Fused pyrimidine systems: XIV. Reaction of 2-alkenyl(alkynyl) sulfanylpyrido[3,4-d]pyrimidin-4(3H)-ones with arylsulfanyl chlorides

Article abstract of DOI:10.1134/S1070428014060189

2-Allylsulfanylpyrido[3,4-d]pyrimidin-4(3H)-one reacted with arylsulfanyl chlorides in chloroform to give addition products to the exocyclic double bond, which were converted into linearly fused arylsulfanylthiazinopyridopyrimidines by the action of sodiu

Full text of DOI:10.1134/S1070428014060189

ISSN 1070-4280, Russian Journal of Organic Chemistry, 2014, Vol. 50, No. 6, pp. 858–863. © Pleiades Publishing, Ltd., 2014.
Original Russian Text © I.V. Dyachenko, A.I. Vas’kevich, R.I. Vas’kevich, M.V. Vovk, 2014, published in Zhurnal Organicheskoi Khimii, 2014, Vol. 50,
No. 6, pp. 874–879.
Fused Pyrimidine Systems: XIV.* Reaction
of 2-Alkenyl(alkynyl)sulfanylpyrido[3,4-d]pyrimidin-4(3H)-ones
with Arylsulfanyl Chlorides
I. V. Dyachenkoa, A. I. Vas’kevichb, R. I. Vas’kevicha, and M. V. Vovka
a Institute of Organic Chemistry, National Academy of Sciences of Ukraine,
ul. Murmanskaya 5, Kiev, 02660 Ukraine
b “Kiev Polytechnic Institute” National Technical University of Ukraine,
pr. Pobedy 37, Kiev, 03056 Ukraine
e-mail: vaskevich@ioch.kiev.ua
Received December 27, 2013
Abstract—2-Allylsulfanylpyrido[3,4-d]pyrimidin-4(3H)-one reacted with arylsulfanyl chlorides in chloroform
to give addition products to the exocyclic double bond, which were converted into linearly fused arylsulfanyl-
thiazinopyridopyrimidines by the action of sodium acetate. The reactions of 2-allyl(cinnamyl, propargyl)sul-
fanylpyrido[3,4-d]pyrimidin-4(3H)-ones with arylsulfanyl chlorides in the presence of an equimolar amount of
lithium perchlorate afforded angularly fused arylsulfanylmethylthiazolo- and -thiazinopyridopyrimidines.
DOI: 10.1134/S1070428014060189
Intramolecular electrophilic cyclizations of unsatu-
rated compounds containing hetaryl fragments by the
action of arylsulfanyl chlorides provides an efficient
method for building up fused heterocyclic systems
with an arylsulfanylmethyl substituent [2]. Intramolec-
ular electrophilic cyclizations underlay convenient pro-
cedures for the annulation of thiazole and thiazine
rings to fused alkenyl(alkynyl)sulfanylpyrimidine
derivatives (quinazolines, thieno[2,3-d]pyrimidines,
pyrazolo[3,4-d]pyrimidines). It was found that the
reaction direction is determined by both structure of
the heterocyclic fragment in the substrate and reaction
conditions [3–6]. It is also important that factors
controlling the ratio of acyclic and cyclic addition
products have been formulated. In order to elucidate
general relations holding in reactions of fused alkenyl-
Scheme 1.
O
O
SAr
CHCl3
NaOAc
NH
Cl
N
N
N
O
N
N
O
S
N
S
ArSCl
SAr
NH
IIa–IIc
IIIa–IIIc
IVa–IVc
CH2
N
S
I
(1) MeNO2, LiClO4
(2) NaOAc
N
N
N
S
ArS
Va–Vc
Ar = Ph (a), 4-MeC6H4 (b), 4-O2NC6H4 (c).
* For communication XIII, see [1].
858

FUSED PYRIMIDINE SYSTEMS: XIV.
859
Scheme 2.
O
O
N
NH
N
(1) MeNO2, LiClO4
(2) NaOAc
S
NH
+
ArSCl
10
N
N
S
Ph
1
Ph
SAr
VI
IIa–IIc
VIIa–VIIc
Ar = Ph (a), 4-MeC6H4 (b), 4-O2NC6H4 (c).
(alkynyl)sulfanylpyrimidines with arylsulfanyl
chlorides, it is necessary to extend the series of fused
pyrimidine substrates, in particular by inclusion of
systems with reduced basicity of the pyrimidine ring,
which could affect the regioselectivity of ring closure.
we obtained salt-like cyclic compounds which were
treated (without additional purification and analytical
characterization) with an aqueous solution of sodium
acetate. The isolated products were 9-(arylsulfanyl-
methyl)-8,9-dihydro-5H-pyrido[4,3-e][1,3]thiazolo-
[3,2-a]pyrimidin-5-ones Va–Vc (yield 56–67%). Their
angularly fused structure was confirmed by both IR
(νC=O 1650–1660 cm–1) [3–5] and 13C NMR spectra
(δC=O 170 ppm) [1].
