Synthesis of C?C aliphatic alcohols by the liquid-phase oxidation of alkanes under pressure

Kamzolkin, V.V.; Bashkirov, A.N.; Khotimskaya, M.I.; Grozhan, N.M.; Yezhenkina, G.M.

doi:10.1016/0031-6458(62)90066-7

Cited by 2 publications

(1 citation statement)

References 2 publications

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“…Orthoboric acid esters were prepared in situ in the synthesis of secondary alcohols by oxidation of paraffi nic hydrocarbons according to the Bashkirov procedure to avoid their further oxidation. [90][91][92][93] The reactivity of the cyclohexyl moiety in the boric acid ester is lower than in cyclohexanol, but somewhat higher than in cyclohexyl acetate (see Table 2). 84…”

Section: Methodsmentioning

confidence: 99%

The specific features of the liquid-phase oxidation of saturated esters. Kinetics, reactivity and mechanisms of formation of destruction products

Perkel

Voronina

2020

Russ Chem Bull

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Data on kinetics, reactivity, and mechanisms of formation of destruction products of the liquid-phase oxidation of saturated esters by molecular oxygen have been systematized and discussed. The ester group has both an activating and deactivating eff ects on the reactivity of the СН bonds of the alkoxyl (α´-, β´-, γ´-, and δ´-) and acyl (α-, β-, and γ-) groups. The activating eff ect in esters is weaker than in alcohols, ketones, and ethers and extends to the αand α´-CH bonds. The reactivity of the β-, β´-, and γ´-СН bonds is signifi cantly lower than that of the secondary СН bonds of hydrocarbons. Oxidation of the β-СН bonds of the acyl moieties of esters leads to НОО • radical, α,β-epoxy-, α,β-dihydroxy-, and α,β-unsaturated esters, but not to hydroperoxides. Upon the oxidation of esters, the highly active α-carboxyalkylperoxy-, α-acyloxyperoxy-, and НОО • -radicals are formed. The recombination reactions involving these radicals occur both with and without chain termination. The specifi city of the decomposition of ester hydroperoxides are due to intra-and intermolecular interactions of the hydroperoxide groups with the ester groups. Labile peroxide intermediates (α-hydroxyperoxyesters, peroxyesters, and peroxylactones) are formed through the corresponding tetrahedral intermediates and decay predominantly by the non-radical pathway. The recombination of the peroxyl radicals and the decay of labile peroxides result in the parallel accumulation of per oxide and non-peroxide products during the oxidation of esters.

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Section: Methodsmentioning

confidence: 99%

The specific features of the liquid-phase oxidation of saturated esters. Kinetics, reactivity and mechanisms of formation of destruction products

Perkel

Voronina

2020

Russ Chem Bull

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Alcohols as Petrochemicals

Kropf

1966

Angew. Chem. Int. Ed. Engl.

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Efficient processes have been developed in recent years for the large‐scale manufacture of alcohols from petrochemicals. These allow production of aliphatic alcohols both with short and with long alkyl groups more economically than was previously possible by fermentation. In this paper the most important principles and the technical execution of the hydration of olefins, the air oxidation of paraffins, and especially the synthesis reactions (e.g. the catalytic hydroformylation of olefins with carbon monoxide and hydrogen according to Roelen, the Reppe synthesis, and the Ziegler growth reaction with ethylene and triethylaluminum) are described.

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Synthesis of C?C aliphatic alcohols by the liquid-phase oxidation of alkanes under pressure

Cited by 2 publications

References 2 publications

The specific features of the liquid-phase oxidation of saturated esters. Kinetics, reactivity and mechanisms of formation of destruction products

The specific features of the liquid-phase oxidation of saturated esters. Kinetics, reactivity and mechanisms of formation of destruction products

Alcohols as Petrochemicals

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