3-芳氧基-1，2-丙二醇的合成研究
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摘要
由于化石能源日益枯竭以及出于环境的考虑,寻找可替代的能源已经受到人类很大的关注。生物柴油可作为石油燃料的替代品,具有可再生性、易生物降解、无毒、含硫量低等优点,属于环境友好的燃料,可具有潜在降低大气污染,减少温室效应。但由生产成本高,制约了其发展空间。生产生物柴油是将植物油和甲醇或乙醇通过酯交换反应制备,同时副产大量的丙三醇。如将丙三醇制备出高附加值产品,将能降低生物柴油生产成本,突破制约生物柴油发展的瓶颈。3-芳氧基-1,2-丙二醇是一种重要的有机合成和医药中间体,用于合成如起释缓神经作用的5-芳氧甲基-2-唑烷酮等。
本文以甘油为原料经二步法和以丙烯醇为原料经双氧水环氧化制备缩水甘油,进而与苯酚反应合成3-芳氧基-1,2-丙二醇。研究了工艺条件对反应的影响,探讨了可能的反应的机理。实验结果表明,碱催化剂对一元氯代甘油成环反应制备缩水甘油有较大的影响;W/MCM-41分子筛催化剂能有效催化H_2O_2氧化丙烯醇制缩水甘油,反应的最佳工艺条件:W/MCM-41催化剂50mg,AAL 1mL,H_2O_2 2.7mL,H_2O 5mL,323K和10 h,缩水甘油的产率为92%;碘化钠用作缩水甘油与苯酚反应的催化剂,以摩尔比为1:1.2,在环己烷为溶剂,碘化钠催化剂30mg,温度72℃,反应时间为3 h的条件下,3-苯氧基-1,2-丙二醇的产率为76%。不同类型的酚和缩水甘油反应的实验结果显示,以环己烷作溶剂,碘化钠作催化剂,较适合于此类型反应。
Petroleum resources are increasingly exhausted.The living environment in the world is deteriorating due to a lot of the mobil vehicles emission and the greenhouse gas emission.Biodiesel,which is the clean renewable,non-toxic energy and a typical "Green energy",can be as the alternative energy of petroleum to resolve the energy and environment problems.However,the high production costs restricted the development of biodiesel industry.Biodiesel is synthesized by transesterification of vegetable oils with alcohols.A large amount of glycerol is byproducts from the transesterification reaction.It is necessary to produce products with high added value in order to reduce the costs of biodiesel production and break out the bottlenecks. 3-aryloxy-1,2-propanediol is the important organic synthesis and pharmaceutical intermediate,which can be used in synthesis of 5-(aryloxymethyl)-2-oxazolidinone and so on.
In the thesis the synthesis of glycidyl and 3-aryloxy-1,2-propanediol were studied.Glycidyl was synthesized by two methods.One was two-step method using glycerol as material,and another was epoxidation method using allyl alcohol as material.3-aryloxy-1,2-propanediol was synthesized from glycidyl and phenols.We studied the effects of technological conditions on synthesis reaction and discussed the synthesis mechanism of 3-aryloxy-1,2-propanediol.The results of test showed that base catalysts had greatly influences on the synthesis of glycidyl from chlorine glycerine by cyclization reaction.W/MCM-41 can effectively catalyze the oxidation from allyl alcohol and H_2O_2 to form glycidyl.The optimum conditions to form glycidyl using W/MCM-41 catalyst were as fellow:W/MCM-41 catalyst 50 mg,AAL 1 mL,H_2O_2 2.7mL,H_2O 5mL,reaction temperature 50℃and feeding time10 h, glycidyl yield can reach 92%.The optimum conditions to form 3-aryloxy-1, 2-propanediol using cyclehexane as solvent were as fellow:NaI catalyst 30 mg,the ratio of phenol to glycidyl 1:1.2,reaction temperature 72℃and feeding time3 h, 3-phenoxy-1,2-propanediol yield can reach 76%.The results of test implied that the conversion rate and yield of different kinds of phenols reacting with glycidyl,on the whole,were better with cyclehexane as solvent,NaI as catalyst.
