Hydrazones as Fluoride Chemosensors
FULL PAPER
1,5-Dibenzylidene thiocarbonohydrazide (2): Yield: 73.3%; m.p. 200–
2018C; white powder; 1H NMR (400 MHz, [D6]DMSO, 258C, TMS): d=
11.65 (brs, 2H; NH), 8.26–8.59 (brs, 2H; CH=N), 7.82 (brs, 4H; ArH),
7.42–7.49 ppm (m, 6H; ArH); 13C NMR (100 MHz, [D6]DMSO, 258C,
TMS): d=174.8, 148.6, 143.3, 134.1, 123.0, 128.7, 127.3 ppm; ESI-mass:
m/z (%): 305.1 (38) [M+Na]+, 587.2 (100) [2M+Na]+.
Acknowledgements
This work was financially supported by the National Natural Science
Foundation of China (NSFC Project 20642003), the Scientific Research
Foundation for the Returned Overseas Chinese Scholars, the Ministry of
Education and Dalian University of Technology (Project 893332 and
0204–872X32). The authors are grateful to Prof. Jingping Qu, Shang Gao
and Jun Hou for helpful discussions. We are also grateful to the anony-
mous referees for their critical and very helpful reviewing of the manu-
script.
1,5-Bis(4-N,N-dimethylaminobenzylidene)thiocarbonohydrazide
(3):
Yield: 66.3%; m.p. 245–2478C; yellow powder; 1H NMR (400 MHz,
[D6]DMSO, 258C, TMS): d=11.50 (brs, 1H; NH), 11.18 (brs, 1H; NH),
8.43 (brs, 1H; CH=N), 7.99 (brs, 1H; CH=N), 7.55–7.67 (brs, m, 4H;
ArH), 6.76 (brs, 4H; ArH), 2.98 ppm (s, 12H; NCH3); 13C NMR
(100 MHz, [D6]DMSO, 258C, TMS): d=173.8, 152.1, 149.7, 144.5, 129.6,
129.1, 1223.3, 121.9, 122.3, 121.9, 112.4, 40.4 ppm; ESI-mass: m/z (%):
369.1 (30) [M+H]+, 759.3 (100) [2M+Na]+.
[1] A. Prasanna de Silva, H. Q. Nimal Gunaratne, T. Gunnlaugsson,
A. J. M. Huxley, C. P. McCoy, J. T. Rademacher, T. E. Rice, Chem.
Rev. 1997, 97, 1515–1566.
[2] A. Robertson, S. Shinkai, Coord. Chem. Rev. 2000, 205, 157–199.
[3] P. D. Beer, P. A. Gale, Angew. Chem. 2001, 113, 502–532; Angew.
Chem. Int. Ed. 2001, 40, 486–516.
[4] M. D. Best, S. L. Tobey, E. V. Anslyn, Coord. Chem. Rev. 2003, 240,
3–15.
[5] R. Martínez-MµÇez, F. Sancenón , Chem. Rev. 2003, 103, 4419–
4476.
p-Dimethylaminobenzaldehydethiocarbonohydrazone (5): Yield: 60.8%;
m.p. 178–1808C; yellow powder; 1H NMR (400 MHz, [D6]DMSO, 258C,
TMS): d=11.19 (s, 1H; NH), 9.55 (s, 1H; NH), 7.89 (s, 1H; CH=N), 7.61
(d, J=8.0 Hz, 2H; ArH), 6.68 (d, J=8.0 Hz, 2H; ArH), 4.80 (s, 2H;
NH2), 2.96 ppm (s, 6H; CH3); ESI-mass: m/z (%): 260.0 (100) [M+Na]+,
497.2 (40) [2M+Na]+.
p-Nitrobenzaldehyde-thiocarbonohydrazone (6): Yield: 88.0%; m.p. 204–
2068C; yellow powder; 1H NMR (400 MHz, [D6]DMSO, 258C, TMS):
d=11.76 (s, 1H; NH), 10.17 (s, 1H; NH), 8.22 (d, J=8.0 Hz, 2H; ArH),
8.13 (d, J=8.0 Hz, 2H; ArH), 8.09 (s, 1H; CH=N), 4.96 ppm (s, 2H;
NH2); ESI-mass: m/z (%): 238.1 (100) [MꢀH]ꢀ, 274.0(74) [M+Cl]ꢀ.
Bisthiocarbonohydrazone of 4-nitroacetophenone (7): Yield: 82.1%; m.p.
