triphenylphosphorane | 133528-11-7

• 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: triphenylphosphorane
• 英文别名: [bis(4-fluorophenyl)methylene]triphenylphosphorane；Bis(4-fluorophenyl)methylidene-triphenyl-lambda5-phosphane；bis(4-fluorophenyl)methylidene-triphenyl-λ5-phosphane
• CAS: 133528-11-7
• 化学式: C₃₁H₂₃F₂P
• 分子量: 464.494
• InChiKey: LNSRFNSRCMURFJ-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  7.4
• 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：
  2

反应信息

• 作为反应物：
  描述：

  triphenylphosphorane 在 sulfur 作用下， 以 甲苯 为溶剂， 生成 4,4'-difluorothiobenzophenone
  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：

  氯代双(4-氟苯基甲烷) 在 sodium amide 作用下， 以 四氢呋喃 、 甲苯 为溶剂， 反应 42.0h， 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。
• 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
• 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.
• 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：——
• Okuma Kentaro, Kojima Kazuki, Kaneko Isao, Tsujimoto Yoshikazu, Ohta Hiro+, J. Chem. Soc. Perkin Trans. 1, (1994) N 15, S 2151-2159
  作者：Okuma Kentaro, Kojima Kazuki, Kaneko Isao, Tsujimoto Yoshikazu, Ohta Hiro+

  DOI：——

  日期：——

表征谱图