triphenylphosphorane | 153785-57-0

• 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: triphenylphosphorane
• 英文别名: [bis(4-methoxyphenyl)methylene]triphenylphosphorane；Bis(4-methoxyphenyl)methylidene-triphenyl-lambda5-phosphane；bis(4-methoxyphenyl)methylidene-triphenyl-λ5-phosphane
• CAS: 153785-57-0
• 化学式: C₃₃H₂₉O₂P
• 分子量: 488.566
• InChiKey: RSPJXSUBEYZFQE-UHFFFAOYSA-N

物化性质

• 沸点：
  641.5±65.0 °C(Predicted)
• 密度：
  1.19±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  7.2
• 重原子数：
  36
• 可旋转键数：
  7
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.06
• 拓扑面积：
  18.5
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  triphenylphosphorane 在 Woollins 试剂 作用下， 以 甲苯 为溶剂， 反应 1.0h， 以100%的产率得到1,1,2,2-四(4-甲氧基苯基)乙烯
  参考文献：
  名称：

  通过还原偶联反应立体选择性地合成烯烃。

  摘要：

  酮和醛通过与2,4-双（苯基）-1,3-二硒二氮杂环戊烷-2,4-二硒化物（PhPSe（2））（2）反应而转化为对称和（E）-烯烃（1-15） ，伍林斯的试剂，在回流的甲苯中；PhC（O）CH（2）C（O）Ph的反应证明了二酮的使用，该化合物以1,83％的产率得到1,2,4,5-四苯基苯（16）。

  DOI：

  10.1039/b702818k
• 作为产物：
  描述：

  二甲氧基苯甲醇 在 sodium amide 作用下， 以 四氢呋喃 、 二氯甲烷 、 甲苯 为溶剂， 反应 16.0h， 生成 triphenylphosphorane
  参考文献：
  名称：

  Hock, Regina; Hillenbrand, Stefanie; Erker, Gerhard, Chemische Berichte, 1993, vol. 126, # 8, p. 1895 - 1904

  摘要：

  DOI：

文献信息

• Metal-Free Hydrogenation of Electron-Poor Allenes and Alkenes
  作者：Blanca Inés、David Palomas、Sigrid Holle、Sebastian Steinberg、Juan A. Nicasio、Manuel Alcarazo

  DOI：10.1002/anie.201205348

  日期：2012.12.3

  The poorer, the better: A metal‐free catalytic procedure for the reduction of electron‐poor allenes and alkenes has been developed. The method employs a frustrated Lewis pair based catalyst. 1,4‐Diazabicyclo[2.2.2]octane (DABCO)/B(C6F5)3 was shown to be the best combination in optimization studies.

  越差越好：已开发出一种用于减少电子贫乏的烯和烯烃的无金属催化方法。该方法使用沮丧的路易斯对基催化剂。1,4-二氮杂双环[2.2.2]辛烷（DABCO）/ B（C 6 F 5）3被证明是优化研究的最佳组合。
• 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。
• A novel reaction of selenobenzophenones with tetracyanoethylene. Formation of a 2,3-dihydroselenophene
  作者：Kentaro Okuma、Kei-ichiro Miyazaki、Seiji Okumura、Yoshikazu Tsujimoto、Kazuki Kojima、Hiroshi Ohta、Yoshinobu Yokomori

  DOI：10.1016/0040-4039(95)01881-h

  日期：1995.11

  The reaction of selenobenzophenones with tetracyanoethylene (TCNE) exclusively affords an unusual type of adduct with the structure of 2,3-dihydroselenophene, sharply different from the reaction between thiobenzophenone and TCNE

  硒代二苯甲酮与四氰基乙烯（TCNE）的反应专门提供了一种异常类型的加合物，其结构为2,3-二氢硒吩苯，与硫代二苯甲酮与TCNE的反应明显不同
• Novel Reaction of Selenobenzophenones with Alkyllithiums Leading to Symmetrical Olefins
  作者：Kentaro Okuma、Gen Koda、Seiji Okumura、Atsuyoshi Ohno

  DOI：10.1246/cl.1996.609

  日期：1996.8

  The reaction of selenobenzophenones with alkyllithiums or Grignard Reagents exclusively affords symmetrical tetraarylethylenes as selenophilic products. The reaction might proceed through episelenide (selenirane) intermediates.

  硒代二苯甲酮与烷基锂或格氏试剂的反应专门提供对称的四芳基乙烯作为亲硒产物。该反应可能通过表硒化物（硒烷）中间体进行。
• Stereochemistry of the [4 + 2] Cycloaddition of Diarylselenoketones with Conjugated Dienes
  作者：Stefanie Wilker、Gerhard Erker

  DOI：10.1021/ja00149a015

  日期：1995.11

  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.

表征谱图