Reactions of 2-(2-propynylsulfanyl)-5,6,7,8-tetrahydrobenzo[b]thieno[2,3-d] pyrimidin-4(3H)-one with arylsulfenyl chlorides

Article abstract of DOI:10.1134/S107042800710020X

2-(2-propynylsulfanyl)-5,6,7,8-tetrahydrobenzo[b]thieno[2,3-d] pyrimidin-4(3H)-one with arylsulfenyl chlorides in chloroform gave products of anti-Markownikoff Ad _E-addition. The use of nitromethane as solvent in the presence of lithium perchlo

Full text of DOI:10.1134/S107042800710020X

ISSN 1070-4280, Russian Journal of Organic Chemistry, 2007, Vol. 43, No. 10, pp. 1526−1531. © Pleiades Publishing, Ltd., 2007.
Original Russian Text © A.I. Vas’kevich, R.I. Vas’kevich, V.I. Staninets, S.A. But, A.N. Chernega, 2007, published in Zhurnal Organicheskoi Khimii,
2007, Vol. 43, No. 10, pp. 1530−1535.
Reactions of 2-(2-Propynylsulfanyl)-
5,6,7,8-tetrahydrobenzo[b]thieno[2,3-d]pyrimidin-4(3H)-one
with Arylsulfenyl Chlorides
A. I. Vas’kevich, R. I. Vas’kevich, V. I. Staninets, S. A. But, and A. N. Chernega
Institute of Organic Chemistry, National Academy of Sciences of Ukraine, Kiev, 02094 Ukraine
e-mail: vaskevich@bpci.kiev.ua
Received June 20, 2006; final version May 18, 2007
Abstract—2-(2-propynylsulfanyl)-5,6,7,8-tetrahydrobenzo[b]thieno[2,3-d]pyrimidin-4(3H)-one with arylsulfenyl
chlorides in chloroform gave products of anti-Markownikoff AdE-addition. The use of nitromethane as solvent in
the presence of lithium perchlorate additives favored intramolecular electrophilic cyclization into 1-arylsulfanyl-
1,2,6,7,8,9-hexahydro-4H-benzo[4,5]thieno[3,2-e][1,3]thiazolo[3,2-a]-pyrimidin-5-one.
DOI: 10.1134/S107042800710020X
Reactions of alkenes with electrophilic reagents are
among the most widely spread and well understood
reactions in the organic chemistry, and it is well known
that if in an appropriated position with respect to the
double bond a nucleophilic site is present then the
electrophilic intramolecular cyclization is in competition
with the AdE-addition. The acetylenes reactivity in addi-
tion reactions and consequently also in cyclizations is
considerably lower that that of compounds with a double
C=C bond. However the cyclization was successfully
carried out in functionally substituted alkynes by the
action of mercury salts [1, 2], palladium [3, 4], halo-
succinimides [5], phenylselenylphthalimide [6], selenyl
and sulfenyl chlorides [7, 8].
IIa–IIc. At the use of p-tolylsulfenyl chloride alongside
the product IIa we isolated from the reaction mixture
16% of cyclic compound IIIa. Evidently the primarily
formed adduct IIa underwent the cyclization at the action
of hydrogen chloride appeared in a small amount in the
reaction mixture through the decomposition of unreacted
sulfenyl chloride. The treatment of addition products IIa–
IIc with hydrogen chloride in CHCl3 led to the formation
of thiazolinothienopyrimidinones IIIa–IIIc in confirma-
tion of the above assumption.
The structure of compound IIIa was unambiguously
established by X-ray diffraction analysis. The location
of substituents at the thiazoline ring of compound IIIa
suggests that the preceding compound IIa is the product
of anti-Markownikoff addition of arylsulfenyl chloride
to alkyne I. The general view of molecule IIIa and its
main bond distances and bond angles are presented on
the figure. The central heterocyclic system S1S3N1N2C1–
7C12 is virtually planar: the deviations of atoms from the
mean-square plain do not exceed 0.132 Å; the dihedral
angles between the central five-membered ring N1N2C3–6
and heterocycles S3C5–7C12 and S1N2C1–3 are only 1.3
and 3.4°. Due to sterical reasons the benzene ring C13–18
is turned with respect to the central tricyclic system by
63.7°. The N2 atom has a planary trigonal configuration
of bonds, the corresponding sum of bond angles at this
atom is 360.0(6)°.
