J ketones

Reaction of a-sulphinyl carboxylic esters 421 with carbonyl compounds has usually been performed using a Grignard reagent as a base. No condensation products are obtained using f-butyllithium or sodium hydride - (equation 251). The condensation products formed are convenient starting materials for the synthesis of a, ) -unsaturated esters and j -ketones . ... 

Fats are much more energy-rich than carbohydrates, proteins, or ketones. Complete combus- i tion of fet results in 9 kcal/g compared with 4 kcal/g derived from carbohydrate, protein, and j ketones. The storage capacity and pathways for utilization of fuels varies with different organs and with the nutritional status of the organism as a whole. The organ-specific patterns of fuel utilization in the well-fed and fasting states are summarized in Table I-ll-l. 

Left ventricular dysfunction Glucose J. Lactate J. Free fatty acids J. Ketones J. 3-Hydroxibutyrate J. Leucine/isoleucine J. Glutamate J. Alanine t (22)... 

J2. Jacobson, B. E., Blanchaer, M. C., and Wrogemann, K., Defective respiration and oxidative phosphorylation in muscle mitochondria of hamsters in the late stages of hereditary muscular dystrophy. Can. J. Biochem. 48, 1037-1042 (1970), J3. Jenkins, K. J., Ketone body metabolism in nutritional myopathy. Can. J. Biochem. 42, 1153-1160 (1964). 

Another case in which the resonance (and other) effects in the enol form just about balance the extra stability of the keto form (due to bond energies) is that of the jS-diketones and j -ketonic esters. For this reason it is here also that the effect of substituents and solvent has been most thoroughly investigated. Unfortunately, for these systems the quantitative estimates of resonance energies (and other effects) are too crude to be of much use. The observed trends, however, are found to conform very well with expectations based upon the tenets we have just outlined. 

Interestingly, the product actually isolated from alkyne hydration is not the vinylic alcohol, or enol (ene + ol), but is instead a ketone. Although the enol is an intermediate in the reaction, it immediately rearranges to a j ketone by a process called keto—enol tautomerism. The individual keto and enol forms are said to be tautomers, a word used to describe constitutional isomers that interconvert rapidly. With few exceptions, the keto-enol tautomeric equilibrium lies on the side of the ketone enols are almost nevei isolated. Well look more closely at this equilibrium in Section 22.1. 

Methyl. [a-i800itroao.n.noayl j.keton.pheoyb hydimon 15,163. 

C H NOs Phenyl-[l0-methoxy-anthranyl (9) J-Keton benzoylimid 9 II171. 

Methyl-3 phenyl-l>[4-amino-phenyl]-triazeD>(l)-ox (l) 16, 742,1414. Athyl-[oh lyl-(8)J-keton-semioarbazon 811308. 

Acetoxy-phenyl]-[l -aoetoxy-naph thyl-(2)]-Keton 8, 358. [2-Acetoxy-phenylj.[2-acetoxy-naph thyl. l)j-keton Oder [2-Acetoxy.phenyl]. [3.aoetoxy-naphthyI-(2)]-keton 8, 358. Dibenzoat des P ogaUoI-l-nietbylftthers... 

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