催化氧化法从重质松节油制高纯度长叶烯及环氧石竹烯  

Preparation of Highly Pure Longifolene and β-Caryophyllene Epoxide from Heavy Turpentine via Catalytic Oxidation

作　　者：黄道战[1] 蓝虹云[1] 赵志勇 

机构地区：[1]广西民族大学化学化工学院广西林产化学与工程重点实验室,广西南宁530008

出　　处：《精细化工》2016年第6期674-679,692,共7页Fine Chemicals

基　　金：国家自然科学基金(31460174);广西林产化学与工程协同创新中心项目(201406)~~

摘　　要：以过氧磷钼钨酸十六烷基吡啶盐(Cat-PMo2W2O24)为催化剂,质量分数30%H2O2为氧化剂,催化重质松节油中β-石竹烯氧化生成环氧石竹烯;产品结构经气质联用谱、红外光谱、1HNMR及13CNMR谱表征确认。考察了反应温度、溶剂种类、催化剂用量、反应物料比、反应时间对催化反应体系相态以及底物转化率与环氧选择性的影响,得出最优反应条件为:重质松节油2.80 g,催化剂用量为重质松节油质量的1.07%,溶剂乙酸乙酯5m L,H2O2与β-石竹烯的物质的量之比1.78,反应温度35℃,反应时间2.5 h。在该条件下,反应体系为环境友好液-液-固相转移催化反应体系,催化剂易分离回收、重复利用;β-石竹烯转化率和环氧石竹烯选择性分别高达98.1%和98.4%,而长叶烯基本不被氧化;反应结束后,反应混合物经冷却、相分离除去水相,过滤回收催化剂,减压分馏得到高纯度长叶烯(GC含量>92%)和环氧石竹烯(GC含量>95%)。Oxidation of β-caryophyllene in heavy turpentine to β-caryophyllene epoxide in presence of mass fraction 30% hydrogen peroxide（ H2O2） aqueous solution by using peroxyphosphotungstomolybdate cetylpyridinium（ Cat-PMo2W2O24） as a catalyst was reported. The product was structurally identified by means of gas chromatography-mass spectrometer（ GC / MS）,infrared spectroscopy（ IR）,and nuclear magnetic resonance spectroscopy（^1HNMR and ^13CNMR）.The reaction parameters such as reaction temperature,solvent type,amount of catalyst,material ratio,and reaction time,had obvious effect on the phase state of the reaction system,the conversion of β-caryophyllene and the selectivity of β-caryophyllene epoxide. An environment-friendly liquid-liquidsolid phase transfer catalytic system was constructed by using ethyl acetate as a solvent in which the catalyst could easily be recycled. Under optimum conditions〔2. 80 g heavy turpentine,catalyst dosage1. 07%（ based on the mass of the heavy turpentine）,5 m L ethyl acetate,molar ration of hydrogen peroxide and β-caryophyllene 1. 78,reaction temperature 35 ℃ reaction time 2. 5 h〕,the conversion of β-caryophyllene and the selectivity of β-caryophyllene epoxide were up to 98. 1% and 98. 4%,respectively,but the conversion of longifolence was hardly found. After reaction,the reaction mixture was cooled to remove aqueous phase by phase separation,and the catalyst was collected by only a simple filtration. At last,high purity longifolene（ GC content 〉92%） and epoxy caryophyllene（ GCcontent 〉95%） were obtained by vacuum fractionation.

关 键 词：重质松节油 β-石竹烯 过氧磷钼钨酸盐 过氧化氢 催化氧化 环氧石竹烯 长叶烯 

分 类 号：TQ351[化学工程] Q624.13[生物学—生物物理学]