Aldonic acids derivatives

One sulfonylated aldonic-acid derivative of this type has been tested, viz., methyl 2,4 5,6-di-0-methylene-3-0-tosyl-n-gluconate. On treatment418 with sodium iodide-acetone at 100° it gave free iodine plus sodium p-toluenesulfonate (50%, 2 hours 57%, 4 hours). If heated with sodium iodide-acetic anhydride under reflux for 2 hours, a 98% yield of sodium p-toluenesulfonate resulted. What contribution the carbomethoxy group makes is, as yet, unknown but there is reason to believe181 that it may be considerable. 

Mostly, these compounds were synthesized by cyclocondensation of aldonic acid derivatives, such as lactones, imidate esters, or thioimidate esters, with acylhydrazines. Thus, reaction of the 2,5-anhydro-D-allono-l,6-lactone derivative 682 with aminoguanidine gave the 3-amino-5-(j8-D-ribofuranosyl)- ,2,4-triazole 684 (75TL985) (Scheme 182). 

Aldol condensation of 2,2-diethyl-l,3-dioxolan-4-one lithium or zirconium enolates with aldehydo sugars has afforded higher carbon aldonic acid derivatives, e.g. 1. The synthesis of L-ribono-1,4-lactone has been achieved from d-isoascorbic acid by way of the tetrose and pentitol derivatives 2 and 3 and the d-ribonolactone derivative 4 has been efficiently epimerized to the L-lyxonolactone 5 (Scheme 1). A selective i yn-epoxidation of racemic 2-0-benzyl-4-alkenamides followed by hydrolysis has afforded 3-deoxy-pentono-1,4-lactones. 

The branched-chain aldonic acid derivative (1) has been shown to be a component of avilamycin by isolation of the product (2) of mild methanolysis and acetylation the latter compound was structurally characterized by X-ray analysis. ... 

Benzoylation of L-rhamnono-5-lactone can, under mild conditions, give the triester, but more forcing reaction conditions can be used to produce either the 3-deoxy-2-ene (8) or the pyranone derivative (9) in good yields. The unsaturated aldonic acid derivatives (10) and (11) were produced each in about 20% yield on heating of the selenoxide (12) the main product was formed by direct elimination between C-2 and C-3. ... 

Reaction of 2,3,5-tri-(9-benzoyl-D-ribose with a Wittig reagent gave access to the unsaturated aldonic acid derivative (25) from which the epoxide (26) was obtained. This was then used to prepare the tetraene (27) and hence (28), which is the slow reacting substance of anaphylaxis. ... 

Aspects of the chemistry of unsaturated aldonic acid derivatives are also referred to in Chapters 8 and 12. 

Other unsaturated aldonic acid derivatives are noted in Chapter 13. Orthoesters derived from the lactone carbonyl groups of D-glucono-D-galactono- and L-glycero-D-gluco-heptono-l.5-lactones and the 2,3-diol of methyl 4,6-substltuted-a-D-raannopyranoside were made by... 

A considerable number of aldonic acid derivatives have been reported. Acyclic derivatives are the substituted free acids (1)) (Scheme 3)" and the pyrazoles (5) (Scheme A). The spiro-... 

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