Tetrazoles: LVII. Preparation and chemical properties of 1-substituted 5-arylsulfonyltetrazoles

Article abstract of DOI:10.1134/S1070428013050229

Oxidation of 1-substituted 5-arylsulfanyltetrazoles with m-chloroperoxybenzoic acid and NaIO₄ in the presence of RuCl ₃ leads to the formation of the 5-arylsulfonyltetrazoles. The microwave activation significantly accelerates the ox

Full text of DOI:10.1134/S1070428013050229

ISSN 1070-4280, Russian Journal of Organic Chemistry, 2013, Vol. 49, No. 5, pp. 754−757. © Pleiades Publishing, Ltd., 2013.
Original English Text © L.V. Myznikov, U.N. Dmitrieva, T.V. Artamonova, S.V. Vorona, N.P. Novoselov, Yu.E. Zevatskiy, 2013, published in Zhurnal Organiches-
koi Khimii, 2013, Vol. 49, No. 5, pp. 771−774.
To the memory of Professor G.I. Koldobskii
Tetrazoles: LVII.* Preparation and Chemical
Properties of 1-Substituted 5-Arylsulfonyltetrazoles
L. V. Myznikov, U. N. Dmitrieva, T. V. Artamonova, S. V. Vorona,
N. P. Novoselov, and Yu. E. Zevatskiy
St. Petersburg State University of Technology and Design, St. Petersburg,191186 Russia
e-mail: myznikov_lv@mail.ru
Received November 9, 2012
Abstract—Oxidation of 1-substituted 5-arylsulfanyltetrazoles with m-chloroperoxybenzoic acid and NaIO4 in the
presence of RuCl3 leads to the formation of the 5-arylsulfonyltetrazoles. The microwave activation significantly
accelerates the oxidation with sodium periodate. The phenylsulfonyl group in compounds obtained underwent
the nucleophilic substitution when treated with ethanol, phenol, or benzimidazole in acetonitrile in the presence
of NaOH.
DOI: 10.1134/S1070428013050229
Substituted sulfonyltetrazoles are promising sub-
stances in view of their biological activity [1] and the pos-
sibility of their application to further functionalization of
tetrazoles [2], yet compared to the 1-substituted 5-alkylsul-
fonyltetrazoles methods of the synthesis and the chemical
properties of the corresponding 5-arylsulfonyltetrazoles
are poorly understood. Recently certain advances were
observed in the development of the method of copper-
catalyzed arylation of heterocyclic thiols, in particular,
the substituted 5-mercapto-tetrazoles [3]. Therefore
the oxidation of the respective 5-arylsulfanyltetrazoles
seems to be the simplest procedure for the preparation
of 1-substituted 5-arylsulfonyltetrazoles.
1-phenyltetrazol-5-one.
In continuation of the examination of the preparation
procedures for the 5-aryl-sulfonyltetrazoles we
studied the oxidation of a series of 1-substituted
5-arylsulfanyltetrazoles with hydrogen peroxide in
acetic acid, with hydrogen peroxide in acetone, with
hydrogen peroxide in the presence of tungstates, with
OXONE oxidant (potassium peroxymonosulfate), with
m-chloroperoxybenzoic acid, and with NaIO4 in the
presence of a catalytic quantity of RuCl3.
Among the oxidants we tested the best results were
obtained only at the use of m-chloroperoxybenzoic acid
and NaIO4 in the presence of RuCl3, in the other cases
the oxidation resulted in a mixture of arylsulfinyl-
and arylsulfanyltetrazoles or was accompanied with
the hydrolysis of the reaction products giving the
corresponding tetrazol-5-ones.
We found formerly that 5-(4-toluenesulfinyl)- and
5-tosyl-1-phenyl-1Н-tetrazoles could be obtained by
the oxidation of 5-(4-tolylsulfanyl)-1-phenyl-1Н-
tetrazole with hydrogen peroxide in acetic acid both at
convection heating and under microwave activation [4].
However the oxidation of 1-phenyl-5-phenylsulfanyl-
1H-tetrazole in the same conditions afforded a mixture
of the corresponding sulfinyl- and sulfonyltetrazoles,
and besides raising the temperature or hydrogen
peroxide concentration resulted in the accumulation of
R
R
O
N
N
а, b
N
N
N
N
R'
S
S
R'
N
N
O
Iа_Ie
(а) 3-ClC6H4COOOH, CHCl3; (b) NaIO4, RuCl3, MeCN–H2O;
R = Ph, R’ = Me (a), MeO (b), NO2 (c), H (d); R = Me, R’ =
H (e).
–––––––––––––––––––
*For Communication LVI, see [1].
