Organic Reaction Mechanisms 1988

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Rate constants and activation parameters have been determined for hydroxyalkylperoxide esters of the types (49) and (50);55multiparameters Taft relations were found. Ester interchange of methyl or ethyl carboxylates with primary or secondary alcohols has been carried out effectively by solid-liquid PTC in the absence of solvent. e. " Organic Reaction Mechanisms 1988 34 The rates of hydrolysis of the perester C6H,CO,OCMe3 in 70% aq. g. 62 Five papers have appeared on the hydrolysis of h a l o e s t e r ~ .

The carbonyls are necessary and, if the second C02H is too remote, a stable anhydride will not form. The mechanism involves attack of the monoanion of the diacid on (105) H+, of the monoanion on (105), and of the dianion on (105). This work is relevant to the mechanism of hydrolysis of peptides catalysed by the aspartate p r ~ t e i n a s e s . b I5 N isotopes were used in the present studies. '^' The mechanism varies from bifunctional to general acid. A non-hydrolytic bimolecular aminolysis reaction catalysed by an antibody has been reported’” and involves the stereospecific formation of an amide (110) from racemic lactone (109) and an aromatic amine, 1 ,Cphenylenediamine (Scheme 6).

Me (161) 0 ( 162) (163) R = MeO, EtO, Me, Ph, p-MeOC,H,, Br, etc. IW Neighbouring hydroxy plays a major role in accelerating the acid- and basecatalysed hydrolysis of 0-( 1-hydroxyalkyl)-N,N-dimethylbenzenesulphonamides (164) to the corresponding sultones (165). Huge rate accelerations are observed which increase with steric bulk of the alkyl substituents: cf. values of kobs x 10s/s-' are (164; R' = H, R2 = Me), 92; (164, R' = R2 = Et), 182; and (164, R' = RZ = Pr'), 1080. 19' The mechanism of intramolecular nucleophilic displacement at sulphonyl sulphur involving either an SN2(S)or a stepwise process was investigated employing the conjugate base of the sultone (l66), which upon intramolecular attack would be transformed into a symmetric However, the base undergoes a rapid degenerate rearrangement rather than forming a symmetrical pentavalent sulphur intermediate of pseudo-trigonal-bipyramidal geometry.

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