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(
6.32 mmol) was dissolved in 25 ml methanol and mixture stirred 134.82, 136.61, 148.28, 149.07, 158.66, 181.26, 181.46. UV-vis,
0
for about 20 min. To this solution 0.70 ml of 2-(2 -aminoethyl) (lmax, methanol (nm)): 448.
pyridine (7.1 mmol) for H-3 and 0.69 ml of 2-thiopheneethylamine 2-((Thiophen-2-yl)ethylamine)naphthalene-1,4-dione; H-4.
7.1 mmol) for H-4 were added drop wise. The reaction mixture Dark red color crystals. Yield: 1.08 g (60.33%). mp. 145.5 C.
ꢂ
(
ꢂ
was stirred for 24 hours at room temperature (26 C) with constant Anal. data calcd for C16
13 2
H O NS (%): C, 67.82; H, 4.62; N, 4.94;
magnetic stirring till completion of the reaction monitored on S, 11.31. Found (%): C, 67.58; H, 4.36; N, 5.02; S, 11.67. FT-IR
ꢁ1
TLC. The reaction mixture was evaporated under the reduced (KBr, nmax (cm )): 3338, 3043, 2915, 1669, 1515, 1593, 1567,
pressure. The residue was column chromatographed over silica gel 1514, 1465, 1434, 1395, 1353, 1336, 1298, 1278, 1242, 1215,
1
in methanol/toluene (1 : 9) solvent system. Red coloured solid 1120, 1098, 1031, 978, 859, 773, 722, 684, 583, 505, 466. H NMR
products were obtained aer evaporation of pure fraction from the (DMSO-d , 499.81 MHz, d (ppm)): 3.12 (t, J ¼ 7 Hz, 2H, –CH ),
6
2
column.
3.45 (t, J ¼ 6.5 Hz, 2H, –CH ), 5.72 (s, 1H, Ar), 6.94 (d, J ¼ 3.5 Hz,
2
1
H, Ar), 6.96 (t, J ¼ 5 Hz, 1H, Ar), 7.33 (d, J ¼ 4.5 Hz, 1H, Ar), 7.55
(
7
t, J ¼ 6 Hz, 1H, –NH), 7.72 (t, J ¼ 7.5 Hz, 1H, Ar), 7.82 (t, J ¼
Characterization
.5 Hz, 1H, Ar), 7.93 (d, J ¼ 8 Hz, 1H, Ar), 7.97 (d, J ¼ 7.5 Hz, 1H,
13
2-((Pyridin-2-yl)methylamino)naphthalene-1,4-dione; H-1. Ar). C NMR (DMSO-d
6
, 125.69 MHz, d (ppm)): 27.55, 43.31,
ꢂ
Dark red colour crystal. Yield: 0.174 g (62.14%). mp 156.42 C. 99.67, 124.27, 125.31, 125.55, 125.87, 127.00, 130.31, 132.17,
Anal. data calcd for C16
Found (%): C, 72.68; H, 4.10; N, 10.32. FT-IR (KBr; nmax (cm )):
12 2 2
H O N (%): C, 72.99; H, 4.21; N, 10.64. 133.07, 148.24, 181.45. UV-vis, (lmax, methanol (nm)): 448.
ꢁ1
3
1
5
4
1
355, 3061, 1672, 1632, 1605, 1593, 1563, 1432, 1373, 1347,
X-ray crystal structures
290, 1214, 1158, 1122, 1091, 1049, 976, 827, 778, 757, 723, 669,
X-ray data for H-1, H-3 and H-4 were collected on D8 Venture
PHOTON 100 CMOS diffractometer using graphite mono-
1
74, 498, 460, 443. H NMR (DMSO-d
6
, 499.81 MHz, d (ppm)):
.52 (d, J ¼ 6 Hz, 2H, –CH ), 5.59 (s, 1H, Ar–CH), 7.30 (t, J ¼ 5 Hz,
2
˚
chromatized Mo-Ka radiation (l ¼ 0.7107 A) with exposure/
H, Ar), 7.37 (d, J ¼ 8 Hz, 1H, Ar), 7.73 (t, J ¼ 8 Hz, 1H, Ar), 7.77
frame ¼ 10 s. The X-ray generator was operated at 50 kV and
(
8
m, J ¼ 8 Hz, 1H, Ar), 7.81 (m, J ¼ 7.5 Hz, 1H, Ar), 7.90 (d, J ¼
30 mA. An initial set of cell constants and an orientation matrix
Hz, 1H, Ar), 8.00 (d, J ¼ 8 Hz, 1H, Ar), 8.08 (t, J ¼ 6.5 Hz, 1H,
were calculated from total 24 frames. The optimized strategy
13
–
NH), 8.55 (d, J ¼ 5 Hz, 1H, Ar). C NMR (DMSO-d
6
, 125.69
used for data collection included different sets of f and u scans
MHz, d (ppm)): 47.40, 101.09, 121.98, 123.00, 125.82, 126.39,
ꢂ
with 0.5 steps in f/u. Crystal to detector distance was 5.00 cm
1
1
30.86, 132.77, 133.47, 135.32, 137.47, 148.87, 149.49, 156.80,
81.95. UV-vis, (lmax, methanol (nm)): 440.
ꢂ
with 512 ꢀ 512 pixels/frame, oscillation/frame ꢁ0.5 , maximum
ꢂ
detector swing angle ¼ ꢁ30.0 , beam centre ¼ (260.2, 252.5), in
2
-((Thiophen-2-yl)methylamino)naphthalene-1,4-dione; H-2.
plane spot width ¼ 1.24. Data integration was carried out by
Bruker SAINT program and empirical absorption correction for
intensity data were carried out using the Bruker SADABS. The
ꢂ
Brown colored solid. Yield: 0.962 g (89.90%). mp 189.73 C.
