Adamantylazoles: XI. Reaction of 1-phenyltetrazole-5-thione with adamantan-1-ol in strong acids

Article abstract of DOI:10.1134/S1070363207120171

The reaction of 1-phenyltetrazole-5-thione with adamantan-1-ol in sulfuric acid gave 3-(1-adamantyl)-1-phenyltetrazole-5-thione having a mesoionic structure, 5-(1-adamantylsulfanyl)-1-phenyltetrazole, and 3-(1-adamantyl)-5-(1- adamantylsulfanyl)-1-phenylt

Full text of DOI:10.1134/S1070363207120171

ISSN 1070-3632, Russian Journal of General Chemistry, 2007, Vol. 77, No. 12, pp. 2186 2191.
Original Russian Text A.V. Logvinov, V.V. Saraev, I.N. Polyakova, Yu.A. Strelenko, E.L. Golod, 2007, published in Zhurnal Obshchei Khimii, 2007,
Vol. 77, No. 12, pp. 2041 2046.
Pleiades Publishing, Ltd., 2007.
Adamantylazoles: XI.1 Reaction of 1-Phenyltetrazole-5-thione
with Adamantan-1-ol in Strong Acids
A. V. Logvinova, V. V. Saraeva, I. N. Polyakovab, Yu. A. Strelenkoc, and E. L. Goloda
a
St. Petersburg State Institute of Technology (Technical University),
Moskovskii pr. 26, St. Petersburg, 190013 Russia
e-mail: golod18@yandex.ru
b Kurnakov Institute of General and Inorganic Chemistry,
Russian Academy of Sciences, Moscow, Russia
c Zelinskii Institute of Organic Chemistry, Russian Academy of Sciences, Moscow, Russia
Received July 9, 2007
Abstract The reaction of 1-phenyltetrazole-5-thione with adamantan-1-ol in sulfuric acid gave 3-(1-ada-
mantyl)-1-phenyltetrazole-5-thione having a mesoionic structure, 5-(1-adamantylsulfanyl)-1-phenyltetrazole,
and 3-(1-adamantyl)-5-(1-adamantylsulfanyl)-1-phenyltetrazolium hydrogen sulfate. Hydrolysis of 5-(1-
adamantylsulfanyl)-1-phenyltetrazole led to the formation of 1-phenyltetrazol-5-one. The adamantylation
process is reversible.
DOI: 10.1134/S1070363207120171
Alkylation of 1-substituted tetrazole-5-thiones in
alkaline or neutral medium leads, as a rule, to the
corresponding 5-alkylsulfanyl derivatives [2 5].
Substitution products at the N4 atom are formed in
reaction with diazomethane [6] or compounds having
a multiple bond [7], as well as by thermal rearrange-
ment of the S-substituted isomer [8, 9]. The reaction
of tetrazole-5-thiones with acetyl chloride was the
only example where three isomers, S-, N2-, and N4-
substituted derivatives, were obtained [10, 11].
tetrazolethiones. According to the results of quantum-
chemical calculations, the basicity of tetrazolethiones
approaches the basicity of unsubstituted 1H-tetrazole
+
(pKBH = 2.7) [13]; therefore, we presumed that tetra-
zolethiones in 94% sulfuric acid, as well as tetrazoles
[14], undergo protonation and react in the protonated
form.
The reaction of compound I with an equimolar
amount of adamantan-1-ol in sulfuric acid in 1.5 h
gave up to 33% of mesoionic 3-(1-adamantyl)-1-
phenyltetrazole-5-thione (III). As far as we know,
In this study we examined adamantylation of
1-phenyltetrazole-5-thione (I) in acid medium.
Acid-catalyzed alkylation of tetrazole-5-thiones was
not reported previously. Compound I was prepared by
reaction of phenyl isothiocyanate (II) with sodium
azide [12].
Ph
S
N
1-AdOH
H2SO4
I
N
N
N
Ad
Ph
S
N
III
N=C=S + NaN3
N
N
Ph
Ph
Ph
S Ad
S Ad
N
N
I
Ph
N
N
II
+
+
X
N
N
N
N
N+
Ad
Adamantylation of 1-phenyltetrazole-5-thione (I)
was carried out in concentrated sulfuric acid. There
are no published experimental data on the basicity of
IV
Va, Vb
1
For communication X, see [1].
