Recognition of Ion Pairs Using Calixarene–Diquinones
FULL PAPER
5
-Nitroisophthalamide triether calix[4]diquinone macrobicycle (4): This
material was prepared in an analogous manner to the preparation of 1
from 18 (0.15 g, 0.13mmol) and [Tl (O CF ]·TFA solution (5 mL). The
crude product was recrystallized from diethyl ether to give the yellow re-
ic extracts were subsequently dried over MgSO
ed in vacuo to give the white solid 13 (2.51 g, 95%). H NMR (300 MHz,
CDCl ): d=0.78 (s, 18H; C(CH ), 1.23(s, 18H; C (CH ), 3.06 (m, 4H;
CH NH ), 3.24 (d, J=13.1 Hz, 4H; ArCHin outAr), 3.76 (m, 12H;
OCH CH OCH CH N), 3.85 (m, 4H; ArOCH CH ), 4.12 (m, 4H;
ArOCH ), 4.26 (d, J=13.1 Hz, 4H; ArCHin outAr), 6.58 (s, 4H; calix
4
, filtered, and concentrat-
1
A
H
E
N
2
3
)
3
3
A
H
R
U
G
3
)
3
A
H
R
U
G
3 3
)
2
2
2
H
1
ceptor 4 (0.08 g, 50%). H NMR (300 MHz, CDCl
3
): d=1.12 (s, 18H; C-
outAr), 3.71–3.85 (m, 28H;
2
2
2
2
2
2
2
2
A
C
H
T
R
E
U
N
G
(CH
3
)
3
), 3.25 (d, J=12.9 Hz, 4H, ArCHin
H
2
H
+
ArOCH
2
CH OCH CH OCH CH N, ArCHin
2
2
2
2
2
H
outAr), 6.80 (s, 4H; QuH),
ArH), 7.02 ppm (s, 4H; calix ArH); ESMS: m/z: 911.61 [M+H] , 937.58
2
+
6
8
3
1
1
.85 (s, 4H; calix ArH), 7.72 (br, 2H; NH), 8.58 (s, 1H; isoph ArH ),
[M+Na] .
4
6
13
3
.93ppm (s, 2H; isoph ArH and H ); C NMR (75.5 MHz, CDCl ): d=
5
,11,17,23-Tetra-tert-butyl-25,27-bis(2-{2-[2-(2-aminoethoxy)ethoxy]-
ethoxy}ethoxy)-26,28-dihydroxycalix[4]arene (14): This material was pre-
pared in an analogous method to the preparation of 13 from 11 (0.79 g,
.63mmol), ethanol (25 mL), and hydrazine monohydrate (1 mL, excess).
1.38, 32.97, 34.02, 40.65, 69.48, 70.05, 70.21, 70.62, 73.31, 125.98, 127.14,
28.89, 128.94, 132.74, 132.82, 136.38, 146.25, 147.68, 154.02, 164.56,
AHCTREUNG
+
+
85.51, 190.13ppm; ESMS: m/z: 1002.49 [M+H] , 1024.46 [M+Na] ; el-
0
emental analysis (%) calcd for C56
found: C 65.0, H 6.1, N 3.9.
H
63
N
3
O
14·2H
2
O: C 64.8, H 6.5, N 4.0;
1
A white solid 14 was isolated (0.52 g, 91%). H NMR (300 MHz, CDCl
3
):
3
d=0.83(s, 18H; C
4H; CH NH ), 3.23 (d, J=13.5 Hz, 4H; ArCHin
CH CH N), 3.60 (m, 8H; OCH CH
4H; OCH ), 3.88 (m, 4H; ArOCH
(d, J=13.5 Hz, 4H; ArCHin outAr), 6.63(s, 4H; calix ArH), 7.00 ppm
(s, 4H; calixArH); ESMS: m/z: 999.72 [M+H] .
