10344 J. Am. Chem. Soc., Vol. 119, No. 43, 1997
Rajca et al.
1.301 (s, 9 H), 1.290 (s, 9 H), 1.269 (s, 9 H), 1.235 (s, 9 H), 1.220 (s,
9 H), 1.209 (s, 18 H), 1.202 (s, 9 H), 1.198 (s, 9 H), 1.194 (s, 9 H),
1.183 (s, 9 H), 1.178 (s, 9 H), 1.175 (s, 36 H), 1.158 (s, 9 H); IR
(cm-1) 3500 (O-H), 1596 (Ar).
(t, J ) 2, 1 H, 7.799, 7.670), 7.568 (t, J ) 2, 1 H, 7.757, 7.481), 7.560
(d, J ) 9, 2 H, 7.219), 7.514 (d, J ) 9, 2 H, 7.258), 7.514 (d, J ) 9,
2 H, 7.219), 7.496 (t, J ) 2, 1 H, 7.857, 7.649), 7.481 (t, J ) 2, 7.670,
7.568), 7.477 (d, J ) 9, 2 H, 7.186), 7.475 (t, J ) 2, 1 H, 7.971, 7.568),
7.472 (d, J ) 9, 2 H, 7.258), 7.468 (t, J ) 2, 1 H, 7.900, 7.712), 7.467
(d, J ) 9, 2 H, 7.279), 7.461 (d, J ) 9, 2 H, 7.210), 7.415 (d, J ) 9,
2 H, 7.245), 7.413 (t, J ) 2, 1 H, 8.182, 7.364), 7.412 (d, J ) 9, 2 H,
7.147), 7.405 (d, J ) 9, 2 H, 7.169), 7.373 (d, J ) 9, 2 H, 7.186),
7.365 (d, J ) 9, 2 H, 7.133), 7.364 (t, J ) 2, 1 H, 8.182, 7.413), 7.360
(d, J ) 9, 2 H, 7.173), 7.329 (d, J ) 9, 2 H, 7.147), 7.311 (d, J ) 9,
2 H, 7.227), 7.279 (d, J ) 9, 2 H, 7.467), 7.271 (t, J ) 2, 1 H, 8.665,
7.629), 7.271 (d, J ) 9, 2 H, 7.791), 7.258 (d, J ) 9, 2 H, 7.514),
7.258 (d, J ) 9, 2 H, 7.472), 7.254 (t, J ) 2, 1 H, 8.272, 8.008), 7.245
(d, J ) 9, 2 H, 7.415), 7.227 (d, J ) 9, 2 H, 7.311), 7.219 (d, J ) 9,
2 H, 7.560), 7.219 (d, J ) 9, 7.514), 7.214 (s, 4 H), 7.210 (d, J ) 9,
2 H, 7.461), 7.186 (d, J ) 9, 2 H, 7.477), 7.186 (d, J ) 9, 2 H, 7.373),
7.181 (bs, 4 H), 7.173 (d, J ) 9, 2 H, 7.360), 7.169 (d, J ) 9, 2 H,
7.405), 7.147 (d, J ) 9, 2 H, 7.412), 7.147 (d, J ) 9, 2 H, 7.329),
7.133 (d, J ) 9, 2 H, 7.365), 3.199 (s, 3 H), 2.976 (s, 3 H), 2.946 (s,
3 H), 2.914 (s, 3 H), 2.912 (s, 3 H), 2.887 (s, 3 H), 2.836 (s, 3 H),
2.815 (s, 3 H), 2.779 (s, 3 H), 2.776 (s, 6 H), 2.762 (s, 3 H), 2.621 (s,
3 H), 2.604 (s, 3 H), 1.316 (s, 9 H), 1.312 (s, 9 H), 1.291 (s, 9 H),
1.288 (s, 9 H), 1.242 (s, 9 H), 1.231 (s, 9 H), 1.227 (s, 9 H), 1.221 (s,
9 H), 1.217 (s, 9 H), 1.210 (s, 9 H), 1.204 (s, 18 H), 1.192 (s, 9 H),
1.189 (s, 9 H), 1.183 (s, 18 H), 1.174 (s, 9 H), 1.161 (s, 9 H); partial
For 9Z: FAB MS (3-NBA) wide-range scan, m/z (% RA for m/z
3400-4100) 3510 (40), 3525 (40), 3541 (100), 3555 (40); narrow-
range scan, m/z (% RA for m/z 3475-3580) at (M - OCH3)+ 3537.3
(20), 3538.3 (30), 3539.3 (55), 3540.3 (85), 3541.3 (100), 3542.3 (90),
3543.3 (65), 3544.3 (35), 3545.3 (30); 1H NMR (CDCl3) 7.857-6.684
(m, Ar-H), 2.719 (s, 6 H), 2.687 (s, 6 H), 2.645 (s, 6 H), 2.613 (s, 6
H), 2.581 (s, 1 H, exchangeable D2O), 2.542 (s, 6 H), 2.198 (s, 1 H,
exchangeable D2O), 2.146 (s, 6 H), 1.341-1.180 (C(CH3)3).
