CAJ | 학술논문

龙脑为重要的香料及医药中间体，工业上主要采用酯化-皂化方法合成，即以α-蒎烯为原料在催化剂硼酐/乙酸酐（或偏硼酸等）作用下，与酯化剂无水草酸反应生成草酸酯再皂化生成龙脑。为了提高合成龙脑产率并降低具有一定副作用的异构体异龙脑含量，国内外从酯化过程中所用催化剂着手展开广泛而深入的研究，催化剂主要集中在含硼类、含钛类、硼钛复合类、固体超强酸类及其他类型如离子液体等。硼酐及偏硼酸是工业上常用催化剂，生产工艺成熟，但催化反应过程剧烈放热，不易控制，产品产率不理想，产品中异龙脑含量较高。偏钛酸催化剂是近年开发且已成功应用于工业生产，性能较平稳，但草酸消耗较大，设备要求高。硼钛复合物和硫酸促进型固体超强酸催化剂，龙脑产率及正龙脑选择性均较好，硼钛复合催化剂结合了硼类及钛类催化剂的优点，效果较好，已进行中试应用；硫酸促进型固体超强酸为绿色催化剂，易于回收再利用，具有较好的应用前景。功能化离子液体、大孔型离子交换树脂和杂多酸等其他新型催化剂的研究也取得进展，在产品产率、选择性、经济性和操作安全可控性等方面各有特点。
용뇌위중요적향료급의약중간체，공업상주요채용지화-조화방법합성，즉이α-파희위원료재최화제붕항/을산항（혹편붕산등）작용하，여지화제무수초산반응생성초산지재조화생성용뇌。위료제고합성용뇌산솔병강저구유일정부작용적이구체이용뇌함량，국내외종지화과정중소용최화제착수전개엄범이심입적연구，최화제주요집중재함붕류、함태류、붕태복합류、고체초강산류급기타류형여리자액체등。붕항급편붕산시공업상상용최화제，생산공예성숙，단최화반응과정극렬방열，불역공제，산품산솔불이상，산품중이용뇌함량교고。편태산최화제시근년개발차이성공응용우공업생산，성능교평은，단초산소모교대，설비요구고。붕태복합물화류산촉진형고체초강산최화제，용뇌산솔급정용뇌선택성균교호，붕태복합최화제결합료붕류급태류최화제적우점，효과교호，이진행중시응용；류산촉진형고체초강산위록색최화제，역우회수재이용，구유교호적응용전경。공능화리자액체、대공형리자교환수지화잡다산등기타신형최화제적연구야취득진전，재산품산솔、선택성、경제성화조작안전가공성등방면각유특점。
Borneol is an important intermediate for perfume and pharmaceutical,and it is synthesized fromα-pinene by the esterification-saponification method in industry under the condition of oxalic acid as the esterification agent,and boric anhydride and acetic anhydride(or metaboric acid,etc)as the catalysts. Many in-depth and detailed studies of the catalysts were reported to improve the yield of borneol and reduce the contents of isoborneol that had a certain side-effect. The reported catalysts were mainly boric compounds,titanic compounds,B / Ti composite compounds,sulfated solid superacids and functionalized ionic liquids,etc. Boric anhydride and metaboric acid were commonly used as the industrial catalysts with the mature production technology,but it was difficult to control the reaction because of the vigorous reaction heat. The yield of borneol was unsatisfactory due to much isoborneol accompanied in the product. Metatitanic acid catalyst was developed and successfully used in industrial production. During the reaction,metatitanic acid catalyst exhibited stable catalytic performance,but oxalic acid consumption was big and equipment requirement was high. B / Ti composite compounds and sulfuric acid promoted solid superacid catalysts possessed higher yield of and better selectivity to borneol. B / Ti composite compounds with the advantages of boric and titanic catalysts had good catalytic effect and was applied in pilot scale. The sulfated solid superacids as green catalysts had wide application prospect due to their good recovery and reusability. The research progress in functionalized ionic liquid,macroporous ion-exchange resin,heteropolyacid and other new types of the catalysts with different performance features such as the yield of and selectivity to products, economy and safety controllability of operation was also reviewed.