Reaction of methyl benzoate with methylaluminium compounds

Starowieyski, K.B.; Pasynkiewicz, S.; Sporzyński, Andrzej; Wiśniewska, Krystyna

doi:10.1016/s0022-328x(00)87990-5

Cited by 17 publications

(8 citation statements)

References 7 publications

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“…However, mechanistic insights were limited to the alternative use of Me 2 AlCl. [18] Although the formation of hemialkoxides has been postulated based on the derivatization of ketonesa nd aldehydesu sing alkylaluminiums, [19] these species have not hitherto been recordedinester-based systems. Meanwhile,t he use of excessT MA has been reported in the alkylation of acetates, [20] and the ketonization of heteroaromatic estersu sing 1equivalent of TMA has been reported.…”

Section: Introductionmentioning

confidence: 99%

“…Moreover, the deployment of excess TMA at high temperature has incurred double methylation and tertiary alcohol formation. However, mechanistic insights were limited to the alternative use of Me 2 AlCl . Although the formation of hemialkoxides has been postulated based on the derivatization of ketones and aldehydes using alkylaluminiums, these species have not hitherto been recorded in ester‐based systems.…”

Section: Introductionmentioning

confidence: 99%

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Reactions of Trimethylaluminium: Modelling the Chemical Degradation of Synthetic Lubricants

Slaughter

Peel

Wheatley

2016

Chemistry A European J

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In investigating and seekingt om imic the reactivity of trimethylaluminium (TMA) with synthetic, ester-based lubricating oils, the reaction of methylp ropionate 1 wase xplored with 1, 2a nd 3equivalents of the organoaluminium reagent. Spectroscopica nalysis pointst ot he formation of the adduct 1(TMA) accompanied only by the low level 1:1 production of Me 2 AlOCEtMe 2 2 and Me 2 AlOMe 3 when an equimolar amount of TMA is applied. The deploymento f excess TMA favoursr eactiont og ive 2 and 3 over 1(TMA) adductf ormation and spectroscopy reveals that in hydrocarbon solution substitution product 2 traps unreacted TMA to yield 2(TMA).

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Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Reactions of Trimethylaluminium: Modelling the Chemical Degradation of Synthetic Lubricants

Slaughter

Peel

Wheatley

2016

Chemistry A European J

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“…The reaction of aluminum trialkyls with the ester group was deeply investigated (Refs.5, 18,19). A nucleophilic attack of uncomplexed AlR3 to the carbonyl group complexed with AlR3 has been postulated.…”

Section: Secondary Reactionsmentioning

confidence: 99%

The chemistry of magnesium chloride supported catalysts for polypropylene

Albizzati

Galimberti

Giannini

et al. 1991

Makromolekulare Chemie. Macromolecular Symposia

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“…22 Thereafter, Me 2 AlCl (but not TMA) was suggested to promote PhCMe 2 OAlMeCl formation, presumably alongside that of MeOAlMeCl, the subsequent reaction of which gave either alkene PhC(CH 2 )Me, presumably alongside HOAl-MeCl, or Ph(t-Bu), presumably alongside O(AlMeCl) 2 . 23 The expected byproduct of methyl ester reaction with TMA itself, Me 2 AlOMe, has been extensively studied. 24 However, whereas the byproducts of methylaluminum chloride reaction with esters proposed in ref 23 were reasonable, direct evidence for their formation was not presented.…”

Section: ■ Introductionmentioning

confidence: 99%

“…23 The expected byproduct of methyl ester reaction with TMA itself, Me 2 AlOMe, has been extensively studied. 24 However, whereas the byproducts of methylaluminum chloride reaction with esters proposed in ref 23 were reasonable, direct evidence for their formation was not presented. Indeed, while some aluminum hydroxides have been reviewed, 24,25 only a very few literature reports of AlCl-incorporating hydroxides 26 and oxides (aluminoxanes) exist.…”

Section: ■ Introductionmentioning

confidence: 99%

Action of Organoaluminum Reagents on Esters: Alkene Production and the Degradation of Synthetic Lubricants

et al. 2018

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Reactions of methylaluminum reagents with ester-based lubricating oils are mimicked through the reaction of trimethylaluminum (TMA) with tetraesters C(CH2OC(O)R)4 (R = C5H11 4 Pent, Bn 4 Bn). Using a 2:1 stoichiometry gave adduct 4 Pent(TMA)4. NMR spectroscopy on 1:1–12:1 TMA/4 Pent systems suggested 4 Pent gave dimethylated adduct C5H11CMe2OAlMe2(TMA), 2 Pent(TMA). Similar combination of TMA with 4 Bn at raised temperatures transformed 4 Bn into C(CH2OAlMe2)4(2 Bn)4 5(2 Bn)4 by sequential reaction of each ester group. Doubly reacted {BnC(O)OCH2}2C(CH2OAlMe2)2(2 Bn)2 7 Bn(2 Bn)2 was isolated and characterized. A Mitsubishi molecule could also be isolated, its formation rationalized by the elimination of 2 Bn and TMA from 5(2 Bn)4. The action of Me n AlCl3–n (n = 1, 1.5, 2) was studied initially on monoester BnC(O)OMe 1 Bn. Combining excess Me2AlCl with 1 Bn gave adduct 1 Bn(Me2AlCl) and small amounts of dimethylated BnCMe2OAlMe2(Me2AlCl), 2 Bn(Me2AlCl), and MeOAlCl2 10. 2 Bn(Me2AlCl) was fully characterized and, in the presence of 10, acted as a source of 2 Bn(MeAlCl2). From this species, a mixture of alkenes could be generated by formal elimination of Me3Al2(OH)Cl2 13, the decomposition of which was presumed to also explain MeH observation. Replacing Me2AlCl with aluminum sesquichloride or MeAlCl2 led to progressively more sluggish but similar reactions. Using Me n AlCl3–n (n = 1, 1.5, 2) with tetraesters suggested similar reactivity to monoesters.

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Reaction of methyl benzoate with methylaluminium compounds

Cited by 17 publications

References 7 publications

Reactions of Trimethylaluminium: Modelling the Chemical Degradation of Synthetic Lubricants

Reactions of Trimethylaluminium: Modelling the Chemical Degradation of Synthetic Lubricants

The chemistry of magnesium chloride supported catalysts for polypropylene

Action of Organoaluminum Reagents on Esters: Alkene Production and the Degradation of Synthetic Lubricants

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