2-Halobenzoyl chlorides in the synthesis of [1,3,4]thiadiazolo[3,2-a]quinazolin-5-one derivatives

Article abstract of DOI:10.1134/S1070428017120156

New nitro and sulfonamide derivatives of [1,3,4]thiadiazolo[3,2-a]quinazolin-5-one have been synthesized by cyclocondensation of 1,3,4-thiadiazol-2-amines with 2-halobenzoyl chlorides containing electron-withdrawing substituents in positions 3, 4, and 5. An improved procedure has been proposed for the preparation of intermediate 2-fluoro-N-(5-methyl-1,3,4-thiadiazol-2-yl)benzamides containing a sulfamoyl group in the 5-position via selective acylation of 5-methyl-1,3,4-thiadiazol-2-amine with 5-chlorosulfonyl-2-fluorobenzoyl chloride, followed by sulfonylation of amines.

Full text of DOI:10.1134/S1070428017120156

ISSN 1070-4280, Russian Journal of Organic Chemistry, 2017, Vol. 53, No. 12, pp. 1870–1877. © Pleiades Publishing, Ltd., 2017.
Original Russian Text © R.M. Shlenev, A.V. Tarasov, S.I. Filimonov, P.A. Agat’ev, A.S. Danilova, K.Yu. Suponitskii, 2017, published in Zhurnal
Organicheskoi Khimii, 2017, Vol. 53, No. 12, pp. 1834–1841.
2-Halobenzoyl Chlorides in the Synthesis
of [1,3,4]Thiadiazolo[3,2-a]quinazolin-5-one Derivatives1
R. M. Shleneva,* A. V. Tarasova, S. I. Filimonova, P. A. Agat’eva,
A. S. Danilovaa, and K. Yu. Suponitskiib
a Yaroslavl State Technical University, Moskovskii pr. 88, Yaroslavl, 150023 Russia
*e-mail: schlenev.roman@yandex.ru
b Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences,
ul. Vavilova 28, Moscow, 119991 Russia
Received July 14, 2016
Abstract—New nitro and sulfonamide derivatives of [1,3,4]thiadiazolo[3,2-a]quinazolin-5-one have been syn-
thesized by cyclocondensation of 1,3,4-thiadiazol-2-amines with 2-halobenzoyl chlorides containing electron-
withdrawing substituents in positions 3, 4, and 5. An improved procedure has been proposed for the preparation
of intermediate 2-fluoro-N-(5-methyl-1,3,4-thiadiazol-2-yl)benzamides containing a sulfamoyl group in the
5-position via selective acylation of 5-methyl-1,3,4-thiadiazol-2-amine with 5-chlorosulfonyl-2-fluorobenzoyl
chloride, followed by sulfonylation of amines.
DOI: 10.1134/S1070428017120156
Cyclocondensation of benzoyl chlorides containing
an activated halogen atom in the 2-position with het-
erocyclic N,N′-binucleophiles [1–6] provides a promis-
ing method for the synthesis of [a]- and [b]-fused
quinazolines, as well as for indirect introduction of
various functional groups into the quinazoline ring
system. However, although a wide series of quinazo-
line derivatives have been obtained in this way, there
are no published data on participation of 2-amino-
1,3,4-thiadiazoles in analogous transformations.
The goal of the present work was to study how the
halogen nature, as well as the nature and position of
Scheme 1.
O
N
O
O
N
R1
R4
R1
R2
R1
R2
N
S
Cl
N
N
N
DMF, ∆
MeCN
H
+
H2N
R4
N
S
Hlg
Hlg
S
R2
4a–4d
N
R3
R3
Me
1a–1c, 1e–1j
2a, 2b
3a–3c, 3e–3n
N
O
O
N
N
N
MeCN
S
Cl
N
+
H
H2N
S
N
Cl
N
Cl
1d
2a
3d
1, Hlg = Cl: R1 = MpSO2 (Mp = morpholin-4-yl), R3 = H, R2 = H (a), Cl (b); R1 = R3 = H, R2 = NO2 (c); R1 = NO2, R3 = H,
R2 = H (e), Cl (f); R2 = R3 = NO2, R1 = MpSO2 (g), NO2 (h); Hlg = F, R2 = R3 = H, R1 = MpSO2 (i), NO2 (j); 2, R4 = H (a), Me (b);
3, Hlg = Cl, R4 = H: R1 = MpSO2, R3 = H, R2 = H (a), Cl (b); R1 = R3 = H, R2 = NO2 (c); R1 = NO2, R3 = H, R2 = H (e), Cl (f);
R1 = MpSO2, R2 = H, R3 = NO2 (g); R1 = MpSO2, R2 = H, R3 = NO2, R4 = Me (h); R1 = R3 = NO2, R2 = H, R4 = H (i), Me (j);
Hlg = F: R1 = MpSO2, R2 = R3 = H, R4 = H (k), Me (l); R1 = NO2, R2 = R3 = H, R4 = H (m), Me (n); 4, R1 = MpSO2, R2 = NO2 (a);
R1 = R2 = NO2 (b); R1 = MpSO2, R2 = H (c); R1 = NO2, R2 = H (d).
1 Supporting information is available at http://link.springer.com/.
1870

2-HALOBENZOYL CHLORIDES IN THE SYNTHESIS OF [1,3,4]THIADIAZOLO...
1871
Cyclocondensation of 5-substituted 2-halo-N-(1,3,4-thiadia-
zol-2-yl)benzamides 3a–3n (Scheme 1)
other substituents, in aromatic acid chlorides 1a–1j
affects the possibility of their non-catalytic cyclocon-
densation with 1,3,4-thiadiazol-2-amines 2a and 2b to
produce new [1,3,4]thiadiazolo[3,2-a]quinazolin-5-one
derivatives 4 (Scheme 1). The substituents in com-
pounds 1 were selected so that to ensure different
degrees of activation of the halogen atom. The acyla-
tion of 2 with acid chlorides 1 was carried out in
acetonitrile using 2 equiv of amine 2, and the cyclo-
condensation of amides 3 thus obtained was accom-
plished by heating in boiling DMF for 3 h (see table).
Run no.
Initial amide
Product
Yield, %
a
01
02
03
04
05
06
07
08
09
10
11
12
13
14
3a
3b
3c
3d
3e
3f
3a
3b
3c
3d
3e
–
–
a
–
a
–
a
–
a
–
b
–
c, d
3g
3h
3i
–
–
70d
b, d
The reactivity of the chlorine atom in intramolec-
ular nucleophilic substitution was estimated in the
series of amides 3a–3n. In comparison to previously
studied compounds structurally related to 3a and 3b
but containing a thiazole ring in the amide moiety [7],
the activation of chlorine by sulfamoyl group (morpho-
line-4-sulfonyl, MpSO2) was no longer sufficient even
if an additional electron-withdrawing substituent
(chlorine atom) was present in the 4-position of the
aromatic ring of 3b. After heating for 3 h in DMF, only
initial compounds 3a and 3b were isolated from the
reaction mixtures (see table; run nos. 1, 2); they were
identified by TLC and melting points.
