FULL PAPER
2 mmol) and stirred for 5 h at room temperature. The solvent was
evaporated under reduced pressure and the crude product purified
2 H, CHCH2), 4.59 and 4.24 (AB spin system, 2J = 7.7 Hz, 4 H,
OCH2O), 2.36–2.10 (m, 8 H, CHCH2CH2), 1.44–1.29 (m, 24 H,
CH2CH2CH2CH3), 0.92 (t, 3J = 7.5 Hz, 6 H, CH3), 0.90 (t, 3J =
by column chromatography (diethyl ether/petroleum ether, 50:50
1
v/v), yield 0.246 g, 43%. H NMR (300 MHz, CDCl3): δ = 7.28 (s, 7.5 Hz, 6 H, CH3) ppm. 13C NMR (75 MHz, CDCl3): δ = 156.54–
1 H, arom. CH), 7.14 (s, 1 H, arom. CH), 7.13 (s, 2 H, arom. CH), 116.68 (arom. C), 99.93 (s, OCH2O), 99.58 (s, OCH2O), 36.53 (s,
6.55 (s, 1 H, arom. CH), 6.47 (s, 2 H, arom. CH), 5.82 and 4.33
CHCH2), 36.43 (s, CHCH2), 32.15 (s, CH2CH2CH3), 30.11 (s,
CHCH2), 30.07 (s, CHCH2), 27.69 (s, CHCH2CH2), 22.82 (s,
CH2CH3), 14.23 (s, CH2CH3) ppm. 31P NMR (121 MHz, CDCl3):
(AB spin system, 2J = 7.6 Hz, 4 H, OCH2O), 5.74 and 4.52 (AB
2
3
spin system, J = 7.2 Hz, 4 H, OCH2O), 4.75 (t, J = 8.2 Hz, 2 H,
3
CHCH2), 4.70 (t, J = 8.2 Hz, 2 H, CHCH2), 2.68–2.59 [m, 2 H, δ = 23.1 [s, P(O)Ph2] ppm. C64H73O9P (1017.23): calcd. C 75.57, H
CH(CH3)2], 2.36–2.19 (m, 8 H, CHCH2CH2), 1.45–1.28 (m, 24 H, 7.23; found C 75.47, H 7.15.
CH2CH2CH2CH3), 1.28 [dd, JPH = 14.8 Hz, 3J = 7.2 Hz, 6 H,
4
5-Diisopropylphosphinoyl-4(24),6(10),12(16),18(22)-tetrameth-
4
3
CH(CH3)2], 1.16 [dd, JPH = 15.2 Hz, J = 7.2 Hz, 6 H, CH(CH3)
ylenedioxy-2,8,14,20-tetrapentylresorcin[4]arene (6): H2O2 (30% in
water, 0.5 mL, 0.62 mmol) was added to a solution of phosphine 4
(0.050 g, 0.05 mmol) in CH2Cl2 (5 mL). The resulting solution was
stirred at room temperature for 2 h and the mixture then treated
with a mixture of CH2Cl2 (5 mL) and water (10 mL). After extrac-
tion of the aqueous layer with CH2Cl2 (2ϫ10 mL), the organic
phases were combined. The resulting solution was washed with
water (2ϫ10 mL), dried with Na2SO4 and evaporated under re-
duced pressure to afford the phosphine oxide 6 as a white solid,
3
3
2], 0.92 (t, J = 7.2 Hz, 6 H, CH2CH3), 0.90 (t, J = 7.3 Hz, 6 H,
CH2CH3) ppm. 13C NMR (75 MHz, CDCl3): δ = 157.53–116.53
(arom. C), 100.58 (s, OCH2O), 99.62 (s, OCH2O), 36.69 (s,
CHCH2), 36.47 (s, CHCH2), 32.14 (s, CH2CH2CH3), 31.89 (s,
CH2CH2CH3), 30.50 (s, CHCH2), 30.01 (s, CHCH2), 27.69 (s,
1
CHCH2CH2), 27.49 (s, CHCH2CH2), 24.15 [d, JPC = 33.5 Hz,
2
CH(CH3)2], 22.80 (s, CH2CH3), 18.68 [d, JPC = 13.1 Hz, CH-
(CH3)2], 14.20 (s, CH2CH3) ppm. 31P NMR (121 MHz, CDCl3): δ
= 41.3 [s, iPr2P(BH3)] ppm. C58H80BO8P (947.03): calcd. C 73.56,
H 8.61; found C 73.64, H 8.42.
