Abstract
A previous study of the effect of a 2-chloro substituent on the rates and the mechanisms of the solvolysis of ethyl chloroformate is extended to the effect of a 3-chloro substituent on the previously studied solvolysis of propyl chloroformate and to the effect of a 4-chloro substituent on the here reported rates of solvolysis of butyl chloroformate. In each comparison, the influence of the chloro substituent is shown to be nicely consistent with the proposal, largely based on the application of the extended Grunwald–Winstein equation, of an addition-elimination mechanism for solvolysis in the solvents of only modest solvent ionizing power, which changes over to an ionization mechanism for solvents of relatively high ionizing power and low nucleophilicity, such as aqueous fluoroalcohols with an appreciable fluoroalcohol content.
Highlights
A recent report [1] concerning the effect of a terminal chlorine substituent on the solvolysis of ethyl chloroformate (1) [2] to give a study of 2-chloroethyl chloroformate (2) allowed a parallel reaction rate study in a range of pure and mixed solvents, mainly with water as one component and for 2,2,2-trifluoroethanol-ethanol (T-E) mixtures
The reaction rate study [3] with propyl chloroformate (3) in the same and similar solvents has been reported, and new studies involving the solvolysis of 3-chloropropyl chloroformate (4), butyl chloroformate (5), and 4-chlorobutyl chloroformate (6) are reported in Table 1 of this manuscript
These studies can be combined with earlier studies of ethyl chloroformate (1) and 1-chloroethyl chloroformate (7) to assess the effect of a terminal chlorine introduced into the alkyl group upon the solvolysis rates of ROCOCl substrates, where R is ethyl, propyl, or butyl
Summary
A recent report [1] concerning the effect of a terminal chlorine substituent on the solvolysis of ethyl chloroformate (1) [2] to give a study of 2-chloroethyl chloroformate (2) allowed a parallel reaction rate study in a range of pure and mixed solvents, mainly with water as one component and for 2,2,2-trifluoroethanol-ethanol (T-E) mixtures. The reaction rate study [3] with propyl chloroformate (3) in the same and similar solvents has been reported, and new studies involving the solvolysis of 3-chloropropyl chloroformate (4), butyl chloroformate (5), and 4-chlorobutyl chloroformate (6) are reported in Table 1 of this manuscript. These studies can be combined with earlier studies of ethyl chloroformate (1) and 1-chloroethyl chloroformate (7) to assess the effect of a terminal chlorine introduced into the alkyl group upon the solvolysis rates of ROCOCl substrates, where R is ethyl, propyl, or butyl. Sci. 2020, 0000, 0000 with specific rates within a linear free energy relationship (LFER) approach in a study of the effect of solvenIntt.vJ.aMArolitla.htSoicoiu.n2g0ho20mn, 0it0nh0o0e,r0ra0e0da0jcutsitomnemntsecchouanldisbme m[4a]d. e, the basic reaction mechanisms believed to operate in theAiSinnsOlotttHhhlhvoe,eAoauslslrtgoyoehlhlsovsvihuosomolgloyywihfsnsinimcosshriioonlnaoffoSdrccrcohjhhuaflldoeoosmrjrtruommoesffostoeamrrnt1mmeetasneaanttstcdseetoec2euero.sssluttdeeilndrrbssbteiihennmemttpahhaderedeeepps,,errtteenhhssceeeeennbbccoaaeefssioaoiccffrsreaaoealssacvootceilltovnvinoeet,nnnmwtt,,mehwwceihhchcahiihncchahicsnamccniaassnnmbbebbeseleribeerrepveelerppiederrsevetessoeenednontetptteedoeddraoaaastpsesSeOraHte, are shSoOwHn, ainreSschhoewmneins 1Scahnedm2es. 1 and 2
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