-Nitroisophthalamide diether calix[4]arene macrobicycle (16): 5-Nitroi-
sophthaloyl dichloride (1.14 mmol) was dissolved in dry CH Cl (175 mL)
A
H
R
U
G
3
)
3
), 1.23(s, 18H; C
A
H
E
N
(CH
3
)
H
3
), 3.05 (t, J=4.4 Hz,
2
Isophthalamide tetraether calix[4]diquinone macrobicycle (5): This mate-
rial was prepared in an analogous manner to the preparation of 1 from
1
product was recrystallized from diethyl ether to give the yellow receptor
5
3
CH
7
2
2
outAr), 3.52 (m, 4H;
O), 3.77 (m,
), 4.13(m, 4H; ArOCH ), 4.26
2
2
2
2
O), 3.68 (m, 4H; CH
CH
2
9 (0.20 g, 0.17 mmol) and [Tl
A
H
R
U
G
2
CF
3
)
3
]·TFA solution (5 mL). The crude
2
2
2
2
2
H
1
+
(0.16 g, 89%). H NMR (300 MHz, CDCl
3
): d=1.05 (s, 18H; C
outAr), 3.45–3.72 (m, 36H; CH
outAr), 6.60 (s, 4H; QuH), 6.78 (s, 4H; calix ArH),
A
H
R
N
(CH
3
)
3
),
2
.18 (d, J=13.5 Hz, 4H; ArCHin
H
2
O,
5
2
N and ArCHin
H
2
2
3
5
3
.20 (t, J=7.7 Hz, 1H; isoph ArH ), 7.61 (s, 2H; NH), 7.99 (d, J=
.7 Hz, 2H; isoph ArH and ArH ), 8.31 ppm (s, 1H; isoph ArH );
and added dropwise to a stirred solution of 9 (0.98 g, 1.19 mmol) and
NEt (0.66 mL) in dry CH Cl (225 mL) at 08C under a nitrogen atmos-
4
6
2
7
3
2
2
1
3
C NMR (75.5 MHz, CDCl
3
): d=31.37, 32.77, 34.02, 40.08, 69.69, 69.97,
phere. The reaction mixture was stirred at room temperature for 3h. The
7
1
0.43, 70.49, 70.64, 72.92, 125.19, 126.90, 129.04, 129.25, 130.75, 132.77,
resulting solution was washed with 1m HCl(aq) (2100 mL), H O (2
2
34.62, 146.29, 147.46, 153.73, 167.03, 189.07; ESMS: m/z: 1067.48
100 mL), 1m NaOH(aq) (2100 mL), H O (100 mL), and brine (100 mL).
2
+
[
M+Na] ; elemental analysis (%) calcd for C60
H
72
N
2
O
14·1.1CHCl
3
: C
The organic layer was dried over MgSO4 and filtered. The filtrate was
6
2.4, H 6.3, N 2.4; found: C 62.2, H 6.6, N 2.2.
concentrated in vacuo and the residue purified by chromatography on
5
,11,17,23-Tetra-tert-butyl-25,27-bis{2-[2-(2-phthalimidoethoxy)ethoxy]-
silica gel (acetone/Et
32%). H NMR (300 MHz, CDCl ): d=0.95 (s, 18H; C(CH ), 1.15 (s,
2
O=20:80, v/v) to give a pure green solid (0.38 g,
1
A
C
H
T
R
E
U
N
G
ethoxy}-26,28-dihydroxycalix[4]arene (10): para-tert-Butylcalix[4]arene
4.70 g, 7.24 mmol) and K CO (2.10 g, 15.2 mmol) were suspended in dry
CH CN (200 mL). Compound 7 (7.85 g, 18.1 mmol) was added, and the
3
A
H
R
U
G
3 3
)
2
(
2
3
18H; C
4H; OCH
OCH CH N), 4.28–4.34 (m, 8H; ArOCH
(s, 4H; calix ArH), 6.99 (s, 4H; calix ArH), 7.47 (s, 2H; OH), 8.02 (br,
A
H
R
U
G
3
)
3
), 3.25 (d, J=3.24 Hz, 4H; ArCHin
H
outAr), 3.64–3.71 (m,
3
2
CH NH and ArOCH CH
2
2
2
O), 3.77 (t, J=4.5 Hz, 4H;
3
resulting mixture was heated to reflux for four days under a nitrogen at-
mosphere. After this time, the suspension was allowed to cool to room
temperature, and the solvent carefully removed in vacuo to give a solid
which was triturated with 1m HCl(aq) (200 mL). The resulting suspension
2
2
2 2
CH O and ArCHinHoutAr), 6.95
4
6
2H; NH), 8.60 (s, 2H; isoph ArH and ArH ), 8.95 ppm (s, 1H; isoph
2
ArH ); ESMS: m/z calcd for C60
H
76
N
3
O
10: 998.5531; found: 998.5521
[M+H] , 1020.54 [M+Na] ; elemental analysis (%) calcd for
10·0.2CHCl : C 70.7, H 7.4, N 4.1; found: C 70.6, H 7.4, N 4.1.
