1-iodo-3,3-dimethyl-1-phenyl-1-butene | 125315-96-0

• 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: 1-iodo-3,3-dimethyl-1-phenyl-1-butene
• 英文别名: (Z)-(3,3-Dimethyl-1-iodo-1-butenyl)benzene；(Z)-(1-Iodo-3,3-dimethyl-1-butenyl)benzene；3,3-dimethyl-1-iodo-1-phenyl-1-butene；[(Z)-1-iodo-3,3-dimethylbut-1-enyl]benzene
• CAS: 125315-96-0
• 化学式: C₁₂H₁₅I
• 分子量: 286.156
• InChiKey: IGBMREOUUMKYBS-LUAWRHEFSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.1
• 重原子数：
  13
• 可旋转键数：
  2
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.33
• 拓扑面积：
  0
• 氢给体数：
  0
• 氢受体数：
  0

反应信息

• 作为产物：
  描述：

  (3,3-二甲基-1-丁炔)-苯 在 aluminum oxide 、 三碘化磷 作用下， 以 二氯甲烷 为溶剂， 反应 36.0h， 以18%的产率得到3,3-二甲基-1-苯基-1-丁酮
  参考文献：
  名称：

  Surface-Mediated Reactions. 4. Hydrohalogenation of Alkynes

  摘要：

  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.

  DOI：

  10.1021/jo00090a031

文献信息

• Silver-Catalyzed Regioselective Carbomagnesiation of Alkynes with Alkyl Halides and Grignard Reagents
  作者：Nobuaki Kambe、Yuusuke Moriwaki、Yuuki Fujii、Takanori Iwasaki、Jun Terao

  DOI：10.1021/ol2018664

  日期：2011.9.2

  A silver-catalyzed carbomagnesiation of alkynes with alkyl halides and Grignard reagents afforded alkenyl Grignard reagents regioselectively, where the alkyl group of the alkyl halide, but not that of the Grignard reagent, was introduced into the alkyne. Application to δ-haloalkylacetylenes yielded cyclopentanes or a tetrahydrofuran containing an exo-methylene substituent via 5-exo-dig cyclization

  银的炔烃与烷基卤化物和格利雅试剂的银催化碳还原反应可选择性地提供烯基格利雅试剂，其中烷基卤的烷基而不是格利雅试剂的烷基被引入炔中。到δ-haloalkylacetylenes得到应用环戊烷或含四氢呋喃外型亚甲基取代基经由5外切挖环化。
• Triethylborane-induced radical addition of alkyl iodides to acetylenes
  作者：Yoshifumi Ichinose、Shin-ichiro Matsunaga、Keigo Fugami、Koichiro Oshima、Kiitiro Utimoto

  DOI：10.1016/s0040-4039(00)99189-5

  日期：——

  Treatment of terminal acetylenes (R1CCH) with secondary or tertiary alkyl iodides (R2I) in the presence of triethylborane provides the corresponding alkenyl iodides (R1C(I)CHR2) in good yields.

  在三乙基硼烷的存在下，用仲或叔烷基碘（R 2 I）处理末端乙炔（R 1 C = CH）可得到相应的烯基碘（R 1 C（I）= CHR 2）。
• Iodine atom transfer addition reactions with alkynes. Part 1: Alkyl iodides
  作者：Dennis P. Curran、Dooseop Kim

  DOI：10.1016/s0040-4020(01)86550-9

  日期：1991.8

  Simple 2° - and 3° -alkyl iodides add smoothly to electron deficient alkynes under standard atom transfer conditions 10% Bu3SnSnBu3, sunlamp photolysis. Mechanistic experiments help to interpret stereochemical and yield trends, and a new model for atom abstraction reactions of rapidly inverting a-vinyl radicals is proposed.

  简单的2°和3°烷基碘在标准原子转移条件下10％Bu 3 SnSnBu 3，日光光解条件下，会平稳地添加到缺电子的炔烃中。力学实验有助于解释立体化学和产量趋势，并提出了一种新的快速反转α-乙烯基自由基的原子抽象反应模型。
• Triethylborane Induced Stereoselective Radical Addition of R₃SiH to Acetylenes and Stereoselective Reduction of Alkenyl Iodides with Tris(trimethylsilyl)silane
  作者：Katsukiyo Miura、Koichiro Oshima、Kiitiro Utimoto

  DOI：10.1246/bcsj.66.2356

  日期：1993.8

  Triethylborane induced radical addition of various organosilanes (R3SiH) to acetylenes has been studied. Among them, tris(trimethylsilyl)silane (TTMSS) proved to be the best reagent for the hydrosilylation of acetylenic compounds in terms of yield and stereoselectivity. For instance, reaction of 1-dodecyne with TTMSS at room temperature for 3 h under Et3B catalyst provided (Z)-1-tris(trimethylsilyl)silyl-1-dodecene

  已经研究了三乙基硼烷引发的各种有机硅烷 (R3SiH) 与乙炔的自由基加成。其中，就产率和立体选择性而言，三（三甲基甲硅烷基）硅烷（TTMSS）被证明是炔类化合物氢化硅烷化的最佳试剂。例如，1-十二炔与 TTMSS 在室温下在 Et3B 催化剂下反应 3 小时，选择性地提供了 (Z)-1-三(三甲基甲硅烷基)甲硅烷基-1-十二烯，产率为 98%。已经研究了用 TTMSS-Et3B 或 n-Bu3SnH-Et3B 还原烯基碘的立体化学过程。在室温下用 TTMSS-Et3B 处理 1-二甲基苯基甲硅烷基-2-碘-1-十二烯，选择性地提供 (Z)-1-二甲基苯基甲硅烷基-1-十二烯 (Z/E > 30/1)。另一方面，用 n-Bu3SnH-Et3B 处理只得到 (E)-1-二甲基苯基甲硅烷基-1-十二烯。
• ICHINOSE, Y.;MATSUNAGA, SH.;FUGAMI, K., TETRAHEDRON LETT., 30,(1989) N4, C. 3155-3158
  作者：ICHINOSE, Y.、MATSUNAGA, SH.、FUGAMI, K.

  DOI：——

  日期：——