Method for preparing epoxy caryophyllene from heavy turpentine oil and separating longifolene

Abstract

The invention discloses a method for preparing epoxy caryophyllene from heavy turpentine oil and separating longifolene. The method comprises the following steps: putting heavy turpentine oil into a reaction container, adding organic solvent ethyl acetate, a catalyst and an oxidant; under normal pressure and at the normal temperature, performing epoxidation reaction on caryophyllene in heavy turpentine oil, wherein the caryophyllene is almost not oxidized; then, cooling a reaction mixture, separating out the catalyst, filtering and recycling, and removing a water phase of filtrate through phase separation, distilling an organic phase under reduced pressure to recycle the organic solvent, and performing fractional distillation and separation under reduced pressure to obtain oily liquid products, namely longifolene and epoxy caryophyllene, further adding a few crystal seeds into the epoxy caryophyllene oily liquid to crystallize and separate out the crystal seeds, filtering and collecting crystals under reduced pressure, and drying in vacuum to obtain an epoxy caryophyllene crystal product. According to the method disclosed by the invention, selective catalytic oxidizing reaction process is adopted, the problem that the existing high-purity longifolene is difficult to separate is solved, the epoxy caryophyllene is prepared, and therefore, the method has the advantages of simple operation process, gentle reaction condition, environment-friendly reaction process and the like, and is suitable for industrial production.

Description

technical field [0001] The invention belongs to the technical field of chemical processing and utilization of forest resources, and relates to a method for preparing epoxycaryophyllene and isolating longifolene by using heavy turpentine as a raw material. Background technique [0002] my country's heavy oil annual heavy turpentine is about 8,000 tons, and the output is very impressive. At present, it is mainly burned as boiler fuel, and a small amount is used as solvent, coal flotation agent and felt binder. This not only causes resources to be wasted, but also affects the normal performance of the economic benefits of each rosin factory. [0003] Heavy turpentine is a very valuable resource, which contains a large amount of sesquiterpenes, mainly longifolene, caryophyllene, cedrene, a-santalene, etc. The content of sesquiterpenes in the heavy oil produced in various parts of my country is between 66.9%-99.5%, and the content of longifolene is the highest, which is 45%-65%...

AI Technical Summary

Problems solved by technology

[0005] Longifolene and β-caryophyllene have little difference in boiling point, so it is difficult to directly isolate and process them by rectification. They can only be selectively separated or processed by taking advantage of their differences in molecular structure and chemical reactivity.

For example, people use β-caryophyllene to contain exocyclic terminal C=C double bonds and intracyclic C=C double bonds, while longifolene only contains exocyclic terminal C=C double bonds, β-caryophyllene is in the Prins condensation reaction ( Jiang Fengchi et al., Chemistry and Industry of Forest Products, 1986, 6(1): 29-35; Li Xicheng et al., Chinese Society of Chemistry and Chemical Engineering of Forest Products: Proceedings of Chinese Symposium on Chemistry and Utilization of Tree Extracts, 1986: 119-124.), acid Catalytic hydration reaction (Huang Yuping, Biomass Chemical Engineering, 2006, 40(6): 37-390), Vilsmeier-Haack formylation reaction (Zhong Ping, Forest Products Chemical Communication, 1990, 25(3): 10-13 .) and other chemical reactions are significantly higher than longifolene, and can be preferentially converted into derivatives with higher boiling points, so that longifolene with a higher content can be separated by vacuum distillation, but these methods mostly use toxic or Corrosive chemical reagents (such as peracetic acid, m-chloroperoxybenzoic acid, formaldehyde, etc.) have serious operational safety hazards, environmental pollution and other problems, which are not conducive to industrialization and application

In addition, Chen Changfa also made an eluent by himself, and reduced the content of β-caryophyllene in heavy turpentine through the elution process (Chen Changfa et al., Forestry Chemistry and Industry, 1997, 17(2): 31-34), and then separated it by fractional distillation Three specifications of longifolene products with contents of 80%, 85%, and 90% were obtained, but there is no public report on the eluent used, its elution mechanism, and the utilization of β-caryophyllene in this method

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