In the present article we describe the reactions of
a series of 2-alkenyl(alkynyl)sulfanyl-substituted pyri-
do[3,4-d]pyrimidin-4(3H)-ones І, VІ, and VІІІ with
arylsulfanyl chlorides ІІa–IIc under different condi-
tions. 2-Allylsulfanylpyrido[3,4-d]pyrimidin-4(3H)-
one (І) reacted with arylsulfanyl chlorides ІІa–IIc in
chloroform at room temperature to give addition prod-
ucts to the exocyclic double bond (compounds IІІa–
IIIc) in 52–73% yield (Scheme 1). The formation of
anti-Markovnikov adducts was confirmed by the sub-
sequent intramolecular cyclization of compounds IІІa–
IIIc to 3-arylsulfanyl-3,4-dihydro-2H,6H-pyrido-
[3′,4′:4,5]pyrimido[2,1-b][1,3]thiazin-6-ones ІVa–IVc
by the action of sodium acetate in DMSO at 50°C
(Scheme 1).
Analogous approach was utilized to accomplish
cyclization of compounds VІ and VIII. 2-Cin-
namylsulfanylpyrido[3,4-d]pyrimidin-4(3H)-one (VІ)
reacted with arylsulfanyl chlorides IIa–IIc in nitro-
methane in the presence of LiClO4 to give the corre-
sponding perchlorates which were converted into free
bases VIIa–VIIc by treatment with sodium acetate
(Scheme 2).
The carbonyl stretching vibration band in the IR
spectra of VIIa–VIIc was observed in the region of
1660 cm–1; however, the carbonyl carbon nucleus
resonated in the 13C NMR spectra at δC 163 ppm,
which corresponds better to linearly fused derivatives.
Therefore, homonuclear correlation spectrum of com-
pound VIIc was recorded, which confirmed its angular
structure. In particular, saturation of the 1-H proton
signal revealed its coupling with 10-H (15%) and
ortho-protons in the phenyl group (2%).
The linearly fused structure of compounds ІVa–IVc
is consistent with their IR spectra in which the car-
bonyl stretching vibration band was observed at 1680–
1710 cm–1 [3–6] and with the 13C NMR spectra where
the carbonyl carbon signal appeared at δC 160–
161 ppm [1].
In order to force the reaction of I with arylsulfanyl
chlorides II to afford cyclization products, it was
carried out in nitromethane in the presence of an equi-
molar amount of lithium perchlorate [7, 8]. As a result,
Analogous relations were also observed in the cy-
clization of 2-propargylsulfanylpyrido[3,4-d]pyrimi-
din-4(3H)-one (VIII) which reacted with compounds
Scheme 3.
O
O
O
N
(1) MeNO2, LiClO4
(2) NaOAc
N
N
NaOAc
NH
+
ArSCl
N
N
N
N
N
S
S
S
CH
ArS
IXa–IXc
ArS
Xa, Xb
VIII
IIa–IIc
IX, Ar = Ph (a), 4-MeC6H4 (b), 4-O2NC6H4 (c); X, Ar = Ph (a), 4-O2NC6H4 (b).
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 50 No. 6 2014

DYACHENKO et al.
860
IIa–IIc in nitromethane in the presence of LiClO4, and
the subsequent treatment with sodium acetate at room
temperature produced angularly fused pyrido[4,3-e]-
[1,3]thiazolo[3,2-a]pyrimidin-5-one derivatives IXa–
IXc (Scheme 3). Structurally related 6-propargylsul-
fanylpyrazolo[3,4-d]pyrimidines failed to react under
similar conditions [5].
2-{[3-Chloro-2-(4-methylphenylsulfanyl)propyl]-
sulfanyl}pyrido[3,4-d]pyrimidin-4(3H)-one (IIIb).
