536
Chem. Pharm. Bull.
Vol. 63, No. 7 (2015)
tion, the mixture was poured into ice/H2O, then was filtered dried over MgSO4, then filtered and concentrated in vacuo.
and concentrated in vacuo. The precipitate was filtered off The precipitate was filtered off and the crude product was pu-
and the crude product was purified by column chromatogra- rified by column chromatography on silica gel, using CH2Cl2
phy on silica gel, using CH2Cl2 as eluent, to give pure com- as eluent, to give pure compounds 7, 8 and 9.
1
pound 2. Yield 80%; mp 184°C; H-NMR (CDCl3, 400MHz)
3,3ʹ-Bis-p-chlorophenylsulfanyl-5,5ʹ-bi-1,2,4-triazine 7
Yield 36%; mp 195–200°C; H-NMR (CDCl3, 400MHz) δ:
δ: 7.24–7.40 (m, 5H), 7.47–7.50 (m, 5H); 13C-NMR (CDCl3,
1
100 MHz) δ: 128.50, 128.64, 129.49, 129.76, 129.81, 131.17, 7.48 (d, J=8.4Hz, 2H), 7.59 (d, J=8.8Hz, 2H), 9.55 (s, 1H);
134.72, 144.88, 155.21, 155.90, 167.73; HR-MS electron ioniza- 13C-NMR (CDCl3, 100MHz) δ: 122.24, 126.69, 126.78, 130.36,
tion (EI, m/z) Calcd for C30H21N6S2 [M+H]+ 529.12636. Found 135.61, 142.27, 150.12, 174.88; HR-MS (ESI, m/z) Calcd for
529.12713.
C18H12N6S2Cl2 [M+H] 447.98516. Found 447.98622.
3,3ʹ-Bis-5,5ʹ6,6ʹ-tetraphenylsulfanyl-1,2,4-triazin-5,5ʹ-
General Procedure for the Synthesis of 3 and 4
To a mixture of 0.14mmol 5,5ʹ-6,6ʹ-tetraphenyl-bis-(1,2,4- bi-1,2,4-triazine 8
triazine)-3,3ʹ-disulfide in 2mL of THF, 0.24mmol amine was Yield 62%; mp 250°C; H-NMR (CDCl3, 400MHz) δ: 7.32
1
added. The mixture was stirred at room temperature for 24h (t, J=8Hz, 2H), 7.39–7.46 (m, 4H), 7.5–7.61 (m, 4H), 9.85 (s,
(monitoring by TLC). The precipitate was concentrated in 1H); 13C-NMR (CDCl3, 100MHz) δ: 128.71, 128.80, 128.54,
vacuo and the crude product was purified by column chroma- 129.54, 129.82, 130.16, 131.44, 134.46, 134.51, 144.01; HR-MS
tography on silica gel, using CH2Cl2 :hexane (3:1) as eluent, (EI, m/z) Calcd for C36H23N12S2 [M+H] 687.16046. Found
to give pure compounds 3 and 4.
687.15833.
5,6-Diphenyl-3-sulfenylmorpholinamide-1,2,4-triazine 3
Yield 20%; mp 115°C; H-NMR (CDCl3, 400MHz) δ: 3.85
3,3ʹ-Bis-benzothiazolesulfanyl-5,5ʹ-bi-1,2,4-triazine 9
Yield 87%; mp 246–250°C; H-NMR (CDCl3, 400MHz) δ:
1
1
(t, J=4.8Hz, 4H), 4.03 (t, J=4.8Hz, 4H), 7.31–7.62 (m, 10H), 7.52 (dt, J=1.2, J=8.2Hz, 1H), 7.58 (dt, J=1.2, J=8.2Hz, 1H),
13C-NMR (CDCl3, 100MHz) δ: 44.0, 66.8, 128.3, 128.7, 129.1, 7.97 (dd, J=0.8Hz, J=8.0Hz 1H), 8.12 (dd, J=0.8, J=8.0,
129.6, 130.2, 136.2, 136.5, 149.0, 155.9, 159.6; HR-MS electron 1H), 9.87 (s, 1H); 13C-NMR (CDCl3, 100MHz) δ: 112.2, 121.4,
spray ionization (ESI, m/z) Calcd for C19H18N4SONa [M+Na]+ 124.7, 127.2, 129.3, 129.9, 140.2, 155.8; HR-MS (ESI, m/z)
373.1103. Found 373.1094.
5,6-Diphenyl-3-sulfenylpyrrolidinamide-1,2,4-triazine 4
Calcd for C20H10N8S4 [M+] 490.99840. Found 490.99530.
