triphenyl(phenylethynyl)phosphonium bromide | 34387-64-9

• 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: triphenyl(phenylethynyl)phosphonium bromide
• 英文别名: (phenylethynyl)triphenylphosphonium bromide；triphenyl(2-phenylethynyl)phosphanium;bromide
• CAS: 34387-64-9
• 化学式: Br*C₂₆H₂₀P
• 分子量: 443.323
• InChiKey: QVTSWQFDFUAKJQ-UHFFFAOYSA-M

计算性质

• 辛醇/水分配系数(LogP)：
  1.99
• 重原子数：
  28
• 可旋转键数：
  5
• 环数：
  4.0
• 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：
  1

反应信息

• 作为反应物：
  描述：

  triphenyl(phenylethynyl)phosphonium bromide 在 sodium ethanolate 、 肼 作用下， 以 乙醇 、 乙腈 为溶剂， 反应 19.5h， 生成 N-[(E)-1,3-Diphenyl-prop-2-en-(E)-ylidene]-N'-[(E)-3-phenyl-prop-2-en-(Z)-ylidene]-hydrazine
  参考文献：
  名称：

  Cyclization of conjugated azines. Synthesis and thermal rearrangements of 1,8-diaryl-4,5-diaza-3-methyl- and -3-phenyl-1,3,5,7-octatetraenes (.alpha.,.beta.-unsaturated azines) to 1-(1-methyl-3-phenyl- and -1,3-diphenyl-1-propenyl)-5-arylpyrazoles

  摘要：

  DOI：

  10.1021/jo00348a008
• 作为产物：
  描述：

  苯甲酰基亚甲基三苯基膦 在 triphenylphosphine dibromide 1:1 addition complex 、 三乙胺 作用下， 以 二氯甲烷 为溶剂， 反应 30.0h， 以88%的产率得到triphenyl(phenylethynyl)phosphonium bromide
  参考文献：
  名称：

  Bestmann, Hans Juergen; Kisielowski, Lothar, Chemische Berichte, 1983, vol. 116, # 4, p. 1320 - 1326

  摘要：

  DOI：

文献信息

• [EN] HSP70 INHIBITORS AND METHODS OF USING SAME<br/>[FR] INHIBITEURS DE HSP70 ET LEURS MÉTHODES D'UTILISATION
  申请人：THE WISTAR INST

  公开号：WO2021202540A1

  公开（公告）日：2021-10-07

  The disclosure provides compounds, and compositions comprising such compounds, that can be used to treat cancer, especially colorectal cancer (CRC). In certain embodiments, the compounds of the disclosure inhibit HSP70. In other embodiments, the compounds of the disclosure promote or increase immune cell recruitment to a cancer. In yet other embodiments, the compounds of the disclosure promote or increase immune cell infiltration in a cancer.

  该披露提供了化合物和含有这些化合物的组合物，可用于治疗癌症，特别是结直肠癌（CRC）。在某些实施方式中，该披露的化合物抑制HSP70。在其他实施方式中，该披露的化合物促进或增加免疫细胞对癌症的招募。在另一些实施方式中，该披露的化合物促进或增加免疫细胞对癌症的浸润。
• Reaktionen von ethinyltriphenylphosphoniumsalzen mit phosphoniumyliden
  作者：Hans Jürgen Bestmann、Lothar Kisielowski

  DOI：10.1016/s0040-4039(00)89049-8

  日期：1990.1

  Ethinylphosphonium salts 4 react with methylenetriphenylphosphorane 5 to give 1.3-bis(triphenylphosphonio)propenid-cation salts 6, whereas from 4 with benzylidenetriphenylphosphorane 10α and isopropylidenetriphenylphosphorane 10β the 1.3-diphosphaallyl-cation salts 13 are formed in a stereospecific reaction.

  Ethinylphosphonium盐4与基亚甲基反应5，得到1.3双（三苯）propenid-阳离子盐6，而从4与benzylidenetriphenylphosphorane 10 α和isopropylidenetriphenylphosphorane 10 β的1.3-diphosphaallyl阳离子盐13在立体特异性反应形成的。
• Reaction of 3a,6a-Diaza-1,4-diphosphapentalene with Substituted Acetylenes
  作者：A. N. Kornev、V. E. Galperin、Yu. S. Panova、V. V. Sushev、G. K. Fukin、E. V. Baranov、G. A. Abakumov

  DOI：10.1134/s1070363219010092

  日期：2019.1

  been formed in this reaction. The reaction in the 3a,6a-diaza-1,4-diphosphapentalene–[Ph3PC≡CPh]Br–carbazole three-component system proceeds as addition of carbazole to the initially formed complex of 3a,6a-diaza-1,4-diphosphapentalene with [Ph3PC≡CPh]Br with the rupture of the P–N bond. The products and intermediates of the reaction have been simulated by B3LYP/6-31+G(d) method.

