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Modification of aluminium alkoxides with dialkylmalonates.

Lichtenberger R, Baumann SO, Bendova M, Puchberger M, Schubert U - Monatsh. Chem. (2010)

Bottom Line: Al(malonate)3 (malonate = dimethyl, diethyl, di-iso-propyl and di-tert-butyl malonate), Al2(OiPr)4(malonate)2 (malonate = di-iso-propyl and di-tert-butyl malonate), Al2(OiPr)2(di-iso-propylmalonate)4 and Al3(OH)(OEt)3(diethylmalonate)5.An Al2(OiPr)2(dialkylmalonate)4 derivative was only obtained by disproportionation of Al2(OiPr)4(di-iso-propylmalonate)2, but not by reaction of Al(OiPr)3 with dialkylmalonates in the corresponding molar ratio.Reactions of Al(OtBu)3 only resulted in Al(malonate)3 derivatives, but no transesterification was observed, contrary to the reaction of Al(OiPr)3 with dimethyl or diethyl malonate.

View Article: PubMed Central - PubMed

Affiliation: Institute of Materials Chemistry, Vienna University of Technology, Vienna, Austria.

ABSTRACT

Abstract: Depending on the reaction conditions, different aluminium dialkylmalonate derivatives were obtained by reaction of aluminium alkoxides Al(OR)3 (R = Et, iPr, tBu) with dialkylmalonates, viz. Al(malonate)3 (malonate = dimethyl, diethyl, di-iso-propyl and di-tert-butyl malonate), Al2(OiPr)4(malonate)2 (malonate = di-iso-propyl and di-tert-butyl malonate), Al2(OiPr)2(di-iso-propylmalonate)4 and Al3(OH)(OEt)3(diethylmalonate)5. All compounds were characterized by NMR spectroscopy, and single crystal structure analyses are reported for each type of compound. An Al2(OiPr)2(dialkylmalonate)4 derivative was only obtained by disproportionation of Al2(OiPr)4(di-iso-propylmalonate)2, but not by reaction of Al(OiPr)3 with dialkylmalonates in the corresponding molar ratio. Reactions of Al(OtBu)3 only resulted in Al(malonate)3 derivatives, but no transesterification was observed, contrary to the reaction of Al(OiPr)3 with dimethyl or diethyl malonate.

No MeSH data available.


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Molecular structure of 3c (hydrogen atoms omitted for clarity)
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Fig7: Molecular structure of 3c (hydrogen atoms omitted for clarity)

Mentions: Storage of 2c, a colourless oil, resulted in the formation of colourless crystals. Single crystal XRD surprisingly revealed that Al2(OiPr)2(diprm)4 (3c) had crystallized rather than 2c (Fig. 7). This is of special interest, since attempts to prepare 3c directly from Al(OiPr)3 with two equivalents of diprm-H at 100 °C had failed and only mixtures of Al2(OiPr)4(diprm)2 (2c) and Al(diprm)3 (1c) had been obtained. Al2(OR)2(β-diketonate)4 derivatives were also reported to disproportionate to Al2(OR)4(β-diketonate)2 and Al(β-diketonate)3 [8]. Only one structure analysis has been reported, viz. that of Al2(OiPr)2(3,5-heptandionate)4 [10]. β-Ketoesterate derivatives of the general formula Al2(OR)2(β-ketoesterate)4 were not obtained [12].Fig. 7


Modification of aluminium alkoxides with dialkylmalonates.

Lichtenberger R, Baumann SO, Bendova M, Puchberger M, Schubert U - Monatsh. Chem. (2010)

Molecular structure of 3c (hydrogen atoms omitted for clarity)
© Copyright Policy
Related In: Results  -  Collection

Show All Figures
getmorefigures.php?uid=PMC4494765&req=5

Fig7: Molecular structure of 3c (hydrogen atoms omitted for clarity)
Mentions: Storage of 2c, a colourless oil, resulted in the formation of colourless crystals. Single crystal XRD surprisingly revealed that Al2(OiPr)2(diprm)4 (3c) had crystallized rather than 2c (Fig. 7). This is of special interest, since attempts to prepare 3c directly from Al(OiPr)3 with two equivalents of diprm-H at 100 °C had failed and only mixtures of Al2(OiPr)4(diprm)2 (2c) and Al(diprm)3 (1c) had been obtained. Al2(OR)2(β-diketonate)4 derivatives were also reported to disproportionate to Al2(OR)4(β-diketonate)2 and Al(β-diketonate)3 [8]. Only one structure analysis has been reported, viz. that of Al2(OiPr)2(3,5-heptandionate)4 [10]. β-Ketoesterate derivatives of the general formula Al2(OR)2(β-ketoesterate)4 were not obtained [12].Fig. 7

Bottom Line: Al(malonate)3 (malonate = dimethyl, diethyl, di-iso-propyl and di-tert-butyl malonate), Al2(OiPr)4(malonate)2 (malonate = di-iso-propyl and di-tert-butyl malonate), Al2(OiPr)2(di-iso-propylmalonate)4 and Al3(OH)(OEt)3(diethylmalonate)5.An Al2(OiPr)2(dialkylmalonate)4 derivative was only obtained by disproportionation of Al2(OiPr)4(di-iso-propylmalonate)2, but not by reaction of Al(OiPr)3 with dialkylmalonates in the corresponding molar ratio.Reactions of Al(OtBu)3 only resulted in Al(malonate)3 derivatives, but no transesterification was observed, contrary to the reaction of Al(OiPr)3 with dimethyl or diethyl malonate.

View Article: PubMed Central - PubMed

Affiliation: Institute of Materials Chemistry, Vienna University of Technology, Vienna, Austria.

ABSTRACT

Abstract: Depending on the reaction conditions, different aluminium dialkylmalonate derivatives were obtained by reaction of aluminium alkoxides Al(OR)3 (R = Et, iPr, tBu) with dialkylmalonates, viz. Al(malonate)3 (malonate = dimethyl, diethyl, di-iso-propyl and di-tert-butyl malonate), Al2(OiPr)4(malonate)2 (malonate = di-iso-propyl and di-tert-butyl malonate), Al2(OiPr)2(di-iso-propylmalonate)4 and Al3(OH)(OEt)3(diethylmalonate)5. All compounds were characterized by NMR spectroscopy, and single crystal structure analyses are reported for each type of compound. An Al2(OiPr)2(dialkylmalonate)4 derivative was only obtained by disproportionation of Al2(OiPr)4(di-iso-propylmalonate)2, but not by reaction of Al(OiPr)3 with dialkylmalonates in the corresponding molar ratio. Reactions of Al(OtBu)3 only resulted in Al(malonate)3 derivatives, but no transesterification was observed, contrary to the reaction of Al(OiPr)3 with dimethyl or diethyl malonate.

No MeSH data available.


Related in: MedlinePlus