一缕青丝万缕愁
At present, the industrial route for the production of cyclohexanone cyclohexane oxidation, there are two First cyclohexane catalytic oxidation, and the other is non-catalytic oxidation of cyclohexane. The traditional process of production of cyclohexyl alcohol and cyclohexanone (KA oil), the process is complex and serious pollution. Therefore, to find a new energy to maximize cyclohexane conversion rate and the selectivity of the alcohol and ketone oxidation method has great significance.Metal porphyrin catalysts to improve the role of traditional crafts shortcomings, showing high activity and selectivity is the main object of study of the catalytic oxidation of cyclohexane.The conversion rate of cyclohexane, cyclohexyl alcohol selectivity of cyclohexanone as the indexes were tetraphenylporphyrin copper (TPPCu), four (m-methylphenyl) porphyrin copper (Tm-MPPCu) (3,4 - dimethylphenyl) porphyrin copper (TDMPPCu) and other three metal porphyrin catalyzed oxidation of cyclohexane synthesis of cyclohexyl alcohol and cyclohexanone experiments, the purpose is to explore the tetraphenylporphyrin copper even methyl substituents at the benzene ring, the number of methyl substituted biomimetic catalytic oxidation of cyclohexane law.The experimental results show that: (1) within the scope of this experimental study, with methyl substituents on the benzene ring of the tetraphenylporphyrin copper, and its catalytic performance has improved, methyl substituted with a base number is more catalytic properties to improve more; (2) three metalloporphyrins have to study indicators of conditions, the optimum catalyst for is TDMPPCu. Suitable reaction conditions: the pressure 1.0MPa, air flow 0.10-0.12m3 / h, the catalyst concentration of 4 × 10-6g / g conditions, the optimum reaction temperature of 150 ° C, the reaction time was 80min. Under these conditions, the cyclohexane conversion rate of 6.23% of alcohol and ketone selectivity of 90.1%.Keywords: cyclohexane; Metalloporphyrins; catalytic oxidation; methyl substituents the number of
细毛1015
一般程序为sulfoxidation 。催化剂的前兆 2 （ 6.3毫克， 0.02 mmol ）被解散， [ bmim ] pf6 （ 0.5毫升） 和甲醇（ 3.2毫升）在20 ml安瓿。硫化物（ 1 mmol ） 接着其次是过氧化氢（ 30 ％ ，水） （ 170 íl ） 。该反应搅拌为在给定的时间（反应 其次是薄层色谱法）后，甲醇被拆除 和残余离子液体提取，用乙醚（三一五毫升） 。合并醚层治疗钠 连二和水洗（三一○毫升） 。乙醚阶段 是干超过硫酸钠，过滤，并集中在真空中。那个 产品纯化常规或biotage闪光色谱法。 对甲苯基甲基亚砜（ 8 B条） 。孤立的产量1 h后的 反应时间， 78 ％ 。核磁共振数据，在根据这些 以前reported.4转换（图3 ）确定 由气相色谱分析反应混合物：的TR （甲苯基甲基硫醚） ） 12.7分钟;的TR （甲苯基甲基亚砜） ） 17.2分钟。 一般程序为回收的离子液体 催化剂体系。催化剂的前体2 （ 6.3毫克， 0.02 mmol ） 被解散， [ bmim ] pf6 （ 0.5毫升）和甲醇（ 3.2毫升）在 20 ml安瓿。硫化物（ 1 mmol ）当时说，其次是 过氧化氢（ 170 íl ） 。反应搅拌为在给定的时间（反应，其次是薄层色谱法）后，其中甲醇 被删除，剩余的离子液体中提取二乙酯 基醚（三一五毫升） 。合并醚层治疗 连二亚硫酸钠和水洗（ 10毫升） 。水相 回到提取用乙醚（三一○毫升） 。合并 醚阶段干燥超过硫酸钠，过滤，并集中在 真空。该产品被孤立的由Flash色谱法。那个 离子液体相后，再用蒸发，其余 乙醚。硫化物（ 1 mmol ）和过氧化氢（ 1.5 equiv ）补充说： 之后，除了甲醇（ 3.2毫升）
