Reactions of 1,3-dehydroadamantane with some aromatic disulfides

Full text of DOI:10.1134/S1070363212060278

ISSN 1070-3632, Russian Journal of General Chemistry, 2012, Vol. 82, No. 6, pp. 1183–1184. © Pleiades Publishing, Ltd., 2012.
Original Russian Text © G.M. Butov, O.M. Ivankina, V.A. Ivanov, V.M. Mokhov, N.V. Zyk, 2012, published in Zhurnal Obshchei Khimii, 2012, Vol. 82,
No. 6, pp. 1049–1050.
LETTERS
TO THE EDITOR
Reactions of 1,3-Dehydroadamantane
with Some Aromatic Disulfides
G. M. Butova, O. M. Ivankinaa, V. A. Ivanova, V. M. Mokhovb, and N. V. Zykс
a Volzhskii Polytechnic Institute, Division of Volgograd State Technical University,
ul. Engel’sa 42a, Volzhskii, 404121 Russia
e-mail: butov@volpi.ru
b Volgograd State Technical University, Volgograd, Russia
c Lomonosov Moscow State University, Moscow, Russia
Received January 12, 2012
DOI: 10.1134/S1070363212060278
The reactions of some propellanes I–IV with disul-
fides are known [1–3]. For example, [1.1.1]propellane
I reacts with diphenyl disulfide when heated [1] or by
the photochemical initiation via a free-radical mecha-
nism [2]. An asymmetric [4.4.1]propellane, 2,3-methano-
2,4-didehydroadamantane II, reacts slowly, but
selectively, in deuterated benzene with dimethyl
disulfide to form 2,4-bis(methylthio)-2,4-methanoproto-
adamantane [3]. No formation of other products was
observed that would confirm the free-radical me-
chanism of this reaction.
The reaction with an unsymmetrical methyl phenyl
disulfide gives rise to a mixture of three products, sym-
metric bisulfides and unsymmetrical 2-(methylthio)-4-
(phenylthio)-2,4-methanoadamantane (1:1:3). The
formation of a bisulfides mixture was observed also in
the reaction of symmetric dimethyl and diphenyl
disulfides. The formation of a mixture of different
bisulfides allows us a conclusion on the free-radical
nature of the reactions of propellanes with disulfides.
The generation of free radicals from [3.1.1]propellane
was proved by the ESR in the reaction with CCl4, as
well as by the product of its reaction with p-
benzoquinone [4].
The dimethyl analog of [3.1.1]propellane, 2,4-(di-
methylmethano)-2,4-didehydroadamantane, also reacts
readily with dimethyl sulfide at room temperature in
benzene-d6 to give bisulfide, 2,4-(methylthio)-2,4-(di-
methylmethano)-2,4-didehydroadamantane [5].
I
II
III
IV
V
The structural analog of [3.1.1]propellane, 2,4-
methano-2,4-didehydroadamantane III, reacts with the
symmetrical disulfide (dimethyl and diphenyl) at room
temperature in benzene-d6 to open a propellane bond
giving symmetric bisulfides: 2,4-bis(methylthio)-2,4-
methanoadamantane and 2,4-bis(phenylthio)-2,4-
methanoadamantane [4].
1,3-Dehydroadamantane V is a promising reagent in
organic synthesis, however, its reactions with the sulfur-
containing compounds were poorly studied [6, 7]. In
this work we investigated the reactions of adamantane
V with various disulfides. The reactions are based on
the previously unknown properties of adamantane V to
cleave the S–S bond in disulfides at 80–110°C.
The reactions of compound V with disulfides
proceed according to the scheme bellow.
MeS−SPh, C6D6 MeS−SMe, PhS−SPh, C6D6
PhS
MeS
PhS
In the case of disulfides VI–VIII there is 100%
selectivity towards the formation of the product of
insertion into the S–S bond. The yields of the target
SMe
SMe +
+
SPh
1183

