3
28
J IRAN CHEM SOC (2012) 9:327–332
organic solvents and inorganic reagents were purified
according to standard anhydrous methods before use. TLC
analysis was performed using pre-coated glass plates.
Column chromatography was performed using silica gel
Synthesis of compound 5
Compound 4 (0.72 g, 1 mmol) and 1,6-dibromohexane
(2.44 g, 10 mmol) with K CO (0.97 g, 7 mmol) were
refluxed in 50 mL anhydrous acetonitrile for overnight
purged with N . After reaction, the mixture was filtered and
evaporated to dryness by rota-vapor. Then the mixture was
further purified by recrystallization in CH OH/CHCl . The
2
3
(
200–300 mesh). IR spectra were recorded on a Perkin-
Elmer PE-983 infrared spectrometer as KBr pellets with
2
-
1 1
absorption in cm . H NMR spectra were recorded in
CDCl3 on a Bruker-ARX 600 instrument at 30 °C.
Chemical shifts are reported in ppm, using tetramethylsil-
ane (TMS) as internal standard. ESI–MS spectra were
obtained from DECAX-30000 LCQ Deca XP mass spec-
trometer. Elemental analyses were performed at Vario EL
III Elemental Analyzer.
3
3
compound 5 was obtained as white solid in yield of 80%.
1
Compound 5: m.p. = 189–192 °C; H NMR (600 MHz,
CDCl
1.28 (s, 36 H, C(CH
CH ), 3.38 (t, 8 H, J = 6.6 Hz, OCH
J = 7.8 Hz, BrCH ), 7.30 (s, 8 H, ArH); MS m/z (%):
) dppm: 1.02 (m, 8 H, CH
), 1.32 (m, 8 H, CH
), 3.82 (t, 8 H,
), 1.15 (m, 8 H, CH
),
3
2
2
)
3
), 1.80 (m, 8 H,
3
2
2
2
2
?
Syntheses of compound 2
1371.64 (M , 100). Anal. calcd for C64
5.98, H 6.75; found C 55.91, H 6.71%.
H O Br S : C
92 4 4 4
5
Compound 1 (0.65 g, 1 mmol) and 1, 6-dibromohexane
1.22 g, 5 mmol) with K CO (0.97 g, 7 mmol) were
(
Synthesis of calix[4]arene ionic liquid 6
2
3
refluxed in 50 mL anhydrous acetonitrile for overnight
purged with N . After reaction, the mixture was filtered and
2
The mixture of compound 5 (0.65 g, 0.5 mmol) and
1-methylimidazole (2 mL) were stirred at 110 °C for 24 h
evaporated to dryness by rota-vapor. Then the mixture was
further purified by column chromatography (SiO 100–200
2
purged with N . After reaction, the excess solvent was
2
mesh, petroleum ether/CH Cl (4:1, V/V) as eluant). The
2
evaporated under vacuum line at 110 °C. Then the residue
was treated in desiccator under reduced pressure for a week
to dryness. The ionic liquid of thiacalix[4]-1,3-methylimi-
dazolium bromide 6 was obtained in almost 100% yield as
2
compound 2 was obtained as white solid in yield of 65%.
1
Compound 2: m.p. = 216–218 °C; H NMR (600 MHz,
CDCl ) dppm: 0.99 (s, 18 H, C(CH ) ), 1.30 (s, 18 H,
3
3 3
C(CH ) ), 1.52 * 2.08 (m, 16 H, CH ), 3.31 (d, 4 H,
soft straw yellow solid. Compound 6: m.p. = 84–87 °C;
3
3
2
1
J = 12.6 Hz, ArCH Ar), 3.47 (t, 4 H, J = 6.6 Hz, OCH ),
2
H NMR (600 MHz, CDCl
and C(CH ), 3.67 * 4.45 (m, 28 H, NCH
and NCH ), 6.91 * 7.33 (m, 16 H, ArH and ImH),
3
) dppm: 1.01 * 2.05 (m, 68 H,
, OCH
2
2
3
.99 (t, 4 H, J = 6.6 Hz, BrCH ), 4.28 (d, 4 H, J = 12.6 Hz,
2
CH
2
3
)
3
3
ArCH Ar), 6.83 (s, 4 H, ArH), 7.04 (s, 4 H, ArH), 7.62(s, 2 H,
2
?
