Glucose reaction with acetone

Deoxy-6-nitro-D-glucose (90) and 6-deoxy-6-nitro-L-idose (91) were the first reducing nitro sugars to be synthesized.98 Nitromethane addition to 1,2-O-isopropylidene-a-D-xy/o-pentodialdo-1,4-furanose (87) produced a mixture of 6-deoxy-l,2-0-isopropylidene-6-nitro-a-D-glucofuranose (88) and -j8-L-idofuranose (89). These C-5 epimers could be separated by reaction with acetone, whereby 89 gave a l,2 3,5-di-isopropylidene acetal more readily than did 88. Acid hydrolysis of the acetone groups then afforded 90 and 91. 

Acetalation. As polyhydroxy compounds, carbohydrates react with aldehydes and ketones to form cycHc acetals (1,13). Examples are the reaction of D-glucose with acetone and a protic or Lewis acid catalyst to form l,2 5,6-di-0-isoprop5lidene-a-D-glucofuranose [582-52-5] and its reaction with benzaldehyde to form 4,6-0-benzyhdene-D-glucopyranose [25152-90-3]. The 4,6-0-(l-carboxyethyhdine) group (related to pymvic acid) occurs naturally in some polysaccharides. 

J. D. Stevens, Septanose carbohydrates. I. Acid-catalysed reaction of D-glucose with acetone, Aust. J. Chem., 28 (1975) 525-557. 

J. D. Stevens, Isolation of aldehydo and septanoside derivatives from the acid-catalyzed reaction of D-glucose and some of its derivatives with acetone-methanol, Carbohydr. Res., 21 (1972) 490-492. 

Stanovnik and co-workers (100,101) systematically investigated the cycloaddition reactions of diazoalkanes with unsaturated nitrogen heterocycles, such as azolo-[l,5-fl]pyridines, pyridazin-3(2/7)-ones, and [fo]-fused azolo- and azinopyridazines. The Stanovnik group have studied the further transformations of the products and reviews of this chemistry are available. In a typical example, the reaction of 6-chlorotetrazolo[l,5-/7]pyridazine (37) with 2-diazopropane yields the NH,NH-dihy-dro-pyrazolo[4,3-(i]tetrazolo[l,5-/7]pyridazine 38 (102) (Scheme 8.11). The latter substrate reacts with acetone to produce an azomethine imine 39 that thermally rearranges to give the fused dihydro-1,2-diazepine 40. The azomethine imine obtained with glucose can be trapped with methyl acrylate to furnish the C-nucleoside 41 (103). 

Much more studied is the reaction of /8-dicarbonyl compounds with 2-amino-2-deoxyaldoses in particular, with 2-amino-2-deoxy-D-glu-cose (55), both in neutral and alkaline medium. In neutral methanol or aqueous acetone, 2-amino-2-deoxy-D-glucose reacts with 2,4-pen-tanedione to give52 54 3-acetyl-2-methyl-5-(D-arabino-tetrahydroxy-butyl)pyrrole (56a), and, with ethyl acetoacetate,55 the pyrrole 56b. Similar (tetrahydroxybutyl)pyrroles have been prepared from other /3-keto esters, such as ethyl 3-oxohexanoate, ethyl thiolacetoacetate, and diethyl 3-oxopentanedioate.53,56,56a... 

The commonest type of acetal in this class has the 1,3-dioxolane ring fused cis to a furanose ring. Formation of 1,2-acetals of a-D-glucofuranose has been proved for reactions of o-glucose with acetone, " cyclohexanone, "... 

This resulted in some improvement of the polymerizations due to a decrease in the concentration of free TEMPO and allowed for an increased reaction yield, but only the IP polymerization appeared to be well-controlled [158]. The poly-dispersities of the pnBA prepared in the presence of either glucose or hydroxy-acetone were always >1.5, with significant tailing to lower molecular weights in the GPC traces. 

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