The Journal of Organic Chemistry
FEATURED ARTICLE
δ 197.8, 169.7, 154.7, 146.2, 134.2, 133.3, 126.6, 125.6, 65.5, 62.3, 34.6,
31.4, 21.3; HRMS (ESI) m/z 871.4392 [(M þ Na)þ calcd for
C52H64O10Na, 871.4397].
(s, 9H), 0.96 (s, 9H); 13C NMR (126 MHz, CDCl3) δ 196.0, 170.0,
155.1, 154.1, 152.6, 147.1, 146.0, 144.8, 136.2, 135.6, 132.6, 131.1, 127.1,
126.3, 125.7, 125.5, 67.0, 63.8, 62.0, 59.3, 34.7, 34.4, 34.1, 31.4, 31.3,
31.0, 21.3; HRMS (ESI) m/z 871.4392 [(M þ Na)þ calcd for
C52H64O10Na, 871.4397].
5,11,17,23-Tetra-tert-butyl-25,26,27,28-tetramethoxy-8,20-dioxo-
2,14-bis(trifluoroacetoxy)calix[4]arene (13a). A mixture of 3a (0.1 g,
0.085 mmol) and 3 mL of trifluoroacetic acid was heated to reflux for 2
h. The solvent was evaporated and the residue recrystallized from
5,11,17,23-Tetra-tert-butyl-25,26,27,28-tetramethoxy-2,20-dioxo-
8,14-bis-trifluoroacetoxycalix[4]arene (13b): yield 33 mg (63%); mp
275ꢀ280 °C; 1H NMR (400 MHz, CDCl3) δ 7.76 (d, J = 2.5 Hz, 2H),
7.75 (d, J = 2.5 Hz, 2H), 7.58 (s, 2H), 7.55 (s, 2H), 7.01 (s, 2H), 3.96
(s, 3H), 3.47 (s, 6H), 2.19 (s, 3H), 1.36 (s, 9H), 1.35 (s, 18H), 0.99
(s, 9H); 13C NMR (126 MHz, CDCl3) δ 195.4, 156.6 (q, J = 42.7 Hz),
154.8, 154.0, 153.6, 147.6, 147.1, 145.4, 135.1, 133.8, 132.7, 129.5, 128.4,
126.6, 126.5, 124.8, 114.7 (q, J = 285.7 Hz), 71.0, 64.0, 62.2, 60.4, 34.7, 34.5,
34.2, 31.2, 30.8; 19F NMR (471 MHz, CDCl3) δ ꢀ75.1 (s); HRMS (ESI)
m/z 957.4007 [(M þ H)þ calcd for C52H59F6O10, 957.4012].
2,14-Diazido-5,11,17,23-tetra-tert-butyl-25,26,27,28-tetramethoxy-
8,20-dioxocalix[4]arene (14). A mixture of 4a (0.10 g, 0.11 mmol),
sodium azide (0.153 g, 2.35 mmol), and 10 mL of TFE was heated at
reflux for 18 h. After evaporation of the solvent, the residue was treated
with 25 mL of CHCl3 and the unreacted NaN3 was removed by
filtration. The filtrate was evaporated, and the residue was recrystallized
from CHCl3/MeOH to give 38 mg (28%) of 14: mp 278ꢀ283 °C; 1H
NMR (500 MHz, CDCl3) δ 7.67 (d, J = 2.5 Hz, 4H), 7.60 (d, J = 2.5 Hz,
4H), 6.12 (s, 2H), 3.19 (s, 12H), 1.36 (s, 36H); 13C NMR (125 MHz,
CDCl3) δ 197.7, 154.6, 146.6, 134.0, 132.5, 127.4, 125.8, 62.8, 55.7, 34.6,
31.3; HRMS (ESI) m/z 837.4310 [(M þ Na)þ calcd for C48H58N6O6-
Na, 837.4316].
