 57%; 3a: 63%; 3b: 76%）。先前未知的2a已得到充分表征。为了探究1a和2a与第13族路易斯酸的反应活性并提供结构表征的手段，进行了相关反应。1a·AlCl3、1a·GaCl3和2a·GaCl3的X射线晶体结构显示，tBu取代基呈反式排列，PC键长符合预期（平均1.64 Å）。
• PC Bonds as Building Blocks for Three- and Four-Membered Heterocyclic Cations: Synthesis, Structures and Mechanistic Studies
  作者：Joshua I. Bates、Derek P. Gates

  DOI：10.1002/chem.201101535

  日期：2012.2.6

  5 equiv) to either 1 a or 1 b affords diphosphetanium salts [RPCHtBuP(Me)RCHtBu]OTf ([3 a]OTf and [3 b]OTf) containing four‐membered P2C2 heterocycles. The phosphenium triflate [tBuP(CH2tBu)]OTf ([5 a]OTf) and methylenephosphonium triflate [tBu(Me)PCHtBu]OTf ([7 a]OTf) are identified spectroscopically as intermediates in the formation of [2 a]+ and [3 a]+, respectively. The phosphenium triflate intermediate

  研究了用亲电子试剂活化磷烯烃的PC键，作为制备和表征不常见的有机磷化合物的方法。RPCH的治疗吨卜（1：R =吨卜;图1b：R = 1-金刚烷基）与HOTf（0.5当量），得到diphosphiranium盐[R P  CH吨卜 P R（CH 2吨丁基） ] OTf（[ 2 a ] OTf和[ 2 b ] OTf），每个均包含一个三元P 2 C环。相反，在1 a或1 b中添加MeOTf（0.5当量）可得到二磷鎓盐[RP  CH吨卜 P（我）R  Ç ħ吨卜]光学传递函数（[ 3 ]光学传递函数和[图3b ] OTF）含有四个元P 2 Ç 2杂环。该三氟甲磺酸酯phosphenium [吨BUP（CH 2吨丁基）]光学传递函数（[ 5 ] OTF）和三氟甲磺酸methylenephosphonium [吨卜（Me）中PCH吨卜]光学传递函数（[ 7 ] OTF）进行光谱鉴定为中间体[
• Chemical functionality of poly(methylenephosphine): phosphine–borane adducts and methylphosphonium ionomers
  作者：Kevin J. T. Noonan、Bastian Feldscher、Joshua I. Bates、Justin J. Kingsley、Mandy Yam、Derek P. Gates

  DOI：10.1039/b718140j

  日期：——

  The chemical functionality of poly(methylenephosphine) n-Bu[MesP–CPh2]nH (2) is examined in reactions with two isoelectronic species, namely BH3 and CH3+. The potential reactivity of polymer 2 is modelled by examining the reactivity of molecular phosphines bearing similar substituents as the polymer. In particular, the phosphine–borane adducts Mes(Me)P(BH3)–CPh2H (4a) and Mes(Me)P(BH3)–CPh2SiMe2H (4b) are prepared from the reaction of BH3·SMe2 with Mes(Me)P–CPh2H (3a) or Mes(Me)P–CPh2SiMe2H (3b), respectively. Treating 3a with MeOTf affords the methylated model compound, [Mes(Me)2P–CPh2H]OTf (5). X-Ray crystal structures are reported for each model compound. The reaction of n-Bu[MesP–CPh2]nH (Mn = 3.89 × 104, PDI = 1.34) with BH3·SMe2 affords the phosphine–borane polymern-Bu[MesP(BH3)–CPh2]nH (6) (Mn = 4.13 × 104, PDI = 1.26). In contrast, methylation of phosphine polymer 2 gives n-Bu[MesP–CPh2]x–/–[MesP(Me)–CPh2]yH·(OTf)y (7) where approximately 50% of the phosphine moieties are methylated (from 31P NMR).

  聚（亚甲基磷）的化学功能性 n-Bu[MesP–CPh2]nH (2) 在与两个等电子物种（即 BH3 和 CH3+）的反应中进行了研究。聚合物 2 的潜在反应性通过考察具有类似取代基的分子磷的反应性进行建模。特别地，磷-硼加合物 Mes(Me)P(BH3)–CPh2H (4a) 和 Mes(Me)P(BH3)–CPh2SiMe2H (4b) 通过将 BH3·SMe2 与 Mes(Me)P–CPh2H (3a) 或 Mes(Me)P–CPh2SiMe2H (3b) 反应得到。用 MeOTf 处理 3a 得到甲基化的模型化合物 [Mes(Me)2P–CPh2H]OTf (5)。每个模型化合物的 X 射线晶体结构均已报道。n-Bu[MesP–CPh2]nH (Mn = 3.89 × 10^4, PDI = 1.34) 与 BH3·SMe2 的反应产生了磷-硼聚合物 n-Bu[MesP(BH3)–CPh2]nH (6) (Mn = 4.13 × 10^4, PDI = 1.26)。相比之下，磷聚合物 2 的甲基化反应生成 n-Bu[MesP–CPh2]x–/–[MesP(Me)–CPh2]yH·(OTf)y (7)，约有 50% 的磷部分进行了甲基化（来自 31P NMR 的结果）。
• 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。
• Destiny of Transient Phosphenium Ions Generated from the Addition of Electrophiles to Phosphaalkenes:  Intramolecular C−H Activation, Donor−Acceptor Formation, and Linear Oligomerization
  作者：Chi-Wing Tsang、Crystal A. Rohrick、Tejindra S. Saini、Brian O. Patrick、Derek P. Gates

  DOI：10.1021/om0495022

  日期：2004.12.1

  temperatures, GaCl3 migrates from phosphorus to carbon to afford the fleeting phosphenium zwitterion Mes*PCH2GaCl3. This undetected transient species immediately oxidatively adds to a C−H bond of an o-tBu group in the P-Mes* substituent, resulting in a GaCl3-coordinated ylide that has been characterized crystallographically. The analogous reaction of GaCl3 with MesPCPh2 gives stable Mes(Cl3Ga)PCPh2, for which

  磷烯烃MesP CPh 2（Mes = 2,4,6-Me 3 C 6 H 2）和Mes * P CH 2（Mes * = 2,4,6- t Bu 3 C 6 H 2）与路易斯的反应已经研究了（AlCl 3，GaCl 3，InCl 3）和质子（HOTf）酸，以评估阳离子聚合进行P C键的可行性。将GaCl 3添加到Mes * P CH 2中会生成加合物Mes *（Cl 3 Ga）P CH 2，可以在193 K下用光谱法检测到。在更高的温度下，GaCl 3从磷迁移到碳，以提供短暂的z两性离子Mes * PCH 2 GaCl 3。这种未被发现的瞬态物质立即氧化添加到P- Mes *取代基中o - t Bu基团的CH键上，从而形成了GaCl 3配位的内立德，该基团已在晶体学上进行了表征。GaCl 3与MesP CPh 2的类似反应可得到稳定的Mes（Cl 3 Ga）P CPh 2，已经对其进行了晶