【作者】 张卫红；

【导师】 冯亚青；

【作者基本信息】 天津大学 ， 应用化学， 2004， 博士

【摘要】 本文以α-D-葡萄糖为原料,合成了D-阿洛糖,5个D-阿洛糖衍生物及差向异构体,并对D-阿洛糖衍生物进行了氧化减碳反应的应用,重点对羟基保护反应、氧化还原法改变羟基构型、异丙叉基选择性水解反应进行研究,主要包括以下内容: 1.研究了葡萄糖及阿洛糖衍生物的羟基保护反应,得到异丙叉化、苯甲酰化及甲磺酰化三种可行的羟基保护方法,分别以丙酮—浓硫酸—硫酸钠体系及新的2,2-二甲氧基丙烷—对甲苯磺酸体系对α-D-葡萄糖进行异丙叉化反应,合成1,2:5,6-氧-二异丙叉基α-D-呋喃葡萄糖（2）,丙酮保护法收率为78%。以固体核磁手段表征了固体α-D-葡萄糖及2,以二异丙叉化阿洛糖衍生物4为起始物,经苯甲酰化合成了苯甲酰化衍生物8。阿洛糖衍生物9,经甲磺酰化合成甲磺酰化衍生物10。 2.研究了以氧化还原手段改变糖的羟基构型的方法,以二异丙叉化呋喃葡萄糖衍生物2为原料,以三氧化铬—吡啶—醋酐体系进行氧化,再进行NaBH₄还原,改变了3—位羟基构型,得到二异丙叉化呋喃阿洛糖衍生物4,两步收率为57.4%。探讨了氧化还原反应的规律及特点,研究了氧化还原反应条件,分离并表征了氧化物3的水合物,建立了切实可行的氧化物及水合物混合物的短柱柱色谱分离法及还原方法。 3.探讨了阿洛糖及葡萄糖衍生物异丙叉基选择性水解反应机理及规律,建立了两种分别以无机酸及新的酸性离子交换树脂为催化剂的可行的水解方法,得到3个带有1,2-位异丙叉基的阿洛糖衍生物及异构体1,2-氧-异丙叉基-α-D-呋喃阿洛糖（6）,1,2-氧-异丙叉基-α-D-呋喃葡萄糖（7）,3-氧-苯甲酰基-1,2-氧-异丙叉基-α-D-呋喃阿洛糖（9）,收率分别为93.1%,84.5%与81.8%,4经完全水解得到D-阿洛糖（5）,分离并表征了选择性水解反应中间物1,2-氧-异丙叉基-5-羟基异丙基-α-D-呋喃葡萄糖,并以¹H-NMR和¹³C-NMR进行结构表征。探讨了不同水解底物的结构与水解选择性的关系。得出阿洛糖衍生物3-位取代基的吸电性的增强,可提高水解反应选择性的结论。 4.初步将阿洛糖衍生物进行应用,以硅胶-高碘酸钠/四氢呋喃氧化体系,进行氧化减碳反应,以6合成1,2-氧-异丙叉基-α-D-呋喃核糖-5-醛（11）。 本论文中各步反应中间体及阿洛糖衍生物,均经¹H-NMR等鉴定结构。更多还原

【Abstract】 With α -D-glucose as starting material, D-allose and five D-allofuranose derivatives and epimers were prepared. Some was applied in carbon-decreasing oxidation. Particularly, hydroxyl group protection, hydroxyl group stereo structure conversion by oxidation / reduction method and isopropylidene group selective hydrolysis methods were studied intensively. They were described as the following:1. The hydroxyl group protecting reactions of D-glucofuranose and D-allofuranose derivatives were studied. The practical methods of isopropylidenation, benzoylation and mesylation were obtained. The isopropylidenation reaction of α -D-glucose was carried out to synthesis l,2:5,6-O-diisopropylidene- α -D-glucofuranose （2） with acetone — conc. H₂SO₄ — Na₂SO₄ system and new 2,2-dimethoxylpropane — p-toluenesulfonic acid system respectively. Solid α -D-glucose and 2 were characterized by solid-state ¹H-NMR spectra. α -D-allofuranose benzoylated derivative 9 was synthesized from isopropylidenated α -D-allofuranose derivative 4 by benzoylation. Mesylated derivative 10 of α -D-allofuranose was synthesized from isopropylidenated α -D-allofuranose derivative 9 by mesylation.2. Hydroxyl group stereo structure conversion in sugar was studied. The 3-position hydroxyl group stereo structure of diisopropylidenated α -D-glucofuranose derivative 2 was converted by CrO₃-pyridine-acetic anhydride oxidation and NaBH₄ reduction. Thus diisopropylidenated α -D-allofuranose derivative 4 was synthesized. Two steps overall yield was 57.4%. The feachers and the conditions of oxidation and reduction were discussed. The hydrate of the oxidation product 3 was separated and characterized. The practical short column chromatography separating method, reduction method for 3 and its hydrate mixture were obtained.3. The mechanism and feachers of isopropylidene group selective hydrolysis reaction with α -D-allo-and α -D-glucofuranose derivatives were discussed. Two practical methods with inorganic acid catalyst and new ion-exchange resin catalyst were obtained. The α -D-allofuranose derivatives or their epimers with one isopropylidene group 1,2-O-isopropylidene α-D-allofuranose （6）, 1,2-0-isopropyl--idene- α -D-glucofuranose （7） and 3-O-benzoyl-1,2-O-isopropylidene- α -D-allofura--nose （9） were synthesized. D-allose （5） was synthesized from 4 by complete hydrolysis. The selective hydrolysis intermediate l,2-O-isopropylidene-5-hydroxyl--isopropyl- a -D-allofuranose was separated and characterized by JH- and 13C-NMR. The relationship of different hydrolysis substrates structures and their hydrolysis selectivity was discussed. The stronger the electron -withdrawing ability of 3-positon substituted group, the higher the hydrolysis selectivity of diisopropylidenated a -D-allofuranose derivative.4. The preliminary application of D-allofuranose derivatives was carried out. 1,2-O-isopropylidene a -D-allofuranose （6） was carbon-decreasing oxidated with silica gel-NaIO4-THF system. Thus 1,2-O-isopropylidene a -D-ribofuranose-5-al （11） was synthesized.In each step, the intermediates and target D-allose derivatives obtained in this paper were characterized by ’H-NMR spectra and methods.更多还原