1
CHCl3/MeOH: yield 68.6 mg (84%); mp 357ꢀ363 °C; H NMR
(500 MHz, CDCl3) δ 7.75 (d, J = 2.5 Hz, 4H), 7.67 (d, J = 2.5 Hz, 4H),
7.33 (s, 2H), 3.24 (s, 12H), 1.37 (36H); 13C NMR (126 MHz, CDCl3)
δ 196.8, 156.30 (q, J = 42.5 Hz), 154.7, 146.9, 133.9, 131.1, 126.6,
126.2, 114.5 (q, J = 286.0 Hz), 69.8, 62.5, 34.6, 31.3; 19F NMR (471
MHz, CDCl3) δ ꢀ75.4 (s); HRMS (ESI) m/z 979.3826 [(M þ Na)þ
calcd for C52H58F6O10Na, 979.3832].
General Procedure for the Reaction of 4b with Alcohols. A
solution of 4b (0.05 g, 0.043 mmol) in a mixture of 5 mL of TFE and
5 mL of the appropriate alcohol was refluxed for 18 h. The solvent was
evaporated and the residue recrystallized from CHCl3/acetonitrile.
5,11,17,23-Tetra-tert-butyl-8,14,25,26,27,28-hexamethoxy-2,20-di-
1
oxocalix[4]arene (7b): yield 25.2 mg (57%); mp 280ꢀ285 °C; H
NMR (500 MHz, CDCl3) δ 7.96 (d, J = 2.4 Hz, 2H), 7.71 (d, J = 2.6 Hz,
2H), 7.47 (s, 2H), 6.79 (s, 2H), 5.86 (s, 2H), 3.94 (s, 3H), 3.54 (s, 6H),
3.39 (s, 6H), 1.88 (s, 3H), 1.38 (s, 18H), 1.35 (s, 9H), 0.92 (s, 9H); 13C
NMR (126 MHz, CDCl3) δ 196.3, 155.7, 154.6, 152.6, 147.2, 146.2,
144.4, 137.1, 135.8, 132.4, 132.3, 126.9, 126.7, 125.3, 125.0, 74.3, 63.2,
61.8, 59.0, 57.4, 34.8, 34.4, 34.1, 31.4, 31.3, 31.0; HRMS (ESI) m/z
793.4674 [(M þ H)þ calcd for C50H65O8, 793.4679].
General Procedure for the Reaction of 4a with Arenes. A
solution of 4a (0.1 g, 0.11 mmol) in a mixture of 1 mL of TFA and
0.1 mL of the appropriate arene was refluxed for 18 h. The solvent was
evaporated and the residue recrystallized from CHCl3/MeOH or
CHCl3/acetonitrile.
5,11,17,23-Tetra-tert-butyl-8,14-diethoxy-25,26,27,28-tetrametho-
xy-2,20-dioxocalix[4]arene (8b): yield 26 mg (56%); mp 240ꢀ245 °C;
1H NMR (400 MHz, CDCl3) δ 7.99 (d, J = 2.6 Hz, 2H), 7.70 (d, J = 2.6
Hz, 2H), 7.46 (s, 2H), 6.79 (s, 2H), 5.98 (s, 2H), 3.92 (s, 3H),
3.73ꢀ3.62 (m, 4H), 3.38 (s, 6H), 1.87 (s, 3H), 1.38 (s, 18H),
1.37ꢀ1.34 (m, 6H), 1.35 (s, 9H), 0.91 (s, 9H); 13C NMR (126
MHz, CDCl3) δ 196.3, 155.7, 154.3, 152.5, 147.1, 146.1, 144.4,
137.7, 135.9, 132.7, 132.4, 126.9, 126.8, 125.20, 125.18, 72.1, 64.9,
63.2, 61.8, 59.0, 34.7, 34.4, 34.0, 31.4, 31.3, 31.0, 15.5; HRMS (ESI)
m/z 821.4987 [(M þ H)þ calcd for C52H69O8, 821.4992].
