羰基基团具有强的反应活性和生物活性，广泛存在于天然生物活性产物和药物分子中，其合成及衍生化反应在化学和医药领域都有着重要的应用。羰基的Norrish型光化学反应一直以来都是有机化学以及药物研究工作者的聚焦热点。 本文以Norrish光化学反应为核心，设计并合成烷基芳基酮类化合物，研究其在液相和固相条件下的不对称合成反应，并对不饱和羰基化合物虾青素脂质体的制备与抗氧化的生物性能进行探索。 合成三种二环和两种链状脂肪族苯基酮衍生物，在液相乙腈为溶剂条件下，经光激发四种含有γ-碳上的氢原子的光照前体化合物均发生Norrish II光化学反应。不含γ-氢结构的β，γ-不饱和醛得到Norrish I型光裂解产物，产物不具有手性结构。含γ-碳上氢原子结构的四种脂肪族苯基酮，经光照得到Norrish II型光化学产物。实验结果表明了连有甲基的羰基邻位碳为季碳时的光化学产物仅为环化产物，没有裂解产物。连有一个氢原子的羰基邻位碳发生的Norrish II型反应，光反应产物中同时得到裂解产物和环化产物。证明了我们提出的羰基与γ-氢之间的距离在(2.7±0.2)Å之内发生Norrish II光化学反应的机理是合理的。 对Norrish II型光化学反应进行固相条件下的不对称合成研究，将具有γ氢结构的四种脂肪族芳基酮制备成羧酸，与手性胺反应形成羧酸铵盐，在固相条件下进行光化学反应。5-甲基-二环[1.1.1]戊烷芳基酮羧酸铵盐，甲基二环[2.1.1]己基芳基酮羧酸铵盐，2-异丁基-苯基异戊基酮羧酸铵盐均获得光环化产物，ee值最高分别为60％，98％和99％；不含甲基的二环[2.1.1]己基芳基酮羧酸铵盐，获得光环化产物和光裂解产物比例为1:4，裂解产物最高ee值为43％。二环[2.1.1]己基芳基酮羧酸铵盐在反应过程中晶体发生熔化现象破坏了晶体的手性空间群构型影响到产物的立体选择性。X射线单晶衍射获得的晶体参数反映产物的立体选择性受自由基中间体p-轨道重叠的控制，对晶体结构中的几何参数〓1和〓4进行理论剖析。2-异丁基-苯基异戊基酮羧酸铵盐在不同温度下可获得构象组成不同的晶体，羧酸铵盐晶体构象是影响立体选择性的主要因素。 选取典型不饱和羰基化合物虾青素为研究对象，对其脂质体的制备方法和抗氧化性能进行了研究。逆向蒸发法制备的脂质体外观上均匀圆整，可得到较好的包封率，是制备虾青素脂质体较适用的方法之一。对虾青素脂质体制备影响因素进行了探索，磷脂与胆固醇的比值，药脂比值，反应温度对制备的脂质体稳定性有不同程度的影响，最佳条件为：磷脂0.4 g，胆固醇0.1 g，0.2％虾青素乙醇溶液15 mL，即磷脂与胆固醇的比(g:g)4:1，药脂比(mL:g)30:1，药物溶液pH5.5，反应温度40℃。以过氧化氢作为活性氧分子诱导剂在紫外线作用下氧化损伤视神经细胞，虾青素脂质体作用下细胞凋亡率明显下降，对氧化损伤致星形胶质细胞凋亡有抑制作用，用虾青素处理后的caspase-3及caspase-9的活性显著下降，其下降趋势与虾青素的剂量和作用时间正相关。 关键词：Norrish型光化学；脂肪族醛酮；固相不对称合成；手性胺；虾青素

 The carbonyl functional groups are strong reactivity and biological activity, they are widely found in natural bioactive products and pharmaceutical molecules. Their synthesis and derivative reactions have significant applications in the field of both chemistry and medicine. The Norrish Type photochemical reaction of carbonyl has always been a hot spot for organic chemists and pharmacologists. Known Norrish photochemical reaction as the core of this paper, Alkyl aryl ketone compounds with γ-hydrogen are designed and synthesized to study the asymmetric syntheses in both liquid phase and solid phase. The preparation and antioxidant properties of unsaturated carbonyl compound astaxanthin have also been investigated. Three types of bridge rings and two types of chain aliphatic phenylketone derivatives were-synthesized. Norrish II photochemical reactions were observed by irritating the hydrogen light precursor compounds in 4 types of γ - carbon under ultraviolet light where acetonitrile was used as solvent. The Norrish I photocleavage products which were chiral free, were obtained by photochemical reaction of β (without γ-hydrogen) and γ-unsaturated aldehyde. The Norrish II photochemistry products were acquired under illumination of 4 aliphatic phenylketones. This experiment indicated that when the ortho carbon work as quaternary carbon, where the ortho carbon are in a carbonyl group with a methyl methyl group attached, there are no photocleavage products but only photocyclic products. Where the Norrish II type reaction took place when a hydrogen atom attaches to carbonyl group, and there were both photocleavage products and photocyclic products as outcome. The above result determines that the distance between the carbonyl and γ-H