methyl(phenyl)chlorophosphine | 540513-01-7

• 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(phenyl)chlorophosphine
• 英文别名: (methyl)(phenyl)chlorophosphane；chloro(methyl)(phenyl)phosphine；Methylphenylchlorophosphine；chloro-methyl-phenylphosphane
• CAS: 540513-01-7
• 化学式: C₇H₈ClP
• mdl: MFCD00013619
• 分子量: 158.567
• InChiKey: JEPQKKGNKYPFIZ-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.3
• 重原子数：
  9
• 可旋转键数：
  1
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.142
• 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(phenyl)chlorophosphine 在 sodium methylate 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：

  (diethylamino)phenylchlorophosphine 在 盐酸 作用下， 以 乙醚 、 Petroleum ether 为溶剂， 反应 2.0h， 生成 methyl(phenyl)chlorophosphine
  参考文献：
  名称：

  Bestmann, Hans Juergen; Lienert, Juergen; Heid, Eckard, Chemische Berichte, 1982, vol. 115, # 12, p. 3875 - 3879

  摘要：

  DOI：

文献信息

• Facile syntheses and interconversions between simple phosphiranium and phosphirenium salts
  作者：David C.R. Hockless、Mark A. McDonald、Michael Pabel、S. Bruce Wild

  DOI：10.1016/s0022-328x(96)06641-7

  日期：1997.2

  has been isolated in 73% yield from the reaction between 1-phenylphosphirane and methyl triflate in benzene. The crystal and molecular structures of 1 have been determined. The phosphiranium ion in 1 undergoes ring opening with water to give (±)-ethylmethylphenylphosphine oxide, and reacts with primary alcohols to give (±)-alkoxyethylmethylphenylphosphonium ions. Treatment of 1 with dimethyl- or methylphenylacetylene

  从1-苯基膦烷和三氟甲磺酸甲酯在苯中的反应中分离出第一膦酸酯盐，即1-甲基-1-苯基phosph三氟甲磺酸酯（1），产率为73％。已确定1的晶体和分子结构。在phosphiranium离子1所经历开环与水，得到（±）-ethylmethylphenylphosphine氧化物，以及与伯醇反应，得到（±）-alkoxyethylmethylphenylphosphonium离子。治疗1用二甲基或甲基苯基乙炔在二氯甲烷中的化合物在一周内以高收率得到相应的取代的磷鎓盐。磷鎓盐还可以通过使氯烷基芳基-或氯二芳基膦和炔与三氟甲磺酸th（I）在二氯甲烷中反应来高产率地制备。已经确定了1,2,3-三甲基-1-苯基phosph三氟甲磺酸盐的晶体和分子结构。在不存在炔烃的情况下，氯甲基苯基膦与三氟甲磺酸（（I）的反应会导致不稳定的三氟甲膦膦酸that，在环境条件下，在磷中迅速进行氯离子交换和/或锥体转化，这是通过可变温度NMR光谱法确定的。
• Reaktionen mit alkylidenephosphoranen—XVIII
  作者：H. Jürgen、Bestmann、I. Tömösközi

  DOI：10.1016/s0040-4020(01)92629-8

  日期：1968.1

  The reaction of alkylidenephosphoranes with acyl chlorides proceeds by transylidation. Starting from an alkylidenephosphorane containing an chiral P-atom and an optical active acyl chloride, partial kinetic resolution of the organophosphorus compound is observed. The reaction of 1-carboethoxyethylidenenaphthylphenylmethylphosphorane with an optical active acyl chloride proceeds by simultaneous kinetic

  亚烷基膦基膦与酰基氯的反应是通过亚烷基化进行的。从包含手性P原子和光学活性酰氯的亚烷基磷烷开始，观察到有机磷化合物的部分动力学拆分。1-碳乙氧基亚乙基萘基苯基甲基磷烷与光学活性酰氯的反应通过同时动力学拆分和部分不对称合成烯丙基羧酸酯来进行。在酯官能团中含有手性中心的碳烷氧基亚甲基-三苯基膦与光学活性酰基氯的反应中也观察到动力学拆分。在反应产物水解后获得光学活性醇。讨论了反应的空间过程，并指定了几种化合物的绝对构型。
• Synthese directe de phosphines tertiaires racemiques et de chlorophosphines dissymetriques
  作者：W. Chodkiewicz、D. Guillerm、D. Jore、E. Mathieu、W. Wodzki

  DOI：10.1016/0022-328x(84)80288-0

  日期：1984.7

  Racemic tertiary phosphines are obtained from dichlorophenylphosphine by a “one pot” synthesis in two steps: (1) condensation of one equivalent of an organocadmium, and (2) substitution of the second chlorine by another organometallic compound.

