4146 J. Am. Chem. Soc., Vol. 121, No. 17, 1999
Stewart and Gutsche
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arene-79,80,81,82,83,84,85,86,87,88,89,90,91-tridecol ([13]). An ana-
lytical sample of [13] was recrystallized three times from CHCl3-
MeOH: mp, shrinks at 248 °C then melts at 313-314 °C (if put in at
280 °C the sample immediately melts, refreezes, and then melts again
only by H NMR (CDCl3) δ 8.98 (br s, 1, ArOH), 6.99 (s, 2, ArH),
3.70 (br s, 2, ArCH2Ar), 1.19 (s, 9, C(CH3)3) and 13C NMR (CDCl3) δ
147.25, 143.97, and 127.63 (Ar), 125.60 (ArH), 33.93 (C(CH3)3), 32.00
(ArCH2Ar), 31.50 (C(CH3)3).
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at 313-314 °C); H NMR (CDCl3) δ 9.45 (s, 1, ArOH), 7.07 (s, 2,
5,11,17,23,29,35,41,47,53,59,65,71,77,83,89,95,101,107,113-Nona-
deca-tert-butylcalix[19]arene-115,116,117,118,119,120,121,122,123,-
124,125,126,127,128,129,130,131,132,133-nonadecol ([19]) was char-
acterized only by 1H NMR (CDCl3) δ 9.06 (br s, 1, ArOH), 6.99 (br s,
2, ArH), 3.70 (v br s, 2, ArCH2Ar), 1.19 (s, 9, C(CH3)3) and 13C NMR
(CDCl3) δ 147.23, 143.88, and 127.53 (Ar), 125.58 (ArH), 33.9
(C(CH3)3), 32.0 (ArCH2Ar), 31.4 (C(CH3)3).
ArH), 3.81 (br s, 2, ArCH2Ar), 1.23 (s, 9, C(CH3)3); 13C NMR (CDCl3)
δ 147.2, 144.1, and 127.5 (Ar), 125.7 (ArH), 33.9 (C(CH3)3), 32.2
(ArCH2Ar), 31.5 (C(CH3)3); MS (FAB) calcd 2107, found 2108. Anal.
Calcd for C143H182O13: C, 81.44; H, 8.70. Found: C, 81.49; H, 8.56.
5,11,17,23,29,35,41,47,53,59,65,71,77,83-Tetradeca-tert-butylcalix-
[14]arene-85,86,87,88,89,90,91,92,93,94,95,96,97,98-tetradecol ([14]).
An analytical sample of [14] was recrystallized three times from CH2-
Cl2-MeOH to give desolvated crystals: mp shrinks at 220 °C, then
melts at 317-320 °C (if the sample is put in at ca. 280 °C it immediately
5,11,17,23,29,35,41,47,53,59,65,71,77,83,89,95,101,107,113,119-
Eicosa-tert-butylcalix[20]arene-121,122,123,124,125,126,127,128,-
129,130,131,132,133,134,135,136,137,138,139,140-eicosol ([20]). An
analytical sample of [20] was recrystallized twice from CHCl3-
MeOH: mp, shrinks at 279 °C, becomes translucent at 288 °C, melts
to a glass at 290-292 °C, becomes a viscous liquid at 309-311 °C
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melts, then remelts at 317-320 °C); H NMR (CDCl3) δ 9.32 (s, 1,
ArOH), 7.03 (s, 2, ArH), 3.75 (s, 2, ArCH2Ar), 1.21 (s, 9, C(CH3)3);
13C NMR (CDCl3) δ 147.1, 144.0, and 127.6 (Ar), 125.7 (ArH), 33.9
(C(CH3)3), 32.2 (ArCH2Ar), 31.5 (C(CH3)3); MS (FAB) calcd 2271,
found 2270. Anal. Calcd for C154H196O14: C, 81.44; H, 8.70. Found:
C, 81.27; H, 8.48.
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and a clear liquid at 325 °C; H NMR (CDCl3) δ 8-10 (overlapping
br s, 1, ArOH), 5.8-7.4 (overlapping br s, 2, ArH), 2.2-4.6 (overlap-
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ping br s, 2, ArCH2Ar), 1.2-1.4 (overlapping br s, 9, C(CH3)3); H
5,11,17,23,29,35,41,47,53,59,65,71,77,83,89-Pentadeca-tert-butylcalix-
[15]arene-91,92,93,94,95,96,97,98,99,100,101,102,103, 104,105-pen-
tadecol ([15]). An analytical sample was recrystallized twice from
CH2Cl2-hexane: mp, shrinks at 222.5-227 °C, turns to a glass,
NMR (CDCl3:pyridine-d5 6:1) δ 7.68 (v br s, 1, ArOH), 7.05 (s, 2,
ArH), 3.88 (s, 2, ArCH2Ar), 1.18 (s, 9, C(CH3)3); 13C NMR (CDCl3)
δ 147, 144, and 127 (v br s, Ar), 125.4 (ArH), 33.9 (C(CH3)3), 30-32
(v br s, ArCH2Ar), 31.5 (C(CH3)3); 13C NMR (CDCl3:pyridine-d5 6:1)
δ 150.4, 143.2, 128.6, and 125.9 (Ar), 34.2 (C(CH3)3), 32.4 (ArCH2-
Ar), 31.7 (C(CH3)3); MS (FAB) calcd 3242.0, found 3242.8. Anal.