210–2128C; yellow powder; 1H NMR (400 MHz, [D6]DMSO, 258C,
TMS): d=11.14 (brs, 2H; NH), 8.28 (d, J=8.0 Hz, 4H; ArH), 8.14 (d,
J=8.0 Hz, 4H; ArH), 2.45 ppm(s, 6H; CH3); ESI-mass: m/z (%): 399.2-
[6] L. Pu, Chem. Rev. 2004, 104, 1687–171.
[7] R. Martínez-MµÇez, F. Sancenón, J. Fluoresc. 2005, 15, 267–285.
[8] a) C. Suksai, T. Tuntulani, Top. Curr. Chem. 2005, 255, 163–198;
b) M.-L. Lehaire, R. Scopelliti, H. Piotrowski, K. Severin, Angew.
Chem. 2002,114, 1477–1480; Angew. Chem. Int. Ed. 2002, 41, 1419–
1422; c) I. H. A. Badr, M. E. Meyerhoff, J. Am. Chem. Soc. 2005,
127, 5318–5319; d) K. H. Lee, H. Y. Lee, D. H. Lee, J. I. Hong, Tet-
rahedron Lett. 2001, 42, 544–5449; e) R. Miao, Q. Y. Zheng, C. F.
Chen, Z. T. Huang, Tetrahedron Lett. 2004, 45, 4959–4962; f) Z. Q.
Liu, M. Shi, F. Y. Li, Q. Fang, Z. H. Chen, T. Yi, C. H. Huang, Org.
Lett. 2005, 7, 5481–5484; g) M. Melaimi, F. P. Gabbai, J. Am. Chem.
Soc. 2005, 127, 9680–9681; h) J. S. Wu, J. H. Zhou, ; P. F. Wang,
X. H. Zhang, S. K. Wu, Org. Lett. 2005, 7, 2133–2136; i) K. J. Wal-
lace, W. J. Belcher, D. R. Turner, K. F. Syed, J. W. Steed, J. Am.
Chem. Soc. 2003, 125, 9699–9715; j) T. Neumann, Y. Dienes, T.
Baumgartner, Org. Lett. 2006, 8, 495–497; k) H. Maeda, Y. Kusu-
nose, Chem. Eur. J. 2005, 11, 5661–5666; l) T. Gunnlaugsson, P. E.
Kruger, P. Jensen, J. Tierney, H. Dato Paduka Ali, G. M. Hussey, J.
Org. Chem. 2005, 70, 10875–10878.
[9] M. Shionoya, H. Furuta, V. Lynch, A. Hamiman, J. L. Sessler, J.
Am. Chem. Soc. 1992, 114, 5714–5722.
[10] C. B. Black, B. Andrioletti, A. C. Try, C. Ruiperez, J. L. Sessler, J.
Am. Chem. Soc. 1999, 121, 10438–10439.
[11] P. Anzenbacher, Jr., K. Jursikova, J. L. Sessler, J. Am. Chem. Soc.
2000, 122, 9350–9351.
[12] a) M. Takeuchi, T. Shioya, T. M. Swager, Angew. Chem. 2001, 113,
3476–3480; Angew. Chem. Int. Ed. 2001, 40, 3372–3376; b) C.
Bohne, H. Ihmels, M. Waidelich, C. Yihwa, J. Am. Chem. Soc. 2005,
127, 17158–17159; c) T. Mizuno, W.-H. Wei, L. R. Eller, J. L. Sess-
ler, J. Am. Chem. Soc. 2002, 124, 1134–1135.
[13] a) Y. Kubo, M. Yamamoto, M. Ikeda, M. Takeuchi, S. Shinkai, S. Ya-
maguchi, K. Tamao, Angew. Chem. 2003, 115, 2082–2086; Angew.
Chem. Int. Ed. 2003, 42, 2036–2040; b) S. Arimori, M. G. Davidson,
T. M. Fyles, T. G. Hibbert, T. D. James, G. I. Kociok-Kçhn, Chem.
Commun. 2004, 1640–1641; c) N. Di Cesare, J. R. Lakowicz, Anal.
Biochem. 2002, 301, 111–116.
A
Bis(4-nitrobenzylidene)hydrazine (9): Yield: 63.7%; m.p. >3008C; light
1
yellow powder; H NMR (400 MHz, [D6]DMSO, 258C, TMS): d=8.88 (s,
2H; CH=N), 8.37 (d, J=8.0 Hz, 4H; ArH), 8.16 ppm (d, J=8.0 Hz, 4H;
ArH); ESI-mass: m/z (%): 298.3 (100) [M+H]+.
