Related Thermal Data.-Table 111lists the heats, entropies and free energies of formation a t 298.16" K. Of the t W 0 silicates from the elements and from
(13) K. IC. Kellcy. ti S Bureau of Mines Hull 477 (19SJ)
phrey, King and Kelley,14 and Todd and Bonnichson.l5 114) G I, Humphrey E G Ktnn and R K g e l l e v u S Bureau
ISERKELEY
The Effect of Sodium Oxide on the Chromium Oxide Catalyzed Conversion of Aldehydes to Ketones' €31, J. R. C O L E YAND ~ V. I. KOMARETSKY
RECEIVED MARCH1, 1952
4,C.\LII;(IHVIA
cess sodium hydroxide. The chromite solution on standing overnight formed a chromium hydroxide gel. The gel was washed anion free, dried a t 110', screened to 8 mesh and heated in an atmosphere of hydrogen at gradually increased temperatures up to 500'. To vary the sodium content, portions of the catalyst, after washing but prior to drying, were agitated in sodium carbonate solutions of varying concentrations, filtered and dried. The method of sodium analysis was a modification of the triple acetate procedure devised by Kahane.4 The catalytic reaction procedure consisted of passing a three to one mixture of nitrogen and vaporized n-butyraldehyde over a granular (8-10 mesh) catalyst bed (volume 50 cc.), maintained a t a temperature of 400' by an electrically heated furnace. A constant liquid space velocity of 0.1 was used for all runs. All products were distilled in a 20-inch viper-ral Heli Grid Podbielniak Coliimn.
In the course of a study3of the action of metallic oxide catalysts on alcohols, i t was found that alcohols and aldehydes of "n" carbon atoms undergo a complex dehydrogenation-condensation reaction when passed over a chromia catalyst a t 400" t o form ketones of "2n - 1" carbon atoms. I t W'IS noted that a sodium hydroxide precipitatetl catalyst was quite active in contrast to a compsxxtivt~lv inactive ammonia precipitated catalyst. Discussion of Results It has therefore been of interest to determine the The results obtained are given in Table I and effect of sodium content in a chromia catalyst upon Fig. 1. this reaction. TABLE I 13 {IA
~ I Y SoniTm
CovrEsr
\\'?,gilt
/,
CHROMIA CATALYSTS wr.Tiic KETONE
OF
J - i R i , r ) c)p
>lola1 conversion of
.Odll,I l l
~ W C I F C alrlehydr t n ketniie.' '
I!.Ol
7
1 .-i
211 :;
2s s 2 6 ,3 22.1
--z --I,-
--* +
c
-I
2.79 Dipropyl ketone, b . p . 144.18".
,
1~;
'ic;
1 .9:; a
,
These results indicate that the sodium content of a chromia catalyst has a definite effect on the catalytic activity for the dehydrogenation-condensation reaction discussed. This is consistent with the aldol mechanism proposedSfor this ketone synthesis. The optimum sodium content was found to be approximately 1.O%. ( 4 ) Ti. Katiane, Bull. soc c k i m . , 47, 382 (1930)
1)EPARThIEST O F CHEMICAL ENGINEERISG I L L I N O I S ISSTITUTE O F TECHXOLOGY
CHICAGO, ILLINOIS
Preparation and Some Reactions of Indenyllithium BY SORMAN H. CROXWELL A N D DAVIDB. CAPPS RECEIVEDMARCH24, 1952 From the Senior Problems of B . M. Joseph and S. C. Mikszta. (2) Research Dent., Standard Oil Co (Indiana), Whiting, Indiana. (3) V. I. Komarewskv a n d J. R . Coley, THISJ O V R V A I . , 63, 700 (1)
32ti!I (1941)
I n connection with a general project in this Laboratory concerned with the synthesis and reactions of cyclic ketones, methods of preparing ,f?-(l-in-