  3a，6a-diaza-1,4-diphosphapentalene与1-溴-2-苯基乙炔的反应导致形成1,1-双（苯基乙炔基）-和1,4-二溴-3a，6a-diaza- 1,4-二磷戊烯。第一种也已经通过不同的路线通过1,4-二氯-3a，6a-重氮-1,4-二磷戊烯与苯基乙炔锂的反应制备，产率为96％。在该反应中没有形成异构的1，4-双（苯基乙炔基）-DDP。在图3a，6a-二氮杂-1,4- diphosphapentalene-反应[PH 3 PC≡CPh]溴咔唑三组分体系进行作为加法咔唑向最初形成的络合物3a的，6a-二氮杂-1,4- -diphosphapentalene与[PH 3 PC≡CPh]溴用P-N键的断裂。反应的产物和中间体已通过B3LYP / 6-31 + G（d）方法进行了模拟。
• A reinvestigation of mono- and bis-ethynyl phosphonium salts: structural and computational studies and new reactivity
  作者：Alex J. Veinot、Angela D.K. Todd、Katherine N. Robertson、Jason D. Masuda

  DOI：10.1139/cjc-2017-0482

  日期：2018.1

  A series of mono- and bis-ethynyl phosphonium salts have been prepared via reaction of bromoacetylenes, Ph–C≡C–Br or Br–C≡C–C₆H₄–C≡C–Br, with various phosphines. Some of the derivatives reported are previously known, ([Ph–C≡C–PPh₃]Br, [Ph–C≡C–PMe₃]Br, [Ph–C≡C–PBu₃]Br, and [Ph₃P–C≡C–C₆H₄–C≡C–PPh₃][Br₂]), however typically these are missing complete spectroscopic characterization and many have been prepared using much more complicated methods. The derivative [Ph–C≡C–PPh₃]Br is capable of inhibiting the growth of tumour cells and has been shown crystallographically to have a significant interaction with the heat shock proteins (HSP70 or DnaK). Thus, solid state structures for all seven phosphonium salts prepared have been reported as they may be of interest to others in this field. Sterically encumbered phosphines such as Mes₃P did not react with Ph–C≡C–Br; however, (2,4,6-MeO–C₆H₂)₃P was found to slowly react at moderate temperature to give the expected alkynyl phosphonium salt. However, at higher temperatures, the alkynyl phosphonium undergoes an intramolecular cyclization to form a phosphonium analogue of a 1,4-oxazine. Finally, electronic structure calculations reveal the positive charge on the acetylenic β-carbon, a result of a significant contribution of other canonical structures. The flexibility of the P–C≡C bond has been investigated showing a low-energy barrier (<5 kcal/mol) for bending up to 40° from the optimized angle in the model [Ph–C≡C–PMe₃]⁺ cation. This ease of bending may be of significance in the development of other alkynyl phosphonium tumour cell growth inhibitors.

  一系列单和双乙炔基磷酸盐通过溴乙炔基，Ph–C≡C–Br或Br–C≡C–C₆H₄–C≡C–Br，与各种膦反应而制备。其中一些衍生物是先前已知的，([Ph–C≡C–PPh₃]Br，[Ph–C≡C–PMe₃]Br，[Ph–C≡C–PBu₃]Br，和[Ph₃P–C≡C–C₆H₄–C≡C–PPh₃][Br₂])，然而通常这些缺少完整的光谱表征，并且许多使用更复杂的方法制备。衍生物[Ph–C≡C–PPh₃]Br能够抑制肿瘤细胞的生长，并已经晶体学上证明与热休克蛋白(HSP70或DnaK)有显着的相互作用。因此，已报告了所有七种制备的磷酸盐的固态结构，因为它们可能对该领域的其他人感兴趣。如Mes₃P等立体障碍的膦没有与Ph–C≡C–Br反应；然而，发现(2,4,6-MeO–C₆H₂)₃P在适度温度下缓慢反应以给出预期的炔基磷酸盐。然而，在较高温度下，炔基磷酸盐会发生分子内环化，形成1,4-氧杂环的磷酸盐类似物。最后，电子结构计算显示了乙炔基β-碳上的正电荷，这是由于其他规范结构的显著贡献所致。已经研究了P–C≡C键的柔性，显示出低能量势垒(<5 kcal/mol)，可以使其从模型[Ph–C≡C–PMe₃]⁺阳离子的优化角度弯曲40°。这种弯曲的易于性可能在开发其他炔基磷酸盐肿瘤细胞生长抑制剂方面具有重要意义。
• Preparation of linear phosphorus compound containing two hypervalent centers. Acetylene-bis[triphenyl(phenylethynyl) phosphorane]
  作者：Satoshi Ogawa、Yoko Tajiri、Naomichi Furukawa

  DOI：10.1016/0040-4039(93)89026-m

  日期：1993.1

  A new linear acetylide-connected bis-phosphorane, acetylene-bis[triphenyl)phosphorane] (2) was synthesized in the reaction of triphenyl(phenylethynyl)phosphonium bromide with dilithioacetylide. Triphenylbis(phenylethynyl)phosphorane (1) was also prepared by a similar treatment of triphenyl(phenylethynyl)-phosphonium bromide with lithium phenylacetylide.

  在三苯基（苯基乙炔基）溴化with与二硫代乙炔的反应中合成了一种新的直链连接乙炔的双膦，乙炔-双[三苯基]膦]（2）。三苯基双（苯基乙炔基）膦（1）也通过对三苯基（苯基乙炔基）-溴化phosph用苯基乙炔锂进行类似处理而制得。