3,4,4-trimethyl-1-phenylpent-1-yn-3-ol | 85051-67-8

• 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: 3,4,4-trimethyl-1-phenylpent-1-yn-3-ol
• CAS: 85051-67-8
• 化学式: C₁₄H₁₈O
• 分子量: 202.296
• InChiKey: FNOTWYZKEJTYEO-UHFFFAOYSA-N

物化性质

• 沸点：
  103-107 °C(Press: 0.998 Torr)
• 密度：
  0.99±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.4
• 重原子数：
  15
• 可旋转键数：
  3
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.43
• 拓扑面积：
  20.2
• 氢给体数：
  1
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  3,4,4-trimethyl-1-phenylpent-1-yn-3-ol 在 间氯过氧苯甲酸 、 sodium iodide 、 三氯乙酸 作用下， 以 乙腈 为溶剂， 以40%的产率得到(E)-2-iodo-3,4,4-trimethyl-1-phenylpent-2-en-1-one
  参考文献：
  名称：

  次碘酸可将叔炔丙醇重排为α-碘烯†

  摘要：

  在氧化剂存在下，碘化钠转化为 次碘酸 从而以高收率将叔炔丙醇重排为α-碘烯。

  DOI：

  10.1039/c2ob26360b
• 作为产物：
  描述：

  (E)-β-chlorostyrene 在 iron(II) chloride 频哪酮 、 potassium tert-butylate 作用下， 以 二甲基亚砜 为溶剂， 反应 3.17h， 生成 3,4,4-trimethyl-1-phenylpent-1-yn-3-ol
  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

• Generation of 1,2-oxathiolium ions from (arysulfonyl)- and (arylsulfinyl)allenes in Brønsted acids. NMR and DFT study of these cations and their reactions
  作者：Stanislav V Lozovskiy、Alexander Yu Ivanov、Olesya V Khoroshilova、Aleksander V Vasilyev

  DOI：10.3762/bjoc.14.268

  日期：——

  In strong Brønsted acids (CF3SO3H, FSO3H, D2SO4), (arysulfonyl)allenes (ArSO2-CR1=C=CR2R3) and (arylsulfinyl)allenes (ArSO-CR1=C=CR2R3) undergo cyclization into the corresponding stable 1,2-oxathiolium ions, which were studied by means of NMR and DFT calculations. Quenching of solutions of these cations with low nucleophilic media, aqueous HCl, leads to their deprotonation with a stereoselective formation

  在强布朗斯台德酸（CF3SO3H，FSO3H，D2SO4）中，（芳磺酰基）烯（ArSO2-CR1 = C = CR2R3）和（芳亚磺酰基）烯（ArSO-CR1 = C = CR2R3）环化成相应的稳定的1,2-氧杂硫鎓离子，通过NMR和DFT计算进行了研究。用低亲核介质（HCl水溶液）淬灭这些阳离子的溶液会导致它们的去质子化，并形成立体选择性的（芳磺酰基）丁二烯（例如，ArSO2-CR1 = CC（Me）= CH2，对于R2 = R3 = Me，收率的87-98％）。TfOH（0.1当量）-HFIP（六氟丙烷-2-醇）体系中的（芳磺酰基）丙二烯反应后水解生成烯丙醇（ArSO2-CR1 = CH-C（OH）R2R3，收率78-99％ ）。在（1当量）TfOH（1当量）存在下，（芳磺酰基）丙二烯溶液的回流导致环化成硫代色素1，1-二氧化物产量高。在TfOH或AlX 3（X ＝ Cl，Br）的作
• Zn(Salen)-Catalyzed Asymmetric Alkynylation of Ketones
  作者：Tsutomu Katsuki、Bunnai Saito

  DOI：10.1055/s-2004-829057

  日期：——

  An in situ generated Zn complex of salen ligand 4 was found to serve as an efficient catalyst for asymmetric addition reaction of an alkynylzinc reagent to various ketones. For example, addition of phenylacetylene to 3,3-dimethyl-2-butanone using the Zn complex as catalyst showed enantioselectivity as high as 91% ee.

