Synthesis of p-tert-Butylthiacalix[4]arene-crowns
removed and the residue extracted with CH2Cl2/CHCl3. The
solution was washed twice with 10% HCl and water and dried
on MgSO4. Solvents were removed under reduced pressure and
the residue was triturated with MeOH to remove unreacted
glycol di-p-toluenesulfonates, yielding after drying white solids.
[M + H]+. Anal. Calcd for C54H74O7S4: C, 67.32; H, 7.74.
Found: C, 67.47; H, 7.99.
5,11,17,23-Tet r a -ter t-b u t yl-25,27-d ip r op oxy-2,8,14,20-
tetr ath iacalix[4]ar en e-m on ocr own -6, 1,3-Alter n ate (11c).10
A suspension of 7 (0.36 g, 0.4 mmol) in acetonitrile (50 mL)
was reacted with 2c (0.22 g, 0.4 mmol). After trituration with
MeOH, column chromatography (SiO2, 2% acetone in CH2Cl2)
was performed to give 11c (0.25 g, 57%): mp > 250 °C (lit.10
mp 280-282 °C). The spectral data are identical to those
reported.10
25,27-Bis(ben zyloxy)-5,11,17,23-tetr a -ter t-bu tyl-2,8,14,-
20-tetr athiacalix[4]ar en e-m onocr own -4,1,3-Alter n ate (12a).
A suspension of 8 (0.40 g, 0.4 mmol) in acetonitrile (50 mL)
was reacted with 2a (0.18 g, 0.4 mmol). After trituration with
MeOH, column chromatography (SiO2, CH2Cl2/hexane 1/1) was
performed to give 12a (0.15 g, 33%): mp > 250 °C; 1H NMR δ
7.39 (s, 4H), 7.07-7.18 (m, 6H), 7.11 (s, 4H) 6.85-6.88 (m,
4H), 5.09 (s, 4H), 4.02-4.05 (m, 4H), 3.52-3.60 (m, 4H), 2.58
(s, 4H), 1.36 (s, 18H), 0.85 (s, 18H); 13C NMR δ 157.7, 155.5,
146.2, 146.2, 137.3, 129.3, 128.8, 127.9, 127.8, 127.7, 127.3,
126.9, 71.2, 70.0, 69.9, 68.6, 34.4, 33.8, 31.4, 30.7; MALDI-
TOF m/z 1015.9 [M + H]+, 1037.9 [M + Na]+, calcd 1015.4 [M
+ H]+. Anal. Calcd for C60H70O6S4: C, 70.97; H, 6.95. Found:
C, 70.82; H, 6.74.
5,11,17,23-Tet r a -ter t-b u t yl-25,27-d im et h oxy-2,8,14,20-
tetr a th ia ca lix[4]a r en e-m on ocr ow n -4, 1,3-Alter n a te (10a ).
A suspension of 6 (1.50 g, 2.0 mmol) in acetonitrile (100 mL)
was reacted with 2a (0.92 g, 2.0 mmol). After trituration with
MeOH, the residue was triturated with CH2Cl2 to give 10a
1
(1.50 g, 87%): mp > 250 °C; H NMR δ 7.49 (s, 4H), 7.30 (s,
4H), 4.10 (t, 4H, J ) 4.0 Hz), 3.54 (t, 4H, J ) 4.0 Hz), 3.32 (s,
6H), 2.51 (s, 4H), 1.33 (s, 18H), 1.30 (s, 18H); 13C NMR δ 157.6,
156.3, 146.3, 145.9, 130.0, 129.3, 127.2, 126.1, 71.0, 70.3, 69.0,
55.7, 34.4, 34.2, 31.4, 31.2; MALDI-TOF m/z 863.9 [M + H]+,
885.8 [M + Na]+, 901.8 [M + K]+, calcd 863.3 [M + H]+. Anal.
Calcd for C48H62O6S4: C, 66.78; H, 7.24. Found: C, 66.94; H,
6.95.
5,11,17,23-Tet r a -ter t-b u t yl-25,27-d im et h oxy-2,8,14,20-
tetr ath iacalix[4]ar en e-m on ocr own -5, 1,3-Alter n ate (10b).10
A suspension of 6 (1.50 g, 2.0 mmol) in acetonitrile (100 mL)
was reacted with 2b (1.05 g, 2.0 mmol) to give 10b (1.68 g,
93%): mp > 250 °C (lit.10 mp 266-268 °C). The spectral data
are identical to those reported.10
5,11,17,23-Tet r a -ter t-b u t yl-25,27-d im et h oxy-2,8,14,20-
tetr ath iacalix[4]ar en e-m on ocr own -6, 1,3-Alter n ate (10c).10
A suspension of 6 (1.75 g, 2.3 mmol) in acetonitrile (100 mL)
was reacted with 2c (1.26 g, 2.3 mmol). After trituration with
MeOH, column chromatography (SiO2, 2% acetone in CH2Cl2)
was performed to give 10c (1.23 g, 59%): mp > 250 °C (lit.10
mp 272-274 °C). The spectral data are identical to those
reported.10
25,27-Bis(ben zyloxy)-5,11,17,23-tetr a -ter t-bu tyl-2,8,14,-
20-tetr ath iacalix[4]ar en e-m on ocr own -5,1,3-Alter n ate (12b)
a n d Con e (18b). A suspension of 8 (0.50 g, 0.6 mmol) in
acetonitrile (50 mL) was reacted with 2b (0.30 g, 0.6 mmol).
