ANALYSIS OF TRIMETHYLSILYL DERIVATIVES OF CARBOHYDRATES BY GAS CHROMATOGRAPHY AND MASS SPECTROMETRY
ANALYSIS OF TRIMETHYLSILYL DERIVATIVES OF CARBOHYDRATES BY GAS CHROMATOGRAPHY AND MASS SPECTROMETRY
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DOI：
10.1021/ja01035a022
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发表时间：
1969-01-01
影响因子：
15
通讯作者：
SWEELEY, CC
中科院分区：
文献类型：
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作者：
DEJONGH, DC;RADFORD, T;SWEELEY, CC
-D-葡萄糖的三甲基甲硅烷基醚及其 1, 2, 3, 4, 5, 6, 6-^ 7, 1-d 和 6, 6-^ 2 类似物，甲基-D-吡喃葡萄糖苷，乙基 ß-D-呋喃半乳糖苷，甲基 3-乙酰氨基-3-脱氧-α-D-吡喃葡萄糖苷及其衍生物的质谱提出了 NHCOCD 3 类似物。使用氘标记和高分辨率测量的精确质量数据来支持解释，详细讨论了这些衍生物的碎片。这些模型化合物的质谱用于鉴定 D-半乳糖、D-葡萄糖及其三种氘代类似物、3-O-甲基-D-葡萄糖和 2-乙酰氨基-2-脱氧-D-半乳糖的平衡混合物的三甲基硅烷化反应中形成的微量组分。使用相同的方法测定 D-半乳糖和 D-葡萄糖的糖苷化产物。这些微量成分的质谱是从气相色谱-质谱联用仪获得的。呋喃糖和呋喃糖苷结构可归属于次要成分。近年来，碳水化合物化学结构测定的经典方法得到了新技术的补充。气液分配色谱 (glpc) 在碳水化合物衍生物中的应用为复杂混合物（例如多糖水解产生的混合物）的检查和小规模分离提供了一种便捷的方法。碳水化合物的 3 种甲基醚、4 种乙酸酯、5、6 和三甲基甲硅烷基 (TMSi) 醚7 已被证明适合这种分析方法。从易于制备和已实现的优异分离来看，三甲基甲硅烷基醚似乎是最合适的。 7 TMSi 衍生物在羟基类固醇的质谱研究中的成功应用，8-11 以及最近在含复杂碳水化合物的抗生素 12-16 以及核苷酸和相关物质的研究中证明了 TMSi 醚的实用性，17
The mass spectra of the trimethylsilyl ethers of-D-glucose and its 1, 2, 3, 4, 5, 6, 6-^ 7, 1-d, and 6, 6-^ 2 analogs, of methyl-D-glucopyranoside, of ethyl ß-D-galactofuranoside, and of methyl 3-acetamido-3-deoxy-aD-glucopyranoside and its NHCOCD 3 analog are presented. The fragmentations of these derivatives are discussed in detail, using deuterium-labeling and exact-mass data from high-resolution measurements to support the inter-pretations. The mass spectra of these model compounds are used in the identification of minor components formed in the trimethylsilylation of equilibrium mixtures of D-galactose, D-glucose and three of its deuterated analogs, 3-O-methyl-D-glucose, and 2-acetamido-2-deoxy-D-galactose. The same approach was used todetermine the products from glycosidation of D-galactose and D-glucose. The mass spectra of these minor components were obtained from a coupled gas chromatograph-mass spectrometer. Furanose and furanoside structures can be assigned to the minor components. n recent years, classical methods of structure determination in carbohydrate chemistry havebeen supplemented by newer techniques. The application of gas-liquid partition chromatography (glpc) to carbohydrate derivatives introduced a convenient method for the examination and small-scale separation of complex mixtures, such as those resulting from hydrolysis of polysaccharides. 3 Methyl ethers, 4 acetates, 5, 6 and trimethylsilyl (TMSi) ethers7 of carbohydrates have been shown to be amenable to this method of analysis. Trimethylsilyl ethers appear to be the most suitable both with regard to their ease of preparation and to the excellent separations which havebeen achieved. 7 The successful use of TMSi derivatives in mass-spectral investigations of hydroxy steroids, 8-11 and the recent demonstrations of the utility of TMSi ethers in the investigation of complex carbohydrate-containing anti-biotics12-16 and nucleotides and related substances, 17