  外消旋的叔膦是通过“一锅法”合成通过两个步骤从二氯苯基膦获得的：两个步骤：（1）缩合一当量的有机镉，以及（2）第二氯被另一种有机金属化合物取代。
• P/O Ligand Systems: Facile Synthesis, Structure, and Catalytic Tests of 2′‐Phosphanyl‐1,1′ ‐phenyl‐2‐ols and 2′‐Phosphanyl‐1,1′‐binaphthyl‐2‐ols
  作者：Renat Kadyrov、Joachim Heinicke、Markus K. Kindermann、Detlef Heller、Christine Fischer、Rüdiger Selke、Axel K. Fischer、Peter G. Jones

  DOI：10.1002/cber.19971301118

  日期：1997.11

  A facile synthesis of 2′-phosphanyl-1,1′-biphenyl- and 2′-phosphanyl-1,1′ -binaphthyl-2-ols and their silyl ethers has been developed, consisting of electron-transfer-catalyzed ring-opening of dibenzofuran and dinaphthofuran, respectively, subsequent reaction with chlorophosphanes, and work-up with acetic acid or ClSiMe3. Studies of the molecular and crystal structures reveals the presence of P—H—O

  已开发了一种简便的合成方法，该方法由电子转移催化的开环组成，可轻松合成2'-膦酰基-1,1'-联苯-和2'-膦酰基-1,1'-联萘-2-醇及其甲硅烷基醚分别将二苯并呋喃和二萘并呋喃与氯膦反应，然后用乙酸或ClSiMe 3进行后处理。对分子和晶体结构的研究表明，在更基本的t BuPhP衍生物中存在PB桥键，而在联苯衍生物中芳基平面几乎垂直排列。在P不对称衍生物3d的情况下，通过NMR确定芳基平面绕CC轴旋转的势垒，通过对映异构和P不对称使用非对映异构体的出现。在均相Rh催化反应中对标题化合物，膦酰基苯酚和膦基萘酚的比较筛选测试表明，在加氢甲酰化反应中具有催化活性，并且联苯和联萘-2-醇衍生物相对于其他P-O配体而言具有优越的性能。
• P/O Ligand Systems: Synthesis, Reactivity, and Structure of Tertiary <i>o</i> ‐Phosphanylphenol Derivatives
  作者：Joachim Heinicke、Renat Kadyrov、Markus K. Kindermann、Manuela Koesling、Peter G. Jones

  DOI：10.1002/cber.19961291223

  日期：1996.12

  P-asymmetric derivatives. Limitations and side reactions by use of 1 in the above synthesis are discussed. Acid-base properties, pH-dependent solubility in water/hexane, and substitution reactions at oxygen and phosphorus of selected representatives of 5 are reported. An example for the separation of enantiomers by esterification with (1S)-()-camphanic acid chloride is given. IR studies revealed intramolecular

  C，O-二锂试剂1（M = M'= Li）或C，O-锂钠试剂1（M = Li，M'= Na）与氯膦的反应生成C，O-二取代产物2或膦基酚盐3其随后用ClSiMe 3处理，得到4-甲基-和大体积的4，6-二叔丁基取代的邻-膦酰基苯酚甲硅烷基醚4。这些被用于制备相应的邻膦基苯酚5，主要是P-不对称衍生物。使用1的局限性和副反应在上面的合成中进行了讨论。报告了酸碱性质，pH依赖于水/己烷的溶解度以及5个选定代表的在氧和磷处的取代反应。给出了通过用（1S）-（）-樟脑酰氯进行酯化来分离对映异构体的实例。红外研究表明分子内的PHO键和2 J（PC）在溶液中苯氧基的首选反式排列。在固态下，通过X射线结构分析检测分子间和分子内PHO键。该反式苯氧基的排列被保留。由于位阻，O取代基向磷原子倾斜，因此产生较大的贯穿空间耦合常数。然而，在庞大的取代的OSnMe 3部分8h中，PSn距离为336.9 pm