(methyl)(methylene)diphenylphosphorane | 4554-22-7

• 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: (methyl)(methylene)diphenylphosphorane
• 英文别名: methyldiphenylphosphonio-methylid；Methylmethylendiphenylphosphoran；Methyl-diphenyl-methylen-phosphoran；Methyl-diphenyl-methylenphosphoran；Methylendiphenylmethylphosphoran；Phosphorane, methylmethylenediphenyl-；methyl-methylidene-diphenyl-λ5-phosphane
• CAS: 4554-22-7
• 化学式: C₁₄H₁₅P
• 分子量: 214.247
• InChiKey: DPUCORLSBXZSNF-UHFFFAOYSA-N

物化性质

• 沸点：
  342.9±25.0 °C(Predicted)
• 密度：
  1.03±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.7
• 重原子数：
  15
• 可旋转键数：
  2
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.07
• 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：

  (methyl)(methylene)diphenylphosphorane 以 not given 为溶剂， 生成
  参考文献：
  名称：

  亚甲基和内酯桥联的双核金（III）络合物的烷基化

  摘要：

  DOI：

  10.1021/om00139a023
• 作为产物：
  描述：

  alkaline earth salt of/the/ methylsulfuric acid 在 双(三甲基硅烷基)氨基钾 作用下， 以 四氢呋喃 为溶剂， 生成 (methyl)(methylene)diphenylphosphorane
  参考文献：
  名称：

  Can C−H⋅⋅⋅C(π) Bonding Be Classified as Hydrogen Bonding? A Systematic Investigation of C−H⋅⋅⋅C(π) Bonding to Cyclopentadienyl Anions

  摘要：

  The following ammonium and phosphonium cyclopentadienide complexes have been prepared, crystallized and investigated structurally: [Cp](-)[Et4N](+), [Cp](-)[Et4P](+), [Cp](-)[Ph3PMe](+), [Cp](-)[Ph2PMe2](+), [tBu(Me)Cp](-)[Ph4P](+) and [Me4C2Cp2](2-) [(Et4P)(2)](2+). The Cp anions in these complexes can not be considered as naked. Intermolecular bonding through characteristic (cation)C-H ... C(Cp-) interactions results in the formation of polymeric networks. Generally, poly meric chains of alternating cations and anions are formed that are reminiscent of the solid-state structures observed for cyclopentadienyl-alkalimetal compounds. Mutual comparison of all the known structures of ammonium and phosphonium cyclopentadienide complexes shows that intermolecular C-H ... C(Cp-) bonding displays hydrogen-bond-like characteristics: i) directionality, ii) correlation between C-H acidity and C-H ... C bond lengths and iii) correlation between the strength of the hydrogen-bond acceptor and C-H ... C bond lengths. These observations are also confirmed by ab initio calculations on coordination complexes of C-H donors (acetylene and methane) and the pi-systems in benzene or the Cp- anion. Likewise, combinations of an alkali metallocene anion and a phosphonium cation show such C-H ... C(Cp-) interactions in the crystalline state.

  DOI：

  10.1002/(sici)1521-3765(19990604)5:6<1852::aid-chem1852>3.0.co;2-i

文献信息

• Structural and Spectroscopic Evidence for the Occurrence ofgauche-Betaine Intermediates in the Thio Wittig Reaction
  作者：Carsten Puke、Gerhard Erker、Birgit Wibbeling、Roland Fröhlich

  DOI：10.1002/(sici)1099-0690(199908)1999:8<1831::aid-ejoc1831>3.0.co;2-r

  日期：1999.8

  averaged 1JPCipso(aryl) coupling constant was used to elucidate the characteristic structural properties of Wittig and thio Wittig intermediates derived by treatment of the series Ph3PCH2 (2a), Ph2MePCH2 (2b), and PhMe2PCH2 (2c) with bis(p-methoxyphenyl) ketone to give 3 or benzophenone (to give 3′) or bis(p-methoxyphenyl) thioketone (to give 5), respectively. The oxaphosphetane series 3′a–3′c shows a strong

  叶立德（环丙基）3PCH2 与 Michler 硫酮 SC(C6H4NMe2)2 在 [D5] 吡啶中的反应得到硫代维蒂希中间体 [(环丙基)3P+–CH2–CAr2–S–]（11；31P NMR：δ = +27.7） . 化合物 11 通过 X 射线衍射表征并显示出具有 S–C–C–P 二面角为 52.9(3)° 和 P…S 分离度为 3.312(2) 的 gauche-甜菜碱型结构A. 特征平均 1JPCipso(aryl) 偶联常数用于阐明 Wittig 和 thio Wittig 中间体的特征结构性质，这些中间体是通过用 bis(p) 处理系列 Ph3PCH2 (2a)、Ph2MePCH2 (2b) 和 PhMe2PCH2 (2c) 而得到的-甲氧基苯基）酮分别得到 3 或二苯甲酮（得到 3'）或双（对甲氧基苯基）硫酮（得到 5）。oxaphosphetane 系列 3'a–3'c
• COMPOUND AND ORGANIC LIGHT-EMITTING DEVICE INCLUDING THE SAME
  申请人：Samsung Display Co., Ltd

  公开号：US20170186979A1

  公开（公告）日：2017-06-29

  A compound is represented by Formula 1 and an organic light-emitting device including the same: wherein Formula 1 is the same as described above.

