l-薄荷醇的合成工艺研究
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摘要
以d-香茅醛为原料,合成了l-薄荷醇。考察了反应温度、反应时间、催化剂用量、催化剂位阻对中间体异胡薄荷醇(Ⅵ)收率的影响。合成中间体Ⅵ的最佳工艺条件:甲苯为溶剂,d-香茅醛为起始原料,以铝原子为中心,三苯基苯酚为配体的催化剂用量为1%(摩尔分数),反应温度0℃以下,反应时间5 h。中间产物Ⅵ经加氢还原得到l-薄荷醇,总收率77%,GC纯度99%以上,反应的优点是异构产物少,选择性高,收率稳定。
1-Menthol was synthesized by using d-citronellal as raw material.The effects of reaction temperature, reaction time, catalyst dosage and catalyst steric hindrance on the yield of l-isoplllcgol(Ⅵ)were investigated. The results showed that the optimal reaction conditionsfor the synthesis of intermediateⅥ were obtained as follows:toluene as solvent, d-citronellal as starting material, the catalyst which was used aluminum atom as center andtriphenylphenol as ligand, catalyst dosage 1%(molar fraction), reaction temperature 0 ℃, and reaction time 3 h. A hydrogenation reduction of intermediateⅥ led to 1-menthol. The total yield was 77%, and the GC purity was above 99%.Few isomeric products, high selectivity and stable yield is the advantage of this reaction.
1-Menthol was synthesized by using d-citronellal as raw material.The effects of reaction temperature, reaction time, catalyst dosage and catalyst steric hindrance on the yield of l-isoplllcgol(Ⅵ)were investigated. The results showed that the optimal reaction conditionsfor the synthesis of intermediateⅥ were obtained as follows:toluene as solvent, d-citronellal as starting material, the catalyst which was used aluminum atom as center andtriphenylphenol as ligand, catalyst dosage 1%(molar fraction), reaction temperature 0 ℃, and reaction time 3 h. A hydrogenation reduction of intermediateⅥ led to 1-menthol. The total yield was 77%, and the GC purity was above 99%.Few isomeric products, high selectivity and stable yield is the advantage of this reaction.
引文
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[13]Fan Chao(樊超),Xie Jianhua(谢建华),Zhou Qilin(周其林).Research progress in asymmetric catalytic synthesis of chiral spices[J].Journal of Applied Science and Technology(应用技术学报),2018,18(3):189-219.
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[15]Takayuki O,Kyohei Y.Microbial resolution of dl-isopulegol[J].Agr BioI Chem,1973,37:1687-1689.
[16]Kuhn Walter,Funk Hans-ulrich.Method for producing menthol:US2006167322(A1)[P].2006-07-27.
[17]Liu L F,Zhang Y H,Xin B W.Synthesis of biaryls and polyaryls by ligand-free Suzuki reaction in aqueous phase[J].Journal of Organic Chemistry,2006,71:3994-3997.
[2]Bhatia S P,McGinty D,Letizia C S,et al.Fragrance material review on l-menthol[J].Food and Chemical Toxicology,2008,46(11):218-223.
[3]Xiang J M,Li B L.The stereoselectivesynthesis of 2-aryl-2-hydroxybutanoic acid via menthylchiralauxiliaries[J].Helv Chim Acta,2010,93(10):2015-2022.
[4]Wang Ling(王玲).Study on the synthesis of l-menthol[D].Hangzhou:Zhejiang University(浙江大学),2013.
[5]Chen Zhifei(陈芝飞),Lu Changtong(芦昶彤),Chen Jin(陈8)),et al.Synthesis and thermal cracking of menthylnitrate[J].Fine Chemicals(精细化工),2016,33(10):1118-1124.
[6]Jiang Yuanyuan(姜圆圆),ZhaoYan(赵岩),Wang Shijie(王士杰),et al.Anticonvulsant activity of l-menthol in peppermint[J].Science and Technology of Food Industry(食品工业科技),2018,39(15):5-9.
[7]Li Zhenxiang(李振翔),Huang Yu’e(黄裕娥),Zheng Xufei(郑旭飞).Synthesis of l-menthol[J].Guangdong Chemical Industry(广东化工),2016,43(17):144-145.
[8]Nian Baoyi(念保义),Xu Gang(徐刚),Yang Lirong(杨立荣).Progress in the synthesis and chiral resolution of l-menthol[J].Chemical Industry and Engineering Progress(化工进展),2006,25(4):401-405.
[9]Jacob R G.Green synthesis of(-)-isopulegol from(+)-citronellal:application to essential oil of citronella[J].Tetrahedron Letters,2003,44(18):3605-3608.
[10]Yamamoto T.Method for purifying(-)-N-isopulegol and citrus perfume composition containing(-)-N-isopulegol obtained by the method:US5773410A[P].1998-06-30.
[11]Takeshi I,Yoshiki O,Yoji H.Methord for producing isopulegol:JP2002212121[P].2002-07-31.
[12]Kazuhide T,Tsuneaki Y,Sei O,et al.Highly enantioselective isomerization of prochiralallylaminescatalyzedby chiral diphosphinerhodium(I)complexes.Preparation of optically active enamines[J].J Am Chem Soc,1984,106,5208-5217.
[13]Fan Chao(樊超),Xie Jianhua(谢建华),Zhou Qilin(周其林).Research progress in asymmetric catalytic synthesis of chiral spices[J].Journal of Applied Science and Technology(应用技术学报),2018,18(3):189-219.
[14]Soichi S,Keiji U,Hisashi Y.Asymmetric cyclization of unsaturated aldehydes catalyzed by a chiral lewisacid[J].Tetrahedron,1986,42:2203-2209.
[15]Takayuki O,Kyohei Y.Microbial resolution of dl-isopulegol[J].Agr BioI Chem,1973,37:1687-1689.
[16]Kuhn Walter,Funk Hans-ulrich.Method for producing menthol:US2006167322(A1)[P].2006-07-27.
[17]Liu L F,Zhang Y H,Xin B W.Synthesis of biaryls and polyaryls by ligand-free Suzuki reaction in aqueous phase[J].Journal of Organic Chemistry,2006,71:3994-3997.