5
4
3
.2 Synthesis of compound 1
Supplementary data
ACCEPTED MANUSCRIPT
1
13
-acetyl-7-diethylamino-2H-chromen-2-one (3)
H NMR, C NMR and HRMS spectra of the intermediate 2
and final product 1 are available. Additional UV-vis absorption
and emission spectra related to this article can be found in ESI.
The intermediate 3 was synthesized according to the
28
literature with a minor modification. 4-N,N-Diethylamino-
salicyaldehyde (1.93 g, 10 mmol), ethyl acetoacetate (1.95 g, 15
mmol), and 3 drops of piperidine were dissolved in 20 mL of
absolute ethanol. After the mixture solution was refluxed for 8 h,
the solvent was removed under reduced pressure. The yellow
solid was precipitated and collected, and the crude product was
References and notes
1. Du, J. J.; Hu, M. M.; Fan, J. L.; Peng, X. J. Chem. Soc. Rev. 2012, 41,
4511-4535.
2
. Ashton, T. D.; Jolliffe, K. A.; Pfeffer, F. M. Chem. Soc. Rev. 2015, 44,
recrystallized from absolute ethanol to afford compound 3 (2.0 g,
4547-4595.
1
7
7%). H NMR (400 MHz, CDCl , TMS) δ: 8.42-8.41 (d, 1H,
3. Lee, M. H.; Kim J. S.; Sessler. J. L. Chem. Soc. Rev. 2015, 44, 4185-4191.
3
4
. Ren, J.; Wu, Z.; Zhou, Y.; Li, Y.; Xu, Z. X. Dyes Pigm. 2011, 91, 442-
J=2.2 Hz), 7.39-7.37 (m, 1H), 6.62-6.59 (m, 1H), 6.46-6.45 (d,
H, J=2.4 Hz), 3.47-3.42 (q, 4H, J=7.2 Hz), 2.67 (t, 3H, J=7.2
Hz), 1.25-1.21 (t, 6H, J=7.2 Hz).
1
445.
5. Ke, B. W.; Chen, W. X.; Ni, N. T.; Cheng, Y. F.; Dai, C. F.; Dinh, H.;
Wang, B. H. Chem. Commun. 2013, 49, 2494-2496.
3
-chloro-3-(7-(diethylamino)-2-oxo-2H-chromen-3-yl) acylalde-
hyde (2)
6
7
. Amalraj, A.; Pius, A. J. Fluorine Chem. 2015, 178, 73-78.
. Bao, Y. Y.; Liu, B.; Wang, H.; Tian, J.; Bai, R. K. Chem. Commun. 2011,
4
7, 3957-3959.
The intermediate 2 was synthesized according to the reported
29-30
8
9
1
1
1
1
1
. Zhang, L.; Wang, L. M.; Zhang, G. J.; Yu, J. J.; Cai, X. F.; Teng, M. S.;
Wu, Y. Chin. J. Chem. 2012, 30, 2823-2826.
method
with a minor modification. In a 100mL three-necked
round bottomed flask, N,N-dimethyl formamide (10.0 mL) and
compound 3 (2.6 g, 10.0 mmol), were taken and cooled to 0-5 °C
with stirring under Ar. To the above solution phosphorous
oxychloride (4.45 g, 2.70 mL, 27.0 mmol) was added dropwise
maintaining the temperature of the reaction mass at 0-5 °C. The
reaction mixture was stirred at 0-5 °C for 3 h, then allowed to
attain room temperature and then heated at 80-85 °C for 8 h.
Subsequently, the reaction mass was cooled to room temperature
and poured in to crushed ice with stirring and deep external
cooling, the clear solution was neutralized with sodium
carbonate to pH 7-8, by keeping the temperature below 10 °C.
The product was filtered, washed with ice cold water and dried.
. Xiong, J.; Sun, L.; Liao, Y; Li, G. N.; Zuo, J. L.; You, X. Z. Tetrahedron
Lett. 2011, 52, 6157-6161.
0. Zhang, J. F.; Zhou, Y.; Yoon, J.; Kim, J. S. Chem. Soc. Rev. 2011, 40,
3
416-3429.
1. Cao, X. W.; Lin, W. Y.; Yu, Q. X.; Wang, J. L. Org. Lett. 2011, 13,
098-6101.
6
2. Yu, M. M.; Xu, J.; Peng, C.; Li, Z. X.; Liu, C. X.; Wei, L. H.
Tetrahedron. 2016, 72, 273-278.
3. Cosentino, P.; Grossman, B.; Shieh, C.; Doi, S.; Xi, H.; Erbland, P. J.
Geotech. Eng. 1995, 121, 610-617.
4. Konieczka, P.; Zygmunt, B.; Namiesnik, J. Bull. Environ. Contam.
Toxicol. 2000, 64, 794-803.