4a
–
–
3j
4b
–
74e
b
3k
3l
–
4c
–
53
b
3m
3n
–
4d
58
a
Only the initial amide was isolated from the reaction mixture.
In the H NMR spectrum, the NH signal intensity decreased,
b
1
indicating replacement of the halogen atom, but the product
structure did not correspond to formula 4.
Neither product nor initial compound was isolated.
Reaction time 40 min, temperature 130°C.
c
d
e
Attempts to increase the reactivity of the chlorine
atom by replacing the sulfamoyl group by endocyclic
nitrogen atom (pyridine derivative 3d) or nitro group
in position 4 or 5 were also unsuccessful, and we failed
to obtain cyclization products 4 from amides 3c–3e
(run nos. 3–5). In these cases, only the initial com-
pounds were isolated from the reaction mixtures. The
cyclocondensation was achieved only with compound
3f possessing an additional electron-withdrawing sub-
stituent (chlorine atom) in the meta position to the
Reaction time 15 min, temperature 130°C.
isolated or identified. Presumably, in this case, as well
as in run no. 6, cyclic structure 4 undergoes side reac-
tions.2 Analogous results were obtained in run nos. 9
and 10. Quinazolinone 4b was selectively obtained
O3
C12
O5
C13
C6
1
C4
2-chlorine atom (run no. 6). In the H NMR spectrum
O6
N1
C7
S1
C3
C2
of the product mixture, the NH signal of the amide
fragment had a low intensity, and the electron impact
mass spectrum displayed a peak corresponding to
cyclic molecular ion. Apart from initial amide 3f,
the reaction mixture contained other impurities which
were difficult to identify.
N5
C5
C9
O4
C10
C11
S2
N3
C1
N4
N2
C8
Amide 3h containing a nitro group in the ortho
position with respect to the 2-chlorine atom was
selectively converted to cyclocondensation product 4a
in 70% yield (run no. 8). The reaction time was 40 min
at 130°C. The structure of 4a was determined by X-ray
analysis (see figure). It crystallized as a 1:1 solvate
with DMF.
O2
O1
C14
Structure of the molecule of 2-methyl-7-(morpholine-4-sul-
fonyl)-9-nitro-5H-[1,3,4]thiadiazolo[3,2-a]quinazolin-5-one
(4a) according to the X-ray diffraction data.
2
After heating amide 3g in boiling DMF (run no. 7),
neither initial compound nor cyclization product was
The nature of these side reactions is the subject of a separate
study, and it is not discussed here.
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 53 No. 12 2017

SHLENEV et al.
1872
Scheme 2.
N
O
F
O
O
N
Me
ClSO2
ClSO2
ClSO2
SOCl2, DMF, ∆
2b, MeCN
S
OH
Cl
N
H
F
F
6
5
O
N
O
F
N
RR'NSO2
N
Me
RR'NSO2
RR'NH, MeCN
DMF, ∆
S
N
H
N
S
N
Me
3l, 3o, 3p
4c, 4e, 4f
3l, 4c, RR′N = morpholin-4-yl; 3o, 4e, RR′N = piperidin-1-yl; 3p, 4f, R = R′ = H.
only from amide 3j. The reaction with 3j was shorter
than with 3h due to stronger activation of the chlorine
atom in the former. As in the above cases, the structure
of the product obtained from amide 3i did not corre-
51 and 36% yield, respectively. The structure of 4e and
4f was confirmed by IR, 1H NMR, and mass spectra.
The results of the present study are consistent with
those discussed previously [7] for analogous cyclocon-
densations of 2-halobenzoyl chlorides with 2-amino-
thiazoles. In these nucleophilic substitution reactions,
the fluorine atom is a better nucleofuge than chlorine.
The yield of quinazolinones 4 increases with increase
in the overall electron-withdrawing power of substit-
uents in initial benzamides 3. Selective formation of
quinazolinones 4 is observed only in reactions of
amides 3 derived from 5-methyl-1,3,4-thiadiazol-
2-amine (2b). Presumably, this is the reason why no
data have been reported on reactions of compounds
like 1 with 1,3,4-thiadiazol-2-amine (2a).
1
spond to 4. However, its H NMR spectrum lacked
amide NH signal, and no molecular ion of 3i was
observed in its electron impact spectrum, which
indicated replacement of the chlorine atom. Thus, the
presence of a methyl group in the 1,3,4-thiadiazole
fragment prevents further transformations of cyclic
structure 4 (R = Me).
The 2-fluorine atom in amides 3 was much more
active in the examined nucleophilic substitution reac-
tions (run nos. 11–14), and the presence of three
electron-withdrawing groups in the aromatic ring is not
necessary. We succeeded in obtaining target quinazo-
linones in run nos. 12 and 14. Unlike the chlorine atom
in 3a and 3e, the activation of fluorine in amides 3l and
3n by both sulfamoyl and nitro group in the para
position is sufficient to ensure cyclocondensation. In
run nos. 11 and 13, the reactions were accompanied by
further transformations of cyclization products 4. In
EXPERIMENTAL
1
The H NMR spectra were recorded on Bruker
DRX-400 (400 MHz) and DRX-500 (500 MHz) spec-
trometers, and the 13C NMR spectra were measured
on a Bruker DRX-500 spectrometer (125 MHz);
DMSO-d6 was used as solvent, and tetramethylsilane,
as internal standard. The IR spectra were recorded on
a Perkin Elmer RX-1 spectrometer from samples
dispersed in mineral oil. The mass spectra (electron
impact, 70 eV) were obtained on a Finnigan MAT
Incos 50 instrument with direct sample admission into
the ion source (ion source temperature 100–220°C), as
well as with a Shimadzu Prominence LCMS-2020
HPLC/MS system (Shim-pack XR-ODS II column;
eluent acetonitrile–0.1% AcOH for compounds 3 or
acetonitrile–DMSO for 4; temperature 40°C).
1
the H NMR spectra of the products we observed no
NH signals typical of initial amides 3k and 3m, and
signals from the aromatic protons changed their shape
due to disappearance of H–F coupling as a result of
substitution of the fluorine atom.
