【作者】 卞金辉；

【导师】 刘雄民；

【作者基本信息】 广西大学 ， 林产化学加工工程， 2007， 硕士

【摘要】 环十五酮是一种高档合成大环麝香，具有天然麝香香气，广泛应用于高档香水和化妆品中。蒜头果是一种产于广西、云南等地的野生植物资源。其油脂中富含15-二十四碳烯酸，是合成环十五酮的理想天然原料。因此，开发蒜头果资源生产名贵香料，对扶持广西老、少、边、山、穷地区经济和促进社会发展具有重要意义。本文开展了以蒜头果油为原料合成环十五酮新方法的研究。主要研究内容和取得的成果有如下几个方面：(1)根据蒜头果油成分含量和分子结构特点，采用三种合成路线合成环十五酮关键中间体——1，15-十五碳二酸二甲酯。三种路线及结果分别如下：路线一：蒜头果油经皂化、酸化、臭氧化和氧化，制得混合长链α，ω-二元脂肪酸，然后酯化得混合α，ω-脂肪二酸二甲酯，其中1，15-十五碳二酸二甲酯收率为26.9％；路线二：蒜头果油经醇解、臭氧化和氧化，制得混合长链α，ω-羧基脂肪酸甲酯，酯化得混合α，ω-脂肪二酸二甲酯，其中1，15-十五碳二酸二甲酯收率为61.7％；路线三：蒜头果油经臭氧化和氧化，制得混合长链α，ω-羧基脂肪酸甘油酯，醇解得混合α，ω-脂肪二酸二甲酯，其中1，15-十五碳二酸二甲酯收率为72.4％。(2)选择出适宜的展开剂，通过柱层析(正己烷∶氯仿=1∶1)和制备薄层色谱(氯仿∶丙酮=9∶0.5)，分离得到1，15-十五碳二酸二甲酯，利用红外和质谱解析了产物结构。(3)对含有多种α，ω-脂肪二酸二甲酯的混合体系，利用偶姻缩合和Clemmensen还原得到产物环十五酮，收率为48.0％。其中关环反应温度为110℃；还原反应温度为100℃，溶剂为冰醋酸。(4)利用层析法分离出环化反应中间体α-羟基环十五酮和环化产物环十五酮，并采用红外光谱(IR)和质谱(MS)进行了结构鉴定。其中环十五酮与标准样品进行比较，结果表明两者的IR和MS一致。更多还原

【Abstract】 Exaltone is a kind of important macrocycle musk compound with natural musk fragrance. It’s widely applied in top grade perfume and cosmetic. Malania oleifera is a kind of wild plant resources in Guangxi and Yunnan. Malania oleifera chunet oil contains massive 15c-tetracosenoic acid, which is an ideal natural raw material for synthesizing exaltone. There’s positive sense in emplodering Malania oleifera to manufacture precious spice for economic development of Guangxi.The novel methods of preparing exaltone from Malania oleifera chunet oil are introduced in the paper. The following aspects are achievements:(1) According to the molecular structure of the compounds in Malania oleifera chunet oil, three processing routs of preparing dimethyl 1,15-pentadecanedioate which is an important intermediary for synthesizing exaltone are introduced in the paper.Route I:α,ω-Binary fatty acid dimethyl ester mixing from Malania oleifera chunet oil is prepared through saponification, acidification, ozonization, oxidation and alcoholysis. The yield of dimethyl 1,15-pentadecanedioate is 26.9%. RouteⅡ:α,ω-Binary fatty acid dimethyl ester mixing from Malania oleifera chunet oil is prepared through alcoholysis, ozonization, oxidation and esterification. The yield of dimethyl 1,15-pentadecanedioate is 61.7%.RouteⅢ:α,ω-Binary fatty acid dimethyl ester mixing from Malania oleifera chunet oil is prepared through ozonization, oxidation and alcoholysis. The yield of dimethyl 1,15-pentadecanedioate is 72.4%.(2)1,15-pentadecanedioate by column chromatography(hexane: chloroform=1:1) and thin layer chromatography(chloroform: acetone=9:0.5), it’s structure is analysised by infrared spectrum and mass spectrum.(3)The yield of exaltone from mixture ofα,ω-binary fatty acid dimethyl ester by acyloin condensation and Clemmensen reduction reaction is 48.0%. The suit temperature of acyloin condensation is 110℃and the temperature of reductive reaction with acetic acid as solvent is 100℃.(4)α-Hydroxycyclopentadecanone and exaltone are isolated by column chromatography and thin layer chromatography. Their structures are confirmed through infrared and mass spectrum and compares exaltone with its standard sample, the result indicates its IR and MS are consistent.更多还原