Preparation of 1-chloroalkyl hydroperoxides by the addition of hydrogen chloride to carbonyl oxides

Abstract

racemic sulfoxide); mp 74.5 °C (pure S enantiomer); [ ]2^= ~54°( c 1.98, CHClg); lH NMR (CDClg) & 2.40 (s, 3 H), 2.69 (s, 3 H), 7.28-7.55 (AA'BB'm, 4 H); NMR analysis with the chiral shift reagent, (S)-(+)-2,2,2-trifluoro-l-(9-anthryl)ethanol indicated the sulfoxide to be enriched in the S enantiomer (i.e., 30% ee).

Reactions between Criegee Intermediates and the Inorganic Acids HCl and HNO3: Kinetics and Atmospheric Implications

“…TheH 2 Oa nd HCl reactions proceed through an insertion mechanism, forming hydroxymethyl hydroperoxide (HMHP) and chloromethyl hydroperoxide (CMHP), respectively.A previous study of the ozonolysis of asymmetric alkenes in the presence of HCl identified CMHP as the product of R1 in the solution phase. [42] While HMHP is also the product of the CI+ +(H 2 O) 2 reaction, the apparent mechanism involves two concerted hydrogen atom transfers;that is,the hydroxy group and the hydroperoxy hydrogen atom end up in different water molecules.T he CI+ +HNO 3 reaction forms the analogous nitrooxymethyl hydroperoxide (NMHP), although the mechanism is not insertion, as the OÀCb ond is formed with the nitro group,r ather than the OH group (see Figure S4). The order-of-magnitude smaller rate constant measured for HCl relative to HNO 3 may be ac onsequence of the significantly smaller density of states in the TS region as that of the latter reaction lies lower in energy and has more low-frequency modes.…”

Photodecomposition of dichloromethane catalyzed by tetrachloroferrate(iii) supported on a Dowex anion exchange resin

“…Another hydrogen abstraction reaction may take place, 16,19,20 leading to dichloromethyl hydroperoxide:…”

Reactions between Criegee Intermediates and the Inorganic Acids HCl and HNO3: Kinetics and Atmospheric Implications

“…A previous study of the ozonolysis of asymmetric alkenes in the presence of HCl identified CMHP as the 7 product of R1 in the solution phase. [42] While HMHP is also the product of the CI + (H2O)2 reaction, the apparent mechanism involves two concerted H-atom transfers; that is, the hydroxyl group and the hydroperoxy H-atom originate in different water molecules. The CI + HNO3 reaction forms the analogous nitrooxymethyl hydroperoxide (NMHP), although the mechanism is not insertion, since the O-C bond is formed with the nitro-group, rather than the -OH group (see Figure S4).…”