[Bis-(4-chloro-phenyl)-methylene]-triphenyl-λ⁵-phosphane | 133528-12-8

• 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: [Bis-(4-chloro-phenyl)-methylene]-triphenyl-λ⁵-phosphane
• 英文别名: Bis(4-chlorophenyl)methylidene-triphenyl-lambda5-phosphane；bis(4-chlorophenyl)methylidene-triphenyl-λ5-phosphane
• CAS: 133528-12-8
• 化学式: C₃₁H₂₃Cl₂P
• 分子量: 497.403
• InChiKey: LRZAXAMNEOIZCY-UHFFFAOYSA-N

物化性质

• 沸点：
  626.1±65.0 °C(Predicted)
• 密度：
  1.28±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  8.5
• 重原子数：
  34
• 可旋转键数：
  5
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.0
• 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：

  [Bis-(4-chloro-phenyl)-methylene]-triphenyl-λ⁵-phosphane 在 sulfur 作用下， 以 甲苯 为溶剂， 25.0~75.0 ℃ 、1200.0 MPa 条件下， 反应 72.0h， 生成 1-氯-4-[1,2,2-三(4-氯苯基)乙烯基]苯
  参考文献：
  名称：

  Stereochemistry of the [4 + 2] Cycloaddition of Diarylselenoketones with Conjugated Dienes

  摘要：

  The ylides Ph(3)P=(CArAr2)-Ar-1 1a-g (Ar C6H5, p-C6H4Cl p-C6H4F, m-C6H4CF3, P-C(6)H4OCH(3), p-C6H4CH3) were treated with elemental selenium (similar to 80 degrees C) to give the corresponding selenoketones Se=CAr(1)Ar2 2 by Staudinger-chalcogenation. Their reaction with trans,trans-2,4-hexadiene proceeds completely stereospecifically to yield the 2,2-diaryl-3,6-dihydro-cis-3,6-dimethyl-2H-selenapyrans 3. In contrast, the reactions of the selenoketones 2 with cis, trans-2,4-hexadiene proceeds stereoselectively, also giving the dihydro-cis-dimethyl-2H-selenapyrans 3 as the major products, now admired with small amounts of the dihydro-trans-dimethyl-2H-selenapyran isomers 4. The [4 + 2] cydoaddition of 2 with cis,trans-2,4-hexadiene proceeds stereospecifically, however, when carried out at a pressure of 12 kbar, now yielding 4 as the major products along with the corresponding tetraarylethenes 8. Along with the results of additional mechanistic studies (determination of solvent and substituent effects) it can be concluded that diarylselenoketones are likely to react by means of a concerted [4 + 2] cycloaddition with very reactive conjugated dienes (such as trans,trans-2,4-hexadiene), whereas a stepwise mechanism, resulting in diene cis/trans-isomerization with subsequent mechanistic ''leakage'' to the concerted pathway, appears to be preferred when a much less reactive conjugated diene such as cis,trans-2,4-hexadiene is employed. The reaction of the corresponding diarylthioketones 5a-g with trans,trans- and cis,trans-2,4-hexadiene, respectively, shows an analogous behavior.

  DOI：

  10.1021/ja00149a015
• 作为产物：
  描述：

  1-[bromo(4-chlorophenyl)methyl]-4-chlorobenzene 在 sodium ethanolate 作用下， 以 苯 为溶剂， 生成 [Bis-(4-chloro-phenyl)-methylene]-triphenyl-λ⁵-phosphane
  参考文献：
  名称：

  亚烷基三苯基正膦与硫的反应

  摘要：

  二芳基亚甲基三苯基膦与硫的反应以良好的产率得到噻吩二苯酮和硫化三苯基膦。亚苄基三苯基膦与硫的反应得到三苯基硫化膦和 5,7-二苯基-1,2,3,4,6-五硫杂环庚烷。更活泼的亚烷基三苯基正膦如异丙叉或仲亚丁基三苯基正膦产生相应的含硫原子的鏻甜菜碱或通过甜菜碱的空气氧化和水解产生的鏻盐。α-苯甲酰基苄叉三苯基正膦不与硫反应。简要讨论了亚烷基正膦对硫的反应性。

  DOI：

  10.1246/bcsj.45.506

文献信息

• Generation of Thiosulfines by Dithiation of Diarylmethylenetriphenylphosphoranes
  作者：Kentaro Okuma、Masashi Shimasaki、Kazuki Kojima、Hiroshi Ohta、Renji Okazaki

  DOI：10.1246/cl.1993.1599

  日期：1993.9

  Reaction of phosphonium ylides with excess sulfur afforded the corresponding thiosulfines, which were trapped with maleic anhydride to give the corresponding cycloadducts (1,2-dithiolanes) in good yields. Intermediary thiosulfines were also formed by sulfurization of thiobenzophenones with elemental sulfur to give the 1,2-dithiolanes in moderate yields.

  磷阳离子与过量硫反应生成相应的硫代亚磺酸盐，这些硫代亚磺酸盐与马来酸酐反应生成相应的环加成物（1,2-二噁烷）且收率良好。通过与元素硫反应使硫苯基酮硫化，同样也形成了中间体硫代亚磺酸盐，从而以中等收率得到1,2-二噁烷。
• An Efficient Synthesis of 1,2-Dithiolanes and 1,2,4-Trithiolanes by the Reaction of Phosphorus Ylides with Elemental Sulfur
  作者：Kentaro Okuma、Kazuki Kojima、Shinji Shibata

  DOI：10.3987/com-00-9057

  日期：——

  Reaction of diaryl methylenetriphenylphosphoranes wi th elemental sulfur followed by the addition of maleic anhydride afforded 1,2-dithiolanes in good yields. When the reaction was carried out in the presence of adamantane-2-thione, two types of 1,2,4-trithiolane were formed. Thiation of thiobenzophenones with elemental sulfur also afforded the corresponding 1,2-dithiolanes.
• Regioselective Synthesis of Bicyclic Diselenides by the Reaction of Phosphonium Ylides with Elemental Selenium
  作者：Kentaro Okuma、Isao Kaneko、Hiroshi Ohta、Yoshinobu Yokomori

  DOI：10.3987/com-90-5598

  日期：——

  Selenabicyclo[2.2.1]heptenes reacted with elemental selenium to produce unusual bicyclic diselenides in 30-40% yield. The reaction of phosphonium ylides with excess of elemental selenium also afforded bicyclic diselenides in good yields. The reactions might proceed via biradical intermediates.
• Hock, Regina; Hillenbrand, Stefanie; Erker, Gerhard, Chemische Berichte, 1993, vol. 126, # 8, p. 1895 - 1904
  作者：Hock, Regina、Hillenbrand, Stefanie、Erker, Gerhard、Krueger, Carl、Werner, Stefan

  DOI：——

  日期：——
• Okuma, Kentaro; Kojima, Kazuki; Kaneko, Isao, Journal of the Chemical Society. Perkin transactions I, 1994, # 15, p. 2151 - 2160
  作者：Okuma, Kentaro、Kojima, Kazuki、Kaneko, Isao、Tsujimoto, Yoshikazu、Ohta, Hiroshi、Yokomori, Yoshinobu

  DOI：——

  日期：——