纳米TiO2催化α-蒎烯空气环氧化反应

 采用硫酸钛和氢氧化钠等无机试剂为原料,经过简单步骤制备出纳米TiO2前驱体,用高压釜在270 ℃和7.07 MPa下进行乙醇热处理,得到锐钛矿型纳米TiO2催化剂,并考察了该催化剂对α-蒎烯空气环氧化反应的催化性能. 结果表明,乙醇高压热处理明显地提高了纳米TiO2的催化活性. 在常压、 70 ℃和6 h条件下, α-蒎烯转化率可达17.02%, 环氧化物选择性为53.47%; 当压力增大到1.01 MPa时,转化率提高到35.24%, 选择性下降到41.20%. 对反应机理进行了探讨.     

AlCl_3／SbCl_3复合体系引发α－蒎烯／苯乙烯阳离子共聚合

比较了ＡｌＣｌ_３和ＡｌＣｌ_３／ＳｂＣｌ_３复合体系的α－蒎烯／苯乙烯阳离子共聚反应及产物的摩尔质量分布。结果表明，由于用ＡｌＣｌ_３体系两种单体活性差大而难以共聚，用ＡｌＣｌ_３／ＳｂＣｌ_３复合体系，苯乙烯聚合速率相对减小，而α－蒎烯聚合速率增大，加之苯乙烯的共催化剂作用，加速α－蒎烯聚合，可使α－蒎烯与苯乙烯进行有效共聚。考察了［Ｓｂ］／［Ａｌ］比、催化剂浓度、单体投料比等对共聚体系α－蒎烯、苯乙烯转化速率及产物Ｍ_ｎ的影响。     

Intramolecular enantiomerism as revealed from Raman optical activity spectrum

An algorithm is employed to retrieve the differential bond polarizabilities (DBP) of the C‐C bonds from the Raman optical activity spectrum of (‐)β‐pinene. (‐)β‐pinene possesses two stereo centers (chiral centers) and a local mirror reflection that interchanges the S type part and R type part in one molecular. It is demonstrated that this local mirror reflection could induce an approximate (or symmetry breaking) mirror reflection that reverses the signs of the DBP of the pair bond coordinates that are related to each other by the mirror reflection.This can be called intramolecular enantiomerism (IE). More cases of IE are discussed by the analysis of (‐)α‐pinene, (R)‐(+)‐4‐isopropyl‐1‐methylcyclohexene and (R)‐(+)‐3‐methylcyclohexanone together with previously studied limonene case. Copyright © 2015 John Wiley & Sons, Ltd.     

Infrared Detection of Criegee Intermediates Formed during the Ozonolysis of β‐Pinene and Their Reactivity towards Sulfur Dioxide

Recently, direct kinetic experiments have shown that the oxidation of sulfur dioxide to sulfur trioxide by reaction with stabilized Criegee intermediates (CIs) is an important source of sulfuric acid in the atmosphere. So far, only small CIs, generated in photolysis experiments, have been directly detected. Herein, it is shown that large, stabilized CIs can be detected in the gas phase by FTIR spectroscopy during the ozonolysis of β‐pinene. Their transient absorption bands between 930 and 830 cm^?1 appear only in the initial phase of the ozonolysis reaction when the scavenging of stabilized CIs by the reaction products is slow. The large CIs react with sulfur dioxide to give sulfur trioxide and nopinone with a yield exceeding 80 %. Reactant consumption and product formation in time‐resolved β‐pinene ozonolysis experiments in the presence of sulfur dioxide have been kinetically modeled. The results suggest a fast reaction of sulfur dioxide with CIs arising from β‐pinene ozonolysis.     

Hydrogen-Peroxide Epoxidation of Natural Olefins Catalyzed by a Dinuclear Manganese Complex

The complex of Mn(IV) with the macrocyclic N-containing ligand 1,4,7-trimethyl-1,4,7-triazacyclononane (L) [L₂Mn₂O₃](PF6)2 catalyzes epoxidation of (+)-limonene in CH₃CN solution at room temperature. Adding CH₃COOH accelerates the reaction. The products are isomers of limonene epoxide with predominance of that with an epoxified ring double bond. Epoxidation of - and -pinene by this system is less effective, apparently due to extensive steric shielding of the double bonds in the pinenes.     

蒎烯常压气相催化加氢制蒎烷的研究

利用固定床连续反应装置 ,研究了催化剂对蒎烯在常压气相加氢制蒎烷的催化性能 ,通过大量的筛选 ,得到一种高效催化剂。考察了反应条件对催化性能的影响。     

蒎烯衍生的有机硼化合物的合成及在不对称还原中的应用

综述了由蒎烯衍生的六种有机硼还原剂的合成方法,并讨论了这些还原剂对十类不同类型酮的还原反应及其应用。     

Improved Synthesis of N,N′‐Disuccinimidyl Carbonate using α‐Pinene as Acid Scavenger

An improved synthesis of N,N′‐disuccinimidyl carbonate (DSC) is described where α‐pinene is utilized as an efficient scavenger of HCl liberated during the reaction of N‐hydroxysuccinimide with triphosgene in THF. The α‐pinene hydrochloride formed is soluble in THF and gives very pure DSC in good yields.     

α—蒎烯异构成β—蒎烯的一个简便方法

β-蒎烯是一个重要的有机合成原料,但我国松节油中的β-蒎烯含量甚少,主要为α-蒎烯·将α-蒎烯异构化成为β-衍生物已有许多报道。本文将三乙基硼氨合物或三乙基苄基铵合硼烷使之与α-蒎烯反应成二(3-蒎烷基)硼烷,再经热异构重排成二(10-蒎烷基)硼烷,最后与双戊烯进行置换反应,顺利地制得了β-蒎烯。与Brown的方法相比,本法简便、安全,并且用我国合成樟脑生产中的副产物双戊烯代替了十二烯-(1)。     

1:2‐sequence‐regulated radical copolymerization of naturally occurring terpenes with maleimide derivatives in fluorinated alcohol

Naturally occurring bulky terpenes, such as (+)‐ and (–)‐limonene and (–)‐β‐pinene, were quantitatively copolymerized with maleimide (MI) derivatives (i.e., phenyl‐, cyclohexyl‐, ethyl‐, and unsubstituted‐MI) in PhC(CF₃)₂OH solvent via selective 1:2‐alternating propagation governed by the penultimate effect, which resulted in 1:2‐sequence regulated polymers with relatively high glass transition temperatures and optical activities. Similar petroleum‐derived bulky olefins possessing cyclohexenyl, cyclohexyl, or additional α‐methyl substituents were copolymerized with phenylmaleimide via preferential 1:2‐alternating propagation with a slightly lower selectivity. A further decrease in the bulkiness of nonpolar olefins increased the 1:1‐alternating sequence. The copolymerization of limonene and acrylonitrile also proceeded approximately via 1:1‐alternating propagation, in which the penultimate effect was less observable. Furthermore, when methylene chloride was used instead of fluorinated alcohol for the copolymerization of limonene and phenylmaleimide, the length of the sequence of MI units increased. Thus, in addition to the characteristic MI skeleton, the bulky and rather specific structure of either limonene or β‐pinene induces 1:2‐selective propagation via the penultimate effect, whereas the fluoroalcohol diminishes the homopropagation of MI via a hydrogen bonding interaction with the MI unit. RAFT copolymerization of limonene and various MI derivatives in PhC(CF₃)₂OH successfully proceeded to give the end‐to‐end 1:2‐sequence‐regulated copolymer with a selective initiating sequence and predominant capping sequence using an appropriate RAFT agent. © 2013 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2013