1070-4272/03/7606-0953 $25.00 C 2003 MAIK [Nauka/Interperiodica]
Russian Journal of Applied Chemistry, Vol. 76, No. 6, 2003, pp. 953!957. Translated from Zhurnal Prikladnoi Khimii, Vol. 76, No. 6, 2003,
Original Russian Text Copyright + 2003 by Pilyugin.
AND INDUSTRIAL ORGANIC CHEMISTRY
Synthesis of 4-Amino-4<-nitrodiphenyl Sulfide
V. S. Pilyugin
Research and Technological Institute of Herbicides and Plant Growth Regulators, Academy of Sciences
of Bashkortostan Republic, Ufa, Bashkortostan, Russia
Received January 9, 2003
Abstract-The possibility of preparing 4-amino-4`-nitrodiphenyl sulfide by reaction of chlorobenzene with
sodium sulfide in a two-phase system composed of water and organic solvent in the presence of a phase-trans-
fer catalyst under continuous hydroacoustic treatment was examined.
4-Amino-4`-nitrodiphenyl sulfide I is an intermedi-
ate in production of 3,4,4`-triaminodiphenyl sulfide,
the synthetic precursor of antihelminth agents of the
Thioethers (sulfides) are prepared by condensation
of alkyl halides or nitro-substituted aryl halides with
sodium sulfide [23 4].
Synthesis of thioethers by reaction of thiocyanates
with alcohols under heating in the presence of stoi-
chiometric amounts of alkali or alkaline-earth metal
hydroxides or alcoholates or those of tertiary amines
is described in a patent .
Dialkyl sulfides can also be prepared by reaction of
alkyl chlorides with an aqueous or aqueous-alcoholic
solution of alkali metal sulfide in an autoclave at high
pressure ; diaryl sulfides are synthesized by reac-
tion of appropriate nitrochlorobenzenes in dimethyl-
formamide (DMF) with an aqueous solution of sodi-
um sulfide in the presence of finely divided sulfur 
or in refluxing alcohol with fine powder of a prelim-
inarily fused mixture of sodium sulfide and sulfur .
There are numerous procedures for reducing nitro
compounds to the corresponding amines ; in some
cases, it is possible to selectively reduce one of the
nitro groups of polynitro compounds with a calculated
amount of sodium (or ammnonium) sulfide (or hydro-
A procedure has been developed for preparing 4,4`-
diaminodiphenyl sulfide I by reaction of 4-nitrochloro-
benzene II with sodium sulfide in DMF, followed by
reduction of the resulting 4,4`-dinitrodiphenyl sulfide
with iron powder in aqueous alcohol in the presence
of ammonium chloride under heating .
Hodson and Wilson  prepared diphenyl sulfide
I as follows. A solution of II in absolute ethanol is
heated almost to reflux, and an aqueous solution of
sodium sulfide is added in small portions. The re-
sulting mixture is refluxed with stirring for 10 h.
Yield of I is about 20% (mp 1383142oC).
According to Radulova and Tapalova’s procedure
, a mixture of II with water and sodium sulfide is
heated, an additional portion of II is added, and, after
prolonged heating, toluene is added; the yield of I is
about 68% (mp 1433144oC).
Zasosov and Gal’chenko prepared sulfide I by
adding a portion of II to a boiling aqueous solution of
sodium sulfide. After stirring for a certain time, the
next portion of II is added, and the mixture is re-
fluxed with stirring. Then an additional small amount
of aqueous sodium sulfide solution is introduced,
and the mixture is refluxed with stirring. The re-
sulting mixture is steam-distilled to remove un-
changed II; yield of I 77380% (mp 1453147oC, from
Raiziss et al.  refluxed a mixture of Na
water, and a part of the required amount of II, after
which they added the remaining part of II, with the
refluxing continued. The resulting mixture was steam-
distilled; yield of I 80% (mp 1413413oC, from eth-
Aminonitrodiphenyl sulfides can also be prepared
by reaction of alkaline solutions of substituted amino-
thiophenols with alcoholic solutions of halonitroben-
All the above procedures for preparing sulfides I
are time- and labor-consuming; the yield and quality
of the target product are poor. The procedures involve