After trituration with MeOH, column chromatography (SiO2,
CH2Cl2/hexane 1/1) was performed to give 12b (0.21 g, 33%);
eluent change to 5% acetone in CH2Cl2 gave 18b (0.12 g, 20%).
1
12b: mp > 250 °C; H NMR δ 7.41 (s, 4H), 7.09 (t, 2H, J )
7.4 Hz), 7.03 (s, 4H), 6.98 (t, 4H, J ) 7.5 Hz), 6.84 (d, 4H, J )
7.6 Hz), 5.03 (s, 4H), 3.94 (t, 4H, J ) 8.1 Hz,), 3.60-3.67 (m,
4H), 3.36-3.44 (m, 4H), 3.05 (t, 4H, J ) 8.2 Hz), 1.38 (s, 18H),
0.85 (s, 18H); 13C NMR δ 156.1, 155.9, 146.2, 146.1, 137.4,
128.5, 127.8, 127.5, 127.4, 127.2, 127.0, 126.8, 73.6, 71.4, 70.4,
70.1, 65.4, 34.4, 33.8, 31.5, 30.8; MALDI-TOF m/z 1059.5 [M
+ H]+, 1081.4 [M + Na]+, 1097.4 [M + K]+, calcd 1059.4 [M +
H]+. Anal. Calcd for C62H74O7S4: C, 70.29; H, 7.04. Found: C,
69.99; H, 7.26. 18b: mp 248-252 °C; 1H NMR δ 7.69 (s, 4H),
7.60 (d, 4H, J ) 6.2 Hz), 7.28-7.39 (m, 6H), 6.86 (s, 4H), 4.99
(s, 4H), 4.45-4.51 (m, 4H), 3.99-4.05 (m, 4H), 3.41-3.44 (m,
8H), 1.33 (s, 18H), 0.84 (s, 18H); 13C NMR δ 160.6, 157.1, 146.1,
137.1, 135.2, 132.6, 130.9, 129.6, 129.0, 128.3, 128.0, 79.0, 73.0,
71.1, 70.6, 69.3, 34.3, 33.9, 31.4, 30.9; MALDI-TOF m/z 1059.7
[M + H]+, 1081.6 [M + Na]+, 1097.6 [M + K]+, calcd 1059.4
[M + H]+. Anal. Calcd for C62H74O7S4: C, 70.29; H, 7.04.
Found: C, 70.06; H, 7.27.
5,11,17,23-Tet r a -ter t-b u t yl-25,27-d ip r op oxy-2,8,14,20-
tetr a th ia ca lix[4]a r en e-m on ocr ow n -4, 1,3-Alter n a te (11a ).
A suspension of 7 (0.50 g, 0.6 mmol) in acetonitrile (50 mL)
was reacted with 2a (0.28 g, 0.6 mmol). After trituration with
MeOH, column chromatography (SiO2, EtOAc/hexane 0.5/9.5)
was performed to give 11a (0.33 g, 58%): mp > 250 °C; 1H
NMR δ 7.37 (s, 4H), 7.31 (s, 4H), 4.00-4.03 (m, 4H), 3.70-
3.76 (m, 4H), 3.52 (t, 4H, J ) 4.0 Hz), 2.48 (s, 4H), 1.31 (s,
18H), 1.26 (s, 18H), 0.80-0.92 (m, 4H), 0.65 (t, 6H, J ) 7.3
Hz); 13C NMR δ 158.0, 156.0, 145.9, 145.7, 128.6, 127.8, 126.8,
71.1, 70.0, 69.5, 68.6, 34.4, 34.2, 31.4, 31.2, 30.2, 29.7, 21.3,
9.7; MALDI-TOF m/z 919.6 [M + H]+, 941.6 [M + Na]+, 957.5
[M + K]+, calcd 919.4 [M + H]+. Anal. Calcd for C52H70O6S4‚
0.3H2O: C, 67.52; H, 7.62. Found: C, 67.50; H, 7.46.
5,11,17,23-Tet r a -ter t-b u t yl-25,27-d ip r op oxy-2,8,14,20-
tetr ath iacalix[4]ar en e-m on ocr own -5, 1,3-Alter n ate (11b),10
P a r tia l Con e (15a ), a n d Con e (17b). A suspension of 7 (0.50
g, 0.6 mmol) in acetonitrile (50 mL) was reacted with 2b (0.30
g, 0.6 mmol). After trituration with MeOH, column chroma-
tography (SiO2, EtOAc/hexane 0.5/9.5) was performed to give
11b10 (0.35 g, 59%), 15a (9 mg, 2%), and 17b (50 mg, 8%).
