Reaction of 2,3-bis(benzotriazol-1-y1)-1,4-naphthoquinone

Full text of DOI:10.1023/A:1012372327103

Russian Journal of General Chemistry, Vol. 71, No. 4, 2001, pp. 655 656. Translated from Zhurnal Obshchei Khimii, Vol. 71, No. 4, 2001, p. 700.
Original Russian Text Copyright
2001 by Romanyuk, Litvin, Ganushchak.
LETTERS
TO THE EDITOR
Reaction of 2,3-Bis(benzotriazol-1-yl)-1,4-naphthoquinone
A. L. Romanyuk, B. L. Litvin, and N. I. Ganushchak
Franko Lviv State University, Lviv, Ukraine
Barva Firm, Ivano-Frankivsk, Ukraine
Received June 15, 2000
Proceeding with our studies [1], we reacted 2,3-bis-
benzotriazol-1-yl)-1,4-naphthoquinone (I) with thio-
phenol. This reaction may involve both mono- and
disubstitution to give 2-(benzotriazol-1-yl)-3-phenyl-
thio-1,4-naphthoquinone (II) and 2,3-bis(phenylthio)-
2-(Benzotriazol-1-yl)-3-phenylthio-1,4-naphtho-
quinone (II). Thiophenol, 1.1 ml, was added to a
suspension of 3.92 g of quinone I in 25 ml of ethanol.
The reaction mixture was heated under reflux for 1 h
and then cooled. The precipitate that formed was
washed with alcohol and recrystallized from ethanol
water (1:2) to obtain 2.57 g (67%) of a brown crystal-
(
1
,4-naphthoquinone (III), respectively.
1
line substance, mp 172 173 C. H NMR spectrum, ,
ppm: 8.13 m (2H), 7.94 m (3H), 7.65 d (1H), 7.54 t
O
O
6
S C H5
HS C H
6
5
(
%
1H), 7.38 m (2H), 7.09 d (2H), 6.92 m (2H). Found,
N
: N 10.72; S 8.41. C H N O S. Calculated, %: N
2
2
13
3
2
N
N
1
0.97; S 8.35.
O
N
N
N
N
2
,3-Bis(phenylthio)-1,4-naphthoquinone (III).
N
N
Thiophenol, 2.4 ml, was added to a suspension of
3.92 g of quinone I in 25 ml of ethanol. The reaction
mixture was heated under reflux for 30 min and then
cooled. The precipitate that formed was filtered off
and recrystallized from ethanol water (1:3) to obtain
2.75 g (73%) of a red crystalline substance, mp 149
II
O
O
6
S C H5
2
HS C H
6 5
I
1
6
S C H5
150 C. H NMR spectrum, , ppm: 7.89 m (2H),
O
7
1
.84 m (2H), 7.39 m (4H), 7.29 m (6H). Found S, %:
7.05. C H O S . Calculated S, %: 17.11.
III
2
2
14
2 2
Reaction of sulfide II with tert-butylamine. tert-
Butylamine, 0.5 ml, was added to a suspension of
.15 g of compound II in 15 ml of ethanol. The reac-
The reaction of compound II with tert-butylamine
affords two products: 3-(benzotriazol-1-yl)-1,4-
naphthoquinone (IV) and disulfide III in a 1:1 ratio.
The formation of compound III can be explained in
the following way: Compound II reacts with tert-
butylamine to give compound IV and thiophenol,
and the latter reacts with sulfide II, yielding disulfide
III.
1
tion mixture was heated under reflux for 1 h and then
cooled. The precipitate that formed was filtered off
and recrystallized first from ethanol water, 1:2, and
then from ethanol. The resulting substance, 0.15 g,
mp 146 148 C, gave no melting point depression
1
with disulfide III and had the same H NMR
spectrum.
O
NHC(CH3)3
The filtrate obtained after the first recrystallization
was diluted three times with water, the precipitate that
formed was filtered off and recrystallized from ethanol
H NC(CH )
N
2
3 3
II
+ III
N
N
to obtain 0.15 g of a yellow crystalline substance, mp
O
1
1
7
65 166 C. H NMR spectrum, , ppm: 8.15 m (2H),
.88 m (2H), 7.95 d (1H), 7.65 d (1H), 7.54 t (1H),
IV
7.44 t (1H), 0.93 s (9H).
1
070-3632/01/7104-0655$25.00 2001 MAIK Nauka/Interperiodica

6
56
ROMANYUK et al.
1
The H NMR spectra were recorded on a Varian
REFERENCES
VXR-300 spectrometer (300 MHz), solvent DMSO-d6,
external reference HMDS. The purity of the synthesi-
zed compounds was established by TLC on Silufol
UV-254 plates, eluent benzene acetone (1:1).
1. Romanyuk, A.L., Lis, R.I., Litvin, B.L., and Ganu-
shchak, N.I., Zh. Org. Khim., 1998, vol. 34, no. 9,
p. 1422.
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 71 No. 4 2001