Bis-[1-(4-nitro-phenyl)ethylidene]hydrazine (10): Yield: 8.8%; m.p.
189.3–190.78C; orange powder; 1H NMR (400 MHz, [D6]DMSO, 258C,
TMS): d=8.31 (d, J=8.0 Hz, 4H; ArH), 8.17 (d, J=8.0 Hz, 4H; ArH),
2.33 ppm (s, 6H; CH3); ESI-mass: m/z (%): 326.3 (100) [MꢀH]ꢀ.
1,5-Bis(4-nitrobenzylidene)carbonohydrazide (11): Yield: 43.5%; m.p.
2528C; light yellow powder; 1H NMR (400 MHz, [D6]DMSO, 258C,
TMS): d=11.22 (brs, 2H; NH), 8.28 (m, 6H), 8.02 ppm (d, J=12.0 Hz,
4H; ArH); ESI-mass: m/z (%): 356.5 (100) [M+H]+.
1,5-Bis(9-anthracylidine) thiocarbonohydrazide (anthracene-9-carbalde-
hydebisthiocarbohydrazone) (12): Yield: 87.0%; m.p. 212–2148C; orange
powder; 1H NMR (400 MHz, [D6]DMSO, 258C, TMS): d=12.12–12.26
(brs, 2H; NH), 9.71 (brs, 1H; CH=N), 9.45 (brs, 1H; CH=N), 8.60–
8.97 (m, 6H; ArH), 8.16–8.18 (m, 4H; ArH), 7.59–7.65 ppm(m, 8H;
ArH); ESI-mass: m/z (%): 482.9 (100) [M+H]+.
X-ray crystallography: The single-crystal structure solution was per-
formed by using SHELXL-97.[49] The single crystal of sensor 2 was grown
by keeping a concentrated solution of the sensor in DMSO in a refrigera-
tor for three months. Crystal data for 2: light yellow column, C15H14N4S,
Mr =282.4, tetragonal, space group Pbca, a=8.291(3), b=18.644(6), c=
18.644 , a=90.00, b=90.00, g=90.008, V=2881.94 3, reflections col-
lected: 14899; independent reflections: 2949 (Rint =0.0399); final R indi-
ces [I>s(I)]: R1 =0.0399, wR2 =0.0994; R indices (all data): R1 =0.0583,
wR2 =0.1098. The single crystal of sensor 12 was grown by slow evapora-
tion of a dilute solution of the sample in THF. Crystal data for 12: light
[14] J. Y. Kwon, Y. J. Jang, S. K. Kim, K. H. Lee, J. S. Kim, J. Yoon, J.
Org. Chem. 2004, 69, 5155–5157.
¯
yellow prism, C31H22N4S, Mr =482.6, triclinic, space group P1, a=
9.027(2), b=10.722(3), c=15.894(4) , a=78.664(3), b=74.134(4), g=
80.434(4)8, V=1440.51 3, reflections collected: 7845; independent re-
flections: 5550 (Rint =0.0149); final R indices [I>s(I)]: R1 =0.0490, wR2 =
0.1217; R indices (all data): R1 =0.0743, wR2 =0.1340. CCDC-612122 (2)
and CCDC-607150 (12) contain the supplementary crystallographic data
for this paper. These data can be obtained free of charge from The Cam-
request/cif.
[15] T.-H. Kim, T. M. Swager, Angew. Chem. 2003, 115, 4951–4954;
Angew. Chem. Int. Ed. 2003, 42, 4803–4806.
[16] a) M. Vµzquez, L. Fabbrizzi, A. Taglietti, R. M. Pedrido, A. M. Gon-
zµlez-Noya, M. R. Bermejo, Angew. Chem. 2004, 116, 1996–1999;
Angew. Chem. Int. Ed. 2004, 43, 1962–1965; b) Y.-M. Zhang, W.-X.
Xu, Y.-Q. Zhou, H. Yao, T.-B. Wei, Acta. Chimica. Sinica. 2006, 64,
79–84; c) V. Amendola, D. Esteban-Gomez, L. Fabbrizzi, M. Lic-
chelli, Acc. Chem. Res. 2006,39, 343–353.
Chem. Eur. J. 2007, 13, 2880 –2892
ꢀ 2007 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
2891