Successful synthesis of quinazolinone 4c from
amide 3l opens prospects of preparing a wide series of
analogous sulfonamide derivatives. The procedure for
the synthesis of initial compounds 3 [7] can be
improved following the reaction sequence shown in
Scheme 2. In this case, the yield of sulfonyl chloride 6
was 93%, and compounds 4e and 4f were isolated in
X-Ray analysis of compound 4a. The X-ray dif-
fraction data for compound 4a were obtained at 120 K
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 53 No. 12 2017

2-HALOBENZOYL CHLORIDES IN THE SYNTHESIS OF [1,3,4]THIADIAZOLO...
1873
on a Smart APEX2 CCD diffractometer (Mo Kα radia-
tion, λ 0.71073 Å; graphite monochromator; ω-scan-
ning, 2θ < 52°]. Monoclinic crystals, 1:1 solvate with
DMF, C14H13N5O6S2·C3H7NO; unit cell parameters:
a = 15.3233(8), b = 12.5903(7), c = 22.5104(12) Å;
β = 102.7170(10)°; V = 4236.3(4) Å3; Z = 8; space
group C2/c; μ = 0.305 mm–1; dcalc = 1.519 g/cm3.
Intensities of 26206 reflections were measured and
processed by SAINT and SADABS implemented in
APEX2 [8]. The structure was solved by the direct
method and was refined against F2hkl by the full-matrix
least-squares method in anisotropic approximation for
non-hydrogen atoms. Hydrogen atoms were placed in
geometrically calculated positions and were refined
according to the riding model. The refinement proce-
(6.0), 56 (58.2), 54 (5.0), 45 (12.8), 42 (6.3), 29 (9.0),
28 (20.8), 18 (7.2), 16 (15.5), 14 (25.1). Found, %:
C 40.03; H 3.36; N 14.34. C13H13ClN4O4S2. Calculat-
ed, %: C 40.15; H 3.37; N 14.41. M 388.85.
Compounds 3b–3n were synthesized in a similar
way.
2,4-Dichloro-5-(morpholine-4-sulfonyl)-N-(1,3,4-
thiadiazol-2-yl)benzamide (3b). Yield 0.441 g (75%),
white crystals, mp 138–142°C. IR spectrum, ν, cm–1:
3164, 3098, 3081 (N–H), 3059 (C–Harom), 1699, 1680,
1672 (C=O, C=N), 1564 (δNH), 1327, 1160 (SO2),
1297, 1260, 1112, 1086, 1066, 1052, 952, 908, 842,
1
758, 714, 680, 589. NMR spectrum (500 MHz), δ,
ppm (J, Hz): 3.24 t [4H, N(CH2)2, 3J = 4.7], 3.63 t [4H,
O(CH2)2, 3J = 4.7], 8.13 s (1H, 3-H), 8.28 s (1H, 6-H),
9.29 s (1H, 5′-H), 13.00–13.67 br.s (1H, CONH). Mass
spectrum, m/z (Irel, %): 389 (2.8) [M – Cl]+, 387 (6.5),
324 (9.1), 323 (5.1), 322 (13.7), 287 (9.4), 277 (10.1),
276 (6.5), 275 (49.8), 273 (72.8), 264 (5.5), 245 (6.2),
239 (14.0), 237 (19.6), 203 (5.0), 189 (6.5), 175 (8.0),
174 (25.2), 173 (14.2), 172 (38.4), 147 (6.3), 146
(19.0), 145 (10.4), 144 (24.3), 138 (5.8), 137 (5.7), 128
(5.2), 111 (7.4), 110 (6.2), 109 (18.0), 87 (6.3), 86
(83.5), 84 (20.5), 75 (5.4), 74 (13.7), 57 (7.8), 56
(100), 54 (8.1), 45 (19.0), 42 (10.3), 41 (6.3), 32
(5.3), 30 (6.0), 29 (14.5), 28 (36.3), 27 (7.7), 16 (9.4),
14 (16.6). Found, %: C 37.03; H 2.83; N 13.18.
C13H12Cl2N4O4S2. Calculated, %: C 36.89; H 2.86;
N 13.24. M 423.29.
dure involved 4146 independent reflections (Rint
=
0.0340). Final divergence factors: wR2 = 0.1009 (all
independent reflections), R1 = 0.0366 [3528 reflections
with I > 2σ(I)]. All calculations were performed using
SHELXTL [9] on an IBM PC AT. The X-ray
diffraction data for compound 4a were deposited to the
Cambridge Crystallographic Data Centre (CCDC entry
no. 1562900).
Initial compounds 1 and 5 were synthesized accord-
ing to standard procedures for the preparation of acid
chlorides [10], by treatment of the corresponding acids
with thionyl chloride in the presence of a catalytic
amount DMF, and were immediately subjected to
further transformations.
2-Chloro-5-(morpholine-4-sulfonyl)-N-(1,3,4-
thiadiazol-2-yl)benzamide (3a). Amine 2a, 0.312 g
(3.085 mmol), was added at room temperature to
a solution of 0.5 g (1.542 mmol) of benzoyl chloride
1a in 5 mL of acetonitrile. The mixture was stirred for
15 min and diluted with 40 mL of water, and the
precipitate was filtered off and purified by recrystal-
lization from DMF–water (1:2). Yield 0.407 g (68%),
white crystals, mp 229–232.5°C. IR spectrum, ν, cm–1:
3232, 3131 (N–H), 1689 (C=O), 1590 (C=Carom), 1547
(δN–H), 1354, 1306, 1172 (SO2), 1263, 1222, 1141,
1114, 1072, 1052, 1031, 949, 910, 840, 807, 778, 724,
2-Chloro-4-nitro-N-(1,3,4-thiadiazol-2-yl)benz-
amide (3c). Yield 0.387 g (60%), white crystals,
mp 263–266°C. IR spectrum, ν, cm–1: 3137, 3098
(N–H), 1685 (C=O), 1540, 1517 (NO2, δNH), 1364,
1320 (NO2), 1258, 1228, 1134, 1115, 1053, 1034, 918,
1
894, 864, 830, 786, 767, 753, 733, 683, 667. H NMR
spectrum (500 MHz), δ, ppm (J, Hz): 8.00 d (1H, 6-H,
3J = 8.4), 8.32 d.d (1H, 5-H, 3J = 8.4, 4J = 2.2), 8.44 d
4
(1H, 3-H, J = 2.2), 9.31 s (1H, 5′-H), 13.50 br.s (1H,
CONH). Mass spectrum, m/z (Irel, %): 286 (11.6) [M]+,
285 (4.9), 284 (29.9) [M]+, 256 (12.2), 251 (6.5),
250 (13.8), 249 (96.0), 222 (5.1), 221 (42.2), 186
(36.6), 185 (9.0), 184 (100), 154 (9.6), 140 (15.1), 138
(43.0), 128 (8.4), 126 (19.1), 112 (7.1), 110 (18.2), 75
(15.2), 74 (8.2), 45 (5.8). Found, %: C 38.06;
H 1.78; N 19.76. C9H5ClN4O3S. Calculated, %:
C 37.97; H 1.77; N 19.68. M 284.68.
