The Kinetics of 1-Chloroether Alcoholysis.

Mechanism of thermolysis of .alpha.-chloro ethers in aprotic solvents

“…Thermolysis of -Chlorobenzyl Alkyl Ethers. Both -chlorobenzyl sec-butyl ether (2) and -chlorobenzyl neopentyl ether (3) were thermolyzed in chlorobenzene to produce benzaldehyde and the corresponding alkyl chloride. However, the reaction of 3 did not proceed as cleanly as the others in that here several extraneous peaks developed in the NMR ( 5.16, 4.38, 4.30, and the aliphatic region) indicating that other products were being formed alongside of the aldehyde and unrearranged neopentyl chloride.…”

“…3439 was used as the means of identification.) When the reaction system was evacuated to distil the total product composition, 2-octene, benzaldehyde, 2-octyl chloride, and sulfolane (solvent) were collected and identified by GLC and NMR criteria: NMR 9.90 (s, 1 H, -CHO), 7.65 (m, 5 H, phenyl), 5.35 2 H, -CH=CH-), 3.88 (m, 1 H, CHC1), 2.40-0.70 (several m's, aliphatic H). The 2-octyl chloride component, 23 and 27% in two different quantitative runs, was subjected to optical rotation measurements whose results are listed in Table V.…”

Solvolytic Displacement Reactions At Saturated Carbon Atoms

“…In pure alcohol the reactions are not acidcatalyzed (414,415). In dioxane, which has a low dielectric constant, the results mean that hydrogen chloride is probably required to help solvate the leaving halide with the formation of an ion-pair (LXXXV).…”

Hydrolysis of esters of oxy acids: pKa values for strong acids; Brønsted relationship for attack of water at methyl; free energies of hydrolysis of esters of oxy acids; and a linear relationship between free energy of hydrolysis and pKa holding over a range of 20 pK units

“…variations in solvation effects is considerable; in particular, the balance between ionization and dissociation constants is likely to be quite different and thus the meaning of the global ionization constant will not be the same for different structural types; (c) it has not been demonstrated as far as one can tell that HCI in trifluoroacetic acid is actually HCI and has not to some considerable extent undergone covalent addition to the acid. HCI has a significant tendency to add to carbonyl groups as shown by chloroalkyl ether formation (36), when the equilibrium is not shifted by dissociation into Hf and Cl-, and trifluoroacetic acid is far more prone to undergo nucleophilic addition than are less electron deficient carboxylic acids (37).…”