SCIENTIFIC
EDITION
(5) Casparis, P., and Bullet, J., Schwcia. mcd. Wochschr..
68, 485(1938).
(6) Jorgensen, P. F.. and Tonnesea, M., Dansk. Tids..
Farm. 14 134(1940).
(7j Schumacher G . , Deul. Apofh.Zfg., 55.312(1940).
(8) Allport, N. 'L., and Jones, N. R., Quarf. J . Pharm.
Pharmacol., 14, 106(1941).
A Synthesis of DDT*
By W. T. SUMERFORDt
A method is described for preparing a good
grade of DDT i n a satisfactory yield by the
use of chlorosulfonic acid as a condensing
agent,
insecticide, DDT, 2,2-bis-(p-chloro-
T HE
pheny1)-1,1,1-trichloroethane(I),was first
prepared seventy-one years ago by Zeidler
(1) who obtained the compound by reacting
one mol of chloral with two mols of chloro-
benzene in the presence of sulfuric acid.
Although Zeidler devoted more attention
to its bromine analogue, DDT has become
extremely important since the discovery in
1939 of its insecticidal properties (2).
Some preliminary tests indicate that the
use of zinc chloride as a condensing agent
gives a superior product (3), but practically
all of the processes used to prepare DDT
are modifications of the original method of
Zeidler (1) using either chloral or chloral
hydrate ( 4 9 ) . While the commercial
methods for manufacturing DDT are ap-
parently good (3), it was thought worth
while to look for a condensing agent, other
than sulfuric acid, which might give an
improved grade of DDT and possibly pro-
vide for the synthesis of some of its homo-
logues and analogues which otherwise could
not readily be prepared. Chlorosulfonic acid
was found to be useful for condensing
* Received July 6. 1945, from the College of Pharmacy,
University of Georgia, Athens, Ga.
t Professor of Pharmaceutical Chemistry, University of
Georgia, Athens, Georgia.
259
(9) Powell C. E. Reagan 0. W., Stevens, A., and Swan-
son E. E. TH;S JOURNAL 30'255(1941).
ri0, Alioort. N. I,.. a i d Cockinr[.T. T., Quarf. J . Pharm
Pharmacol: 5 341(1932).
(11) Briie 'B. A. Rev. Sci. lnsfvumenfs 8,279(1937).
(12) vos, B. J., fr., THISJOURNAL, 32, i38(1943).
(13) Grove, D.C., ibid., 30,260(1941).
chloral and chlorobenzene if it 2s handled
with care.
EXPERIMENTAL
All operations were carried out under a hood
Fifteen and five-tenths grams (0.105 mol) of chloral
was obtained by mixing the required amount of
U. S. P. chloral hydrate with twice its weight d sul-
furic acid, and distilling the chloral layer which
readily separates. The chloral was dissolved in
22.5 Gm. (0.2 mol) of chlorobenzene (Eastman,
Practical grade) and the solution was cooled to 5" C.
under constant stirring. A temperature of from
5 t o 10' C. was maintained, and t o the solution,
under constant stirring, were added dropwise
twelve 1-cc. portions of chlorosulfonic acid (East-
man, Practical grade) at ten-minute intervals.
The acid can be added safely with the use of a 5-cc.
pipette. After about 8 cc. of the acid was added a
solid began t o separate, and within a few minutes
the entire mixture became pasty. After the last
portion of acid was added the stirring was continued
for one hour at 10-15' C.,and then for two hours at
room temperature. At the end of this period t h e
reaction mixture was mixed with chipped ice, and
the crude DDT was filtered off with suction. The
crude product was stirred into ten times its weight of
boiling water to remove occluded acid. The product
was again collected on a Biichner funnel, and
washed with an equal weight of cold methanol or
recrystallized once from a mixture of three parts of
methanol and one part of diethyl ether. The
washed product melted at 106-107" C. (uncorr.) and
the recrystallized product melted a t 107-108" C.
(uncorr.). The yield of the purified compound was
65-70%.
REFERENCES
(1) Zeidler, O.,Ber.. 7, 1180(1874).
(2) British Patent 547,871.
(3) Gunther, F.A,, J . Chcm. Educafion. 22,238(1945).
(4) British Patent 547 874.
( 5 ) Anon., Chcm. Mef.'Eng., 51, 112 (1944).
(6) Iris, R.C.. and Leyva. R. D., Rev. ins!. salubridad y cn-
fcrmcdades frop. ( M e x . ) 5 71(1944).
I . _1. k.:
(7) Breckenridne. . Can. Chcm. Process I n d . .. 28.. 570.
(1944).
(8) Bailes E. L. J . Chcm. Educafion 22, lZZ(l945).
(9) DarliLg, S.F:,ibid.. 22.170(1945).'