2,2-Dimethyl-5,6,6-triphenyl-5-hexen-3-one

• 分子结构分类: 有机化合物 - 苯丙烷和聚酮 - 二苯乙烯类
• 英文名称: 2,2-Dimethyl-5,6,6-triphenyl-5-hexen-3-one
• 英文别名: 2,2-Dimethyl-5,6,6-triphenylhex-5-en-3-one
• 化学式: C₂₆H₂₆O
• 分子量: 354.492
• InChiKey: OZLOXABSSXXWBB-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  7.4
• 重原子数：
  27
• 可旋转键数：
  6
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.19
• 拓扑面积：
  17.1
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为产物：
  描述：

  三苯溴乙烯 在 频哪酮 、 potassium tert-butylate 作用下， 以 二甲基亚砜 为溶剂， 反应 3.0h， 以60%的产率得到2,2-Dimethyl-5,6,6-triphenyl-5-hexen-3-one
  参考文献：
  名称：

  Competition of Mechanisms in Nucleophilic Substitution of Vinyl Halides. An Unequivocal Example of the Vinylic SRN1 Route1

  摘要：

  In a search for an unambiguous example of the vinylic S(RN)1 route, several vinyl bromides and iodides were reacted mostly with (-)CH(2)COCMe(3), and sometimes with (-)CH(2)COPh, (CH)-C--(Me)COEt, and (EtO)(2)PO- ions, under Fe2+- or photostimulation in Me(2)SO. Vinyl halides having vinylic hydrogens, such as beta-bromostyrene, gave acetylenic products, e.g., phenylacetylene or a tertiary PhC=C-substituted alcohol, whereas vinyl halides with allylic hydrogens, such as Me(2)C=C(I)CHMe(2), gave a substituted allene. Reduction products of the halogen, as well as substitution and rearranged substitution products, were also formed. The operation of ionic elimination-addition routes accounts for formation of most of the products, while the reduction products arise from an intermediate vinyl radical. Ph(2)C=C(Br)Ph (20) and Me(2)C=C(Br)Ph (25) gave both substitution and reduction products, but Me(2)C=C(Br)-t-Bu (23) gave only a reduction product. Formation of substitution products from the conjugated 20 and 25 was ascribed to a reaction via a vinylic S(RN)1 route, while lack of substitution in 23 is related to its nonconjugated system and to the consequent higher energy that the radical anion of the substitution product would have. The one here reported seems to be the first case of an exclusive genuine vinylic S(RN)1 process.

  DOI：

  10.1021/jo00101a045

文献信息

• Competition of Mechanisms in the Photochemical Cleavage of the C−X Bond of Aryl-Substituted Vinyl Halides
  作者：Carlo Galli、Patrizia Gentili、Alessandra Guarnieri、Shinjiro Kobayashi、Zvi Rappoport

  DOI：10.1021/jo981164p

  日期：1998.12.1

  The photolysis of aryl halides causes homolysis of the carbon-halogen bond and formation of aryl radicals. In contrast, photolysis of vinyl halides can induce both heterolysis of the C-X bond, thereby generating vinyl cations, and homolysis, giving vinyl radicals. Examples of this competition among pathways is reported here for three vinylic precursors, namely, 1,2,2-triphenylbromoethene (1), 1-phenyl-2,2-bis(o-methoxyphenyl)-1-bromoethene (11), and beta-bromostyrene (19). Incursion of the photoinduced S(RN)1 process, through the intermediacy of the vinyl radical, is verified in the presence of reducing nucleophiles, such as the enolate ions of ketones, and in part with (EtO)(2)PO-. Conversely, incursion of the heterolytic path, and intermediacy of the vinyl cation, occurs in the presence of weak electron-donor anions, such as NO2-, N-3(-), and Cl-. The vinyl cation produced from 19, which is less stable than those derived from 1 and 11, gives phenylacetylene via an E1-type elimination. An estimate is provided for the intramolecular rate of interception of the vinyl cation derived from 11 by the ortho-methoxy groups of the beta-o-anisyl substituents. Finally, evidence against a photoinduced electron transfer from RO- ions to vinyl halide 1 is presented.
• S_RN1 Photostimulated Reaction of Triphenylvinyl Bromide with Carbanions in DMSO
  作者：Ana N. Santiago、Gonzalo Lassaga、Zvi Rappoport、Roberto A. Rossi

  DOI：10.1021/jo951144c

  日期：1996.1.1
• Galli Carlo, Gentili Patrizia, Rappoport Zvi, J. Org. Chem, 59 (1994) N 22, S 6786-6795
  作者：Galli Carlo, Gentili Patrizia, Rappoport Zvi

  DOI：——

  日期：——