Triple-calix[4]arene Tetradecaethers 1-(OMe)14. Sodium hydride
(0.30 g of 60% dispersion in mineral oil) was washed with pentane
under nitrogen flow followed by addition of THF (3 mL). One-half
(1.5 mL) of the resultant suspension was transferred to a solution of
diol 9Y (31.2 mg in 1 mL of THF) at 0 °C; the other half (1.5 mL)
was transferred to a solution of diol 9Z (24.1 mg in 1 mL of THF) at
0 °C. After 10 min, iodomethane (0.1 mL) was added to each reaction
mixture. The reactions were quenched with a few drops of methanol
followed by aqueous workup. PTLC (hexane/ether, 10:1) followed by
treatment with methanol gave tetradecaethers 1Y-(OMe)14 (5.8 mg,
18%) and 1Z-(OMe)14 (4.9 mg, 20%). Tetradecaether 1X-(OMe)14
(7.0 mg, 20%) was obtained by the same method from 34.2 mg of diol
9X.
1
(methoxy and tert-butyl groups) H NMR (500 MHz, EM ) -1.85,
For 1X-(OMe)14: FAB MS (3-NBA) wide-range scan, m/z (% RA
for m/z 700-4800) 3538 (40), 3570 (100); narrow-range scan, m/z (%
RA for m/z 3520-3585) at (M - OCH3)+ 3565.5 (15), 3566.5 (20),
3567.5 (50), 3568.5 (80), 3569.5 (100), 3570.5 (90), 3571.5 (65), 3572.5
(35), 3573.4 (15); Calcd for C255H297O13 at (M - OCH3)+ 3567.3 (25),
3568.3 (70), 3569.3 (100), 3570.3 (100), 3571.3 (70), 3572.3 (40),
GB ) 1.20, C6D6, 328 K) 3.168 (s, 3 H), 2.966 (s, 3 H), 2.945 (s, 3
H), 2.923 (s, 3 H), 2.901 (s, 3 H), 2.896 (s, 3 H), 2.812 (s, 3 H), 2.794
(s, 3 H), 2.780 (s, 3 H), 2.769 (s, 3 H), 2.756 (s, 3 H), 2.753 (s, 3 H),
2.648 (s, 3 H), 2.575 (bs, 3 H), 1.315 (s, 9 H), 1.306 (s, 9 H), 1.298 (s,
9 H), 1.283 (s, 9 H), 1.247 (s, 9 H), 1.239 (s, 9 H), 1.227 (s, 9 H),
1.222 (s, 9 H), 1.215 (s, 9 H), 1.206 (s, 9 H), 1.201 (s, 9 H), 1.197 (s,
9 H), 1.194 (s, 9 H), 1.191 (s, 9 H), 1.184 (s, 9 H), 1.178 (s, 9 H),
1.170 (s, 9 H), 1.153 (s, 9 H).