本文以甘油为原料经二步法和以丙烯醇为原料经双氧水环氧化制备缩水甘油,进而与苯酚反应合成3-芳氧基-1,2-丙二醇。研究了工艺条件对反应的影响,探讨了可能的反应的机理。实验结果表明,碱催化剂对一元氯代甘油成环反应制备缩水甘油有较大的影响;W/MCM-41分子筛催化剂能有效催化H_2O_2氧化丙烯醇制缩水甘油,反应的最佳工艺条件:W/MCM-41催化剂50mg,AAL 1mL,H_2O_2 2.7mL,H_2O 5mL,323K和10 h,缩水甘油的产率为92%;碘化钠用作缩水甘油与苯酚反应的催化剂,以摩尔比为1:1.2,在环己烷为溶剂,碘化钠催化剂30mg,温度72℃,反应时间为3 h的条件下,3-苯氧基-1,2-丙二醇的产率为76%。不同类型的酚和缩水甘油反应的实验结果显示,以环己烷作溶剂,碘化钠作催化剂,较适合于此类型反应。
Petroleum resources are increasingly exhausted.The living environment in the world is deteriorating due to a lot of the mobil vehicles emission and the greenhouse gas emission.Biodiesel,which is the clean renewable,non-toxic energy and a typical "Green energy",can be as the alternative energy of petroleum to resolve the energy and environment problems.However,the high production costs restricted the development of biodiesel industry.Biodiesel is synthesized by transesterification of vegetable oils with alcohols.A large amount of glycerol is byproducts from the transesterification reaction.It is necessary to produce products with high added value in order to reduce the costs of biodiesel production and break out the bottlenecks. 3-aryloxy-1,2-propanediol is the important organic synthesis and pharmaceutical intermediate,which can be used in synthesis of 5-(aryloxymethyl)-2-oxazolidinone and so on.
In the thesis the synthesis of glycidyl and 3-aryloxy-1,2-propanediol were studied.Glycidyl was synthesized by two methods.One was two-step method using glycerol as material,and another was epoxidation method using allyl alcohol as material.3-aryloxy-1,2-propanediol was synthesized from glycidyl and phenols.We studied the effects of technological conditions on synthesis reaction and discussed the synthesis mechanism of 3-aryloxy-1,2-propanediol.The results of test showed that base catalysts had greatly influences on the synthesis of glycidyl from chlorine glycerine by cyclization reaction.W/MCM-41 can effectively catalyze the oxidation from allyl alcohol and H_2O_2 to form glycidyl.The optimum conditions to form glycidyl using W/MCM-41 catalyst were as fellow:W/MCM-41 catalyst 50 mg,AAL 1 mL,H_2O_2 2.7mL,H_2O 5mL,reaction temperature 50℃and feeding time10 h, glycidyl yield can reach 92%.The optimum conditions to form 3-aryloxy-1, 2-propanediol using cyclehexane as solvent were as fellow:NaI catalyst 30 mg,the ratio of phenol to glycidyl 1:1.2,reaction temperature 72℃and feeding time3 h, 3-phenoxy-1,2-propanediol yield can reach 76%.The results of test implied that the conversion rate and yield of different kinds of phenols reacting with glycidyl,on the whole,were better with cyclehexane as solvent,NaI as catalyst.
引文
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[2]韩德奇,徐会林等.生物柴油的现状与发展前景[J].国际石油经济,2002,10(5):20-23.
[3]Fangrui Ma,Milford A.Hanna.Biodiesel production:a review[J].Bioresource Technology,1999,70:1-15.
[4]Siti Zullaikah,Chao-Chin Lai,Shaik Ramjan Vali,Yi-Hsu Ju.A two-step acid-catalyzed process for the production of biodiesel from rice bran oil[J].Bioresource Technology,2005,96:1889-1896.
[5]T.Michael Barnard,Nicholas E.Leadbeater,Matthew B.Boucher,et.al.Continuous-Flow Preparation of Biodiesel Using Microwave Heating[J].Energy & Fuels,2007,21:1777-1781.
[6]曹龙奎,张学娟,包鸿慧等.生物柴油制备技术及应用前景[J].农产品加工2005,3:67-70.
[7]何灼成,魏小平,朱瑞国.生物柴油的制备方法及研究进展[J].润滑油与燃料,2006,16(3):7-10.
[8]邹世能.甘油生产的状况和未来[J].日用化学工业,1996,3:36-38.
[9]马慧武.甘油的用途[J].青海教育,2003,7-8:92-92.
