Сообщение
Chem_DM » Чт июл 11, 2013 10:28 pm
PhCH2CH2NH2 (I) (5 g.) added portionwise with cooling to 8 g. BzCH2CO2Et in 1 ml. abs. EtOH gave after 1 hr. in a refrigerator 10.3 g. PhCH2CH2N:CPhCH2CO2Et.H2O (II), m. 49.5-50.5° (Et2O), which turned oily unless kept below 0°. Analogously, 7.2 g. I and 7.7 g. AcCH2CO2Et yielded 10.7 g. PhCH2CH2N:CMeCH2CO2Et (III), b7 170-1°. Attempts to hydrogenate the C:N bond in II and III over Pd-C or PtO2 failed. A similar condensation of 1.3 g. I with 2 g. PhCH2COCO2Et (IV) gave abnormally 2.12 g. PhCH2CH2NHCOC(OH)(CH2Ph)CHPhCOCO2Et, m. 139-41° (EtOH), which heated at 100°/5-6 mm. gave 99% PhCH2CH2NHCOC(CH2Ph).O.CO.CO.CHPh, yellowish wax. Prepn. of IV according to Hemmerl´e (CA 11, 2455) was modified; the crude product was chilled several hrs. at -15°, filtered, and the solid part crystd. from petr. ether to yield the α-isomer of IV, m. 51°, while the oil gave on distn. the β-isomer, b15 149-51°; the total yield of both forms was 32%.
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