5,11,17,23-Tetra-tert-butyl-2,14-bis(p-tert-butylphenyl)-25,26,27,-
28-tetramethoxy-8,20-dioxocalix[4]arene (15): yield 82.7 mg (74%);
mp 370ꢀ375 °C; 1H NMR (400 MHz, CDCl3) δ 7.52 (d, J = 2.5 Hz,
4H), 7.37 (d, J = 2.5 Hz, 4H), 7.25 (d, J = 8.2 Hz, 4H), 7.00 (d, J = 8.2
Hz, 4H), 6.00 (s, 2H), 3.18 (s, 12H), 1.30 (s, 18H), 1.28 (s, 36H); 13C
NMR (126 MHz, CDCl3) δ 199.8, 155.7, 148.6, 145.5, 140.7, 136.5, 134.5,
130.5, 128.5, 124.9, 123.9, 62.5, 39.6, 34.4, 34.3, 31.3; HRMS (ESI) m/z
1019.6160 [(M þ Na)þ calcd for C68H84O6Na, 1019.6166].
5,11,17,23-Tetra-tert-butyl-25,26,27,28-tetramethoxy-2,20-dioxo-8,
14-diisopropoxycalix[4]arene (9b): yield 30 mg (63%); mp 230ꢀ
1
235 °C; H NMR (500 MHz, CDCl3) δ 8.00 (d, J = 2.6 Hz, 2H),
7.69 (d, J = 2.5 Hz, 2H), 7.47 (s, 2H), 6.81 (s, 2H), 6.17 (s, 2H), 3.92
(s, 3H), 3.80 (h, J = 6.1 Hz, 2H), 3.40 (s, 6H), 1.84 (s, 3H), 1.38
(s, 18H), 1.35 (d, J = 5.9 Hz, 6H), 1.35 (s, 9H), 1.30 (d, J = 6.0 Hz, 6H),
0.91 (s, 9H); 13C NMR (126 MHz, CDCl3) δ 196.44, 155.70, 153.90,
152.44, 147.06, 145.93, 144.42, 138.05, 135.96, 132.80, 132.45, 127.23,
126.74, 125.51, 125.13, 69.19, 69.07, 63.40, 61.78, 58.99, 34.72, 34.40,
34.02, 31.43, 31.28, 30.96, 22.79, 21.83; HRMS (ESI) m/z 849.5300
[(M þ H)þ calcd for C54H73O8, 849.5305].
5,11,17,23-Tetra-tert-butyl-25,26,27,28-tetramethoxy-8,20-dioxo-2,
14-di(p-tolyl)calix[4]arene (16): yield 60 mg (59%); mp 360ꢀ
1
365 °C; H NMR (400 MHz, CDCl3) δ 7.52 (d, J = 2.5 Hz, 4H),
7.34 (d, J = 2.5 Hz, 4H), 7.06 (d, J = 8.1 Hz, 4H), 6.98 (d, J = 8.0 Hz, 4H),
5.99 (s, 2H), 3.17 (s, 12H), 2.32 (s, 6H), 1.27 (s, 36H); 13C NMR (126
MHz, CDCl3) δ 199.7, 155.7, 145.6, 140.8, 136.5, 135.3, 134.5, 130.4,
128.8, 123.9, 62.4, 39.7, 34.4, 31.3, 20.9; HRMS (ESI) m/z 913.5402
[(M þ H)þ calcd for C62H73O6, 913.5407].