X = HSO4 (a), ClO4 (b).
2186

ADAMANTYLAZOLES: XI.
2187
Table 1. Hydrogen bond parameters in the crystal structure of compound III
Distance,
X Y
X H Y angle,
X H Y
Symmetry transformation for the Y atom
deg
H Y
C3 H3 N2
C7 H7 S1
C7 H7 N4
C3 H3 S1
x, y, z
x, y, z
x, y,
x, y,
2.896(2)
3.394(2)
3.414(2)
3.907(2)
2.68(2)
2.89(3)
2.47(3)
3.07(3)
92.1(15)
112.4(18)
160(2)
1
z
z
142.1(18)
such alkylation pathway of tetrazolethiones was not
reported previously. Apart from compound III, the
reaction mixture contained a small amount of isomeric
5-(1-adamantylsulfanyl)-1-phenyltetrazole (IV). Com-
pounds III and IV undergo further alkylation to
produce 3-(1-adamantyl)-5-(1-adamantylsulfanyl)-1-
phenyltetrazolium salt V which can be isolated as
hydrogen sulfate Va or perchlorate Vb.
along the z axis (Fig. 2). Neighboring molecules are
linked through hydrogen bonds C7 H7 N4 (1 x, y,
z) to give centrosymmetric dimers. Weaker inter-
molecular contacts C3 H3 S1 ( x, y, z) link the
dimers to form a ribbon.
Some difficulties encountered while identifying
compound IV. IR absorption bands belonging to
vibrations of C=S and C S C groups are weakly
The C5 carbon nuclei in the tetrazole ring of III
1
characteristic. The H and 13C NMR spectra could
resonates in the 13C NMR spectrum at
173 ppm,
C
also be interpreted with ambiguity. According to [15],
the chemical shift of the C=S carbon nuclei in
in keeping with published data for 3-ethyl-1-phenyl-
tetrazole-5-thione [15] and 1,3-diphenyl- [16] and
1,3-dimethyltetrazole-5-thiones [17]. The structure of
III was proved by X-ray analysis. It crystallized as
prisms belonging to the monoclinic crystal system with
the following unit cell parameters: a = 7.0652(10),
1-phenyltetrazole-5-thione is
chemical shift of C5 in 5-methylsulfanyl-1-phenyl-
tetrazole is 155.1 ppm. In the spectrum of IV, the
C5 carbon atCom resonated at
151.07 ppm; these
163.8 ppm, and the
C
C
data did not allow us to determine its structure un-
equivocally. Therefore, we examined the 15N NMR
spectrum of compound IV. It contained four clearly
b = 11.712(3), c = 19.603(6)
;
= 99.502(18) ;
3
V = 1599.9(7) 3; dcalc = 1.297 g cm ; (Cu) =
1
1.801 mm ; Z = 4; space group P21/n. The structure
defined signals at
10.731, 10.306, 52.593, and
N
of molecule III is shown in Fig. 1; selected bond
lengths and bond angles are given in Table 1, and
hydrogen bond parameters, in Table 2. The tetrazole
ring is planar: deviations of the N1 N4 and C1 atoms
from the mean-square plane formed by these atoms do
not exceed 0.0024 . The S1, C2, and C8 atoms are
also located in that plane; the corresponding devia-
tions are 0.002(2), 0.021(2), and 0.058(2) , respec-
tively. The benzene C2 C7 and tetrazole rings form a
dihedral angle of 48.96(7) . Their mutual orientation
is stabilized by weak intramolecular hydrogen bonds
C3 H3 N2 and C7 H7 S1.
137.610 ppm (relative to nitromethane).
Using Priroda software (triple zeta basis set) [19]
we simulated four possible isomeric adamantylation
C17
C12
C13
C15
C11
C14
C16
C8
N3
C10
N2
N1
The bond lengths in the thioxotetrazole fragment
imply delocalization of electron density over the entire
fragment. A similar geometry is typical of 1,3-di-
phenyltetrazole-5-thione [18] for which the bond
lengths in the S1 C1 N1 N2 N3 N4 C1 sequence are
C9
C4
C3
C2
C7
N4
C5
C1
S1
C6
1.663, 1.390, 1.331, 1.294, 1.334, and 1.349
,
respectively, and the internal bond angles coincide
with those found in molecule III. Molecules III in
crystal are packed in such a way that the adamantyl
groups and phenyltetrazole fragments appear in dif-
ferent layers parallel to the xy plane and alternating
Fig. 1. Structure of the molecule of 3-(1-adamantyl)-1-
phenyltetrazole-5-thione (III) according to the X-ray
diffraction data.