754

TETRAZOLES: LVII.
755
Oxidation of 1-substituted 5-arylsulfanyltetrazoles at the
convection heating
The oxidation of 1-substituted 5-arylsulfanyltetrazoles
proceeds cleanly at the treatment with a triple excess of
of m-chloroperoxybenzoic acid in chloroform at 40°С
within 0.5–5 h (method а). In the course of the reaction
the formation of intermediate arylsulfinyltetrazoles was
observed, but we failed to isolate them for simultaneously
a considerable amount of the completely oxidized product
was obtained.
Method а
Method b
Comnd.
no.
reaction
reaction
yield, %
yield, %
time, h
time, h
Iа
Ib
Ic
Id
Ie
0.5
0.5
5
93
89
67
96
63
1.5
6
95
70
85
88
–
6
Interestingly, the microwave activation did not affect
this process. The duration of the oxidation and the yields
in the reaction occurring at the dielectric and convection
heating practically coincided.
2
2.5
–
1
At the oxidation of substituted 5-arylsulfanyltetrazoles
with excess NaIO4 in the presence of a catalytic quantity
of RuCl3 (method b) notwithstanding the ratio substrate–
NaIO4 only the corresponding sulfonyltetrazoles were
obtained. The reaction time depends on the amount
of RuCl3 and on the temperature. At the molar ratio
RuCl3–(Id) equal ~1 : 10000 the reaction goes to the
completion within 48 h at the room temperature, at 70°С
under convection heating, within 2–2.5 h, and at the
microwave activation at this temperature, in 3 min. The
yields were 91, 92, and 96% respectively. The quantity of
RuCl3 may be reduced to ~1 : 1000000 without essential
decrease in the yield and increase in the reaction duration
(see the table).
ethanol in acetonitrile at room temperature. Good yields
with phenol and benzimidazole we succeeded to obtain
only in DMF medium, and the attempts to carry out the
reactions with piperidine and malonodinitrile under the
above conditions were unsuccessful. At heating in all
events 1-phenyl-tetrazole-5-one was obtained.
Ph
Ph
O
S
N
N
RH, NaOH
MeCN
N
N
N
N
R
N
IIа_IIc
N
O
Id
Iг
R = EtO (а), PhO (b), benzimidazolyl (c).
Thus the developed methods of oxidation of 1-sub-
stituted 5-arylsulfanyltetrazoles made it possible to obtain
1-substituted 5-arylsulfonyltetrazoles in good yields. It was
shown that the microwave activation significantly acceler-
ated the oxidation of 1-substituted 5-arylsulfanyltetrazoles
with sodium periodate and did not affect their oxidation
with m-chloroperoxybenzoic acid.
Aplying the mentioned oxidants we synthesized a
series of 1-substituted 5-arylsulfanyltetrazoles.
One method of tetrazoles functionalization consists in
the substitution of leaving groups at the carbon atom of
the heterocycle. First of all the nucleophilic substitution
in the series of 1-R-5-halotetrazoles [5] and electrophilic
substitution of the hydrogen in the 1-substituted tetrazoles
[6] should be mentioned. However the substituted
5-halotetrazoles are difficultly available compounds,
and the hydrogen substitution requires severe condi-
tions and can be used only with the limited range of
substrates. It was shown before [2] that 1-substituted
5-methylsulfonyltetrazoles possess sufficiently high
reactivity with respect to C-, N-, and O-nucleophiles
of various structures. Besides in [7] the nucleophilic
substitution of the tolylsulfonyl group with aliphatic and
aromatic thiols was used for subsequent functionalization
of tetrazoles.
EXPERIMENTAL
IR spectra were recorded on a spectrophotometer
Shimadzu FTIR-8400S from pellets with KBr. 1Н NMR
spectra were registered on a spectrometer Bruker WM-
400 (400 MHz) from solutions in DMSO-d6. Elemental
analysis was carried out on an analyzer LECO CHNS-
932. The reactions under microwave activation were
performed in a reactor Milestone MicroSynth. The
monitoring of the reaction progress and checking of the
purity and homogeneity of compounds obtained was car-
ried out by TLC on Silufol UV-254 plates. 1-Substituted
5-arylsulfanyl-tetrazoles were prepared by the method [3].
By an example of compound Id we investigated the
nucleophilic substitution with С-, N-, О-nucleophiles by
procedure [2] in acetonitrile in the presence of NaOH.
1-Phenyl-5-phenylsulfonyltetrazole (Id) reacted with
5-Tosyl-1-phenyl-1Н-tetrazole (Iа). а. To a solution
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MYZNIKOV et al.
