【作者】 周忠；

【导师】 王建新；

【作者基本信息】 江南大学 ， 应用化学， 2004， 硕士

【摘要】 本论文主要研究了天然的抗氧剂和化妆品助剂——大豆黄素（大豆、葛根等植物中的主要活性成分）和芒柄花素（三叶草、黄芪类中药等植物中的主要活性成分）的合成工艺的探索和优化,产品鉴定以及美白和抗氧化性能。采用脱氧安息香路线两步法合成大豆黄素和芒柄花素。其中第一步2,4,4’-三羟基脱氧安息香和2,4-二羟基-4’-甲氧基脱氧安息香的制备分别是合成大豆黄素和芒柄花素的关键中间体。它们是在路易斯酸催化下,由原料间苯二酚分别与对羟基苯乙酸和对甲氧基苯乙酸经傅-克酰化反应得到。产品经重结晶和脱色后,通过熔点、紫外和红外光谱分析鉴定为2,4,4’-三羟基脱氧安息香和2,4-二羟基-4’-甲氧基脱氧安息香。对它们合成工艺条件进行了优化,收率分别达到了85.83%和95.23%。同时对纯化条件也进行了研究。大豆黄素和芒柄花素分别是由2,4,4’-三羟基脱氧安息香和2,4-二羟基-4’-甲氧基脱氧安息香与环合试剂作用,经过增碳-关环反应得到。实验中探索了四种不同的环合方法,最后找到了较适宜的催化剂和两种环合试剂。产品纯化后,通过熔点、紫外、红外、1H-核磁共振谱和质谱分析鉴定为大豆黄素和芒柄花素。大豆黄素是以DMF-POCl₃为环合试剂制得,经过单因素实验优化后收率达到了89.15%,纯化后产品用HPLC分析纯度为96.43%。芒柄花素则是以DMF-PCl5为环合试剂制得,经过单因素实验优化后收率达到了97.60%,高于文献报道的最好收率90%,纯化后产品用HPLC分析纯度为96.87%。同时对它们的优化条件也作了初步研究。优化后的脱氧安息香路线是一条反应条件相对较温和、可控性较好、步骤少操作简便以及反应时间短的合成路线,为工业化大规模合成大豆黄素和芒柄花素提供了可能.研究了油溶性美白剂的抑制酪氨酸酶活性的测试体系。通过测定油溶性美白剂异甘草素在有机溶剂和水中的溶解性,以及有机溶剂对酪氨酸酶的抑制率,以及找到了一个较合适的复配有机溶剂（v）丙二醇:（v）乙酸乙酯=9:1。它与水组成的测试体系可用于测定油溶性和水溶性美白剂对酪氨酸酶活性的抑制率,弥补了目前基于水的化学分析法只适用于水溶性美白剂的局限。从而为开发和评价安全、对皮肤渗透性好及功效更佳的油溶性美白剂提供了一种简便的方法。用该体系测定了异甘草素、甘草素、大豆黄素、芒柄花素以及熊果苷对酪氨酸酶活性的抑制率,最高抑制率分别为97.5%、62.2%、94.2%、32.7%和60.9%。由此可见异甘草素和大豆黄素的抑制效果明显好于熊果苷,是优良的油溶性美白剂。采用经典的Schaal烘箱法,测试大豆黄素和芒柄花素对大豆色拉油的抗氧化作用,并与VE乙酸酯的抗氧化性能相比较。结果表明大豆黄素的抗氧化性略好于芒柄花素,而它们的抗氧化作用均要好于VE乙酸酯。因此,大豆黄素和芒柄花素可作为天然安全的抗氧化剂在化妆品中使用起到延缓皮肤衰老的功效。更多还原

【Abstract】 In this thesis, the synthesis and optimization, performance identification,lightening and antioxidant activities of two natural antioxidants and cosmeticsadditives: daidzein(the main activity constituent of Soybean and Pueraria radix,etc.)and formononetin(the main activity constituent of Trifolium and Hedysarum,etc.)were primarily researched. Using deoxybenzoins route involving two steps to prepare daidzein andformononetin. 2,4,4’-trihydroxydeoxybenzoin and 2,4-dihydroxy-4’-methoxyldeoxybenzoin were the crucial intermediates in the synthesis of daidzein andformononetin ,respectively. They were prepared by Friedel-Crafts acylation ofresorcinol with p-hydroxyphenylacetic acid and p-methoxylphenylacetic acid in thepresence of lewis acid catalyst. After being recrystallizated and decolorized, theproducts were identified to be 2,4,4’-trihydroxydeoxybenzoin and 2,4-dihydroxy-4’-methoxyldeoxybenzoin by m.p., UV and IR. Their synthesis technologicalconditions of the two intermediates were optimized, the yield reached 85.83% and95.23%,respectively. Their purification conditions were also researched.Daidzein and formononetin were obtained by 2,4,4’-trihydroxydeoxybenzoin and2,4-dihydroxy-4’-methoxyldeoxybenzoin reaction with cyclization regents,respectively. Four cyclization methods were researched, and the better catalyst,twocyclization regents were found. After being purified, the products were identifiedto be daidzein and formononetin by m.p., UV, IR, 1H-NMR and MS. were achieved by singlefactor optimization experiments,and the purification conditions were also researched.Daidzein was prepared by DMF-POCl3 as cyclization regents, and the highest yieldrearched 89.15% by single factor optimization experiments. After being purified,thepurity reached 96.43% by HPLC. Formononetin was peepared by DMF-PCl5 as cyclizationregents, and the highest yield rearched 97.60% by single factor optimizationexperiments, which was better than 9O% reported. After being purified,the purity alsoreached 96.87% by HPLC.After being optimized, the deoxybenzoins route became a relatively mild easycontrol, simple manipulation and short reaction time route that could be applied tosynthesis of diadzein and formononetin on a large scale in industry,The test system of oil-soluble lighteners against tyrosinase was researched. Bydetermining the dissolution parameters of oil-soluble lightener isoliquiritigeninin organic solvents and water, and the inhibitory rates of these organic solventsagainst tyrosinase , a test system consisting a compound organic solvent( V(propanediol):V(ethyl acetate)=9:1) and water was found, which could be used todetermine inhibitory rates of oil-soluble or water-soluble lightenersagainst tyrosinase. This test system changed the restriction that the chemicalanalyticmethod on the basis of water could only be applied to water-soluble lighteners.That gave an easy method for development and evaluation of safe, good penetrationcapacity and more efficient oil-soluble lighteners. By this method, the inhibitoryrates of isoliquiritigenin,liquiritigenin,daidzein,formononetin and arbutinagainst tyrosinase were determined, the highest inhibitory rate rearched 97.5%,62.6% , 94.2% , 32.7% and 60.9%, respectively. It showed that daidzein andisoliquiritigenin were perfect oil-soluble lighteners.By critical Schaal oven method, the antioxidant activities of daidzein andformononetin on soybean salad oil were tested and compared with VE aceticester. Theresults showed that the antioxidant activity of daidzein was a little better thanformononetin, and their antioxidant activities were both better than VE aceticester.So daidzein and formononetin couled be used in cosmetics as natural safe antioxitantsto against skin aging.更多还原