1
691, 670, 642, 606. H NMR spectrum (500 MHz), δ,
ppm (J, Hz): 2.96 t [4H, N(CH2)2, 3J = 4.7], 3.65 t [4H,
O(CH2)2, 3J = 4.7], 7.89 m (2H, 3-H, 4-H), 8.07 d (1H,
6-H, 4J = 1.8), 9.29 s (1H, 5′-H), 13.29–13.43 br.s (1H,
CONH). Mass spectrum, m/z (Irel, %): 353 (15.3)
[M – Cl]+, 345 (7.0), 290 (7.9), 289 (5.4), 288 (20.0),
253 (5.0), 241 (38.2), 240 (14.4), 239 (100), 230 (7.0),
223 (8.7), 205 (8.8), 203 (24.1), 203 (14.6), 141 (7.2),
140 (13.2), 139 (23.7), 138 (33.4), 128 (6.4), 112
(11.8), 111 (7.9), 110 (31.0), 86 (59.9), 75 (21.22), 74
2-Chloro-N-(1,3,4-thiadiazol-2-yl)pyridine-3-car-
boxamide (3d). Yield 0.320 g (47%), white crystals,
mp 215–217°C. IR spectrum, ν, cm–1: 3395, 3345,
3147, 3100 (N–H), 3070 (C–Harom), 1680 (C=O), 1645
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 53 No. 12 2017

SHLENEV et al.
1874
(C=N), 1616, 1581 (C–Carom), 1562, 1536 (δNH),
1400, 1330, 1221, 1210, 1154, 1130, 1076, 1058,
1034, 986, 916, 890, 848, 814, 784, 758, 726, 699,
(11.3), 75 (8.1), 74 (38.8), 73 (15.6), 69 (5.1), 59 (7.3),
58 (6.0), 46 (12.6), 45 (55.3), 32 (7.4), 30 (21.6), 28
(10.8), 18 (5.0), 14 (5.8). Found, %: C 33.78; H 1.27;
N 17.50. C9H4Cl2N4O3S. Calculated, %: C 33.87;
H 1.26; N 17.56. M 319.12.
1
651, 613. H NMR spectrum (400 MHz), δ, ppm
3
3
(J, Hz): 7.59 d.d (1H, 5-H, J5,6 = 4.9, J5,4 = 7.8),
3
4
8.18 d.d (1H, 4-H, J = 7.8, J = 1.8), 8.58 d.d (1H,
2-Chloro-5-(morpholine-4-sulfonyl)-3-nitro-
N-(1,3,4-thiadiazol-2-yl)benzamide (3g). Yield
0.495 g (84%), yellow crystals, mp 214–216°C. IR
spectrum, ν, cm–1: 3389, 3249, 3196 (N–H), 1690
(C=O), 1656, 1549 (NO2, δNH), 1364, 1350, 1313
(SO2, NO2), 1263, 1219, 1177, 1162 (SO2), 1129, 1103,
1075, 1060, 1036, 947, 902, 892, 845, 832, 811, 772,
3
4
6-H, J = 4.9, J = 1.8), 9.29 s (1H, 5′-H), 13.33 br.s
(1H, CONH). Mass spectrum, m/z (Irel, %): 243 (0.6)
[M + 2H]+, 242 (5.2) [M + H]+, 240 (14.3) [M]+, 206
(6.8), 205 (60.2), 177 (25.9), 142 (32.4), 140 (100),
114 (21.6), 112 (67.1), 85 (10.7), 77 (7.9), 76 (34.3),
51 (7.7), 50 (9.9), 45 (19.1). Found, %: C 40.08;
H 2.10; N 23.20. C8H5ClN4OS. Calculated, %:
C 39.92; H 2.09; N 23.28. M 240.67.
1
754, 719, 692, 634, 602. H NMR spectrum
3
(400 MHz), δ, ppm (J, Hz): 3.05 t [4H, N(CH2)2, J =
3
2-Chloro-5-nitro-N-(1,3,4-thiadiazol-2-yl)benz-
amide (3e). Yield 0.413 g (64%), white crystals,
mp 244–246°C. IR spectrum, ν, cm–1: 3345, 3101
(N–H), 3070 (C–Harom), 1685 (C=O), 1646 (C=N),
1608, 1574 (C=Carom), 1543, 1521 (NO2, δNH), 1314
(NO2), 1269, 1258, 1235, 1218, 1146, 1134, 1114,
1058, 1030, 928, 907, 859, 850, 834, 807, 759, 738,
4.6], 3.66 t [4H, O(CH2)2, J = 4.6], 8.44 d (1H, 6-H,
4J = 1.9), 8.56 d (1H, 4-H, 4J = 1.9), 9.31 s (1H, 5′-H),
13.46 br.s (1H, CONH). Mass spectrum (ESI): m/z 432
(100) [M]+, 396 (26.7). Found, %: C 36.09; H 2.80;
N 16.19. C13H12ClN5O6S2. Calculated, %: C 35.99;
H 2.79; N 16.14. M 433.85.
1
2-Chloro-N-(5-methyl-1,3,4-thiadiazol-2-yl)-
5-(morpholine-4-sulfonyl)-3-nitrobenzamide (3h).
Yield 0.532 g (88%), yellow crystals, mp 233–235°C.
IR spectrum, ν, cm–1: 3373, 3271, 3161 (N–H), 3066
(C–Harom), 1693 (C=O), 1656 (C=N), 1579 (C=Carom),
1545 (NO2, δNH), 1358, 1329 (SO2, NO2), 1294,
1262, 1207, 1176, 1166 (SO2), 1124, 1111, 1074, 1056,
946, 902, 894, 853, 823, 784, 768, 726, 694, 648, 624,
711, 661, 618, 579. H NMR spectrum (400 MHz), δ,
3
ppm (J, Hz): 7.91 d (1H, 3-H, J = 8.8), 8.39 d.d (1H,
3
4
4
4-H, J = 8.8, J = 2.7), 8.64 d (1H, 6-H, J = 2.7),
9.30 s (1H, 5′-H), 13.42 br.s (1H, CONH). Mass spec-
trum, m/z (Irel, %): 286 (4.6) [M]+, 284 (11.9) [M]+, 256
(6.0), 250 (7.4), 249 (60.7), 221 (24.6), 186 (33.6), 185
(8.4), 184 (100), 140 (18.1), 138 (53.2), 128 (7.2), 126
(5.8), 112 (11.1), 110 (35.9), 109 (5.1), 75 (25.2), 74
(16.6), 45 (14.4). Found, %: C 37.85; H 1.76; N 19.78.
