J. Sk aꢀ cel et al. / Tetrahedron xxx (2015) 1e7
5
(
1
1
cmꢁ1): 3238.7, 2964.9, 2933.8, 2876.4, 1649.5, 1590.2, 1521.9,
480.9, 1458.7, 1430.8, 1348.4, 1315.9, 1286.0, 1214.3, 1161.4, 1123.8,
J¼16.8, 10.6 Hz, COeCHeCH
J¼17.2, 2.0 Hz, COeCHeCH
COeCHeCH
), 4.30 (d, 4H, J¼13.3 Hz, AreCH
J¼6.5 Hz, ArOeCH eCH eCH ), 3.45 (d, 4H, J¼13.3 Hz,
AreCH eAr), 2.07 (m, 4H, ArOeCH eCH eCH ), 1.29 (t, 6H,
J¼7.4 Hz, ArOeCH eCH eCH ),1.04 (s,18H, AreCe(CH
(100 MHz, CDCl , 293 K) (ppm): 189.62, 158.46, 149.77, 147.89,
32.60, 132.06, 129.95, 128.67, 128.56, 128.41, 125.93, 77.20, 34.17,
2
), 6.94 (s, 4H, AreH), 6.35 (dd, 2H,
2
), 5.84 (dd, 2H, J¼10.6, 2.0 Hz,
077.1, 1059.6, 957.9, 909.9, 864.4, 842.8, 768.4, 730.9. HRMS-ESI
2
2
eAr), 3.99 (t, 4H,
þ
(
C
48
H
42
O
10
N
2
) m/z (% int.) calcd: 829.2732 [MþNa] , found:
2
2
3
þ
8
29.2730 [MþNa] (73%).
2
2
2
3
1
3
2
2
3
3 3
) ). C NMR
4
.3. General procedure for FriedeleCrafts ipso-acylation of 8
3
d
1
ꢁ1
Calixarene 9 (1 equiv) was dissolved in dry 1,2-dichloroethane
31.69, 31.18, 23.43, 10.86. IR (KBr)
n (cm ): 3251.3, 3048.2, 2962.0,
ꢁ
1
(
c¼6e9 mmol l ), then AlCl
3
(4 equiv) was added and the mix-
2874.9, 2355.8, 1732.7, 1662.9, 1589.8, 1480.8, 1428.6, 1399.9,
1362.8, 1316.6, 1293.6, 1272.6, 1197.2, 1172.3, 1105.2, 1060.2, 962.8,
ture was vigorously stirred for 5 min. During this time the reaction
mixture turned yellow and the corresponding acyl chloride
942.1, 909.8, 878.5, 792.1, 733.1, 698.8, 635.0, 586.5. HRMS-ESI
þ
(
2 equiv) was quickly added (directly by Hamilton syringe for liq-
(C48
H
56
O
6
) m/z (% int.) calcd: 751.3969 [MþNa] , found: 751.3978
þ
uids or as solution in 1,2-dichloroethane for solids). The reaction
was monitored by TLC and after completion it was quenched by
addition of 1 M HCl (aq). The layers were separated and water layer
[MþNa] (100%).
4.4. General procedure for O-acylation of 9
was extracted with CH
washed with NaHCO
(1ꢂ), water (2ꢂ) and dried over MgSO
MgSO was filtered off and the solvent was evaporated under re-
duced pressure. The crude product was purified by precipitation
from CH Cl /MeOH or by preparative TLC.
2
Cl
2
(3ꢂ). The combined organic layers were
3
4
. The
Calixarene
9
(1 equiv) was dissolved in dry DMF
ꢁ
1
ꢀ
4
(c¼25e27 mmol l ) and the mixture was cooled down to ꢁ5 C in
an ice/salt bath. Then, NaH (2.1 equiv) was added and the mixture
was stirred for 30 min. Upon reaction completion (as determined
2
2
by cessation of H
2
release), the corresponding acyl chloride
4
.3.1. Synthesis of 5,17-diacetyl-11,23-di-tert-butyl-25,27-
(4 equiv) was added slowly with a syringe. The reaction was
dipropoxycalix[4]arene (10a). The general procedure was applied
to compound 9 (200 mg, 0.273 mmol) and acetyl chloride. Pure
product was obtained after preparative TLC on silica gel as a white
monitored with TLC and after completion (w2 d) it was quenched
by addition of 1 M HCl (aq), and diluted with CH
were separated and water layer was extracted with CH
Organic layers were collected and washed with NaHCO
(1ꢂ), water
(2ꢂ) and dried over MgSO . The MgSO was filtered off and the
solvent was evaporated under reduced pressure. The crude product
2
Cl
2
. The layers
2
Cl
2
(3ꢂ).
