July, 1942 NOTES 1737

diazotization of m-aminophenol, subsequent re-

placement with the cyano group and hydrolysis,2
by alkaline fusion of the sodium m-sulfonate of
benzoic acid,a and by action of nitrous acid on m-
v aminobenzoic acid, followed by hydrolysis of the
Experimental Part diazonium salt.4
1,3,3-Triphenyloxindole (11) and 1,2,3-Triphenylindole- It has been found in this Laboratory that the
oxi&-2,3 (I).-N-phenylisatin (0.025 mole) was added acid can be prepared conveniently from methyl
slowly, over a period of one hour, to a solution of phenyl- m-aminobenzoate, The ester is used rather than
magnesium bromide (0.125 mole) in 150 ml. of dry ether. the acid since methyl m-nitrobenzoate is readily
After addition of the last portion the mixture was heated obtained in a pure state, is easily reduced, and is
a t the boiling temperature for one hour and then poured
into a mixture of ice and concentrated sulfuric acid. The an intermediate in the preparation of m-nitro-
ether layer was separated, dried over anhydrous sodium benzoic acid.6
sulfate and the ether removed under reduced pressure. The reduction of methyl m-nitrobenzoate may
The yellow mass which was obtained was crystallized from be carried out catalytically with Raney nickel
ethyl alcohol. Repeated crystallization yielded 5.75 g. of either under low pressure or more rapidly under
colorless plates; m. p. 161", and a small yield of yellow
crystalline powder, m. p. 238'. The yellow compound high pressure and a t a slightly elevated tempera-
exhibited marked fluorescence in solution. ture. The yields in the reduction are 93-95%.
Anal. of compound m. p. 161' (11). Calcd. for CmHio- Diazotization and hydrolysis of methyl m-
ON: N, 3.87. Found: N, 3.84,3.67. Anal. of compound aminobenzoate give m-hydroxybenzoic acid di-
m. p. 238" (I). Calcd. for CZBHlgON: N, 3.87. Found: rectly in yields of 80-87010,
N, 3.87.
Compound 11. By the Friedel-Crafts Reaction.-Pow- Experimental
dered anhydrous aluminum chloride (0.05 mole) wasMethyl m-Aminobenzoate.-Methyl m-nitrobenzoate
added slowly to a solution of 3,3-dichloro-l-phenyloxindole
(20 g.)6 in ethyl acetate (100 cc.) was reduced with hydro-
(0.01 mole) in 40 ml. dry benzene and the reaction mixture
gen a t 50 lb. in the presence of Raney nickel (3 g.). The
heated for one hour at 60'. The benzene was removed
theoretical amount of hydrogen was absorbed in twelve
under reduced pressure and the residue treated with ice
hours. A 100-g. sample of the nitro compound in 100 cc.
and hydrochloric acid. The entire reaction mixture was
of methanol could be reduced at 50" in two and one-half
then extracted with ether and the ether removed under re-
hours at 2000-3000 lb. with Raney nickel (3 g.). After
duced pressure after decolorizing with charcoal and drying
removal of catalyst and solvent the product was dried in
over anhydrous sodium sulfate. The product was purified
ether solution. The ether was distilled off and the residual
by crystallization from ethyl alcohol from which it sepa-
oil distilled under reduced pressure. The pure methyl m-
rated as colorless plates, m. p. 161'. Mixed melting
aminobenzoate boiled a t 152-153' (11 mm.); f. p. 37'
points with samples of the colorless compound from
(from the cooling curve); yield 93-95%.
the Grignard reaction showed no depression. Acetyl Derivative.-The acetyl derivative was obtained
2,2-Dichloro-l,3,3-triphenyl-di-hydrohdole (V).-A
by refluxing the amine for twenty minutes with acetic
mixture of 2 g. of 1,3,3-triphenyloxindole (11) with 10 g. of
anhydride. It melted a t 136-137' after crystallization
phosphorus pentachloride was heated for four hours a t
from water.