We showed formerly by an example of S-alkenyl-
substituted pyrimidinones that the character of the
sulfenyl chloride and the substituents at the double bond
of the olefin significantly affected the composition and
ratio of the reaction products [9, 10]. In extension of
our studies we attempted to reveal the behavior in this
process of alkynylsulfanyl-substituted substrates. As
a model compound 2-(2-propynylsulfanyl)-5,6,7,8-
tetrahydrobenzo-[b]-thieno[2,3-d]pyrimidin-4(3H)-one
(I) was selected, and its reactions were studied with p-
tolyl-, phenyl-, p-nitro-phenylsulfenyl chlorides.
Compound I with ArSCl in chloroform formed
products of AdE-addition against the Markownikoff rule
1526

REACTIONS OF 2-(2-PROPYNYLSULFANYL)-
O
1527
O
N
[H+]
NH
N
S
S
N
S
S
ClH2C
ArSCl,
CHCl3
Cl
_ S
SAr
Ar
IIIa IIIc
IIa_IIc
O
N
O
NH
ArSCl
NH
_
ClO4
CH3NO2 + LiClO4
+
S
I
S
N
S
S
(1) 2Br2, CHCl3
(2) Acetone
HC
S
Ar
(3) AcONa, DMSO
IVa_IVc
O
N
AcONa,
DMSO
O
N
S
S
N
BrHC
N
S
S
VII
O
N
HC
S
Ar
Va_Vc
N
S
AcONa, DMSO
D
S
ArSH
K2CO3
H2C
S
Ar
VIa_VIc
Ar = 4-CH3C6H4 (a), C6H5 (b), 4-NO2C6H4 (c).
The reaction of S-propargyl-substituted thieno-
pyrimidinone I with ArSCl under conditions of “doping
addition” (nitromethane as solvent with LiClO4 additive)
led to the formation in 53–60% yield of intramolecular
cyclization products of angular structure IVa–IVc. At
the use of 4-NO2C6H4SCl alongside the cyclic compound
IVc formed 12% of adduct IIc. Perchlorates IVa–IVc
were converted into the corresponding bases Va–Vc by
treating with sodium acetate in DMSO. At heating
compounds Va–Vc with sodium acetate the exocyclic
double bond migrated into the thiazole ring giving
compounds VIa–VIc.
To confirm the structure of compounds VIa–VIc and
to establish the position of the multiple bond in cycliza-
tion products Va–Vc an independent synthesis was
performed. In the first stage by treating compound I with
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 43 No. 10 2007

VAS’KEVICH et al.
1528
appeared as a doublet in the region 4.42–4.49 ppm with
a coupling constant 2.0 Hz. The methine proton =CHSAr
gave rise to a triplet at 6.69–6.80 ppm (J 2.0 Hz).
In the 1H NMR spectra of compounds VIa–VIc the
singlet of CH2SAr group appeared in the region 4.49–
4.82 ppm, and the singlet of methine proton of the
thiazole ring, in the range 6.89–7.24 ppm.
EXPERIMENTAL
IR spectra of compounds II–VII were recorded on
a spectrophotometer UR-20 from pellets with KBr.
1H NMR spectra from solutions of compounds II–VII
in DMSO-d6 were registered on a spectrometer Varian
VXR-300 (300 MHz), internal reference TMS.
General view of compound IIIa molecule. Bond distances (Å)
and bond angles (deg): C1–C2 1.538(3), C2–N2 1.469(3), N2–
C3 1.363(3), C3–S1 1.740(2), S1–C1 1.806(3), S3–C12 1.737(3),
C12–C7 1.351(3), C7–C5 1.440(3), C5–C6 1.368(3), C6–S3
1.722(2), C5–C4 1.456(3), O1–C4 1.221(3), C4–N1 1.403(3),
N1–C3 1.293(3), C6–N2 1.386(3), Cl1–C20 1.782(3), C2–S2
1.840(2), S2–C13 1.771(2); C2N2C3117.64(18),
C2N2C6126.61(18), C6N2C3115.74(19), C3S1C1 92.86(11),
C2S2C13102.66(11), C3N1C4119.7(2), C12S3C6 90.74(12).