C9H5ClN4O3S. Calculated, %: C 37.97; H 1.77;
N 19.68. M 284.68.
1
593, 580. H NMR spectrum (400 MHz), δ, ppm
3
(J, Hz): 2.68 s (3H, CH3), 3.05 t [4H, N(CH2)2, J =
3
4.6], 3.66 t [4H, O(CH2)2, J = 4.6], 8.41 d (1H, 6-H,
4
4J = 2.1), 8.54 d (1H, 4-H, J = 2.1), 13.29 br.s (1H,
2,4-Dichloro-5-nitro-N-(1,3,4-thiadiazol-2-yl)-
benzamide (3f). Yield 0.398 g (63%), white crystals,
mp 247–249°C. IR spectrum, ν, cm–1: 3094 (N–H,
C–Harom), 1682 (C=O), 1642 (C=N), 1600 (C=Carom),
1552, 1526 (NO2, δNH), 1354, 1337, 1317 (NO2),
1288, 1270, 1241, 1218, 1154, 1125, 1091, 1036, 958,
CONH). Mass spectrum, m/z (Irel, %): 412 (1.4)
[M – Cl]+, 411 (1.7), 347 (6.5), 300 (21.4), 299 (8.7),
298 (54.6), 291 (20.2), 287 (9.3), 276 (10.1), 262
(15.6), 261 (15.1), 252 (14.0), 248 (7.6), 216 (13.3),
215 (18.1), 200 (5.3), 187 (7.3), 184 (8.0), 183 (10.5),
157 (9.2), 142 (30.2), 138 (6.3), 137 (6.8), 116 (6.3),
115 (64.5), 111 (11.1), 110 (5.6), 109 (25.9), 99 (5.2),
88 (5.7), 87 (8.4), 86 (100), 84 (6.1), 74 (33.8), 59
(13.7), 56 (36.6), 41 (8.4), 40 (5.8), 38 (6.0), 36 (17.0),
28 (12.2), 18 (15.6), 16 (10.4), 14 (20.4). Found, %:
C 37.65; H 3.14; N 15.69. C14H14ClN5O6S2. Calculat-
ed, %: C 37.54; H 3.15; N 15.64. M 447.87.
1
922, 878, 860, 833, 773, 746, 713, 625. H NMR
spectrum (400 MHz), δ, ppm (J, Hz): 8.24 s (1H, 3-H),
8.58 s (1H, 6-H), 9.30 s (1H, 5′- H), 13.47 br.s (1H,
CONH). Mass spectrum, m/z (Irel, %): 320 (12.8) [M]+,
318 (18.5) [M]+, 292 (9.4), 290 (13.5), 286 (7.7), 285
(60.9), 284 (21.4), 283 (98.5), 257 (19.2), 256 (6.8),
255 (51.8), 249 (9.2), 237 (14.1), 222 (26.1), 221
(15.3), 220 (99.2), 218 (99.7), 186 (6.2), 184 (18.1),
176 (18.0), 175 (9.8), 174 (100), 173 (16.7), 172
(98.1), 162 (8.6), 160 (14.7), 148 (8.1), 147 (5.3), 146
(53.5), 145 (11.1), 144 (93.1), 143 (8.2), 138 (10.3),
137 (8.6), 132 (6.4), 128 (27.8), 111 (17.1), 110 (15.8),
109 (55.8), 108 (15.7), 97 (10.5), 87 (5.1), 86 (7.9), 84
2-Chloro-3,5-dinitro-N-(1,3,4-thiadiazol-2-yl)-
benzamide (3i). Yield 0.409 g (66%), white crystals,
mp 202–205°C. IR spectrum, ν, cm–1: 3355, 3168
(N–H), 3080 (C–Harom), 1675 (C=O), 1608, 1551, 1538
(δNH, NO2), 1377, 1355, 1325 (NO2), 1224, 1176,
1062, 1045, 953, 932, 910, 885, 842, 813, 790, 777,
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 53 No. 12 2017

2-HALOBENZOYL CHLORIDES IN THE SYNTHESIS OF [1,3,4]THIADIAZOLO...
1875
1
756, 720. H NMR spectrum (400 MHz), δ, ppm
0.406 g (65%), 0.333 g (58%; as described below for
the synthesis of 3o); white crystals, mp 227–229°C. IR
spectrum, ν, cm–1: 3350, 3328 (N–H), 1674 (C=O),
1610, 1578 (C=Carom), 1539 (δNH), 1349, 1332, 1309,
1171 (SO2), 1263, 1233, 1136, 1125, 1110, 1073, 944,
918, 836, 796, 771, 737, 716, 696, 670, 648, 622, 564.
1H NMR spectrum (400 MHz), δ, ppm (J, Hz): 2.66 s
4
(J, Hz): 8.96 d (1H, 6-H, J = 2.6), 9.10 d (1H, 4-H,
4J = 2.6), 9.32 s (1H, 5′-H), 13.54 br.s (1H, CONH).
Mass spectrum, m/z (Irel, %): 331 (5.8) [M]+, 329 (14.5)
[M]+, 295 (9.6), 294 (74.2), 267 (7.0), 266 (63.1), 248
(8.0), 231 (25.2), 230 (7.1), 229 (77.7), 185 (26.4), 184
(8.7), 183 (80.7), 139 (10.4), 137 (35.9), 128 (81.3),
111 (32.9), 110 (10.4), 109 (100), 101 (5.4), 99 (5.8),
97 (12.3), 88 (8.0), 87 (5.4), 86 (12.7), 85 (5.5), 75
(9.6), 74 (69.4), 69 (10.1), 62 (7.6), 61 (5.8), 59 (7.1),
46 (18.4), 45 (46.4), 32 (5.9), 30 (34.9), 16 (5.0),
14 (9.7). Found, %: C 32.91; H 1.23; N 21.14.
C9H4ClN5O5S. Calculated, %: C 32.79; H 1.22;
N 21.24. M 329.68.
3
(3H, CH3), 2.95 t [4H, N(CH2)2, J = 4.6], 3.65 t [4H,
3
O(CH2)2, J = 4.6], 7.67 pseudo-triplet (1H, 3-H,
3
3
3JHH = JHF = 9.2), 7.99 d.d.d (1H, 4-H, JHH = 9.2,
4JHF = 4.7, JHH = 2.4), 8.13 d.d (1H, 6-H, JHF = 6.3,
4JHH = 2.4), 13.22 br.s (1H, CONH). Mass spectrum
(ESI): m/z 387 (Irel 100%) [M]+. Found, %: C 43.40;
H 3.89; N 14.55. C14H15FN4O4S2. Calculated, %:
C 43.51; H 3.91; N 14.50. M 386.42.