  发现原位生成的 salen 配体 4 的 Zn 配合物可用作炔基锌试剂与各种酮的不对称加成反应的有效催化剂。例如，使用 Zn 配合物作为催化剂将苯乙炔加成到 3,3-二甲基-2-丁酮中显示出高达 91% ee 的对映选择性。
• Scope and Mechanistic Analysis of the Enantioselective Synthesis of Allenes by Rhodium-Catalyzed Tandem Ylide Formation/[2,3]-Sigmatropic Rearrangement between Donor/Acceptor Carbenoids and Propargylic Alcohols
  作者：Zhanjie Li、Vyacheslav Boyarskikh、Jørn H. Hansen、Jochen Autschbach、Djamaladdin G. Musaev、Huw M. L. Davies

  DOI：10.1021/ja3061529

  日期：2012.9.19

  Rhodium-catalyzed reactions of tertiary propargylic alcohols with methyl aryl- and styryldiazoacetates result in tandem reactions, consisting of oxonium ylide formation followed by [2,3]-sigmatropic rearrangement. This process competes favorably with the standard O-H insertion reaction of carbenoids. The resulting allenes are produced with high enantioselectivity (88-98% ee) when the reaction is catalyzed by the

  炔丙基叔醇与甲基芳基乙酸酯和苯乙烯基重氮乙酸酯的铑催化反应导致串联反应，包括氧鎓叶立德形成，然后是 [2,3]-σ 重排。该过程与类卡宾的标准 OH 插入反应相得益彰。当反应由四脯氨酸二铑配合物 Rh(2)(S-DOSP)(4) 催化时，生成的丙二烯具有高对映选择性 (88-98% ee)。当外消旋叔炔丙醇用作底物时，可以进行动力学拆分。在动力学拆分条件下，形成的丙二烯具有良好的非对映选择性和对映选择性（高达6.1:1 dr，88-93% ee），未反应的醇被对映体富集到65-95% ee。计算研究表明，高不对称诱导是通过涉及两点连接的有组织的过渡态获得的：醇氧与类卡宾之间的叶立德形成以及醇与羧酸盐配体的氢键合。2,3-sigmatropic 重排通过 OH 键的初始裂解进行，生成具有紧密开壳单线态、三线态和闭壳单线态电子态的中间体。该中间体将具有显着的双自由基特征，这与供体/受体类卡宾和更高度官能化的炔丙醇有利于
• Synthesis of Propargylic Alcohols by base promoted Alkynylation of Ketones with Ethynylbenzene using Ionic Liquid [(bmim) PF₆]
  作者：Sachin R. Jagtap、Bhalchandra M. Bhanage

  DOI：10.3184/030823407x225509

  日期：2007.6

  A mild and efficient addition of ethynylbenzene with ketones using KOH in ionic liquid 1-butyl-3-methylimidazolium hexaflurophosphate [(bmim) PF₆] gives propargylic alcohols in high yields.

  在离子液体 1-丁基-3-甲基咪唑六氟磷酸盐[(bmim) PF6]中使用 KOH 对乙炔苯与酮进行温和而高效的加成反应，可获得高产率的丙炔醇。
• Rhodium-Catalyzed and Chiral Zinc Carboxylate-Assisted Allenylation of Benzamides via Kinetic Resolution
  作者：Ruxia Mao、Yanliang Zhao、Xiaohan Zhu、Fen Wang、Wei-Qiao Deng、Xingwei Li

  DOI：10.1021/acs.orglett.1c02398

  日期：2021.9.17

  In this work, kinetic resolution of tertiary propargyl alcohols as an allenylating reagent has been realized via rhodium(III)-catalyzed C–H allenylation of benzamides. The reaction proceeded efficiently under mild conditions, and both the allenylated products and the propargyl alcohols were obtained in high enantioselectivities with an s-factor of up to 139. The resolution results from bias of the

  对映体富集的丙二烯是重要的组成部分。虽然它们已通过其他偶联方法获得，但很少通过 C-H 活化获得对映体富集的丙二烯。在这项工作中，通过铑（III）催化的苯甲酰胺的 C-H 烯丙基化实现了叔炔丙醇作为烯丙基化试剂的动力学拆分。该反应在温和的条件下有效进行，并以高对映选择性获得了s因子高达 139的烯丙基化产物和炔丙醇。分辨率来自两个炔丙基取代基的偏向性，并由手性羧酸锌辅助添加剂。