  一种化合物由化学式1表示，包括该化合物的有机发光器件：其中化学式1与上述描述相同。
• [EN] GOLD (I)-PHOSPHINE COMPOUNDS AS ANTI-BACTERIAL AGENTS<br/>[FR] COMPOSÉS À BASE D'OR (I)-PHOSPHINE EN TANT QU'AGENTS ANTI-BACTÉRIENS
  申请人：AUSPHERIX LTD

  公开号：WO2015181550A1

  公开（公告）日：2015-12-03

  A compound of formula (I) for use in the prevention or treatment of a bacterial infection wherein RP1 is either methyl, ethyl, isopropyl, cyclohexyl or phenyl; RP2 is selected from methyl, ethyl, isopropyl, cyclohexyl and phenyl; RP3 is either ethyl, isopropyl, cyclohexyl, phenyl or pyridyl; A is either S or Se; RA is selected from wherein each of Y1, Y2, Y3, Y4 and Y9 is independently selected from CH or N, wherein at least three of Y1, Y2, Y3, Y4 and Y9 are CH; V is selected from O, CH-ORO1, N-CO2-RC2 or N-RN2; one of Y5, Y6, Y7 and Y8 is selected from CH and N, and the others are CH; X is selected from NH, S or O; RC1 is selected from O-RO2 or NHRN1; RO1 is selected from H and C1-3 unbranched alkyl; RO2 is C1-3 unbranched alkyl; RN1 is selected from H and C1-3 unbranched alkyl; RN2 is C1-3 unbranched alkyl; RC2 is either C1-3 unbranched alkyl or C3-4 branched alkyl; RC3 is selected from C1-3 unbranched alkyl and C2H4CO2H; RC4 is either H or Me; RC5 is either H or Me; RC6 represents one or two optional methyl substituents; and n is an integer from 2 to 8.

  公式（I）的化合物用于预防或治疗细菌感染，其中RP1为甲基、乙基、异丙基、环己基或苯基之一；RP2从甲基、乙基、异丙基、环己基和苯基中选择；RP3为乙基、异丙基、环己基、苯基或吡啶基之一；A为S或Se；RA从Y1、Y2、Y3、Y4和Y9中选择，其中Y1、Y2、Y3、Y4和Y9中至少有三个是CH；V从O、CH-ORO1、N-CO2-RC2或N-RN2中选择；Y5、Y6、Y7和Y8中的一个从CH和N中选择，其余为CH；X从NH、S或O中选择；RC1从O-RO2或NHRN1中选择；RO1从H和C1-3直链烷基中选择；RO2为C1-3直链烷基；RN1从H和C1-3直链烷基中选择；RN2为C1-3直链烷基；RC2为C1-3直链烷基或C3-4支链烷基之一；RC3从C1-3直链烷基和C2H4 H中选择；RC4为H或Me；RC5为H或Me；RC6代表一个或两个可选的甲基取代基；n为2到8之间的整数。
• Reactivity of phosphonium diylids with aldehydes and ketones
  作者：Henri-Jean Cristau、Yves Ribeill、Laurent Chiche、Françoise Plénat

  DOI：10.1016/0022-328x(88)83131-0

  日期：1988.9

  Non-stabilized and semi-stabilized phosphonium diylids of the type (C6H5)2P(CHR)(CHLiR) (5) show a greater nucleophilic reactivity toward carbonyl compounds than the corresponding monoylids (C6H5)2P(CHR)(CH2R) (8). Thus diylid 5a reacts readily at room temperature with sterically hindered ketones such as fenchone or di-t-butylketone. However, the residual negative charge in the intermediate adduct

  （C 6 H 5）2 P（CHR）（CHLiR）（5）类型的非稳定化和半稳定化的磷鎓二碘化物对羰基化合物的亲核反应性高于相应的单酰基（C 6 H 5）2 P（ CHR）（CH 2 R）（8）。因此，二碘化物5a在室温下容易与空间受阻的酮例如fenchone或二叔丁基酮反应。然而，中间加合物13中残留的负电荷减慢了向维蒂希产物的分解，并且可能是造成E中观察到的变化（通常增强）的原因。在非稳定的和半稳定的脂质的情况下的-选择性。
• Formation of Methane versus Benzene in the Reactions of (C ₅ Me ₅ ) ₂ Th(CH ₃ ) ₂ with [CH ₃ PPh ₃ ]X (X=Cl, Br, I) Yielding Thorium‐Carbene or Thorium‐Ylide Complexes
  作者：Pokpong Rungthanaphatsophon、Adrien Bathelier、Ludovic Castro、Andrew C. Behrle、Charles L. Barnes、Laurent Maron、Justin R. Walensky

  DOI：10.1002/anie.201706496

  日期：2017.10.9

  equivalent of methane is lost with concomitant formation of benzene from an unstable phosphorus(V) intermediate, yielding (C5Me5)2Th[κ2‐(C,C′)‐(CH2)(CH2)PPh2]Cl. Density functional theory (DFT) investigations of the reaction energy profiles for [CH3PPh3]X, X=Cl and I showed that in the case of iodide, thermodynamics prevents the production of benzene and favors formation of the carbene.

  研究了（C 5 Me 5）2 Th（CH 3）2与phospho盐[CH 3 PPh 3 ] X（X = Cl，Br，I）的反应。当X = Br和I时，释放出两当量的甲烷，得到（C 5 Me 5）2 Th [CHPPh 3] X，稀有的末端磷稳定的car与with。这些络合物具有迄今为止报道的最短的–碳键（≈2.30Å），并且电子结构计算显示出一定程度的多重键合。然而，当X =氯，甲烷的仅一个当量的失去了与从不稳定磷伴随形成苯的（V）中间体，得到（C 5我5）2的Th [κ 2 - （C，C'） - （CH 2）（CH 2）PPh 2 ] Cl。[CH 3 PPh 3的反应能量分布的密度泛函理论（DFT）研究] X，X ＝ Cl和I表明，在碘化物的情况下，热力学阻止了苯的产生并有利于卡宾的形成。