−1
1
=
(KBr, cm ): m(C O) 1666s. H NMR (300 MHz, CDCl3): d 9.04
(Rf = 0.5, SiO2, AcOEt–CH2Cl2, 2 : 98, v/v). Yield: 2.920 g, 90%;
◦
3
−1
1
=
(s, 2H, OH), 7.75, (s, 4H, m-ArH), 6.97 (d, 4H, m-ArH, J =
mp >250 C. IR (KBr, cm ): m(C O) 1671s. H NMR (300 MHz,
CDCl3): d 9.13 (s, 1H, OH), 8.27 (s, 1H, OH), 7.76 (s, 2H, m-ArH
of acylated ring), 7.08 (d, 2H, m-ArH, 3J = 7.4 Hz), 6.96 (d, 4H,
3
7.6 Hz), 6.79 (t, 2H, p-ArH, J = 7.6 Hz), 4.31 and 3.48 (AB
2
spin system, 8H, ArCH2Ar, J = 12.8 Hz), 4.01 (t, 4H, OCH2,
3J = 6.2 Hz), 2.55 (s, 6H, C(O)CH3), 2.08 (m, 4H, OCH2CH2),
m-ArH, J = 7.5 Hz), 6.78 (t, 2H, p-ArH, J = 7.6 Hz), 6.67 (t,
3
3
1.33 (t, 6H, CH2CH3, J = 7.4 Hz). 13C{ H} NMR (75 MHz,
CDCl3): d 196.90 (s, C(O)), 158.39, 151.75, 132.69, 129.58, 129.30,
128.89, 127.95 and 125.60 (8s, aryl C), 78.54 (s, OCH2), 31.42 (s,
ArCH2Ar), 26.28 (s, C(O)CH3), 23.51 (s, OCH2CH2), 10.92 (s,
CH2CH3). Found: C, 77.05; H, 6.91. Calc. for C38H40O6 (Mr =
592.73) C, 77.00; H, 6.80%.
1H, p-ArH, J = 7.4 Hz), 4.34 and 3.48 (AB spin system, 4H,
3
1
3
2
ArCH2Ar, J = 13.0 Hz), 4.34 and 3.41 (AB spin system, 4H,
ArCH2Ar, 2J = 13.0 Hz), 4.01 (t, 4H, OCH2, 3J = 6.2 Hz), 2.56 (s,
3H, C(O)CH3), 2.08 (m, 4H, OCH2CH2), 1.34 (t, 6H, CH2CH3,
3J = 7.4 Hz). 13C{ H} NMR (75 MHz, CDCl3): d 196.94 (s, C(O)),
1
158.54–119.08 (aryl and quat.-C), 78.45 (s, OCH2), 31.48 and 31.44
(2s, ArCH2Ar), 26.29 (s, C(O)CH3), 23.54 (s, OCH2CH2), 10.96
(s, CH2CH3). Found: C, 78.16; H, 6.84. Calc. for C36H38O5 (Mr =
550.69) C, 78.52; H, 6.96%.
5,17-Diacetyl-25,26,27,28-tetrapropoxycalix[4]arene
(1,3-
alternate (3a) and partial cone (3b)). K2CO3 (0.467 g, 3.38 mmol)
was added to a solution of 1 (1.000 g, 1.69 mmol) in refluxing
acetonitrile (100 mL). After 1 h, n-PrBr (0.624 g, 5.07 mmol)
was added and the suspension was maintained under reflux. The
reaction was monitored by TLC (Rf = 0.7 (3b), Rf = 0.4 (3a),
SiO2, AcOEt–CH2Cl2, 5 : 95, v/v) and heating was stopped after
7 d. After filtration the solution was evaporated to dryness and
the two isomers were separated by column chromatography on
silica gel using AcOEt–CH2Cl2 (5 : 95, v/v) ◦as eluent.