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 77 No. 12 2007

2188
LOGVINOV et al.
Table 2. Bond lengths and bond angles in the molecule of 3-(1-adamantyl)-1-phenyltetrazole-5-thione (III)
Bond
S1 C1
d,
Bond
d,
Angle
, deg
1.6781(17)
1.3396(18)
1.3867(19)
1.424(2)
1.2917(18)
1.3365(18)
1.4942(19)
1.346(2)
1.379(2)
1.382(2)
1.376(3)
1.378(3)
C6 C7
1.378(3)
1.522(2)
1.523(2)
1.531(2)
1.535(3)
1.518(3)
1.519(4)
1.517(3)
1.524(4)
1.541(3)
1.542(3)
1.505(4)
1.520(4)
N2N1C1
N2N1C2
C1N1C2
N3N2N1
N2N3N4
N2N3C8
N4N3C8
N3N4C1
N4C1N1
N4C1S1
N1C1S1
111.21(12)
118.56(12)
130.20(13)
102.57(12)
116.13(12)
122.02(13)
121.85(12)
104.63(12)
105.46(13)
127.23(12)
127.31(11)
N1 N2
N1 C1
N1 C2
N2 N3
N3 N4
N3 C8
N4 C1
C2 C7
C2 C3
C3 C4
C4 C5
C5 C6
C8 C9
C8 C13
C8 C14
C9 C10
C10 C11
C10 C16
C11 C12
C12 C17
C12 C13
C14 C15
C15 C17
C15 C16
1.377(3)
products of 1-phenyltetrazole-5-thione, compounds
III, IV, VI, and VII.
shifts only for structure IV, 5-(1-adamantylsulfanyl)-
1-phenyltetrazole (Y = 8.8141 + 1.1629X; Fig. 3); this
may be regarded as an independent proof for the
product structure and assignment of the 15N signals.
Ph
Ph
S
S
N
N
N
N
N
N
The structure of compound IV was also confirmed
by chemical transformations. It is known that 5-alkyl-
sulfanyl-1-aryltetrazoles in alkaline medium undergo
hydrolysis at the C S bond with formation of the
corresponding tetrazol-5-ones [20]. By heating com-
pound IV in alcoholic alkali we obtained 1-phenyl-
Ad Ad
N
N
VI
VII
The calculations revealed a linear dependence
between the calculated and experimental 15N chemical
a
0
c
b
Fig. 2. Fragment of the crystal structure of compound III.
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 77 No. 12 2007

ADAMANTYLAZOLES: XI.
tetrazol-5-one (VIII) which was identified by com-
2189
parison with an authentic sample.
0
Ph
O
N
EtOH, NaOH
NH
N
IV
50
N
VIII
100
The major product of the reaction of compound I
with 2 equiv of adamantan-1-ol in sulfuric acid was
3-(1-adamantyl)-5-(1-adamantylsulfanyl)-1-phenyl-
tetrazolium salt V which was formed with a high
yield. The structure of salts Va and Vb was confirmed
1
2
3
4
150
200
1
by IR and H and 13C NMR spectroscopy. Hydrolysis
of tetrazolium hydrogen sulfate Va on heating in
water releases adamantan-1-ol. The reaction involves
preferentially the N3 atom with formation of com-
pound IV (yield 53%) and at the S CAd bond to give
17% of mesoionic structure III.
200 150
100
50
0
N(exp.), ppm
Fig. 3. Correlation between the calculated and experi-
mental N chemical shifts for compounds (1) III, (2) IV,
(3) VI, and (4) VII.
15
H2O
Va
III + IV.
AdOH
A mixture of phosphoric and acetic acids at a ratio
of 4:1 (by weight) was proposed in [22] for ada-
mantylation of diazoles. An advantage of this system
is its lower acidity (as compared to sulfuric acid)
which is insufficient to promote ionization of ada-
mantan-1-ol and formation of adamantyl cation.
Adamantylation of 1-phenyltetrazole-5-thione (I) in
the above system gives rise to a different product
ratio. The yield of mesoionic compound III becomes
insignificant, the yield of isomer IV increases to 8%,
and the yield of tetrazolium salt Vb increases to 46%.
