Ethylphenylmalonic acid

QH12N2 19275-55-9) see Etodolac ethylphenylmalondiamide (C11H14N2O2 7206-76-0) see Primidone ethylphenylmalonic acid diethyl ester see under diethyl cthylphenylmalonate... 

Primidone Primidone, 5-ethyl-5-phenylhexahydropyrimidinedione-4,6 (9.2.1) is synthesized by reacting ethylphenylmalonic acid diamide with formamide [5,6]. An alternative method is the electrolytic reduction of phenobarbital or the catalytic reduction of the appropriate 2-thiobarbituric acid [7]. 

The cholesteric mesophase formed by cholesteryl p-nitrobenzoate at 200 °C has been used as the solvent to effect an asymmetric synthesis lrans-but-2-enyl p-tolyl ether gave the product of an ortho-Claisen rearrangement, 2-(but-1 -en-3 -yl)-4-methylphenol. This material exhibited circular dichroism, although neither the optical yield nor the configuration of the product is yet known.262 Decarboxylation of ethylphenylmalonic acid in cholesteryl benzoate at 160 °C (cholesteric liquid-crystalline phase) also proceeded with asymmetric induction to give (R)-(—)-2-phenylbutyric acid, with 18% optical yield.263 Electric dipole moments are reported for some esters of 5a-cholest-8(14)-en-3j8-ol there is some slight correlation with melting points.264... 

Ethyl-3-methylbutylmalonic acid [Pg.340]

As early as 1904, Marckwald et al. [4] reported the thermal decarboxylation of ethyl(methyl)malonic acid 1 at 170°C in the presence of brucine affording (S)-2-methylbutyric acid 2 in 10% ee (Scheme 3.2). While this report might probably be considered as the first asymmetric transformation, this result could not be successfully reproduced several decades later [6]. In 1975, Verbit et al. [7] reported the decarboxylation of ethylphenylmalonic acid 3 in cholesteryl benzoate at 160°C giving rise to (/ )-phenylbutanoic acid 4 in 18% ee (Scheme 3.2). However, Kagan et al. [8] failed to obtain any enantioenriched phenylbutanoic acid 4 under the same reaction conditions. 

A similar retrosynthetic analysis for 5-ethyl-5-phenylbarbituric acid (94) discloses urea and diethyl ethylphenylmalonate. 

Methyls are trans in NN, PP cis in OO, QQ, RR (b) NN is resolvable. 22. See p. 1087. 23. (a) Ethyl acetate (b) methacrylic acid (c) phenylacetamide. 24. (a) /i-Propyl formate (b) methyl propionate (c) ethyl acetate. 25. SS, benzyl acetate TT, methyl phenylacetate UU, hydrocinnamic acid, PhCH2CH2COOH. 26. Ethyl anisate. 27. VV, vinyl acetate. 28. (a) Ethyl adipate (b) ethyl ethylphenylmalonate ethyl aoet-amidomalonate. 

Many derivatives of barbituric acid with certain substituents at C-5, which are made by using C-substituted malonates, are very useful as hypnotics. The most famous is phenobarbital (4.24), whieh has been used clinically for many years. This compound can be made from diethyl ethylphenylmalonate (Scheme 4.23). 

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