(diphenylthiophosphinoyl)acetonitrile | 69039-10-7

• 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: (diphenylthiophosphinoyl)acetonitrile
• 英文别名: (diphenylthiophosphoryl)acetonitrile；diphenylphosphinothioylacetonitrile；diphenylthiophosphorylacetonitrile；thiophosphorylacetonitrile；Diphenyl-acetonitril-phosphinsulfid；Acetonitrile, (diphenylphosphinothioyl)-；2-diphenylphosphinothioylacetonitrile
• CAS: 69039-10-7
• 化学式: C₁₄H₁₂NPS
• 分子量: 257.296
• InChiKey: DZFGWKIOBXKODU-UHFFFAOYSA-N

物化性质

• 熔点：
  50.0-50.2 °C
• 沸点：
  149-151 °C(Press: 0.25 Torr)
• 密度：
  1.2033 g/cm3(Temp: 25 °C)

计算性质

• 辛醇/水分配系数(LogP)：
  4
• 重原子数：
  17
• 可旋转键数：
  3
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.07
• 拓扑面积：
  55.9
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  (diphenylthiophosphinoyl)acetonitrile 在 二硫代磷酸-O,O-二(1-甲基乙基)酯 作用下， 以 甲醇 为溶剂， 反应 168.0h， 以61%的产率得到2-(diphenylthiophosphoryl)ethanethioamide
  参考文献：
  名称：

  Factors Determining the Stereochemical Structure of 2-(Phosphorus Substituted) Methylidene-thiazolidine- 4-ones in Solid State and in Solution

  摘要：

  Regioselective synthesis of novel 2-(phosphorus substituted) methylidene-thiazolidine-4-ones 5a-c was performed via condensation of phosphorus-substituted acetic acid thioamides 4a-c with dimethyl acetylenedicarboxylate. Thiazolidine-4-ones 5a,b bearing thiophosphoryl or dithiophosphoryl moiety were obtained as E,Z-isomers while their analog 5c with triphenylphosphonium group was formed as a Z,Z-isomer. The structures of thiazolidin-4-ones 5a-c obtained were determined by single crystal X-ray diffraction. According to quantum-chemical calculations, the isomers observed in the solid state are thermodynamically more stable. In solution, thio- and dithiophosphorylated thiazolidinones 5a, b undergo E,Z Z,Z isomerization relative to C2 carbon atom of the heterocycle proceeding via an imine-enamine mechanism.

  DOI：

  10.1080/10426500802715544
• 作为产物：
  描述：

  (二苯基磷酰)乙腈 在 劳森试剂 作用下， 以 甲苯 为溶剂， 反应 8.0h， 以76%的产率得到(diphenylthiophosphinoyl)acetonitrile
  参考文献：
  名称：

  Odinets; Artyushin; Kalyanova, Russian Journal of General Chemistry, 1996, vol. 66, # 1, p. 43 - 53

  摘要：

  DOI：

文献信息

• Reactions of phosphoryl- and thiophosphorylacetonitriles with poly(bromomethyl)arenes containing closely-spaced bromomethyl groups. New types of phosphorus-substituted fused systems
  作者：I. L. Odinets、O. I. Artyushin、G. V. Bodrin、M. P. Passechnik、K. A. Lyssenko、I. V. Fedyanin、P. V. Petrovskii、T. A. Mastryukova

  DOI：10.1007/s11172-005-0317-1

  日期：2005.3

  closely-spaced bromomethyl groups under conditions of phase-transfer catalysis occur as cycloalkylation to form new types of fused systems, in which aromatic rings are annelated with a five-, six-, or seven-membered ring containing the exocyclic phosphorus containing and cyano substituents. The reaction pathway is independent of the reagent ratio. Under the same conditions, the reaction with 1,3,5-tris(bromomethyl)-2

  在相转移催化条件下，磷酰基和硫代磷酰基乙腈与含有紧密间隔的溴甲基的聚（溴甲基）芳烃的反应以环烷基化的形式发生，形成新型稠合系统，其中芳环与五、六- ，或含有环外含磷和氰基取代基的七元环。反应途径与试剂比例无关。在相同条件下，与 1,3,5-三(溴甲基)-2,4,6-的反应三甲苯在起始底物的所有亲电子基团上提供单烷基化产物。在所得化合物中，磷原子上的烷氧基很容易通过相应的甲硅烷基醚转化为羟基，得到相应的磷酸，而氰基是化学惰性的。
• Diastereoselective cycloalkylation of phosphoryl and thiophosphoryl acetonitriles by α,ψ-dihalogenalkanes under phase transfer catalysis conditions
  作者：I. L. Odinets、N. M. Vinogradova、K. A. Lyssenko、P. V. Petrovskii、T. A. Mastryukova、G-V. Röschenthaler

