2,2,6,6-四甲基庚-3,4-二烯 | 42066-39-7

• 分子结构分类: 有机化合物 - 叠烯 - 无环联烯
• 中文名称: 2,2,6,6-四甲基庚-3,4-二烯
• 英文名称: 1,3-di-tert-butylallene
• 英文别名: 2,2,6,6-tetramethyl-3,4-heptadiene；(+)-1,3-Di-t-butylallen；2,2,5,5-Tetramethyl-3,4-heptadiene
• CAS: 42066-39-7
• 化学式: C₁₁H₂₀
• 分子量: 152.28
• InChiKey: FHXBUDRDWFMOLC-UHFFFAOYSA-N

物化性质

• 沸点：
  42-43 °C(Press: 12 Torr)
• 密度：
  0.752±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.9
• 重原子数：
  11
• 可旋转键数：
  2
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.73
• 拓扑面积：
  0
• 氢给体数：
  0
• 氢受体数：
  0

反应信息

• 作为反应物：
  描述：

  2,2,6,6-四甲基庚-3,4-二烯 在 二甲基二环氧乙烷 、 potassium carbonate 作用下， 以 丙酮 为溶剂， 反应 0.42h， 以98%的产率得到2,5-di-tert-butyl-1,4-dioxaspiro<2.2>pentane
  参考文献：
  名称：

  1,4-Dioxaspiro[2.2]pentanes. Synthesis, spectroscopic properties, and reactions with nucleophiles

  摘要：

  A number of simple allenes have been converted cleanly to the corresponding 1,4-dioxaspiro[2.2]pentanes in good yields by oxidation with dimethyldioxirane. Mono- and trisubstituted allenes give the anti diastereomers with good stereoselectivity, whereas 1,3-disubstituted allenes show only a slight preference for the anti,anti isomers, unless steric effects are extreme. Stereochemical assignments are based on steric considerations and a consistent set of NMR characteristics that permit structural attributions. The addition of a range of nucleophiles (water, alcohols, amines, thiophenol, acetate, chloride, and fluoride) to these intermediates proceeded smoothly under buffered conditions to give highly functionalized products of general type 5. These reactions were shown to take place with the appropriate selectivities for S(N)2 substitutions in instances where these features were observable, namely, regioselective attack at the less-substituted epoxide carbon and inversion of configuration at the site of substitution. Under acidic conditions dioxaspiropentanes gave mixtures of other types of products, which appear to arise from carbocationic processes.

  DOI：

  10.1021/jo00003a044
• 作为产物：
  描述：

  trans-di-tert-butylcyclopropanone 在 sodium hydride 作用下， 120.0~190.0 ℃ 、53.33 Pa 条件下， 反应 2.0h， 生成 2,2,6,6-四甲基庚-3,4-二烯
  参考文献：
  名称：

  A cyclopropanone - tosylhydrazide adduct: dehydration to a tosylhydrazone and decomposition; oxidative ring-expansion to a beta-lactam

  摘要：

  DOI：

  10.1016/s0040-4039(01)87120-3

文献信息

• Reactions of 3-alkyl- and 3,3-dialkyl-1-bromoallenes with organocuprates: Effects of the nature of the cuprate reagent on the regio- and stereoselectivity
  作者：Anna Maria Caporusso、Carmela Polizzi、Luciano Lardicci

  DOI：10.1016/s0040-4039(00)96867-9

  日期：1987.1

  Organocuprates induce 1,3- and direct substitution in 3-alkyl- and 3,3-dialkyl-1-bromo-1,2-dienes leading respectively to either terminal acetylenes or allenic hydrocarbons. The nature of the cuprate exerts a prominent role in determining both the regio- and the stereochemistry of these reactions.

