Glucose, acetic anhydride reaction derivatives

Another highly versatile building block derived from diacetone-glucose 54 is the 1,2-acetonide of 3-C-methyl-a-D-allose in its furanoid form 57, which has been utilized as the key compound in a convergent total synthesis of ACRL Toxin I (63). Its elaboration from 54 starts with a pyridinium dichromate / acetic anhydride oxidation (64), is followed by carbonyl olefination of the respective 3-ulose with methyl (triphenyl)phosphonium bromide and hydrogenation (— 55 56), and is completed by acid cleavage of the 5,6-isopropylidene group. This four-step process 54 -> 57, upon optimization of reaction conditions and workup procedure, allows an overall yield of 58 % (63), as compared to the 22 % obtained previously (65). 

Incidental reactions that have been reported include the preparation of derivatives of 5-(hydroxymethyl)-2-furaldehyde by reaction of D-fructose in acetic or propionic acid in the presence of the respective anhydride.158 The condensation of D-glucose with phenol has been effected in acetic acid in the presence of dry hydrogen chloride, prior to resinification,157 and the reaction of sucrose with thionyl chloride in acetic acid-acetic anhydride produced partially acetylated chlorodeoxysucroses.158 Sucrose has been condensed with maleic anhydride in acetic anhydride mixed with acetic acid or formic acid, to give solid products having an undetermined structure.159... 

Amyloid.—When treated with concentrated sulphuric acid cellulose dissolves and undergoes hydrolysis. If the solution is diluted with water a gelatinous product is obtained which gives the blue color with iodine characteristic of starch. This product is known as amyloid. When boiled in the dilute acid the amyloid is hydrolyzed and dextrin and finally glucose are obtained. Concentrated hydrofluoric acid and phosphoric acid also dissolve cellulose. With glacial acetic acid in the presence of acetic anhydride and sulphuric acid cellulose yields acetyl derivatives indicating its alcoholic character. From the products of this reaction the acetate of a di-saccharose is obtained. 

Amino groups in dithioacetals undergo normal substitution reactions. Conventional reactions have been reported to occur with acetic anhydride,88,90,91 benzoyl chloride,46,92 l-fluoro-2,4-dinitrobenzene,250 p-toluenesulfonyl chloride,247 and benzyloxycarbonyl chloride92 the reported92 application of sodium chloride and methyl iodide to the conversion of 2-amino-2-deoxy-D-glucose diethyl dithioacetal hydrochloride into a pentamethyl derivative is presumed to be an error. Although crude 2-acetamido-2-deoxy-D-glucose diethyl dithioacetal was in one instance converted in low yield into a poorly... 

Condensation of D- and L-arabinose, D-ribose, D-xylose, D-galactose, D-glucose and D-mannose with 2-hydrazino-6-methyl-4-oxopyrimidine afforded intermediate sugar (6-methyl-4-oxo-2-pyrimidinyl)hydrazones. Treatment of the latter in one pot with bromine-acetic acid-sodium acetate then acetic anhydride (to effect a cyclization-acetylation reaction) gave, after purification and de-O-acetyla-tion, derivatives 19 (n = 3 or 4, stereochemistry as defined by the starting aldose). ... 

The use of GC was mentioned in the preceding section. It requires, prior to sample injection into the GC column, some sample cleanup and derivatization to produce volatile species. Several different derivatives, such as penta-trimethylsilyl derivative, aldono-nitrile acetate, diacetone glucose, and others, have been suggested allowing the separate determination of the two anomeric species. For mass spectrometric detection, the reaction of o-glucose with -but-ylboronic acid (BBA) followed by acetic anhydride leading to a quantitative conversion to glucose-BBA can be utilized. A fused silica capillary column coated with SE-54 may be considered for separation of different aldohexoses. 

In 2010, the Sato group disclosed the synthesis of tetrodotoxin 86 starting from d-glucose, in which the Perrier carbocyclization of enol acetate 92 was employed for the construction of the cyclohexane core of tetrodotoxin. 4,6-O-Benzylidene derivative 99 was converted into pyranoside 93 possessing an exo-methylene group at C-3 (Scheme 12.47). m-CPBA oxidation of 93 stereoselectively provided epoxide 183. Alkaline hydrolysis of the epoxide in 183 followed by acetonide formation gave primary alcohol 184. Oxidation of 184 afforded aldehyde 185, which was converted into (Z)-enol acetate 92 by the action of acetic anhydride and potassium carbonate. When enol acetate 92 reacted with Hg(OAc)2, followed by NaCl treatment, the Perrier carbocyclization reaction successfully took place to afford a mixture of... 

Limousin et al. (1997) have observed peracetylation of D-glucose to give the acetyl derivative with a small excess of acetic anhydride in presence of catalyst anhydrous potassium or sodium acetate, or zinc chloride quantitatively in less than 15 min with microwave heating. These reactions were found highly p-selective with potassium or sodium acetate under classical conditions. In presence of zinc dichloride and microwave irradiation, a 1 1 mixture of a/p pentacetates was obtained, where as a ratio of 7 3 was resulted under conventional oil bath heating conditions. 

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