trans-3,3-Dimethyl-1-butenylacetat | 52291-59-5

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: trans-3,3-Dimethyl-1-butenylacetat
• 英文别名: [(E)-3,3-dimethylbut-1-enyl] acetate
• CAS: 52291-59-5
• 化学式: C₈H₁₄O₂
• 分子量: 142.198
• InChiKey: VQLBWYHONMEASZ-AATRIKPKSA-N

物化性质

• 沸点：
  80 °C(Press: 50 Torr)
• 密度：
  0.901±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.1
• 重原子数：
  10
• 可旋转键数：
  3
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.62
• 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：

  trans-3,3-Dimethyl-1-butenylacetat 在 二甲基二环氧乙烷 作用下， 以 丙酮 为溶剂， 生成 Acetic acid (2S,3S)-3-tert-butyl-oxiranyl ester
  参考文献：
  名称：

  EPOXIDATION OF cis/trans-ENOL ESTERS BY DIMETHYLDIOXIRANE: KINETICS

  摘要：

  DOI：

  10.1515/hc.2003.9.5.433
• 作为产物：
  描述：

  mercury(II) diacetate 、 [(E)-3,3-二甲基-1-丁烯基]氯化汞 在 palladium diacetate 作用下， 以 四氢呋喃 为溶剂， 反应 48.0h， 以42%的产率得到trans-3,3-Dimethyl-1-butenylacetat
  参考文献：
  名称：

  Mercury in organic chemistry. 17. A convenient stereospecific synthesis of enol esters from vinylmercurials

  摘要：

  DOI：

  10.1021/ja00526a035

文献信息

• Ruthenium-catalyzed selective anti-Markovnikov trans addition of carboxylic acids and tail-to-tail dimerization of terminal alkynes
  作者：Karen Melis、Pawel Samulkiewicz、Jacek Rynkowski、Francis Verpoort

  DOI：10.1016/s0040-4039(02)00366-0

  日期：2002.4

  Carboxylic acids react with terminal alkynes in the presence of a catalytic amount of RuClx(p-cymene)(triazol-5-ylidene) to selective generate Z-alk-1-en-1-yl esters. The anti-Markovnikov and trans addition on the terminal alkyne gives access to Z-alkene derivatives of phenylacetylene, t-butylacetylene, 1-octyne, 4-pentynoic acid and 1,7-octadiyne. The dimerization of terminal alkynes catalyzed with the same

  羧酸在催化量的RuCl x（对-异丙基）（三唑-5-亚烷基）的存在下与末端炔烃反应，以选择性生成Z -alk-1-en-1-yl酯。在末端炔烃上的反马尔科夫尼科夫和反式加成反应可以得到苯乙炔，叔丁基乙炔，1-辛炔，4-戊酸和1,7-辛二炔的Z-烯烃衍生物。用相同的Ru-络合物催化的末端炔烃的二聚化优先产生尾-尾偶联反应。
• Stereoselective synthesis of enol acetates by the reaction of alkenylboronates with (diacetoxyiodo)benzene and sodium iodide
  作者：Miki Murata、Kaname Satoh、Shinji Watanabe、Yuzuru Masuda

  DOI：10.1039/a801469h

  日期：——

  Stereochemically pure (E)- and (Z)-alk-1-en-1-yl acetates have been easily prepared by acetoxylation of the (Z)- and (E)-alk-1-en-1-ylboronic acids or their esters, respectively, with (diacetoxyiodo)benzene and sodium iodide, in reasonable yields.