150", the mixture cooled and water added, the residue
Anal. Calcd. for C1oHllOsN: C, 62.17; H, 5.70.
collected and crystallized from ethyl alcohol from which
Found: C, 62.16; H, 5.87.1
it separated as colorless prisms; m. p. 200'.
m-Hydroxybenzoic Acid.-Methyl m-aminobenzoate
Anal. Calcd. for CzaHloNCIL:N, 3.36. Found: N,
(50 g.) was dissolved in a solution of 75 cc. of concentrated
3.36, 3.33. sulfuric acid and 150 g. of ice. The solution was then
This work has been supported by a research treated with 100 g. of ice, cooled t o 0' and diazotized by
grant (A.A.A.S.) received through the Ken- the addition of 25 g. of sodium nitrite in 60 cc. of water.
tucky Academy of Science. The resulting diazonium salt solution was added all at
once to a hot solution of 100 g. of anhydrous sodium sulfate
DEPARTMENT OF CHEMISTRY
and 40 cc. of concentrated sulfuric acid in 400 cc. of water.
WESTERNKENTUCKY STATE TEACHERS
COLLEGE
BOWLING GREEN,KY. MAY11, 1942 The mixture was refluxed for three hours. Then the re-
RECEIVED
~
action mixture was boiled with norite, filtered, and allowed
The Preparation of m-Hydroxybenzoic Acid (2) Ahrens, Be?., 20,2953 (1887).
(3) Offermann, Ann., 880, 6 (1894); Graebe and Kraft, Bey., 89,
AND A. S. HENICK
BY H. E. UNGNADE 2512 (1906).
(4) Fischer, Ann., 117, 148 (1863); Bryd, Roczniki Chcm., 7, 436
m-Hydroxybenzoic acid kas been prepared by (1927); Chcm. Abs., 2S, 2372 (1928).
(5) "Org. Syntheses," Coll. Vol. I, 2nd ed., 392 (1941).
fusion of m-chlorobenzoic acid with alkali,l by (6) "Org. Syntheses," Coll. Vol. I , 2nd ed., 372 (1941).
(1) Dembey, A n n . . 148,222 (1868). (7) Semi-microanalysis by E. Milberger.
1’738 NOTES VOl. ti4

to crystallize. The acid was filtered with suction and In Table I are listed the melting points and mer-
dried 2% vacuo; yield 3 7 4 1 g. Recrystallization from cury analyses5-’ of the compounds successfully
water gave a nearly white product melting a t 199-200’.
prepared. Due to low solubility in boiling eth-
CHEMISTRY DEPARTMENT
UNIVERSITY OF MISSOURI anol, the purification of the mercury derivatives
COLUMBIA, MISSOURI RECEIVED APRIL 15, 1942 of p-anisamide and m-chlorobenzamide must be
111--

accomplished by leaching.
Identification of Amides through the Mercury TABLEI
Derivatives M. p. of
5.p . , mercury
BY JONATHAN w. WILLIAMS,WILLIAM’r. RAINEY,JK., Amide
C. derivative, -Mercury,
(uncor.) OC. (uncor.) Calcd. Found
%--
AND ROBERTS. LEOPOLU
Acetamide 82 196-197 .. ..
In characterizing amides the most general pro- Propionamide 79 20 1 58.2 57.8 58.5
cedure is hydrolysis, followed by identification of Butyramide 115 222-224 53.8 53.3 d3.4
the two products. With unsubstituted amides, Benzamide 128 222 45.5 45.1 45.2
solid derivatives may be prepared directly by re- m-Chlorobenzamide 134 245 39.2 39.0 38.6
p-Chlorobenzamide 178 258 39.2 38.9 39.1
action with phthalyl chloride. Another proced- n-Bromobenzamide 155 242 33.5 33.5 ..
