H-3), 3.87 and 3.45 (AB spin system, 8H, ArCH2Ar, 2J = 14 H
z), 2.58–0.69 (86H, 2 × cholesteryl), 1.35 (s, 18H, C(CH3)3),
5,11,17,23-Tetra-tert-butyl-25,27-
bis(cholesteryloxycarbonyloxy)-
0.97 (s, 18H, C(CH3)3). 13C{ H} NMR (50 MHz, CDCl3):
26,28-bis(dipheno xyphosphanyloxy)calix[4]arene (L3)
1
d 153.31–142.28 (aryl C), 139.38 (C-5 tentative assignment),
131.87–125.90 (aryl C), 123.16 (s, C-6), 79.22 (s, C-3), 56.79
(s, C-14), 56.25 (s, C-17), 50.09 (s, C-9), 42.41 (s, C-13), 39.83 (s,
C-12), 39.61 (s, C-1 tentative assignment), 38.03 (s, CH2), 36.99
(s, CH2), 36.68 (s, C-10), 36.29 (s, CH2), 35.88 (s, CH), 34.01 (s,
C(CH3)3), 33.2 (s, ArCH2Ar), 31.98 (s, C-7), 31.78 and 31.12 (2s,
C(CH3)3), 28.32 (s, C-16), 28.09 (s, CH), 27.71 (s, CH2), 24.38
(s, CH2), 23.93 (s, CH2), 22.91 (s, CH3), 22.66 (s, CH3), 21.16
(s, C-11), 19.36 (s, CH3), 18.82 (s, CH3), 11.96 (s, CH3). Found:
81.52, H 9.80%. Calc. for C100H144O8 (Mr = 1474.21): C 81.47,
H 9.84%.
To a solution of diisopropylamine (0.63 cm3, 4.80 mmol) in
THF (20 cm3) was added, at −78 ◦C, a 1.6 M solution of n-
BuLi/hexane (3.0 cm3, 4.80 mmol). After stirring for 0.5 h, the
solution was transferred via canula to a solution of 3 (3.538 g,
2.40 mmol) in THF (100 cm3). After stirring for 1 h, (PhO)2PCl
(1.213 g, 4.80 mmol, ca. 1.0 cm3) was added and the resulting
mixture stirred for an additional hour. The mixture was allowed
to reach room temperature (2 h). The solvent was removed in
vacuo and the residue was taken up with toluene (50 cm3). The
insoluble lithium salt was filtered off using Celite and washed
with toluene (2 × 10 cm3). The filtrate and washing solutions
were evaporated to dryness to afford L3 as a white powder.
5,11,17,23-Tetra-tert-butyl-25,27-dipropoxy-26,28-
Yield: 3.853 g, 2.02 mmol, 84%; mp 93–95 ◦C, IR (KBr, cm−1):
bis(diphenoxyphosphanyloxy)calix[4]arene (L1)
1
=
m(C O) = 1756 s, 1727 sh. H NMR (300 MHz, CDCl3): d 7.24–
The reaction was carried out at −78 ◦C. To a solution of 1
(1.990 g, 2.70 mmol) in THF (150 cm3) was added a 1.3 M
solution of n-BuLi/hexane (4.2 cm3, 5.40 mmol). After 0.5 h,
(PhO)2PCl (1.364 g, 5.40 mmol, ca. 1.1 cm3) was added. The
resulting mixture was stirred for 2 h and then warmed to
room temperature (30 min). After evaporation to dryness the
residue was taken up with toluene (50 cm3). The lithium salt was
removed by filtration through a bed of Celite and washed with
toluene (2 × 10 cm3). The filtered solution was evaporated to
dryness upon which the residue was then redissolved in CH2Cl2.
