N. I. Kapustina

Oxidation of 1-alkylcycloalkanols with PbIV and MnIII compounds under mechanical activation

A mechanoactivated solid-state oxidative decyclization of 1-alkylcycloalkanols under the action of the Pb(OAc)4−MX or Mn(OAc)3−MX systems (MX is a metal halide) was carried out for the first time. The reaction affords exclusively ω-haloalkanones.

Oxidation of aliphatic alcohols with the lead tetraacetate—metal halide system under mechanical activation

The mechanochemical oxidation ofn-pentanol,n-hexanol, andn-octanol with the Pb(OAc)4-MHal system (M=Li, K; Hal=Cl, Br) in the absence of a solvent affords esters. and secondary alcohols with the composition C8H17OH and C9H19OH give ketones.

Bromination of alkenols with the H2O2—LiBr—CeIII and H2O2—LiBr—CeIV systems

Reactions of alkenols with H2O2—LiBr—Ce(NO3)3·6H2O or H2O2—LiBr—Ce(NH4)2(NO3)6 system led to bromination of the double bond to yield vicinal dibromoalkanols. The reaction proceeded highly selectively, no oxidation of the hydroxyl group virtually occurred.

Primary alkanols: oxidative homocondensation in water and cross-condensation in methanol

Water was used as a reaction medium and a reagent in oxidation of primary alkanols to dimeric esters and alkanoic acids using either molecular bromine or a hydrogen peroxide—hydrobromic acid mixture as the oxidants. The similar reaction in methanol produced methyl alkanoates.

Bromination of ketones with the systems H2O2-LiBr-CeIII and H2O2-LiBr-CeIV

A new method for the synthesis of α-bromoketones was suggested. The C5-C11 linear and branched ketones in the reaction with the systems H2O2-LiBr-CeIII and H2O2-LiBr-CeIV in acetonitrile were brominated at α-position. The reaction is highly selective.

Solid-phase oxoalkylation of pyridines and quinolines with 1-methylcycloalkanols under the action of lead tetraacetate

A new procedure was developed for the introduction of the oxoalkyl fragment into N-heteroaromatic compounds of the pyridine and quinoline series. The procedure is based on the solid-phase reactions of lead tetraacetate with aromatic N-heterocycles and tertiary cycloalkanols.

Oxoalkylation of Pyrazine by 1-Methylcycloalkanols Upon Mechanical Activation

Solid-phase reactions and reactions in the absence of solvent have recently attracted considerable attention [1, 2]. We have already shown that the solid-phase reaction of protonated pyridine and 4-picoline with tertiary cyclic alcohols, which proceeds by the action of Pb(OAc)4, leads to the products of the oxoalkylation of these heterocyclic compounds in high yield [3]. However, the oxoalkylation of pyrazine could not be achieved under analogous conditions.

Electrochemical oxidative ring opening of 1-methylcyclobutanol

The manganese(III) acetate-mediated electrooxidative ring opening of 1-methylcyclobutanol (1) in acetic acid affords pentane-2-one (2) as the major product. The reaction of 1-methylcyclobutanol with Mn(OAc)3-LiCl gives 5-chloropentane-2-one (4.

A H2O2/HBr system – several directions but one choice: oxidation–bromination of secondary alcohols into mono- or dibromo ketones

In this work we found that a H2O2–HBr(aq) system allows synthesis of α-monobromo ketones and α,α′-dibromo ketones from aliphatic and secondary benzylic alcohols with yields up to 91%. It is possible to selectively direct the process toward the formation of mono- or dibromo ketones by varying the amount of hydrogen peroxide and hydrobromic acid. The convenience of application, simple equipment, multifaceted reactivity, and compliance with green chemistry principles make the application of the H2O2–HBr(aq) system very attractive in laboratories and industry. The proposed oxidation–bromination process is selective in spite of known properties of ketones to be oxidized by the Baeyer–Villiger reaction or peroxidated with the formation of compounds with the O–O moiety in the presence of hydrogen peroxide and Bronsted acids.

solid-state reaction of a lead tetraacetate-metal halide system with naphthalene under mechanical activation

A mechanically activated solid-state reaction of halogenation of naphthalene with a Pb(OAc)4—alkaline or alkaline-earth metal halide system was carried out to yield 1-halonaphthalene as the main reaction product and 1,4-dihalonaphthalene. The solid-state halogenation of naphthalene is more selective than a liquid-phase reaction.