[10]范凯.甘油生产、应用及国内市场[J].现代化工,1996,5:33-36.
[11]赵国志.开发甘油新用途[J].粮食与油脂,2004,10:50-50.[19]
[12]Robert M.Hanson.The Synthetic Methodology of Nonracemic Glycidol and Related 2,3-Epoxy Alcohols[J].Chemical Reviews,1991,91(4):437-475.
[13]倪永全,杜志云.缩水甘油制备用及单甘酯的合成[J].石油化工,25(8):535-538.
[14]Lee Ho-Seong,Yun Jin-Won,KIM Seong-Jin,et.at.Process for the preparation of glycidyl derivatives[P].PCT002093.2004.
[15]Fan Kai.Production and application of glycerine and its domestic market[J].现代化工,1996,5:33-36.
[16]Kaushik A,Kyle J.Eash,Micholas M,et al.A facile and efficient method for the rearrangement of aryl-substituted epoxides to aldehydes and ketones using bimuth triflate[J].Tethraherton Letters,2001,42:8129-8132.
[17]Janice Gorzynski Smith.Synthetically Reactions of Epoxides[J].Synthesis,1984630-656.
[18]邢其毅,裴伟伟,徐瑞秋等..基础有机化学(上册)[M].北京:高等教育出版社,2005.
[19]D.V.Zakharychev,S.N.Lazarev,Z.A.Bredikhina,et al.Crystallization of chiral compounds 3.3-Phenoxypropane-1,2-diol and 3-(2-halophenoxy)propane-1,2-diols[J].Russian Chemical Bulletin,2006,55(2):230-237.
[20]Nigel R.Baker,Nick G.Byrne,Apollp P.Ecnomides et al.Studies oa new phosphodiesterase inhibitors,Ⅰ.Synthesis of 1(2,3-epoxypropoxy)-2(4)-fluorobenzenes and 1-(2-hydroxy-3-mor Pholinopropoxy and poperzaino)fluorobenzene derivatives[J].Chem.Pharm.Bull, 1995,43(6):1045-1048.
[21]Soon Bang Kang,Eu Jin Ahn,Youseung Kim.A Facile Synthesis of,4(S)-(-)-7,8-dithydro-3-methyl-2H-1,4- benzoxazine by Zinc Chloride Assisted Mitsunobu Cyclization Reaction[J].Tetrahedron Letters,1996.52(37):9317-9320.
[22]Takehiko lida,Noriyoshi Yamamoto,Shigeki Matsunaga,et al.Enantioselective Ring Opening of Epoxides with 4-Methoxyphenol Catalyzed by Gallium Heterobimetallic Complexes:An Efficient Method for the Synthesis of Optically Activel,2-Diol Monoethers[J].CommuniCations,1998,37:2223-2226.
[23]Wende L.Nelson,John E.Wennerstrom,S.Ramnan Sankar.Absolute configuration of glycerol derivatives.3.Synthesis and cupra a circular dichrosm spectra of some chiral 3-aryloxy-1,2-propanediolsand3-aryloxy-1-amino-2-propaneols[J].J.Org.Chem,1977,42(6):1006-1010.
[24]张娟,范晓东,刘毅锋等.5-芳氧甲基-2-唑烷酮的合成及表征[J].应用化学,2006,23(12):1401-1403.
[25]ScaifeM,Shah J.US 6 683 102[P],2004;US 6 407 128[P],2002.
[26]Robert M.Hanson,K.Barry Sharpless.Procedure for the Catalytic Asymmetric Epoxidation of Allylic Alcohols in the Presence of Molecular Sieves[J].J.Org.CHem,1986,51:1922-1925.
[27]Janice M.Klunder,So0 Y.KO,et al.Asymmetric Epoxidation of Allyl Alcohol:Efficient Routes to Homochiralβ-Adrenergic Blocking Agents.J.Org.Chen.1986,51,3710-3712.
[28]李姝,乔兆森.β受体阻滞剂的临床进展.中华临床医学研究杂志[M],2007,13(11):1156-1156.
[29]Michael P.Kirkup,Razia Rizvi,Bandarpalle B.Shankar,et al.(-)-SCH 57939:Pharacological properties of a potent,metabolically stable cholesterol absorption inhibitor.[J].Bioorganic & Medicinal Chemistry Letters,1996,6(17):2069-2072.
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