Mechanism of the effect of boric acid on liquid-phase oxidation of paraffin hydrocarbons

Novak, Filip; Kamzolkin, V.V.; Talyzenkov, Yu. A.; Bashkirov, A.N.

doi:10.1016/0031-6458(67)90010-x

Cited by 3 publications

(2 citation statements)

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“…Is it relevant, for example, to the apparent weakening for the peroxide bond when a peroxyborane reacts with an organoborane as shown in equation ( 10)? It might even provide an answer to the mechanism of the commercially important but enigmatic Bashkirov reaction, 100,101 in which the presence of boric oxide during the autoxidation of an alkane, diverts the reaction from forming ketone and alcohol into giving principally the alcohol. A reaction analogous to that of equation ( 10), 102 as shown in equations ( 75)-( 78), now seems an attractive possibility.…”

Section: B O H H R B O H + Hrmentioning

confidence: 99%

Autoxidation of Organoboranes and Related Organometallics: Radicals and their Ramifications

Davies

2008

Journal of Chemical Research

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The identification, 50 years ago, of the autoxidation products of organoboranes as organoperoxyboranes, and of the mechanism of the reaction as a radical chain, has had far-reaching consequences in organometallic and organic chemistry in the identification of organic radicals and of other radical reactions, in the use of organoboron compounds in synthesis and catalysis, in the parallel chemistry of other metals (particularly, currently, of zinc), and of the behaviour of metals as hydrogen equivalents. This review traces the course of some of those developments in the radical chemistry of compounds in which oxygen forms a bond with boron and related metals, and summarises the present position.

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Section: B O H H R B O H + Hrmentioning

confidence: 99%

Autoxidation of Organoboranes and Related Organometallics: Radicals and their Ramifications

Davies

2008

Journal of Chemical Research

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“…One concept that has been reported for improving alcohol selectivity in alkane oxidations is the Bashkirov process, which involves the use of boron compounds such as boric acid, boric oxide and borate esters [17][18][19]. These boron species function as Lewis acids which direct the oxidation towards the formation of alcohols, and subsequently trap the alcohols in the form of borate esters to protect them from over-oxidation [20][21][22][23][24]. This idea formed the basis of several industrial-scale processes for the oxidation of cyclohexane to cyclohexanol/cyclohexanone, used as intermediate for the production of nylon-6, oxidation of cyclododecane to cyclododecanol/cyclododecanone used as intermediates for nylon-12, as well as the oxidation of C 10 -C 20 alkanes for the synthesis of higher aliphatic alcohols used in the manufacture of detergents and surfactants [20,25,26].…”

Section: N-alkanementioning

confidence: 99%

Borate-assisted liquid-phase selective oxidation of n-pentane

Aworinde¹,

Wang²,

Lapkin³

2018

Applied Catalysis A: General

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Oxidation of n-pentane with molecular oxygen to sec-pentanols was performed in the presence of a free radical initiator (di-tert-butyl peroxide) and a boron compound (sec-butyl metaborate), with in situ adsorption of water on molecular sieve 3A. Kinetics of the reaction was studied in a laboratory-scale batch reactor over a broad range of conditions (130-150°C, 20-30 bar, 5-10 vol% O 2) in order to establish the optimum parameters for maximising the selectivity and yield of sec-pentanols. Results show that the initiator markedly improves the rate of oxidation, and hence yield, compared to thermal oxidation without an initiator, while the boron species enhances the selectivity to sec-pentanols. Under the conditions investigated, maximum secpentanol selectivity is 56% with an alcohol-to-ketone ratio of 3.6:1 for the borate-assisted oxidation compared to 33% and 1.1:1, respectively, for the oxidation without borate. This work demonstrates the feasibility of oxyfunctionalization of n-pentane with industrially relevant selectivity and yield.

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Review Lecture: Novel organic chemical processes

Stanley¹

1968

Proc. R. Soc. Lond. A

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The purpose of this paper is to review some recent developments in industrial organic chemistry which have led, or seem likely to lead, to the establishment of new industrial processes for the production of bulk organic chemical products. The significance of some of the new and cheap, or potentially cheap, intermediates produced in such processes is pointed out in a few selected cases. In this review I shall concentrate on major new processes leading to large-scale organic chemical production. This invariably means continuous processes using as raw materials either petroleum hydrocarbons, including natural gas, or their cracked products. Because many important organic chemicals are oxygenated compounds, it is quite natural that the reaction of hydrocarbons with oxygen or air should have become quantitatively the most important area of industrial organic chemistry, apart that is from the field of polymerization. Certain processes involving the simultaneous reaction of hydrocarbons with oxygen and with a third reactant (such as hydrogen chloride, ammonia, etc.) have recently become very important industrially and will be reviewed in some detail. The potentialities of reactions involving hydrocarbons and carbon monoxide, cheap and readily available raw materials, will also be considered.

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Mechanism of the effect of boric acid on liquid-phase oxidation of paraffin hydrocarbons

Cited by 3 publications

References 0 publications

Autoxidation of Organoboranes and Related Organometallics: Radicals and their Ramifications

Autoxidation of Organoboranes and Related Organometallics: Radicals and their Ramifications

Borate-assisted liquid-phase selective oxidation of n-pentane

Review Lecture: Novel organic chemical processes

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