α-pinene

• 分子结构分类: 有机化合物 - 碳氢化合物 - 不饱和烃
• 英文名称: α-pinene
• 英文别名: (1S,5R)-3,6,6-trimethylbicyclo[3.1.1]hept-2-ene
• 化学式: C₁₀H₁₆
• 分子量: 136.237
• InChiKey: ZJUDTXCEVUJEOX-BDAKNGLRSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.0
• 重原子数：
  10.0
• 可旋转键数：
  0.0
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.8
• 拓扑面积：
  0.0
• 氢给体数：
  0.0
• 氢受体数：
  0.0

反应信息

• 作为反应物：
  描述：

  α-pinene 在 2-吡啶甲酸 、 6-甲基-2-吡啶甲酸 、 双氧水 、 iron(II) acetate 作用下， 以 水 、 乙腈 为溶剂， 反应 0.25h， 以2%的产率得到α-pinene oxide
  参考文献：
  名称：

  两种简单的吡啶甲酸配体在无卤反应条件下的组合，对铁链烯烃进行实用的铁催化过氧化氢环氧化

  摘要：

  AbstractHigh‐yield syntheses of epoxides using an iron complex having two types of picolinates in the presence of hydrogen peroxide under halide‐free reaction conditions were achieved. The reaction is very simple. The complex, prepared with iron(II) acetate, 2‐picolinic acid (picH) and 6‐methyl‐2‐picolinic acid (Me‐picH) in acetonitrile, quickly catalyzed an epoxidation of styrene (15 min.) at 25 °C with 1.40 equivalents of 35% aqueous hydrogen peroxide solution to afford styrene oxide in 95% yield with 96% selectivity. We also carried out a 100‐g scale epoxidation of styrene using 1.25 equivalents of 35% aqueous hydrogen peroxide solution with the iron catalyst to give styrene oxide in 80% isolated yield. The developed iron catalyst was efficiently applicable to the epoxidation of various aromatic olefins to give the corresponding epoxides in high yields. To obtain more information about this catalytic system, the pre‐catalyst of this reaction was isolated and the structure was determined to be [Fe(pic)(Me‐pic)2] by single‐crystal X‐ray analysis. The [Fe(pic)(Me‐pic)2] catalyst effectively epoxidized styrene to styrene oxide in 93% yields. The system should be suitable for large‐scale preparations of aromatic olefins due to the employment of simple ligands with halide‐ and amine‐free reaction conditions.magnified image

  DOI：

  10.1002/adsc.201300774

文献信息

• Anti‐Markovnikov Radical Hydro‐ and Deuteroamidation of Unactivated Alkenes
  作者：Heng Jiang、Armido Studer

  DOI：10.1002/chem.201901566

  日期：2019.5.23

  Radical anti‐Markovnikov hydro‐ and deuteroamidation of unactivated alkenes was achieved by merging photoredox and thiol catalysis. Reactions proceed by addition of the electrophilic CbzHN‐radical (Cbz=carbobenzyloxy), readily generated by single‐electron‐transfer (SET) oxidation of an α‐Cbz‐amino‐oxy acid to an alkene. The adduct radical is reduced by thiophenol added as an organic polarity reversal

  通过结合光氧化还原和硫醇催化，实现未活化烯烃的自由基抗马尔科夫尼科夫加氢和氘代氨基酰胺化反应。反应通过添加亲电子的CbzHN自由基（Cbz =羰基苄氧基）进行，该过程很容易通过α-Cbz-氨基氧基酸的单电子转移（SET）氧化反应生成烯烃。加成物自由基被作为有机极性反转助催化剂加入的苯硫酚还原，后者介导H从H 2 O转移至烷基自由基中间体。因此，通过使用D 2，以优异的D掺入实现了烯烃的氘代氨基酰胺化。O为化学计量形式的自由基还原剂。该反应具有低氧化还原催化剂负载量，出色的抗马尔可夫尼科夫选择性，并且不需要使用大量的过量烯烃。通过这种方法可以得到各种Cbz保护的伯胺，包括β氘代的胺。
• Molecular Addition Compounds. 13. <i>N,N</i>-Diisopropyl-<i>N</i>-isobutylamine−Borane:  The First Highly Reactive Trialkylamine−Borane Reagent for Hydroborations
  作者：Herbert C. Brown、J. V. Bhaskar Kanth、Marek Zaidlewicz