1
yield 0.050 g, 99%. H NMR (300 MHz, CDCl3): δ = 7.31 (s, 1 H,
arom. CH), 7.14 (s, 1 H, arom. CH), 7.11 (s, 2 H, arom. CH), 6.52
(s, 1 H, arom. CH), 6.48 (s, 2 H, arom. CH), 5.76 and 4.45 (AB
spin system, 2J = 6.9 Hz, 4 H, OCH2O), 5.74 and 4.33 (AB spin
system, 2J = 6.9 Hz, 4 H, OCH2O), 4.76 (t, 3J = 8.1 Hz, 2 H,
CHCH2), 4.73 (t, 3J = 8.1 Hz), 2.37–2.31 [m, 2 H, CH(CH3)2],
2.30–2.17 (m, 8 H, CHCH2 CH2 ), 1.40–1.25 (m, 24 H,
5-Diisopropylphosphanyl-4(24),6(10),12(16),18(22)-tetramethylene-
dioxy-2,8,14,20-tetrapentylresorcin[4]arene (4): A solution of 3
(0.200 g, 0.21 mmol) in degassed Et2NH (2 mL) was heated at re-
flux for 16 h. After cooling to room temperature, the reaction mix-
ture was evaporated to dryness. The residue was then taken up in
toluene and the resulting suspension filtered through a pad of Ce-
4
CH2CH2CH2CH3, 2 H, CHCH2), 1.26 [dd, JPH = 15.9 Hz, 3J =
1
4
3
lite to afford 4, yield 0.194 g, 98%. H NMR (300 MHz, C6D6): δ
7.2 Hz, 6 H, CH(CH3)2], 1.08 [dd, JPH = 16.3 Hz, J = 7.2 Hz, 6
3
3
= 7.57 (s, 2 H, arom. CH), 7.56 (s, 1 H, arom. CH), 7.49 (s, 1 H,
arom. CH), 6.81 (s, 2 H, arom. CH), 6.18 (s, 1 H, arom. CH), 5.78
and 4.40 (AB spin system, 2J = 7.3 Hz, 4 H, OCH2O), 5.54 and
4.30 (AB spin system, 2J = 7.3 Hz, 4 H, OCH2O), 5.22 (t, 3J =
8.1 Hz, 2 H, CHCH2), 5.14 (t, 3J = 8.1 Hz, 2 H, CHCH2), 2.36–
2.23 (m, 8 H, CHCH2CH2), 2.13–2.01 [m, 2 H, CH(CH3)2], 1.42–
H, CH(CH3)2], 0.91 (t, J = 6.9 Hz, 6 H, CH2CH3), 0.90 (t, J =
7.2 Hz, 6 H, CH2CH3) ppm. 13C NMR (75 MHz, CDCl3): δ =
156.77–116.43 (arom. C), 100.43 (s, OCH2O), 99.78 (s, OCH2O),
36.58 (s, CHCH2), 36.48 (s, CHCH2), 32.18 (s, CH2CH2CH3), 32.01
(s, CH2CH2CH3), 30.27 (s, CHCH2), 30.06 (s, CHCH2), 28.31 [s,
CH(CH3)2], 27.77 [s, CH(CH3)2], 27.71 (s, CHCH2CH2), 27.60 (s,
CHCH2CH2), 22.84 (s, CH2CH3), 17.19 [s, CH(CH3)2], 16.42 [s,
CH(CH3)2], 14.25 (s, CH2CH3) ppm. 31P NMR (121 MHz,
4
3
1.20 (m, 24 H, CH2CH2CH2CH3), 1.08 [dd, JPH = 10.2 Hz, J =
6.9 Hz, 6 H, CH(CH3)2], 0.83 (t, 3J = 7.2 Hz, 12 H, CH2CH3), 0.47
[dd, 4JPH = 12.9 Hz, J = 6.9 Hz, 6 H, CH(CH3)2] ppm. 13C NMR CDCl3): δ = 55.5 [s, P(O)iPr2] ppm. C58H77O9P (949.20): calcd. C
3
(75 MHz, C6D6): δ = 159.68–116.93 (arom. C), 100.12 (s, OCH2O),
99.27 (s, OCH2O), 37.38 (s, CHCH2), 36.97 (s, CHCH2), 32.33 (s,
CH2CH2CH3), 32.13 (s, CH2CH2CH3), 30.83 (s, CHCH2), 30.45 (s,
CHCH2), 28.00 (s, CHCH2CH2), 27.93 (s, CHCH2CH2), 23.98 [d,
1JPC = 14.5 Hz, CH(CH3)2], 23.96 (s, CH2CH3), 23.07 (s, CH2CH3),
21.47 [d, JPC = 23.1 Hz, CH(CH3)2], 20.85 [d, JPC = 12.7 Hz,
CH(CH3)2], 14.29 (s, CH2CH3) ppm. 31P NMR (121 MHz, C6D6):
δ = 7.1 (s, iPr2P) ppm.