Addition of pentane and cooling at −78 ◦C afforded L1 as a white
7.11 and 7.01–6.89 (m, 24H, m-ArH and P(OPh)2), 6.60 (s, 4H,
m-ArH), 5.20 (d, 2H, H-6 of cholesteryl, 3J = 4.9 Hz), 4.58 and
2
3.24 (AB spin system, 4H, ArCH2Ar, J = 13.1 Hz), 4.60 and
2
3.24 (AB quartet, J = 13.2 Hz, 4H, ArCH2Ar), 4.23 (m, 2H,
H-3 of cholesteryl), 2.36–0.67 (86H, cholesteryl), 1.36 (s, 18H,
C(CH3)3), 0.90 (s, 18H, C(CH3)3). 13C{ H} NMR (75 MHz,
1
CDCl3): d 154.69–143.77 (aryl Cquat), 139.88 (s, C-5 or aryl C),
135.25–125.05 (aryl Cquat), 123.04 (C-6 tentative assignment),
122.36–120.83 (aryl C), 78.59 (s, C-3), 56.69 (s, C-14), 56.15 (s,
C-17), 49.92 (s, C-9), 42.33 (s, C-13), 39.75 (s, Cquat-12), 39.54 (s,
C-1, tentative assignment), 37.43 (s, CH2), 37.00 (s, CH2), 36.53
(s, C-10), 36.20 (s, CH2), 35.82 (s, CH), 34.21 (s, C(CH3)3), 33.84
(s, C(CH3)3), 32.30 (s, ArCH2Ar), 31.85 (s, ArCH2Ar), 31.69
(s, C(CH3)3), 31.11 (s, C(CH3)3), 28.25 (s, C-16), 28.04 (s, CH),
27.08 (s, CH2), 24.31 (s, CH2), 23.86 (s, CH2), 22.85 (s, CH3),
22.58 (s, CH3), 21.04 (s, C-11), 19.53 (s, CH3), 18.74 (s, CH3),
◦
1
powder. Yield: 1.521 g, 1.305 mmol, 48%; mp 210–211 C. H
NMR (300 MHz, CDCl3): d 7.27–7.22 and 7.08–6.97 (m, 24H,
m-ArH and P(OPh)2), 6.66 (s, 4H, m-ArH), 4.64 and 3.16 (AB
spin system, 8H, ArCH2Ar, 2J = 12.9 Hz), 3.92 (t, 4H, OCH ,
2
J = 8.2 Hz), 2.08 (m, 4H, CH2CH3), 1.25 (s, 18H, C(CH3)3), 0.96
1
1
(s, 18H, C(CH3)3), 0.78 (t, 6H, CH2CH3, 3J = 7.4 Hz). 13C{ H}
11.87 (s, CH3); 31P{ H} NMR (121 MHz, CDCl3): d 127.62
NMR (75 MHz, CDCl3): d 154.34–133.97 (Cquat), 129.52–120.10
(aryl C), 76.86 (s, OCH2), 33.98 (s, C(CH3)3), 33.77 (s, C(CH3)3),
32.31 (s, ArCH2Ar), 31.62 (s, C(CH3)3), 31.43 (s, C(CH3)3),
(s, P(OPh)2). Found: C 78.47 H 8.31%. Calc. for C124H162O12P2
(Mr = 1906.55): C 78.12, H 8.56%.
1
22.96 (s, CH2CH3), 9.94 (s, CH2CH3). 31P{ H} NMR (121 MHz,
5,11,17,23-Tetra-tert-butyl-25,27-
CDCl3): d 135.26 (s, P(OPh)2). Found: C 73.79, H 7.58%. Calc.
for C74H86O8P2·0.5 CH2Cl2 (Mr = 1165.45 + 42.47): C, 74.08;
H, 7.26%.
bis(cholesteryloxycarbonyloxy)-26,28-
bis(diphenylphosphanyloxy)calix[4]arene (L6)
To a solution of diisopropylamine (0.73 cm3, 5.60 mmol) in
THF (20 cm3) was added, at −78 ◦C, a 1.6 M solution of n-
BuLi/hexane (3.5 cm3, 5.60 mmol). After stirring for 30 minutes,
the solution was transferred via a canula to a solution of 3
(4.080 g, 2.77 mmol) in THF (100 cm3). After stirring for 1 h,
Ph2PCl (1.222 g, 5.54 mmol, ca. 1.0 cm3) was added and the
resulting mixture stirred for an additional hour. The mixture was
warmed to room temperature (2 h). The solvent was evaporated
and the residue was redissolved in toluene (50 cm3). The lithium
salt was filtered off using a bed of Celite and washed with toluene
(2 × 10 cm3). The filtrate and washing solutions were evaporated
5,11,17,23-Tetra-tert-butyl-25,27-bis(ethoxycarbonylmethoxy)-
26,28-bis(diphenoxy phosphanyloxy)calix[4]arene (L2)
To a solution of diisopropylamine (0.63 cm3, 4.80 mmol) in
THF (20 cm3) was added, at −78 ◦C, a 1.6 M solution of n-
BuLi/hexane (3.0 cm3, 4.80 mmol). After stirring for 0.5 h, the
solution was transferred via canula to a solution of 2 (1.935 g,
2.36 mmol) in THF (100 cm3). After stirring for 1 h, (PhO)2PCl
(1.192 g, 4.72 mmol, ca. 1.0 cm3) was added and the resulting
mixture stirred for a further hour at −78 ◦C. The mixture
was then allowed to reach room temperature. The solvent was
evaporated and the residue taken up with toluene (50 cm3). The
insoluble lithium salt was filtered off using Celite and washed
with toluene (2 × 10 cm3). The filtrate and washing solutions
were evaporated under vacuum to afford L2◦ as a white powder.