5-Acetyl-25,26,27,28-tetrapropoxycalix[4]arene (1,3-alternate)
(6). A suspension of K2CO3 (0.467 g, 3.38 mmol) and 5-acetyl-
25,27-dipropoxy-26,28-dihydroxycalix[4]arene (cone) (5) (1.000 g,
1.69 mmol) was stirred in refluxing acetonitrile (100 mL) for 1 h.
Then n-PrBr (0.624 g, 5.07 mmol) was added and the suspension
was further stirred at 60 ◦C for 1 week. Product formation was
monitored by TLC (Rf = 0.6, SiO2, AcOEt–CH2Cl2, 2 : 98, v/v).
After filtration, the solution was evaporated to dryness. The
product was recrystallised from CH2Cl2–MeOH. Yield: 0.805 g,
(3a) Yield: 0.721 g, 63%; mp 223–226 C; IR (KBr, cm−1):
1
=
m(C O) 1676s. H NMR (300 MHz, CDCl3): d 7.64 (s, 4H, m-ArH
of acylated Ar), 6.99 (d, 4H, m-ArH, 3J = 7.5 Hz), 6.65 (t, 2H, p-
ArH, 3J = 7.5 Hz), 3.71–3.65 (8H, OCH2), 3.61 and 3.54 (AB spin
◦
−1
1
=
75%; mp 156–158 C; IR (KBr, cm ): m(C O) 1680s. H NMR
(300 MHz, CDCl3): d 7.70 (s, 2H, m-ArH of acylated Ar), 7.03–
6.97 (6H, m-ArH,), 6.65 (t, 2H, p-ArH, 3J = 7.5 Hz), 6.54 (pseudo-
t, 1H, p-ArH, 3J = 7.5 Hz), 3.69–3.56 (16H, OCH2 and ArCH2Ar),
2.58 (s, 3H, C(O)CH3), 1.87–1.74 (8H, CH2CH3), 1.07–1.02 (12H,
2
system, 8H, ArCH2Ar, J = 13.4 Hz), 2.47 (s, 6H, C(O)CH3),
1.95–1.79 (8H, CH2CH3), 1.09–1.01 (12H, CH2CH3). 13C{ H}
1
NMR (75 MHz, CDCl3): d 197.69 (s, C(O)), 160.85–121.77 (aryl
and quat.-C), 74.80 (s, OCH2), 35.37 (s, ArCH2Ar), 26.40 (s,
C(O)CH3), 23.92 (s, CH2CH3), 10.64 (s, CH2CH3). Found: C,
77.88; H, 8.02. Calc. for C44H52O6 (Mr = 676.89) C, 78.07; H,
7.74%.
CH2CH3). 13C{ H} NMR (75 MHz, CDCl3): d 197.78 (s, C(O)),
1
160.76–121.24 (aryl and quat.-C), 74.79, 74.59 and 74.39 (3s,
OCH2), 35.41 and 35.38 (2s, ArCH2Ar), 26.52 (s, C(O)CH3),
23.88 and 23.85 (2s, CH2CH3), 10.69 (s, CH2CH3). Found: C,
79.54; H, 7.93. Calc. for C42H50O5 (Mr = 634.86) C, 79.46; H,
7.94%.
◦
(3b) Yield: 0.314 g, 26%; mp 224–226 C; IR (KBr, cm−1):
m(C O) 1677s. H NMR (300 MHz, CDCl3): d 7.93 and 7.74
1
=
3
(2s, 2H each, m-ArH of acylated Ar), 6.94 (d, 2H, m-ArH, J =
7.5 Hz), 6.45 (two overlapping d, 2H, p-ArH, 3J = Jꢀ = 7.5 Hz),
3
6.25 (d, 2H, m-ArH, 3J = 7.5 Hz), 4.08 and 3.14 (AB spin system,
2-Haloacetylated calixarenes
2
4H, ArCH2Ar, J = 13.4 Hz), 3.85–3.80 (m, 4H, OCH2), 3.74
5,17-Bis(2-bromoacetyl)-25,26,27,28-tetrapropoxycalix[4]arene-
(1,3-alternate) (4). To a solution of 5,17-diacetyl-25,26,27,28-
tetrapropoxycalix[4]arene (3a) (4.000 g, 5.91 mmol) in CHCl3
(30 mL) at 40 ◦C was slowly added a solution of Br2 (1.940 g,
12.11 mmol) in CHCl3 (10 mL). After being stirred for 5 min the
solution was washed successively with 10% Na2SO3 (10 mL) and
10% NaHCO3 (20 mL), then dried with MgSO4, and concentrated.