X-ray diffraction study on a single crystal of
compound IIIa of linear dimensions 0.24×0.37×0.58 mm
was carried out at room temperature on an automatic
CCD diffractometer Bruker Apex II (MoKα-radiation,
λ 0.71069 Å, θmax 26°, –16 ≤ h ≤ 16, –17 ≤ k ≤ 15, –25 ≤
l ≤ 25). 24403 reflections were collected (2551
independent reflections, Rint 0.027). Crystals of compound
IIIa rhombic, a 13.3526(2), b 14.3976(3), c 20.7577(4)
Å, V 3990.6(1) Å3, M 435.03, Z 8, dcalc 1.45 g/cm3,
μ 5.19 cm–1, F(000) 1808, space group Pbca (N 61).
The structure was solved by the direct method and refined
by the least-squares procedure in a full-matrix anisotropic
approximation using software CRYSTALS [12]. In the
refinement 2551 reflections were used with I > 3σ(I)
(244 refined parameters, 10.5 reflections per parameter).
All hydrogen atoms were revealed from the difference
synthesis of the electron density and were involved in
the refinement with the fixed position and thermal
parameters. In the refinement weight Chebyshev scheme
was used [13] with five parameters: 1.81, 0.203, 2.06,
0.0604, and 0.665. The final values of divergence factors
are R 0.033 and RW 0.035, GOF 1.125. The residual
electron density from the difference Fourier series was
–0.29 and 0.39 e/Å3. The complete set of X-ray data for
compound IIIa was deposited into Cambridge Structural
Database (CCDC 604010).
bromine we obtained bromomethylidene-substituted
thiazolinothienopyrimidinone VII that was subjected to
reaction with thiophenol and para-thiocresol. The
bromine in compound VII is not labile, and its
substitution is accompanied by a simultaneous migration
of the multiple bond into the thiazole ring [11]. Therefore
on bromine substitution with a thioaryl moiety formed
compounds VI and not products V with an exocyclic
double bond.
The difference in the reactivity of sulfenyl chlorides
and bromine should be emphasized. Whereas the bromine
reacted with compound I in chloroform forming a
cyclization product VII, the arylsulfenyl chlorides under
similar conditions yielded addition products II and only
the use of a polar solvent and introducing into the reaction
medium of “doping-additives” led to the formation of
cyclic compounds IVa–IVc.
In the IR spectra of compounds IVa–IVc the carbonyl
absorption band appeared at 1720–1710 cm–1, besides
the vibrations of the perchlorate anion were observed in
the range 1120–1100 cm–1. The carbonyl absorption band
in the spectra of compounds Va–Vc was observed at
1645–1640 cm–1, in those of their isomers VIa–VIc, at
1620 cm–1. The absorption band of the carbonyl group
appeared in the spectra of acyclic IIa–IIc at 1670–1665
cm–1, and of isomeric cyclic structures IIIa–IIIc, at
1650–1640 cm–1.
2-(2-Propynylsulfanyl)-5,6,7,8-tetrahydro-benzo[b]-
thieno[2,3-d]pyrimidin-4(3H)-one (I) was obtained by
procedure [14].
Reaction of compound I withArSCl in chloroform.
To a dispersion of 0.55 g (2 mmol) of compound I in 10
ml of chloroform at 15–20°C while stirring was added
dropwise a solution of 2.1 mmol of ArSCl in 10 ml of
chloroform. The mixture was stirred for 12–16 h, then
1
In the H NMR spectra of compounds Va–Vc the
signal of the methylene group of the thiazoline ring
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 43 No. 10 2007

REACTIONS OF 2-(2-PROPYNYLSULFANYL)-
1529
additionally was added 0.3 mmol of arylsulfenyl chloride,
and the stirring was continued for 10 h. The separated
precipitate of compounds IIa–IIc was filtered off, and
washed on the filter with ether. Additional portion of
compounds IIa–IIc was obtained by removing the
solvent. At the use of p-CH3C6H4SCl a mixture formed
of substances IIa and IIIa which was separated by
fractional crystallization from ethanol. Compound IIa
crystallized first, and after evaporation of filtrate 0.14 g
(16%) of compound IIIa was obtained.
in a vacuum. The residue was treated with 10 ml of
acetone, filtered off, and washed with ether on the filter.