ure, the use of which obviates hydrolysis, is the m-Bromobenzamide 155 23 5 33.5 33.2 33.2
preparation of the mercury derivative. This pro- p-Bromobenzamide 191 266 33.5 33.1 33.5
cedure is simple and gives satisfactory derivatives n-Toluamide 158 196 42.6 42.4 42.5
for a large number of unsubstituted amides. m-Toluamide 94 200 42.6 43.1 42.3
p-Toluamide 166 260 42.6 42.6 . .*
The reaction represented by the equation o-Anisamide 128 24 1 40.1 39.8 40.3
2R-C-NH2 + HgO --+ (R-C-NK12Hg 4- H20 p-Anisamide 167 222 40.1 39.9 40.3
I‘ I‘
0
Salicylamide 139 190 42.4 42.7 , .
0
was first reported in 1852 by Dessaignes,2 who Unsuccessful attempts were made to prepare
prepared the mercury derivatives of benzamide the mercury derivatives of isovaleramide, stear-
and acetamide. Mercury derivatives of several amide, m-anisamide and benzenesulfonamide.
other amides have since been de~cribed.~ In the first two cases, decomposition occurred a t
Two general procedures were investigated for the temperature used, making isolation of the mer-
the preparation of these mercury compounds. cury derivative impossible. With the latter two
Procedure 1, patterned after the work of Dessaig- substances, reaction occurred readily, but the
nes,2 consisted of bringing a mixture of yellow products obtained could not be rendered analyti-
mercuric oxide and excess amide t o the melting cally pure.
point of the amide, maintaining that tempera-
Experimental
ture and adding more mercuric oxide in small
portions until no further reaction occurred, and Procedure 1.-In a test-tube were placed 1.5 g. of the
amide and 0.5 g. of yellow mercuric oxide. Vsing a small
then purifying the product by recrystallization flame, the mixture was heated a t the melting point of the
from ethanol or by leaching with hot ethanol. amide until all mercuric oxide had reacted (disappearance
This process is the more generally applicable one, of color) and the water vapor had been dispelled. More
and the one that must be used with aliphatic mercuric oxide was then added in small portions until no
amides. Procedure 2 , based on the process de- more would react. If an excess of mercuric oxide was ob-
tained, enough of the amide to react with it was added and
scribed by Mann and S a ~ n d e r sconsisted
,~ of re- the yellow color removed completely. The melt was
fluxing about 0.04 mole of amide with excess cooled somewhat, then taken up in the minimum amount
(around 0.025 mole) yellow mercuric oxide in 50 of boiling ethanol and allowed to cool. The crystals were
ml. of 95% ethanol for one hour, filtering while filtered and washed with cold ethanol or ether. Consider-
hot, cooling, removing the crystalline mercury able variations were found in the solubilities of the mercury
derivatives in alcohol. The derivatives of aliphatic
derivative, and purifying by recrystallization or amides were quite soluble, even in cold ethanol. On the
leaching. other hand, the derivatives of p-anisamide, m-chloro-
( 1 ) Evans and Dehn, Tms JOURNAL, 61, 3651 (1929). henzamide and benzenesulfonamide were quite insoluble in
$2) Dessaignes, A n n , 89, 231 (1862).
(3) For summary and complete references, see Whitmore, “Or- ( 5 ) Rauscher, I n d . Eng. Chem., Anal. E d . , 10,331 (1938).
ganic Compounds of Mercury,” Chemical Catalog Company (Rein- (6) Shiner, “Quantitative Analysis of Organic Compounds,”
hold Publishing torpoiation), New York, N . Y.,1921, pp 150-161 Edwards Brothers, Ann Arbor, Mich., 1938, p. 31.
(4) Mann and Saunders, “Practical Organic Chemistry,” L o w - (7) Shukis and Tallman, i n d . Eng. Chcm., A n a l . E d . , 12, 123
mans, Green and Company, London, 1988, p 79 i 1940)