4
4
2-Chloro-N-(5-methyl-1,3,4-thiadiazol-2-yl)-3,5-
dinitrobenzamide (3j). Yield 0.465 g (72%), light
yellow crystals; it was impossible to determine its
melting point because of fast cyclization. IR spectrum,
ν, cm–1: 3148 (N–H), 3076 (C–Harom), 1690 (C=O),
1612, 1589, 1537 (δNH, NO2), 1348 (NO2), 1328,
1316, 1263, 1202, 1164, 1088, 1059, 948, 930, 845,
2-Fluoro-5-nitro-N-(1,3,4-thiadiazol-2-yl)benz-
amide (3m). Yield 0.480 g (73%), white crystals,
mp 235–237°C. IR spectrum, ν, cm–1: 3129, 3107
(N–H), 3078 (C–Harom), 1689 (C=O), 1628 (C=N),
1586, 1489 (C=Carom), 1542, 1526 (NO2, δNH), 1412,
1355, 1328 (NO2), 1313, 1270, 1256, 1244, 1222,
1137, 1120, 1080, 1033, 937, 920, 864, 844, 824, 778,
1
771, 754, 734, 720, 693. H NMR spectrum
1
(400 MHz), δ, ppm (J, Hz): 2.67 s (3H, CH3), 8.93 d
758, 744, 724, 672, 636. H NMR spectrum
4
4
(1H, 6-H, J = 2.5), 9.09 d (1H, 4-H, J = 2.5),
13.45 br.s (1H, CONH). Mass spectrum (ESI), m/z
(Irel, %): 344 (47.3) [M]+, 343 (16.7), 342 (100) [M]+,
306 (24.9), 113 (7.9). Found, %: C 34.81;
H 1.75; N 20.48. C10H6ClN5O5S. Calculated, %:
C 34.94; H 1.76; N 20.38. M 343.70.
(400 MHz), δ, ppm (J, Hz): 7.70 pseudo-triplet (1H,
3
3
3
3-H, JHH = JHF4 = 9.2), 8.51 d.d.d (1H, 4-H, JHH
=
=
4
4
9.2, JHF = 4.4, JHH = 2.8), 8.69 d.d (1H, 6-H, JHF
4
6.2, JHH = 2.8), 9.28 s (1H, 5′-H), 13.43 br.s (1H,
CONH). Mass spectrum, m/z (Irel, %): 268 (19.3) [M]+,
249 (23.5), 240 (28.2), 221 (11.7), 169 (7.6), 168
(100), 123 (6.3), 122 (86.2), 110 (5.5), 94 (65.3), 74
(6.1), 68 (6.2), 45 (6.8). Found, %: C 40.44; H 1.89;
N 20.79. C9H5FN4O3S. Calculated, %: C 40.30;
H 1.88; N 20.89. M 268.22.
2-Fluoro-5-(morpholine-4-sulfonyl)-N-(1,3,4-
thiadiazol-2-yl)benzamide (3k). Yield 0.484 g (80%),
white crystals, mp 208–209.5°C. IR spectrum, ν, cm–1:
3232, 3167, 3085 (N–H), 1689 (C=O), 1608, 1491
(C=Carom), 1547 (δNH), 1352, 1322, 1171 (SO2), 1297,
1274, 1261, 1230, 1113, 1080, 1070, 1043, 979, 945,
908, 853, 836, 744, 714, 689, 654, 625, 610, 564, 552.
1H NMR spectrum (400 MHz), δ, ppm (J, Hz): 2.95 t
[4H, N(CH2)2, 3J = 4.6], 3.65 t [4H, O(CH2)2, 3J = 4.6],
2-Fluoro-N-(5-methyl-1,3,4-thiadiazol-2-yl)-
5-nitrobenzamide (3n). Yield 0.538 g (78%), white
crystals, mp 194–196°C. IR spectrum, ν, cm–1: 3160,
3120 (N–H), 3081 (C–Harom), 1683, 1674 (C=O), 1630
(C=N), 1586 (C=Carom), 1565, 1526 (NO2, δNH),
1352, 1319 (NO2), 1261, 1205, 1122, 1092, 1072, 934,
913, 865, 847, 837, 746, 724, 673, 649, 634, 621.
1H NMR spectrum (400 MHz), δ, ppm (J, Hz): 2.66 s
3
3
7.69 pseudo-triplet (1H, 3-H, JHH = JHF = 9.2),
8.00 d.d.d (1H, 4-H, 3JHH = 9.2, 4JHF = 4.7, 4JHH = 2.4),
4
4
8.14 d.d (1H, 6-H, JHF = 6.3, JHH = 2.4), 9.28 s (1H,
5′-H), 12.76 br.s (1H, CONH). Mass spectrum, m/z
(Irel, %): 372 (0.8) [M]+, 329 (8.2), 287 (10.4), 272
(11.81), 237 (5.3), 225 (5.0), 224 (13.5), 223 (100),
214 (8.3), 187 (16.7), 123 (9.1), 122 (16.0), 94 (14.2),
86 (15.7), 56 (10.6). Found, %: C 42.09; H 3.53;
N 14.98. C13H13FN4O4S2. Calculated, %: C 41.93;
H 3.52; N 15.04. M 372.40.
(3H, CH3), 7.68 pseudo-triplet (1H, 3-H, 3JHH = 3JHF
=
=
9.2), 8.50 d.d.d (1H, 4-H, 3JHH = 9.2, 4JHF = 4.4, 4JHH
4
4
2.9), 8.69 d.d (1H, 6-H, JHF = 6.2, JHH = 2.9),
13.33 br.s (1H, CONH). Mass spectrum (ESI), m/z
(Irel, %): 283 (47.9) [M]+, 243 (53.6), 143 (100).
Found, %: C 42.64; H 2.51; N 19.77. C10H7FN4O3S.
Calculated, %: C 42.55; H 2.50; N 19.85. M 282.25.
2-Fluoro-N-(5-methyl-1,3,4-thiadiazol-2-yl)-
5-(morpholine-4-sulfonyl)benzamide (3l). Yield
2-Fluoro-N-(5-methyl-1,3,4-thiadiazol-2-yl)-
5-(piperidine-1-sulfonyl)benzamide (3o). Piperidine,
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 53 No. 12 2017

SHLENEV et al.