1-(4-Tolylsulfanyl)-1-chloromethyl-1,2,6,7,8,9-
hexahydro-5H-benzo-[4,5]thieno[3,2-e][1,3]thiazolo-
[3,2-a]pyrimidin-5-one (IIIa). Yield 0.28 g (64%), mp
190–192°C (acetone). IR spectrum, ν, cm–1: 1640 (C=O),
1
1570, 1530, 1440, 1370. H NMR spectrum, δ, ppm:
1.74–1.86 m (4H, 2CH2), 2.31 s (3H, CH3), 2.78–2.89 m
(4H, 2CH2), 3.72 d (1H, CH, J 13.2 Hz), 4.01 d (1H,
CH, J 13.5 Hz), 4.48 d (1H, CH, J 14.4 Hz), 4.68 d (1H,
CH, J 12.6 Hz), 7.19–7.25 m (4Harom). Found, %:
C 55.13; H 4.34; Cl 8.09; N 6.33; S 22.07.
C20H19ClN2OS3. Calculated, %: C 55.22; H 4.40; Cl 8.15;
N 6.44; S 22.11.
2-[2-(4-Tolylsulfanyl)-3-chloro-2-propenyl-
sulfanyl]-5,6,7,8-tetrahydrobenzo[b]thieno[2,3-d]-
pyrimidin-4(3H)-one (IIa). Yield 0.62 g (71%), mp
217–219°C (ethanol–DMSO). IR spectrum, ν, cm–1:
1680 (C=O), 1570, 1510, 1420, 1340. 1H NMR spectrum,
δ, ppm: 1.77 m (4H, 2CH2), 2.26 s (3H, CH3), 2.70–
2.82 m (4H, 2CH2), 4.13 s (2H, CH2), 6.88 s (1H, CH),
7.15 d (2Harom, J 8.1 Hz), 7.25 d (2Harom, J 8.4 Hz),
12.60 s (1H, NH). Found, %: C 55.12; H 4.31; Cl 8.11;
N 6.37; S 22.06. C20H19ClN2OS3. Calculated, %: C 55.22;
H 4.40; Cl 8.15; N 6.44; S 22.11.
1-Phenylsulfanyl-1-chloromethyl-1,2,6,7,8,9-
hexahydro-5H-benzo[4,5]-thieno[3,2-e][1,3]thiazolo-
[3,2-a]pyrimidin-5-one (IIIb). Yield 0.31 g (74%), mp
169–171°C (acetone). IR spectrum, ν, cm–1: 1640 (C=O),
1
1570, 1535, 1470, 1435, 1370. H NMR spectrum, δ,
ppm: 1.71–1.87 m (4H, 2CH2), 2.78–2.90 m (4H, 2CH2),
3.74 d (1H, CH, J 13.5 Hz), 4.04 d (1H, CH, J 13.2 Hz),
4.53 d (1H, CH, J 12.6 Hz), 4.70 d (1H, CH, J 12.9 Hz),
7.32 d (2Harom, J 6.9 Hz), 7.43 t (2Harom, J 7.5 Hz),
7.54 t (1Harom, J 7.5 Hz). Found, %: C 54.06; H 4.02;
Cl 8.37; N 6.49; S 22.77. C19H17ClN2OS3. Calculated,
%: C 54.21; H 4.07; Cl 8.42; N 6.65; S 22.85.
2-(2-Phenylsulfanyl-3-chloro-2-propenylsulfanyl)-
5,6,7,8-tetrahydrobenzo[b]thieno[2,3-d]pyrimidin-
4(3H)-one (IIb). Yield 0.63 g (75%), mp 208–210°C
(ethanol–DMSO). IR spectrum, ν, cm–1: 1670 (C=O),
1
1560, 1410. H NMR spectrum, δ, ppm: 1.77 m (4H,
2CH2), 2.72–2.84 m (4H, 2CH2), 4.19 s (2H, CH2),
6.99 s (1H, CH), 7.37 m (5Harom), 12.63 s (1H, NH).
Found, %: C 54.03; H 4.05; Cl 8.34; N 6.51; S 22.73.
C19H17ClN2OS3. Calculated, %: C 54.21; H 4.07; Cl 8.42;
N 6.65; S 22.85.
