9276 J . Org. Chem., Vol. 63, No. 25, 1998
Xie and Gutsche
of 2 was redissolved in 15 mL of dry CH2Cl2. The solution
was added dropwise to a CH2Cl2 solution containing 0.11 g
(0.42 mmol) of bis[2-(3,5-dimethyl-1-pyrazoyl-ethyl)]amine and
0.05 g (0.5 mmol) of Et3N, and the reaction mixture was stirred
at room temperature for 3 h. The reaction was then quenched
with H2O. The organic layer was separated, washed with H2O
and brine, and dried over Na2SO4, and the solvent was
removed by evaporation to leave a residue which was chro-
matographed to give 0.51 g (80%) of 4: mp ca. 150 °C (dec);
1H NMR (CDCl3) δ 7.82-7.66 (m, 16H), 6.83 (t, 1H, J ) 7.6
Hz), 6.64-6.57 (m, 4H), 6.42 (s, 2H), 6.31 (d, 4H, J ) 7.6 Hz),
by column chromatography using 1.5% MeOH -CHCl3 (v/v)-
as an eluent: mp ca. 96 °C (dec); 1H NMR (CDCl3) δ 7.78-
7.65 (m, 16H), 6.55 (s, 4H), 6.41 (s, 4H), 5.75 (s, 4H), 3.81-
3.73 (m, 12H), 2.83 (t, 8H, J ) 6.7 Hz), 2.55 (t, 4H, J ) 8.1
Hz), 2.47 (d, 4H, J ) 14.0 Hz), 2.33 (t, 4H, J ) 8.1 Hz), 2.19
(s, 12H), 2.17 (s, 12H), 0.97 (s, 18H); 13C NMR (CDCl3) δ 148.9,
147.4, 143.3, 142.0, 139.0, 138.1, 135.5, 134.6, 134.2, 133.9,
132.7, 132.2, 131.0, 129.3, 125.8, 104.9, 57.2, 54.5, 47.2, 34.1,
33.1, 31.2, 31.1, 13.5, 11.0. Anal. Calcd for C92H102N10O12
Br4S4: C, 55.59, H, 5.17. Found: C, 55.78; H, 4.98.
-
5,17-B i s (c y a n o m e t h y l)-25,26,27,28-t e t r a k i s [{(p -
br om op h en yl)su lfon yl}oxy]ca lix[4]a r en e (9). To a solu-
tion of 1.22 g (2.4 mmol) of 5,17-bis(cyanomethyl)calix[4]-
25,26,27,28-tetrol in 80 mL of THF was added 1.16 g of NaH
(60% oil dispersion, 28.8 mmol). The reaction mixture was
stirred for 30 min, treated with 3 g (12.2 mmol) of p-
bromobenzenesulfonyl chloride, and allowed to stir at room
temperature for 3 h. The solvent was removed under vacuum,
and the residue was treated with 80 mL of CH2Cl2 and poured
into 80 g of crushed ice. The organic layer was separated,
washed with H2O and brine, and dried over Na2SO4, and the
solvent was removed by evaporation leaving a residue which
was chromatographed (eluent 10% n-hexanes-CHCl3 (v/v)) to
1
5.79 (s, 1H), 5.74 (s, H), 4.12 (t, 2H, J ) 5.7 Hz), 3.82 (t, 2H,
J ) 5.7 Hz), 3.75 (d + d, 4H, J ) 14.6 and 14.5 Hz), 3.66 (t,
2H, J ) 5.7 Hz), 3.23 (t, 2H, J ) 5.7 Hz), 2.94 (s, 2H), 2.53 (d
+ d, 4H, J ) 14.5 and 14.9 Hz), 2.20 (s, 3H), 2.17 (s, 3H), 2.12
(s, 3H), 2.02 (s, 3H); 13C NMR (CDCl3) δ 171.0, 148.3, 145.4,
144.5, 144.3, 139.9, 139.5, 136.1, 135.0, 134.8, 134.5, 134.4,
132.8, 132.6, 132.4, 131.0, 130.8, 130.1, 129.4, 129.0, 126.1,
126.0, 105.6, 105.2, 48.7, 46.7, 46.3, 45.7, 38.6, 31.33, 31.30,
13.6, 13.5, 10.8, 10.7; IR (KBr, cm-1) 1649 (CO), 1552 (pyra-
zole). Anal. Calcd for C68H59N5O13S4Br4: C, 50.97; H, 3.69;
N, 4.37. Found: C, 50.92; H, 3.79; N, 4.31.
5-[N,N-b is-2-(3,5-d im et h yl-1-p yr a zolyl)et h yla m in o]-
eth yl-25,26,27,28-tetr akis[{(p-br om oph en yl)su lfon yl}oxy]-
ca lix[4]a r en e (5). To a sample of 0.8 g (0.5 mmol) of 4, 10
mL of a 1.0 M solution of B2H6 in THF was added at 0 °C, and
the mixture was stirred at room temperature for 1 h. A few
drops of MeOH were then added to destroy the excess B2H6.