Yield 0.19 g (52%), mp 163–170°C. IR spectrum, ν,
cm–1: 1690, 1570, 1520, 1460, 1430, 1330, 1270, 1180,
1050, 980, 820, 810, 690, 650. H NMR spectrum, δ,
ppm: 2.33 s (3H, CH3), 3.55–3.68 m (2H, CH2), 3.82–
3.87 m (1H, CH), 3.92–4.00 m (2H, CH2), 7.22 d (2H,
1
H
arom, J = 7.6 Hz), 7.45–7.79 m (3H, Harom), 7.85–
9-Arylsulfanylmethylidene derivatives IXa–IXc
turned out to undergo thermal isomerization in the
presence of bases [5]. On heating in DMSO com-
pounds IXa and IXc underwent hydrogen shift and
double bond migration into the thiazole ring with
formation of 9-(arylsulfanylmethyl)-5H-pyrido[4,3-e]-
[1,3]thiazolo[3,2-a]pyrimidin-5-ones Xa and Xb. The
structure of intramolecular cyclization products IXa–
IXc, Xa, and Xb was consistent with the IR (νC=O
7.86 m (1H, 5-H), 8.54–8.59 m (2H, 6-H, 8-H), 12.98 s
(1H, NH). 13C NMR spectrum, δC, ppm: 21.15 (CH3),
32.82 (CH2), 47.46 (CH), 49.94 (CH2), 61.55 (C5),
118.74 (Carom), 125.60 (Carom), 130.45 (Carom), 133.44
(C4a), 138.33 (C8a), 145.56 (C8), 149.43 (C6), 157.84
(C2), 160.66 (C4). Found, %: C 54.03; H 4.27; Cl 9.38;
N 11.12; S 16.97. C17H16ClN3OS2. Calculated, %:
C 54.12; H 4.26; Cl 9.47; N 11.04; S 17.06.
1650–1660 cm–1) and 13C NMR data (δC
169 ppm).
5
2-{[3-Chloro-2-(4-nitrophenylsulfanyl)propyl]-
sulfanyl}pyrido[3,4-d]pyrimidin-4(3H)-one (IIIc).
Yield 0.30 g (73%), mp 234–237°C. IR spectrum, ν,
cm–1: 1690, 1580, 1510, 1420, 1335, 1250, 1165, 1080,
EXPERIMENTAL
1
The IR spectra were recorded on a Bruker Vertex
70 spectrometer from samples prepared as KBr pellets.
960, 855, 840, 740, 690, 640. H NMR spectrum, δ,
ppm: 3.68–3.76 m (2H, CH2), 4.03–4.15 m (2H, CH2),
4.33–4.41 m (1H, CH), 7.72 d (2H, Harom, J = 8.8 Hz),
7.86 d (1H, 5-H, J = 4.4 Hz), 8.14 d (2H, Harom, J =
8 Hz), 8.57 d (1H, 6-H, J = 5.2 Hz), 8.73 s (1H, 8-H),
13.00 s (1H, NH). 13C NMR spectrum, δC, ppm: 32.78
(CH2), 47.36 (CH2), 47.69 (CH), 118.66 (5-H), 124.33
(Carom), 125.73 (Carom), 129.19 (C4a), 143.42 (Carom),
144.84 (C8a), 145.71 (Carom), 145.91 (C8), 149.11 (C6),
157.81 (C2), 160.68 (C4). Found, %: C 47.00; H 3.20;
Cl 8.67; N 13.70; S 15.68. C16H13ClN4O3S2. Calculat-
ed, %: C 47.13; H 3.14; Cl 8.75; N 13.62; S 15.74.
1
The H and 13C NMR spectra were measured on
a Varian VXR-400 spectrometer at 399.97 and
125.74 MHz, respectively, using tetramethylsilane as
internal reference.
Compounds IIIa–IIIc (general procedure). A solu-
tion of 1.2 mmol of arylsulfanyl chloride IIa–IIc in
10 mL of chloroform was added dropwise to a suspen-
sion of 0.22 g (1 mmol) of compound I in 10 mL of
chloroform, and the mixture was stirred for 12 h at
room temperature. The mixture was left to stand
overnight, and the precipitate was filtered off, washed
with chloroform and diethyl ether, and recrystallized
from DMSO.
Compounds IVa–IVc (general procedure). Com-
pound IIIa–IIIc, 1 mmol, was dispersed in 5 mL of
DMSO, 0.15 g (1.85 mmol) of sodium acetate was
added, and the mixture was stirred for 1.5 h at 50°C.
The mixture was diluted with 10 mL of water, and the
precipitate was filtered off and washed on a filter with
water, alcohol, and diethyl ether.
2-{[3-Chloro-2-(phenylsulfanyl)propyl]sulfanyl}-
pyrido[3,4-d]pyrimidin-4(3H)-one (IIIa). Yield
0.26 g (72%), mp 161–166°C. IR spectrum, ν, cm–1:
1710, 1580, 1425, 1320, 1265, 1180, 1050, 970, 850,
1
805, 740, 690, 610, 530. H NMR spectrum, δ, ppm:
3-Phenylsulfanyl-3,4-dihydro-2H,6H-pyrido-
[3′,4′:4,5]pyrimido[2,1-b][1,3]thiazin-6-one (IVa).
