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IR (Nujol): 841, 1008, 1030, 1170 cm–1.
HRMS: m/z [M]+ calcd for C17H20O2: 256.1458; found: 256.1459.
4-Chlorophenyl(2,4-dimethoxyphenyl)iodonium Tosylate (1g)
Recrystallization (Et2O–MeOH); white powder; yield: 726 mg
(75%); mp 163–164 °C.
IR (Nujol): 820, 1029, 1050, 1152, 1232 cm–1.
1H NMR (500 MHz, DMSO-d6): δ = 8.18 (d, J = 8.9 Hz, 1 H), 8.05
(d, J = 8.5 Hz, 2 H), 7.55 (d, J = 8.9 Hz, 2 H), 7.45 (d, J = 8.0 Hz, 2
H), 7.09 (d, J = 7.8 Hz, 2 H), 6.79 (d, J = 2.6 Hz, 1 H), 6.68 (dd,
J = 8.9, 2.8 Hz, 1 H), 3.91 (s, 3 H), 3.82 (s, 3 H), 2.27 (s, 3 H).
13C NMR (125 MHz, DMSO-d6): δ = 164.7, 158.2, 145.7, 138.4,
137.6, 136.9, 136.5, 131.5, 128.1, 125.5, 114.3, 108.9, 99.7, 96.2,
57.2, 56.0, 20.8.
4-Methoxyphenyl Phenyl Ether (2c)
Colorless oil; yield: 90.0 mg (90%).
IR (neat): 1037, 1224, 1505, 1589 cm–1.
1H NMR (500 MHz, CDCl3): δ = 7.29 (dd, J = 8.6, 7.4 Hz, 2 H),
7.03 (t, J = 7.5 Hz, 1 H), 6.98 (d, J = 8.9 Hz, 2 H), 6.94 (d, J = 8.6
Hz, 2 H), 6.87 (d, J = 8.9 Hz, 2 H), 3.79 (s, 3 H).
13C NMR (125 MHz, CDCl3): δ = 158.5, 155.9, 150.1, 129.6, 122.4,
120.8, 117.5, 114.8, 55.6.
HRMS: m/z [M]+ calcd for C13H12O2 200.0837; found: 200.0831.
4-Chlorophenyl 4-Methoxyphenyl Ether (2d)
Recrystallization (Et2O–hexane); white powder; yield: 91.5 mg
(78%); mp 52–53 °C (Lit.15 54 °C).
IR (Nujol): 824, 1042, 1231, 1506 cm–1.
1H NMR (400 MHz, CDCl3): δ = 7.24 (d, J = 9.1 Hz, 2 H), 6.96 (d,
J = 8.8 Hz, 2 H), 6.88 (d, J = 9.1 Hz, 2 H), 6.86 (d, J = 8.8 Hz, 2 H),
3.80 (s, 3 H).
13C NMR (100 MHz, CDCl3): δ = 157.2, 156.1, 149.8, 129.5, 127.3,
120.8, 118.7, 114.9, 55.6.
HRMS: m/z [M]+ calcd for C13H1135ClO2: 234.0448; found:
234.0440.
HRMS: m/z [M]+ calcd for C14H1335ClIO2: 374.9643; found:
374.9634.
2,4-Dimethoxyphenyl(4-methylphenyl)iodonium Tosylate (1h)
Recrystallization (Et2O–MeOH); white powder; yield: 671 mg
(60%); mp 174–175 °C.
IR (Nujol): 818, 1007, 1022, 1155, 1214 cm–1.
1H NMR (500 MHz, DMSO-d6): δ = 8.17 (d, J = 8.8 Hz, 1 H), 7.93
(d, J = 8.3 Hz, 2 H), 7.46 (d, J = 8.3 Hz, 2 H), 7.27 (d, J = 8.0 Hz, 2
H), 7.09 (d, J = 8.0 Hz, 2 H), 6.77 (d, J = 2.5 Hz, 1 H), 6.65 (dd,
J = 8.9, 2.6 Hz, 1 H), 3.91 (s, 3 H), 3.81 (s, 3 H), 2.31 (s, 3 H), 2.27
(s, 3 H).
13C NMR (125 MHz, DMSO-d6): δ = 164.6, 158.2, 145.8, 142.1,
138.3, 137.6, 134.7, 132.1, 128.1, 125.5, 112.8, 108.8, 99.7, 96.1,
57.1, 56.0, 20.84, 20.81.
4-Methoxyphenyl 4-Methylphenyl Ether (2e)
White powder; yield: 98.5 mg (92%); mp 49–50 °C (Lit.16 49–50
°C).
IR (Nujol): 1043, 1229, 1499 cm–1.
HRMS: m/z [M]+ calcd for C15H16IO2: 355.0819; found: 355.0179.
1H NMR (500 MHz, CDCl3): δ = 7.09 (d, J = 8.5 Hz, 2 H), 6.95 (d,
J = 9.2 Hz, 2 H), 6.86 (d, J = 9.2 Hz, 2 H), 6.85 (d, J = 8.5 Hz, 2 H),
3.79 (s, 3 H), 2.31 (s, 3 H).
