B. Xi et al. / Tetrahedron xxx (2015) 1e10
9
(300 MHz, CDCl3)
(s, 1H), 8.24e8.21 (d, J¼7.8 Hz, 1H), 8.08e8.04 (dd, J¼8.7 Hz, 1.8 Hz,
1H), 8.68e8.34 (m, 9H). 13C NMR (75 MHz, CDCl3)
: 181.9, 176.8,
152.6, 142.8, 141.6, 137.8, 136.8, 130.0, 128.1, 127.0, 126.9, 125.4,
124.7, 123.8, 123.0, 120.9, 120.7, 119.8, 110.3. EIeTOFeMS (m/z):
calcd for [C22H14N2OS]þ 354.1 (100%), 355.1 (24.0%), 356.1 (4.7%),
found 354.1 (100%), 355.1 (5.8%), 356.1 (0.4%). Anal. Calcd for
d
: 10.05 (s, 1H), 8.86e8.85 (d, J¼1.5 Hz, 1H), 8.44
(s, 2H). 13C NMR (75 MHz, CDCl3)
d
: 143.7, 140.7, 136.4, 133.6, 127.3,
126.8, 126.7, 126.0, 125.9, 123.3, 123.2, 120.2, 120.0, 109.7.
EIeTOFeMS (m/z): calcd for [C44H32N4S2]þ 680.2 (100%), 681.2
(49.6%), 682.2 (12.5%), found 680.2 (100%), 681.2 (23.2%), 682.2
(1.9%). Anal. Calcd for C44H32N4S2: C, 77.62, H, 4.74, N, 8.23%. Found:
C, 77.51, H, 4.98, N, 8.34%. Compound 4a: Mp: 177e180 ꢀC. Main
FTIR absorptions (KBr pellets, cmꢂ1): 3429 (m), 2923 (w), 1589 (s),
1489 (m), 1444 (m), 1323 (s), 1277 (s), 1108 (m), 847 (w), 815 (w),
d
C
22H14N2OS: C, 74.55, H, 3.98, N, 7.90%. Found: C, 74.41, H, 3.83, N,
8.07%.
755 (m), 696 (s), 630 (w), 505 (m). 1H NMR (300 MHz, CDCl3)
d:
7.75e7.70 (d, J¼8.7 Hz, 2H), 7.44 (d, J¼1.2 Hz,1H), 7.31e7.25 (m, 4H),
7.14e7.04 (m, 8H), 2.48 (s, 3H). EIeTOFeMS (m/z): calcd for
[C22H18N2S]þ 342.1 (100%), 343.1 (25.3%), 344.1 (4.5%), found 342.2
(100%), 343.2 (11.9%), 344.2 (1.1%). Anal. Calcd for C22H18N2S: C,
77.16, H, 5.30, N, 8.18%. Found: C, 77.07, H, 5.23, N, 8.23%.
4.2.4. Compound 7. TiCl4 (0.62 mL, 5.63 mmol) dissolved in anhy-
drous dichloromethane (10 mL) was carefully added into dry THF
(30 mL) at 0 ꢀC.23 Zinc dust (0.73 g, 11.3 mmol) was added and then
the mixture was refluxed at 85 ꢀC for 2 h. Pyridine (0.48 mL,
5.63 mmol) was added and the mixture was refluxed for another
1 h. After cooling to ambient temperature, a solution of compound
1 (0.40 g,1.13 mmol) in dry THF (20 mL) was added and the reaction
mixture was refluxed at 85 ꢀC for 2 days. The reaction was
quenched with water at 0 ꢀC, then the mixture was extracted with
CHCl3 (3ꢁ40 mL) and washed with saturated NH4Cl (50 mL) and
H2O (3ꢁ40 mL), and then dried over anhydrous MgSO4. After re-
moving the solvent in vacuo, the crude product was purified by
column chromatography on silica gel with petroleum ether
(60e90 ꢀC) and dichloromethane (v/v¼2:1) as eluent to produce
0.20 g (52%) compound 7 as orange solid. Mp: 213e215 ꢀC. Main
FTIR absorptions (KBr pellets, cmꢂ1): 3450 (m), 1586 (s), 1486 (s),
1321 (m), 1274 (s), 1180 (w), 933 (w), 830 (w), 795 (m), 754 (m), 693
4.2.7. Compound 11. The synthetic procedure of compound 11 was
the same as that of compound 7 except that aldehyde 5 (0.40 g,
1.13 mmol) was used instead of aldehyde 1. Compound 11 was
obtained as light yellow solid in a yield of 0.12 g (31%) after column
chromatography of the crude product on silica gel with hexane/
DCM (v/v¼1:2) as eluent. Mp: 211e213 ꢀC. Main FTIR absorptions
(KBr pellets, cmꢂ1): 3452 (m), 2960 (m), 2853 (m), 1715 (w), 1597
(m), 1514 (m), 1444 (s), 1341 (m), 1261 (s), 1223 (w), 1097 (s), 1024
(s), 805 (s), 743 (m), 629 (w). 1H NMR (300 MHz, CDCl3)
d:
8.22e8.16 (dd, J¼12.3 Hz, 7.8 Hz, 8H), 7.89 (s, 2H), 7.73e7.70 (d,
J¼8.7 Hz, 4H), 7.52e7.31 (m, 14H), 7.14 (s, 2H). EIeTOFeMS (m/z):
calcd for [C44H28N4S2]þ 676.2 (100%), 677.2 (47.9%), 344.1 (12.5%),
found 676.1 (100%), 677.1 (59.4%), 344.2 (7.4%). Anal. Calcd for
(m), 511 (m). 1H NMR (300 MHz, CDCl3)
2.7 Hz, 4H), 7.30e7.28 (m, 6H), 7.25 (s, 2H), 7.14e7.11 (m, 10H),
7.08e7.02 (m, 8H), 6.99e6.97 (m, 4H). 13C NMR (75 MHz, CDCl3)
d: 7.48e7.44 (dt, J¼8.7 Hz,
C44H28N4S2: C, 78.08, H, 4.17, N, 8.28%. Found: C, 78.19, H, 4.35, N,
d:
8.39%.
