Synthesis of 3,3-Dimethylbutanol and 3,3-Dimethylbutanal, Important Intermediates in the Synthesis of Neotame

• Published in: Topics in catalysis Vol. 55; no. 7-10; pp. 625 - 630
• Main Authors: Tanielyan, Setrak K., Augustine, Robert L.
• Format: Journal Article
• Language: English
• Published: Boston Springer US 01.07.2012
• Subjects: Catalysis; Characterization and Evaluation of Materials; Chemistry; Chemistry and Materials Science; Industrial Chemistry/Chemical Engineering; Original Paper; Pharmacy; Physical Chemistry; Isobutene condensation; Dimethylbutanol oxidation; Alkylsulfate hydrolysis; Ethylene–alkene condensation; Dimethylbutanol dehydrogenation; 3,3-Dimethylbutanol formation
• ISSN: 1022-5528; 1572-9028
• DOI: 10.1007/s11244-012-9841-z

It has been shown that some N -alkyl derivatives of Aspartame ( 1 ) are enhanced sweetening agents [ 1 ]. In particular, the 3,3-dimethylbutyl derivative, 2 , (Neotame) is about 70 times sweeter than Aspartame. With this in mind a research program directed toward the synthesis of 3,3-dimethylbutanal ( 3 ) was begun. The first phase of this research involved the synthesis of 3,3-dimethylbutanol ( 4 ) by the acid catalyzed alkylation of isobutene with ethylene to give the sulfate ester [ 2 ] which was readily hydrolyzed to the alcohol, 4 , in isolated yields in the 70–75 % range. It was found that the most efficient method for the conversion of 4 to the aldehyde, 3 , was by a vapor phase dehydrogenation over a copper catalyst. The effect which the reaction variables have on the production of 4 will be discussed. This will include factors such as the ethylene pressure, the acid/isobutene ratio, the use of a hydrocarbon solvent, the reaction temperature and the mode of addition of the isobutene. The discussion of the dehydrogenation procedure will include the nature of the catalyst used and the reaction parameters needed to maximize the formation of 3 and keeping the amount of the over-oxidation carboxylic acid product below 1 %.