ꢀ
1
solid (63 mg, 33%), mp: 266e272 C. H NMR (400 MHz, CDCl
93 K) (ppm): 9.03 (s, 2H, AreOH), 7.73 (s, 4H, AreH), 6.95 (s, 4H,
AreH), 4.30 (d, 4H, J¼13.3 Hz, AreCH eAr), 3.99 (t, 4H, J¼6.5 Hz,
ArOeCH eCH eCH eAr), 2.53 (s,
), 3.45 (d, 4H, J¼12.9 Hz, AreCH
H, ArCOeCH ), 2.06 (m, 4H, ArOeCH eCH eCH ), 1.29 (t, 6H,
J¼7.4 Hz, ArOeCH eCH eCH ),1.06 (s,18H, AreCe(CH
100 MHz, CDCl , 293 K) (ppm): 196.86, 158.19, 149.73, 147.78,
32.07, 129.35, 128.80, 128.22, 125.85, 78.34, 34.11, 31.58, 31.13,
3
,
3
2
d
4
4
2
2
2
3
2
2 2
was purified by precipitation from CH Cl /MeOH or by crystalliza-
tion from acetone/MeOH.
6
3
2
2
3
1
3
2
2
3
3 3
) ). C NMR
(
3
d
4.4.1. Synthesis of 5,11,17,23-tetra-tert-butyl-26,28-diacetyloxy-
25,27-dipropoxycalix[4]arene (11a). The general procedure was
applied to compound 9 (200 mg, 0.273 mmol) and acetyl chloride.
Pure product was obtained after crystallization in the form of white
1
ꢁ
1
2
6.23, 23.38, 10.81. IR (KBr)
874.7, 1670.7, 1593.9, 1481.0, 1481.0, 1428.8, 1387.0, 1357.6, 1313.5,
296.8, 1283.1, 1190.2, 1109.0, 1089.5, 1061.0, 997.2, 962.7, 942.1,
n (cm ): 3255.0, 2962.3, 2934.9,
2
1
ꢀ
1
crystals (172 mg, 77%), mp: 211e215 C. H NMR (400 MHz, CDCl
293 K) (ppm): 7.18 (s, 4H, AreH), 6.71 (s, 4H, AreH), 4.11 (d, 4H,
J¼12.9 Hz, AreCH
.26 (d, 4H, J¼12.9 Hz, AreCH
(m, 4H, ArOeCH eCH eCH ), 1.32 (s, 18H, AreC-(CH
J¼7.4 Hz, ArOeCH eCH eCH ), 0.91 (s, 18H, AreCe(CH
NMR (100 MHz, CDCl , 293 K)
3
,
9
10.9, 942.1, 910.9, 876.2, 732.6. HRMS-ESI (C46
H
56
O
6
) m/z (% int.)
d
þ
þ
calcd: 727.3969 [MþNa] , found: 727.3977 [MþNa] (100%).
2
eAr), 3.69 (t, 4H, J¼7.4 Hz, ArOeCH
2
eCH
2
eCH
3
),
3
2
eAr), 2.68 (s, 6H, ArCOeCH
3
), 1.91
4
.3.2. Synthesis of 5,17-dibenzoyl-11,23-di-tert-butyl-25,27-
2
2
3
3
)
3
), 1.02 (t, 6H,
1
3
dipropoxycalix[4]arene (10b). The general procedure was applied
to compound 9 (200 mg, 0.273 mmol) and benzoyl chloride. Pure
product was obtained by precipitation as a white solid (206 mg,
2
2
3
3 3
) ).