The compound 2 was crystallized from ethanol as brick red
1
1
1
5. Zhou, Y.; Zhang, J. F.; Yoon, J. Chem. Rev. 2014, 114, 5511-5571.
6. Gai, L. Z.; Mack, J.; Lu, H.; Nyokong, T.; Li, Z. F.; Kobayashi, N.; Shen,
Z. Coord. Chem. Rev. 2015, 285, 24-51.
power (2.0 g, 65%). H NMR (400 MHz, CDCl , TMS) δ: 10.27
3
(
1
d, 1H, J=6.8 Hz), 8.37 (s, 1H), 7.67 (d, 1H, J=6.8 Hz), 7.40 (d,
H, J=8.8 Hz), 6.66-6.63 (dd, 1H, J=8.8 Hz, 8.8Hz), 6.48 (d, 1H,
J=2.4 Hz), 3.50-3.44 (q, 4H, J=6.8 Hz), 1.27-1.23 (t, 6H, J=6.8
1
1
1
2
2
2
2
2
2
2
7. Hu, J. Y.; Liu, R.; Cai, X.; Shu, M. L.; Zhu, H. J. Tetrahedron. 2015, 71,
13
3
838-3843.
Hz); C NMR (100 MHz, CDCl , TMS) δ: 192.35, 158.39,
3
8. Wang, J. B.; Zong, Q. S.; Wu, Q. Q.; Shen, J. J.; Dai, F. Y.; Wu, C . J.
Tetrahedron. 2015, 71, 9611-9616.
1
1
56.78, 152.66, 145.22, 144.82, 131.01, 126.17, 112.94, 109.93,
08.38, 96.49, 45.19, 12.47. HRMS (ESI) calcd for C H ClNO
16
16
3
+
9. Ding, L.; Wu, M. J.; Li, Y. R.; Chen, Y.; Su, J. H. Tetrahedron Lett.
MH 328.0716, found 328.0714.
2
014, 55, 4711-4715.
3
-chloro-3-(7-(diethylamino)-2-oxo-2H-chromen-3-yl)allylidene-
hydrazinecarbothioamide (1)
0. Lu, W.; Zhang, M. Y.; Liu, K. Y.; Fan, B.; Xia, Z.; Jiang, L. M. Sens.
Actuators B. 2011, 160, 1005-1010.
1. Sharma, S.; Hundal, M. S.; Hundal, G. Tetrahedron Lett. 2013, 54, 2423-
Compound 2 (0.305 g, 1 mmol), thiosemicarbazide (0.091 g,
mmol), and 20 mL of ethanol were added to 100 mL round-
2
427.
2. Peng, X. J.; Wu, Y. K.; Fan, J. L.; Tian, M. Z.; Han, K. L. J. Org. Chem.
005, 70, 10524-10531.
3. De Silva, A. P.; Moody, T. S.; Wright, G. D. Analyst. 2009, 134, 2385-
393.
1
bottom flask, and then 5 drops of CH COOH was added to the
3
2
system. The reaction mixture was stirred at 80 °C for 8 h. The
precipitate was filtered after the final reaction mixture was
cooled to room temperature. The precipitate was washed
repeatedly with ethanol and dried under vacuum to obtain orange
2
4. Wang, C. Y.; Yang, S.; Yi, M.; Liu, C. H.; Wang, Y. J.; Li, J. S.; Li, Y.
H.; Yang, R. H. Appl. Mater. Interfaces. 2014, 6, 9768-9775.
1
compound 1 (0.20 g, 82%). MP: 226-228°C. H NMR (400
5. Zhou, X. Q.; Lai, R.; Li, H.; Stains, C. I. Anal. Chem.2015, 87, 4081-
MHz, DMSO-d , TMS) δ: 11.56 (s,1H), 8.34 (s, 1H), 8.28 (d,
6
4
086.
1
7
1
H, J=9.2 Hz), 8.26 (s, 1H), 7.86 (s, 1H), 7.81 (d, 1H, J=9.2 Hz),
.63 (d, 1H, J=9.2 Hz), 6.75 (dd, 1H, J=8.8 Hz, 9.2Hz), 6.56 (d,
H, J=2.0Hz), 3.49-3.44 (q, 4H, J=6.8 Hz), 1.16-1.12 (t, 6H,
6. Tan, W. B.; Leng, T. H.; Lai, G. Q.; Li, Z. F.; Wu, J. F.; Shen, Y. J.;
Wang, C. Y. Chin. J. Chem. 2016, 34, 809-813.
13
27. Wu, J. F.; Lai, G. Q.; Li, Z. F.; Lu, Y. X.; Leng, T. H.; Shen, Y. J.; Wang,
J=6.8 Hz); C NMR (100 MHz, DMSO-d , TMS) δ: 177.66,
6
C. Y. Dyes Pigm. 2016, 124, 268-276.
1
1
58.22, 155.39, 151.70, 142.25, 141.49, 132.32, 130.84, 124.35,
2
2
3
8. Wu, J. S.; Sheng, R. L.; Liu, W. M.; Wang, P. F.; Zhang, H. Y.; Ma, J. J.
Tetrahedron. 2012, 68, 5458-5463.
13.12, 109.87, 107.76, 95.68, 44.27, 12.28. HRMS (ESI) calcd
+
for C H ClN O S MH 379.0996, found 379.0999.
17
19
4
2
9. Debnath, T.; Dana, J.; Maity, P.; Lobo, H.; Shankarling, G. S.; Ghosh, H.
N. Chem. Eur. J. 2015, 21, 5704-5708.
Acknowledgements
0. Debnath, T.; Dana, J.; Maity, P.; Lobo, H.; Singh, B.; Shankarling, G. S.;
Ghosh, H. N. Chem. Eur. J. 2014, 20, 3510-3519.
We gratefully acknowledge the financial support by the
Natural Science Foundation of Shanghai (16ZR1408000), and
the National Key Program of China (2016YFA0200302).