+
+
was extracted with CH
had cleared and the combined organic extracts were washed with H
2100 mL), dried over MgSO , filtered, and the filtrate concentrated in
vacuo. Purification by chromatography on silica gel (CHCl /acetone=
5:5, v/v) gave the pure white solid 10 (4.97 g, 60%). H NMR
300 MHz, CDCl ): d=0.93(s, 18H; C (CH ), 1.26 (s, 18H; C(CH ),
2 2
Cl (3100 mL), after which the aqueous phase
2
O
C
60
H
75
N
3
O
3
(
4
Isophthalamide triether calix[4]arene macrobicycle (17): This material
was prepared in an analogous manner to the preparation of 15: Solutions
of 13 (1.0 g, 1.1 mmol) in dry CH Cl (100 mL) and isophthaloyl chloride
(0.22 g, 1.1 mmol) in dry CH Cl (100 mL) were added to a solution of
2 2
2 2
triethylamine (1 mL, excess) in dry CH Cl (800 mL). Purification by
3
1
9
(
3
2
2
3
A
H
R
U
G
3
)
3
A
H
R
U
G
3
)
3
2
.24 (d,
CH
.6 Hz, 4H; CH
J=13.2 Hz, 4H; ArCHin
H
outAr), 3.72 (m, 12H;
3
3
OCH
4
1
2
2
OCH
2
CH
2
O), 3.85 (t, J=6.6 Hz, 4H; ArOCH
2
), 3.89 (t, J=
N), 4.31 (d, J=
chromatography on silica gel (EtOAc/acetone=95:5, v/v) gave the prod-
uct 17 as a white solid (0.79 g, 69%). H NMR (300 MHz, CDCl ): d=
3
2
1
3
2
2
CH
2
N), 4.07 (t, J=4.6 Hz, 4H; CH
2
3.2 Hz, 4H; ArCHin
H
outAr), 6.75 (s, 4H; calix ArH), 7.07 (s, 4H; calix
0.89 (s, 18H; C
A
H
R
U
G
A
H
R
U
G
3 3
(CH ) ), 1.30 (s, 18H; C(CH ) ), 3.25 (d, J=13.1 Hz, 4H;
3
3
3
4
3
ArH), 7.67 (dd, J=5.5 Hz, J=3.0 Hz, 2H; PhthH), 7.80 ppm (dd, J=
5
in out 2 2 2 2 2
ArCH H Ar), 3.69 (m, 20H; CH OCH CH OCH CH N), 4.03(m, 4H;
4
+
2
.5 Hz, J=3.0 Hz, 2H; PhthH); ESMS: m/z: 1193.61 [M+Na] .