11b: mp > 250 °C (lit.10 mp 262-264 °C). The spectral data
are identical to those reported.10 15a : mp > 250 °C; 1H NMR
δ 7.63 (d, 2H, J ) 2.2 Hz), 7.55 (s, 2H), 7.35 (s, 2H), 7.32 (d,
2H, J ) 2.2 Hz), 4.00-4.06 (m, 8H), 3.74-3.76 (m, 4H), 3.51-
3.59 (m, 6H), 3.09 (t, 2H, J ) 6.2 Hz), 1.85-1.97 (m, 2H), 1.42
(s, 9H), 1.28 (s, 18H), 1.06 (s, 9H), 1.03 (t, 3H, J ) 7.5 Hz),
0.38-0.49 (m, 2H), 0.02 (t, 3H, J ) 7.3 Hz); 13C NMR 158.1,
157.7, 146.4, 146.0, 145.9, 134.0, 131.1, 129.9, 129.4, 128.9,
128.0, 127.7, 79.2, 73.6, 71.2, 71.0, 70.6, 70.3, 34.3, 34.1, 31.4,
31.3, 31.0, 29.7, 23.1, 22.2, 10.6, 10.0; MALDI-TOF m/z 963.4
[M + H]+, 985.4 [M + Na]+, 1001.4 [M + K]+, calcd 963.4 [M
+ H]+. Anal. Calcd for C54H74O7S4: C, 67.32; H, 7.74. Found:
25,27-Bis(ben zyloxy)-5,11,17,23-tetr a -ter t-bu tyl-2,8,14,-
20-tetr ath iacalix[4]ar en e-m on ocr own -6,1,3-Alter n ate (12c)
a n d Con e (18c). A suspension of 8 (1.0 g, 1.1 mmol) in
acetonitrile (75 mL) was reacted with 2c (0.60 g, 1.1 mmol).
After trituration with MeOH, column chromatography (SiO2,
CH2Cl2/hexane 1/1) was performed to give 12c (0.29 g, 24%);
eluent change to 10% acetone in CH2Cl2 gave 18c (0.25 g, 20%).
12c: mp 227-230 °C; 1H NMR δ 7.43 (s, 4H), 7.12 (d, 2H, J )
7.3 Hz), 7.07 (s, 4H), 7.03 (t, 4H, J ) 7.3 Hz), 6.88 (d, 4H, J )
7.0 Hz), 5.06 (s, 4H), 3.96 (t, 4H, J ) 7.3 Hz), 3.59 (s, 4H),
3.52 (s, 8H), 3.06 (t, 4H, J ) 7.5 Hz), 1.38 (s, 18H), 0.87 (s,
18H); 13C NMR δ 156.4, 156.1, 146.4, 146.1, 137.4, 128.7, 127.8,
127.6, 127.2, 126.8, 71.5, 71.4, 70.8, 70.2, 69.5, 66.8, 34.4, 33.8,
31.4, 30.7; MALDI-TOF m/z 1103.7 [M + H]+, 1125.6 [M +
Na]+, 1141.6 [M + K]+, calcd 1103.5 [M + H]+. Anal. Calcd
for C64H78O8S4: C, 69.66; H, 7.12. Found: C, 69.56; H, 7.10.
1
1
C, 67.24; H, 7.69. 17b: mp > 250 °C; H NMR δ 7.70 (s, 4H),
18c: mp 229-234 °C; H NMR δ 7.67 (s, 4H), 7.58-7.61 (m,
6.84 (s, 4H), 4.55-4.61 (m, 4H), 4.25-4.31 (m, 4H), 3.90 (t,
4H, J ) 7.0 Hz), 3.82 (s, 8H), 1.89-2.01 (m, 4H), 1.34 (s, 18H),
1.10 (t, 6H, J ) 7.5 Hz), 0.82 (s, 18H); 13C NMR δ 160.8, 157.9,
146.1, 145.8, 135.3, 132.5, 131.0, 128.7, 79.3, 72.9, 71.5, 71.0,
69.6, 34.4, 33.8, 31.5, 31.3, 30.9, 23.4, 10.8; MALDI-TOF m/z
963.6 [M + H]+, 985.6 [M + Na]+, 1001.6 [M + K]+, calcd 963.4
4H), 7.31-7.41 (m, 6H), 6.87 (s, 4H), 5.01 (s, 4H), 4.43-4.48
(m, 4H), 3.95-4.00 (m, 4H), 3.56 (s, 8H), 3.52-3.55 (m, 4H),
3.37-3.41 (m, 4H), 1.32 (s, 18H), 0.84 (s, 18H); 13C NMR δ
160.5, 157.2, 146.2, 137.1, 135.2, 132.7, 131.0, 129.5, 129.1,
128.3, 128.1, 79.0, 72.8, 70.9, 70.5, 69.6, 34.4, 33.9, 31.4, 30.9;
MALDI-TOF m/z 1103.5 [M + H]+, 1125.5 [M + Na]+, 1141.4
J . Org. Chem, Vol. 69, No. 11, 2004 3935