【作者】 丁兴红；

【导师】 林中祥；

【作者基本信息】 南京林业大学 ， 林产化学加工工程， 2003， 硕士

【摘要】 本文以江西吉安林化厂生产的α-蒎烯为原料，对微波辐射下α-蒎烯与脂肪醇、羧酸的加成反应进行了研究，探索了各种因素对α-蒎烯加成反应的影响，确定了较好的工艺条件。 在α-蒎烯与脂肪醇的加成反应中，采用微波辐射下常压回流反应方式，较好的工艺条件为：α-蒎烯0.03mol、甲醇0.12mol、硫酸催化剂用量1.34×10^-3mol、微波功率70W、反应时间100min。采用GC、GC-IR、GC-MS、IR、H¹-NMR等对反应产物进行定量和定性分析，结果表明：微波辐射下α-蒎烯与甲醇的反应产物含有莰烯、柠檬烯、α-小茴香甲醚、异松油烯、异菠基甲醚、菠基甲醚、α-松油基甲醚等，在较好的工艺条件下，主产物α-松油基甲醚的得率为42.5％，选择性为44.7％。参照国内外文献和进行的对比实验可知，微波辐射下α-蒎烯与甲醇加成反应的产物组成与文献报道基本相同，但反应速率提高了近5倍，而且主产物的得率和选择性都有一定的提高。 在α-蒎烯与羧酸的加成反应中，采用低温下微波辐射反应方式，较好的工艺条件为：α-蒎烯0.03mol、甲酸0.15mol、硫酸催化剂用量7.14×10^-4mol、微波功率700W、反应时间40min。采用GC、GC-IR、GC-MS等对反应产物进行定量和定性分析，结果表明：微波辐射下α-蒎烯与甲酸的反应产物含有三环烯、莰烯、对-伞花烃、α-松油烯、γ-松油烯、柠檬烯、异松油烯、甲酸葑醇酯、甲酸异龙脑酯、甲酸龙脑酯、甲酸芳樟酯、甲酸松油酯。参照国内外文献，首次在α-蒎烯与羧酸的加成反应中发现甲酸芳樟酯。在较好的工艺条件下，主产物甲酸松油酯的得率为60.4％，选择性为64.5％。对比实验表明，微波辐射下α-蒎烯与甲酸的加成反应产物成分与对比实验普通加热条件下反应基本相同，但反应速率和主产物的得率和选择性都有一定的提高。 微波辐射下α-蒎烯与甲酸、甲醇的加成反应，缩短了反应时间，提高了反应的选择性，优化了工艺条件，这不仅进一步证实了微波反应速率快、选择性高的优点，同时也为α-蒎烯制备林产精细化学品及其他香料、药物中间体的研发和工业化生产提供新的方法和依据。更多还原

【Abstract】 In this paper,the author used a -pinene as material in the experiment,whichwas produced by the Jian forestry chemical factory in Jiangxi province .By researched some kinds of addition reactions of -pinene with carboxylic acid , methanol under microwave irradiation,the author studied many factors on the reactions and got the optimum process conditions.Microwave irradiation was used as an kind of heating means in addition reaction of a -pinene and methanol,and the optimun experiment factors are as follows: 0.03 mol of a -pinene ,0.12 mol of methanol, 1.34 10-3mol of sulfuric acid (catalyst), 70W of the microwave power, and 100 min of the reaction time.By means of GC, GC-MS, GC-IR, IR, H1-NMR,the reaction products were investigated and the results showed that there are camphene, limoneneN terpinolene, Me a -fenchyl ether, Me -terpinyl ether, Me bornyl ether and Me isobornyl ether containing in the products,and the content of the main product Me a -terpinyl ether is up to 42.5%,the selectivity is 44.7%. Compared with reported papers and comparative experiment,the reactions under microwave irradiation not only have 5 times reaction velocity than that of comparative reactions,but have better productivity and selectivity.Microwave irradiation was used in addition reaction of a -pinene and formic acid ,which was deposed in a cooling environment,and the optimun experiment factors are as follows: O.OSmol of a -pinene, O.lSmol of formic acid, 7 .14 10-4mol of sulfuric acid(catalyst) , 700W of the microwave power, 40 min of the reaction time. By means of GC, GC-MS, GC-IR, the reaction products were investigated and the results showed that there are triylene, camphene, limonene, p-cymene, terpinolene -terpinene, -terpinene, -fenchyl formate, linalyl formate, terpinyl formate, bornyl formate and isobornyl formate containing in the products,and linalyl formate was first discovered in addition reaction of a -pinene and formic acid .The content of the main product terpinyl formate is up to 60.4%,the selectivity is 64.5%. Compared with comparative experiment,the reactions under microwave irradiation have rapid reaction velocity , better productivity and selectivity.This paper studied addition reaction of a -pinene with alcohol(formic acid)under microwave irradiation. The enhancement of significant reaction velocity and the reduction of the reaction time were observed through those addition reaction,and the main product yield was improved. It not only supplied a new evidence in microwave irradiation enhancing reaction rate ,but also provide a new approch in making and a reliable scientific basis for industrialization producing.更多还原