1-(4-Nitrophenylsulfanyl)-1-chloromethyl-
1,2,6,7,8,9-hexahydro-5H-benzo[4,5]thieno[3,2-e]-
[1,3]thiazolo[3,2-a]pyrimidin-5-one (IIIc). Yield
0.32 g (69%), mp 220–221°C (ethanol–DMSO). IR
spectrum, ν, cm–1: 1650 (C=O), 1580, 1540, 1440, 1380,
1350. 1H NMR spectrum, δ, ppm: 1.79 m (4H, 2CH2),
2.77–2.89 m (4H, 2CH2), 3.76 d (1H, CH, J 13.8 Hz),
4.10 d (1H, CH, J 15.0 Hz), 4.59 d (1H, CH, J 12.6 Hz),
4.65 d (1H, CH, J 12.9 Hz), 7.62 d (2Harom, J 8.4 Hz),
8.24 d (2Harom, J 9.3 Hz). Found, %: C 48.86; H 3.34;
Cl 7.56; N 8.94; S 20.56. C19H16ClN3O3S3. Calculated,
%: C 48.97; H 3.46; Cl 7.61; N 9.02; S 20.64.
2-[2-(4-Nitrophenylsulfanyl)-3-chloro-2-propenyl-
sulfanyl]-5,6,7,8-tetrahydrobenzo[b]-thieno[2,3-d]-
pyrimidin-4(3H)-one (IIc). Yield 0.78 g (84%), mp 237–
239°C (ethanol–DMSO). IR spectrum, ν, cm–1: 1665
(C=O), 1560, 1520, 1420, 1360. 1H NMR spectrum, δ,
ppm: 1.75 m (4H, 2CH2), 2.67–2.78 m (4H, 2CH2),
4.33 s (2H, CH2), 7.34 s(1H, CH), 7.44 d (2Harom
,
Reaction of compound I withArSCl in nitroethane
with lithium perchlorate additive. To a dispersion of
0.55 g (2 mmol) of compound I in 10 ml nitromethane at
15–20°C was added while stirring a solution of 0.22 g
(2 mmol) of LiClO4 in 10 ml of nitromethane, then
a solution of 2.1 mmol ofArSCl in 10 ml of nitromethane.
The mixture was stirred for 5–6 h and left standing for
12 h. The separated precipitate was filtered off and
washed with water on the filter.
J 9.3 Hz), 8.06 d (2Harom, J 9.3 Hz), 12.56 s (1H, NH).
Found, %: C 48.81; H 3.29; Cl 7.58; N 9.03; S 20.49.
C19H16ClN3O3S3. Calculated, %: C 48.97; H 3.46; Cl 7.61;
N 9.02; S 20.64.
1-Arylsulfanyl-1-chloromethyl-1,2,6,7,8,9-hexa-
hydro-5H-benzo[4,5]thieno[3,2-e][1,3]thiazolo-
[3,2-a]pyrimidin-5-ones IIIa–IIIc.Asolution of 1 mmol
of an appropriate compound IIa–IIc in 10 ml of
chloroform at 15–20°C was saturated while stirring with
dry hydrogen chloride for 30 min, then the mixture was
stirred for 12 h, and afterwards chloroform was removed
1-(4-Tolylsulfanylmethylidene)-1,2,6,7,8,9-hexa-
hydro-4H-benzo[4,5]thieno[3,2-e]-[1,3]thiazolo-
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 43 No. 10 2007

VAS’KEVICH et al.
1530
[3,2-a]pyrimidin-5-one perchlorate (IVa). Yield
0.53 g (53%), mp 215–217°C. IR spectrum, ν, cm–1: 1720
(C=O), 1650, 1580, 1540, 1510, 1420, 1380, 1100 (ClO–4).
1H NMR spectrum, δ, ppm: 1.76 m (4H, 2CH2), 2.31 C
(3H, CH3), 2.72–2.86 m (4H, 2CH2), 4.42 d (2H, CH2,
1-(4-Nitrophenylsulfanylmethylidene)-1,2,6,7,8,9-
hexahydro-5H-benzo[4,5]thieno[3,2-e]-[1,3]thiazolo-
[3,2-a]pyrimidin-5-one (Vc). To a dispersion of 0.55 g
(2 mmol) of compound I in 10 ml of nitromethane at
15–20°C was added while stirring a solution of 0.22 g
(2 mmol) of LiClO4 in 10 ml of nitromethane, then
a solution of 0.40 g (2.1 mmol) of p-nitrophenylsulfenyl
chloride in 10 ml of nitromethane. The mixture was
stirred for 5–6 h and left standing for 12 h. The solvent
was removed, and the residue was dissolved in DMSO
and treated with 5 ml of 20% water solution of sodium
acetate. The separated precipitate was filtered off, washed
with water, and recrystallized from dimethyl sulfoxide.
