but-3-en-1-yne-1,3-diyldicyclohexane

• 分子结构分类: 有机化合物 - 碳氢化合物 - 不饱和烃
• 英文名称: but-3-en-1-yne-1,3-diyldicyclohexane
• 英文别名: 2,4-dicyclohexyl-1-buten-3-yne；2,4-cyclohexyl-1-buten-3-yne；3-Cyclohexylbut-3-en-1-ynylcyclohexane
• 化学式: C₁₆H₂₄
• 分子量: 216.367
• InChiKey: JSGIRUHKFWMJOF-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  6.8
• 重原子数：
  16
• 可旋转键数：
  2
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.75
• 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：

  2-环己基乙炔基(三甲基)硅烷 在 gallium(III) trichloride 、 2,6-二叔丁基-4-甲基吡啶 作用下， 以 甲基环己烷 为溶剂， 反应 0.5h， 以81%的产率得到but-3-en-1-yne-1,3-diyldicyclohexane
  参考文献：
  名称：

  Alkynyldichlorogalliums are Unstable in Hydrocarbon Solvents Dimerization of AlkynyldichlorogalliumsviaCarbogallation

  摘要：

  炔基二氯镓在烃类溶剂中通过碳化作用发生二聚反应，生成 1,1 二甲基-1-丁烯-3-炔衍生物。

  DOI：

  10.1246/cl.1995.1093

文献信息

• Gold-Catalyzed Regioselective Dimerization of Aliphatic Terminal Alkynes
  作者：Liming Zhang、Sheng Sun、Julien Kroll、Yingdong Luo

  DOI：10.1055/s-0031-1289567

  日期：2012.1

  A gold-catalyzed regioselective homodimerization of ­aliphatic terminal alkynes is described. Bulky and less Lewis acidic t-BuXPhosAuNTf2 is the preferred catalyst, and the additive, anhydrous NaOAc, substantially facilitates the reaction.

  描述了一种金催化的区域选择性脂肪族末端炔烃的同二聚化反应。体积较大且较少路易斯酸性的 t-BuXPhosAuNTf2 是首选催化剂，助剂无水醋酸钠显著促进了反应。
• Verkade Base in FLP Chemistry–From Stoichiometric C–H Bond Cleavage to the Catalytic Dimerization of Alkynes
  作者：Amandeep Brar、Suresh Mummadi、Daniel K. Unruh、Clemens Krempner

  DOI：10.1021/acs.organomet.0c00411

  日期：2020.12.14

  terminal alkynes with various FLPs and Lewis acid–base adducts have been investigated. Reactions of phenylacetylene with FLPs composed of the Verkade base N[CH2CH2NPri]3P (1) and the Lewis acids BPh3, 9-hexyl-BBN, and 9-BBN gave [N(CH2CH2NPri)3PH][PhC≡C-BPh3] (2), [N(CH2CH2NPri)3PH][9-hexyl-9-PhC≡C-BBN] (3), and [N(CH2CH2NPri)3PH][9-PhCH═CH-9-PhC≡C-BBN] (4). The binuclear Lewis acid–base adduct (C6F5

  已经研究了末端炔烃与各种FLP和Lewis酸碱加合物的化学计量和催化反应。通过一串FLP苯乙炔的反应中Verkade基组成的N [CH 2 CH 2 NPR我] 3 P（1）和路易斯酸BPH 3，9-己基-BBN，和9-BBN，得到[N（CH 2 CH 2 NPR我）3 PH] [PhC≡C-BPH 3 ]（2），[N（CH 2 CH 2 NPR我）3 PH] [9己基-9-PhC≡C-BBN]（3），和[N （CH 2 CH 2NPr i）3 PH] [9-PhCH═CH-9-PhC≡C-BBN]（4）。双核路易斯酸碱加合物（C 6 F 5）3 Al–N [CH 2 CH 2 NPr i ] 3 P–Al（C 6 F 5）3（6）有效催化末端炔烃二聚为宝石-1 ，3-烯炔。
• Regioselective Homo- and Codimerization of 1-Alkynes Leading to 2,4-Disubstituted 1-Buten-3-ynes by Catalysis of a (η⁵-C₅Me₅)₂TiCl₂/RMgX System
  作者：Munetaka Akita、Hajime Yasuda、Akira Nakamura

  DOI：10.1246/bcsj.57.480

  日期：1984.2

  A series of 1-alkynes (RC≡CH where R=Et, n-Pr, n-Bu, n-C6H13, cyclohexyl, Ph, Me3Si, Me3SiCH2, and Me3SiOCH2) was found to dimerize regioselectively (>99%) to 2,4-disubstituted 1-buten-3-ynes in 92–99% yields by catalysis of (η5-C5Me5)2TiCl2/i-PrMgBr at 30 °C in 1–3 h. The catalyst system is also effective for the regioselective codimerization of various 1-alkynes with 1-ethynylcyclohexene or ethynylbenzene.

  发现一系列1-炔烃（RC≡CH，其中R=乙基、正丙基、正丁基、正己基、环己基、苯基、三甲基硅基、三甲基硅基亚甲基和三甲基硅氧亚甲基）在30°C下通过(η5-C5Me5)2TiCl2/i-PrMgBr催化，经过1-3小时的反应，能够选择性二聚化（>99%），生成2,4-二取代的1-丁烯-3-炔，产率在92%-99%之间。该催化体系对于各种1-炔烃与1-乙炔基环己烯或乙炔基苯的选择性共二聚化也同样有效。
• Permethyltitanocene-bis(trimethylsilyl) acetylene, an efficient catalyst for the head-to-tail dimerization of 1-alkynes
  作者：Vojtech Varga、Lidmila Petrusová、Jiří Čejka、Vladimír Hanuǔs、Karel Mach

  DOI：10.1016/0022-328x(95)05806-z

  日期：1996.3

  In the series of the (C(5)H(5-n)Me(n))(2)Ti[eta(2)-C-2(SiMe(3))(2)] (n=0-5) (1A-1F) complexes only (C(5)Me(5))(2)Ti[eta(2)-C-2(SiMe(3))(2)] (1F) catalyzed the linear head-to-tail dimerization of 1-alkynes. A selectivity of better than 98% and a turnover number (TN) in the range 1200-1500 mmol of 1-alkyne per mmol of Ti was obtained after 14 d at 30 degrees C for 1-pentyne, 1-hexyne, cyclohexylethyne, phenylethyne and trimethylsilylethyne. Among other complexes in the series, 1A-1D attained TN less than or equal to 25 after 5 d at 30 degrees C and produced mainly a mixture of 1,3,5- and 1,2,4-trisubstituted benzene derivatives. The complex (C(5)HMe(4))(2)Ti[eta(2)-C-2(SiMe(3))(2)] (1E) afforded ca. 20% of the head-to-tail dimers in addition to cyclotrimers but its activity was extremely low, corresponding to TN similar to 7. The rate of dimerization by 1F is controlled by the slow exchange rate of 1-alkynes with bis(trimethylsilyl)acetylene.