73.39, H 8.18; found C 73.44, H 8.01.
trans-P,P-Dichloridobis[5-diphenylphosphanyl-4(24),6(10),
12(16),18(22)-tetramethylenedioxy-2,8,14,20-tetrapentylresorcin-
[4]arene]palladium(II) (7): A solution of [PdCl2(cod)] (0.010 g,
0.035 mmol) in CH2Cl2 (5 mL) was added to a stirred solution of
2 (0.070 g, 0.070 mmol) in CH2Cl2 (5 mL). After stirring at room
temperature for 0.5 h, the reaction mixture was concentrated to
about 2 mL and then n-hexane (20 mL) was added. The yellow pre-
cipitate formed was separated by filtration and dried under vac-
2
2
5-Diphenylphosphinoyl-4(24),6(10),12(16),18(22)-tetramethylene-
dioxy-2,8,14,20-tetrapentylresorcin[4]arene (5): H2O2 (30% in water,
1 mL, 1.25 mmol) was added to a solution of phosphine 2 (0.100 g,
0.10 mmol) in CH2Cl2 (10 mL). The resulting solution was stirred
at room temperature for 2 h and the mixture then treated with a
1
uum, yield 0.073 g, 96%. H NMR (CDCl3, 300 MHz): δ = 7.82–
7.76 (m, 4 H, arom. CH of PPh2), 7.55–7.42 (m, 6 H, arom. CH
of PPh2), 7.38 (s, 1 H, arom. CH of resorcinarene), 7.24 (s, 1 H,
arom. CH of resorcinarene), 7.23 (s, 2 H, arom. CH of resorcinar-
mixture of CH2Cl2 (10 mL) and water (20 mL). After extraction of ene), 6.67 (s, 1 H, arom. CH of resorcinarene), 6.48 (s, 2 H, arom.
2
the aqueous layer with CH2Cl2 (2ϫ 10 mL), the organic phases CH of resorcinarene), 5.84 and 4.74 (AB spin system, J = 7.2 Hz,
2
were combined. The resulting solution was washed with water
(2ϫ10 mL), dried with Na2SO4 and evaporated under reduced
pressure to afford the phosphine oxide 5 as a white solid, yield
4 H, OCH2O), 5.38 and 4.29 (AB spin system, J = 7.5 Hz, 4 H,
3
3
OCH2O), 4.86 (t, J = 8.1 Hz, 2 H, CHCH2), 4.76 (t, J = 7.8 Hz,
2 H, CHCH2), 2.38–2.28 (m, 8 H, CHCH2CH2), 1.58–1.41 (m, 24
H, CH2CH2CH2CH3), 1.04 (t, J = 6.9 Hz, 6 H, CH3), 1.03 (t, J
= 6.9 Hz, 6 H, CH3) ppm. 13C NMR (75 MHz, CDCl3): δ =
157.18–116.80 (arom. C), 100.50 (s, OCH2O), 99.41 (s, OCH2O),
36.67 (s, CHCH2), 36.52 (s, CHCH2), 32.17 (s, CH2CH2CH3), 31.97
1
3
3
0.101 g, 100%. H NMR (300 MHz, CDCl3): δ = 7.74–7.66 (m, 4
H, arom. CH of PPh2), 7.49–7.39 (m, 6 H, arom. CH of PPh2),
7.38 (s, 1 H, arom. CH of resorcinarene), 7.09 (s, 1 H, arom. CH
of resorcinarene), 7.06 (s, 2 H, arom. CH of resorcinarene), 6.57
(s, 1 H, arom. CH of resorcinarene), 6.42 (s, 2 H, arom. CH of (s, CH2CH2CH3), 30.43 (s, CHCH2), 30.04 (s, CHCH2), 27.72 (s,
resorcinarene), 5.72 and 4.55 (AB spin system, 2J = 7.2 Hz, 4 H,
OCH2O), 4.70 (t, J = 8.1 Hz, 2 H, CHCH2), 4.63 (t, J = 8.2 Hz,
CHCH2CH2), 27.53 (s, CHCH2CH2), 22.83 (s, CH2CH3), 22.79 (s,
3
3
CH2CH3), 14.24 (s, CH2CH3) ppm. 31P NMR (121 MHz, CDCl3):
Eur. J. Inorg. Chem. 2014, 1364–1372
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© 2014 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim