ꢁꢁꢁꢂ
4ꢀ ꢀA. Lozynskyi et al.: New chromeno[4′,3′:4,5]thiopyrano[2,3-d]thiazoles
(
m, 1H, 5-H), 4.08 (d, 1H, Jꢀ=ꢀ4.8 Hz, 11b-H), 5.32 (t, 1H, Jꢀ=ꢀ6.3 Hz, X-ray crystallographic study
6
-H), 6.85 (d, 1H, Jꢀ=ꢀ8.7 Hz, arom.), 7.22–7.31 (m, 2H, arom.), 7.71 (d,
H, Jꢀ=ꢀ6.0 Hz, OH), 11.40 (s, 1H, NH); 1 C NMR: δ 20.8, 30.5, 35.4, 93.2,
3
1
1
Crystallographic data for 2i: Empirical formula C H NO S ꢀ·ꢀH O, for-
1
9
15
3
2
2
03.8, 118.9, 119.1, 124.4, 125.1, 128.7, 129.0, 129.4, 151.2, 170.9; ESI-MS:
mula weight 387.45, light-brown block crystals, crystal system mono-
+
m/z 342 (Mꢀ+ꢀH) . Anal. Calcd for C H ClNO S : C, 49.19; H, 3.54; N,
14
12
3 2
clinic, space group P2 /c, aꢀ=ꢀ10.9127(4), bꢀ=ꢀ15.1717(4), cꢀ=ꢀ11.2980(4)
1
4
.10. Found: C, 49.22; H, 3.55; N, 4.12.
3
3
Å, βꢀ=ꢀ111.457(4)°, Vꢀ=ꢀ1740.90(11) Å , Zꢀ=ꢀ4, D ꢀ=ꢀ1.478 g/cm . A light-
calc
brown crystal (benzene-acetone) (0.17ꢀ×ꢀ0.13ꢀ×ꢀ0.07 mm) was used to
record 17 948 (CuKα-radiation, θmaxꢀ=ꢀ76.38°) intensities on a Super
Nova diffractometer. The supplementary crystallographic data of 2i
have been deposited at the Cambridge Crystallography Data Cen-
tre (CCDC) as supplementary publication CCDC 1497433. Copies of
the data can be obtained, free of charge, on application to CCDC,
rel-(5S,5aR,6R,11bS)-10-Bromo-6-hydroxy-5-methyl-3,5a,6,11b-
tetrahydro-2H,5H-chromeno[4′,3′:4,5]thiopyrano[2,3-d][1,3]
1
thiazole-2-one (2h)ꢁYield 72%; mp 182–184°C (PhMe); H NMR: δ
1
.43 (d, 3H, Jꢀ=ꢀ6.9 Hz, CH ), 2.19 (dd, 1H, Jꢀ=ꢀ5.1,11.6 Hz, 5a-H), 3.52 (m,
3
1
H, 5-H), 4.08 (d, 1H, Jꢀ=ꢀ5.0 Hz, 11b-H), 5.31 (t, 1H, Jꢀ=ꢀ6.0 Hz, 6-H),
6
.79 (d, 1H, Jꢀ=ꢀ8.7 Hz, arom.), 7.33 (d, 1H, Jꢀ=ꢀ8.5 Hz, arom.), 7.42 (s, 1H,
1
2 Union Road, Cambridge CB2 1EZ, UK, (fax: +44-(0)1223-336033 or
13
arom.), 7.70 (d, 1H, Jꢀ=ꢀ6.3 Hz, OH), 11.40 (s, 1H, NH); C NMR: δ 20.7,
e-mail: deposit@ccdc.cam.ac.uk).
3
0.6, 35.4, 93.2, 103.8, 111.9, 125.7, 125.8, 128.7, 129.4, 131.9, 151.7, 170.9.
+
ESI-MS m/z 386/388 (Mꢀ+ꢀH) . Anal. Calcd for C H BrNO S : C, 43.53;
14
12
3 2
Acknowledgments: This work was partially supported by
the Ministry of Education and Science of Ukraine (Ukrain-
rel-(5S,5aR,6R,11bS)-6-hydroxy-5-phenyl-3,5a,6,11b-tetrahydro- ian-France program ‘Dnipro’ M/188-2015; 06.11.2015).
H, 3.13; N, 3.63. Found: C, 43.54; H, 3.14; N, 3.65.