Yield 0.26 g (79%), mp 99–104°C. IR spectrum, ν,
cm–1: 1680, 1535, 1470, 1420, 1385, 1305, 1240, 1110,
3.61–3.69 m (2H, CH2), 3.95–4.04 m (3H, CH2, CH),
7.38–7.44 m (3H, Harom), 7.58 d (2H, Harom, J =
6.4 Hz), 7.85–7.86 m (1H, 5-H), 8.55–8.56 m (1H,
6-H), 8.63 s (1H, 8-H), 13.00 s (1H, NH). 13C NMR
spectrum, δC, ppm: 32.87 (CH2), 47.50 (CH2), 49.34
(CH), 61.55 (C5), 118.76 (Carom), 125.60 (Carom),
128.24 (Carom), 129.62 (Carom), 132.50 (C4a), 133.42
(C8a), 145.56 (C8), 149.37 (C6), 157.83 (C2), 160.65
(C4). Found, %: C 52.81; H 3.88; Cl 9.74; N 11.55;
S 17.62. C16H14ClN3OS2. Calculated, %: C 52.65;
H 3.71; Cl 9.84; N 11.63; S 17.48.
1
1060, 950, 800, 730, 695, 655, 400. H NMR spec-
trum, δ, ppm: 3.59–3.64 m (1H, CH2), 4.03–4.09 m
(1H, CH2), 4.20–4.24 m (1H, CH2), 4.38–4.42 m (1H,
CH2), 7.39–7.40 m (3H, Harom), 7.51–7.53 m (2H,
H
arom), 7.87–7.88 m (1H, 7-H), 8.55–8.57 m (1H, 8-H),
8.89–8.90 m (1H, 10-H). 13C NMR spectrum, δC, ppm:
32.26 (C2), 45.97 (C3), 118.95 (C4), 124.01 (C7),
128.44 (Carom), 129.93 (Carom), 129.96 (Carom), 132.36
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 50 No. 6 2014

FUSED PYRIMIDINE SYSTEMS: XIV.
861
(Carom), 142.08 (C6a), 145.18 (C10a), 149.45 (C10),
156.82 (C8), 156.84 (C11a), 160.15 (C6). Found, %:
C 58.69; H 4.00; N 12.83; S 19.59. C16H13N3OS2. Cal-
culated, %: C 58.57; H 4.12; N 12.76; S 19.65.
9-(Phenylsulfanylmethyl)-8,9-dihydro-5H-pyr-
ido[4,3-e][1,3]thiazolo[3,2-a]pyrimidin-5-one (Va).
Yield 0.22 g (67%), mp 155–160°C. IR spectrum, ν,
cm–1: 1650, 1580, 1510, 1460, 1390, 1250, 1090, 810,
1
730, 700. H NMR spectrum, δ, ppm: 3.45–3.49 m
3-(4-Methylphenylsulfanyl)-3,4-dihydro-2H,6H-
pyrido[3′,4′:4,5]pyrimido[2,1-b][1,3]thiazin-6-one
(IVb). Yield 0.20 g (60%), mp 126–130°C. IR spec-
trum, ν, cm–1: 1680, 1540, 1480, 1420, 1310, 1235,
(1H, CH), 3.56–3.57 m (1H, CH), 3.64–3.69 m and
3.92–3.97 m (1H each, 8-H), 5.62–5.65 m (1H, 9-H),
7.14–7.15 m (3H, Harom), 7.23–7.27 m (2H, Harom),
7.58 d (1H, 4-H, J = 5.2 Hz), 8.54 d (1H, 3-H, J =
5.6 Hz), 8.74 s (1H, 1-H). 13C NMR spectrum, δC,
ppm: 31.47 (C8), 35.50 (CH2), 61.55 (C9), 119.95 (C4),
122.44 (C4a), 127.28 (Carom), 129.50 (Carom), 130.06
(Carom), 134.36 (Carom), 134.57 (C11a), 139.34 (C1),
145.51 (C3), 165.84 (C6a), 170.34 (C5). Found, %:
C 58.69; H 4.00; N 12.83; S 19.59. C16H13N3OS2. Cal-
culated, %: C 58.77; H 4.12; N 12.76; S 19.45.
