NOTES 3705

fused sodium acetate (1.0 g), and glacial acetic acid protection against electroshock-induced seizures. These
(10 ml) was heated in a flask on a hot plate, until the compounds decreased motor activity in mice and blocked
mixture was completely liquidified; the heating was then conditioned avoidance response in trained rats non-
continued for 2 to 3 h on a steam bath. The reaction specifically.
mixture was cooled and diluted with cold water. The
crystals were collected, filtered, and washed with hot Acknowledgments
water, and then recrystallized from alcohol, m.p.
The authors gratefully acknowledge financial
Can. J. Chem. Downloaded from www.nrcresearchpress.com by Georgia Institute of Technology on 11/10/14

227-228 "C, yield 1.2 g.

The other compounds listed in Table I were prepared support from the Council of Scientific and Indus-
by the same procedure, using 0.01 molar quantities of the trial Research, New Delhi, India and the Sadtler
appropriate trimethox~benzaldeh~deand 3-benzo~l-2- Research Laboratories, Philadelphia, U.S.A.,
thio-hydantoin or hydantoin.
for carrying out the infrared spectral studies.
Cot~uersiotlof Thiohydarltoin to Hydar~toin
A mixture of 2-thio-5-(trimethoxybenzylidene) hydan-
toin (2.0 g) and monocl~loroaceticacid (1.0 g in 10 ml of 1. R. H. HERBSTand F. B. JOHNSON.J. Am. Chem.
water) was boiled for 4 h. The mixture was then diluted Sot. 54, 2463 (1932).
with alcohol and h a l l y evaporated at 100 OC. The crys- 2. V. S. P A L K A ~ and P- F. ShllTH. J- Med. (3x11.
tals obtained by this process were first washed with cold 8, 883 (1965).
water and then with boiling water. These were recrys- 3. V. S. PALKAR and P. J. Org. CIIem. 20,
125 (1965).
tallized from alcohol/or acetic acid. 4. H. H. MERRITand F. J. PUTNAM. Epilepsia, 3, 51
The hydantoins prepared by both different methods (1945).
gave exactly the same infrared spectra. 5. J. G. LOMBARDINO and C. F. GERBER. J. Med. Chem.
7, 97 (1964).
Pl~armacologicalScreer~irzg 6. A. NOVELLIand A. M. D E S A N ~ SJ.. Med. Chem.
On pharmacological screening of these compounds, it 11, 176 (1968).
was observed that the thiohydantoin derivatives protected 7. W. OLDFIELDand C. H. CASHIN. J. Med. Chem. 8,
rats markedly against electroshock-induced seizures. All 239 (1965).
For personal use only.

of the three compounds reduced the duration of the tonic 8. J. W. SHAFFER,E. STEINBERG, V. KRIMSLEY,and
phase of convulsion significantly, but no appreciable effect B. WINsTEAD. J. Med. 462
on clonic convulsion was seen. The compound 2-thiod-
(2,4,5-trimethoxybenzylidene)hydantoin also reduced the
9'~2in~$~~k~s."5.0,S7"$~$62
10. M. JANSEN. Rec. T ~chim. ~ 50,
~ 291
M' K'
. (1931).
duration of the Post convulsion coma significantly 11. FR.SCHAAF and A. LABOUCHERE. Helv. Chim. Acta,
(P < 0.05). Hydantoin derivatives failed to offer any 7,357 (1924).

Hydrogen transfer reactions. I. Reduction of carbonyl compounds

by alcohols catalyzed by alumina
D. V. RAMANA
AND C. N. PILLAI'
Department of Clletnistry, lizdiatz Itzstitute of Technology, Madras-36, In&
Received February 25, 1969

Alumina containing about 2.2% by weight of N a + has been found to be an effective catalyst for the
vapor phase reduction of carbonyl compounds by alcohols and for the reverse reaction, the oxidation
of the alcohols by carbonyl compounds. The reduction of a number of aliphatic and aromatic aldehydes
and ketones by isopropyl alcohol and the oxidation of a number of primary and secondary alcohols by
ketones like acetone and cyclohexanone are reported.
Canadian Journal of Chemistry, 47, 3705 (19G9)