  有机酸盐诱导3-烷基-和3,3-二烷基-1-溴-1,2-二烯中的1,3-和直接取代，分别导致末端乙炔或烯丙烃。铜酸盐的性质在确定这些反应的区域化学和立体化学中起着重要作用。
• Reaction of 1-bromo-1,2-dienes with alkylcuprates as a regio- and stereo-selective route to acetylenic or allenic compounds
  作者：Carmela Polizzi、Carla Consoloni、Luciano Lardicci、Anna Maria Caporusso

  DOI：10.1016/0022-328x(91)80179-n

  日期：1991.10

  Alkylcuprates react with 1-bromo-1,2-dienes to give allenic and/or acetylenic products. The selectivity of the crosscoupling is markedly dependent on the nature of the copper reagent, which plays a prominent role in determining both the regio- and the stereo-chemistry. The preparative aspects of these copper-induced reactions are discussed and their possible mechanism discussed.

  烷基杯酸酯与1-溴-1,2-二烯反应生成烯丙基和/或炔属产物。交叉偶联的选择性显着取决于铜试剂的性质，铜试剂在决定区域化学和立体化学方面都起着重要的作用。讨论了这些铜诱导的反应的制备方面，并讨论了其可能的机理。
• Coupling of chiral 1-bromo-1,2-dienes with zinc-based cuprates: a new procedure for the regio and stereoselective synthesis of functionalized acetylenic compounds
  作者：Anna Maria Caporusso、Sara Filippi、Federica Barontini、Piero Salvadori

  DOI：10.1016/s0040-4039(99)02249-2

  日期：2000.2

  are found to be active in the cross-coupling reaction with allenic bromides affording acetylenic products with a high regio and stereoselective 1,3-anti substitution. The coupling process, which has been successfully extended to functionalized cuprates, can also be performed with alkylzinc chlorides in the presence of catalytic amounts of cuprous salts.

  发现烷基氰基古朴酸锌（Knochel试剂）在与烯丙基溴的交叉偶联反应中具有活性，从而提供具有高区域和立体选择性1,3-抗取代作用的炔属产物。偶联过程已经成功地扩展到官能化的铜酸盐，也可以在催化量的亚铜盐存在下用烷基锌氯化物进行偶联。
• Electrophilic additions to allenes—II
  作者：Dennis G. Garratt、Pierre L. Beaulieu、M.Dominic Ryan

  DOI：10.1016/s0040-4020(01)83115-x

  日期：1980.1

  Benzeneselenenyl chloride reacts with 1,3-dialkyl-substituted allenes in methylene chloride solution to give 1:1-adducts. Attack by selenium is found to occur exclusively at the central allenic carbon. In contrast to the analogous reaction of arenesulphenyl chlorides, the preferential formation of the Z-alkene is observed. A mechanism involving the preequilibrium formation of alkylideneseleniranium

  苯硒基氯与二氯甲烷中的1,3-二烷基取代的丙二烯反应，生成1：1的加合物。发现硒的攻击仅发生在中心艾伦碳上。与芳烃磺酰氯的类似反应相反，观察到Z-烯烃的优先形成。提出了一种机制，该机制涉及烷基亚烯基亚硒酸根离子和/或亚烷基亚乙基二硒基呋喃的预平衡形成，在产物确定步骤中，该化合物通过氯在环的次甲基碳上的抗攻击而崩解成产物，以解决Z-优先形成的问题。异构体。
• Etude de la cycloaddition du dimethylcetene aux allenes—I
  作者：M. Bertrand、R. Maurin、J.L. Gras、G. Gil

  DOI：10.1016/0040-4020(75)80090-1

  日期：1975.1

  Thermal cycloaddition of dialkylketenes to 1,2 dienes is a versatile synthetic route to conjugated alkylidenecyclobutanones. The central carbons of the allene and of the ketene react together resulting in a regiospecific addition.

  将二烷基烯酮热环加成至1,2二烯是共轭亚烷基环丁酮的通用合成路线。丙二烯和乙烯酮的中心碳一起反应，从而产生区域特异性的加成。