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their analytical data were in perfect agreement with the
authentic samples.
medium by EtOAc (4 6 50 mL) as an organic layer. Then, the
combined organic solutions were washed with brine, dried
over Na2SO4 and solvent evaporated by rotary evaporator, so, a
pure product was obtained. The resulting products were
Preparation of 1,19-hexane-1,6-diylbis (3-methylpyridinium)
tetrachloronickelate (II) ([C6(mpy)2] [NiCl4]22
)
1
analyzed by H NMR and IR spectroscopic methods.
The ionic liquid was synthesized (Scheme 2) and discussed in
detail in our previous reported work.11 3-Methyl pyridine (0.04
mol, 3.89 mL) is dissolved in 25 mL toluene at RT. 1,
6-dibromohexane (0.02 mol, 3.07 mL) was added slowly into
the flask within 30 min in an ice bath. The stirring was
continued at this temperature for 30 min before elevating the
temperature to 110 uC for 12 h. An off-white solid was formed.
Upon completed the reaction, the solvent was removed by
decanting. The reaction mixture was extracted with ethyl
acetate (3 6 30 mL) and then dried under vacuum oven at 70
uC for 5 h.
1,19-hexane-1,6-diylbis (3-methylpyridinium) dibromide
[C6(mpy)2] Br22: 1H NMR (400 MHz, DMSO-d6, d (ppm) relative
to TMS) 9.09 (s, 2H), 8.98 (d, 2H, J = 8 Hz), 8.43 (d, 2H, J = 8
Hz), 8.01 (dd, 2H, J = 6 Hz), 4.57 (t, 4H, J = 7.9 Hz), 3.49 (s, 6H),
1.91 (m, 4H), 1.30 (m, 4H). 13C NMR (400 MHz, DMSO-d6): dH
(ppm) 146.20, 144.76, 142.44, 139.08, 127.71, 60.55, 30.66,
25.04, 18.29.
Spectral data of aniline derivatives. All compounds were
identified by spectral comparison with samples purchased
from commercial sources.
Table 4, entries 1–6, 8–11
Aniline. IR (neat) n 3446, 3356, 3212, 3070, 3034, 1619, 1600,
1497, 1466, 1289, 1174, 879, 750, 690 cm21; 1H NMR (400 MHz,
CDCl3) d 3.60 (bs, 2H), 6.69 (d, 2H), 6.78 (t, 1H), 7.18 (d, 2H)
2-Aminophenol. IR (KBr) n 3373, 3302, 3052, 2848, 2583,
2031, 1761, 1599, 1510, 1459, 1279, 1084, 891, 845, 739 cm21
;
1H NMR (400 MHz, DMSO-d6) d 4.40 (bs, 2H), 6.32 (ddd, 1H),
6.36 (ddd, 1H), 6.50 (ddd, 1H), 6.59 (ddd, 1H).
4-Aminophenol. IR (KBr) n 3348, 3280, 1864, 1613, 1508,
1471, 1384, 1091, 966, 822, 748, 646 cm21; 1H NMR (400 MHz,
DMSO-d6) d 4.32 (bs, 2H), 6.39 (d, 2H), 6.46 (d, 2H), 8.30 (s, 1H)
3-Toluidine. IR (neat) n 3446, 3358, 3033, 2919, 1620, 1492,
1376, 1291, 1169, 995, 853, 772, 689 cm21; 1H NMR (400 MHz,
CDCl3) d 2.11 (s, 3H), 4.86 (bs, 2H), 6.27 (ddd, 1H), 6.34 (dd,
1H), 6.35 (ddd, 1H), 6.87 (dd, 1H)
1,19-hexane-1,6-diylbis (3-methylpyridinium) dibromide
2
[C6(Mpy)2] Br2 (0.007 mol) and NiCl2?6H2O (0.017 mol) were
4-Toluidine. IR (neat) n 3417, 3337, 3220, 3094, 3010, 2912,
2859, 2357, 1878, 1621, 1580, 1513, 1323, 1280, 1268, 1177,
dissolved in ethanol and stirred at room temperature for four
days. After completion of the reaction the solvent evaporated
in rotatory evaporator to give the green color solid. The
obtained product was washed with Ethyl acetate several times
and dried in vacuum at 80 uC for 5 h. LRMS (FAB+) calcd for
C18H26N2Cl4Ni?(M-[NiCl4])+ 135.10 found 135.14
1
1122, 1071, 952, 874, 830, 811, 757, 672 cm21; H NMR (400
MHz, CDCl3) d 2.23 (s, 3H), 3.50 (bs, 2H), 6.57 (d, 2H), 6.96 (d,
2H)
1, 4-Phenylenedine. IR (KBr) n 3409, 3383, 3372, 3200, 3044,
3008, 2895, 1867, 1629, 1604, 1513, 1374, 1309, 1260, 1127,
1064, 1040, 972, 822, 795, 665 cm21 1H NMR (400 MHz,
;
Electrospinning
DMSO-d6) d 4.13 (bs, 4H), 6.31 (s, 4H).