must be within (2.7±0.2)Å is an essential condition for the occurrence of Norrish II photochemical reactions. The Norrish II photochemical asymmetric syntheses in solid phase have been studied. Produce carboxylic acids from the 4 aliphatic phenyl ketones with γ-H to react with chiral amine and form carboxylic acid ammonium salts. Norrish II photochemical reactions were carried out with these salts in solid phase. The carboxylic acid ammonium salt of 5-Methyl-bicyclo[l.l.l]pentaniyl-ketone, methyl-bicyclo[2.1.1]hexyl-aryl-ketone and 2-isobutyl-phenyl-isopentyl-ketone all produced photocyclic products, the maximum enantiomer excess (ee value) is 60 %, 98% and 99 %, respectively. For the bicyclo[2.1.1]ammonium hexyl arylketone carboxylate without methyl, both photocyclic products and photolysis products were simultaneously obtained at a ratio of 1:4, where the maximum ee valve of photolysis products is 43%. The crystals of bicyclo[2.1.1]ammonium hexyl arylketone carboxylate melted down of during the reaction broke the chiral space structure thus affected the stereoselectivity of products. The crystal parameters obtained by X-ray single crystal diffraction reflect that the stereoselectivity of the product is controlled by the free radical intermediate p-orbital overlap, and the theoretical analysis and interpretation of the geometric parameters 〓1 and 〓4 obtained in the crystal structure were carried out. 2-isobutyl-phenyl iso-amyl-ketone carboxylate ammonium salt produces various crystals at different temperatures, therefore crystal of ammonium salt is a main factor of stereoselectivity. The preparation process and antioxidant properties of the typical unsaturated carbonyl compound astaxanthin liposome were studied. The liposomes prepared by reverse evaporation method were uniform in appearance, and able to achieve a good encapsulation rate. It is one of the appropriate methods for preparing astaxanthin liposomes. The factors influenced the preparation of astaxanthin liposome were explored. The ratio of phospholipids to cholesterol, drug lipid ratio and the reaction temperature had different degrees of influence on the stability of the preparation of liposomes. The best conditions were: phospholipids 0.4 g, cholesterol 0.1 g, 0.2 % astaxanthin ethanol solution 15 mL hence phospholipid to cholesterol ratio (g:g) 4:1, drug lipids ratio(mL:g) 30:1, solution pH 5.5, reaction temperature 40℃. Using hydrogen peroxide as a reactive oxygen molecule inducer to oxidize the optic nerve cells under ultraviolet light, the apoptosis rate was formed to decrease significantly under the influence of astaxanthin liposome, the apoptosis of astrocytes caused by oxidative damage and were partially inhibited. There was an obvious decline shown in the liveness of caspase-3 and caspase-9 declined after being in contact with astaxanthin, and the decreasing trend was positively related to the dose and action time of astaxanthin. Keywords: Norrish type photochemistry, aliphatic aldehydes, solid phase asymmetric synthesis, chiral amine, astaxanthin