cf. CA 54, 1406h. Ar = 3,4,5-(MeO)3C6H2 throughout this abstract The piperidine-catalyzed condensation of RCHO with NCCH2CO2H (I) yielded the isomeric RCH:C(CN)CO2H (II), which, decarboxylated, gave RCH:CHCN (III). II reacted further with I to yield ArCH(CH2CN)2 (IV). PhCH:C(CN)CO2H (V) (10.88 g.) distilled during 1 hr. at 230, the small amount of distillate dissolved in C6H6 and treated with aqueous Na2CO3, and the C6H6 removed gave 1.06 g. PhCH:CHCN, b16 127-31°; the resinous residue yielded 2.39 g. unchanged V, m. about 170°. RCHO (2.42 g.) shaken with I in aqueous NaOH and filtered, and the residue stirred into 6N HCl, gave 2.61 g. II, m. 221-3°; 0.31 g. RCHO was recovered unchanged. II heated 15 min. at 210°, and the resinous residue ground with C6H6 yielded unchanged II; the C6H6 phase evaporated left a brown resin. RCHO (5.00 g.) and 2.26 g. tech. I refluxed 5 hrs. with 1.00 cc. piperidine and evaporated in vacuo, the oily brown residue dissolved in C6H6 and washed, and the C6H6 evaporated gave 4.63 g. III, yellowish needles, m. 95-7° (aqueous MeOH). RCHO (7.00 g.) and 3.15 g. tech. I in 30 cc. C5H5N refluxed 4 hrs. with 0.25 cc. piperidine and evaporated, the brown, oily residue dissolved in C6H6, the warm solution diluted with H2O and shaken, the precipitated II filtered off, the residue washed with C6H6, and the combined C6H6 solutions worked up gave 4.49 g. II, m. 95-7° (aqueous MeOH). II dissolved in hot C6H6 and cooled slowly deposited canary-yellow needles of the high melting isomer (VIa) of II, m. 219-21°, followed by the low melting isomer (VIb), light yellow needles, m. 170-2°. VIb exposed 2 and 5 days to sunlight m. 168-71° and 168-70°, resp. VIb irradiated 18 hrs. with a Hg-vapor lamp m. 169-89°; however, this material recrystallized from C6H6 m. 170-2°. Via irradiated 11.5 hrs. with a Hg-vapor lamp m. 217-20°. VIa (0.34 g.) in 5 cc. C5H5N refluxed 5 hrs. with 0.50 cc. piperidine and acidified, and the product isolated with C6H6 gave 0.23 g. III, m. 94-7° (ligroine). RCHO (7.34 g.) and 7.65 g. I in 30 cc. C5H5N refluxed 4 hrs. with 1.10 cc. piperidine and evaporated in vacuo, the brown, and oily residue dissolved in 50 cc C6H6 washed and allowed to stand deposited 2.83 g. IV; the mother liquor evaporated, the residual brown oil (5.43 g.) allowed to stand, and the crystalline deposit recrystallized from C6H6-petr. ether gave 3.52 g. IV; the combined crops of crude IV extracted several days in a Soxhlet apparatus with petr. ether removed 0.82 g. III, m. 95°, and left 5.38 g. IV, m. 110-12°. IV (1.00 g.) in 10 cc. concentrated H2SO4 kept 3 days at room temperature, poured into H2O, neutralized with NH4OH, and evaporated on the water bath, the crystalline residue boiled with 150 cc. MeOH, filtered, and washed with three 50-cc. portions MeOH, the combined extracts evaporated, the viscous residue (1.37 g.) ground with Me2CO, and the insoluble material filtered off yielded 0.58 g. ArCH(CH2CONH2)2, light gray, m. 167-70° (PhNO2). IV (2.45 g.) and 3.67 g. KOH in 9.5 cc. H2O refluxed 5 hrs., cooled, filtered from 0.70 g. unchanged IV, and acidified with aqueous HCl yielded 1.77 g. ArCH(CH2CO2H)2 (VI), m. 193-7° (EtOAc-petr. ether). VI (1.61 g.) and 10 cc. AcCl heated 2 hrs. on the water bath and evaporated in vacuo yielded 1.51 g. anhydride (VII) of VI, needles, m. 174-5° (ligroine). VII (0.22 g.) and 10 cc. concentrated NH4OH kept several days, treated with an addnl. 5 cc. NH4OH, and evaporated on the water bath, the residue treated with concentrated HCl and evaporated, and the product isolated with EtOAc yielded 0.23 g. monoamide of VI, m. 170-1°. VII (1.40 g.) and excess MeOH refluxed 10 hrs. and evaporated gave 1.55 g. di-Me ester of VI, needles, m. 109-10° (sublimed from 175° on). II (0.30 g.), 3.42 g. I, 15 cc. C5H5N, and 0.25 cc. piperidine refluxed 4 hrs. and worked up in the usual manner, and the crude product boiled with ligroine and allowed to stand gave 0.23 g. IV, needles, m. 104-7°. III (0.22 g.), 2.02 g. I, 5 cc. C5H5N, and 3 drops piperidine refluxed 5 hrs., poured into concentrated aqueous HCl, and extracted with C6H6, and the extract analyzed by ultraviolet spectroscopy showed the presence of 85% unchanged III. trans-RCH:CHCO2H (VIII) (20.80 g.) in 100 cc. CHCl3 treated with 8.93 g. Et3N in 75 cc. CHCl3, cooled to room temperature, treated with 10.06 g. ClCO2Et in 65 cc. CHCl3, kept 1 hr., treated with 100 cc. concentrated NH4OH, and kept 4 hrs. with occasional shaking, the aqueous phase evaporated, the residue ground with concentrated HCl, filtered off after 15 hrs., and extracted with Et2O in a Soxhlet apparatus gave 3.56 g. unchanged VIII, m. 125-6°; the CHCl3 phase washed with CHCl3 and evaporated, and the residue (16.04 g.) extracted with Et2O in a Soxhlet apparatus left 14.05 g. trans-RCH:CHCONH2 (IX), needles, m. 167-9° (MeOH). IX (8.26 g.) in 65 cc. C5H5N treated gradually with 11.22 g. POCl3, cooled rapidly to room temperature, kept 24 hrs., and evaporated in vacuo at about 50°, the residue treated with H2O, and the precipitate (6.66 g.) extracted with Et2O in a Soxhlet apparatus left 5.60 g. III, m. 92-6°.