Mekhtiev and Narimanbekov (1) have reported
the reduction of a number of aliphatic aldehydes
and ketones in the vapor phase at 400 "C, cata-
lyzed by magnesium oxide. The use of alumina as
a catalyst for the liquid phase reduction of benz-
'Author to whom communications regarding this paper
should be addressed.
aldehydes by methanol at room temperature
has also been reported (2). The present communi-
cation reports results which demonstrate the use
of alumina impregnated with 2.2 % by weight of
Na+ as an effective catalyst for the vapor phase
reduction of carbonyl compounds by alcohols and
for the reverse reaction. -
The alumina was prepared by the hydrolysis of
 CANADIAN JOURNAL O F CHEMISTRY. VOL. 47, 1969

TABLE I
Reduction of carbonyl compounds and olefins by isopropyl alcohol

Series Carbonyl compound Feed

No. or olefin composition" Product? Conversion:
Butyraldehyde Bu tanol-1
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Cyclohexanone Cyclohexanol
Cyclohexanone Cyclohexanol
Butanone-2 Butanol-2
3,3-Dimethylbutanone-2 3,3-Din~ethylbutanol-2
Ment hone Menthol (32)
Neornenthol (68)
Benzophenone Benzhydrol
Acetophenone 1-Phenylethanol
Methyl isobutyl ketone Methyl isobutyl carbinol
Hydrocinnarnaldehyde Hydrocimamyl alcohol
Cinnamaldehyde Cimamyl alcohol (26)
Hydrocimarnyl alcohol (66)
Hydrocinnarnaldehyde (8)
Crotonaldehyde Crotyl alcohol (60)
Butanol-1 (40)
Mesityl oxide Methyl isobutyl ketone (80)
Methyl isobutyl carbinol (20)
Methyl isobutenyl carbinol
(traces)
Cinnan~ylalcohol Hydrocinnarnyl alcohol
Allyl alcohol Propanol
Cinnarnyl alcohol Hydrocinnarnyl alcohol (50)
For personal use only.

Cinnarnaldehyde (50)
o-Chlorobenzaldehyde o-Chlorobenzyl alcohol
p-Chlorobenzaldehyde p-Chlorobenzyl alcohol
Benzaldehyde Benzyl alcohol
111-Tolualdehyde m-Methylbenzyl alcohol
p-Tolualdehyde p-Methylbenzyl alcohol
rrr-Methoxybenzaldehyde rn-Methoxybenzyl alcohol
p-Methoxybenzaldehyde p-Methoxybenzyl alcohol
p-Methoxybenzaldehyde p-Methoxybenzyl alcohol
NOTE: Catalyst: AI2O3 containing 2.2 wt% Na+ (Gg). Temperature: 300 'C. Flow rate: 15 ml/h.
*Mole ratio, carbonyl compound or olefin : isopropyl alcohol.
?Numbers in parentheses indicate the percent composition of the product mixture when more than one product are
formed.
$Conversion, percentages based on the carbonyl compound or olefin.
gCinnamyl alcohol alone was passed over the catalyst without the addition of any isopropyl alcohol.

