Full Paper
13C{1H} NMR (101 MHz, CDCl3): d=180.5 (q, J=35.2 Hz), 151.1,
140.2, 137.0, 133.9, 133.7, 131.0, 130.82, 130.75, 130.2, 129.0, 128.9,
128.1, 127.0, 126.5, 126.3, 125.7, 116.7 (q, J=192.6 Hz), 98.8,
56.0 ppm; HRMS: m/z calcd for C40H28F6O6Na [M+Na]+: 741.1688;
found: 741.1680.
Acknowledgements
This work was financially supported by the National Science
Foundation of China (grant nos. 21502127, 21232005,
J1103315, and J1310008) and the National Program on Key
Basic Research Project of China (973 Program, 2013CB328905).
Synthesis and characterization of 4
After compound 8 (0.175 mmol, 0.125 g) was dissolved in CH2Cl2/
MeOH (20 mL/20 mL), HCl (4 mL, 12 N in water) was added slowly,
and the mixture was stirred at room temperature, overnight. A sat-
urated aqueous solution of NaHCO3 was added to quench the re-
action. The organic layer was separated, and the aqueous layer
was extracted with dichloromethane (3ꢁ30 mL). The combined or-
ganic extracts were washed with brine (3ꢁ30 mL) and dried over
Na2SO4. After evaporation of the solvent, the residue was purified
by column chromatography on silica gel eluted with petroleum
ether/ethyl acetate (5:1) to afford compound 4 as a white solid
Keywords: amines · fluorescence · molecular recognition ·
sensors · trifluoromethyl ketones
[1] a) K. Eller, E. Henkes, R. Rossbacher, H. Hçke, Amines, Aliphatic in Ull-
mann’s Encyclopedia of Industrial Chemistry, 2005, Wiley-VCH, Weinheim;
b) R. Cary, S. Dobson, J. Delic, 1,2-Diaminoethane (Ethylenediamine): Con-
cise International Chemical Assessment Document 15, World Health Or-
ganization, Geneva, 1999.
K. M. Solntsev, S. Miao, L. M. Tolbert, O. R. Miranda, V. M. Rotello, U. H. F.
[3] For fluorescent sensing of polyamines, see: a) B. Bao, L. Yuwen, X.
9628–9634; b) S. Koersten, G. J. Mohr, Chem. Eur. J. 2011, 17, 969–975;
c) M. Ikeda, T. Yoshii, T. Matsui, T. Tanida, H. Komatsu, I. Hamachi, J. Am.
1
(90%, 0.158 mmol, 0.100 g). [a]D =À71.2 (c=0.21, CHCl3); H NMR
(400 MHz, CDCl3): d=8.47 (s, 2H), 8.15–8.07 (m, 6H), 7.98 (d, J=
7.9 Hz, 2H), 7.67 (t, J=7.8 Hz, 2H), 7.48–7.43 (m, 2H), 7.42–7.36 (m,
2H), 7.24 (d, J=8.4 Hz, 2H), 5.37 ppm (s, 2H); 19F NMR (376 MHz,
CDCl3): d=À71.22 ppm (s, 6F); 13C{1H} NMR (101 MHz, CDCl3): d=
180.5 (q, J=35.2 Hz), 150.1, 138.7, 136.8, 133.1, 132.1, 131.2, 130.0,
129.4, 129.2, 129.0, 128.8, 128.7, 128.2, 124.9, 124.0, 116.7 (q, J=
292.6 Hz), 111.8 ppm; HRMS: m/z calcd for C36H20F6O4 [M]À:
629.1188; found: 629.1182.
Synthesis and characterization of 18
[4] a) K. Azuma, Y. Kinoshita, R. Monobe, T. Miyatake, S. I. Sasaki, Tetrahedron
2013, 69, 1987–1993; b) M. Nakamura, T. Sanji, M. Tanaka, Chem. Eur. J.
After compound 4 (0.1 mmol, 0.063 g) was dissolved in CH2Cl2
(30 mL), dry 4 ꢂ molecular sieves was added. Compound 14
(1 mmol, 0.060 g) was added, with stirring, to the mixture. The re-
sulting mixture was stirred and heated at reflux for 18 h. It was
then cooled to room temperature, and passed through a filter
paper. After evaporation of the solvent, the residue was purified by
column chromatography on silica gel eluted with petroleum ether/
ethyl acetate (1:1) to afford compound 18 as a white solid (32%,
0.032 mmol, 0.023 g). [a]D =À30.2 (c=0.13, CHCl3); 1H NMR
(400 MHz, CDCl3): d=8.07 (s, 2H), 8.04 (s, 2H), 7.93 (d, J=8.0 Hz,
2H), 7.75 (d, J=7.7 Hz, 2H), 7.67 (d, J=7.8 Hz, 2H), 7.50 (t, J=
7.8 Hz, 2H), 7.43–7.37 (m, 2H), 7.37–7.30 (m, 2H), 7.21 (d, J=
8.4 Hz, 2H), 5.49 (s, 2H), 3.21 (d, J=5.3 Hz, 4H), 3.11 (d, J=4.8 Hz,
4H), 2.44 ppm (s, 4H); 19F NMR (376 MHz, CDCl3) d=À78.82 ppm
(s, 6F); 13C{1H} NMR (101 MHz, CDCl3): d=150.2, 138.6, 137.7, 133.0,
131.7, 130.3, 130.1, 129.5, 128.6, 128.2, 127.7, 127.5, 126.1, 124.6,
124.2, 112.3, 83.3 (q, J=28.6 Hz), 46.9 ppm; HRMS: m/z calcd for
C40H32F6O4 [M]À: 713.2351; found: 713.2351.
[5] For selected reports on using trifluoromethyl ketones in the molecular
recognition of amines, see: a) G. J. Mohr, C. Demuth, U. E. Spichiger-
E. Park, D.-S. Kim, S. Yan, J. Y. Lee, B.-Y. Chang, K. H. Ahn, J. Am. Chem.
[6] a) S. S. Yu, W. Plunkett, M. Kim, E. Wu, M. Sabat, L. Pu, J. Org. Chem.
Cox, W. Wang, V. Snieckus, Tetrahedron Lett. 1992, 17, 2253.
[12] A. P. de Silva, H. Q. N. Gunaratne, T. Gunnalaugsson, A. J. M. Huxley, C. P.
Preparation of samples for fluorescent measurement for in-
teractions with the diamines and monoamines
Stock solutions of 1.0 mm 4 and 8 in CH2Cl2 were freshly prepared
for each measurement. For the fluorescent enhancement study,
a solution of 4 or 8 (10À5 m, 2.5 mL) was mixed with various equiva-
lents of solutions of the di- or monoamine (50 mm in CH2Cl2) in
a 3.5 mL test tube. The resulting solution was allowed to stand at
room temperature for 30 s and the fluorescent spectra were re-
corded within 1 h.
Received: April 2, 2016
Published online on && &&, 0000
Chem. Eur. J. 2016, 22, 1 – 8
7
ꢀ 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
&
&
These are not the final page numbers! ÞÞ