6,6'-Diesters of trehalose and process for the synthesis thereof
OwnerAvraham Liav, Mayer B. Goreninventors
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Abstract
An improved process is described for synthesizing simple and complex 6,6'-diacyl esters of trehalose and intermediates useful therein. Novel 6,6'-diacyl esters of trehalose and novel intermediates useful in the process of the invention are also disclosed. The inventive process is capable of producing the desired compounds economically and in pure form from readily available starting materials.
Claims35
A compound selected from the group consisting of
- I. Compounds having the following structural formula ##STR9## wherein Y and W are monovalent radicals selected from the group consisting of -O-trityl, -O-H, -O-mesyl, -O-tosyl, desoxy bromo, desoxy iodo, and -O-acyl radicals containing 10-100 carbon atoms, and Bz in each instance is a monovalent benzyl radical;
- II. 6,6'-di-O-[p-(hexadecyloxy-phenyl)-4-butyryl]-trehalose;
- and
- III. 6,6'-di-O-[3,4-di-(hexadecyloxy-phenyl)-.gamma.-butyryl]-trehalose.
A process for preparing 6,6'-diacyl esters of trehalose comprising dehexabenzylating 2,3,4,2',3',4'-hexa-O-benzyl-6,6'-di-O-acyl trehalose by hydrogenolysis with gaseous elemental hydrogen under pressure, the acyl groups containing 10-100 carbon atoms, the reactants in the said hydrogenolysis consisting essentially of the said 2,3,4,2',3',4'-hexa-O-benzyl-6,6'-di-O-acyl trehalose and elemental hydrogen, the said 2,3,4,2',3',4'-hexa-O-benzyl-6,6'-di-O-acyl trehalose being reacted with elemental hydrogen in the said hydrogenolysis to thereby remove all of the six benzyl radicals thereof and replace them with hydrogen and thereby produce a reaction mixture containing the corresponding 6,6'-diacyl ester of trehalose as the desired product and toluene as the by-product, and thereafter isolating the desired 6,6'-diacyl ester of trehalose thus produced from the reaction mixture.
A process for preparing the compound 2,3,4,2',3',4'-hexa-O-benzyl-6,6'-di-O-acyl trehalose comprising acylating 2,3,4,2',3',4'-hexa-O-benzyl trehalose in each of the 6 and 6' positions with an acylating agent selected from the group consisting of carboxylic acid halides and carboxylic acid anhydrides containing 10-100 carbon atoms to thereby produce 2,3,4,2',3',4'-hexa-O-benzyl-6,6'-di-O-acyl trehalose containing impurities, and separating the 2,3,4,2',3',4'-hexa-O-benzyl-6,6'-di-O-acyl trehalose thus produced from the impurities by chromatography to produce purified 2,3,4,2'3',4'-hexa-O-benzyl-6,6'-di-O-acyl trehalose.
A process for preparing the compound 2,3,4,2',3',4'-hexa-O-benzyl-6,6'-di-O-acyl trehalose comprising acylating a compound selected from the group consisting of the 6,6'-di-O-mesyl, di-O-tosyl, didesoxy dibromo and di-iodo derivatives of 2,3,4,2',3',4'-hexa-O-benzyl trehalose in each of the 6 and 6'-positions by reacting with a salt of a carboxylic acid containing 10-100 carbon atoms, the said compound being reacted in organic solvent solution in the presence of a stoichiometric excess of the said carboxylic acid salt to thereby produce 2,3,4,2',3',4'-hexa-O-benzyl-6,6'-di-O-acyl trehalose containing impurities, and separating the 2,3,4,2',3',4'-hexa-O-benzyl-6,6'-di-O-acyl trehalose thus produced from the impurities by chromatography to produce purified 2,3,4,2',3',4'-hexa-O-benzyl-6,6'-di-O-acyl trehalose.
A process for preparing the compound 2,3,4,2',3',4'-hexa-O-benzyl trehalose comprising hydrolyzing 2,3,4,2',3',4'-hexa-O-benzyl-6,6'-di-O-trityl trehalose in an acid aqueous medium to remove the trityl groups from the 6 and 6' positions without disturbing the benzyl groups in the 2,3,4,2',3',4'-positions to thereby produce 2,3,4,2',3',4'-hexa-O-benzyl trehalose containing impurities, the aqueous medium being acidified with an acid which does not permanently enter into the hydrolysis reaction and the reactants in the said hydrolysis consisting essentially of the said 2,3,4,2',3',4'-hexa-O-benzyl-6,6'-di-O-trityl trehalose and the acidic aqueous medium, and separating the 2,3,4,2',3',4'-hexa-O-benzyl trehalose thus produced from impurities by chromatography.
Dependencies are inferred from the claim text.