1-chloro-4-(3,3-difluoroprop-1-yn-1-yl)benzene | 573979-98-3

• 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-chloro-4-(3,3-difluoroprop-1-yn-1-yl)benzene
• 英文别名: Benzene, 1-chloro-4-(3,3-difluoro-1-propynyl)-；1-chloro-4-(3,3-difluoroprop-1-ynyl)benzene
• CAS: 573979-98-3
• 化学式: C₉H₅ClF₂
• 分子量: 186.589
• InChiKey: PBTXWPSXOAWJPO-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.6
• 重原子数：
  12
• 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：
  2

反应信息

• 作为反应物：
  描述：

  溴丁基-镁 、 1-chloro-4-(3,3-difluoroprop-1-yn-1-yl)benzene 在 copper(I) bromide 作用下， 以 四氢呋喃 为溶剂， 反应 2.0h， 以55%的产率得到(Z)-3-(4-chlorophenyl)-1,1-difluoro-2-heptene
  参考文献：
  名称：

  A Highly Regio- and Stereoselective Carbocupration of Fluoroalkylated Internal Alkynes:  A Short Total Synthesis of the Antiestrogenic Drug Panomifene

  摘要：

  A highly regio- and stereoselective carbometalation reaction of fluoroalkylated internal alkynes with organocopper reagents is described. This reaction is utilized successfully in the short, stereoselective total synthesis of the antiestrogenic drug panomifene.

  DOI：

  10.1021/ol036440n
• 作为产物：
  描述：

  对氯碘苯 、 (Z)-2,3,3-trifluoro-1-iodoprop-1-ene 在 正丁基锂 、 dichloro(N,N,N’,N‘-tetramethylethylenediamine)zinc 、 四(三苯基膦)钯 作用下， 以 四氢呋喃 、 正己烷 为溶剂， 反应 5.25h， 以70%的产率得到1-chloro-4-(3,3-difluoroprop-1-yn-1-yl)benzene
  参考文献：
  名称：

  Facile syntheses of various per- or polyfluoroalkylated internal acetylene derivatives

  摘要：

  Treatment of per- or polyfluoroalkylated vinyl iodides 5 with 2 equiv. of n-BuLi in THF produced the corresponding lithium acetylides in situ, which were transformed into zinc acetylides by the addition of ZnCl2.TMEDA complex into the reaction mixture. The in situ generated zinc acetylides were exposed to the cross-coupling conditions such as ArI/cat. Pd(PPh3)(4), reflux, 6-12 h, giving rise to the desired per- or polyfluoroalkylated acetylenes in high yields. In the case of trifluoromethylated acetylene, commercially available 2-bromo-3,3,3-trifluoropropene 6 could also be used instead of 5 as the starting material. In the acetylenes having a fluoroalkyl group and an aliphatic side chain, vinyl iodides 7, prepared by radical addition of perfluoroalkyl iodide to terminal acetylenes, were treated with t-BuOK at room temperature or at the reflux temperature of benzene, affording the desired compounds in good yields. (C) 2003 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/s0040-4020(03)01199-2

文献信息

• Highly regio- and stereo-selective carbometallation reaction of fluorine-containing internal acetylenes with organocopper reagents
  作者：Tsutomu Konno、Takeshi Daitoh、Atsushi Noiri、Jungha Chae、Takashi Ishihara、Hiroki Yamanaka

  DOI：10.1016/j.tet.2005.07.022

  日期：2005.9

  The carbometallation reactions of fluoroalkylated internal alkynes with various organocopper reagents derived from organolithium, Grignard, and organozinc reagents were examined. All carbocupration reactions proceeded smoothly in a highly regio- and stereo-selective manner to give the corresponding vinylcopper intermediates. The intermediates reacted with H+ smoothly, leading to the trisubstituted

  考察了氟代烷基化内部炔烃与衍生自有机锂，格利雅（Grignard）和有机锌试剂的各种有机铜试剂的碳金属化反应。所有的碳吸收反应均以高度区域选择性和立体选择性的方式顺利进行，得到相应的乙烯基铜中间体。中间体与H +反应平稳地生成三取代烯烃，产率高至优异，而它们仅与严格限定的碳亲电试剂（如烯丙基，巴豆基，甲基烯丙基溴等）反应，这可能是由于吸电子氟代烷基的低反应性所致。用碘处理乙烯基铜导致相应的乙烯基碘的高收率，已成功用于铃木-宫浦和Sonogashira的交叉偶联反应。此外，碳键合和铃木-宫浦交叉偶联反应这两个关键反应实现了抗雌激素药泛美芬的第一个高度立体选择性的全合成。
• Regioselective cobalt(II)-catalyzed [2 + 3] cycloaddition reaction of fluoroalkylated alkynes with 2-formylphenylboronic acids: easy access to 2-fluoroalkylated indenols
  作者：Tatsuya Kumon、Miroku Shimada、Jianyan Wu、Shigeyuki Yamada、Tsutomu Konno

