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X.-L. LIU ET AL.
slowly, at room temperature. After stirring for 4 h at 80 ꢁC, Synthesis of methylresorcin[4]arene(O2P(S)Ph)4 (2a)
S8 (0.33 g, 1.30 mmol) was added and the mixture was
To a solution of 2 (2.18 g, 3.33 mmol) in 35 mL dry pyridine,
stirred again for 3 h. The solvent was removed under vac-
dichlorophenylphosphine (2.41 g, 13.49 mmol) was added
uum and the crude product was washed with water and
slowly at room temperature. After stirring for 4 h at 80 ꢁC,
dried under vacuum. Pure product was obtained as a white
S8 (0.43 g, 1.66 mmol) was added and the mixture was
solid by recrystallization from acetone/water (v:v ¼ 5:1) in
stirred again for 3 h. The solvent was removed under vac-
1
ca. 56% yield (1.62 g). H NMR (CDCl3): d (ppm) 8.19 (dd,
uum and the crude was washed with water and dried under
8H, P(O)ArHo), 7.54 (m, 4H þ 8H, P(O)ArHm þ P(O)ArHp),
vacuum. Pure product was obtained as white solid by recrys-
7.30 (s, 4H, ArHlower), 6.69 (s, 4H, ArHupper), 4.65 (t, 4H,
tallization from tetrahydrofuran/ethanol (v:v ¼ 4:1) in ca.
3J ¼ 3.6 Hz, bridge CH), 2.39 (m, 8H, CH2CH3), 1.06 (t,
1
72% yield (2.90 g). H NMR (CDCl3): d (ppm) 8.21 (dd, 8H,
12H, 3J ¼ 3.4 Hz, CH2CH3); 31P NMR (CDCl3): d (ppm)
P(O)ArHo), 7.59 (m, 4H þ 8H, P(O)ArHm þ P(O)ArHp),
79.49 (s). Selected IR (KBr, cmꢂ1): ꢀP–Ph ¼ 1432.7,
7.16 (s, 4H, ArCH), 4.95 (t, 4H, 3J ¼ 3.2 Hz, bridge CH),
ꢀP–O ¼ 1051.2, ꢀP¼S ¼ 686.2. Anal. Calc. for C60H52O8P4S4:
2
3.75 (s, 12H, ArCH3), 1.85 (d, 12H, J ¼ 3.2 Hz, CH2CH3);
C 62.49%, H 4.55%; Found: C 62.52%, H 4.58%.
31P NMR (CDCl3) d (ppm): 74.96 (s). Selected IR (KBr,
cmꢂ1): ꢀP–Ph ¼ 1432.7, ꢀP–O ¼ 1088.5, ꢀP¼S ¼ 690.7. Anal.
Calc. for C60H52O8P4S4: C 62.49%, H 4.55%; Found: C
62.46%, H 4.51%.
Synthesis of resorcin[4]arene(O2P(S)Ph)4 (1b)
This was prepared similar to 1a. Pure product was obtained
as a white solid by recrystallization from acetone/water
1
Synthesis of methylresorcin[4]arene(O2P(S)Ph)4 (2b)
(v:v ¼ 4:1). Yield: 2.26 g, 75%. H NMR (CDCl3): d (ppm)
8.16 (dd, 8H, P(O)ArHo), 7.54 (m, 4H þ 8H,
P(O)ArHm þ P(O)ArHp), 7.29 (s, 4H, ArHlower), 6.71 (s, 4H,
This was prepared similar to 2a. Pure product was obtained
as white solid by recrystallization from tetrahydrofuran/
2
1
ArHupper), 4.34 (d, 4H, J ¼ 6.0 Hz, bridge CH), 2.97 (m, 4H,
methanol (v:v ¼ 4:1). Yield: 3.75 g, 89%. H NMR (CDCl3): d
2
CH(CH3)2), 1.08 (d, 24H, J ¼ 3.0 Hz, CH(CH3)2); 31P NMR
(ppm) 8.19 (dd, 8H, P(O)ArHo), 7.53 (m, 4H þ 8H,
P(O)ArHm þ P(O)ArHp), 6.25 (s, 4H, ArCH), 4.65 (t, 4H,
(CDCl3): d (ppm) 78.95 (s). Selected IR (KBr, cmꢂ1):
ꢀP–Ph ¼ 1441.0, ꢀP–O ¼ 1059.4, ꢀP¼S ¼ 690.3. Anal. Calc. for
C64H60O8P4S4: C 63.56%, H 5.00%; Found: C 63.59%,
H 5.02%.
3
3J ¼ 3.6 Hz, bridge CH), 2.39 (t, 8H, J ¼ 3.6 Hz, CH2CH3),
3
2.18 (s, 12H, ArCH3), 1.06 (t, 12H, J ¼ 3.4 Hz, CH2CH3);
31P NMR (CDCl3) d (ppm): 75.12 (s). Selected IR (KBr,
cmꢂ1): ꢀP–Ph ¼ 1436.9, ꢀP–O ¼ 1068.1, ꢀP¼S ¼ 686.2. Anal.
