保护的氨基葡萄糖苷结构测定中的核磁共振光谱研究  

NMR Study on the Determination of Structure in the Protected Glucosamineoside

作　　者：郭振楚[1] 韩亮[1] 胡博[1] 熊兴泉[1] 

机构地区：[1]湖南科技大学化学化工学院,湖南湘潭411201

出　　处：《光谱学与光谱分析》2004年第11期1476-1481,共6页Spectroscopy and Spectral Analysis

基　　金：湖南省有机化学"十五"重点学科(湘教通[2001]179号)资助项目

摘　　要：以D-氨基葡萄糖盐酸盐、三氯乙晴、三氯乙氧甲酰氯和三甲基硅三氟甲基磺酸酯(TMSOTF)为主要原料,合成了保护的氨基葡萄糖5,8,9,12,13和两种保护的2脱氧2氨基葡二糖10和11,它们均为新化合物。用1HNMR和13CNMR谱等进行了表征。所列核磁共振氢谱数据表明保护的氨基葡萄糖、保护的氨基葡二糖中的NH上质子化学位移(δ)显著地移向低场至507～526。9,10,11,12,13化合物中的J1,2值在72～88Hz,均为β糖苷;而J1,2值在300和496Hz,为α糖苷(5和6)。H2的化学位移一般处在较高场,δ在310～430。所列13C谱数据表明C1的化学位移处于最低场,C2处于较高场,相应的氢有类似情况。一般C1的δ>100(如化合物91019)为β苷;而δ<100(如化合物5δ=9520,化合物6δ=9721)为α糖苷。讨论了糖环上其他H和C的化学位移特征。用DEPT(DistortionlessEnhancementbyPolarizationTransfer)法配合13CNMR谱方便而清楚地鉴别了化合物6中碳原子的级数。The protected glucosamines 5,8,9,12, 13 and the protected diglucosamines 10 and 11 were prepared from D-glucosamine hydrochloride, trichloroacetonitrile, trichlorocthoxycarbonyl chloride and trimethylsilyl trifluoromethanesulfonate(TMSOTf). They were new products and their structures were characterized by means of H-1 NMR and C-13 NMR. The data of H-1 NMR indicated that the chemical shift of NH of them were moved remarkably to the low field 5.07-5.26 compared with that of D-glucosamine hydrochloride. The data J(1,2) of the compounds 9,10,11,12,13 were between 7.2 and 8.8 Hz, which showed their structures were beta configuration, while the data J(1,2) were between 3.00 and 4.96 Hz in the compounds 5 and 6, which showed their structures were a configuration. H-2 was situated in the higher field, which delta was between 3.10 and 4.30. The data of C-13 NMR showed that the delta of C-1 laid in the lowest field and the delta of C-2 laid in the higher field, as were the delta of H-1 and H-2 in NMR. Commonly speaking, if the delta of C-1 was greater than 100, the structure of the compound was beta configuration such as compound 9 (delta = 101.9). On the contrary, if the delta of C-1 was less than 100, the structures were alpha configuration like compound 5 (delta = 95.20) and 6(delta = 97.21). The chemical shift of other carbon and hydrogen in the ring were discussed. The progression of Carbon in the compound 6 were distinguished conveniently and clearly by using DEPT (Distortionless Enhancement by Polarization Transfer)and C-13 NMR.

关 键 词：糖苷 低场 氨基葡萄糖 结构测定 新化合物 化学位移 核磁共振光谱 高场 类似 级数 

分 类 号：O629[理学—有机化学] R284[理学—化学]