3,5-di-tert-butyl-1-thia-2,4-diphosphole | 151961-31-8

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 杂芳族化合物
• 英文名称: 3,5-di-tert-butyl-1-thia-2,4-diphosphole
• 英文别名: 3,5-di-tert-butyl-1,2,4-thiadiphosphole；1,2,4-Thiadiphosphole, 3,5-bis(1,1-dimethylethyl)-；3,5-ditert-butyl-1,2,4-thiadiphosphole
• CAS: 151961-31-8
• 化学式: C₁₀H₁₈P₂S
• 分子量: 232.266
• InChiKey: KXFNBJDDFKODHB-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.3
• 重原子数：
  13
• 可旋转键数：
  2
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.8
• 拓扑面积：
  25.3
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  2,2-二甲基丙基次基膦 、 3,5-di-tert-butyl-1-thia-2,4-diphosphole 以 甲苯 为溶剂， 反应 8.0h， 以0.35 g的产率得到2,3,6,9-Tetratert-butyl-5-thia-1,4,7,8-tetraphosphatetracyclo[4.3.0.02,4.03,7]non-8-ene
  参考文献：
  名称：

  Chemistry and ligating properties of the 1,2,4-thiadiphosphole P2SC2But2

  摘要：

  New synthetic routes to the 1,2,4- and 1,3,4-thiadiphospholes, P2SC2Bu'(2), are presented. Both eta(1)-W(CO)(5) and eta(5)-M(CO)(3) complexes (M = Mo, W) of the 1,2,4-thiadiphosphole ring are described and the molecular structure of the former determined by a single crystal X-ray study is in good agreement with theoretical calculations. The thermal conversion of the eta(1)-M(CO)(5) complex to the eta(5)-M(CO)(3) complex is attributable to the entropy change in the reaction. A sequence of [4+2] and [2+2+2] cyclo-addition reactions of the 1,2,4-thiadiphosphole, P2SC2Bu'(2), with the phosphaalkyne, P=CBu' affords the tetracyclic cage compound P4SC4Bu'(4) which has also been structurally characterised. (C) 2002 Published by Elsevier Science B.V.

  DOI：

  10.1016/s0022-328x(02)01397-9
• 作为产物：
  描述：

  2,2-二甲基丙基次基膦 在 1,2,3,4,5,6,7,8-八硫杂环辛烷 、 tantalum thiochloride 、 三苯基膦 作用下， 以 甲苯 、 正戊烷 为溶剂， 反应 20.0h， 以66%的产率得到3,5-di-tert-butyl-1-thia-2,4-diphosphole
  参考文献：
  名称：

  1,2,4-噻二唑和功能化的1,2-噻唑的新方法

  摘要：

  磷炔1在硫代钽（V）化合物2的存在下发生区域特异性反应，得到1,2,4-噻二磷3。这些化合物可以如η功能既1和η 5个配位体络合物中与基团的6族金属。[4 + 2]环加成反应仅在以磷炔烃或高反应性乙炔为反应伙伴的情况下发生。这些反应一方面提供了官能化的1，2-硫代磷腈17，另一方面提供了δ-环烷酮23和11。后者随后会发生值得注意的反应。在合成1,2-噻唑的过程中17也可以分离出痕量的四环笼化合物18和19。

  DOI：

  10.1002/1099-0690(200205)2002:10<1664::aid-ejoc1664>3.0.co;2-s

文献信息

• Darstellung und Eigenschaften von und Reaktionen mit metallhaltigen Heterocyclen
  作者：Ekkehard Lindner、Tilman Schlenker、Cornelius Haase

  DOI：10.1016/0022-328x(94)87029-2

  日期：1994.1

  3,5-Di-tert-butyl-1-thia-2,4-diphosphole (3) has been formed by insertion of tBuCP (2) into the P?S bond of the (η2- thiophosphinito)cobalt complex (OC)2Ph3PCo(η2-PEt2?S) (1), followed by [2+2] cycloaddition of the resulting intermediate (OC) 2Ph3P with a second phosphaalkyne 2 and elimination of the (OC)2Ph3PCoPEt 2 fragment.