1184
BUTOV et al.
R
S
R
R
R
+
S
S
S
V
VI−VIII
(VII),
(VIII).
R =
(VI),
Br
NH2
products reach 50–52%. The formation of the target
products was confirmed by the GC-MS method and
thin layer chromatography.
1,3-Bis(p-aminopheniltio) adamantane (VIII). To
a solution of 0.1 g (0.0004 mol) of p,p'-bis(amino-
phenyl) disulfide in 10 ml of benzene was added a solu-
tion of 0.049 g (0.00037 mol) of the freshly sublimated
1,3-dehydroadamantane [p,p'-bis(aminophenyl) disulfide:
1,3-dehydroadamantane = 1.1:1] in 10 ml of benzene
in a nitrogen atmosphere at room temperature. The
reaction mixture was heated at 80°C for 9 h, and then
benzene was removed. The residue was recrystallized
from benzene. Yield 0.08 g (52%), white crystals, mp
215°C. Mass spectrum, m/z (I, %): 382 (10%) [M]+•,
258 (40%) [M – NH2C6H4S]+, 135 (4%) [C10H15]+, 124
(100%) [NH2C6H4S]+. Found, %: С 70.32; Н 7.36.
С22Н26N2S2. Calculated, %: С 69.11; Н 6.81.
1,3-Bis(phenylthio)adamantane (VI). To
a
solution of 1.33 g (0.0061 mol) of diphenyldisulfide in
10 ml of anhydrous diethyl ether was added a solution
of 0.74 g (0.0055 mol) of the freshly sublimated 1,3-
dehydroadamantane (diphenyl disulfide:1,3-dehydroada-
mantane = 1.1:1) in 10 ml of anhydrous diethyl ether in
a nitrogen atmosphere at room temperature. The ether
was removed, and the reaction was carried out for 2 h
at 100–110°C in the disulfide melt. The reaction
mixture was recrystallized from benzene. Yield 0.37 g
(50%), yellow-brown crystals, resinification point 315°
C. Mass spectrum, m/z (I, %): 352 (11%) [M]+•, 243
(100%) [M – PhS]+, 187 (33%) [M – PhSC4H8]+, 133
(44%) [C10H13]+, 109 (66%) [PhS]+, 91 (53%) [C7H7]+,
77 (26%) [C6H5]+. Found, %: С 75.82; Н 7.76.
С22Н24S2. Calculated, %: С 75.00; Н 6.82.
The mass spectra were recorded on a Hewlett
Packard GC 5890 Series II/MSD 5972 Series GC mass
spectrometer. The thin layer chromatography was per-
formed on a Silufol UV 254 plates, eluent – benzene.
REFERENCES
1,3-Bis(p-bromophenylthio)adamantane (VII). To
a solution of 0.6 g (0.0016 mol) of p,p'-bis(bromo-
phenyl) disulfide in 5 ml of THF was added a solution
of 0.19 g (0.00145 mol) of the freshly sublimated 1,3-
dehydroadamantane [p,p'-bis(bromophenyl) disulfide:
1,3-dehydroadamantane = 1.1:1] in 5 ml of THF in a
nitrogen atmosphere at room temperature. The solvent
was distilled off, and the reaction was performed for
2 h at 100–110°C in the disulfide melt. Then the reac-
tion mixture was boiled at 35°C for 2 h and recrystal-
lized from benzene. Yield 0.37 g (50%), yellow-brown
crystals, resinification point 235°C. Mass spectrum, m/z
(I, %): 510 (6%) [M]+•, 323 (87%) [M – BrC6H4S]+,
187 (49%) [BrC6H4S]+, 133 (82%) [C10H13]+, 109
(73%) [PhS]+, 91 (100%) [C7H7]+. Found, %: С 52.62;
Н 4.76. С22Н22S2Br2. Calculated, %: С 51.77; Н 4.31.
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RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 82 No. 6 2012