  DOI：10.3762/bjoc.16.184

  日期：——

  [2 + 3] cycloaddition reactions of fluorinated alkynes with 2-formylphenylboronic acids under the influence of Co(acac)2·2H2O in two-component solvents of acetonitrile/2-propanol at reflux temperature for 18 h took place smoothly, affording the corresponding fluoroalkylated indenol derivatives in good yields. This reaction shows excellent regioselectivity, giving 2-fluoroalkylated indenols, together

  Co（acac）2 ·2H 2 O在乙腈/ 2-丙醇双组分溶剂中回流下，氟化炔烃与2-甲酰基苯基硼酸的[2 + 3]环加成反应顺利进行18 h，得到相应的氟代烷基化的茚满醇衍生物，收率很高。该反应显示出优异的区域选择性，得到2-氟烷基化的茚基，以及非常少量的3-氟烷基化的茚满酮作为副产物。
• Remarkable access to fluoroalkylated trisubstituted alkenes via highly stereoselective cobalt-catalyzed hydrosilylation reaction of fluoroalkylated alkynes
  作者：Tsutomu Konno、Ken-ichi Taku、Shigeyuki Yamada、Kazuki Moriyasu、Takashi Ishihara

  DOI：10.1039/b819476a

  日期：——

  Hydrosilylation reaction of various fluoroalkylated alkynes with Et3SiH in the presence of a catalytic amount of Co2(CO)8 was investigated. The hydrosilylation of the alkynes having fluoroalkyl and aryl groups took place smoothly with good regioselectivity (ca. 80:20). In sharp contrast, the reaction of the alkynes having a fluoroalkyl group and a benzyl-type substituent, or various propargyl alcohols gave the corresponding vinylsilanes in an excellent regio- and stereoselective manner. Treatment of the vinylsilanes with various aldehydes in the presence of Zn(OTf)2 and TBAF afforded the coupling products in good yields.

  在催化剂 Co2(CO)8 的存在下，研究了各种氟烷基炔烃与 Et3SiH 的氢硅化反应。具有氟烷基和芳基的炔烃顺利发生了氢硅烷化反应，且具有良好的区域选择性（约为 80:20）。与此形成鲜明对比的是，具有氟烷基和苄基取代基的炔烃或各种丙炔醇以极好的区域和立体选择性反应生成相应的乙烯基硅烷。在 Zn(OTf)2 和 TBAF 的存在下，用各种醛处理乙烯基硅烷，可以得到产率很高的偶联产物。
• A sequential highly stereoselective hydroboration and Suzuki–Miyaura cross-coupling reaction of fluoroalkylated internal acetylenes: a practical one-pot synthesis of fluoroalkylated trisubstituted alkenes
  作者：Tsutomu Konno、Jungha Chae、Tomoo Tanaka、Takashi Ishihara、Hiroki Yamanaka

  DOI：10.1039/b316065c

  日期：——

  The one-pot synthesis of trisubstituted alkenes starting from fluoroalkylated internal alkynes was investigated. Hydroboration of the alkynes proceeded in a highly regio- and stereoselective manner to give the corresponding vinylboranes in excellent yields. Without isolation, treatment of the vinylboranes with various aryl halides under the Suzuki-Miyaura cross-coupling conditions gave the fluoroalkylated

  研究了从氟代烷基化内部炔烃一锅法合成三取代烯烃。炔烃的硼氢化以高度区域选择性和立体选择性的方式进行，从而以优异的产率得到相应的乙烯基硼烷。在不分离的情况下，在铃木-宫浦（Suzuki-Miyaura）交叉偶联条件下用各种芳基卤化物处理乙烯基硼烷，得到高收率的氟烷基化三取代烯烃，并完全保留了烯烃的几何形状。
• A Facile Synthesis of Various Fluorine-Containing Indole Derivatives via Palladium-Catalyzed Annulation of Internal Alkynes
  作者：Jungha Chae、Tsutomu Konno、Takashi Ishihara、Hiroki Yamanaka

  DOI：10.1246/cl.2004.314

  日期：2004.3

  The palladium-catalyzed annulation reaction of a variety of fluorine-containing internal alkynes with 2-iodoaniline derivatives took place smoothly to give the corresponding 2,3-disubstituted indol...

  钯催化的各种含氟内炔与2-碘苯胺衍生物的环化反应顺利进行，得到相应的2,3-二取代吲哚...