1
1110, 820, 695, 620, 540. H NMR spectrum, δ, ppm:
2.31 s (3H, CH3), 3.20–3.23 m (1H, CH), 3.56–3.58 m
(1H, CH), 3.97–4.15 m (2H, CH2), 4.37–4.39 m (1H,
CH), 7.22 d (2H, Harom, J = 7.2 Hz), 7.41 d (2H, Harom
,
J = 7.2 Hz), 7.86 d (1H, 7-H, J = 4.4 Hz), 8.55 d (1H,
8-H, J = 4.0 Hz), 8.88 s (1H, 10-H). 13C NMR spec-
trum, δC, ppm: 21.15 (CH3), 32.24 (C2), 40.42 (C3),
45.98 (C4), 118.93 (C7), 123.99 (Carom), 128.49 (Carom),
130.58 (Carom), 133.24 (4′-CH3), 138.48 (C6a), 142.07
(C10a), 145.15 (C10), 149.44 (C8), 156.85 (C11a), 160.14
(C6). Found, %: C 59.80; H 4.43; N 12.31; S 18.78.
C17H15N3OS2. Calculated, %: C 59.89; H 4.49;
N 12.22; S 18.84.
9-(4-Methylphenylsulfanylmethyl)-8,9-dihydro-
5H-pyrido[4,3-e][1,3]thiazolo[3,2-a]pyrimidin-5-one
(Vb). Yield 0.21 g (63%), mp 178–184°C. IR spec-
trum, ν, cm–1: 1655, 1580, 1520, 1450, 1390, 1340,
1
1260, 1240, 1090, 800, 710, 620. H NMR spectrum,
3-(4-Nitrophenylsulfanyl)-3,4-dihydro-2H,6H-
pyrido[3′,4′:4,5]pyrimido[2,1-b][1,3]thiazin-6-one
(IVc). Yield 0.32 g (87%), mp 325–328°C. IR spec-
trum, ν, cm–1: 1690, 1550, 1500, 1380, 1335, 1230,
δ, ppm: 2.51 s (3H, CH3), 3.35–3.42 m (2H, CH2),
3.55–3.58 m and 3.61–3.66 m (1H each, 8-H), 3.90–
3.95 m (1H, 9-H), 5.56–5.59 m (1H, Harom), 6.92 d
(2H, Harom, J = 7.2 Hz), 7.15 d (2H, Harom, J = 7.6 Hz),
7.67 d (1H, 4-H, J = 5.2 Hz), 8.54 d (1H, 3-H, J =
5.2 Hz), 8.69 s (1H, 1-H). 13C NMR spectrum, δC,
ppm: 21.04 (CH3), 31.28 (C8), 36.09 (CH2), 61.61 (C9),
119.84 (C4), 122.43 (C4a), 130.13 (Carom), 130.44
(Carom), 130.59 (Carom), 134.51 (Carom), 137.02 (C11a),
139.25 (C1), 145.43 (C3), 165.89 (C6a), 170.34 (C5).
Found, %: C 59.08; H 4.43; N 12.31; S 18.78.
C17H15N3OS2. Calculated, %: C 59.16; H 4.35;
N 12.20; S 18.84.
1
1145, 1090, 940, 850, 740, 695, 650, 540. H NMR
spectrum, δ, ppm: 3.40–3.45 m (1H, CH), 3.69–3.74 m
(1H, CH), 4.19–4.26 m (1H, CH), 4.40–4.44 m (1H,
CH), 4.57–4.65 m (1H, CH), 7.70 d (2H, Harom, J =
8.4 Hz), 7.86 d (1H, 7-H, J = 5.2 Hz), 8.18 d (2H,
Harom, J = 8.8 Hz), 8.56 d (1H, 8-H, J = 5.2 Hz), 8.90 s
(1H, 10-H). 13C NMR spectrum, δC, ppm: 36.96 (C2),
40.27 (C3), 47.54 (C4), 120.80 (Carom), 125.84 (C7),
131.04 (Carom), 135.72 (C6a), 144.26 (Carom), 145.49
(C10a), 147.90 (C4′), 151.30 (C8), 158.43 (C11a), 162.00
(C6). Found, %: C 51.60; H 3.25; N 15.04; S 17.22.
C16H12N4O3S2. Calculated, %: C 51.54; H 3.16;
N 15.17; S 17.29.
9-(4-Nitrophenylsulfanylmethyl)-8,9-dihydro-
5H-pyrido[4,3-e][1,3]thiazolo[3,2-a]pyrimidin-5-one
(Vc). Yield 0.21 g (56%), mp 279–283°C. IR spec-
trum, ν, cm–1: 1655, 1580, 1520, 1450, 1390, 1340,
Compounds Va–Vc, VIIa–VIIc, and IXa–IXc
(general procedure). A solution of 1.1 mmol of aryl-
sulfanyl chloride IIa–IIc in 5 mL of nitromethane was
added dropwise under stirring at 15–20°C to a suspen-
sion of 1 mmol of 2-R-sulfanyl-substituted pyridopyri-
midinone I, VI, and VIII and 0.11 g (1 mmol) of
lithium perchlorate in 10 mL of nitromethane. The
mixture was stirred for 5–6 h and left overnight. The
precipitate was filtered off, washed with nitromethane
and hexane, and dissolved in 5 mL of DMSO, and
a 20% aqueous solution of sodium acetate was added.
