Rovira, Santiago published the artcileAlkaline hydrolysis with high-boiling alcohols, Category: ethers-buliding-blocks, the publication is Annales de Chimie (Paris, France) (1945), 660-700, database is CAplus.
Compounds which are hydrolyzed with difficulty by EtOK or AmOK are saponified by using KOH in PhCH2OH (I), (CH2OH)2 (II), or HOCH(CH2OH)2 (III). With nitriles and amides, the liberated NH3 is titrated at intervals and in this way the kinetics of the reaction is studied. Amides such as AcNH2, EtCONH2, PrCONH2, MeOCH2CONH2, BzNH2, phthalimide, and Bz3N are quant. saponified when boiled for 1 h. with KOH in I. OC(NH2)2 (IV) under these conditions requires 3 h. With II in lieu of I, IV is saponified in 2 h., and with III, in 45 min. OC(NH2)NHPh and OC(NH2) NHC6H4OEt are saponified in 1-2 h. with KOH in III while OC(NHPh)2 is not attacked. With Ph-substituted amides, PhNH2 is formed. Nitriles such as p-MeC6H4CN, PhCH2CN, Ph(CH2)3CN, C12H25CN, PhMeCHCN, PhMe2CCN, PhCH2CHPhCN, CH2(OH)CH2CN, C5H11OCH2CN, and amygdalin, when boiled with KOH in I, are quant. saponified in 1 h. while PhCN requires 2 h. PhBuCHCN is 85% saponified in 4 h. and PhBu2CCN only 11% in 4 h. due to steric hindrance. H2NCO2Et and H2NCO2CH2CHMe2 with KOH in III are quant. saponified in 90 min. Bu, cyclohexyl, and m-xylyl allophanates and KOH in I are not completely saponified but with KOH in III, allophanates are quant. hydrolyzed in 1.5 h. Semicarbazones of the low-mol. ketones and aldehydes are readily saponified in 1-2 h. with KOH in III while the saponification is retarded with the nature of the radical. While Me abietate is saponified with EtOK only 50% in 4 h., it is saponified quant. with KOH in I in 4 h. Saponification of glycerol abietate with 0.5 N EtOK requires 8 h., with 0.1 N PhCH2OK only 1 h. Carnauba wax is saponified with 0.5 N EtOK in 4 h. and with 0.1 N PhCH2OK in 1 h. Boiling of caffeine for 1 h. or theobromine with KOH in III for 8 h. liberates 1 mol. NH3 and 2 mols. NH2Me. From theophylline 27.4% N is split off as NH3 and NH2Me after 25 h. (calculated for 3 N, 23.33%, for 4 N, 31.11%); from uric acid, 26.73% N after 27 h. (calculated for 3 N, 25.0%, for 4 N, 33.33%); and from xanthine, 35.42% N after 71 h. (calculated for 3 N, 27.63%, for 4 N, 36.24%). These results show that the velocity of decomposition depends upon the substituent at the N atoms. Finally, attempts are made to replace halogens in aromatic rings by OH with the preparation of phenols. While the halogen in PhBr, p-C6H4Br2, o-BrC6H4Me, 2,3,5-Br3C6H2OH, 2,5,6-bromo-m-xylenol, 2-C10H7Br, and eosin is almost quant. split off with KOH and I at 250°, the Cl in PhCl and in p-C6H4Cl2 is split off only 10-15% at 250-300°
Annales de Chimie (Paris, France) published new progress about 16332-06-2. 16332-06-2 belongs to ethers-buliding-blocks, auxiliary class Amine,Aliphatic hydrocarbon chain,Amide,Ether, name is 2-Methoxyacetamide, and the molecular formula is C3H7NO2, Category: ethers-buliding-blocks.
Referemce:
https://en.wikipedia.org/wiki/Ether,
Ether | (C2H5)2O – PubChem