under vacuum to afford L6 as◦a white powder. Yield: 4.08 g,
−1
=
2.22 mmol, 80%; mp 138–140 C, IR (KBr, cm ): m(C O) =
1
1771 and 1742. H NMR (300 MHz, CDCl3): d 7.79–7.74 and
7.41–7.17 (m, 20H, PPh2), 7.01 (s, 4H, m-ArH), 6.44 (s, 4H, m-
3
ArH), 5.26 (d, 2H, H-6, J = 4.5 Hz), 4.55 (m, 2H, H-3), 3.95
Yield: 2.325 g, 1.85 mmol, 78%; mp 39–40 C, IR (KBr, cm−1):
and 2.81 (AB spin system, 4H, ArCH2Ar, J = 13.3 Hz), 3.92
2
1
m(C O) = 1761. H NMR (300 MHz, CDCl3): d 7.26–7.21 and
and 2.81 (AB spin system, 4H, ArCH2Ar, 2J = 13.3 Hz), 2.37–
=
7.07–6.99 (m, 24H, m-ArH and P(OPh)2), 6.63 (s, 4H, m-ArH),
0.70 (86H, 2 × cholesteryl), 1.29 (s, 18H, C(CH3)3, 0.84 (s, 18H,
2
1
4.95 and 3.24 (AB spin system, 8H, ArCH2Ar, J = 13.4 Hz),
C(CH3)3. 13C{ H} NMR (75 MHz, CDCl3): d 152.24–140.63
3
4.95 (s, 4H, OCH2CO2), 3.99 (q, 4H, CH2CH3, J = 7.1 Hz),
(quaternary aryl C), 140.25 (s, C-5 or aryl C), 134.90–125.05
(aryl C), 122.28 (s, C-6 tentative assignment), 78.07 (s, C-3),
56.83 (s, C-14), 56.23 (s, C-17), 50.07 (s, C-9), 42.39 (s, C-13),
39.85 (s, C-12), 39.56 (s, C-1 tentative assignment), 37.88 (s,
CH2), 37.18 (s, CH2), 36.61 (s, C-10), 36.24 (s, CH2), 35.85 (s,
CH), 34.17 (s, C(CH3)3), 33.68 (s, C(CH3)3), 32.04 (s, ArCH2Ar),
31.94 (s, ArCH2Ar), 31.62 (s, C(CH3)3), 31.17 (s, C(CH3)3), 30.98
(s, Cquat), 30.77 (s, Cquat), 28.30 (s, C-16), 28.06 (s, CH), 27.55
(s, CH2), 24.37 (s, CH2), 23.89 (s, CH2), 22.87 (s, CH3), 22.61
1.26 (s, 18H, C(CH3)3), 1.12 (t, 6H, CH2CH3, 3J = 7.1 Hz), 0.95
(s, 18H, C(CH3)3). 13C{ H} NMR (75 MHz, CDCl3): d 170.51
1
(s, CO2), 153.40–129.70 (Cquat), 129.52–120.43 (aryl C), 70.52
(s, OCH2CO2), 60.27 (s, CH2CH3), 34.03 (s, C(CH3)3), 33.79
(s, C(CH3)3), 33.02 (s, ArCH2Ar), 31.61 (s, C(CH3)3), 31.18
(s, C(CH3)3), 14.05 (s, CH2CH3). 31P{ H} NMR (121 MHz,
1
CDCl3): d 130.54 (s, P(OPh)2). Found: C 72.18, H 6.96%. Calc.
for C76H86O12P2 (Mr = 1253.44): C 72.82, H 6.92%.
1 3 0 6
D a l t o n T r a n s . , 2 0 0 5 , 1 3 0 1 – 1 3 0 9