  DOI：10.1021/om980629z

  日期：1999.3.1

  the hydroboration of simple, unhindered olefins to the trialkylborane stage. Moderately hindered olefins, such as cyclohexene and 2-methyl-2-butene, give the corresponding dialkylboranes rapidly, with further hydroboration to the trialkylborane stage slower. However, the hindered α-pinene and 2,3-dimethyl-2-butene structures give stable monoalkylboranes very rapidly, with further hydroboration proceeding

  当将乙硼烷鼓泡到纯胺中时，N，N-二异丙基-N-异丁胺（1）形成稳定的液态硼烷加合物（在BH 3中为4.7 M ）。这样形成的加合物在惰性气氛下在室温下无限稳定。使用这种新的高反应性胺-硼烷加合物H 3 B：NPr i进行硼氢化研究2卜我（2）和代表性的烯烃，如1-己烯，苯乙烯，β-pine烯，环戊烯，降冰片烯，环己烯，2-甲基-2-丁烯，α-pine烯和2,3-二甲基-2-丁烯于室温（22±3°C），选定的溶剂，四氢呋喃，二恶烷，叔丁基甲基醚，正戊烷和二氯甲烷中萃取。在二恶烷和正己烷中反应更快-戊烷，需要约2小时才能将简单的无阻烯烃加氢硼化为三烷基硼烷阶段。中度受阻的烯烃，例如环己烯和2-甲基-2-丁烯，可以快速生成相应的二烷基硼烷，而硼氢化进一步进行到三烷基硼烷阶段则较慢。然而，受阻的α-pine烯和2，3-二甲基-2-丁烯结构非常迅速地产生稳定的单烷基硼烷，而进一步的硼氢化反应则相对
• Kinetics of the Oxygenation of Unsaturated Organics with Singlet Oxygen Generated from H₂O₂ by a Heterogeneous Molybdenum Catalyst
  作者：Bert F. Sels、Dirk E. De Vos、Pierre A. Jacobs

  DOI：10.1021/ja065849f

  日期：2007.5.1

  A heterogeneous catalyst containing MoO42- exchanged on layered double hydroxides (Mo-LDHs) is used to produce O-1(2) from H2O2, and with this dark O-1(2), unsaturated hydrocarbons are oxidized in allylic peroxides. The oxidation kinetics are studied in detail and are compared with the kinetics of oxidation by O-1(2), formed from H2O2 by a homogeneous catalyst. A model is proposed for the heterogeneously catalyzed O-1(2) generation and peroxide formation. The model divides the reaction suspension in two compartments: (1) the intralamellar and intragranular zones of the LDH catalyst; (2) the bulk solution. The 2-compartment model correctly predicts the oxidant efficiency and peroxide yield for a series of olefin peroxidation reactions. O-1(2) is generated at a high rate by the heterogeneous catalyst, but somewhat more O-1(2) is lost by quenching with the heterogeneous catalyst than using the homogeneous catalyst. Quenching occurs mainly as a result of collision with the LDH hydroxyl surface, as is evidenced by using LDH supports containing strong O-1(2) deactivators such as Ni2+. A total of 15 organic substrates were peroxidized on a preparative scale using the best Mo-LDH catalyst under optimal conditions.
• Joulain,D.; Rouessac,F., Bulletin de la Societe Chimique de France, 1973, p. 1428 - 1433
  作者：Joulain,D.、Rouessac,F.

  DOI：——

  日期：——
• New approaches to the development of high-performance hydrocarbon propellants
  作者：M. V. Savos’kin、L. M. Kapkan、G. E. Vaiman、A. N. Vdovichenko、O. A. Gorkunenko、A. P. Yaroshenko、A. F. Popov、A. N. Mashchenko、V. A. Tkachev、M. L. Voloshin、Yu. F. Potapov

  DOI：10.1134/s1070427207010065

  日期：2007.1

  An approach to express screening of promising hydrocarbon propellants, based on the calculation of the specific impulse of an engine from the results of quantum-chemical calculation of their heats of combustion, was suggested. The approach ensures high accuracy irrespective of the composition and structure of the compounds under consideration. Polycyclic and framework hydrocarbons with small rings were suggested as promising propellants.