After removal of the solvent by evaporation, the residue was
treated with a mixture 3 mL of H2O, 20 mL of MeOH, and 3
mL of concentrated HCl, and the mixture was refluxed for 1
h. The solvent was removed by evaporation, and the residue
was treated with 15 mL of H2O and neutralized with 20%
NaOH to precipitate a white solid. The crude product was
collected by suction filtration and chromatographed by using
1% MeOH-CHCl3 (v/v) to yield 0.70 g (88%) of 5 as a white
1
give 2.66 g (80%) of 9: mp ca. 181 °C (dec); H NMR (CDCl3)
δ 7.79-7.72 (m, 16H), 6.81 (t, 2H, J ) 7.6 Hz), 6.54 (m, 8H),
3.80 (d, 4H, J ) 14.5 Hz), 3.50 (s, 4H), 2.55 (d, 4H, J ) 14.5
Hz); 13C NMR (CDCl3) δ 144.8, 144.7, 136.3, 134.9, 134.2,
134.1, 132.6, 130.9, 130.8, 129.7, 129.6, 129.4, 128.5, 128.0,
126.6, 117.8, 31.4, 22.6. Anal. Calcd for C56H38O12Br4S4: C,
48.78; H, 2.78. Found: C, 48.81; H, 2.85.
5,17-Bis(ca r boxym eth yl)-25,26,27,28-tetr a k is[{(p-br o-
m op h en yl)-su lfon yl}oxy]ca lix[4]a r en e (10) was prepared
in quantitative yield by the procedure described for 2, using 9
as the starting material. An analytical sample was obtained
as a white solid by recrystallization from acetone-hexanes:
1
mp ca. 220 °C (dec); H NMR (CDCl3) δ 8.37 (brs, 2H), 7.79-
1
solid: mp ca. 119 °C (dec); H NMR (CDCl3) δ 7.82-7.68 (m,
7.67 (m, 16H), 6.68 (m, 6H), 6.50 (d, 4H, J ) 7.6 Hz), 3.83 (d,
4H, J ) 14.3 Hz), 3.34 (s, 4H), 2.55 (d, 4H, J ) 14.3 Hz); 13C
NMR (CDCl3 + 1 drop of DMSO-d6) δ 177.0, 144.4, 144.3,
136.0, 134.7, 134.4, 134.2, 132.6, 131.4, 131.1, 130.8, 130.3,
129.5, 129.1, 129.0, 126.3, 40.1, 31.2. Anal. Calcd for C56H40O16-
Br4S4: C, 47.47; H, 2.85. Found: C, 47.59; H, 2.78.
16H), 6.81 (t, 1H, J ) 7.5 Hz), 6.65-6.60 (m, 4H), 6.30 (m,
6H), 5.76 (s, 2H), 3.84-3.69 (m, 8H), 2.87 (t, 4H, J ) 6.7 Hz),
2.60-2.35 (m, 8H), 2.20 (s, 12H); 13C NMR (CDCl3) δ 147.5,
145.3, 144.5, 143.7, 139.0, 138.1, 136.1, 135.7, 135.0, 134.9,
134.5, 134.4, 132.6, 132.4, 131.0, 130.9, 130.8, 129.6, 129.4,
129.3, 129.0, 128.9, 126.0, 104.9, 56.8, 54.5, 47.2, 33.2, 31.4,
31.2, 13.5, 11.1. Anal. Calcd for C68H61N5O12S4Br4: C, 51.43;
H, 3.87. Found: C, 51.09; H, 3.62.
5,17-Bis[(N,N-bis-2-{3,5-dim eth ylpyr azolyl}eth ylam in o)-
ca r bon yl]m eth yl-25,26,27,28-tetr a k is[{(p-br om op h en yl)-
su lfon yl}oxy]ca lix[4]a r en e (11) was prepared in 77% yield
by the procedure described for 6, using 10 as the starting
material. An analytical sample was obtained by column
chromatography using 3% MeOH-CHCl3 (v/v) as eluent: mp
5,17-B is [(N ,N -b is -2-{3,5-d im e t h y lp y r a zo ly l}e t h y l-
a m in o)ca r b on yl]m et h yl-11,23-d i-ter t-b u t yl-25,26,27,28-
tetr akis[{(p-br om oph en yl)su lfon yl}oxy]calix[4]ar en e (6).
A 1.39 g (0.91 mmol) sample of 5,17-bis(carboxymethyl)-11,-
23-di-tert-butyl-25,26,27,28-tetrakis[{(p-bromophenyl)sulfonyl}-
oxy]calix[4]arene was mixed with 0.96 g (3.64 mmol) of bis[2-
(3,5-dimethyl-1-pyrazoyl-ethyl)]amine and 0.563 g of dicyclo-
hexylcarbodimide and 0.37 g of 1-hydroxybenzotriazole in 40
mL of dry CH2Cl2, and refluxed for 12 h. The mixture was
worked up in conventional fashion to give 1.37 g (75%) of 6.
