Methanolysis of benzoyl chloride

Biordi (15) has studied the methanolysis of benzoyl chloride at 25 °C in methanol solution. 

Combinations of product studies with kinetic data provide particularly powerful indications of reaction mechanisms. Either the presence or absence of a rate-product correlation may be of mechanistic significance. First, we have an explanation of rate-product correlations using the example of competing methanolysis (second-order rate constant, IcMeOH) and aminolysis (second-order rate constant, kam) of benzoyl chloride (59) in Scheme 2.21. The mechanism is initially assumed to involve independent competing pathways, as shown, so that the equations of correlation can be derived. 

The neighboring-group concept of Winstein has been used to explain the difference in reactivity exhibited by anomeric pairs of halides. This suggestion is by no means improbable, and would explain the facts that tri-0-benzoyl-/3-D-ribopyranosyl bromide is 19 times more reactive at 20° in 1 9 dioxane-methanol than is the a anomer, and that the rate for the trans-l3 chloride shows an 85-fold increase over that of the cis-a chloride. However, in view of the properties of the series XXVII to XXX, steric effects from the whole molecule may be equally important, although the disadvantage of this concept is that hindrance as assessed from models is difficult to define precisely. It is of interest to compare the rates of methanolysis of tri-O-benzoyl-a-D-xylopyranosyl bromide and of tri-O-acetyl-a-D-xylopyranosyl bromide [10 fc ° = 51(sec ) in 1 9 dioxane-methanol and = 139(sec 0 in 100% methanol, respectively]. Although the... 

ChlorocarbonyUition. The reaction of adamantane (1) with one equivalent of oxalyl chloride under free-radical conditions (benzoyl peroxide) followed by methanolysis gives a mixture of methyl adamantane-1- and -2-carboxylate, (2 and 3) easily separable by fractional distillation. Chlorocarbonylation with a fivefold excess of reagent followed by methanolysis gives a mixture of methyl adamantane-... 

In addition to the approach outlined in Scheme 4, several other approaches to the synthesis of glycofuranosides have been reported during the past year. Hanessian and Banoub have used cyclic amide acetals derived from vicinal diols as the source of the aglycone in condensations with l-0-acetyl-2,3,5-tri-0-benzoyl-jS-D-ribofuranose in the presence of stannic chloride (Scheme 5). Disaccharide derivatives are obtained when the cyclic amide acetal is derived from carbohydrate vicinal diols (Scheme 6), and selective methanolysis of the formate ester exposed an hydroxy-group that can be subjected to further manipulation or glycosylation. 2,3,5-Tri-0-benzoyl-a)8-L-arabinofuranosyl bromide or chloride has been condensed with 4-nitrophenyl 2,3-di-O-acetyl-a-L-arabinofuranoside to yield, after deacylation, 4-nitrophenyl 5-O-a-L-arabinofuranosyl-a-L-arabino-furanoside, with jS-peltatin A [isolated from podophyllin Podophyllum peltatum)] in glycosidation of the phenolic 8-OH group in an attempt to reduce... 

A lipoprotein lipase from Pseudomonas sp. effected not only regioselective acetylation of the orthoester 95 without observing the acylation of the axial hydroxyl groups but also enantioselective butyroylation (>95% ee) of symmetrical 4,6-dibenzoate 203 which was derived from the acetate 202 by benzoylation and acidic methanolysis (Scheme 4-10). 79 Regioselective chemical acylation of the equatorial hydroxyl group in 95 was also reported using benzoyl (64% yield) and p-nitrobenzoyl chlorides (51%).79... 

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