chloromethylphenylphosphine sulfide | 13639-62-8

• 物质功能分类: 化学试剂 - 有机试剂 - 膦配体
• 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: chloromethylphenylphosphine sulfide
• 英文别名: Methyl-phenyl-thiophosphinsaeurechlorid；Methyl-phenyl-thiophosphinsaerechlorid；methylphenylphosphinothioic chloride；Methylphenylthiophosphinic chloride；(+/-)-Methylphenylthiophosphinsaeurechlorid；Methyl-phenyl-thiophosphinsaeure-chlorid；Methyl(phenyl)phosphinothioic chloride；chloro-methyl-phenyl-sulfanylidene-λ5-phosphane
• CAS: 13639-62-8
• 化学式: C₇H₈ClPS
• 分子量: 190.633
• InChiKey: XZRUGUOJBDGYPS-UHFFFAOYSA-N

物化性质

• 沸点：
  91-94 °C(Press: 0.01 Torr)
• 密度：
  1.2541 g/cm3

计算性质

• 辛醇/水分配系数(LogP)：
  3.4
• 重原子数：
  10
• 可旋转键数：
  1
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.14
• 拓扑面积：
  32.1
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  chloromethylphenylphosphine sulfide 在 sodium methylate 亚磷酸三苯酯 、 正丁基锂 、 四甲基乙二胺 作用下， 以 甲醇 、 苯 为溶剂， 生成 r-2--t-4,t-6-dimethyl-1,3-dithiane
  参考文献：
  名称：

  Conformational Preference in 1,3-Dithianes Containing 2-Phosphoryl, -(thiophosphoryl), and -(selenophosphoryl) groups. Chemical and Crystallographic Implications of the Nature of the Anomeric Effect

  摘要：

  The operation of the anomeric effect in all the title compounds studied was found. The magnitude of the anomeric effect was found to be larger than 10 kJ/mol. Crystallographic, spectroscopic, and thermodynamic data suggest that the n(S)-sigma*(C-P) hyperconjugative interaction is one of the factors responsible for the anomeric effect. The second interaction stabilizing the axial position of phosphorus can be P=Y...H(4 or 6) hydrogen bond formation. Some other interactions are also possible, namely sigma(C(4,6)-S)-sigma*(C(2)-P) (preferring the equatorial position of phosphorus) and sigma(C(4,6)-S)-pi(P=Y) hyperconjugations and the n(S)-n(Y) repulsions. The latter interaction was also proposed as MO counterpart of lone pair-lone pair repulsions suggested by molecular mechanics calculations. It was proved that various conformation probes can afford different equilibrium constants, if weighted average method and conformationally fixed models are applied. Most of the physical quantities are dependent on the alkyl substitution in the 1,3-dithiane ring. Thus, the relevant procedure for the selection of conformational probe was presented. Since the gamma-effect value in C-13 NMR spectra was found to be very sensitive to the position of a substituent connected with the anomeric carbon atom of 1,3-dithianes, it was applied as a conformational probe. A long range (4)J(C-P) coupling constant in the C-13 NMR spectra and P-31 spin-lattice T-1(DD) relaxation times suggest the existence of close contact(s) between a heteroatom Y(Y=O,S,Se) connected with the axial phosphorus P=Y and axial protons H(4,6) in the 1,3-dithiane ring. Crystallographic data show that the distance from Y to one of these protons is usually much smaller than to the other one and smaller than the sum of H,Y van der Waals radii. The possibility of H..Y hydrogen bond formation is discussed.

  DOI：

  10.1021/jo00086a016
• 作为产物：
  描述：

  meso-1,2-dimethyl-1,2-diphenyldiphosphine disulfide 在 氯 作用下， 生成 chloromethylphenylphosphine sulfide
  参考文献：
  名称：

  Diphosphine disulfides. III. Influence of structure on the course of phosphinothioic halide-Grignard reactions

  摘要：

  DOI：

  10.1021/jo01285a015

文献信息

• Intermolecular-directed reactivity in solid media. Radiogenic formation of phosphorus-centered radicals in chiral diphosphine disulfides studied by ESR
  作者：Olav M. Aagaard、Rene A. J. Janssen、Bas F. M. De Waal、Jan A. Kanters、Arie Schouten、Henk M. Buck