2 in out
ArOCH ), 4.28 (d, J=13.1 Hz, 4H; ArCH H Ar), 6.70 (s, 4H, calix
3
5
ArH), 7.05 (s, 4H; calix ArH), 7.58 (t, J=7.6 Hz, 1H; isoph ArH ), 7.69
5
,11,17,23-Tetra-tert-butyl-25,27-bis(2-{2-[2-(2-
3
4
6
(
(
br, 2H; NH), 8.11 (d, J=7.6 Hz, 2H; isoph ArH and ArH ), 8.39 ppm
s, 1H; isoph ArH ); ESMS: m/z 1041.63[ M+H] , 1063.60 [M+Na] ; el-
phthalimidoethoxy)ethoxy]eth
11): This material was prepared in an analogous method to the prepara-
tion of 10 from para-tert-butylcalix[4]arene (1.36 g, 2.1 mmol), K CO
CN (75 mL). Purifica-
/acetone=90:10, v/v) gave
): d=
), 3.20 (d, J=13.1 Hz, 4H;
OCH CH O), 3.81 (m, 8H;
N), 4.27 (d, J=
A
H
R
U
G
2
+
+
(
emental analysis (%) calcd for C64
found: C 71.7, H 7.9, N 2.5.
84 2 2
H N O10·2H O: C 71.4, H 8.2, N 2.6;
2
3
(
0.70 g, 5.1 mmol), and 8 (2.52 g, 5.3mmol) in CH
3
tion by chromatography on silica gel (CHCl
3
5-Nitroisophthalamide triether calix[4]arene macrobicycle (18): This ma-
terial was prepared in an analogous manner to the preparation of 15: Sol-
utions of 13 (0.55 g, 0.60 mmol) in dry CH Cl (75 mL) and 5-nitroisoph-
thaloyl chloride (0.60 mmol) in dry CH Cl (75 mL) were added to a so-
2 2
2 2
lution of triethylamine (1 mL, excess) in dry CH Cl (400 mL). The crude
1
the pure white solid 11 (0.79 g, 33%). H NMR (300 MHz, CDCl
3
2
0
.87 (s, 18H; C
A
C
H
T
R
E
U
N
G
(CH
3
)
3
), 1.21 (s, 18H; C
A
H
R
U
G
3 3
)
2
2
ArCHin
ArOCH
3.1 Hz, 4H; ArCHin
H
outAr), 3.60 (m, 20H; CH
2
2
2
2
2
3
2
2
, CH
2
CH
2
N), 4.06 (t, J=4.7 Hz, 4H; CH
2
1
H
outAr), 6.69 (s, 4H; calix ArH), 6.96 (s, 4H; calix
product was purified by chromatography on silica gel (EtOAc/acetone=
3
4
3
ArH), 7.62 (dd, J=5.5 Hz, J=3.1 Hz, 2H; PhthH), 7.76 ppm (dd, J=
5
90:10, v/v) to give the pale-yellow solid product 18 (0.28 g, 50%).
4
+
1
.5 Hz, J=3.1 Hz, 2H; PhthH); ESMS: m/z: 1281.62 [M+Na] .
A
H
R
U
G
3 3
H NMR (300 MHz, CDCl ): d=0.84 (s, 18H; C(CH ) ), 1.31 (s, 18H; C-
3
2
A
H
R
U
G
3
)
3
), 3.21 (d, J=12.9 Hz, 4H; ArCHin
H
outAr), 3.72 (m, 20H;
), 4.20 (m, 4H; Ar-
5
2
,11,17,23-Tetra-tert-butyl-25,27-bis{2-[2-(2-aminoethoxy)ethoxy]ethoxy}-
6,28-dihydroxycalix[4]arene (13): Hydrazine monohydrate (3mL,
2
2
CH OCH CH N), 4.02 (m, 4H; ArOCH
2
2
2
2
CHin
H
excess) was added to 10 (3.40 g, 2.9 mmol) was suspended in ethanol
70 mL). This suspension was then heated under reflux for 18 h, during
which time the solid was seen to dissolve. The reaction mixture was al-
lowed to cool, then added to H O (200 mL) to give a white suspension,
which was extracted with ethyl acetate (350 mL). The combined organ-
2
4
6
2
H; NH), 8.62 (s, 1H; isoph ArH ), 8.79 ppm (s, 2H; ArH and ArH );
(
+
ESMS: m/z 1086.63[ M+H] .
2
Isophthalamide tetraether calix[4]arene macrobicycle (19): This material
was prepared in an analogous manner to the preparation of 15: Solutions
Chem. Eur. J. 2008, 14, 2248 – 2263ꢀ 2008 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
2261