Preparation of .gamma.,.delta.-unsaturated ketones by the Carrol

Organic compounds -- part of the class 532-570 series – Organic compounds – Oxygen containing

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568383, 568388, 568398, 423625, 554 38, 556170, C07C 4500

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active

060517417

ABSTRACT:
A process for preparing .gamma.,.delta.-unsaturated ketones of the general formula I ##STR1## by reacting an allyl alcohol of the general formula II ##STR2## in which R.sup.1 is H or a hydrocarbon radical having 1 to 20 carbon atoms, with diketene or an alkyl acetoacetate of the general formula III ##STR3## in which R.sup.2 is alkyl having 1 to 4 carbon atoms in an unmodified or modified Carroll reaction in the presence of an aluminum catalyst, wherein aluminum compounds which are stable liquids at room temperature, or a mixture of such aluminum compounds, which comprise at least one radical formed from an alkyl acetoacetate and 1 or 2 alkoxy radicals, or else comprise exclusively radicals formed from alkyl acetoacetates, which are esterified with sec-butanol or isobutanol, or else are esterified with at least two different alcohols, are used as aluminum catalyst. Also claimed are the novel mixtures of aluminum compounds which comprise radicals which are formed exclusively from alkyl acetoacetates and are esterified with at least two different alkanols, and the batchwise and continuous preparation of the liquid aluminum catalysts.

REFERENCES:
patent: 2795617 (1957-06-01), Kimel et al.
Walter Kimel, et al., "The Rearrangement of Allyl-Type Esters of .beta.-Keto Acids", J. Am. Chem. Soc., vol. 65, 1943, pp. 1992-1998.
R. K. Mehrotra, et al., "Reactions of Aluminum Alkoxides with Acetylacetone, Benzoylacetone, and Ethyl Acetoacetate", Can. J. Chem., vol. 39, 1961, pp. 795-798.
Walter Kimel, et al. "Total Synthesis of Pseudoionone and an Isomeric Ketone", J. Org. Chem., vol. 23, No. 2, 1958, pp. 153-157.
J. Weichet, et al., "Studies in der Vitamin-K- und Vitamin-E-Reihe XIL,* Synthese von 2-Methyl-3-Difarnesyl-1,4-Naphthochinon und verwandten Verbindungen", Collect. Czech. Chem. Comm., vol. 25, 1960, pp. 1914-1921.

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