Acyloxymethyl as a drug protecting group. Kinetics and mechanism of the hydrolysis of N-acyloxymethylbenzamides was written by Iley, Jim;Moreira, Rui;Rosa, Eduarda. And the article was included in Journal of the Chemical Society, Perkin Transactions 2: Physical Organic Chemistry (1972-1999) in 1991.Safety of Chloromethyl benzoate This article mentions the following:
Acyloxymethyl derivatives of secondary and tertiary amides R1CONRCH2O2CR1 [R = H, Me; R1,R2 = (un)substituted phenyl] undergo hydrolysis via acid-catalyzed, base-catalyzed and pH-independent processes. The pH-independent pathway involves rate-limiting iminium ion formation and is characterized by the following: a Hammett Ï value for the substituent in the benzamide moiety of ca. -1.2 for both types of substrate; the absence of general-base or nucleophilic catalysis; a common benzoate ion effect; a solvent deuterium isotope effect of ca. 1.6; ÎSâ?/sup> values of -4 and -12 J K-1 mol-1 for secondary and tertiary substrates resp.; and higher reactivity of the tertiary amides over their secondary counterparts. The acid-catalyzed process involves protonation of a substrate followed by iminium ion formation, and is characterized by the following: a Hammett Ï value of ca. -1.5 for the substituent effect of the benzamide moiety; a solvent deuterium isotope effect of ca. 0.4; a monotonic rise in the pseudo-first-order rate constant with increasing [H2SO4]; ÎSâ?/sup> values >0 J K-1 mol-1; higher reactivity of the tertiary substrates over their secondary counterparts; and a value of 0.85 for the Broensted coefficient, βlg, for the carboxylate nucleofuge. The base-catalyzed hydrolysis of tertiary substrates involves normal ester hydrolysis via acyl-oxygen bond cleavage, and is characterized by a Hammett Ï value of +0.38, a solvent deuterium isotope effect of 0.85, and a ÎSâ?/sup> value of -96 J K-1 mol-1. The corresponding base-catalyzed process for the secondary substrates involves imine formation via an E2 elimination reaction. The secondary acyloxymethylamides are some 7 à 104 times more reactive than their tertiary counterparts in the base-catalyzed region. Hammett Ï values of +1.1 and +0.6 are obtained for the substituents in the ester and amide moieties, resp. Buffer catalysis is observed, and the value of ca. 0.5 for the Broensted β coefficient identifies the amide proton as approx. 50% transferred to the buffer species in the transition state. Heats of formation, ÎHf, calculated using the AM1 SCF MO package reveal that iminium ion formation is thermodynamically equi-energetic for cyclic and acyclic systems. Iminium ion formation from tertiary substrates is favored by ca. 25 kJ mol-1 over the corresponding secondary analogs. In the experiment, the researchers used many compounds, for example, Chloromethyl benzoate (cas: 5335-05-7Safety of Chloromethyl benzoate).
Chloromethyl benzoate (cas: 5335-05-7) belongs to organic chlorides. Organic chlorides can cause corrosion in pipelines, valves and condensers, and cause catalyst poisoning. The hydrocarbon processing industry (HPI) and others are affected by damage caused by these substances. Alkyl chlorides are versatile building blocks in organic chemistry. While alkyl bromides and iodides are more reactive, alkyl chlorides tend to be less expensive and more readily available.Safety of Chloromethyl benzoate
Referemce:
Chloride – Wikipedia,
Chlorides – an overview | ScienceDirect Topics