Addition of MeOH afforded a white microcrystalline powder.
2
and 3.67 (AB spin system, 4H, ArCH2Ar, J = 12.7 Hz), 3.55
(m, 2H, OCH2), 3.30 (m, 2H, OCH2), 2.63 and 2.62 (2s, 3H
each, C(O)CH3), 2.00–1.89 (6H, CH2CH3), 1.35–1.27 (m, 2H,
CH2CH3), 1.13–1.05 (9H, CH2CH3), 0.62 (t, 3H, CH2CH3 3J =
7.5 Hz). 13C{ H} NMR (75 MHz, CDCl3): d 197.69 and 197.27 (2s,
1
C(O)), 162.19–121.80 (aryl and quat.-C), 76.36, 75.70 and 75.01
(3s, OCH2), 35.82 and 30.52 (2s, ArCH2Ar), 26.62 and 26.48 (2s,
CH3C(O)), 24.16, 23.87 and 22.12 (3s, CH2CH3), 10.88, 10.63 and
9.31 (3s, CH2CH3). Found: C, 78.03; H, 7.80. Calc. for C44H52O6
(Mr = 676.89) C, 78.07; H, 7.74%.
◦
−1
=
Yield: 4.730 g, 96%; mp 123–126 C; IR (KBr, cm ): m(C O)
1668s. 1H NMR (300 MHz, CDCl3): d 7.67 (s, 4H, m-ArH), 6.98
3
3
(d, 4H, m-ArH, J = 7.5 Hz), 6.63 (t, 2H, p-ArH, J = 7.5 Hz),
3
5-Acetyl-25,27-dipropoxy-26,28-dihydroxycalix[4]arene (cone)
(5). To a solution of 1 (3.000 g, 5.90 mmol) in nitrobenzene
(250 mL) was added acetyl chloride (0.467 g, 5.95 mmol). A
solution of AlCl3 (0.790 g, 5.95 mmol) in nitrobenzene (50 mL)
was then added dropwise over 2 h. The resulting brownish solution
was stirred for a further 10 min and then quenched with 2 M
HCl (200 mL). The organic phase was separated and washed
with water (2 × 100 mL). Removal of the solvent in vacuo under
heating at 120 ◦C gave a residue which was purified by column
chromatography using AcOEt–CH2Cl2 (2 : 98, v/v) as eluant
4.36 (s, 4H, C(O)CH2Br), 3.74 (t, 4H, OCH2, J = 7.0 Hz), 3.73
(t, 4H, OCH2, 3J = 7.3 Hz), 3.57 and 3.52 (AB spin system, 8H,
ArCH2Ar, 2J = 13.1 Hz), 2.09–1.97 (m, 4H, CH2CH3), 1.97–1.83
3
(m, 4H, CH2CH3), 1.16 (t, 6H, CH2CH3, J = 7.4 Hz), 1.10 (t,
6H, CH2CH3, J = 7.4 Hz). 13C{ H} NMR (75 MHz, CDCl3):
d 191.04 (s, C(O)), 161.49–121.96 (aryl and quat.-C), 75.40 (s,
OCH2), 34.78 (s, ArCH2Ar), 31.44 (s, C(O)CH2Br), 24.15 and
24.08 (2s, CH2CH3), 10.79 and 10.74 (2s, CH2CH3). Found: C,
63.19; H, 5.89. Calc. for C44H50Br2O6 (Mr = 834.69): C, 63.32; H,
6.04%.
3
1
3654 | Dalton Trans., 2006, 3647–3659
This journal is
The Royal Society of Chemistry 2006
©