NOTES
2257
trntvtl :iiiiiiioiiiiini liydror.ic!c. The bomb is then closed TABLE I ;iiid Iir~ntctla1 107-101)o for twelve hours, cooled, and the ISOMERS FOR MONODENTATE GROUPS rcac1ioii iiiikiiire transferred to a desiccator and evapoConfiguraOptically Optically rated. l'lie noli-volatile product, 21.2 g., m. p. 114tion. T active inactive Total IL"", coiitaiiih 8 @ . 5 ~of o the remainder M 0 1 1 lwiiii: iiicotiiiic acid.' 'l'hc yicld of amide is 72.66y0, 8a \fr LT iI V ( I rccryztallizations from e!hyl acetate, the amide 7ab 2 M 2 4 i i i c l t , :I[ 1 2 1 - i50'. and the mixed melting point with pure 4 M 12 6a2b 16 iiicutiiiniiiidc > h o w no depression. M 26 2 6abc 28 .4m;. Calcd. for C&ONz: C, 59.01; H, 4.9.5; N, M 22 i; 28 22.9! I ~ o u i i t l : ' C. 58.97, 59.06; H, 4.9, 5.11; N, 22.80, 5a3b 5a2bc 84 2'' $2. 78 6 168 0 168 Tlic :irnidr may, howercr, he extracted directly in the re- Sahcd ac!ioii n;i\l,,irc in very pure condition by ethyl acetate, 4a4b M 32 6 38 Y-iiig tlii.. rroccd\:re, we have obtained a product con- 4a3bc 134 6 140 of amide and melting a t 129-130'. t:iiiiiiie !N 216 204 12 Addit ioii of sotliiini hydroxide to the reaction mixture 4a2b2c 4a2bcd 414 6 420 re.iiltz i i i ninrkcdly speeding up the reaction, with a n inrrcawd protlurt ion of nicotinic acid and a corresponding 840 4abcde 0 840 d ~~ xi - ci i i the yield of amide. 3a3b2c 268 12 280 IIyrimgeri pcroside (3.5 moles in 30% solution) added 0 560 560 iioiiiutn hydroxide (2 moles) and nitrile (1 mole) 3a2bcd 828 12 840 he rcartion time and gives increased yields (94 3a2b3cd , The product, however, contains more nico- 3a2bcde 1,680 0 1,680 1 i : i i t - acid atid mcslts over a wide range of temperature. 3abcdef 3.360 3.360 0 ktydrogeii pcrosidr (3.5moles in 30% solution), sodium 1,252 22 1,274 hydroxide (0.3 mole), and the nitrile (1 mole) heated for 2a2b2c2d 2a2b2cde 2,508 12 2,520 six houri at 50" give. yields of 89 and 9301,. The protlrict ii diicolored and is less easily purified than the 2a2bcdef 5,040 0 5,040 prodtict ol,t;iiiiec! by the use of ammonia alone. 2abcdefg 10,080 0 10,080 T h e obserral i o n that ariiinoiiium hydroside may hyabcdefgh 20,160 0 20,160 tfrolyzc nitrile< i o the corresponding amide without the use 11indicates that the isomer count was also determined of !Iydrogeii I):m\itie niay make it possible to obtain ainitlcs froni iiifriiea oxidized or polymerized by the per- by the construction of models and it was found in agreement :vith the number obtained by the use of Lunn and o\idc.. Senior's method. :!;I C b . Kreu'\oii, A m . J . Phurm., 116, 122-125 (1043). 1 7The ev.iiwration of solutions of nicotinic acid in ammonia re.i>i:.iri rli~soci:itionof m y ummonitim nicotinate present and leaves , re;i