1
3573.3 (20), 3574.3 (10); H NMR (500 MHz, C6D6, 298 K) 8.756-
6.990 (m, ArH), 3.099 (s, 3 H), 2.982 (s, 3 H), 2.946 (s, 3 H), 2.897
(s, 3 H), 2.871 (s, 3 H), 2.853 (s, 3 H), 2.788 (s, 3 H), 2.771 (s, 3 H),
2.727 (s, 3 H), 2.685 (s, 3 H), 2.666 (s, 9 H), 2.312 (s, 3 H), 1.331 (s,
9 H), 1.321 (s, 9 H), 1.290 (s, 9 H), 1.276 (s, 9 H), 1.270 (s, 9 H),
1.249 (s, 9 H), 1.233 (s, 9 H), 1.209 (s, 9 H), 1.202 (s, 18 H), 1.199 (s,
9 H), 1.190 (s, 9 H), 1.174 (s, 9 H), 1.160 (s, 9 H), 1.156 (s, 18 H),
1.120 (s, 9 H), 1.072 (s, 9 H); 1H NMR (500 MHz, EM ) -1.85, GB
) 1.20, C6D6, 348 K) 8.652 (t, J ) 2, 1 H), 8.153 (t, J ) 2, 1 H),
8.085 (t, J ) 2, 1 H), 8.072 (t, J ) 2, 1 H), 7.890 (t, J ) 2, 1 H), 7.846
(t, J ) 2, 1 H), 7.820 (t, J ) 2, 1 H), 7.804 (d, J ) 9, 1 H), 7.788 (t,
J ) 2, 1 H), 7.734 (t, J ) 2, 1 H), 7.724 (t, J ) 2, 1 H), 7.692 (t, J )
2, 1 H), 7.669 (t, J ) 2, 1 H), 7.654 (t, J ) 2, 1 H), 7.627 (t, J ) 2,
1 H), 7.593 (d, J ) 9, 1 H), 7.530 (t, J ) 2, 1 H), 7.511-7.150 (m,
ArH), 7.127 (d, J ) 9, 1 H), 7.104 (d, J ) 9, 1 H), 7.076 (d, J ) 9, 1
H), 7.033 (d, J ) 9, 1 H), 6.991 (t, J ) 2, 1 H), 3.210 (s, 3 H), 2.975
(s, 3 H), 2.917 (s, 6 H), 2.892 (s, 3 H), 2.851 (s, 3 H), 2.847 (s, 3 H),
2.820 (s, 3 H), 2.815 (s, 3 H), 2.803 (s, 3 H), 2.758 (s, 3 H), 2.750 (s,
3 H), 2.724 (s, 3 H), 2.430 (s, 3 H), 1.329 (s, 9 H), 1.317 (s, 9 H),
1.308 (s, 9 H), 1.263 (s, 9 H), 1.243 (s, 9 H), 1.240 (s, 9 H), 1.233 (s,
9 H), 1.222 (s, 9 H), 1.221 (s, 9 H), 1.214 (s, 9 H), 1.205 (s, 9 H),
1.198 (s, 18 H), 1.186 (s, 9 H), 1.181 (s, 9 H), 1.165 (s, 9 H), 1.151 (s,
9 H), 1.129 (s, 9 H).
For 1Z-(OMe)14: FAB MS (3-NBA) wide-range scan, m/z (% RA
for m/z 700-4800) 3538 (40), 3570 (100); narrow-range scan, m/z (%
RA for m/z 3510-3595) at (M - OCH3)+ 3566.5 (20), 3567.5 (50),
3568.5 (85), 3569.5 (100), 3570.5 (95), 3571.5 (65), 3572.5 (40), 3573.5
1
(20); H NMR (500 MHz, cyclohexane-d12, 298 K) 8.297 (bs, ArH),
7.447 (s, ArH), 7.288-6.939 (m, ArH), 7.795 (s, ArH), 7.697 (s, ArH),
2.779 (bs, OCH3), 2.693 (s, OCH3), 2.619 (s, OCH3), 2.423-1.810 (2
bs, OCH3), 1.381-1.217 (overlapped, C(CH3)3); 1H NMR (500 MHz,
1
EM ) -1.85, GB ) 1.20, cyclohexane-d12, 348 K, H-1H COSY45
cross-peak) 8.087 (t, J ) 2, 2 H, 6.948, 6.682), 7.547 (t, J ) 2, 2 H,
7.079, 6.936, after 2-Hz Gaussian broadening in both dimensions), 7.344
(t, J ) 2, 2 H, 7.251, 6.878), 7.271 (d, J ) 9, 4 H, 7.167), 7.251 (t, J
) 2, 2 H, 7.344, 6.878), 7.211 (t, J ) 2, 2 H, 7.190, 7.001), 7.190 (t,
J ) 2, 2 H, 7.211, 7.001), 7.177 (d, J ) 9, 4 H, 7.103), 7.167 (d, J )
9, 4 H, 7.271), 7.160 (d, J ) 9, 4 H, 7.075), 7.140 (d, J ) 9, 4 H,
7.066), 7.131 (d, J ) 9, 2 H, 7.016), 7.103 (d, J ) 9, 4 H, 7.177),
7.079 (d, J ) 9, 4 H, 6.836), 7.075 (d, J ) 9, 4 H, 7.160), 7.079 (t, J
) 2, 2 H, 7.547, 6.936), 7.071 (d, J ) 9, 4 H, 7.031), 7.066 (d, J ) 9,
4 H, 7.140), 7.050 (d, J ) 9, 2 H, 7.014), 7.050 (d, J ) 9, 4 H, 7.031),
7.031 (d, J ) 9, 4 H, 7.050), 7.031 (d, J ) 9, 4 H, 7.071), 7.016 (d, J
) 9, 2 H, 7.131), 7.014 (d, J ) 9, 2 H, 7.050), 7.010 (d, J ) 9, 4 H,
6.845), 7.001 (t, J ) 2, 2 H, 7.211, 7.190), 6.948 (t, J ) 2, 2 H, 8.087,
6.682), 6.936 (t, J ) 2, 2 H, 7.547, 7.079), 6.878 (t, J ) 2, 2 H, 7.251,
7.344), 6.845 (d, J ) 9, 4 H, 7.010), 6.836 (d, J ) 9, 4 H, 7.079),
6.682 (t, J ) 2, 2 H, 8.087, 6.948), 2.841 (s, 6 H), 2.707 (s, 6 H),
2.680 (s, 6 H), 2.637 (s, 6 H), 2.607 (s, 6 H), 2.486 (s, 6 H), 2.156 (bs,
6 H), 1.380 (bs, cyclohexane-d12 possibly overlapping some resonances
for t-Bu groups), 1.293 (s, 18 H), 1.252 (s, 54 H), 1.245 (s, 18 H),
1.239 (s, 18 H), 1.232 (s, 18 H), 1.214 (s, 18 H).