The precipitate was filtered off and washed with water
on a filter.
1
1260, 1240, 1090, 800, 710, 620. H NMR spectrum,
δ, ppm: 3.55–3.56 m and 3.68–3.73 m (1H each, 8-H),
3.87–3.99 m (2H, CH2), 5.83–5.85 m (1H, 9-H), 7.41 d
(2H, Harom, J = 8.8 Hz), 7.64 d (1H, 4-H, J = 5.2 Hz),
7.89 d (2H, Harom, J = 8.4 Hz), 8.57 d (1H, 3-H, J =
4.8 Hz), 9.01 s (1H, 1-H). 13C NMR spectrum, δC,
ppm: 31.71 (C8), 34.63 (CH2), 61.26 (C9), 119.71 (C4),
122.31 (C4a), 124.11 (Carom), 128.50 (Carom), 134.67
(Carom), 139.81 (C1), 145.21 (Carom), 145.47 (C10a),
145.65 (C3), 165.74 (C6a), 170.42 (C5). Found, %:
C 51.60; H 3.25; N 15.04; S 17.22. C16H12N4O3S2. Cal-
culated, %: C 51.69; H 3.18; N 15.12; S 17.15.
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DYACHENKO et al.
862
10-Phenyl-9-phenylsulfanyl-9,10-dihydro-
9-(Phenylsulfanylmethylidene)-8,9-dihydro-5H-
pyrido[4,3-e][1,3]thiazolo[3,2-a]pyrimidin-5-one
(IXa). Yield 0.25 g (76%), mp 194–204°C. IR spec-
trum, ν, cm–1: 1650, 1570, 1500, 1460, 1440, 1370,
5H,8H-pyrido[4′,3′:5,6]pyrimido[2,1-b][1,3]thiazin-
5-one (VIIa). Yield 0.34 g (86%), mp 249–253°C. IR
spectrum, ν, sm–1: 1660, 1500, 1460, 1360, 1260,
1
1
1100, 810, 750, 700, 500. H NMR spectrum, δ, ppm:
1280, 1235, 1200, 1090, 750, 700. H NMR spectrum,
3.05–3.08 m and 3.14–3.17 m (1H each, 9-H), 4.72–
4.73 m (1H, 7-H), 6.29–6.31 m (1H, 8-H), 7.35–
7.40 m (6H, Harom), 7.44–7.47 m (2H, Harom), 7.61 d
(2H, Harom, J = 7.5 Hz), 7.92 d (1H, 4-H, J = 5.0 Hz),
8.63 d (1H, 3-H, J = 5.0 Hz), 8.75 s (1H, 1-H). 13C NMR
spectrum, δC, ppm: 28.30 (C8), 45.91 (C9), 61.52 (C10),
120.02 (C4), 125.49 (Carom), 126.47 (Carom), 128.66
(Carom), 129.39 (Carom), 129.90 (Carom), 129.99 (Carom),
132.24 (Carom), 132.65 (Carom), 136.88 (C11a), 138.25
(C1), 146.68 (C3), 163.52 (C6a), 164.13 (C5). Found, %:
C 65.48; H 4.25; N 12.41; S 15.89. C22H17N3OS2. Cal-
culated, %: C 65.58; H 4.14; N 12.49; S 15.77.
δ, ppm: 4.44 s (2H, 8-H), 7.14 s (1H, CH2), 7.28–
7.31 m (1H, Harom), 7.37–7.40 m (2H, Harom), 7.45–
7.47 m (2H, Harom), 7.91 d (1H, 4-H, J = 4.8 Hz),
8.68 d (1H, 3-H, J = 4.5 Hz), 9.36 s (1H, 1-H).
13C NMR spectrum, δC, ppm: 31.33 (C8), 111.28 (CH),
120.12 (C4), 123.65 (C4a), 127.32 (Carom), 128.64
(Carom), 129.87 (Carom), 134.19 (Carom), 134.62 (C9),
137.34 (C10a), 140.14 (C1), 146.36 (C3), 165.20 (C6a),
169.40 (C5). Found, %: C 56.06; H 3.41; N 12.91;
S 19.71. C16H11N3OS2. Calculated, %: C 56.19;
H 3.34; N 12.84; S 19.82.