Anal. data calcd for C15
S, 11.90. Found (%) C, 66.44; H, 3.84; N, 5.16; S, 11.65. FT-IR
11 2
H O NS (%): C, 66.89; H, 4.11; N, 5.20;
2
6
programs are integrated in APEX II package. The data were
corrected for Lorentz and polarization effect. The structure was
solved by direct method using the SHELX-97 (ref. 27) with the
ꢁ1
(KBr; nmax (cm )): 3354, 1670, 1599, 1506, 1453, 1429, 1306,
1
4
252, 1216, 1147, 1056, 1025, 835, 778, 708, 687, 627, 557, 542,
1
93, 444. H NMR (DMSO-d
6
, 499.81 MHz, d (ppm)): 4.16 (s, 2H,
), 5.74 (s, 1H, Ar–CH), 6.97 (t, J ¼ 4.5 Hz, 1H, Ar), 7.10 (d, J
2.5 Hz, 1H, Ar), 7.40 (d, J ¼ 4.5 Hz, 1H, Ar), 7.71 (t, J ¼ 7.5 Hz,
nal renement of the structure performed by a full-matrix
–
CH
2
least-squares technique with anisotropic thermal data for
non-hydrogen atoms on F . The non-hydrogen atoms were
rened anisotropically where the hydrogen atoms were rened
at the calculated positions as riding atoms with isotropic
displacement parameters. Molecular diagrams were generated
using the ORTEP-3 (ref. 28) and Mercury programs. Structural
calculations were performed using SHELXTL and PLATON.
¼
2
1
H, Ar), 7.80 (t, J ¼ 7 Hz, 1H, Ar), 7.90 (d, J ¼ 7.5 Hz, 1H, Ar), 7.97
1
3
(
(
1
1
d, J ¼ 7.5 Hz, 1H, Ar), 8.11 (t, J ¼ 6.5, 1H, –NH). C NMR
DMSO-d , 125.69 MHz, d (ppm)): 40.42, 100.67, 125.31, 125.33,
25.86, 126.10, 126.75, 130.32, 132.27, 132.87, 134.82, 140.38,
48.00, 181.48, 181.53. UV-vis, (lmax, methanol (nm)): 435.
-((Pyridin-2-yl)ethylamino)naphthalene-1,4-dione;
6
27
2
9
30
31
2
H-3.
ꢂ
Dark red color crystal. Yield: 1.126 g (64.01%). mp. 128.58 C.
Anal. data calcd for C H O N (%): C, 73.36; H, 5.07; N, 11.49.
Found (%): C, 72.98; H, 5.10; N, 11.36. FT-IR (KBr, nmax (cm )):
Metal ion binding studies, Job plot, competitive binding
studies, pH studies and limit of detection (LOD) experiments
1
7
14 2 2
ꢁ1
3
1
8
336, 3043, 2960, 2914, 2868, 1772, 1672, 1600, 1570, 1518, Metal ion binding studies were evaluated by following methods,
467, 1435, 1356, 1284, 1261, 1215, 1155, 1103, 1057, 1022, 983, (i) in methanol, (ii) in 1 : 1 methanol–water, (iii) in presence of
1
62, 785, 721, 669, 596, 559, 507, 476. H NMR (DMSO-d
6
, 499.81 triethylamine in (i) and (ii). In typical experiments 2 ml of H-1
MHz, d (ppm)): 3.04 (t, J ¼ 5 Hz, 2H, –CH
2
), 3.54 (t, J ¼ 5 Hz, 2H, and H-3 was mixed with 2 ml of metal ion solutions at room
ꢂ
–
1
7
5
CH
2
), 5.71 (s, 1H, Ar), 7.23 (t, J ¼ 5 Hz, 1H, Ar), 7.32 (d, J ¼ 5 Hz, temperature (26 C). 1 ml of triethylamine was added in che-
H, Ar), 7.62 (t, J ¼ 5 Hz, 1H, –NH), 7.705 (t, J ¼ 5 Hz, 1H, Ar), mosensor solution in case of (i) and (ii) prior to addition of metal
.72 (t, J ¼ 5 Hz, 1H, Ar), 7.81 (t, J ¼ 10 Hz, 1H, Ar), 7.92 (d, J ¼ ion solutions. UV-visible and uorescence spectra of all solutions
ꢁ
4
Hz, 1H, Ar), 7.95 (d, J ¼ 10 Hz, 1H, Ar), 8.51 (d, J ¼ 5 Hz, 1H, were measured; the concentration of ꢃ2.5 ꢀ 10 M was used.
1
3
Ar). C NMR (DMSO-d
6
, 125.69 MHz, d (ppm)): 35.34, 41.61,
Micromolar concentration (10–100 mM) of H-1, H-3 and metal
99.51, 121.69, 123.35, 125.31, 125.85, 130.32, 132.14, 133.10, ions was used for Jobs plot experiment. Solutions were prepared
55166 | RSC Adv., 2017, 7, 55163–55174
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