2
H,5H-chromeno[4′,3′:4,5]thiopyrano[2,3-d][1,3]thiazole-2-one
1
(
2i)ꢁYield 71%; mp 188–190°C (PhMe); H NMR (400 MHz, DMSO-
d ): δ 2.59 (dd, 1H, Jꢀ=ꢀ4.3, 8.7 Hz, 5a-H), 3.98 (d, 1H, Jꢀ=ꢀ3.6 Hz, 11b-
H), 4.38 (d, 1H, Jꢀ=ꢀ8.8 Hz, 5-H), 5.01 (t, 1H, Jꢀ=ꢀ3.9 Hz, 6-H), 6.76 (d,
6
References
1
H, Jꢀ=ꢀ8.1 Hz, arom.), 6.66 (t, 1H, Jꢀ=ꢀ7.4 Hz, arom.), 7.08–7.14 (m, 2H,
13
arom.), 7.49 (d, 1H, Jꢀ=ꢀ4.9 Hz, OH), 11.32 (s, 1H, NH); C NMR: δ 30.3,
[
[
1] Boger, D.; Weinreb, S. Hetero Diels-Alder Methodology in
4
1.6, 44.0, 91.4, 103.6, 117.4, 120.3, 121.4, 123.4, 125.8, 128.7, 128.8, 128.9,
st
Organic Synthesis; 1 Edition. Academic Press: San Diego, 1987.
+
1
29.4, 138.3, 150.1, 171.1; ESI-MS: m/z 370 (Mꢀ+ꢀH) . Anal. Calcd for
2] Omar, M. T.; El-Aasar, N. K.; Saied, K. F. Stereochemistry of the
C H NO S : C, 61.77; H, 4.09; N, 3.79. Found: C, 61.75; H, 4.07; N, 3.80.
1
9
15
3
2
[4+2] cycloaddition reactions of 5-arylmethylene-2,4-dithioxo-
1
,3-thiazolidines with acrylonitrile, 1-ethoxy-3-phenyl-E-2-pro-
rel-(5S,5aR,6R,11bS)-6-Hydroxy-8-methoxy-5-phenyl-3,5a,6,11b-
tetrahydro-2H,5H-chromeno[4′,3′:4,5]thiopyrano[2,3-d][1,3]
pen-1-one and 3-phenyl-E-2-propen-1-one. J. Chem. Research,
Miniprint 2001, 11, 1127–1143.
1
thiazole-2-one (2j)ꢁYield 90%; mp 170–172°C (PhMe); H NMR: δ
[
3] Marchand, A.; Pradere, J.-P.; Guingant, A. Synthesis of (+,–)
3,4-disubstituted 3,4-dihydro-2H-thiopyrans via a diastereose-
lective hetero Diels-Alder reaction. Tetrahedron Lett. 1997, 38,
2
.33 (m, 1H, 5a-H), 3.77 (s, 3H, CH O), 3.90 (m, 1H, 11b-H), 4.41 (d, 1H,
3
Jꢀ=ꢀ9.2 Hz, 5-H), 5.08 (t, 1H, Jꢀ=ꢀ3.9 Hz, 6-H), 6.80–6.87 (m, 3H, arom.),
7
.34–7.40 (m, 6H, arom., OH), 11.35 (s, 1H, NH); 13C NMR: δ 30.5, 41.5,
1
033–1036.
4
3.9, 56.0, 91.5, 103.9, 111.5, 120.2, 120.4, 120.9, 123.7, 128.7, 128.8, 129.4,
[
4] Metwally, N. H.; Badawy, M. A.; Okpy, D. S. Synthesis and anti-
cancer activity of some new thiopyrano[2,3-d]thiazoles incorpo-
rating pyrazole moiety. Chem. Pharm. Bull. 2015, 63, 495–503.
5] Badawy, M. A.; Metwally, N. H.; Okpy, D. S. Synthesis of some
new 5-substituted-3-phenyl-4-thioxo-2-thiazolidinones and
their fused thiopyrano[2,3-d]thiazole derivatives. J. Sulfur
Chem. 2015, 36, 511–525.
+
138.6, 140.6, 148.7, 171.2; ESI-MS: m/z 400 (Mꢀ+ꢀH) . Anal. Calcd for
C H NO S : C, 60.13; H, 3.29; N, 3.51. Found: C, 60.12; H, 3.28; N, 3.53.