C
3
d
(ppm): 171.29, 151.46, 147.57,
144.80, 144.20, 134.44, 132.11, 125.25, 125.04, 77.98, 34.19, 33.68,
ꢀ
1
ꢁ1
9
9
7
1%), mp: 273e275 C. H NMR (400 MHz, CDCl
.29 (s, 2H, AreOH), 7.74 (d, 4H, J¼7.4 Hz, AreH), 7.65 (s, 4H, AreH),
.57 (t, 2H, J¼7.4 Hz, AreH), 7.46 (t, 4H, J¼7.8 Hz, AreH), 7.02 (s, 4H,
AreH), 4.32 (d, 4H, J¼12.9 Hz, AreCH eAr), 4.00 (t, 4H, J¼6.3 Hz,
ArOeCH eCH eCH eAr), 2.10 (m,
), 3.45 (d, 4H, J¼12.9 Hz, AreCH
H, ArOeCH eCH eCH ), 1.32 (t, 6H,
ArOeCH eCH eCH ), 1.16 (s, 18H, AreCe(CH
100 MHz, CDCl , 293 K)
38.88, 132.35, 131.61, 129.75, 128.52, 128.03, 126.01, 78.50, 34.27,
3
, 293 K)
d
(ppm):
31.56, 31.06, 30.99, 30.42, 23.50, 22.72, 10.42. IR (KBr)
n
(cm ):
2961.6, 2872.7, 2253.0, 1752.8, 1597.8, 1479.5, 1415.0, 1388.8, 1364.9,
1299.1, 1277.0, 1237.5, 1222.6, 1181.8, 1121.8, 1065.1, 1042.6, 1007.1,
2
964.9, 911.7, 871.0, 821.3, 799.5, 733.2, 648.3, 635.8, 572.8, 551.1.
þ
2
2
3
2
HRMS-ESI (C54
839.5228 [MþNa] (100%).
H
72
O
6
) m/z (% int.) calcd: 839.5221 [MþNa] , found:
þ
4
2
2
3
J¼7.2
Hz,
NMR
1
3
2
2
3
3
)
3
).
C
(
1
3
2
1
1
3
d
(ppm): 195.77, 158.28, 149.88, 147.84,
4.4.2. Synthesis of 5,11,17,23-tetra-tert-butyl-26,28-dibenzoyloxy-
25,27-dipropoxycalix[4]arene (11b). The general procedure was
applied to compound 9 (200 mg, 0.273 mmol) and acetyl chloride.
Pure product was obtained after precipitation in the form of white
ꢁ
1
1.78, 31.28, 23.45, 10.93. IR (KBr)
n
(cm ): 3281.7, 3060.4, 2957.9,
932.4, 2876.0, 2360.5, 2339.5, 1958.3, 1725.7, 1649.1, 1598.4,
480.9, 1446.8, 1429.0, 1389.0, 1362.3, 1322.0, 1216.4, 1175.0, 1126.5,
101.8, 1061.4, 1007.9, 962.1, 942.1, 906.1, 877.9, 717.9, 693.3, 632.5,
ꢀ
1
crystals (215 mg, 84%), mp: 332e335 C. H NMR (400 MHz, CDCl
293 K)
(ppm): 8.61 (d, 4H, J¼7.4 Hz, AreH), 7.75 (t, 2H, J¼7.4 Hz,
AreH), 7.64 (t, 4H, J¼7.0 Hz, AreH), 7.16 (s, 4H, AreH), 6.64 (s, 4H,
AreH), 4.19 (d, 4H, J¼12.9 Hz, AreCH eAr), 4.12 (t, 4H, J¼8.2 Hz,
ArOeCH eCH eCH eAr), 1.62 (m,
), 3.24 (d, 4H, J¼13.3 Hz, AreCH
4H, ArOeCH eCH eCH ), 1.36 (s, 18H, AreCe(CH ), 0.91 (s, 18H,
AreCe(CH eCH
), 0.53 (t, 6H, J¼7.2 Hz, ArOeCH
(100 MHz, CDCl , 293 K) (ppm): 166.20, 152.97, 146.54, 145.36,
3
,
d
5
85.3, 564.7. HRMS-ESI (C56
H
60
O
6
) m/z (% int.) calcd: 851.4282
þ
þ
[MþNa] , found: 851.4287 [MþNa] (100%).
2
2
2
3
2
4
.3.3. Synthesis of 5,17-diacryloyl-11,23-di-tert-butyl-25,27-
2
2
3
3 3
)
13
dipropoxycalix[4]arene (10c). The general procedure was applied
to compound 9 (200 mg, 0.273 mmol) and acroyl chloride. Pure
product was obtained by preparative TLC on silica gel as a white
3
)
3
2
2 3
eCH ). C NMR
3
d
142.74, 135.29, 133.39, 131.51, 130.46, 130.28, 128.17, 125.76, 124.78,
ꢀ
1
ꢁ1
solid (52 mg, 26%), mp: 235e238 C. H NMR (400 MHz, CDCl
3
,
76.18, 34.07, 33.78, 31.70, 31.61, 31.07, 22.11, 9.20. IR (KBr)
n
(cm ):
2
93 K) (ppm): 9.07 (s, 2H, AreOH), 7.76 (s, 4H, AreH), 7.14 (dd, 2H,
d
2960.6, 2872.4,1958.4,1730.8,1600.8,1479.7,1385.3,1361.9,1302.5,