V O L U M E 28, NO. 5, M A Y 1 9 5 6 The water-methanol system was satisfactory only by virtue of the inversion of the order of migration of some of the hydrazones when compared with their movement in the other systems. While capable of good resolution, the low capacity and tendency to streak limits the general use of this system. A tenfold excess of the 2,4-dinitrophenylhydrazine reagent was used in formation of the carbonyl derivative. When the reagent was present in only onefold excess, it was found that the amount of the acetaldehyde derivative was considerably below that found present when a tenfold excess was employed. However, crotona’dehyde, which was detectable in only trace amounts in the presence of a tenfold excess of reagent, was found in significant quantities (30 y per cigarette) when a onefold excess of reagent &-asused. These observations seem to indicate that the actual amount of crotonaldehyde in smoke is very low. The higher amounts of crotonaldehyde viere probably due to selfcondensation of acetaldehyde which could occur under conditions of low hydrazine-aldehyde ratios. The resulting aldol upon dehydration would give rise to the unsaturated aldehyde. Acetaldehyde is known to undergo readily such a reaction under the warm acidic conditions employed in this reaction ( 2 ) . Table I11 shows the total aldehyde and ketone content to be between 3 and 3.5 mg. per cigarette. Acetaldehyde was present in the highest concentration and accounted for one third of the total amount. Propionaldehyde and butyraldehyde were present in considerably smaller amounts. Formaldehyde was present in small amounts and represented only approximately 1% of the total carbonyl compounds listed in Table 111. There appear to be no pronounced differences between ?he amounts of the constituents found in the smoke of the various tobaccos. However, the bright tobacco contained a relatively higher amount of furfural than did the burley. The presence of furfural in smoke obtained by the destructive distillation of tobacco has been reported (II), but sufficient data were not presented a t that time to establish conclusively its identity. I n addition to the chromatographic matching of the mobility of furfural from smoke with that of an authentic sample, this present report adds further evidence for its presence: both the cis and the trans isomers mere isolated; the trans isomer is much redder in color than most of the other 2,4-dinitrophenylhydrazones and this pronounced red color appeared in the band parallel to the authentic trans isomer; and ?he hydrazones of furfural exhibited spectra which mere superimposable upon the spectra of the furfural hydrazones isolated from smoke. ACKNOWLEDGRIENTS
The cooperation of the Research Laboratories of the American Tobacco Co. and of the Liggett and Myers Tobacco Co. is gratefully acknowledged. The work was supported in part by grants from the Damon Runyon Memorial Fund. LITERATURE CITED
Conant, J. B., Bartlett, P. D., J. Am. Chem. SOC.54,2881 (1932). Fieser, L. F., Fieser, M., “Organic Chemistry,” 2nd ed., p. 210, Heath, Boston, 1950. Kissling, R., “Handbuch der Tabakkunde,” 3rd ed., Paul Parey, Berlin, 1919. Kosak, A. I., Esperientia 10, 69 (1954). Neigh, D. F., .l‘ature 170, 579 (1952). Seuberg, C., Burkard, J., Biochem. 2.243, 472 (1931). Osborne, J. S., Adamek, S., Hobbs, >I. E., A N ~ LCHEM. . in press. Pfyl, B.. 2. Unfersuch. Lebensm. 6 6 , 501 (1933). Rayburn, C. H., Harlan, W. R., Hanmer, H. R., ANAL.CHEM 25, 1419 (1953).
Rice. R . G., Keller, G. J., Kirchner, J. G., I b i d . , 23, 194 (1951). Roffo, A. H., Biol. Inst. M e d . Ezptl. Estud. Cancer. 15, 349 (1939).
Sykora, V.,Procharka, Z., C h e m . L i s t y 47, 1674 (1953). Tarbell, D. S.,others, J . Am. Chem. SOC.7 7 , 767 (1955). Touey, G. P., ASAL. CHEM.17, 1788 (1955). R E C E I W Dfor reriew November 5 , 1955, Accepted J a n u a r y 13, 1556
913
CRYSTALLOGRAPHIC DATA
117. Cerium Tetraiodate, Ce(lO,), E U G E N E STARITZKY and DON T. C R O M E R The University of California, Los Alamos Scientific Laboratory, Lor Alamos, N. M. tetraiodate is prepared by mixing aqueous solutions of The resulting amorphous precipitate was recrystallized from concentrated nitric acid. ERIUM
C cerium disulfate and sodium iodate.
CRYSTAL MORPHOLOGY System and Class. Tetragonal, tetragonal-dipyramidal. Axial Elements. a : c = 1:0.537 (derived from unit cell dimensions). Habit. Dipyramidal { I l l ) ,usually with [ O O l ) ; (100) occasionally present.
Partial Powder X-Ray Diffraction Pattern of Ce(IO& hkl 110 200 101 111 LO1 220 211, 121 310, 130 221 301 311, 131 002 102 112 400 321, 231 202 330 212, 122 401 420, 240 411, 141 331 222 302 421, 241 312, 132 510, 150 322, 232 431, 341, 501 511, 151 402 412, 142 332 440 103 521, 251 113 422, 242 530, 350
d,
h.,
CalCd. 7.00 4.95 4.65 4.24 3.62 3.50 3.40 3 13 2.52 2.80 2.70 2.66 2.57 2.487 2.476 2.440 2.343 2,333). 2.280 2.244 2.214 2.189 2.137 2.118 2 .O i l 2.044 2.027 1.942 1.911 1,856
1,824 1.812 1,782
;1 . E;} 74b 1.737 1.719 1 .702 1.698
d, A Measi:“
... 4.91 4.64
...
3:47 3.38 3.11
...
I/Iib
..
5