OH); MS m/z (%): 975.22 (M , 100). Anal. calcd for
2
-1
10.19 * 10.59 (m, 4 H, ImH); IR/cm : 3,427, 3,065,
2,945, 2,863, 1,631, 1,569, 1,445, 1,361, 1,266, 1,168,
C H O Br : C 69.05, H 8.07; found C 69.01, H 8.02%.
5
6
78
4
2
1,089, 998, 876, 763, 649; Anal. calcd for
Synthesis of calix[4]arene ionic liquid 3
C
80
H
116
N
8
S
4
Br O : C 56.46, H 6.87; found C 56.42, H
4 6
6.81%.
The mixture of compound 2 (0.49 g, 0.05 mmol) and
1
-methylimidazole (2 mL) were stirred at 110 °C for 24 h
Synthesis of compound 8
purged with N . After reaction, the excess solvent was
2
evaporated under vacuum line at 110 °C. Then the residue
was treated in desiccator under reduced pressure for a week
to dryness. The ionic liquid of calix[4]-1,3-methylimida-
zolium bromide 3 was obtained in almost 100% yield as
Compound 7 (0.75 g, 5 mmol) and 1,6-dibromohexane
(4.88 g, 20 mmol) with K
refluxed in 50 mL anhydrous acetonitrile for overnight
purged with N . After reaction, the mixture was filtered and
evaporated to dryness by rota-vapor. Then the mixture was
further purified by column chromatography (SiO 100–200
mesh, petroleum ether/CH Cl (5:1, V/V) as eluant). The
CO (2.76 g, 20 mmol) were
2
3
2
1
soft straw yellow solid. Compound 3: m.p. = 95–98 °C; H
NMR (600 MHz, CDCl ) dppm: 0.93 (s, 18 H, C(CH ) ),
2
3
3 3
1
.29 (s, 18 H, C(CH ) ), 1.49 * 2.08 (m, 16 H, CH ), 3.31
2
2
3
3
2
(
d, 4 H, J = 13.2 Hz, ArCH Ar), 3.91 (t, 4 H, J = 6.6 Hz,
2
compound 8 was obtained as white solid in yield of 84%.
1
OCH ), 4.06 (s, 6 H, NCH ), 4.21 (d, 4 H, J = 13.2 Hz,
3
Compound 8: m.p. = 76–78 °C; H NMR (600 MHz,
2
ArCH Ar), 4.51 (t, 4 H, J = 6.6 Hz, NCH ), 6.77 (s, 4 H,
2
CDCl
1.55 (m, 2 H, CH
J = 6.6 Hz, OCH ), 3.78 (t, 2 H, J = 6.6 Hz, BrCH
2
3
) dppm: 1.17 (m, 4 H, CH
2
), 1.25 (s, 9 H, C(CH
), 3.53 (t, 2 H,
),
3 3
) ),
2
ArH), 7.07 (s, 4 H, ArH), 7.41(s, 2 H, ImH), 7.45 (s, 2 H,
2
), 1.63(m, 2 H, CH
2
-
1
:
ImH), 7.71(s, 2H, OH), 10.29 (s, 2H, ImH); IR/cm
410, 2956, 2864, 1569, 1482, 1361, 1298, 1201, 1116;
Anal. calcd for C H O N Br : C 67.54, H 7.97; found C
2
3
7.06 (d, 2 H, J = 9.6 Hz, ArH), 7.39 (d, 2 H, J = 9.6 Hz,
?
ArH); MS m/z (%): 313.02 (M , 100). Anal. calcd for
6
4
90
4
4
2
6
7.52, H 7.90%.
C H25OBr: C 61.41, H 8.05; found C 61.33, H 8.01%.
16
1
23