Abstract: 1. When the potassium derivative of 2-methyldihydroresorcinol was treated with bromomethyl 1-hydroxycyclohexyl ketone (II), in methanol solution, the corresponding enol ether (III) was formed in 40% yield. Under the same conditions, reaction between the potassium derivative of 2-methyldihydroresorcinol and 2-bromoacetophenone gave the C-derivative (V) in 44% yield. 2. When boiled for three hours with methyl iodine in a methanol medium, 3-methyltetrocic acid (XI) was not methylated, whereas 2-methyl-1,3-indandione gave the C-methyl derivatives (OX) in 70% yield. 3. Unlike dihydroresorcinol, 2-methyl-1,3-indandione readily undergoes C-methylation in ry dioxene. 4. In condensations with acrylonitrile, 2-methyl-1,3-indandione reacts more readily than dihydroresorcinol derivatives and 3-alkyltetronic acids. 5. In aqueous dioxane in presence of caustic alkali, the cyanoethylation of ethyl 2-oxocyclohexanecarboxylate is more difficult than that of ethyl 2-oxocyclopentanecarboxylate. 6. These examples of low nucleophilic reactivity in keto-enol compounds is to be explained by the deactivating effect of enolization.

Cite: Nazarov I.N. , Zavylov S.I. , Burmistrovа M.S.
Ect of enolization on the ability of 8-dicarbonyl compounds to undergo Michael and C-alkylation reactions
Bulletin of the Academy of Sciences of the USSR, Division of Chemical Science. 1956. V.5. N2. P.197-203. DOI: 10.1007/bf01177644 OpenAlex

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W2081816588

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