Valeramide

Bei der WiLLGERODT-Reaktion mit Phenyl-n-butylketon- [/ -D2] ent-hielt das entstandene 6-Phenyl-valeramid nur noch 5 % vom Deuterium-gehalt des Ausgangsketons, wie Cerwonka, Anderson und Brown (46) fanden. Die Reaktion muB also iiber eine ungesattigte Zwischenstufe verlaufen. Dieses Ergebnis laBt sich z. B. nach dem Reaktionsmechanis-mus von Carmack und de Tar (41) deuten, die eine Zwischenstufe mit einer Dreifachbindung annehmen. 

Glutarimides disubstituted in a or positions were hydrogenolyzed by sodium borohydride in aqueous methanol mainly to disubstituted y-hydroxy-valeramides [7725], but 7V-methylglutarimide was reduced electrolytically in sulfuric acid to a mixture of JV-methylpiperidone (15-68%) and 7V-methylpi-peridine (7-62%) [7727], and by lithium aluminum hydride in ether to N-methylpiperidine in 85% yield [7725]. 

Problem 17.15 Use CH,CH2CH20H and H2C(COOC HJ, as the only organic reagents to synthesize valeramide, CH,CH,CH,CHjCONH,. <4... 

L-4-Dimethylamino-2,2-diphenyl valeramide [6078-64-4] M 296.4, 136.5-137.5°. Crystd from pet ether or EtOH. 

Similarly Zum240 found that the acidic hydrolysis of 6-hydroxy valeramide and y-hydroxybutyramide were much faster than the hydrolysis of the corresponding tt-alkyl-carboamides. 

Cone, sulfuric acid (11 ml) was added to 4-(N,N-dimethylamino)-2-phenyl-2-(2-pyridyl)-valeronitrile (6.3 g) at 0°C. Then water (1 ml) was added thereto. After being heated at 90°C for 3 hours, the mixture was poured into ice-water, adjusted to pH 10 with 10% aqueous sodium hydroxide and extracted with ethyl acetate (3x50ml). The extracts were combined, and washed with water, dried over magnesium sulfate and evaporated under reduced pressure. The obtained crude crystal was recrystallized from diethyl ether to give 4-(N,N-dimethylamino)-2-phenyl-2-(2-pyridyl)-valeramide (1.89 g). MP 132-134°C. 

BAL-resin = 5-(4-formyl-3,5-dimethoxyphenoxy)valeramide resin (Applied Biosystems, Framingham, MA). 

Valnoctamide Axiquel nirvanil McNeil (J J) Recordati (Italy) Valeramide 400-800 p.o. 

Synthesis of 5-Cyano Valeramide by Nitrile Hydratase from Pseudomonas chlororaphis B23 (E. C. 4.2.1.84)[106, 1071... 

Figure 19-39. Comparison of chemical and biocatalytical synthesis of 5-cyano-valeramide (DuPont).

Synthesis of 5-Cyano Valeramide by Nitrile Hydratase from Pseudomonas... 

Table 3. Comamonas Nil activity on adiponitrile, ammonium 5-cyanovalerate, 5-cyano valeramide, ammonium adipamate and adipamide...

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