9-(4-Methylphenylsulfanylmethylidene)-8,9-di-
hydro-5H-pyrido[4,3-e][1,3]thiazolo[3,2-a]pyrimi-
din-5-one (IXb). Yield 0.25 g (74%), mp 189–193°C.
IR spectrum, ν, cm–1: 1660, 1575, 1520, 1440, 1375,
1310, 1280, 1240, 1200, 1090, 1000, 800, 695, 570,
9-(4-Methylphenylsulfanyl)-10-phenyl-9,10-
dihydro-5H,8H-pyrido[4′,3′:5,6]pyrimido[2,1-b]-
[1,3]thiazin-5-one (VIIb). Yield 0.34 g (82%),
mp 250–254°C. IR spectrum, ν, cm–1: 1660, 1500,
1
1
1460, 1380, 1260, 1180, 820, 750, 700, 500. H NMR
490, 440. H NMR spectrum, δ, ppm: 2.29 s (3H,
spectrum, δ, ppm: 3.01–3.13 m (2H, CH2), 3.40 s (3H,
CH3), 4.62–4.63 m (1H, 9-H), 6.25 s (1H, 10-H),
7.18 d (2H, Harom, J = 7.6 Hz), 7.36–7.50 m (7H,
CH3), 4.42 s (2H, 8-H), 7.08 s (1H, CH), 7.20 d (2H,
Harom, J = 6.5 Hz), 7.36 d (2H, Harom, J = 8.0 Hz),
7.88–7.89 m (1H, 4-H), 8.66–8.67 m (1H, 3-H), 9.33 s
(1H, 1-H). 13C NMR spectrum, δC, ppm: 21.04 (CH3),
31.30 (C8), 122.27 (CH), 120.12 (C4), 123.62 (C4a),
129.20 (Carom), 130.49 (Carom), 130.86 (Carom), 134.14
(C9), 136.30 (Carom), 137.17 (C10a), 140.00 (Carom),
146.31 (C3), 165.14 (C6a), 169.32 (C5). Found, %:
C 60.15; H 3.86; N 12.38; S 18.89. C17H13N3OS2. Cal-
culated, %: C 60.17; H 3.88; N 12.36; S 18.86.
H
arom), 7.90–7.92 m (1H, 4-H), 8.63–8.64 m (1H, 3-H),
8.74 s (1H, 1-H). 13C NMR spectrum, δC, ppm: 21.06
(CH3), 28.21 (C8), 46.13 (C8), 61.48 (C10), 120.08 (C4),
125.48 (Carom), 126.39 (Carom), 128.37 (Carom), 129.27
(Carom), 129.84 (Carom), 130.54 (Carom), 133.37 (Carom),
136.93 (C1), 138.19 (Carom), 138.70(C10a), 136.67 (C3),
163.51 (C6a), 164.16 (C5). Found, %: C 66.16; H 4.59;
N 10.06; S 15.36. C23H19N3OS2. Calculated, %:
C 66.24; H 4.67; N 9.97; S 15.28.
9-(4-Nitrophenylsulfanylmethylidene)-8,9-dihy-
dro-5H-pyrido[4,3-e][1,3]thiazolo[3,2-a]pyrimidin-
5-one (IXc). Yield 0.25 g (67%), mp 249–253°C. IR
spectrum, ν, cm–1: 1655, 1575, 1500, 1465, 1440,
9-(4-Nitrophenylsulfanyl)-10-phenyl-9,10-dihy-
dro-5H,8H-pyrido[4′,3′:5,6]pyrimido[2,1-b][1,3]-
thiazin-5-one (VIIc). Yield 0.35 g (78%), mp 275–
279°C. IR spectrum, ν, cm–1: 1660, 1580, 1510, 1460,
1
1395, 1340, 1240, 1090, 840, 740, 700, 450. H NMR
spectrum, δ, ppm: 4.46 s (2H, 8-H) 7.25 s (1H, CH2),
7.66 d (2H, Harom, J = 6.8 Hz), 7.92 m (1H, 4-H),
8.17 d (2H, Harom, J = 9.9 Hz), 8.70 d (1H, 3-H, J =
9.6 Hz), 6.41 s (1H, 1-H). 13C NMR spectrum, δC,
ppm: 31.31 (C8), 107.50 (CH), 120.14 (C4), 123.67
(C4a), 124.58 (Carom), 127.67 (Carom), 134.12 (C9),
140.35 (C1), 141.20 (Carom), 145.08 (C10a), 145.89
(Carom), 146.58 (C3), 165.16 (C6a), 169.68 (C5). Found,
%: C 51.88; H 2.72; N 15.13; S 17.31. C16H10N4O3S2.