For 1Y-(OMe)14: FAB MS (3-NBA) wide-range scan, m/z (% RA
for m/z 700-4800) 3538 (45), 3570 (100); narrow-range scan, m/z (%
RA for m/z 3515-3590) at (M - OCH3)+ 3565.5 (15), 3566.5 (20),
3567.5 (45), 3568.5 (80), 3569.5 (100), 3570.5 (85), 3571.5 (65), 3572.5
(35), 3573.5 (20), 3574.4 (10); 1H NMR (500 MHz, C6D6, 298 K)
8.752-6.989 (m, ArH), 3.111 (s, 3 H), 3.001 (s, 3 H), 2.938 (s, 3 H),
2.903 (s, 3 H), 2.879 (s, 3 H), 2.798-2.709 (27 H), 1.299 (s, 9 H),
1.283 (s, 9 H), 1.273 (s, 9 H), 1.253 (s, 9 H), 1.220 (s, 9 H), 1.211 (bs,
18 H), 1.194 (s, 27 H), 1.190 (s, 9 H), 1.182 (s, 9 H), 1.161 (bs, 27 H),
1
1.136 (s, 9 H); H NMR (500 MHz, EM ) -1.85, GB ) 1.20, C6D6,
Reaction of Tetradecaethers 1-(OMe)14 with Na/K and MeOH
Quenching Product 1-(H)14. A drop of Na/K alloy was added to a
stirred tetradecaether (∼1 mg) in THF (∼0.5 mL) in a Schlenk vessel.
After 4 days of stirring, MeOH (few drops) was added. The usual
aqueous workup with ether gave crude product. Preparative TLC (2%
ether in hexane) gave 1-(H)14 (∼1 mg), most likely, as a mixture of
isomers: 1H NMR (500 MHz, acetone-d6) 7.7-6.2 (bm, 96 H), 5.6-
4.8 (bm, ∼14 H), 1.5-1.0 (bm, ∼200 H); FAB MS (3-NBA) wide-
range scan, m/z (% RA for m/z 1150-4900) 1399 (90), 3180 (100);
348 K, 1H-1H COSY cross-peak) 8.665 (t, J ) 2, 1 H, 7.629, 7.271),
8.272 (t, J ) 2, 1 H, 8.008, 7.254), 8.182 (t, J ) 2, 1 H, 7.413, 7.364),
8.008 (t, J ) 2, 1 H, 8.272, 7.254), 7.971 (t, J ) 2, 1 H, 7.614, 7.475),
7.900 (t, J ) 2, 1 H, 7.712, 7.468), 7.857 (t, J ) 2, 1 H, 7.649, 7.496),
7.799 (t, J ) 2, 1 H, 7.670, 7.601), 7.791 (d, J ) 9, 2 H, 7.271), 7.757
(t, J ) 2, 1 H, 7.568, 7.481), 7.712 (t, J ) 2, 1 H, 7.900, 7.486), 7.670
(t, J ) 2, 1 H, 7.799, 7.601), 7.649 (t, J ) 2, 1 H, 7.857, 7.496), 7.629
(t, J ) 2, 1 H, 8.665, 7.271), 7.614 (t, J ) 2, 1 H, 7.971, 7.475), 7.601