  DOI：10.1021/ja00170a006

  日期：1990.7

  process have been studied.4d Substituted diphosphine disulfides (R,R,P(S)P(S)R,R,) can serve as good probes to study phosphoranyl radical formation because of their intrinsic ability to adopt various radical configurations from a single molecule (Figure l).’ X irradiation of a diphosphine disulfide almost invariably results in the formation of an electron-capture radical in which the unpaired electron is

  已经进行了 AWct 单晶、粉末和冷冻基质 ESR 实验，以研究几种非对映异构和不对称二硫化二膦 (R,RzP(S)P(S)R3R4) 的放射电子捕获特性。确定了几种以磷为中心的自由基构型的超精细耦合的主值，并与自旋密度分布相关。注意力集中在苯基和甲苯基取代的二硫化二膦的内消旋和外消旋形式之间观察到的放射特性的强烈差异。最显着的结果是结晶内消旋化合物 MePhP(S)P(S)MePh, Me@-Tol)P(S)P(S)Me@-Tol) 的 X 辐照，和 Ph(PhCHZ)P(S)P(S)Ph(CH2Ph) 不会导致三电子键 PAP u* 自由基的形成，但总是导致未配对电子主要位于一半的构型分子。另一方面，相应外消旋形式的 X 辐射会产生 PLP u* 构型。观察到的对称和不对称构型之间的区别是根据影响初始电子添加后前体分子几何弛豫的分子间空间相互作用来解释的。对于定量评估，使用 X 射线晶体学数据计算了由分子各自晶格中
• Organische Phosphorverbindungen XIII. Über einige Reaktionen des Methylthiophosphonsäure-dibromids CH₃P(S)Br₂und verwandter Verbindungen [1]
  作者：Ludwig Maier

  DOI：10.1002/hlca.19640470608

  日期：——

  Several insecticides containing a P-C bond have been prepared. The physical properties and the insecticidal activity of these compounds are reported. The structure of phosphinothionic anhydrides has been elucidated.

  已经制备了几种含有PC键的杀虫剂。报道了这些化合物的物理性质和杀虫活性。已经阐明了次膦酸酯基酸酐的结构。
• Darstellung und schwingungsspektren von trimethylzinndiorganothiophosphinaten Me3SnOSPR′R″ (R′R″ = Me2, MePh, Ph2). Die kristallstruktur von Me3SnOSPMe2
  作者：Abdel-Fattah Shihada、Ihsan Abdel-Amir Jassim、Frank Weller

  DOI：10.1016/0022-328x(84)80239-9

  日期：1984.6

  A series of trimethyltin diorganothiophosphinates Me3SnOSPR′R″ (R′R″ = Me2, MePh, Ph2) was prepared from (Me3Sn)2O and R′R″PSCl in cyclohexane solution. A close study of the vibrational spectra is given; 31P NMR and mass spectra are also reported. The structural investigation of Me3SnOSPMe2 by means of X-ray diffraction (R 5.2%, 1697 observed independent reflexions) shows the compound to consists of

  由（Me 3 Sn）2 O和R'R''PSCl在环己烷溶液中制备一系列三甲基锡二有机硫代亚膦酸酯Me 3 SnOSPR'R“（R'R” = Me 2，MePh，Ph 2）。仔细研究了振动光谱。还报道了31 P NMR和质谱。通过X射线衍射对Me 3 SnOSPMe 2进行结构研究（R 5.2％，观察到独立反射1697）显示该化合物由链组成，其中平面SnMe 3单元和四面体OSPMe 2基团通过O-连接和硫代次膦酸酯的S原子。
• Synthesis of alkenes with P-(α-lithioalkyl)phosphinothioic amides
  作者：Carl R. Johnson、Robert C. Elliott

  DOI：10.1021/ja00389a026

  日期：1982.12
• Horner, L.; Flemming, H. W., Phosphorus and Sulfur and the Related Elements, 1983, vol. 14, p. 245 - 252
  作者：Horner, L.、Flemming, H. W.

  DOI：——

  日期：——