  立体化学纯的（E）-和（Z）-烷基-1-烯-1-基乙酸酯很容易通过（Z）-和（E）-烷基-1-烯-1-基硼酸或其酸的乙酰氧基化制备（二乙酰氧基碘）苯和碘化钠分别以合理的收率得到酯。
• Atom transfer radical addition and enol-ester synthesis catalyzed by Ru–vinylidene complexes
  作者：Tom Opstal、Francis Verpoort

  DOI：10.1016/s0040-4039(02)02233-5

  日期：2002.12

  L) (L=PCy3 or N-heterocyclic carbenes) reveal themselves as a versatile catalyst for the atom transfer radical addition (ATRA) of polyhalogenated alkanes to olefins, such as methylmethacrylate, styrene and 1-octene. Furthermore, these systems are excellent catalysts for the nucleophilic addition of carboxylic acids to terminal alkynes and yielded exclusively alk-1-en-2-yl esters. These complexes can

  Ru-亚乙烯基络合物，Cl 2 Ru CC（H）t But}（PCy 3）（L）（L = PCy 3或N-杂环卡宾）揭示了它们本身是原子转移自由基加成的通用催化剂（将多卤代烷烃转化为烯烃（例如甲基丙烯酸甲酯，苯乙烯和1-辛烯）。此外，这些系统是将羧酸亲核加成至末端炔烃的极佳催化剂，并且仅产生烷基-1-烯-2-基酯。这些络合物也可以通过用AgBF 4处理中性络合物而转化为它们的阳离子对应物，并研究它们在ATRA和乙烯基化反应中的催化潜力。
• Synthesis of Enol Esters and Dimerization of Terminal Alkynes Catalyzed by Neutral and Cationic Vinylidene Ruthenium Complexes
  作者：Francis Verpoort、Tom Opstal

  DOI：10.1055/s-2003-37106

  日期：——

  In the current study Ru(II) vinylidene complexes of the general type: Cl 2 Ru=C=C(H)R}(PR' 3 )L (R = Ph, SiMe 3 , R'=Ph, Cyclohexyl (Cy) and L = phosphine or N-heterocyclic carbene) are synthesized and tested for the addition of carboxylic acids to terminal alkynes. A careful choice of the catalytic system, substrate and carboxylic acid gives access to alk-1-en-2-yl esters, alk-1-en-1-yl esters or

  在目前的研究中，一般类型的 Ru(II) 亚乙烯基配合物：Cl 2 Ru=C=C(H)R}(PR' 3 )L (R = Ph, SiMe 3 , R'=Ph, Cyclohexyl (Cy ) 和 L = 膦或 N-杂环卡宾) 被合成并测试羧酸与末端炔烃的加成。仔细选择催化体系、底物和羧酸可以获得 alk-1-en-2-yl 酯、alk-1-en-1-yl 酯或 enyne 二聚产物。此外，通过用 AgBF 4 处理其中一种配合物，对合成类似的 14 电子物种进行了扩展，并研究了其对催化活性和选择性的影响。
• Catalytic application of a Ru-alkylidene in the nucleophilic addition of several carboxylic acids on terminal alkynes and the homo-coupling of 1-alkynes
  作者：Karen Melis、Dirk De Vos、Pierre Jacobs、Francis Verpoort

  DOI：10.1016/s0022-328x(03)00074-3

  日期：2003.4

  Thermal treatment of Ru-alkylidene (4) bearing a triazol-5-ylidene (NHC) ligand (2) at 110 degreesC and addition of a terminal alkyne generates a ruthenium vinylidene. The thermolysed Ru-alkylidene catalyses the vinylation and dimerisation of 1-alkynes. The nucleophilic addition of acetic acid on terminal alkynes proceeds smoothly and regioselective towards the Markovnikov addition. The addition reaction can be tuned by changing the acidity of the carboxylic acid. At increasing acidity, higher conversion of the triple bond is obtained and the vinylation/dimerisation ratio increases. The direct coupling between two 1-alkynes shows a reactivity order, which decreases from 1-octyne > 1,7-octadiyne > phenylacetylene > 3,3 dimethyl-1-butyne. The regioselectivity is strongly dependent on the nature of the terminal alkyne. (C) 2003 Elsevier Science B.V. All rights reserved.