Scheibler, Helmuth; Beiser, Willy; Cobler, Heinz; Schmidt, Anton published the artcile< Compounds of bivalent carbon. VIII. Some derivatives of diethoxyacetic acid and their adaptation to carbon monoxide acetal cleavage>, COA of Formula: C6H11NO2, the main research area is .
In the reaction between (EtO)2CHCO2Et and NaOEt or Et2NMgBr the C(OEt)2 formed by the cleavage of the C chain readily reacts with the EtOH which is split off simultaneously, forming pentaethoxyethane and heptaethoxypropane. Since the sec. NHEt2, is indifferent toward C(OEt)2, attempts were made to prepare dialkylamides of (EtO)2CHCO2H for use instead of (EtO)2CHCO2Et for the C(OEt)2 cleavage. These dialkylamides cannot be prepared under the usual conditions but (EtO)2CHCONMe2 (I) was finally obtained by heating the components in a sealed tube at 100° in the presence of CaCl2 to bind the EtOH set free, and (EtO)2CHCON(CH2Ph)2 (II) was obtained from (EtO)2CHCO2Et and (PhCH2)2NMgBr in boiling C6H6. When I and II were treated with Me2NMgBr and (PhCH2)2NMgBr, resp., and, after removal of the ether (both that used as solvent and the ether of constitution), the products were subjected to dry distillation in vacuo, the product obtained from Me2NMgBr yielded a compound m. 134° containing no trace of EtO (Zeisel) and giving NH3 instead of NHMe2 on hydrolysis. Analysis indicated that it was OHCCONH2.3H2O, and from the low-boiling products of the reaction (condensed in liquid air) was isolated Et2O after removal of the NHMe2 with C6H4(CO)2O in the presence of quinoline. In the experiment with II there was obtained no low-boiling distillate; the product was N(CH2Ph)3. formed according to the scheme (EtO)2CHC(OMgBr)[N(CH2Ph)2]2 → N(CH2Ph)3 + (EtO)2CHC(OMgBr):NCH2Ph. These dialkylamides are therefore not adapted to the C(OEt)2 cleavage. As (EtO)2CHCO2Et can be used for this purpose but the EtOH formed simultaneously gives rise to secondary reactions, attempts were made to prepare the Ph instead of the Et ester. (EtO)2CHCOCl cannot be made because 1 of the 2 EtO groups in (EtO)2CHCO2H immediately reacts with PCl5 or SOCl2. The Ph ester can be obtained by treating the acid in the presence of excess of pyridine first with SOCl2 and then with PhOH, but the. ester so prepared is difficultly purified. Favorable results were obtained only when ClSO2Ph was used with the acid in ether in the presence of pyridine, the resulting (EtO)2CHCOOSO2Ph decomposing on heating in ether into SO2 and (EtO)2CHCO2Ph. As the ester is very sensitive to acids it was freed from admixed pyridine with MeI. With Et2NMgBr the ester gave (EtO)2CHCONEt2 but the chief product was a non-distillable mass which decomposed at higher temperatures and was perhaps formed by combination of PhOH with a polymerization product of C(OEt)2. Furthermore, in the part of the product consisting chiefly of NHEt2, monomeric C(OEt)2 was detected and determined by means of HgCl2 after it had been hydrolyzed to HCO2H with dilute alkali. Diethoxyacetdimethylamide (I), b12 105°; yield, 50.5%. Dibenzylamide (II), light yellow, b1 168-70° (yield, 26%). Ph diethoxyacetate, b13 150-2°; yield, 61.1%. Diethoxyacetonitrile, obtained in 30% yield from the amide in quinoline slowly treated at 90° with P2O6, b12 55-6°.
Berichte der Deutschen Chemischen Gesellschaft [Abteilung] B: Abhandlungen published new progress about 6136-93-2. 6136-93-2 belongs to class nitriles-buliding-blocks, and the molecular formula is C6H11NO2, COA of Formula: C6H11NO2.
Referemce:
Nitrile – Wikipedia,
Nitriles – Chemistry LibreTexts