In the reaction of I with 2 equiv of adamantan-1-ol in
a mixture of phosphoric and acetic acids, tetrazolium
salt Vb was obtained in 95% yield.
The formation of adamantyl-substituted tetrazole-5-
thiones in acid medium is reversible. Protonation of
the heteroatoms in sulfuric acid is followed by
cleavage of the N CAd and S CAd bonds with forma-
tion of adamantyl cation which is involved in sec-
ondary adamantylation processes. This was con-
firmed by a series of experiments in which com-
pounds III, IV, and Vb and excess 3-nitro-1,2,4-tri-
azole were kept in concentrated sulfuric acid, and the
mixture was then analyzed by TLC.
It is known that 1,2,4-triazoles readily react with
adamantan-1-ols with formation of the corresponding
1-(1-adamantyl)triazoles [21]. We have found that
compound IV undergoes complete deadamantylation
in 2 h; the reaction mixture contains 1-(1-adamantyl)-
3-nitro-1,2,4-triazole, initial 1-phenyltetrazole-5-
thione (I), and mesoionic compounds III. Under the
same conditions, partial deadamantylation of III and
tetrazolium perchlorate Vb occurs to produce 1-(1-
adamantyl)-3-nitro-1,2,4-triazole. These findings led
us to presume that adamantylation of 1-phenyltetra-
zole-5-thione (I) in sulfuric acid is an equilibrium
process which may be represented by the following
scheme:
EXPERIMENTAL
1
The H and 13C NMR spectra were recorded on
Bruker WM-400 and Bruker AC-200 spectrometers
using DMSO-d6 as solvent and tetramethylsilane as
reference. The 13C NMR spectra were measured with
complete decoupling from protons. The 15N NMR
spectra were recorded on a Bruker AM-500 instru-
ment using 10-mm ampules; chloroform was used as
solvent, and nitromethane, as reference. The IR spec-
tra were recorded in KBr on an FTIR-8400 spectrom-
eter. The elemental compositions were determined
on a Hewlett Packard 185B analyzer. Thin-layer
chromatography was performed on Sorbfil and Silufol
UV-254 plates; eluent chloroform, chloroform ethyl
acetate (4:1), or chloroform ethyl acetate alcohol
(4:1:1); development with UV light or treatment
with iodine vapor.
Ad+
III
I
H+
Ad+
H+ Ad+
Ad+
Va
IV
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 77 No. 12 2007

2190
LOGVINOV et al.
The experimental set of reflection intensities for a
56.98 s, 42.21 s, 40.79 s, 35.10 s, 34.77 s, 29.79 s,
28.95 s (1-Ad). Found, %: C 58.90; H 6.71; N 10.50.
C27H35N4SClO4. Calculated, %: C 59.28; H 6.40;
N 10.25.
0.18 0.30 0.66-mm single crystal of III was
acquired on a CAD-4 automatic diffractometer at
room temperature (CuK radiation, graphite mono-
chromator). Total of 3276 reflections were measured in
the range from 2.3 to 76.9 , 3191 of which were
independent (Rint = 0.0157). The structure was solved
by the direct method. Hydrogen atoms were localized
using Fourier difference syntheses. The positions of
atoms were refined by the least-squares procedure in
anisotropic approximation for non-hydrogen atoms
and isotropic approximation for hydrogen atoms
with account taken of secondary extinction [c =
0.042(4)]. The final divergence factors were R1 =
0.0455 and wR2 = 0.1307 for 2900 reflections with
I > 2 (I) and R1 = 0.0490 and wR2 = 0.1352 for all
independent reflections; goodness of fit 1.052. The
residual electron density was estimated at 0.498 <
< 0.390 e 3. No correction for absorption was
introduced. The calculations were performed using
SHELX97 software package [23].
When the reaction was performed in 95% sulfuric
acid (reaction time 1.5 h), the yield of III was 33%,
and that of Vb, 16%; however, in this case, the
amount of impurities increased, and we failed to
purify compound III by recrystallization.