Calculated, %: C 51.96; H 2.64; N 15.25; S 17.22.
1
1380, 1340, 1290, 1100, 860, 800. H NMR spectrum,
δ, ppm: 3.24–3.25 m (2H, CH2), 5.06–5.07 m (1H,
7-H), 6.48–6.50 m (1H, 8-H), 7.43–7.48 m (5H, Harom),
7.85 d (2H, Harom, J = 7.5 Hz), 7.91–7.92 m (1H, 4-H),
8.20 d (2H, Harom, J = 8 Hz), 8.63–8.64 m (1H, 3-H),
8.85 s (1H, 1-H). 13C NMR spectrum, δC, ppm: 28.44
(C8), 44.52 (C9), 61.88 (C10), 120.01 (C4), 124.67
(Carom), 125.54 (C4a), 126.63 (Carom), 129.49 (Carom),
129.91 (Carom), 130.24 (Carom), 136.69 (Carom), 136.92
(Carom), 138.53 (C1), 143.04 (Carom), 146.38 (C11a),
146.79 (C3), 163.48 (C6a), 163.81 (C5). Found, %:
C 58.91; H 3.60; N 12.49; S 14.30. C22H16N4O3S2. Cal-
culated, %: C 58.84; H 3.68; N 12.56; S 14.21.
Compounds Xa and Xb (general procedure).
A solution of 0.16 g (1.5 mmol) of sodium acetate was
added to a solution of 1 mmol of compound IXa or
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 50 No. 6 2014

FUSED PYRIMIDINE SYSTEMS: XIV.
863
IXc in 10 mL of dimethyl sulfoxide, and the mixture
was heated for 1.5 h at 60°C on a water bath. The mix-
ture was diluted with 10 mL of water, and the precip-
itate was filtered off and washed with water, alcohol,
and diethyl ether.
8.8 Hz), 8.82 d (1H, 3-H, J = 5.6 Hz), 9.61 s (1H,
1-H). 13C NMR spectrum, δC, ppm: 32.83 (CH2),
110.75 (C8), 120.54 (C4), 124.21 (C4a), 124.37 (Carom),
128.82 (Carom), 134.42 (Carom), 140.80 (C1), 144.32
(C10a), 145.32 (C9), 147.39 (C3), 163.55 (C6a), 169.44
(C5). Found, %: C 51.88; H 2.72; N 15.13; S 17.31.
C16H10N4O3S2. Calculated, %: C 51.79; H 2.83;
N 15.05; S 17.43.
9-(Phenylsulfanylmethyl)-5H-pyrido[4,3-e][1,3]-
thiazolo[3,2-a]pyrimidin-5-one (Xa). Yield 0.23 g
(70%), mp 218–222°C. IR spectrum, ν, cm–1: 3060,
1630, 1570, 1505, 1460, 1360, 1290, 1250, 1150,
1
REFERENCES
1010, 890, 850, 820, 750, 690, 520. H NMR spec-
trum, δ, ppm: 4.93 s (2H, CH2), 7.12 s (1H, 8-H),
7.23–7.36 m (5H, Harom), 8.05 d (1H, 4-H, J = 4.4 Hz),
8.81 d (1H, 3-H, J = 5.6 Hz), 9.59 s (1H, 1-H).
13C NMR spectrum, δC, ppm: 34.76 (CH2), 110.61
(C8), 120.47 (C4), 124.12 (C4a), 127.96 (Carom), 129.62
(Carom), 131.47 (Carom), 133.07 (Carom), 134.30 (C9),
135.03 (C10a), 141.03 (C1), 147.34 (C3), 163.56 (C6a),
169.38 (C5). Found, %: C 59.06; H 3.41; N 12.91;
S 19.71. C16H11N3OS2. Calculated, %: C 59.15;
H 3.30; N 13.02; S 19.64.
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9-(4-Nitrophenylsulfanylmethyl)-5H-pyrido-
[4,3-e][1,3]thiazolo[3,2-a]pyrimidin-5-one (Xb).
Yield 0.25 g (63%), mp 244–247°C. IR spectrum, ν,
cm–1: 3070, 2900, 1650, 1570, 1510, 1460, 1420, 1360,
1340, 1280, 1190, 1120, 1090, 1000, 910, 850, 790,
740, 690, 520. 1H NMR spectrum, δ, ppm: 5.19 s (2H,
CH2), 7.34 s (1H, 8-H), 7.64 d (2H, Harom, J = 8.4 Hz),
8.07 d (1H, 4-H, J = 4.8 Hz), 8.14 d (2H, Harom, J =
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 50 No. 6 2014