An analytical sample was obtained by recrystallization from
CHCl3-hexanes as very small colorless needles: mp ca. 167
1
ca. 140 °C (dec); H NMR (CDCl3) δ 7.87 (d, 4H, J ) 8.6 Hz),
7.72-7.28 (m, 12H), 6.76 (s, 4H), 6.34 (t, 2H, J ) 7.6 Hz), 5.97
(d, 4H, J ) 7.6 Hz), 5.82 (s, 2H), 5.76 (s, 2H), 4.17 (t, 4H, J )
5.6 Hz), 3.89 (t, 4H, J ) 5.4 Hz), 3.71 (m, 8H), 3.33 (t, 4H, J
) 5.2 Hz), 3.19 (s, 4H), 2.49 (d, 4H, J ) 14.6 Hz), 2.20 (s, 6H),
2.19 (s, 6H), 2.15 (s, 6H), 2.10 (s, 6H); 13C NMR (CDCl3) δ
171.0, 148.3, 148.0, 145.0, 143.6, 139.8, 139.5, 137.1, 134.4,
134.3, 133.6, 133.0, 132.7, 132.2, 131.1, 130.53, 130.49, 129.4,
129.3, 128.5, 125.9, 105.6, 105.2, 48.6, 46.7, 46.3, 45.7, 38.7,
31.2, 13.51, 13.47, 10.7. Anal. Calcd for C84H82N10O14Br4S4:
C, 53.00; H, 4.34. Found: C, 52.95; H, 4.38.
1
°C (dec); H NMR (CDCl3) δ 7.78 (d, 2H, J ) 8.7 Hz), 7.68 (d,
2H, J ) 8.7 Hz), 7.64 (m, 12H), 6.62 (s, 4H), 6.52 (s, 4H), 5.78
(s, 2H), 5.75 (s, 2H), 4.12 (t, 4, J ) 5.6 Hz), 3.78 (d, 4H, J )
14.1 Hz), 3.68 (t, 4H, J ) 5.6 Hz), 3.62 (t, 4H, J ) 5.6 Hz),
3.24 (t, 4H, J ) 5.9 Hz), 3.09 (s, 4H), 2.52 (d, 4H, J ) 14.1
Hz), 2.20 (s, 6H), 2.18 (s, 6H), 2.10 (s, 6H), 2.02 (s, 6H)), 0.91
(s, 18H); 13C NMR (CDCl3) δ 170.8, 149.1, 148.2, 148.0, 143.9,
141.9, 140.0, 139.3, 136.0, 134.5, 134.2, 133.6, 132.8, 132.6,
132.2, 131.0, 129.8, 129.3, 125.9, 105.5, 105.2, 49.0, 47.4, 46.3,
5,17-Bis[(N,N-bis-2-{3,5-dim eth ylpyr azolyl}eth ylam in o)]-
eth yl-25,26,27,28-tetr akis[{(p-br om oph en yl)su lfon yl}oxy]-
ca lix[4]a r en e (12) was prepared in 85% yield by the proce-
dure described for 5, using 11 as the starting material. An
analytical sample was obtained by column chromatography
using 2% MeOH-CHCl3 (v/v) as eluent: mp ca. 110 °C (dec);
1H NMR (CDCl3) δ 7.85 (d, 4H, J ) 8.7 Hz), 7.72 (d, 4H, J )
8.7 Hz), 7.68-7.59 (m, 8H), 6.64 (s, 4H), 6.34 (t, 2H, J ) 7.6
Hz), 5.91 (d, 4H, J ) 7.6 Hz), 5.77 (s, 4H), 3.86 (t, 8H, J ) 6.8
Hz), 3.72 (d, 4H, J ) 14.5 Hz), 2.94 (t, 8H, J ) 6.8 Hz), 2.69-
2.67 (m, 4H), 2.61-2.58 (m, 4H), 2.47 (d, 4H, J ) 14.5 Hz),
2.23 (s, 12H), 2.20 (s, 12H); 13C NMR (CDCl3) δ 147.5, 144.6,
143.6, 139.1, 138.5, 136.8, 134.6, 134.4, 133.7, 132.7, 132.2,
131.1, 130.6, 130.1, 129.4, 129.2, 128.4, 125.8, 105.0, 56.9, 54.5,
45.8, 38.9, 34.0, 31.2, 31.0, 13.6, 13.5, 10.7, 10.6; IR (KBr, cm-1
1649.2 (CON), 1552.8 (DMP). Anal. Calcd for C92H98N10O14
)
-
Br4S4: C, 54.82, H, 4.90; N, 6.95. Found: C, 54.35; H, 4.88;
N, 6.67.
5,17-Bis[N,N-bis-2-(3,5-d im eth ylp yr a zolyl)eth yla m in o]-
e t h y l-11,23-d i -t er t -b u t y l-25,26,27,28-t e t r a k i s [{(p -
br om op h en yl)su lfon yl}oxy]ca lix[4]a r en e (7) was prepared
in 85% yield following the procedure described above for 5
using 2 h of reaction time. An analytical sample was obtained
47.3, 33.4, 31.3, 13.5, 11.1. Anal. Calcd for C84H86N10O12
Br4S4: C, 53.79; H, 4.62. Found: C, 53.64; H, 4.73.
-