Manbeck et al.
1H, -CH2-), 3.77 (s, 3H, -OMe), 2.13-1.89 (m, 3H, -CH2-),
1.76 (m, 1H, -CH2-). 13C{1H} NMR (CDCl3, 25 °C): δ 153.6
(s, 1C, quat), 152.8 (s, 1C, quat), 115.2 (s, 2C, -C6H4OMe),
114.3 (s, 2C, -C6H4OMe), 76.9 (s, 1C, -CH-), 70.8 (s, 1C,
-CH2-), 68.3 (s, 1C, -CH2-), 55.4 (s, 1C, -OMe), 27.9 (s, 1C,
-CH2-), 25.4 (s, 1C, -CH2-).
The above procedure was repeated in the presence of air
without deoxygenating the reagents or solvent. Molecular
sieves were not added to this reaction. The reaction mixture
was stirred at 110 °C for 8 h, and the title compound was
isolated in 78% yield (0.14 g).
Preparation of 4-Tetrahydrofurfuryloxyanisole (Table
1, Entry 2): Method B. The general procedure was followed
using 2 (0.008 g, 4.1 µmol), 4-iodoanisole (0.20 g, 0.85 mmol),
molecular sieves (0.5 g), and Cs2CO3 (0.56 g, 1.7 mmol). The
reactor vial was evacuated and refilled with nitrogen before
addition of the tetrahydrofurfuryl alcohol (1.50 mL, 15.5
mmol). The microwave settings were as follows: temperature
) 125 °C, maximum microwave power ) 50 W, maximum
pressure ) 300 psi, and reaction time ) 3 h. The reaction
mixture was cooled to room temperature, filtered through a
small plug of silica gel, and dried under vacuum with gentle
heating. Purification by column chromatography (silica gel
hexane/ethyl acetate 2:1) afforded 0.14 g (78%) of the title
compound as a pale brown oil.
The above procedure was repeated in the presence of air
without deoxygenating the reagents or solvent. Molecular
sieves were not added to this reaction. The microwave power
and pressure settings were the same in these experiments,
but the reaction time was increased to 4 h. The title compound
was isolated in 73% yield (0.13 g).
(silica: hexane/ethyl acetate 2:1), affording 0.14 g (84%) of the
title compound as a dull yellow oil.
The above procedure was repeated in the presence of air
without deoxygenating the reagents or solvent. Molecular
sieves were not added to this reaction. The reaction was
irradiated for 7 h with the same microwave settings as above,
and the title compound was isolated in 80% yield (0.133 g)
yield.
Preparation of 1-Tetrahydrofurfuryloxynaphthalene
(Table 1, Entry 4): Method A. The general procedure was
followed using 2 (0.008 g, 4.1 µmol), 1-iodonaphthalene (0.11
mL, 0.75 mmol), and Cs2CO3 (0.50 g, 1.5 mmol). The test tube
was evacuated and refilled with nitrogen, and tetrahydrofur-
furyl alcohol (1.50 mL, 15.5 mmol) was added by syringe. The
reaction mixture was stirred at 110 °C for 4 h, cooled to room
temperature, and filtered through a short plug of silica gel
eluting with ethyl acetate. The excess alcohol was removed
under vacuum with gentle heating. Purification of the residue
by column chromatography (silica gel: hexane/ethyl acetate
2:1) afforded 0.16 g (93%) of the title compound as a pale brown
oil. Anal. Calcd for C15H16O2: C, 78.92; H, 7.06. Found: C,
78.88; H, 7.10. 1H NMR (CDCl3, 25 °C): δ 8.18 (m, 1H,
-OC10H7), 7.64 (m, 1H, -OC10H7), 7.37-7.19 (m, 4H, -OC10H7),
6.64 (d, 1H, J ) 7.5, -OC10H7), 4.28 (m, 1H, -CH-), 3.95 (m,
2H, -CH2-), 3.84 (m, 1H, -CH2-), 3.72 (m, 1H, -CH2-),
2.00-1.70 (m, 4H, -CH2-). 13C{1H} NMR (CDCl3, 25 °C): δ
154.4 (s, 1C, quat), 134.3 (s, 1C, quat), 127.2 (s, 1C, -C10H7),
126.1 (s, 1C, -C10H7), 125.6 (s, 1C, -C10H7), 125.4 (s, quat),
124.9 (s, 1C, -C10H7), 121.9 (s, 1C, -C10H7), 120.1 (s, 1C,
-C10H7), 104.5 (s, 1C, -C10H7), 76.8 (s, 1C, -CH-), 70.3 (s,
1C, -CH2-), 68.4 (s, 1C, -CH2-), 28.1 (s, 1C, -CH2-), 25.6
(s, 1C, -CH2-).