TABLE 11
Oxidation of alcohols

Series Oxidizing Feed

No. Alcohol agent composition" Product Conversion-f
1 Butanol-1 Cyclohexanone 1 :3 Butyraldehyde 37
2 Propanol-1 Cyclohexanone 1 :3 Propionaldehyde 43
3 Isobutyl alcohol Cyclohexanone 1 :3 Isobutyraldehyde 37
4 Cimarnyl alcohol Cyclohexanone 1 :3 Cinnamaldehydez 40
5 Benzyl alcohol Cyclohexanone 1 :3 Benzaldehyde 31
6 Hydrocinnarnyl alcohol Cyclo hexanone 1 :3 Hydrocinnarnaldehyde 32
7 Arnyl alcohol Cyclohexanone 1 :3 Valeraldehyde 37
8 Butanol-2 Cyclohexanone 1 :3 Butanone-2 81
9 Isobutyl methyl carbinol Cyclohexanone 1 :3 Isobutyl methyl ketone 81
10 Menthol Cyclohexanone 1 :I0 Menthone 32
11 Cyclohexanol Acetone 1 :1 Cyclohexanone 34
12 Benzyl alcohol Acetone 1 :1 Benzaldehyde 34
13 Menthol Acetone 1 :I0 Menthone 40
14 Neornenthol Acetone 1 :I0 Menthone 73
NOTE: Catalyst: AI2O3 containing 2.2 wt % Na+ (Gg). Temperature: 300 "C. Flow rate: 15 ml/h.
*Mole ratio, alcohol: oxidizing agent.
tConversion, percentages based on alcohol.
:Traces of hydrocinnamyl alcohol and hydrocinnamaldehyde were also formed.
 NOTES 3707

aluminium isopropoxide and after conversion to sodium, considerable dehydration of alcohols

118 in. pellets, was calcined at 600 "C in a stream
of nitrogen for 6 h. The pellets were then im-
pregnated with a solution of sodium carbonate of
sufficient strength to obtain the required catalyst
containing 2.2% by weight of sodium ions. This
Can. J. Chem. Downloaded from www.nrcresearchpress.com by Georgia Institute of Technology on 11/10/14
took place. Some of the typical results are listed
in Tables I and 11. The products were analyzed by
gas-liquid chromatography and were isolated in
most cases by distillation.
The reaction is formally similar to the Meer-

catalyst was calcined at 500 "C for 6 h in a stream
of nitrogen and the reactions were carried out in
a flow reactor at 300 "C. At higher temperatures,
side reactions, especially condensation reactions
of the carbonyl compounds became apparent. On
alumina catalysts containing lesser amounts of
wein-Pondorff reduction and the Oppenauer
oxidation and a hydride transfer from the alcohol
to the carbonyl group seems to be involved here
also. The following surface reaction mechanism
can be tentatively proposed for the oxidation
reduction process :

Acknowledgments M. V. C. Sastri and Dr. J. C. Kuriacose for their

For personal use only.

Grateful acknowledgment is made to the interest and

donors of the Petroleum Research Fund admin- S4 D. MEKmIEV and 0.A. NARIMANBEKOV. Dokl.
istered by the American Chemical Society for the Akad. Nauk Azerb. SSR, 20(4), 33 (1964); Chem.
financial support of this research. The authors Abstr. 61, 10579 (1964).
2. V. J. HRUBY. Proc. N. Dak. Acad. Sci., 16, 12 (1962);
also wish to express their thanks to Professor them. ~ b 62, 1589
~ (1965).
~ ~ .

Proton magnetic resonance spectrum of 2,6-dichlorobenzaldoxime. Signs and

magnitudes of long-range spin-spin couplings. Degree of nonplanarity
T. SCHAEFER AND R. WASYLISHEN
Chemistry Department, University of Manitoba, Winnipeg, Mannitoba
Received May 7, 1969

From the sign and magnitude of the coupling constant between the C-H proton in the sidechain and
the para ring proton in 2,6-dichlorobenzaldoximeit is estimated that the deviation from coplanarity of
the sidechain is at least 40'. The hydroxyl proton shift in dimethylsulfoxide solution of - 11.7 p.p.m.,
relative to internal tetrarnethylsilane, indicates a cis arrangement of the hydroxyl and aromatic groups.
Canadian Journal of Chemistry, 47, 3707 (1969)

Spectl.al Analysis
At 60 MHz the proton magnetic resonance
of a 4 mole % solution of 2,6-dichlorobenzald-
oxime, 1, in acetone consists of a tightly coupled
AB,X spectrum (the hydroxyl proton is involved
in exchange-averaged hydrogen-bonding equi-
libria with solvent and solute molecules and is not
observed to couple to other protons). Because of