1-碘-1-苯基-丙-1-烯 | 32780-80-6

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 中文名称: 1-碘-1-苯基-丙-1-烯
• 英文名称: (E)-(1-iodoprop-1-en-1-yl)benzene
• 英文别名: [(E)-1-iodoprop-1-enyl]benzene
• CAS: 32780-80-6
• 化学式: C₉H₉I
• 分子量: 244.075
• InChiKey: LFVLNOJSMBNWDU-XNWCZRBMSA-N

物化性质

• 沸点：
  257.1±10.0 °C(Predicted)
• 密度：
  1.599±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.8
• 重原子数：
  10
• 可旋转键数：
  1
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.11
• 拓扑面积：
  0
• 氢给体数：
  0
• 氢受体数：
  0

反应信息

• 作为反应物：
  描述：

  1-碘-1-苯基-丙-1-烯 、 苯甲醛 在 diethylzinc 、 乙酰基丙酮锂 、 3,3'-bis-pyrrolidin-1-ylmethyl-[1,1']binaphthalenyl-2,2'-diol 作用下， 以 N-甲基吡咯烷酮 、 二氯甲烷 为溶剂， 反应 16.0h， 以79%的产率得到(R,E)-1,2-diphenylbut-2-en-1-ol
  参考文献：
  名称：

  乙烯基碘的活化对醛的高度对映选择性加成

  摘要：

  温和且耐受：乙烯基碘试剂是由乙烯基碘化物与ZnEt 2在温和的反应条件下反应直接制备的。发现化合物（S）-1可以催化将乙烯基锌试剂添加到各种醛中，从而以高收率和对映选择性生成结构多样的烯丙基醇。该催化过程可以耐受底物上的官能团，例如酯，氯，醚和甲硅烷基醚。acac =乙酰丙酮酸酯，NMP = N-甲基-2-吡咯烷酮。

  DOI：

  10.1002/anie.201007351
• 作为产物：
  描述：

  1-苯基-1-丙炔 在 氢碘酸 作用下， 以 甲苯 为溶剂， 反应 3.0h， 以73%的产率得到1-碘-1-苯基-丙-1-烯
  参考文献：
  名称：

  用异位生成的 HI 对内炔进行区域和立体选择性氢碘化反应

  摘要：

  在本文中，我们报道了使用HI内炔的有效且实用的碘氢化生成易地从容易获得的三乙基硅烷和我2。该系统具有高区域选择性和立体选择性，可在温和条件下以良好的收率提供 ( E )-乙烯基碘化物。此外，氢碘化反应显示出对烷基、甲氧基、卤素、三氟甲基、氰基、酯、卤代甲基、酸敏感性甲硅烷基醚和缩醛部分的高官能团耐受性。

  DOI：

  10.1021/acs.orglett.1c02218

文献信息

• Metal-Free Transfer Hydroiodination of C–C Multiple Bonds
  作者：Weiqiang Chen、Johannes C. L. Walker、Martin Oestreich

  DOI：10.1021/jacs.8b12318

  日期：2019.1.16

  The design and a gram-scale synthesis of a bench-stable cyclohexa-1,4-diene-based surrogate of gaseous hydrogen iodide are described. By initiation with a moderately strong Brønsted acid, hydrogen iodide is transferred from the surrogate onto C-C multiple bonds such as alkynes and allenes without the involvement of free hydrogen iodide. The surrogate fragments into toluene and ethylene, easy-to-remove

  描述了基于环己-1,4-二烯的气态碘化氢替代品的设计和克级合成。通过用中等强度的布朗斯台德酸引发，碘化氢从替代物转移到 CC 多重键上，例如炔烃和丙二烯，而没有游离碘化氢的参与。代用品碎片化为甲苯和乙烯，易挥发废物。这种氢碘化反应避免了对碘化氢或氢碘酸的不稳定处理。通过这种方式，可以以立体控制的方式访问范围广泛的以前未知或难以制备的乙烯基碘。
• A convergent approach to (R)-Tiagabine by a regio- and stereocontrolled hydroiodination of alkynes
  作者：Giuseppe Bartoli、Roberto Cipolletti、Giustino Di Antonio、Riccardo Giovannini、Silvia Lanari、Mauro Marcolini、Enrico Marcantoni