  3,5-二叔丁基-1-硫杂-2,4- diphosphole（3）已被插入形成吨BuCP（2）到P的（η的S键？2 - thiophosphinito）钴络合物（OC）2博士3 PCO（η 2 -PET 2？S）（1），然后按[2 + 2]得到的中间体（OC）的环加成2博士3 P与第二phosphaalkyne 2和消除（ OC）2 Ph 3 PCoPEt 2片段。
• Novel Diphosphetene Derivatives by Reactions of Di(isopropyl)aminophosphaethyne with Chalcogens or Halogens
  作者：Joseph Grobe、Duc Le Van、Torsten Pohlmeyer、Franz Immel、Heike Pucknat、Bernt Krebs、Joachim Kuchinke、Mechtild Läge

  DOI：10.1016/s0040-4020(99)00769-3

  日期：2000.1

  The 1 lambda(3)sigma(2),3 lambda(5)sigma(4)-diphosphetene derivatives 6a, 6b are formed in quantitative yields by reactions of di(isopropyl)aminophosphaethyne 1a with sulphur and selenium, respectively, at 25 degrees C. 6a is also produced slowly from 1a and CS2. The tert-butylphosphaalkyne P=C-tBu (1b), however, does not react with sulphur or selenium, but undergoes a slow reaction with CS2 to give the five-membered heterocycle 3,5-di-tert-butyl-1-thia-2,4-diphosphole as one of the main products. Halogenation of 1a using SO2Cl2, Br-2 or I-2 as reagents leads to the 1 lambda(3)sigma(2),3 lambda(3)sigma(3)-diphosphetenium salts 9a-9c. X-ray diffraction studies of 6a and 6b prove that the easy formation of the four-membered diphospha-heterocycles is obviously governed by electronically delocalized phosphaallyl units within the unsaturated rings. (C) 1999 Elsevier Science Ltd. All rights reserved.
• Syntheses and Theoretical and Mechanistic Aspects of 1-Thia-2,4- and 1-Thia-3,4-diphosphole Formed from CS₂ and ^tBuCP and Crystal and Molecular Structure of the First 1-Thia-3,4-diphosphole Complex:  cis-[{PtCl₂(PEt₃)}₂(P₂SC₂^tBu₂)]
  作者：Sarah E. d'Arbeloff-Wilson、Peter B. Hitchcock、Steffen Krill、John F. Nixon、László Nyulászi、Manfred Regitz

  DOI：10.1021/ja992325p

  日期：2000.5.1

  The reaction of (BuCP)-Bu-1 with CS2 (or its ylide type complexes such as R3PCS2 (R = Et, Ph, cyclohexyl), (C5H10N)(2)CCS2, or (C4H8NO)(2)CCS2) gives a mixture of 3,5-di-tert-butyl-1-thia-2,4-diphosphole and 2,5-di-tert-butyl-1-thia-3,4-diphosphole, which were characterized by NMR spectroscopy. The latter was also characterized by the single-crystal X-ray structure determination of its bis(platinum(II)) complex [(PtCl2PEt3)(2)(mu-(P2SC2Bu2)-Bu-t)] This is the first structural characterization of a 1-thia-3,4-diphosphole ring. The mechanism of these reactions was explored by B3LTP/6-311+G** level quantum chemical calculations. The reaction pathway involves a phosphadithiolediylcarbene and its diphosphatetrathiafulvalene dimer as intermediates. Several other possible reaction pathways were ruled out.
• Lindner, Ekkehard; Haase, Cornelius; Mayer, Hermann A., Angewandte Chemie, 1993, vol. 105, # 10, p. 1521 - 1523
  作者：Lindner, Ekkehard、Haase, Cornelius、Mayer, Hermann A.、Kemmler, Martin、Fawzi, Riad、Steimann, Manfred

  DOI：——

  日期：——
• Synthetic, structural and theoretical studies on the new 2,3-dihydro-1,2,4-thia-, selena- and tellura-diphospholes, P2EC2But2(H)Me, (E=S, Se, Te) and their [M(CO)5] complexes (M=Cr, Mo, W)
  作者：Monte L. Helm、Peter B. Hitchcock、John F. Nixon、László Nyulászi、Dénes Szieberth

  DOI：10.1016/s0022-328x(02)01706-0

  日期：2002.10

  Methylation of the 1,2,4-thia-, selena- and tellura-diphospholes P2EC2Bu2' (E = S, Se, Te) with MeLi, followed by protonation 2 with HCl, affords the new 2,3-dihydro-1,2,4-thia-, selena- and tellura-diphospholes. Further treatment with [M(CO)(5)(THF)] (M = Cr, Mo, W) yields the corresponding eta(1)-metal pentacarbonyl complexes, of which [M(CO)(5)eta(1)-P2EC2Bu2'(H)Me}], (E = S, M = W; E = Se, M = Cr, M = Mo, M = W) have been structurally characterised by single crystal X-ray diffraction studies. Theoretical calculations carried out on the different isomers of the 2,3-dihydro-1,2,4-thia-, selena- and tellura-diphospholes. and the 2,3-dihydro-1H-1,2,4-triphosphole are also presented and discussed. (C) 2002 Elsevier Science B.V. All rights reserved.