(1,3-dithian-2-yl)diphenylphosphine | 135139-10-5

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 二噻烷
• 英文名称: (1,3-dithian-2-yl)diphenylphosphine
• 英文别名: 2-(Diphenylphosphinyl)-1,3-dithiane；1,3-Dithian-2-yldiphenylphosphine；1,3-dithian-2-yl(diphenyl)phosphane
• CAS: 135139-10-5
• 化学式: C₁₆H₁₇PS₂
• 分子量: 304.417
• InChiKey: KUKMOCDDDFINQM-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.7
• 重原子数：
  19
• 可旋转键数：
  3
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.25
• 拓扑面积：
  50.6
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  (1,3-dithian-2-yl)diphenylphosphine 在 正丁基锂 、 重水 、 氧气 作用下， 以 四氢呋喃 为溶剂， 反应 1.5h， 生成 2-deuterio-2-diphenylphosphoryl-1,3-dithiane
  参考文献：
  名称：

  2-二苯基膦酰基-和2-二苯基硫代膦酰基-2- [1,3]二噻吩基锂作为试剂的相对反应性

  摘要：

  研究了标题碳负离子与几种醛和酮的反应，得到相应的烯酮二硫缩酮。发现P ＝ O有机锂试剂与两种类型的羰基底物均以良好至优异的产率反应。另一方面，尽管收率很低，PS试剂选择性地与醛反应。此对比行为不能归因于后者负碳离子的更大的稳定性，因为一个ΔpK一个测量显示，更稳定的有机锂（0.33±O.O8一个的pK一个单位）也更具反应性。P ＝ S类似物的较低反应性可以用氧杂磷杂环丁烷中间体形成中的动力学抑制和/或该五配位磷物质以硫（相对于氧气）作为配体的热力学不稳定性来解释。

  DOI：

  10.1016/s0040-4020(01)87612-2
• 作为产物：
  描述：

  isopropyl diphenylphosphinite 在 N-氯代丁二酰亚胺 、 tetraphosphorus decasulfide 、 N,N-二乙基苯胺 、 三(二甲胺基)膦 作用下， 以 二氯甲烷 、 苯 为溶剂， 反应 19.66h， 生成 (1,3-dithian-2-yl)diphenylphosphine
  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

文献信息

• Synthesis and Conformational Behavior of 2-Phosphonio- and 2-Phosphinyl-1,3-dithianes. Operation of the Generalized Anomeric Effect in the S-C-P+ System
  作者：Marian Mikolajczyk、Piotr P. Graczyk

  DOI：10.1021/jo00121a043

  日期：1995.8

  A stereoselective preparation of various 2-phosphinyl- and 2-phosphonio-1,3-dithianes by desulfurization of the appropriate 2-thiophosphoryl-1,3-dithianes was described. The structure of the title compounds was studied by means of H-1, C-13, and P-31 NMR methods. Configurational assignments were also based on chemical correlation and X-ray structure determination. Both the NMR studies of conformationally labile models and equilibration of diastereomeric compounds showed an increased preference of the phosphinyl and phosphonium groups for the axial orientation. Magnitude of the anomeric effect found varies in the range from ca. 6 kJ/mol in phosphines to more than 10 kJ/mol in phosphonium salts. The anomeric effect could stem from the n(s)-sigma*(c-p) hyperconjugative interaction. If phenyl groups are connected with phosphorus, overlap repulsion involving lone electron pairs of the endocyclic sulfur atoms and pi-electrons of phenyl rings should also be taken into account. The reverse anomeric effect was not observed. No manifestation of the exo anomeric effect in 2-phosphinyl-1,3-dithianes was found.
• Sulfur-carbon phosphorus anomeric interactions. 9. Effect of the coordination at phosphorus in the conformational equilibria of 2-P-substituted-1,3-dithianes
  作者：Eusebio Juaristi、Miguel A. Aguilar

  DOI：10.1021/jo00020a039

  日期：1991.9

  The conformational energies (A values) of the (diphenylphosphinyl)borane and diphenylphosphinyl groups were determined by multinuclear (H-1, C-13, P-31) NMR analysis of mobile (cis-4-phenylcyclohexyl)diphenylphosphine-borane, as well as the corresponding phosphine, and conformationally fixed models. The equatorial preferences observed are -DELTA-G-degrees(P(BH3)Ph2) = 3.3 kcal/mol and -DELTA-G-degrees(PPh2) = 1.8 kcal/mol. The conformational preference of these groups in the 1,3-dithian-2-yl ring were also determined by NMR analysis: -0.1 and -0.3 kcal/mol, respectively. The slight predominance of the equatorial isomers reflects nonetheless the influence of substantial S-C-P(BH3) and S-C-P: anomeric interactions, worth 1.8 and 1.0 kcal/mol, respectively. Evaluation of these values, together with previous data obtained for S-C-P(O) and S-C-P(S) systems, supports the participation of endo and exo hyperconjugative interactions, although the participation of 3p-3d electron donation among the sulfur and phosphorus atoms could also account for the results. Alternative rationalizations that have been considered to account for the strong S-C-P(O) anomeric effect appear now to play a minor role in the conformational equilibria of 2-P-substituted 1,3-dithianes.
• Conformational Preference in 1,3-Dithianes Containing 2-Phosphoryl, -(thiophosphoryl), and -(selenophosphoryl) groups. Chemical and Crystallographic Implications of the Nature of the Anomeric Effect
  作者：Marian Mikolajczyk、Piotr P. Graczyk、Michal W. Wieczorek

  DOI：10.1021/jo00086a016

  日期：1994.4

  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.
• Relative reactivity of 2-diphenylphosphinoyl- and 2-diphenyl-thiophosphinoyl-2-[1,3]dithianyllithium as reagents wittig-horner/corey-seebach
  作者：Eusebio Juaristi、Barbara Gordillo、Lucia Valle

  DOI：10.1016/s0040-4020(01)87612-2

  日期：1986.1

  The reaction of the title carbanions with several aldehydes and ketones to afford the corresponding ketene dithioketals was studied. It was found that the PO organolithium reagent reacted with both types of carbonyl substrates in good to excellent yields. On the other hand, the PS reagent reacted selectively with aldehydes although in poor yield. This contrasting behavior can not be ascribed to a

  研究了标题碳负离子与几种醛和酮的反应，得到相应的烯酮二硫缩酮。发现P ＝ O有机锂试剂与两种类型的羰基底物均以良好至优异的产率反应。另一方面，尽管收率很低，PS试剂选择性地与醛反应。此对比行为不能归因于后者负碳离子的更大的稳定性，因为一个ΔpK一个测量显示，更稳定的有机锂（0.33±O.O8一个的pK一个单位）也更具反应性。P ＝ S类似物的较低反应性可以用氧杂磷杂环丁烷中间体形成中的动力学抑制和/或该五配位磷物质以硫（相对于氧气）作为配体的热力学不稳定性来解释。