  DOI：10.1002/hc.20186

  日期：——

  Cycloalkylation of phosphoryl and thiophosphoryl acetonitriles 2 by α,ψ-dihalogenalkanes was found to proceed diastereoselectively under phase transfer catalytic conditions yielding 1-(phosphoryl)-2-methyl-cycloalkane carbonitriles as trans-isomers with identical configuration of asymmetric cyclic carbon atoms (RC* RC*). In the case of additional asymmetric phosphorus atom in the starting substrate

  发现 α,ψ-二卤代烷烃对磷酰基和硫代磷酰基乙腈 2 的环烷基化在相转移催化条件下非对映选择性地进行，产生 1-（磷酰基）-2-甲基-环烷烃腈作为反式异构体，具有相同的不对称环碳原子构型（RC * RC*）。在起始底物中额外的不对称磷原子的情况下，反式异构体形成为磷原子构型不同的非对映异构体的混合物（SP* RC* RC* 和 RP* RC* RC*）。© 2006 Wiley Periodicals, Inc. 杂原子化学 17:13–21, 2006; 在线发表于 Wiley InterScience (www.interscience.wiley.com)。DOI 10.1002/hc.20186
• Intramolecular cyclization of ?-haloalkylsubstituted thiophosphorylacetonitriles: Synthesis and stereochemistry of 3-cyano-2-oxo-1,2-thiaphosphacyclanes
  作者：Irene L. Odinets、Natalya M. Vinogradova、Konstantin A. Lyssenko、Michail Yu. Antipin、Pavel V. Petrovskii、Tatyana A. Mastryukova

  DOI：10.1002/hc.1101

  日期：——

  Intramolecular S-alkylation in a series of ω-haloalkyl-substituted thiophosphorylacetonitriles 5–7 presents an effective synthetic route to the hitherto unknown 3-cyano-2-oxo-1,2-thiaphospholanes 14 and thiaphosphinanes 15. The compounds were obtained as a mixture of cis- and trans-isomers that were resolved to individual stereoisomers in most cases. For some of them, X-ray diffraction analysis has

  一系列 ω-卤代烷基取代的硫代磷酰乙腈 5-7 中的分子内 S-烷基化为迄今为止未知的 3-氰基-2-氧代-1,2-硫代磷烷 14 和硫代膦烷 15 提供了一种有效的合成途径。顺式和反式异构体的混合物，在大多数情况下分解为单个立体异构体。对于其中一些，已经进行了 X 射线衍射分析。结果表明，31P NMR 光谱可用于确定 3-cyano-2-oxo-1,2-thiaphosphacyclanes 的立体化学。© 2002 John Wiley & Sons, Inc. 杂原子化学 13:1–21, 2002; DOI 10.1002/hc.1101
• Selective monoalkylation of phosphorus-substituted CH acids with (bromomethyl)- and 1,4-bis(bromomethyl)benzenes
  作者：I. L. Odinets、O. I. Artyushin、S. V. Lenevich、G. V. Bodrin、K. A. Lyssenko、I. V. Fedyanin、P. V. Petrovskii、T. A. Mastryukova

  DOI：10.1023/b:rucb.0000024852.47670.5d

  日期：2004.1

  C-Alkylation of phosphorus-substituted CH acids with various substituted (bromomethyl)arenes under phase transfer catalysis conditions (K2CO3/MeCN) proceeds with high selectivity (75-100%) as monoalkylation.
• ——
  作者：I. L. Odinets

  DOI：10.1023/a:1023906822755

  日期：——

  Under conditions of the phase transfer catalysis, acylation of (thio)phosphorylacetonitriles by (het)aroyl chlorides affords the Z-enol forms of C-acylation products in high yields. Their configurations were studied by IR spectroscopy, dipole moment measurements, and ab initio quantum-chemical calculations [B3LYP/6-31G(d)]. The C=C double bond and the phosphoryl or thiophosphoryl group have an s-cis arrangement. The possibility of strong intramolecular hydrogen bonding in these conformers is the governing factor responsible for the three-dimensional structures of the compounds under investigation. Derivatives of nicotinic acid existing in the individual form as zwitterions are the only exceptions.