X-Ray Analysis X-Ray data of 7 were collected on
Yield 57%; mp 178°C; 1H-NMR (CDCl3, 400MHz) δ: the Bruker SMART APEX II CCD diffractometer; crys-
2.04–2.08 (m, 4H), 3.78 (brs, 4H), 7.26–7.32 (m, 5H), 7.76–7.45 tal sizes 0.69×0.66×0.15mm, CuKα (λ=0.1.54178Å) ra-
(m, 3H), 7.50–7.53 (m, 2H); 13C-NMR (CDCl3, 100MHz) δ: diation, φ and ω scans, multi-scan absorption correction (Tmin
/
25.5, 46.6, 155.9, 158.3, 127.9, 128.2, 129.1, 129.7, 129.9, 136.7, Tmax=0.1086/0.5086.21) The structure was solved by direct
147.8; HR-MS electron spray ionization (ESI, m/z) Calcd for methods using SHELXS9722) and refined by full-matrix least-
C19H19N4S [M+H]+ 335.13249. Found 335.13070.
General Procedure for the Synthesis of 5 and 6
squares with SHELXL97.18) The H atoms were positioned
geometrically and treated as riding on their parent C atoms
To a mixture of 0.19mmol of 5,6-diphenyl-3-sulfenyl- with C–H distances of 0.93Å (aromatic). All H atoms were
pyridin-1,2,4-triazine (4) in 10mL of CH2Cl2, 0.39mmol of refined with isotropic displacement parameters taken as 1.5
m-chloroperbenzoic acid (m-CPBA) was added. The mixture times those of the respective parent atoms. Compound 7
was stirred at 0°C for 24h (monitoring by TLC). The pre- crystallized in non-centrosymmetric space group P21 with
cipitate was concentrated in vacuo and the crude product four molecules in asymmetric part of the unit cell. These
was purified by column chromatography on silica gel, using four independent molecules are almost perfectly related by
CH2Cl2 : CH3COCH3 (100:1) as eluent, to give pure compound two pseudo-inversion centers located at (0.066, 0.088, 0.433)
5 and 6.
5,6-Diphenyl-3-sulfinylpyrrolidinamide-1,2,4-triazine 5
and (0.438, 0.078, 0.060), which confirms the occurrence of
non-crystallographic symmetry (NCS)23) in crystal of 7. The
1
Yield 39%; mp 191°C; H-NMR (CDCl3, 400MHz) δ: 2.04 refinement of the structure gave Flack parameter of 0.45(2) for
(brs, 4H), 4.05 (brs, 4H), 7.26–7.41 (m, 10H), 13C-NMR 5214 Friedel pairs, suggesting that the crystal is possibly in-
(CDCl3, 100MHz) δ: 25.2, 25.5, 46.7, 46.9, 128.5, 128.6, 129.3, version twined. Therefore, in last cycles of refinement the ap-
129.4, 131.0, 135.3, 136.2, 159.4, 162.9; HR-MS (ESI, m/z) propriate TWIN/BASF instructions of SHELXL97 were used
Calcd for C19H18N4SO [M+H]+ 350.12043. Found 350.12093.
5,6-Diphenyl-3-sulfonylpyrrolidinamide-1,2,4-triazine 6
giving the fractional contributions of the twin components
of 0.48/0.52. All calculations were performed using WINGX
Yield 40%; mp 167°C; 1H-NMR (CDCl3, 400MHz) δ: version 1.64.05 package.24) CCDC-1030065 contains the
2.04 (brs, 4H), 4.05 (brs, 4H), 7.26–7.41 (m, 10H), 13C-NMR supplementary crystallographic data for this paper. These data
129.4, 131.0, 135.3, 136.2, 159.4, 162.9; HR-MS (ESI, m/z) retrieving.html [or from the Cambridge Crystallographic Data
Calcd for C19H18N4SO2 [M+H]+ 366.16046. Found 366.16833.
General Procedure for the Synthesis of 7–9
To a mixture of 0.66g (4.79mmol) of K2CO3 in 7mL of
DMSO, 4.39mmol of thiol was added. The mixture was
Centre (CCDC), 12 Union Road, Cambridge CB2 1EZ, UK;
Fax: +44(0)–1223–336–033; e-mail: deposit@ccdc.cam.ac.uk].
Crystal Data of 7
C18H10N6S2Cl2, M=445.34, monoclinic, space group P21,
stirred at room temperature for 15min. After that 2.18mmol a=18.9516(9), b=7.2403(3), c=27.8497(13) Å, β=96.201(2)°,
of 3,3ʹ-bis-chloro-5,5ʹ-bi-1,2,4-triazine 2 was added. The mix- V=3799.0(3) Å3, Z=8, dcalc=1.557mgm−3, F(000)=1808,
ture was stirred for 24h (monitoring by TLC). After the end µ(CuKα)=5.282 mm−1, T=150K, 30715 measured reflections
of reaction, the mixture was poured into ice/H2O and was (θ range 2.34–67.52°), 12531 unique reflections (Rint=0.047),
extracted with ether (5×10mL). The combined extracts were final R=0.048, wR=0.128, S=1.032 for 11295 reflections with