LYLE, ADEL, AND LYLE
how-ever, were similar in properties to
Thus,the hydrates of 1-methyl-3- and -4-piperidonehydrochlorides must be represented by the
and IV. The protection of the carbonylgroup of 1-methyl-3-piperidone hydrochloride
by the formation of the hydrate
wouldexplain the greater stability to air of the hydro-chloride as compared to the base (VI).The double melting points of
deter-mined on a hot stage led to the attempted prepara-tion of the anhydrous hydrochlorides
bysublimation of the hydrates. This technique gave
melting point corresponding to that re-ported by Craig and T~bell.~he infrared absorp-tion spectrum of
solid mull gave a very smallband at 3300 cm.-' but a strong broad band at 1733cm.-' This shift of 18 cm.-l of the carbonyl stretch-ing frequency on formation of the salt is
result ofthe repression of delocalization of the
electrons ofthe carbonyl group due to the proximity of theformal charge on the nitrogen. The absorption ofthe
bond of the salt was altered also. Thestrueture of the band was very complex and wasshifted to lower frequencies
2500 cm.-l). Thischange also reflects the interaction of the carbonylfunction and the positive nitrogen.The anhydrous hydrochloride
of l-methyl-3-piperidone did not appear
the sublimate butcould be formed by heating the hydrate
underreduced pressure. The halogen analysis of
cor-responded to the anhydrous hydrochloride, and theinfrared absorption spectrum also supported thisstructure. The spectrum showed strong absorptionat 1725 cm.-', indicating
free carbonyl, and the
absorption band was complex and shifted
about 2470 cm.-l. These changes are closelyrelated to those observed with
The methobromides of 1-methyl-3- and -4-piperi-dones behaved similarly to the hydrochlorides. Thesalts,
were prepared in anhydrousether, and the analyses and infrared absorptionspectra indicated only traces of the hydrates.The carbonyl stretching frequencies were 1723
cm.-'. Recrystallization ofthe methobromides from water-acetone gave thecorresponding hydrates. The infrared spectrum of
piperidone methobromide hydrate
gave an hydroxyl band at 3360 cm.-' and
weak band at 1723 cm.-'. The spectrum of
methyl-3-piperidone methobromide hydrate
indicated the presence of the hydroxyl groups byabsorption at 3080 and 3300 cm.-'. The meltingpoints of the hydrates
and XIVa wereidentical with anhydrous salts
un-less the hydrates were introduced into
in which case they both melted completely.This study proved that the salts of l-methyl-3-and -4-piperidones form stable hydrates of thecarbonyl, and that the isolation of the anhydrousforms of the hydrochlorides
difficult. Thus it
evident that there is the possibility that the salt ofany amino ketone may add readily the elementsof water necessitating
careful examination of anyamino ketone salt.
Infrared absorption spectra.
The infrared absorption spectrawere determined using a Perkin-Elmer, Model 21, infraredspectrophotometer, with sodium chloride optics. The spectra
solids were determined as mulls in series 11-14 Halocarbonoi116 from 1300 to 4000 cm.-l and in Nujol from 650 to 1300cm.
I-Methyl-4-piperidone hydrochloride hydTate
Thematerial used in this investigation was prepared by themethod
McEIvain and co-workers.8
(XI). A solution
4-benzyl-0xypyridine-t-oxide1~ in 15 ml. of cold chloroform wastreated with 1.9 ml. of phosphorus trichloride. The sohtionwas heated at 70-80' for
hr., cooled, and diluted with
water. The mixture was neutralized with sodiumhydroxide, and the layers weie separated The aqueous layerwas extracted three times with chloroform, and the com-bined chloroform layers were dried over anhydrous potassiumcarbonate. Fractional distillation of the solution gave0.45 g. (49%)
4-benzyloxypyridine (XI), b.p. 193-196'/20 mm., m.p. 49-52''; lit.'? b.p. 155-160°/4 mm., m.p. 55-56'. The methiodide
4-benzyloxypyridine (XI) was pre-pared in acetone and melted at 148-151'.
solution of 5.29 g. of 4-benzyloxvprridine methiodide in 50ml. of methanol was treated with 1.5 g.
sodium borohy-dride. The solvent (31 ml.) was removed by distillation, andwater was added
the residue. Anhydrous potassium rar-bonate
added, and the aqueous solution was extractedwith four poitions of ether. After drying over potassiumcarbonate, the ether solution was concentrated, and theresidue was distilled under reduced pressure to give 2.81 g.(86.4%)
ether (XII), b.p. 170-175/17 mm.,
C13HI~NO: , 76.80;
8.43. Found: C,76.49:
2.31 g. of XI1 in10ml.
concentrated hydrochloric acid and 4 ml.
waterwas heated under reflux for
hr On cooling, the solution wasextracted with ether to remove the benzyl alcohol, and theremaining acidic solution was neutralized with potassiumcarbonate and extracted with ether. The ether extract wasdried and fractionally distilled to give 0.92 g. (71.5%)
b.p. 68-71'/17 mm.,
1-Methyl-4-piperidone hydrochloride hydrate
solu-tion of I-methyl-4-piperidone in dilute hydrochloric acid wasevaporated under reduced pressure. The residue crystallized
washing with acetone to give
m.p. 88-91' in
hot stage the solid melted at
resolidified,and melted at 157-163'.
CsH&lN02: C1, 21.15. Found: 21.10,21.02.
Anhydrous I-methyl-d-piperidone hydrochloride
was sublimed under
pressure of 2 mm. at 120".The sublimate melted at 165-168', lit.9 m.p. 164-167'.
CaHl&lNO: C1, 23.70. Found: C1, 23.70,23.77.
Anhydrous I-methyl-d-piperidone methobromide
in ether wassaturated with methyl bromide. The precipitate whichformed was removed by filtration to give
l-methyl-4-piperidone methobromide (XIII), m.p. 187-190°.