Polymer solution of PVDF-[C6(mpy)2][NiCl4]22 for electrospin-
ning were prepared by dissolving the polymer in N,N-
Dimethylformamide (DMF) and stirred at 30–40 uC till to get
homogeneous solution. PVDF concentration was kept at 15
wt% with respect to DMF and dicationic counter ions with
tetrachloronickelate (II) anion (IL) was 2.5 and 5 wt% with
respect solvent. The electrospinning apparatus used in this
study consisted of a high voltage power supply, syringe pump,
syringe needle (0.21 mm.), and grounded collector (aluminum
foil). The needle was connected to the high voltage supply. The
spinning distance between the tip of needle and the collector
was in the range of 18–21 cm. Positive voltage of 20–22 KV was
applied to polymer solutions. The solution flow rates were
controlled with syringe pump ranging from 2–3 mL h21. All
electrospinning experiments were carried out at room tem-
perature.
4-Chloroaniline. IR (KBr) n 3472, 3382, 3198, 1881, 1614,
1492, 1288, 1181, 1089, 1005, 819, 637 cm21 1H NMR (400
;
MHz, CDCl3) d 3.63 (bs, 2H), 6.60 (d, 2H), 7.10 (d, 2H).
3-Chloroaniline. IR (neat) n 3367, 3214, 3032, 1619, 1596,
1484, 1300, 1266, 1162, 1076, 992, 887, 848, 766, 680 cm21; 1H
NMR (400 MHz, CDCl3) d 3.70 (bs, 2H), 6.53 (ddd, 1H), 6.66
(dd, 1H), 6.72 (ddd, 1H), 7.06 (dd, 1H)
4-Bromoaniline. IR (KBr) n 3446, 3348, 3033, 1869, 1600,
1488, 1298, 1173, 1128, 1069, 816 cm21; H NMR (400 MHz,
1
CDCl3) d 3.64 (bs, 2H), 6.56 (d, 2H), 7.23 (d, 2H)
3-Iodoaniline. IR (neat) n 3445, 3357, 3211, 3069, 3012, 1922,
1617, 1599, 1566, 1519, 1476, 1439, 1268, 1153, 1059, 851, 681,
657 cm21 1H NMR (400 MHz, CDCl3) d 3.63 (bs, 2H), 6.58
;
(ddd, 1H), 6.67 (dd, 1H), 6.87 (ddd, 1H), 7.08 (dd, 1H)
General procedure for aromatic nitro compounds reduction
Acknowledgements
To a solution of nitro compounds and IL (tetrachloronickelate
(II) anion with dicationic counter ions) in water was stirred at
room temperature for a few seconds. Then weighed amount of
NaBH4 added in portion by slowly within 3 min. The progress
of the reaction was monitored by Thin Layer Chromatography
(TLC) using hexane/EtOAc (7 : 3) as an eluent. After comple-
tion of the reaction, the reaction mixture was quenched with
NaCl solution and the product was extracted from the aqueous
This study was supported by a grant (#10035574) from the
"Platform Chemical Process Technology from Lignocellulosic
Biomass Conversion" R&D Program funded by the Ministry of
Knowledge Economy and by Priority Research Centers
Program through the National Research Foundation of Korea
(NRF) funded by the Ministry of Education, Science and
Technology (2012-0006693).
This journal is ß The Royal Society of Chemistry 2013
RSC Adv., 2013, 3, 3399–3406 | 3405