  DOI：10.1039/c005042c

  日期：——

  The occurrence of unsaturated systems in natural products combined with the mildness and the wide range of applicability of CeCl3 promoted methodologies suggest several potential future synthetic applications within the field of total synthesis of biologically active molecules. On this concept, the use of CeCl3·7H2O–NaI system as an efficient heterogeneous promoter has been highlighted in the iodofunctionalization of carbon–carbon triple bonds. The study has shown that this method would be particularly interesting for the stereoselective formation of trisubstituted (Z)- or (E)-iodoalkenes by simply changing the nature of the solvent. The methodology has been successfully applied to the synthesis of (R)-1-[4,4-bis-(3-methyl-2-thienyl)-3-butenyl]-3-piperidinecarboxylic acid 1, named (R)-Tiagabine, which is a potent and selective γ-aminobutyric acid (GABA) uptake inhibitor with proven anticonvulsant efficacy in humans.

  不饱和体系在天然产物中的出现，以及CeCl3促进的方法所具有的温和性和广泛的适用性，提示在生物活性分子的全合成领域存在多个潜在的未来合成应用。在这个概念下，使用 ·7H2O–NaI体系作为有效的异相促进剂，在碳-碳三重键的碘功能化中得到了强调。研究表明，这种方法对于立体选择性合成三取代的（Z）或（E）碘烯特别有趣，只需改变溶剂的性质。该方法已成功应用于合成（R）-1-[4,4-双-(3-甲基-2-噻吩基)-3-丁烯基]-3-哌啶甲酸1，即（R）-Tiagabine，这是一种有效且选择性的γ-氨基丁酸（GABA）摄取抑制剂，在人类中具有经过验证的抗癫痫疗效。
• Titanium Tetraiodide-promoted Tandem Prins Reaction of Alkynes with Acetals: Synthesis of (<i>Z</i>,<i>Z</i>)-1,5-Diiodo-1,3,5-triarylpenta-1,4-dienes
  作者：Makoto Shimizu、Kanako Okura、Takuya Arai、Iwao Hachiya

  DOI：10.1246/cl.2010.1052

  日期：2010.10.5

  In the presence of titanium tetraiodide, a tandem Prins reaction of alkynes proceeded with acetals to give (Z,Z)-1,5-diiodo-1,3,5-triarylpenta-1,4-dienes in good yields, where an intriguing reversal of the stereoselectivity was observed among titanium tetrahalides.

  在四碘化钛存在的情况下，炔烃与乙醛发生串联 Prins 反应，得到 (Z,Z)-1,5 二碘-1,3,5-三芳基戊-1,4-二烯，产率很高。
• Mechanism, regiochemistry, and stereochemistry of the insertion reaction of alkynes with methyl(2,4-pentanedionato)(triphenylphosphine)nickel. A cis insertion that leads to trans kinetic products
  作者：John M. Huggins、Robert G. Bergman

  DOI：10.1021/ja00401a016

  日期：1981.6
• Surface-Mediated Reactions. 4. Hydrohalogenation of Alkynes
  作者：Paul J. Kropp、Scott D. Crawford

  DOI：10.1021/jo00090a031

  日期：1994.6

  The use of appropriately prepared silica gel and alumina has been found to mediate the addition of hydrogen halides to alkynes. The technique has been rendered even more convenient by the use of various organic and inorganic acid halides that react in the presence of silica gel or alumina to generate hydrogen halides in situ. Treatment in this fashion of 1-propynylbenzene (1), which underwent no reaction in CH2Cl2 solution saturated with HCl, readily afforded the syn addition product, alkenyl chloride (E)-4a. On extended treatment (E)-4a underwent subsequent isomerization to the thermodynamically more stable Z isomer. Thus either isomer of 4a could be obtained in good yield depending on the reaction conditions. In a similar way bromides (E)- and (Z)-4b were obtained without competing formation of the radical products (E)- and (Z)-5, which occurred in solution. In contrast with solution-phase hydriodination of alkyne 1, which slowly afforded iodide (E)-4c, surface-mediated addition readily afforded (E)-4c, followed by isomerization to the Z isomer. E reversible arrow Z equilibration of the alkenyl halides 4 was shown to involve, at least in part, addition-elimination via the gem-dihalides 13. Analogous behavior was exhibited by the phenylalkynes 2 and 3 on surface-mediated hydrohalogenation. Surface-mediated addition of Hbr and HI to the internal alkylalkyne 14 afforded principally the anti addition products (Z)-15b,c. Treatment of the terminal alkynes 17 and 22 with (COBr)(2) over alumina gave the dibromides 20 and 24/25,respectively, whereas use of acetyl bromide as the Hbr precursor afforded the alkenyl bromides 18b and 23.