2
0
17
4 2
[
rel-(5S,5aR,6R,11bS)-10-Chloro-6-hydroxy-5-phenyl-3,5a,6,11b-
tetrahydro-2H,5H-chromeno[4′,3′:4,5]thiopyrano[2,3-d][1,3]
1
thiazole-2-one (2k)ꢁYield 78%, mp 190–192°C (PhMe); H NMR:
δ 2.75 (dd, 1H, Jꢀ=ꢀ4.8, 9.6 Hz, 5a-H), 4.10 (d, 1H, Jꢀ=ꢀ4.8 Hz, 11b-H),
[6] Kassab, N. A. L.; Messeha, N. A. Reactions with 5-substituted
2-thiazolidinone-4-thiones (isorhodanines). III. J. prakt. Chem.
1973, 315, 1017–1024.
[7] Zelisko, N.; Atamanyuk, D.; Vasylenko, O.; Grellier, P.; Lesyk, R.
Synthesis and antitrypanosomal activity of new 6,6,7-trisubsti-
tuted thiopyrano[2,3-d][1,3]thiazoles. Bioorg. Med. Chem. Lett.
2012, 22, 7071–7074.
4
.36 (d, 1H, Jꢀ=ꢀ9.4 Hz, 5-H), 4.98 (t, 1H, Jꢀ=ꢀ4.6 Hz, 6-H), 6.87 (d, 1H,
Jꢀ=ꢀ8.7 Hz, arom.), 7.12–7.20 (m, 2H, arom.), 7.65 (d, 1H, Jꢀ=ꢀ4.6 Hz, OH),
1
3
1
1
1.44 (s, 1H, NH). C NMR: δ 30.2, 41.0, 43.9, 91.4, 102.6, 119.4, 121.0,
24.9, 125.8, 128.4, 128.6, 128.7, 128.9, 129.4, 137.8, 149.8, 171.1; ESI-MS:
+
m/z 404/406 (Mꢀ+ꢀH) . Anal. Calcd for C H ClNO S : C, 56.50; H, 3.49;
19
14
3 2
N, 3.47. Found: C, 56.52; H, 3.51; N, 3.46.
[
8] Zelisko, N.; Atamanyuk, D.; Ostapiuk, Y.; Bryhas, A.; Matiychuk,
V.; Gzella, A.; Lesyk, R. Synthesis of fused thiopyrano[2,3-d]
[1,3]thiazoles via hetero-Diels–Alder reaction related tandem
and domino processes. Tetrahedron 2015, 71, 9501–9508.
rel-(5S,5aR,6R,11bS)-10-Bromo-6-hydroxy-5-phenyl-3,5a,6,11b-
tetrahydro-2H,5H-chromeno[4′,3′:4,5]thiopyrano[2,3-d][1,3]
1
thiazole-2-one (2l)ꢁYield 75%, mp 217–219°C (PhMe); H NMR: δ
2
.62 (dd, 1H, Jꢀ=ꢀ5.6, 10.9 Hz, 5a-H), 4.03 (m, 1H, 11b-H), 4.31 (d, 1H,
[9] Ead, H. A.; Abdallah, S. O.; Kassab, N. A.; Metwalli, N. H.;
Saleh, Y. E. 5-(Ethoxymethylene)thiazolidine-2,4-dione deriva-
tives: reactions and biological activities. Arch. Pharm. Chem.
Life Sci. 1987, 320, 1227–1232.
Jꢀ=ꢀ9.5 Hz, 5-H), 4.97 (m, 1H, 6-H), 6.74 (d, 1H, Jꢀ=ꢀ8.4 Hz, arom.), 7.26 (d,
1
3
1
H, Jꢀ=ꢀ7.6 Hz, arom.), 7.31–7.51 (m, 2H, OH, arom.), 11.44 (s, 1H, NH); C
NMR: δ 30.1, 41.0, 43.9, 91.4, 102.5, 112.6, 119.9, 121.0, 126.2, 128.9, 129.4,
+
1
31.3, 131.6, 17.8, 150.3, 171.1; ESI-MS: m/z 448/450 (Mꢀ+ꢀH) . Anal. [10] Abd Allah, S. O.; Hammouda, H. A.; Ali, F. A. Heterodiene
Calcd for C H BrNO S : C, 50.90; H, 3.15; N, 3.12. Found: C, 50.91; H,
synthesis: syntheses of fused thiopyranol 2,3-dithiazole and
thiazolo[3,4-c]triazine derivatives. Pharmazie 1986, 41, 101–103.
1
9
14
3 2
3
.13; N, 3.14.
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