Yield 0.74 g (86%), mp 252–254°C (DMSO). IR
spectrum, ν, cm–1: 1645 (C=O), 1585, 1550, 1440, 1390,
J 2.7 Hz), 6.71 m (1H, CH), 7.23 d (2Harom, J 8.1 Hz),
7.35 d (2Harom, J 8.4 Hz). Found, %: C 48.03; H 3.71;
Cl 7.09; N 5.54; S 19.06. C20H19ClN2O5S3. Calculated,
%: C 48.14; H 3.84; Cl 7.10; N 5.61; S 19.28.
1-Phenylsulfanylmethylidene-1,2,6,7,8,9-hexa-
hydro-4H-benzo[4,5]thieno[3,2-e]-[1,3]thiazolo-
[3,2-a]pyrimidin-5-one perchlorate (IVb). Yield
0.58 g (60%), mp 191–193°C. IR spectrum, ν, cm–1: 1710
(C=O), 1660, 1580, 1540, 1480, 1430, 1370, 1120 (ClO–4).
1H NMR spectrum, δ, ppm: 1.76 m (4H, 2CH2), 2.72–
2.86 m (4H, 2CH2), 4.45 d (2H, CH2, J 2.4 Hz), 6.74 t
(1H, CH, J 2.1 Hz), 7.29–7.47 m (5Harom). Found, %:
C 47.01; H 3.67; Cl 7.23; N 5.67; S 19.77. C19H17ClN2O5S3.
Calculated, %: C 47.05; H 3.53; Cl 7.31; N 5.78; S 19.83.
1
1340. H NMR spectrum, δ, ppm: 1.79 m (4H, 2CH2),
2.76–2.89 m (4H, 2CH2), 4.49 d (2H, CH2, J 2.7 Hz),
6.80 t (1H, CH, J 2.4 Hz), 7.65 d (2Harom, J 9.0 Hz),
8.20 d (2Harom, J 9.3 Hz). Found, %: C 53.05; H 3.48;
N 9.72; S 22.33. C19H15N3O3S3. Calculated, %: C 53.13;
H 3.52; N 9.78; S 22.40.
1-Arylsulfanylmethylidene-1,2,6,7,8,9-hexa-
hydro-5H-benzo[4,5]thieno[3,2-e][1,3]thiazolo-
[3,2-a]pyrimidin-5-ones Va and Vb. To a solution of
1 mmol of compound IVa or IVb in 10 ml of DMSO
was added 5 ml of 20% water solution of sodium acetate
and was the mixture left standing for 2–3 h. The separated
precipitate was filtered off, washed with water, and
recrystallized from an appropriated solvent.
1-Arylsulfanylmethyl-6,7,8,9-tetrahydro-5H-
benzo[4,5]thieno[3,2-e]-[1,3]thiazolo[3,2-a]-
pyrimidin-5-ones VIa–VIc. a. To a solution of 1 mmol
of an appropriate compound Va–Vc in 15 ml of DMSO
was added a solution of 0.16 g (2 mmol) of sodium acetate
in 2 ml of water, and the mixture was heated on a water
bath at 70°C for 1 h, then 10 ml of water was added, the
separated precipitate was filtered off, washed with water,
and recrystallized.
1-(4-Tolylsulfanylmethylidene)-1,2,6,7,8,9-
hexahydro-5H-benzo[4,5]-thieno[3,2-e][1,3]thiazolo-
[3,2-a]pyrimidin-5-one (Va). Yield 0.32 g (80%), mp
226–228°C (ethanol). IR spectrum, ν, cm–1: 1640 (C=O),
b. A solution of 0.36 g (1 mmol) of compound VII,
0.28 g (2 mmol) of potassium hydrogen carbonate, and
1.5 mmol of the corresponding thiol in 20 ml of DMF
was heated at stirring on a water bath at 60°C for 1 h.