Calcd for C220H280O20: C, 81.44; H, 8.70. Found: C, 81.42; H, 8.82.
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becomes liquid by 295 °C; H NMR (CDCl3) δ 9.13 (s, 1, ArOH),
7.03 (s, 2, ArH), 3.74 (br s, 2, ArCH2Ar), 1.21 (s, 9, C(CH3)3); 13C
NMR (CDCl3) δ 147.1, 144.0, and 127.6 (Ar), 125.6 (ArH), 33.9
(C(CH3)3), 32.0 (ArCH2Ar), 31.5 (C(CH3)3); MS (FAB) calcd 2431,
found 2431 (stronger signal at 2413). Anal. Calcd for C165H210O15: C,
81.44; H, 8.70. Found: C, 81.18; H, 8.69.
5,11,17,23,29,35,41,47,53,59,65,71,77,83,89,95-Hexadeca-
tert-butylcalix[16]arene-97,98,99,100,101,102,103,104,105,106,107,-
108,109,110,111,112-hexadecol ([16]). An analytical sample of [16]
was recrystallized twice from EtOAc and once from CHCl3-MeOH:
mp, shrinks from 200 to 300 °C, then melts at 310-312 °C (if put in
at 300 °C melts quickly implying a phase change at 250-300 °C); 1H
NMR (CDCl3) δ 9.02 (s, 1, ArOH), 6.98 (s, 2, ArH), 3.69 (v br s, 2,
ArCH2Ar), 1.21 (s, 9, C(CH3)3); 13C NMR (CDCl3) δ 147.0, 143.9,
and 127.8 (Ar), 125.5 (ArH), 33.9 (C(CH3)3), 31.9 (ArCH2Ar), 31.4
(C(CH3)3); MS (FAB) calcd 2593.67, found 2593.7. Anal. Calcd for
Acknowledgment. We are indebted to the Robert A. Welch
Foundation and the National Science Foundation for generous
support of this work. For mass spectrographic determinations
we are indebted to Professor Clive A. Slaughter and Dr. Bikash
C. Pramanik, University of Texas Southwestern Medical Center
at Dallas, and to the Washington University Mass Spectrometry
Resource Center partially supported by NIH Grant No. RR00954.
Supporting Information Available: Plot of the average
molecular weights of the reaction mixtures as a function of
concentration in the acid-catalyzed condensation of p-tert-
butylphenol and s-trioxane; plots of concentration of products
as a function of time from the acid-catalyzed reaction of p-tert-
butylphenol and s-trioxane; plots of total energies, bond energies,
angle energies, Lennard-Jones energies, and electrostatic ener-
gies for energy-minimized structures of p-tert-butylcalix[n]-
arenes (n ) 4-20); and pictures of computer-generated energy-
minimized structures for p-tert-butylcalix[n]arenes (n ) 4-20)
(PDF). This material is available free of charge via the Internet
C176H224O16: C, 81.44; H, 8.70. Found: C, 81.05; H, 8.71.
5,11,17,23,29,35,41,47,53,59,65,71,77,83,89,95,101-Heptadeca-tert-
butylcalix[17]arene-103,104,105,106,107,108,109,110,111,112,113,-
114,115,116,117,118,119-heptadecol ([17]) was characterized only by
1H NMR (CDCl3) δ 9.02 (s, 1, ArOH), 7.02 (s, 2, ArH), 3.71 (br s, 2,
ArCH2Ar), 1.21 (s, 9, C(CH3)3) and 13C NMR (CDCl3) δ 147.25,
144.00, and 127.63 (Ar), 125.7 (ArH), 33.93 (C(CH3)3), 31.99 (ArCH2-
Ar), 31.50 (C(CH3)3).
5,11,17,23,29,35,41,47,53,59,65,71,77,83,89,95,101,107-Octadeca-
tert-butylcalix[18]arene-109,110,111,112,113,114,115,116,117,118,-
119,120,121,122,123,124,125,126-octadecol ([18]) was characterized
JA983964N