Reaction of 1-phenyltetrazole-5-thione (I) with
2 equiv of adamantan-1-ol in sulfuric acid. A solu-
tion of 0.0118 mol of adamantan-1-ol and 0.0056 mol
of 1-phenyltetrazole-5-thione (I) in 40 ml of 94% sul-
furic acid was stirred for 2 h at room temperature. The
mixture was poured onto ice and filtered, and the
filtrate was extracted with 250 ml of chloroform. The
extract was dried over sodium sulfate, the solvent was
distilled off, and the residue was crystallized from
propan-2-ol hexane (1:2). The product was dissolved
in methylene chloride, and the solution was evap-
orated to remove traces of propan-2-ol. Yield of
3-(1-adamantyl)-5-(1-adamantylsulfanyl)-1-phenyl-
tetrazolium hydrogen sulfate (Va) 2.52 g (83%), mp
Reaction of 1-phenyltetrazole-5-thione (I) with
adamantan-1-ol (equimolar reactant ratio) in sul-
furic acid. A solution of 0.0059 mol of adamantan-1-
ol and 0.0056 mol of 1-phenyltetrazole-5-thione (I)
was dissolved in 30 ml of 94% sulfuric acid was
stirred for 2 h at room temperature. The mixture was
then poured onto ice. According to the TLC data, the
precipitate contained compounds III and IV. It was
filtered off, washed with water, and recrystallized
from propan-2-ol. Yield of 3-(1-adamantyl)-1-phenyl-
tetrazole-5-thione (III) 0.36 g (21%), mp 207 C
1
125 C (decomp.). H NMR spectrum (DMSO-d6), ,
ppm: 7.80 7.71 m (5H, Ph); 2.43 s, 2.37 s, 2.17 d,
1
1.84 s, 1.74 s (30H, 1-Ad). IR spectrum, , cm :
2912, 1493, 1454, 1435, 1396, 1342, 1296, 1230,
1176, 1065, 1030, 1011, 849, 748, 690, 582. 13C
NMR spectrum (DMSO-d6), C, ppm: 57.70 s (C S);
132.80 s, 131.53 s, 130.24 s, 125.95 s (Ph); 70.78 s,
56.93 s, 42.24 s, 40.79 s, 35.10 s, 34.77 s, 29.76 s,
28.95 s (1-Ad). Found, %: C 59.30; H 6.15; N 9.83.
C27H36N4S2O4. Calculated, %: C 59.56; H 6.60;
N 10.29.
1
(decomp.). H NMR spectrum (DMSO-d6), , ppm:
7.94 d and 7.57 d (5H, Ph); 2.34 s and 1.80 s (15H,
1
1-Ad). IR spectrum, , cm : 2908, 1593, 1497, 1458,
1365, 1354, 1304, 1280, 1250, 1173, 1103, 1072,
As in the reaction with equimolar amounts of the
reactants, the use of 95% sulfuric acid is undesirable,
for it favors formation of impurities.
1018, 999, 837, 756, 710, 687, 594. 13C NMR spec-
trum (DMSO-d6), C, ppm: 173.04 s (C=S); 134.06 s,
129.72 s, 128.75 s, 124.66 s (Carom); 67.28 s, 40.62 s,
34.96 s, 28.79 s (1-Ad). Found, %: C 65.30; H 6.30;
N 18.13. C17H20N4S. Calculated, %: C 65.38; H 6.41;
N 17.95.
Hydrolysis of 3-(1-adamantyl)-5-(1-adamantyl-
sulfanyl)-1-phenyltetrazolium hydrogen sulfate
(Va). A solution of 0.00132 mol of compound Va in
40 ml of water was heated for 1 h at the boiling point.
After cooling, the precipitate was filtered off, washed
with water, dried, and extracted with hexane. The
undissolved material was compound III, yield 0.07 g
(17%). Evaporation of the hexane solution gave
5-(1-adamantylsulfanyl)-1-phenyltetrazole (IV), yield
A dilute solution of perchloric acid was added to
the aqueous filtrate, and the precipitate was filtered
off and washed with water. Yield of 3-(1-adamantyl)-
5-(1-adamantylsulfanyl)-1-phenyltetrazolium per-
chlorate (Vb) 0.46 g (15%), mp 204 C (decomp.;
1
1
0.22 g (53%), mp 126 127 C (from propan-2-ol). H
from ethanol chloroform, 9:1). H NMR spectrum
NMR spectrum (DMSO-d6), , ppm: 7.61 s, 7.56 s
(DMSO-d6), , ppm 7.78 7.74 m (5H, Ph); 2.44 s,
(5H, Ph); 2.08 s, 1.69 s (15H, 1-Ad). IR spectrum, ,
2.38 s, 2.18 d, 1.84 s, 1.74 s (30H, 1-Ad). IR spec-
1
1
cm : 2912, 1593, 1497, 1454, 1385, 1342, 1300,
trum, , cm : 2908, 1589, 1497, 1443, 1404, 1350,
1304, 1188, 1095, 1034, 957, 771, 687. 13C NMR
spectrum (DMSO-d6), C, ppm 157.76 s (C=S);
132.80 s, 131.51 s, 130.24 s, 125.90 s (Ph); 70.84 s,
1261, 1230, 1088, 1072, 1041, 1014, 972, 756, 694,
687. 13C NMR spectrum (DMSO-d6), C, ppm:
151.07 s (C=S); 133.34 s, 130.59 s, 129.73 s,
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 77 No. 12 2007

ADAMANTYLAZOLES: XI.