1876
0.29 mL (2.978 mmol), was added to a mixture of
0.5 g (1.489 mmol) of sulfonyl chloride 6 and 3 mL of
an ice–water mixture. The mixture was stirred for
10 min, diluted with 10 mL of water, and acidified to
pH 2–3 by adding several drops of concentrated
aqueous HCl. The precipitate was filtered off and
purified by recrystallization from DMF–water (1:2).
Yield 0.362 g (63%), white crystals, mp 199–201°C.
IR spectrum, ν, cm–1: 3417, 3333, 3238, 3182 (N–H),
1676 (C=O), 1609, 1549 (δNH), 1345, 1315, 1170
(SO2), 1280, 1262, 1209, 1131, 1108, 1086, 1053,
1027, 964, 933, 918, 835, 795, 766, 732, 671, 654,
(500 MHz), δ, ppm (J, Hz): 2.65 s (3H, CH3), 3.01 t
[4H, N(CH2)2, 3J = 4.5], 3.65 t [4H, O(CH2)2, 3J = 4.5],
4
4
8.49 d (1H, 6-H, J = 1.9), 8.78 d (1H, 8-H, J = 1.9).
13C NMR spectrum (125 MHz), δC, ppm: 45.91 (2C),
65.28 (2C), 120.26, 126.57, 129.81, 130.40, 133.09,
139.31, 157.74, 162.35, 162.68, 167.92. Mass spec-
trum, m/z (Irel, %): 411 (10.9) [M]+, 368 (5.6), 354
(33.3), 348 (5.4), 347 (29.4), 327 (7.5), 325 (22.0), 293
(5.2), 292 (12.3), 291 (85.9), 277 (10.9), 276 (40.8),
263 (8.6), 262 (48.5), 261 (49.4), 216 (21.2), 215
(44.4), 187 (11.6), 116 (6.0), 95 (5.0), 88 (11.5), 87
(7.8), 86 (100), 57 (5.2), 56 (64.4). C14H13N5O6S2.
Calculated: M 411.41.
1
618, 584, 574, 555. H NMR spectrum (400 MHz), δ,
ppm (J, Hz): 1.35–1.42 m (2H, 4″-H), 1.51–1.60 m
(4H, 3″-H, 5″-H), 2.66 s (3H, CH3), 2.95 t (4H, 2″-H,
2-Methyl-7,9-dinitro-5H-[1,3,4]thiadiazolo-
[3,2-a]quinazolin-5-one (4b) was synthesized in
a similar way; reaction time 15 min. Yield 0.197 g
(74%), light brown crystals, mp 276–278°C. IR spec-
trum, ν, cm–1: 1658 (C=O), 1616, 1601 (C=Carom),
1561, 1534, 1348 (NO2), 1262, 1208, 1187, 1152,
1127, 1082, 1022, 954, 944, 928, 887, 830, 792, 780,
3
3
6″-H, J = 5.0), 7.65 pseudo-triplet (1H, 3-H, JHH
=
3JHF = 9.2), 7.98 d.d.d (1H, 4-H, 3JHH = 9.2, 4JHF = 4.7,
4
4
4JHH = 2.4), 8.11 d.d (1H, 6-H, JHF = 6.2, JHH = 2.4),
13.17 br.s (1H, CONH). Mass spectrum (ESI): m/z 385
(Irel 100%) [M]+. Found, %: C 46.97; H 4.44; N 14.65.
C15H17FN4O3S2. Calculated, %: C 46.86; H 4.46;
N 14.57. M 384.45.
1
760, 738, 726, 676, 660, 616. H NMR spectrum
(400 MHz), δ, ppm (J, Hz): 2.65 s (3H, CH3), 8.92 d
4
4
2-Fluoro-N-(5-methyl-1,3,4-thiadiazol-2-yl)-
5-sulfamoylbenzamide (3p) was synthesized in
a similar way. Yield 0.442 g (94%), white crystals,
mp 220–222°C. IR spectrum, ν, cm–1: 3410, 3370,
3267 (N–H), 1670 (C=O), 1610, 1557 (δNH), 1322,
1157 (SO2), 1266, 1246, 1222, 1206, 1109, 1090,
1074, 938, 852, 795, 766, 722, 696, 685, 659, 648,
(1H, 6-H, J = 2.6), 9.29 d (1H, 8-H, J = 2.6). Mass
spectrum (ESI), m/z 308 (Irel 100%) [M]+. Found, %:
C 39.24; H 1.63; N 22.72. C10H5N5O5S. Calculated, %:
C 39.09; H 1.64; N 22.79. M 307.24.
Compounds 4c–3f were synthesized in a similar
way; the reaction mixtures were heated for 3 h under
reflux.
1
598, 581, 569. H NMR spectrum (400 MHz), δ, ppm
2-Methyl-7-(morpholine-4-sulfonyl)-5H-[1,3,4]-
thiadiazolo[3,2-a]quinazolin-5-one (4c). Yield
0.150 g (53%), white crystals, mp 283–285°C. IR
spectrum, ν, cm–1: 3080 (C–Harom), 1658, 1649 (C=O),
1604, 1591, 1509 (C=Carom), 1435, 1350, 1157 (SO2),
1328, 1300, 1262, 1244, 1218, 1190, 1126, 1117, 1102,
1070, 1032, 1009, 951, 927, 906, 883, 853, 833, 786,
(J, Hz): 2.66 m (3H, CH3), 7.52 br.s (2H, SO2NH2),
3
3
7.60 pseudo-triplet (1H, 3-H, JHH = JHF = 8.9),
8.05 d.d.d (1H, 4-H, 3JHH = 8.9, 4JHF = 4.7, 4JHH = 2.5),
4
4
8.20 d.d (1H, 6-H, JHF = 6.5, JHH = 2.5), 13.21 br.s
(1H, CONH). Mass spectrum (ESI), m/z (Irel, %): 317
(100) [M]+, 260 (21.7), 143 (45.0). Found, %: C 37.83;
H 2.88; N 17.78. C10H9FN4O3S2. Calculated, %:
C 37.97; H 2.87; N 17.71. M 316.33.
1
734, 699, 637, 622, 606, 579, 558. H NMR spectrum
(400 MHz), δ, ppm (J, Hz): 2.74 s (3H, CH3), 2.93 t
[4H, N(CH2)2, 3J = 4.5], 3.64 t [4H, O(CH2)2, 3J = 4.6],
8.18 d.d (1H, 8-H, 3J = 8.7, 4J = 1.9), 8.23 d (1H, 9-H,
2-Methyl-7-(morpholine-4-sulfonyl)-9-nitro-
5H-[1,3,4]thiadiazolo[3,2-a]quinazolin-5-one (4a).