147.3,142.8,141.0,129.2,128.1,127.3,126.3,124.5,123.4,123.1,122.6,
121.0. EIeTOFeMS (m/z): calcd for [C46H34N2S2]þ 678.2 (100%),
679.2 (51.7%), 680.2 (13.3%), found 677.9 (100%), 679.1 (68.7%),
680.0 (6.7%). Anal. Calcd for C46H34N2S2: C, 81.38, H, 5.05, N, 4.13%.
Found: C, 81.23, H, 5.11, N, 4.08%.
Acknowledgements
This work was financially supported by the Major State Basic
Research Development Programs (Nos. 2013CB922101 and
2011CB933300), the National Natural Science Foundation of China
(No. 21171088), and the Natural Science Foundation of Jiangsu
Province (Nos. BK20130054 and BE2014147-1).
4.2.5. Compound 8. Synthesis of this compound was similar to that
described for compound 7 except that compound 2 (0.40 g,
1.13 mmol) was used instead of compound 1. Compound 8 was
obtained as pale yellow powder in a yield of 0.18 g (47%) after
column chromatography of the crude product on silica gel with
petroleum ether/CH2Cl2 (v/v¼2:1) as eluent. Mp: 211e213 ꢀC. Main
FTIR absorptions (KBr pellets, cmꢂ1): 3426 (m), 2918 (s), 2850 (m),
1601 (m), 1513 (s), 1450 (s), 1326 (m), 1229 (m), 1110 (m), 802 (m),
Supplementary data
Supplementary data (FTIR, EIeTOFeMS, 1H and 13C NMR spec-
tra, TGA diagrams, HOMOs/LUMOs and temperature-dependent
750 (s), 723 (m), 505 (m). 1H NMR (300 MHz, CDCl3)
(dd, J¼12.3 Hz, 7.8 Hz, 8H), 7.89 (s, 2H), 7.73e7.70 (d, J¼8.7 Hz, 4H),
7.52e7.30 (m, 14H), 7.14 (s, 2H). 13C NMR (75 MHz, CDCl3)
: 166.6,
d
: 8.22e8.16
IeV
curves
for
related
compounds.
CCDC
numbers
1052650e1052654 contain the supplementary crystallographic
data for this paper. These data can be obtained free of charge at
Crystallographic Data Centre, 12, Union Road, Cambridge CB2 1EZ,
UK; Fax: (internat.) þ44-1223/336-033; E-mail: depos-
d
149.7, 146.9, 142.7, 136.2, 129.4, 127.4, 126.6, 125.2, 123.8, 121.9,
120.6. EIeTOFeMS (m/z): calcd for [C46H30N2S2]þ 674.2 (100%),
675.2 (50.1%), 676.2 (13.5%), found 674.2 (100%), 675.3 (76.9%),
676.3 (6.6%). Anal. Calcd for C46H30N2S2: C, 81.87, H, 4.48, N, 4.15%.
Found: C, 81.78, H, 4.63, N, 4.20%.
4.2.6. Compounds 10 and 4a. The procedure for preparing com-
pound 7 was repeated except that thiazole based aldehyde 4
(0.40 g,1.13 mmol) was used instead of thiophene based aldehyde 1.
Compound 4a was obtained as a by-product of this reaction.
Compounds 10 and 4a were purified by silica gel column chroma-
tography of the crude product using hexane and dichloromethane
(v/v¼1:2) as eluent to give 10 as orange solid and 4a as colorless
solid in the yields of 0.17 g (45%) and 0.04 g (10%), respectively.
Compound 10: Mp: 210e212 ꢀC. Main FTIR absorptions (KBr pellets,
cmꢂ1): 3439 (m), 1587 (s), 1492 (s), 1439 (m), 1410 (m), 1323 (m),
1281 (s), 1180 (w), 1146 (w), 834 (w), 755 (w), 696 (m), 629 (w), 588
References and notes
(w), 515 (w). 1H NMR (300 MHz, CDCl3)
1.8 Hz, 8H), 7.70 (s, 2H), 7.33e7.28 (m, 8H), 7.16e7.06 (m, 16H), 6.97
d: 7.79e7.76 (dt, J¼8.7 Hz,