5,11,17,23-Tetra-tert-butyl-25,26,27,28-tetramethoxy-2,20-dioxo-8,
14-bis-trifluoroethoxycalix[4]arene (10b): yield 28 mg (55%); mp
5,11,17,23-Tetra-tert-butyl-25,26,27,28-tetramethoxy-8,20-dioxo-2,
14-bis(m-xylyl)calix[4]arene (17): yield 44.3 mg (42%); mp 330ꢀ
1
1
255ꢀ260 °C; H NMR (400 MHz, CDCl3) δ 7.93 (d, J = 2.5 Hz,
335 °C; H NMR (500 MHz, CDCl3) δ 7.49 (d, J = 2.5 Hz, 4H),
2H), 7.72 (d, J = 2.5 Hz, 2H), 7.53 (s, 2H), 6.89 (s, 2H), 6.20 (s, 2H),
4.13ꢀ3.91 (m, 4H), 3.91 (s, 3H), 3.37 (s, 6H), 2.01 (s, 3H), 1.37
(s, 18H), 1.35 (s, 9H), 0.94 (s, 9H); 13C NMR (126 MHz, CDCl3)
δ 195.9, 155.5, 154.4, 153.1, 147.5, 146.6, 144.9, 135.6, 135.4, 132.6,
131.2, 127.7, 126.2, 125.9, 125.7, 124.1 (q, J = 279.2 Hz), 73.6, 66.3 (q,
J = 34.2 Hz), 63.6, 62.0, 60.0, 34.7, 34.4, 34.1, 31.4, 31.3, 30.9; 19F NMR
(471 MHz, CDCl3) δ ꢀ73.4 (t, J = 8.6 Hz); HRMS (ESI) m/z 929.4422
[(M þ H)þ calcd for C52H63F6O8, 929.4427].
7.15 (d, J = 2.5 Hz, 4H), 7.09 (d, J = 8.4 Hz, 2H), 6.94 (d, J = 5.4 Hz, 4H),
5.99 (s, 2H), 3.14 (s, 12H), 2.29 (s, 6H), 1.96 (s, 6H), 1.24 (s, 36H); 13C
NMR (125 MHz, CDCl3) δ 199.7, 154.8, 144.9, 137.4, 136.4, 135.72,
135.65, 134.2, 131.7, 130.2, 128.5, 126.2, 124.2, 62.2, 38.5, 34.3, 31.3,
20.8, 20.7; HRMS (ESI) m/z 963.5534 [(M þ Na)þ calcd for
C64H76O6Na, 963.5540].
5,11,17,23-Tetra-tert-butyl-2,14-dimesityl-25,26,27,28-tetrametho-
xy-8,20-dioxocalix[4]arene (18): yield 77 mg (71%); mp 305ꢀ310 °C;
1H NMR (400 MHz, CDCl3) δ 7.52 (d, J = 2.5 Hz, 2H), 7.49 (d, J = 2.6
Hz, 2H), 7.06 (m, 4H), 6.80 (s, 2H), 6.79 (s, 2H), 5.98 (s, 2H), 3.22
(s, 6H), 2.86 (s, 6H), 2.26 (s, 6H), 2.14 (s, 6H), 1.79 (s, 6H), 1.19 (s,
18H), 1.12 (s, 18H); 13C NMR (126 MHz, CDCl3) δ 198.9, 156.9,
156.4, 145.4, 144.4, 139.4, 136.7, 136.5, 136.4, 135.6, 135.0, 134.5,
8,14-Diacetoxy-5,11,17,23-tetra-tert-butyl-25,26,27,28-tetrametho-
xy-2,20-dioxocalix[4]arene (12b): yield 32 mg (67%); mp 290ꢀ
1
295 °C; H NMR (500 MHz, CDCl3) δ 7.77 (dd, J = 2.5, 0.5 Hz,
2H), 7.72 (d, J = 2.5 Hz, 2H), 7.49 (s, 2H), 7.46 (s, 2H), 6.89 (s, 2H),
3.91 (s, 3H), 3.48 (s, 6H), 2.25 (s, 6H), 1.99 (s, 3H), 1.37 (s, 18H), 1.35
3673
dx.doi.org/10.1021/jo200580m |J. Org. Chem. 2011, 76, 3664–3675