756
of 0.42 g (1.56 mmol) of 5-(4-tolylsulfanyl)-1-phenyl-1Н-
tetrazole in 12 ml of CHCl3 was added 1.34 g (4.68 mmol)
of 60% 3-chloroperoxybenzoic acid, and the mixture was
stirred for 30 min at 40°С, cooled to room temperature,
and diluted with 12 ml of chloroform. The mixture was
washed in succession with 5% water solution of NaHCO3
(3 × 25 ml), water (2 × 25 ml), and brine (25 ml). The
organic layer was separated, dried with Na2SO4, and
evaporated. Yield 0.43 g (92%), mp 129°С (2-propanol).
627. 1Н NMR spectrum (CDCl3), δ, ppm: 7.67–7.73 m
(5Harom), 8.22–8.25 d (2Harom, J 12 Hz), 8.47–8.50 d
(2Harom, J 12 Hz). Found, %: С 47.01; H 2.70; N 20.97;
S 9.80. C13H9N5O4S. Calculated , %: C 47.13; H 2.74;
N 21.14; S 9.68.
1-Phenyl-5-(phenylsulfonyl)-1Н-tetrazole (Id).
Colorless crystals, mp 135–136°С (2-propanol). IR
spectrum, ν, cm–1: 3083 (C–H), 3070, 3019, 1595, 1581
(C=N), 1499, 1478, 1451, 1427, 1406, 1338, 1327, 1319,
1292, 1274, 1238, 1176, 1167, 1161 (SO2), 1106, 1084,
1073, 1051, 1015, 997, 977, 918, 763, 728, 695, 687, 615.
1Н NMR spectrum (acetone-d6), δ, ppm: 7.68–7.76 m
(7Harom), 7.87–7.93 m (3Harom). Found, %: С 54.65;
H 3.43; N 19.44; S 11.38. C13H10N4O2S. Calculated , %:
C 54.54; H 3.52; N 19.57; S 11.20.
Compounds Ib–Ie were synthesized analogously by
the method а, the reaction time and yields were given in
the table.
b. To a solution of 0.42 g (1.56 mmol) of 5-(4-tolyl-
sulfanyl)-1-phenyl-1Н-tetrazole in 40 ml of acetonitrile
was added a solution of NaIO4 in 20 ml of water and 40 μl
of freshly prepared solution of RuCl3·3H2O (10 mg l–1
RuCl3) in a mixture MeCN–H2O, 2:1. The reaction mix-
ture was stirred for 1.5 h at 70°С and then it was diluted
with 75 ml of water. The separated precipitate was filtered
off. Yield 0.43 g (95%), colorless crystals, mp 129–130°С
[4] (2-propanol). IR spectrum, ν, cm–1: 3061, 3040, 3025,
2924 (С–Н), 1593 (С=N), 1500 (С=С), 1490, 1454, 1418,
1393, 1367 (С–Н bend.), 1289, 1269, 1229, 1167, 1101
(SO2), 1089, 1063, 1042, 1014, 968, 922, 811, 763, 722,
1-Methyl-5-(phenylsulfonyl)-1Н-tetrazole (Ie).
Colorless crystals, mp 92–93°С (2-propanol). IR
spectrum, ν, cm–1: 3096 (C–H), 3070, 1584 (C=N), 1464,
1447, 1400, 1350, 1336, 1311, 1284, 1208, 1188, 1155,
1091 (SO2), 1079, 1068, 758, 741, 718, 689, 679, 610.
1Н NMR spectrum, δ, ppm (CDCl3): 4.42 s (3H, СН3),
7.67–7.71 m (1Harom), 7.81–7.84 m (1Harom), 8.13–8.14 d
(2Нarom, J 4 Hz). Found, %: С 42.78; H 3.68; N 24.91;
S 14.19. C8H8N4O2S. Calculated , %: C 42.85; H 3.60;
N 24.99; S 14.30.
1
689, 620. Н NMR spectrum (acetone-d6), δ, ppm: 2.49 s
1-Phenyl-5-ethoxy-1Н-tetrazole (IIа). To a solution
of 0.2 g (0.69 mmol) of compound Id in 10 ml of aceto-
nitrile was added 1 ml of ethanol and 0.03 g (0.75 mmol)
of NaOH. The mixture was stirred for 30 min and poured
into 50 ml of water, the formed precipitate was filtered off.
Yield 0.08 g (62%), colorless crystals, mp 70°С (EtOH)
[2]. IR spectrum, ν, cm–1: 3074, 2988, 2941, 2904, 2867,
1711, 1595, 1572, 1506, 1476, 1457, 1442, 1388, 1362,
1320, 1302, 1138, 1115, 1071, 1030, 990, 902, 816, 764,
(3H, CH3), 7.51–7.52 d (2Нarom, J 4 Hz), 7.68–7.72 m
(5Harom), 7.74–7.75 d (2Нarom, J 4 Hz).