A solution of 0.3 g (0.670 mmol) of compound 3h in
3 mL of DMF was heated for 40 min at 130°C. The
mixture was cooled, 2 mL of acetonitrile and 1 mL of
water were added, and the precipitate was filtered off
and dried. Yield 0.194 g (70%), light yellow crystals,
mp 298–300°C. IR spectrum, ν, cm–1: 3074 (C–Harom),
1680, 1658 (C=O), 1611, 1601 (C=Carom), 1559, 1548,
1533 (NO2), 1515, 1410, 1352 (SO2, NO2), 1301,
1264, 1204, 1188, 1161 (SO2), 1134, 1114, 1080, 1016,
955, 926, 908, 896, 876, 854, 799, 786, 752, 742,
4
3J = 8.7), 8.36 d (1H, 6-H, J = 1.9). Mass spectrum
(ESI): m/z 365 (Irel 100%) [M]+. Found, %: C 46.05;
H 3.87; N 15.24. C14H14N4O4S2. Calculated, %:
C 45.89; H 3.85; N 15.29. M 366.42.
2-Methyl-7-nitro-5H-[1,3,4]thiadiazolo[3,2-a]-
quinazolin-5-one (4d). Yield 0.161 g (58%), light
brown crystals, mp 249–251°C. IR spectrum, ν, cm–1:
3080 (C–Harom), 1656 (C=O), 1616, 1600 (C=Carom),
1565, 1519, 1341 (NO2), 1256, 1189, 1158, 1126,
1106, 1062, 1007, 921, 899, 854, 836, 786, 768, 749,
1
722, 668, 657, 640, 612, 579. H NMR spectrum
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 53 No. 12 2017

2-HALOBENZOYL CHLORIDES IN THE SYNTHESIS OF [1,3,4]THIADIAZOLO...
1877
1
684, 662, 635. H NMR spectrum (400 MHz), δ, ppm
m/z 297 (Irel 100%) [M]+. Found, %: C 40.42; H 2.71;
N 18.82. C10H8N4O3S2. Calculated, %: C 40.53;
H 2.72; N 18.91. M 296.33.
3
(J, Hz): 2.74 s (3H, CH3), 8.17 d (1H, 9-H, J = 9.1),
8.63 d.d (1H, 8-H, 3J = 9.1, 4J = 2.5), 8.76 d (1H, 6-H,
4J = 2.5). Mass spectrum (ESI): m/z 263 (Irel 100%)
[M]+. Found, %: C 45.65; H 2.31; N 21.46.
C10H6N4O3S2. Calculated, %: C 45.80; H 2.31;
N 21.36. M 262.24.
REFERENCES
1. Deetz, M.J., Malerich, J.P., Beatty, A.M., and
Smith, B.D., Tetrahedron Lett., 2001, vol. 42, p. 1851.
2-Methyl-7-(piperidine-1-sulfonyl)-5H-[1,3,4]-
thiadiazolo[3,2-a]quinazolin-5-one (4e). Yield
0.145 g (51%), white crystals, mp 240–242°C. IR
spectrum, ν, cm–1: 3073 (C–Harom), 1661, 1651 (C=O),
1604, 1590, 1509 (C=Carom), 1436, 1424, 1342, 1162,
1150 (SO2), 1329, 1315, 1281, 1244, 1211, 1190, 1098,
1053, 1029, 1008, 928, 905, 884, 862, 834, 787, 732,
2. Lipunova, G.N., Nosova, E.V., Laeva, A.A.,
Kodess, M.I., and Charushin, V.N., Russ. J. Org. Chem.,
2005, vol. 41, no. 7, p. 1071.
3. Nosova, E.V., Lipunova, G.N., Laeva, A.A., and
Charushin, V.N., Russ. J. Org. Chem., 2005, vol. 41,
no. 11, p. 1671.
1
4. Nosova, E.V., Lipunova, G.N., Kravchenko, M.A.,
Laeva, A.A., and Charushin, V.N., Pharm. Chem. J.,
2008, vol. 42, no. 4, p. 169.
702, 638, 611, 593, 578. H NMR spectrum
(400 MHz), δ, ppm (J, Hz): 1.32–1.39 (2H, 4′-H),
1.52–1.59 (4H, 3′-H, 5′-H), 2.74 s (3H, CH33), 2.95 t
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5. Nosova, E.V., Laeva, A.A., Trashakhova, T.V.,
Golovchenko, A.V., Lipunova, G.N., Slepukhin, P.A.,
and Charushin, V.N., Russ. J. Org. Chem., 2009, vol. 45,
no. 6, p. 904.
(4H, 2′-H, 6′-H, J = 5.1), 8.18 d.d (1H, 8-H, J = 8.7,
4J = 1.8), 8.22 d (1H, 9-H, J = 8.7), 8.35 d (1H, 6-H,
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4J = 1.8). Mass spectrum (ESI): m/z 365 (Irel 100%)
[M]+. Found, %: C 49.25; H 4.44; N 15.42.
C15H16N4O3S2. Calculated, %: C 49.43; H 4.43;
N 15.37. M 364.44.
6. Nosova, E.V., Lipunova, G.N., and Charushin, V.N.,
Russ. Chem. Rev., 2009, vol. 78, p. 387.
7. Shlenev, R.M., Filimonov, S.I., Tarasov, A.V., Dani-
lova, A.S., and Agat’ev, P.A., Russ. J. Org. Chem., 2016,
vol. 52, no. 1, p. 69.
2-Methyl-7-sulfamoyl-5H-[1,3,4]thiadiazolo-
[3,2-a]quinazolin-5-one (4f). Yield 0.102 g (36%),
white crystals, mp 305–308°C. IR spectrum, ν, cm–1:
3227 (NH2), 1643 (C=O), 1603, 1590 (C–Carom), 1510,
1429, 1357, 1328, 1166 (SO2), 1254, 1191, 1120, 1105,
1061, 917, 903, 838, 795, 787, 766, 669, 640, 619,
586, 566. H NMR spectrum (400 MHz), δ, ppm
(J, Hz): 2.73 s (3H, CH3), 7.61 s (NH2), 8.18 d (1H,
9-H, J = 8.6), 8.26 d.d (1H, 8-H, J = 8.6, J = 2.0),
8.56 d (1H, 6-H, J = 2.0). Mass spectrum (ESI):
8. APEX2, SAINT, Madison, Wisconsin, USA: Bruker
AXS, 2009.
9. Sheldrick, G.M., Acta Crystallogr., Sect. A, 2008,
vol. 64, p. 112.
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10. Becker, H.G.O., et al., Organikum. Organisch-
chemisches Grundpraktikum, Weinheim: Wiley, 2004,
22nd ed. Translated under the title Organikum, Moscow:
Mir, 2008, vol. 2, p. 93.
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RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 53 No. 12 2017