Analgesics. Part I.
Esters and Ketones derived from -Amino--cyano-,-diarylalkanesBy D. J. Dupré. J. Elks. B. A. Hems. (Miss) K. N. Speyer and (in part) R. M. EvansJ. Chem. Soc. 500-510 (1949)
(
https://www.thevespiary.org/rhodium/Rhodium/pdf/amidone.analgesics-1.pdf)
AbstractA number of basic cyanides (
V) have been prepared either (
a) by reaction of a diarylmethyl cyanide with a chloro-amine R
2N[CH
2]
nCl, or (
b) by treatment of a diarylmethyl cyanide with an
,
-dihalogeno-paraffin, and reaction of the resulting halogeno-cyanide with a secondary amine. The amino-cyanides were converted into amino-ketones by treatment with Grignard reagents. and into amino-esters by direct esterification with alcoholic sulphuric acid.
The acids R
2NCH
2CH
2CPh
2CO
2H (R = Me or Et) on treatment with thionyl chloride gave the 3,3-diphenyl-1-alkylpyrrolid-2-one; the homologous acid. Et
2NCH
2CH
2CH
2CPh
2CO
2H, on similar treatment, gave an acid chloride which showed no tendency to cyclise.
The analgesic activities of the amino-esters and amino-ketones are given.
____ ___ __ _
Analgesics. Part II.
The Synthesis of Amidone and Some of its AnaloguesBy J. Attenburrow. J. Elks. B. A. Hems. and (Miss) K. N. SpeyerJ. Chem. Soc. 510-518 (1949)
(
https://www.thevespiary.org/rhodium/Rhodium/pdf/amidone.analgesics-2.pdf)
AbstractTreatment of 1-chloro-2-dimethylaminopropane with diphenylmethyl cyanide in the presence of sodamide gave a mixture of compounds. from which 3-dimethylamino-1,1-diphenylbutyl cyanide (
II) was isolated in 36% overall yield. Amidone (
III) was obtained from (
II) by treatment with ethylmagnesium iodide. Both 1-chloro-2-morpholinopropane and 2-chloro-1-morpholinopropane, on reaction with diphenylmethyl cyanide. gave a mixture of 1,1-diphenyl-3-morpholinobutyl cyanide (
VIII) and 1,1-diphenyl-3-morpholinoisobutyl cyanide (
XI), both of which have been converted into the corresponding ethyl ketones.
Treatment of diphenylmethyl cyanide with ethylene oxide or propylene oxide gave lactones instead of the hydroxy-cyanides required. Attempts to prepare the cyanide (
VIII) by addition of hydrogen bromide or hydrogen iodide to 1,1-diphenylbut-3-enyl cyanide (
XII) and reaction of the product with morpholine gave the required compound. but only in poor yield. Attempts to reduce selectively the double bond of 3-bromo-1,1-diphenylbut-3-enyl cyanide (
XXI) were unsuccessful.