13C NMR (125 MHz, CDCl3): δ = 156.1, 155.6, 150.7, 132.0, 130.1,
120.3, 117.8, 114.8, 55.6, 20.6.
Diphenyl Ether (2j)
Diphenyliodonium tosylate (1c, 270 mg, 0.6 mmol) was added to a
soln of phenol (47 mg, 0.5 mmol) and K2CO3 (140 mg, 1.0 mmol)
in MeCN (3 mL) at 50 °C and the obtained mixture was stirred for
6 h at 50 °C. The mixture was quenched with H2O (10 mL) and then
extracted with CHCl3 (3 × 25 mL). The combined organic layers
were dried (Na2SO4) and concentrated in vacuo. The residue was
purified by short column chromatography (silica gel, hexane–
EtOAc, 5:1) to give 2j; yield: 79 mg (93%).
HRMS: m/z [M]+ calcd for C14H14O2: 234.0448; found: 234.0440.
4-tert-Butylphenyl 4-Methylphenyl Ether (2f)
Colorless oil; yield: 117.8 mg (98%).
IR (neat): 826, 1014, 1240, 1502, 1601 cm–1.
1H NMR (500 MHz, CDCl3): δ = 7.32 (d, J = 8.9 Hz, 2 H), 7.12 (d,
J = 8.7 Hz, 2 H), 6.91 (d, J = 8.9 Hz, 2 H), 6.91 (d, J = 8.9 Hz, 2 H),
2.32 (s, 3 H), 1.31 (s, 9 H).
13C NMR (125 MHz, CDCl3): δ = 155.3, 155.0, 145.7, 132.6, 130.1,
126.4, 18.9, 117.9, 34.2, 31.5, 20.7.
Diaryl Ethers 2; General Procedure
The appropriate diaryliodonium tosylate 1 (0.6 mmol) was added to
a soln of the phenol (0.5 mmol) and K2CO3 (140 mg, 1.0 mmol) in
MeCN (3 mL) at 50 °C and the obtained mixture was stirred for 6 h
at 50 °C. The mixture was quenched with H2O (10 mL) and then ex-
tracted with CHCl3 (3 × 25 mL). The combined organic layers were
dried (Na2SO4) and concentrated in vacuo. The residue was purified
by short column chromatography (silica gel) to give the diaryl ether.
HRMS: m/z [M]+ calcd for C17H20O: 240.1509; found: 240.1509.
4-Methylphenyl Phenyl Ether (2g)
Bis(4-methoxyphenyl) Ether (2a)
Colorless oil; yield: 90.3 mg (98%).
White powder; yield: 78.3 mg (68%); mp 50–51 °C (Lit.9a 51–
52 °C).
IR (neat): 1023, 1238, 1507, 1590 cm–1.
1H NMR (400 MHz, CDCl3): δ = 7.28 (dd, J = 8.6, 7.4 Hz, 2 H),
7.11 (d, J = 8.4 Hz, 2 H), 7.04 (t, J = 7.4 Hz, 1 H), 6.96 (d, J = 8.6
Hz, 2 H), 6.90 (d, J = 8.4 Hz, 2 H), 2.31 (s, 3 H).
13C NMR (100 MHz, CDCl3): δ = 157.8, 154.7, 132.8, 130.2, 129.6,
122.8, 119.1, 118.3, 20.7.
IR (Nujol): 819, 1037, 1246, 1507, 1590 cm–1.
1H NMR (400 MHz, CDCl3): δ = 6.92 (d, J = 9.1 Hz, 4 H), 6.85 (d,
J = 9.1 Hz, 4 H), 3.79 (s, 6 H).
13C NMR (100 MHz, CDCl3): δ = 155.3, 151.6, 119.5, 114.7, 55.7.
HRMS: m/z [M]+ calcd for C13H12O: 184.0883; found: 184.0880.
4-tert-Butylphenyl 4-Methoxyphenyl Ether (2b)
Colorless oil; yield: 93.6 mg (73%).
4-Chlorophenyl 4-Methylphenyl Ether (2h)
IR (neat): 828, 1043, 1231, 1501, 1615 cm–1.
White powder; yield: 104.9 mg (96%); mp 54–55 °C (Lit.17 56 °C).
1H NMR (500 MHz, CDCl3): δ = 7.30 (d, J = 8.9 Hz, 2 H), 6.97 (d,
J = 9.1 Hz, 2 H), 6.88 (d, J = 8.8 Hz, 2 H), 6.87 (d, J = 9.2 Hz, 2 H),
3.80 (s, 3 H), 1.31 (s, 9 H).
13C NMR (125 MHz, CDCl3): δ = 156.0, 155.7, 150.5, 145.3, 126.4,
120.6, 117.1, 114.8, 55.6, 34.2, 31.5.
IR (Nujol): 821, 1012, 1242, 1507, 1592 cm–1.
1H NMR (400 MHz, CDCl3): δ = 7.25 (d, J = 9.0 Hz, 2 H), 7.14 (d,
J = 9.0 Hz, 2 H), 6.90 (d, J = 9.0 Hz, 2 H), 6.90 (d, J = 9.0 Hz, 2 H),
2.33 (s, 3 H).
Synthesis 2013, 45, 183–188
© Georg Thieme Verlag Stuttgart · New York