Calc. for C64H60O8P4S4: C 63.56%, H 5.00%; Found: C
63.60%, H 5.04%.
Synthesis of resorcin[4]arene(O2P(S)Ph)4 (1c)
This was prepared similar to 1a. Pure product was obtained
as a white solid by recrystallization from acetone/methanol
1
Synthesis of methylresorcin[4]arene(O2P(S)Ph)4 (2c)
(v:v ¼ 5:2). Yield: 2.66 g, 88%. H NMR (CDCl3): d (ppm)
8.15 (dd, 8H, P(O)ArHo), 7.54 (m, 4H þ 8H,
P(O)ArHm þ P(O)ArHp), 7.00 (s, 4H, ArHlower), 6.70 (s, 4H,
This was prepared similar to 2a. Pure product was obtained
as white solid by recrystallization from tetrahydrofuran/
3
1
ArHupper), 4.29 (t, 4H, J ¼ 5.8 Hz, bridge CH), 2.92 (m, 8H,
methanol (v:v ¼ 5:2). Yield: 2.36 g, 56%. H NMR (CDCl3): d
CH2CH2CH3), 1.43 (m, 8H, CH2CH2CH3), 1.02 (t, 12H,
3J ¼ 5.0 Hz, CH2CH2CH3); 31P NMR (CDCl3): d (ppm) 78.85
(s). Selected IR (KBr, cmꢂ1): ꢀP–Ph ¼ 1432.7, ꢀP–O ¼ 1063.6,
ꢀP¼S ¼ 690.3. Anal. Calc. for C64H60O8P4S4: C 63.56%, H
5.00%; Found: C 63.51%, H 4.97%.
(ppm) 8.21 (dd, 8H, P(O)ArHo), 7.54 (m, 4H þ 8H,
P(O)ArHm þ P(O)ArHp), 7.13 (s, 4H, ArCH), 4.29 (d, 4H,
2J ¼ 5.6 Hz, bridge CH), 2.95 (m, 4H, CH(CH3)2), 2.15 (s,
12H, ArCH3), 1.05 (s, 24H, CH(CH3)2); 31P NMR (CDCl3):
d (ppm) 74.14(s). Selected IR (KBr, cmꢂ1): ꢀP–Ph ¼ 1432.7,
ꢀP–O ¼ 1071.9, ꢀP¼S ¼ 686.2. Anal. Calc. for C68H68O8P4S4:
C 64.54%, H 5.42%; Found: C 64.56%, H 5.46%.
Synthesis of resorcin[4]arene(O2P(S)Ph)4 (1d)
This was prepared similar to 1a. Pure product was obtained
Synthesis of methylresorcin[4]arene(O2P(S)Ph)4 (2d)
as a white solid by recrystallization from acetone/methanol
1
(v:v ¼ 5:1). Yield: 2.46 g, 78%. H NMR (CDCl3): d (ppm)
This was prepared similar to 2a. Pure product was obtained
8.15 (dd, 8H, P(O)ArHo), 7.54 (m, 4H þ 8H, as white solid by recrystallization from tetrahydrofuran/
1
P(O)ArHm þ P(O)ArHp), 7.29 (s, 4H, ArHlower), 6.66 (s, 4H, methanol (v:v ¼ 5:2). Yield: 3.14 g, 72%. H NMR (CDCl3): d
3
ArHupper), 4.91 (t, 4H, J ¼ 4.2 Hz, bridge CH), 2.23 (m, 8H, (ppm) 8.20 (dd, 8H, P(O)ArHo), 7.54 (m, 4H þ 8H,
CH2(CH2)2CH3), 1.64 (m, 16H, CH2(CH2)2CH3), 1.07 (t, P(O)ArHm þ P(O)ArHp), 7.13 (s, 4H, ArCH), 4.73 (t, 4H,
12H, 3J ¼ 3.4 Hz, CH2(CH2)2CH3); 31P NMR (CDCl3): d 3J ¼ 5.4 Hz, bridge CH), 2.29 (m, 8H, CH2CH2CH3), 2.12 (s,
(ppm) 79.62 (s). Selected IR (KBr, cmꢂ1): ꢀP–Ph ¼ 1441.0, 12H, ArCH3), 1.42 (m, 8H, CH2CH2CH3), 1.04 (t, 12H,
ꢀP–O ¼ 1084.3, ꢀP¼S ¼ 682.0. Anal. Calc. for C68H68O8P4S4: 3J ¼ 3.4 Hz, CH2CH2CH3); 31P NMR (CDCl3): d (ppm)
C 64.54%, H 5.42%; Found: C 64.55%, H 5.44%.
74.86(s). Selected IR (KBr, cmꢂ1): ꢀP–Ph ¼ 1432.7,