2191
125.58 s (Ph); 53.26, 42.51 s, 35.23 s, 29.52 s (1-Ad).
15N NMR spectrum (CDCl3), N, ppm: 10.731,
10.306, 52.593, 137.61. Found, %: C 65.63; H
6.54; N 18.34. C17H20N4S. Calculated, %: C 65.38;
H 6.41; N 17.95.
3. L’abbé, G., Toppet, S., Verhelst, G., and Martens, C.,
J. Org. Chem., 1974, vol. 39, no. 25, p. 3770.
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vol. 15, no. 2, p. 54.
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Chem., 1978, vol. 43, no. 6, p. 1197.
Hydrolysis of 5-(1-adamantylsulfanyl)-1-phenyl-
tetrazole (IV). Compound IV, 0.2 g, was dissolved
in 20 ml of a 5% alcoholic solution of sodium hy-
droxide, and the mixture was heated for 20 h under
reflux with stirring. It was then diluted with water and
filtered, and the filtrate was extracted with chloroform.
The aqueous phase was acidified with hydrochloric
acid and extracted with chloroform. The extracts were
dried over sodium sulfate, and the solvent was
distilled off. According to the TLC data, the residue
contained 1-phenyltetrazol-5-one (VIII). IR spectrum,
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1
, cm : 2912, 1716 (S=O), 1597, 1504, 1462, 1392,
10. Lippmann, E., Reifegerste, D., and Kleinpeter, E.,
1350, 1292, 1165, 1149, 1061, 972, 910, 752, 733,
687, 656, 579, 501. A reference sample of compound
VIII was synthesized according to the procedure
described in [20].
Z. Chem., 1974, vol. 14, no. 1, p. 16.
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Reaction of compounds III, IV, and Vb with
3-nitro-1,2,4-triazole (general procedure). A solution
of 0.32 mmol of compound III, IV, or Vb and
0.44 mmol of 3-nitro-1,2,4-triazole in 5 ml of 95%
sulfuric acid was stirred for 20 h at room temperature.
The mixture was diluted with water and extracted with
ethyl acetate, and the extract was analyzed by TLC
using an authentic sample of 1-(1-adamantyl)-3-nitro-
1,2,4-triazole [21].
vol. 37, no. 1, p. 101.
13. Poplavskaya, Yu.V., Trifonov, R.E., Shcherbinin, M.B.,
and Koldobskii, G.I., Russ. J. Org. Chem., 2000,
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p. 3725.
Reaction of 1-phenyltetrazole-5-thione (I) with
adamantan-1-ol (equimolar reactant ratio) in a
mixture of phosphoric and acetic acids. A solution
of 0.0059 mol of adamantan-1-ol and 0.0056 mol of
1-phenyltetrazole-5-thione (I) in 25 ml of a mixture
of phosphoric and acetic acids (4:1, by weight) was
stirred for 1.5 h at 50 60 C. The mixture was diluted
with cold water, the precipitate was filtered off,
washed with water, dried, and treated with hot hexane,
and the undissolved material was crystallized from
propan-2-ol to obtain 0.08 g (4%) of compound III.
From the hexane extract we isolated 0.14 g (8%) of
5-(1-adamantylsulfanyl)-1-phenyltetrazole (IV). Dilute
perchloric acid was added to the aqueous filtrate, and
the precipitate was filtered off and washed with water.
Yield of tetrazolium perchlorate Vb 1.40 g (46%).
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RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 77 No. 12 2007