CAJ | 학술논문

在固体超强酸催化作用下β - 蒎烯和无水草酸平稳地发生酯化反应,生成草酸龙脑酯;加入氢氧化钠溶液发生皂化反应得到龙脑.酯化反应采用程序升温的方式(65℃、 1h, 75℃、 4h, 90℃、 1h),皂化反应时间为1h.在上述反应条件下,当催化剂SO_4~(2-)/ZrO_2用量为7%时(以β - 蒎烯质量计,下同),粗龙脑产率为62.0%,产品中正、异龙脑比为13.6: 48.7;当催化剂S_2O_8~(2-) /ZrO_2用量为7%时,粗龙脑产率为66.7%,正、异龙脑比为11.5: 49.5;这两种催化剂对正龙脑选择性比较差.当用稀土复合固体超强酸SO_4~(2-) /ZrO_2 - CeO_2为催化剂,用量3%时,粗龙脑产率为56.1%,但对正龙脑的选择性高于其他催化剂,正、异龙脑比为46.0: 23.2.
재고체초강산최화작용하β - 파희화무수초산평은지발생지화반응,생성초산용뇌지;가입경양화납용액발생조화반응득도용뇌.지화반응채용정서승온적방식(65℃、 1h, 75℃、 4h, 90℃、 1h),조화반응시간위1h.재상술반응조건하,당최화제SO_4~(2-)/ZrO_2용량위7%시(이β - 파희질량계,하동),조용뇌산솔위62.0%,산품중정、이용뇌비위13.6: 48.7;당최화제S_2O_8~(2-) /ZrO_2용량위7%시,조용뇌산솔위66.7%,정、이용뇌비위11.5: 49.5;저량충최화제대정용뇌선택성비교차.당용희토복합고체초강산SO_4~(2-) /ZrO_2 - CeO_2위최화제,용량3%시,조용뇌산솔위56.1%,단대정용뇌적선택성고우기타최화제,정、이용뇌비위46.0: 23.2.
Bornyl oxalate was formed smoothly by esterification of β-pinene with anhydrous oxalic acid using solid superacid as catalyst. Borneol was obtained by saponification of bornyl oxalate with NaOH solution. Esterification was conducted by temperature programming method (65℃ 1h, 75℃ 4h, 90℃ 1h)and the time of saponification was 1 h. When the amount of SO_4~(2-) /ZrO_2 catalyst was 7% of the mass of β-pinene, the yield of product was 62.0%,and the mass ratio of borneol to isoborneol in the product was 13.6: 48.7. When the amount of S_2 O_8~(2-) /ZrO_2 catalyst was 7% of the mass of β-pinene, the yield of product was 66.7%,the mass ratio of borneol to isoborneol in the product was 11.5: 49.5. Both two catalysts were poor for borneol selectivity. The yield of product was 56.1% when rare-earth composite solid superacid SO_4~(2-)/ZrO_2 - CeO_2 was used as catalyst at dosage of 3% of the mass of β-pinene, while mass ratio of borneol to isoborneol in the product reached 46.0: 23.2, showing higher borneol selectivity than other catalysts.