Syntheses of compounds Iа–Id by the method b under
the microwave heating were similarly performed. The
reaction time and yields under convection heating were
given in the table.
5-[(4-Methoxyphenyl)sulfonyl]-1-phenyl-1Н-
tetrazole (Ib). Colorless crystals, mp 135–136°С
(AcOH–H2O, 3:1). IR spectrum, ν, cm–1: 3100, 3080,
2971, 2845, 1597 (C=N), 1578, 1498, 1459, 1419, 1340,
1319, 1272, 1186, 1157, 1088, 1023, 1015, 843, 807,
763, 678, 601. 1Н NMR spectrum (CDCl3), δ, ppm:
3.39 s (3H, CH3), 7.04–7.07 d (2Нarom, J 12 Hz), 7.62–
7.65 m (5Harom), 7.87–7.90 d (2Нarom, J 12 Hz). Found,
%: С 52.99; H 4.09; N 17.63; S 10.19. C14H12N4O3S.
Calculated , %: C 53.16; H 3.82; N 17.71; S 10.14.
1
733, 688, 683. Н NMR spectrum (DMSO-d6), δ, ppm:
1.36–1.38 t (3H, Me, J 4 Hz), 4.53–4.63 q (2H, CH2),
7.29–7.51 m (5Harom).
1-Phenyl-5-phenoxy-1H-tetrazole (IIb). To a
solution of 0.2 g (0.69 mmol) of compound Id in 10 ml of
DMF was added 0.065 g (0.70 mmol) of phenol and 0.03 g
(0.75 mmol) of NaOH. The mixture was stirred for 1.5 h
and poured into 50 ml of water, the formed precipitate
was filtered off. Yield 0.16 g (96%), colorless crystals,
mp 124–125°С (EtOH) [2]. IR spectrum, ν, cm–1: 3067,
2961, 1597, 1539, 1508, 1480, 1454, 1324, 1297, 1286,
1179, 1157, 1121, 1103, 1074, 1048, 1018, 848, 803,
5-[(4-Nitrophenyl)sulfonyl]-1-phenyl-1Н-tetrazole
(Ic). Colorless crystals, mp 176–177°С (2-propanol–
DMF, 5:1). IR spectrum, ν, cm–1: 3114 (C–H), 3066
(C–H), 1609 (C=N), 1545 (NO2), 1534, 1497, 1457,
1405, 1370 (NO2), 1347, 1317, 1310, 1291, 1227, 1171
(SO2), 1110, 1084, 1012, 856, 761, 751, 743, 691, 679,
1
768, 737, 691. Н NMR spectrum (DMSO-d6), δ, ppm:
7.24–7.34 m (5Harom), 7.45–7.67 m (5Harom).
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TETRAZOLES: LVII.
1995, vol. 31, p. 1726.
757
5-(Benzimidazol-1-yl)-1-phenyl-1H-tetrazole (IIc)
was obtained similarly. Yield 55%, colorless crystals, mp
189°С (EtOH) [2]. IR spectrum, ν, cm–1: 3129, 3075,
1711, 1595, 1557, 1498, 1442, 1350, 1303, 1281, 1249,
1172, 1118, 1095, 990, 969, 883, 781, 770, 763, 742,
690, 618. 1Н NMR spectrum (DMSO-d6), δ, ppm:
7.16–7.34 m (2Harom), 7.46–7.74 m (2Harom), 7.54 m
(5Harom), 7.92 s (1Harom).
3. Niu, L.-F., Cai, Y., Liang, C., Hui, X.-P., and Xu, P.-F., Tet-
rahedron, 2011, vol. 67, p. 2878; Dmitrieva, U.N., Ramsh,
S.M., Zevatskii, Yu.E., Artamonova, T.V., and Myznikov,
L.V., Khim. Geterotsikl. Soedin., 2012, p. 377.
4. Dmitrieva, U.N., Zevatskii, Yu.E., Ramsh, S.M.,
Artamonova, T.V., and Myznikov, L.V., Khim.
Geterotsikl. Soedin., 2012, p. 404.
5. Frija, L., Khmelinskii, I.V., and Lurdes, C.M., J. Org.
Chem., 2006, vol. 71, p. 3583.
6. Spulak, M., Lubojacky, R., Senel, P., and Kunes, J., Pour,
M. J. Org. Chem., 2010, vol. 75, p. 241.
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