3,3-dimethylbut-1-en-2-yl benzoate | 13988-61-9

• 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: 3,3-dimethylbut-1-en-2-yl benzoate
• CAS: 13988-61-9
• 化学式: C₁₃H₁₆O₂
• 分子量: 204.269
• InChiKey: MTKAZIRCQKOZNB-UHFFFAOYSA-N

物化性质

• 沸点：
  275.8±13.0 °C(Predicted)
• 密度：
  0.997±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.9
• 重原子数：
  15
• 可旋转键数：
  4
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.31
• 拓扑面积：
  26.3
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  3,3-dimethylbut-1-en-2-yl benzoate 在 sodium amide 作用下， 生成 4,4-二甲基-1-苯戊烷-1,3-二酮
  参考文献：
  名称：

  Acylation. I. The Mechanisms of Enol Ester and 1,3-Diketone Formation in the Reaction of Ketone—Enol Systems with Acyl Halides

  摘要：

  DOI：

  10.1021/jo01349a070
• 作为产物：
  描述：

  Te-(2,2-dimethylpropanoyl)methyl benzenecarbotelluroate 反应 5.0h， 以32%的产率得到3,3-dimethylbut-1-en-2-yl benzoate
  参考文献：
  名称：

  Te-1-Acylmethyl and Te-1-Iminoalkyl Telluroesters: Synthesis and Thermolysis Leading to 1,3-Diketones and O-Alkenyl and O-Imino Esters

  摘要：

  A series of Te-1-acylmethyl carbotelluroates was prepared in good isolated yields from the reaction of potassium carbotelluroates with -haloketones in acetonitrile. Thermolysis of the telluroesters afforded vinyl esters in 20-50% yields, while treatment of the carbotellurorates with potassium t-butanolate led to 1,3-diketones in 30-75% yields with the liberation of black tellurium. The reaction of potassium carbotelluroates with -haloaceto oximes gave O-acyl oximes in 50-70% yields via Te-1-iminomethylcarbotelluroates.

  DOI：

  10.1080/10426501003769728

文献信息

• Regioselective Formation of Enol Esters from the Ruthenium-Catalyzed Markovnikov Addition of Carboxylic Acids to Alkynes
  作者：Janine Jeschke、Christian Gäbler、Heinrich Lang

  DOI：10.1021/acs.joc.5b02293

  日期：2016.1.15

  selectivities with up to 99% of the Markovnikov product were achieved. The electronic influence of the substrates on the reaction rate was quantified by Hammett plots. By the use of electron-rich alkynes or highly acidic carboxylic acids, the reaction rate could be increased. Hence, the addition of highly acidic pentafluorobenzoic acid to electron-rich 4-methoxyphenylacetylene can even be carried out

  钌络合物[Ru（CO）2（P（p -C 6 H 4 -X）3）2（O 2 CPh）2 ]（1a，X = CF 3 ; 1b，X = Cl; 1c，X = H ；1d，X = Me；1e，X = OMe）已成功应用于末端区域炔烃的区域选择性马尔可夫尼可夫加成反应，生成了有价值的烯醇酯。催化剂筛选显示出膦的电子性质对活性和选择性有重大影响。催化剂1a达到最高活性，具有最吸电子的膦配体。通过添加催化量的AgOTf，可以进一步提高选择性和活性。此外，Markovnikov产品的选择性高达99％。底物对反应速率的电子影响通过哈米特图定量。通过使用富电子炔烃或高酸性羧酸，可以提高反应速率。因此，甚至可以在25°C下在4小时内定量地向富含电子的4-甲氧基苯基乙炔中添加高酸性五氟苯甲酸。此外，在温和的反应条件下（25–70°C），可以分离出种类繁多的简单的，电子或空间上具有挑战性的底物，具有良好的产率，具有很高的区域选择性。
• Ruthenium(IV)-Catalyzed Markovnikov Addition of Carboxylic Acids to Terminal Alkynes in Aqueous Medium
  作者：Victorio Cadierno、Javier Francos、José Gimeno

  DOI：10.1021/om1010325

  日期：2011.2.28

  promote the selective Markovnikov addition of both aromatic and aliphatic carboxylic acids to a large variety of terminal alkynes, enynes, and diynes as well as propargylic alcohols. In this way, a wide number of enol esters and β-oxo esters could be synthesized in moderate to good yields under mild conditions (60 °C) in an aqueous medium.

