5159-42-2

Upstream product

• 64-19-7 acetic acid 
• 76-05-1 trifluoroacetic acid 
• 108-67-8 1,3,5-trimethyl-benzene 
• 127-08-2 potassium acetate 
• 127-09-3 sodium acetate 

Downstream Products

• 27129-87-9 3,5-dimethylbenzyl alcohol 

Relevant academic research and scientific papers

Electron Transfer Reactions in Organic Chemistry. VII. Oxidative Acetoxylation of Aromatic Compounds by Tungsten Hexachloride

Tungsten hexachloride, a high-potential oxidant, causes fast oxidative acetoxylation of ring and/or α positions of aromatic compounds, even as difficalty oxidizable ones as mesitylene and p-xylene.Chlorination is a completing reaction which cannnot be completely suppressed.The acetoxylation process in all likelihood proceeds via an electron transfer mechanism, involving initial formation of the radical cation of the substrate.

COMPETITION BETWEEN NUCLEAR AND SIDE-CHAIN SUBSTITUTION IN THE OXIDATION OF SOME ALKYLAROMATIC COMPOUNDS BY CERIUM(IV) AMMONIUM NITRATE AND COBALT(III) ACETATE

The distribution between nuclear and side-chain substitution (N:S ratio) in the oxidations of m-methoxytoluene, 2-methylnaphtalene, mesitylene, and fluorene by cerium(IV) ammonium nitrate (CAN) and cobalt(III) acetate in acetic acid has been determined.The two oxidants exhibit remarkably different behaviours, the propensity for nuclear substitution being much stronger with CAN than with Co(OAc)3.For example, with m-methoxytoluene, CAN affords only products of nuclear acetoxylation, whereas Co(OAc)3 gives side-chain acetoxylation exclusively.The N:S ratio and the isomeric distribution for the CAN-induced reactions are consistent with a mechanism involving a common radical cation intermediate for the side-chain and nuclear substitution.The same mechanism might hold in the reactions with Co(OAc)3; however, in this case, the simultaneous operation of two different mechanisms is an additional possibility: a radical cation mechanism for the nuclear substitution and a hydrogen atom transfer mechanism for the side-chain reaction.

The Liquid-phase Oxidation of the Methylbenzenes by the Cobalt-Copper-Bromide System

The liquid-phase oxidation of the methylbenzenes catalyzed by a catalyst system composed of cobalt(II) and copper(II) acetates and sodium bromide was carried out in the acetic acid at 150 deg C.The corresponding benzyl acetates and benzaldehydes were obtained in high selectivities in most cases.A nuclear-brominated product, i.e., 3-bromo-4-methoxytoluene was also obtained in the oxidation of p-methoxytoluene, wich has two different reaction sites, i.e., o-positions to the electron-donating methoxyl substituent and the benzyl position.However, the substitution of the bromide ion for the acetate ion in the catalyst system gave satisfactory selectivities for the side-chain oxidation products.In the p-xylene oxidation, α,α'-diacetoxy-p-xylene and p-(acetoxymethyl)benzoic acid were also obtained, as well as p-methylbenzyl acetate, though their amounts were small.The oxidation of polymethylbenzenes was also carried out.

Metal Ion Oxidation. VIII. Oxidation of Organic Compounds by Copper(III)

The copper(III) complex of biuret has been shown to oxidize aromatic and alicyclic compounds in acetic and trifluoroacetic acid, yielding acetates and dehydro dimers.The product pattern of these reactions supports an electron transfer mechanism.Aryl halides, e.g. fluorobenzene, are hydrolyzed to phenols and the mechanism is postulated to be an electron transfer chain mechanism, the SON2 mechanism.Substituted arylacetic acids are decarboxylated when treated with 1 in acetic acid at reflux temperature.This decarboxylation is proposed to be a one-electron process, the rate-determining step being the decomposition of an arylacetic acid-copper(III) complex to a benzylic radical.

Metal Ion Oxidation. VII. Oxidation of Aromatic Hydrocarbons by Potassium 12-Wolframocobalt(III)ate, a "Soluble Anode"

The oxidation of aromatic compounds with potassium 12-wolframocobalt(II)ate in acetic acid media has been investigated.A wide range of alkylaromatics can be acetoxylated in the α position, whereas nuclear substitution can be effected in the presence of acetate ion.In a few cases acetoxymethylation is observed, presumably via intermediate arylacetic acid. 4-Fluoroanisole is converted to 4-acetoxyanisole.In all preparative aspects, the reaction is closely similar to anodic and Ag(II) mediated acetoxylation.A study of substituted effects upon α acetoxylation showed a good linear relationship between log krel and Eo for oxidation of the alkylaromatic substrates (slope -3.2 V-1).A strong deuterium isotope effect (KH/kD ca. 6) is indicative of a rate-determining step involving hydrogen atom transfer ("concerted electron/proton transfer") from the α C-H bond to an oxygen of the heteropoly ion.

Electron-transfer Chain Catalysis of Substitution Reactions. Experimental Evidence for the SON2 Mechanism

Two possible cases of an oxidative electron-transfer chain catalysis mechanism, the SON2 mechanism, are presented: the anionic 'oxidation' of 4-fluoroanisole in the presence of acetate ion to give 4-acetoxyanisole, and the CuIII 'oxidation' of chloro- and fluoro-benzene in the presence of water to give phenol.