The mixture was cooled, 10 ml of water was added, the
separated precipitate was filtered off, washed on the filter
with ethanol and ether.
1
1580, 1550, 1495, 1430, 1380. H NMR spectrum, δ,
ppm: 1.76 m (4H, 2CH2), 2.31 s (3H, CH3), 2.72–2.86 m
(4H, 2CH2), 4.42 d (2H, CH2, J 2.1 Hz), 6.69 t (1H, CH,
J 2.1 Hz), 7.23 d (2Harom, J 8.1 Hz), 7.35 d (2Harom
,
J 8.4 Hz). Found, %: C 60.14; H 4.47; N 7.01; S 24.09.
C20H18N2OS3. Calculated, %: C 60.27; H 4.55; N 7.03;
S 24.14.
1-(4-Tolylsulfanylmethyl)-6,7,8,9-tetrahydro-5H-
benzo[4,5]thieno[3,2-e][1,3]thiazolo[3,2-a]-
pyrimidin-5-one (VIa). Yield 0.34 g (85%) (a), 0.23 g
(58%) (b), mp 253–255°C (ethanol). IR spectrum, ν,
cm–1: 1620 (C=O), 1570, 1530, 1465, 1415, 1380, 1330.
1H NMR spectrum, δ, ppm: 1.76–1.84 m (4H, 2CH2),
2.29 s (3H, CH3), 2.79–2.95 m (4H, 2CH2), 4.49 s (2H,
CH2), 6.89 s (1H, CH), 7.16 d (2Harom, J 7.8 Hz), 7.27 d
(2Harom, J 8.1 Hz). Found, %: C 60.16; H 4.43; N 7.04;
S 24.11. C20H18N2OS3. Calculated, %: C 60.27; H 4.55;
N 7.03; S 24.14.
1-Phenylsulfanylmethylidene-1,2,6,7,8,9-hexa-
hydro-5H-benzo[4,5]thieno[3,2-e][1,3]thiazolo-
[3,2-a]pyrimidin-5-one (Vb). Yield 0.31 g (81%), mp
206–208°C. IR spectrum, ν, cm–1: 1645 (C=O), 1570,
1
1540, 1480, 1430, 1380, 1340. H NMR spectrum, δ,
ppm: 1.76 m (4H, 2CH2), 2.72–2.86 m (4H, 2CH2),
4.44 d (2H, CH2, J 1.8 Hz), 6.73 t (1H, CH, J 2.1 Hz),
7.28–7.46 m (5Harom). Found, %: C 59.26; H 4.10; N 7.17;
S 25.00. C19H16N2OS3. Calculated, %: C 59.34; H 4.19;
N 7.28; S 25.02.
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 43 No. 10 2007

REACTIONS OF 2-(2-PROPYNYLSULFANYL)-
1531
1-Phenylsulfanylmethyl-6,7,8,9-tetrahydro-5H-
benzo[4,5]thieno[3,2-e][1,3]thiazolo[3,2-a]-
pyrimidin-5-one (VIb). Yield 0.35 g (91%) (a), 0.28 g
(73%) (b), mp 234–236°C (ethanol). IR spectrum, ν,
cm–1: 1620 (C=O), 1570, 1530, 1465, 1415, 1380.
1H NMR spectrum, δ, ppm: 1.75–1.88 m (4H, 2CH2),
2.79–2.97 m (4H, 2CH2), 4.56 s (2H, CH2), 6.96 s (1H,
CH), 7.28–7.43 m (5Harom). Found, %: C 59.29; H 4.13;
N 7.21; S 24.97. C19H16N2OS3. Calculated, %: C 59.34;
H 4.19; N 7.28; S 25.02.
1.87 m (4H, 2CH2), 2.74–2.85 m (4H, 2CH2), 4.34 d
(2H, CH2, J 2.1 Hz), 6.95 t (1H, CH, J 2.1 Hz). Found,
%: C 43.87; H 3.03; Br 22.42; N 7.76; S 17.97.
C13H11BrN2OS2. Calculated, %: C 43.95; H 3.12;
Br 22.49; N 7.89; S 18.05.
