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Diethyl ketomalonate, reagent employed in Wittig and Aza-Wittig reactions for synthesis of triazoles, and 2-azadienes, respectively.
D. Basavaiah; V. V. L. Gownswari. Diethyl Ketomalonate: A Fast Reacting Substrate for Baylis-Hillman Reaction. Synthetic Communications: An International Journal for Rapid Communication of Synthetic Organic Chemistry. 1989,(13-14), 6898-6904.
M. Sugawara; M.M. Baizer. Electrogenerated bases VII. Novel syntheses of ethyl glyoxalate and diethyl ketomalonate via electrogenerated superoxide. Tetrahedron Letters. 1983,24(22), 2223-2226.
The carbonyl group behaves as a heterodienophile towards simple dienes. Curtius degradation of the gem-diester to carbonyl completes a synthesis of ß-unsaturated δ-lactones: Rocz. Chem., 38, 707 (1964); J. Am. Chem. Soc., 97, 6892 (1975); J. Org. Chem., 42, 4095 (1977):
For asymmetric Diels-Alder reaction, see: J. Chem. Soc., Chem. Commun., 676 (1987). For addition to aza-dienes, see: Tetrahedron Lett, 30, 2685 (1989).
Ene-addition to alkenes occurs at the less-substituted carbon. Oxidative degradation leads to ß-unsaturated carboxylic acids: J. Am. Chem. Soc., 102, 2473 (1980); 106, 3797 (1984):
Thus, the reagent could be regarded as a CO2 equivalent in both the above sequences.
Undergoes the Baylis-Hillman reaction in which a carbanionic species, generated by the reversible addition of 1,4-Diazabicyclo[2.2.2]octane, A14003, to a Michael acceptor, adds to the carbonyl group: Synth. Commun., 19, 2461 (1989).
Reacts with activated arenes under Friedel-Crafts conditions, or with aryllithium or Grignard derivatives, to give aryl hydroxymalonates, hydrolysis and decarboxylation of which gives substituted mandelic acids: Org. Synth. Coll., 3, 326 (1955). Alternatively, they may be transformed reductively to arylmalonates and hence to ester enolates: J. Org. Chem., 47, 4692 (1982).
Hazard Statements: H315-H319-H335
Causes skin irritation. Causes serious eye irritation. May cause respiratory irritation.
Precautionary Statements: P261-P264b-P271-P280-P302+P352-P304+P340-P305+P351+P338-P312-P332+P313-P337+P313-P362-P501c
Avoid breathing dust/fume/gas/mist/vapours/spray. Wash face, hands and any exposed skin thoroughly after handling Use only outdoors or in a well-ventilated area. Wear protective gloves/protective clothing/eye protection/face protection. IF ON SKIN: Wash with plenty of soap and water. IF INHALED: Remove to fresh air and keep at rest in a position comfortable for breathing. IF IN EYES: Rinse cautiously with water for several minutes. Remove contact lenses, if present and easy to do. Continue rinsing. Call a POISON CENTER or doctor/physician if you feel unwell. If skin irritation occurs: Get medical advice/attention. If eye irritation persists: Take off contaminated clothing and wash before reuse. Dispose of contents/ container to an approved waste disposal plant