  二聚的双（烯丙基）合钌（IV）配合物[的RuCl（μ-Cl）的（η 3：η 3 -C 10 ħ 16）} 2 ]（C 10 H ^ 16 = 2,7-二甲-2,6-二烯-1,8-二基）（5）和单核几个物种的反式-将[RuCl 2（η 3：η 3 -C 10 ħ 16）（L）]（L =二电子给体配体）（6）衍生的从5起已检查过使用水作为绿色反应介质将羧酸加成到末端炔烃上的催化剂。在活动和区域选择性方面的最佳结果与单核获得衍生物的反式-将[RuCl 2（η 3：η 3 -C 10 ħ 16）（PPH 3）]（6A），这是能够促进选择性Markovnikov加成芳族和脂族羧酸都可以用于各种末端炔烃，烯炔和二炔以及炔丙醇。以此方式，可以在温和条件下（60℃）在水性介质中以中等至良好的产率合成大量的烯醇酯和β-氧代酯。
• A unique annulation of 7-azaindoles with alkenyl esters to produce π-conjugated 7-azaindole derivatives
  作者：Shuai-Shuai Li、Chen-Fei Liu、Ying-Qi Xia、Wei-Huan Li、Guo-Tai Zhang、Xiao-Mei Zhang、Lin Dong

  DOI：10.1039/c6ob00730a

  日期：——

  Rhodium(III)-catalyzed N-directed ortho C–H activation and subsequent roll-over C–H activation represents an important strategy to synthesize fused polycyclic compounds. Herein, the novel methodology broadens the scope of the coupling partner to alkenes, which working smoothly with 7-azaindoles has been proven to be an efficient and atom-economical strategy to access complex π-conjugated 7-azaindole

  铑（III）催化的N定向邻位C–H活化和随后的C–H翻转活化是合成稠合多环化合物的重要策略。在本文中，该新方法将偶联伙伴的范围拓宽至烯烃，已证明与7-氮杂吲哚平稳地工作是访问复杂的π-共轭7-氮杂吲哚衍生物的有效且原子经济的策略。
• Regiocontrolled Ru-catalyzed addition of carboxylic acids to alkynes: practical protocols for the synthesis of vinyl estersWe thank Prof. Dr. M. T. Reetz for generous support and constant encouragement, and gratefully acknowledge the DFG, the FCI, and the BMBF for financial support.
  作者：Lukas J. Goossen、Jens Paetzold、Debasis Koley

  DOI：10.1039/b211277a

  日期：2003.3.6

  The catalytic activity of commercially available, air and water stable ruthenium complexes in the addition of carboxylic acids to terminal alkynes was found to be drastically enhanced by the addition of small quantities of base. Moreover, the regioselectivity of the reaction can be controlled by the choice of the base so that both the Markovnikov (Na2CO3) and the anti-Markovnikov products (DMAP) are now easily accessible in excellent selectivities.

  商业可得的，在空气和水中稳定的钌配合物在羧酸与末端炔烃加成反应中的催化活性，采用少量碱的添加后显著增强。此外，反应的区域选择性可以通过选择不同的碱来控制，从而使得Markovnikov（Na2CO3）和反Markovnikov产物（DMAP）都能以优良的选择性轻松获得。
• Rhodium-Catalyzed Selective <i>anti</i>-Markovnikov Addition of Carboxylic Acids to Alkynes
  作者：Alexandre Lumbroso、Nicolas R. Vautravers、Bernhard Breit

  DOI：10.1021/ol102365e

  日期：2010.12.3

  The selective intermolecular anti-Markovnikov addition of carboxylic acids to terminal alkynes yielding valuable Z-enol esters has been achieved for the first time under rhodium-catalyzed conditions. The catalyst system is applicable to a broad substrate scope and displays a wide functional group tolerance.

  在铑催化的条件下，首次实现了将羧酸选择性地分子间反Markovnikov加成到末端炔烃上，从而生成有价值的Z-烯醇酯。该催化剂体系适用于广泛的底物范围并显示出广泛的官能团耐受性。