REFERENCES
1.Jellal, A., Grimaldi, J., and Santelly, M., Tetrahedron Lett.,
1984, vol. 25, p. 3179.
2.Yamamoto, M., Yoshitake, M., and Yamada, K., Chem.
Commun., 1983, p. 991.
1-(4-Nitrophenylsulfanylmethyl)-6,7,8,9-
tetrahydro-5H-benzo[4,5]thieno[3,2-e][1,3]thiazolo-
[3,2-a]pyrimidin-5-one (VIc). Yield 0.38 g (88%) (a),
mp 267–269°C (ethanol–DMSO). IR spectrum, ν, cm–1:
1620 (C=O), 1570, 1520, 1460, 1420, 1380, 1340.
1H NMR spectrum, δ, ppm: 1.72–1.86 m (4H, 2CH2),
2.77–2.95 m (4H, 2CH2), 4.82 s (2H, CH2), 7.24 m (1H,
CH), 7.69 d (2Harom, J 8.4 Hz), 8.16 d (2Harom, J 8.7 Hz).
Found, %: C 53.02; H 3.49; N 9.77; S 22.36.
C19H15N3O3S3. Calculated, %: C 53.13; H 3.52; N 9.78;
S 22.40.
3.Mizutani, M. and Sanemitsu, Y., Tetrahedron Lett., 1985,
vol. 26, p. 1237.
4.Lambert, C., Utimoto, K., and Nozaki, H., Tetrahedron
Lett., 1984, vol. 25, p. 5323.
5.Sofia, M.J., Chakravarty, P.K., and Katzenellenbogen, J.A.,
J. Org. Chem., 1983, vol. 48, p. 3318.
6.Toru, T., Fujita, S., and Maekawa, E., Chem. Commun.,
1985, p. 1082.
7.Toru, T., Fujita, S., Saito, M., and Maekawa, E., J. Chem.
Soc., Perkin, Trans. 1, 1986, p. 1999.
8.Kitamura, T., Takachi, T., Kawasato, H., and Tanigu-
chi, H., J. Chem. Soc. Perkin Trans. 1, 1992, p. 1969.
9.Vas’kevich, A.I., Gevaza, Yu.I., Vas’kevich, R.I., and
Staninets, V.I., Khim. Geterotsikl. Soedin., 2004, p. 1251.
10. Vas’kevich, A.I. and Staninets, V.I., Ukr. Khim. Zh., 2006,
vol. 72, p. 44.
11. Zborovskii, Yu.L., Orysyk, V.V., Staninets, V.I., Nadto-
chii, S.N., Boguslavskii, A.Yu., Sagach, V.F., Dmitrie-
va, A.V., and Chernega,A.N., Zh. Org. Farm. Khim., 2003,
vol. 1, p. 80.
12. Watkin, D.J., Prout, C.K., Carruthers, J.R., and Bette-
ridge, P.W., CRYSTALS Issue 10, Univ. of Oxford., 1996.
13. Carruthers, J.R. and Watkin, D.J., Acta Cryst. A, 1979,
vol. 35, p. 698.
14. Vas’kevich, R.I., Khripak, S.M., Staninets, V.I., Zborov-
skii, Yu.L., and Chernega, A.N., Zh. Org. Khim., 2000,
vol. 36, p. 1091.
1-Bromomethylidene-6,7,8,9-tetrahydro-5H-
benzo[4,5]thieno[3,2-e][1,3]thiazolo[3,2-a]pyrimidin-
5-one (VII). To a dispersion of 0.55 g (2 mmol) of
compound I in 20 ml of chloroform at 15–20°C was
added while stirring a solution of 0.24 ml (4 mmol) of
bromine in 10 ml of chloroform. The mixture was stirred
for 6–8 h and left standing for 12 h. The separated
precipitate was filtered off, washed on the filter with
ether, then treated with 15 ml of acetone and stirred for
1 h. The formed precipitate was filtered off and washed
on the filter with acetone, then it was dissolved in 20 ml
of DMSO, and 5 ml of 20% water solution of sodium
acetate was added. The separated precipitate was filtered
off, washed on the filter with ethanol and ether. Yield
0.43 g (61%), mp 207–209°C. IR spectrum, ν, cm–1: 1640
1
(C=O), 1580, 1550. H NMR spectrum, δ, ppm: 1.70–
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 43 No. 10 2007