Preparation of 2-Tetrahydrofurfuryloxytoluene (Table
1, Entry 3): Method A. The general procedure was followed
using 2 (0.008 g, 4.1 µmol), 2-iodotoluene (0.11 mL, 0.86 mmol),
molecular sieves (0.5 g), and Cs2CO3 (0.56 g, 1.7 mmol). The
reaction flask was evacuated and refilled with nitrogen before
addition of tetrahydrofurfuryl alcohol (1.5 mL, 15.5 mmol).
After being stirred at 100 °C for 10 h, the reaction mixture
was transferred to a round-bottom flask, and the excess alcohol
was removed under vacuum with gentle heating. The residue
was extracted with ethyl acetate, filtered through a short
column of silica gel (1 cm), and purified by column chroma-
tography (silica hexane/ethyl acetate 2:1) to afford 0.15 g (90%)
of the title compound as a dull yellow oil. Anal. Calcd for
C12H16O2: C, 74.97; H, 8.39. Found: C, 75.12; H, 8.22. 1H NMR
(CDCl3, 25 °C): δ 7.20 (m, 2H, -C6H4Me), 6.91 (t, 1H, J ) 7.4
Hz, -C6H4Me), 6.86 (d, 1H, J ) 8.4 Hz, -C6H4Me), 4.37 (m,
1H, -CH-), 4.02 (m, 3H, -CH2-), 3.90 (m, 1H, -CH2-), 2.32
(s, 3H, -C6H4Me), 2.20-1.85 (m, 4H, -CH2-). 13C{1H} NMR
(CDCl3, 25 °C): δ 156.9 (s, 1C, quat), 130.5 (s, 1C, -C6H4Me),
126.7 (s, 1C, quat), 126.6 (s, 1C, -C6H4Me), 120.3 (s, 1C,
-C6H4Me), 110.8 (s, 1C, -C6H4Me), 77.0 (s, 1C, -CH-), 70.3
(s, 1C, -CH2-), 68.5 (s, 1C, -CH2-), 28.1 (s, 1C, -CH2-), 25.7
(s, 1C, -CH2-), 16.1 (s, 1C, -C6H4Me).
The above procedure was repeated in the presence of air
without deoxygenating the reagents or solvent. Molecular
sieves were not added to this reaction. The reaction was stirred
at 110 °C for 24 h, and the title compound was isolated in 84%
yield (0.14 g).
Preparation of 2-Tetrahydrofurfuryloxytoluene (Table
1, Entry 3): Method B. The general procedure was followed
using 2 (0.008 g, 4.1 µmol), 2-iodotoluene (0.11 mL, 0.86 mmol),
molecular sieves (0.5 g), and Cs2CO3 (0.56 g, 1.7 mmol). The
reaction flask was evacuated and refilled with nitrogen before
the addition of tetrahydrofurfuryl alcohol (1.5 mL, 15.5 mmol).
The microwave settings were as follows: temperature )
125 °C, maximum microwave power ) 50 W, maximum
pressure ) 300 psi, and reaction time ) 5 h. The reaction
mixture was cooled to room temperature, filtered through a
short plug of silica, and dried under vacuum with gentle
heating. The residue was purified by column chromatography
The above procedure was repeated in the presence of air
without deoxygenating the reagents or solvent. Molecular
sieves were not added to this reaction. The reaction was stirred
at at 110 °C for 5 h, and the title compound was isolated in
90% yield (0.155 g).
Preparation of 1-Tetrahydrofurfuryloxynaphthalene
(Table 1, Entry 4): Method B. The general procedure was
followed using 2 (0.008 g, 4.1 µmol), 1-iodonaphthalene (0.11
mL, 0.75 mmol), and Cs2CO3 (0.50 g, 1.5 mmol). The test tube
was evacuated and refilled with nitrogen, and tetrahydrofur-
furyl alcohol (1.50 mL, 15.5 mmol) was added by syringe. The
microwave settings were as follows: temperature ) 125 °C,
maximum microwave power ) 50 W, maximum pressure )
300 psi, and reaction time ) 1 h. The reaction mixture was
cooled to room temperature, filtered through a small plug of
silica gel, and dried under vacuum with gentle heating.
Purification by column chromatography (silica: hexane/ethyl
acetate 2:1) afforded 0.16 g (93%) of the title compound as a
pale brown oil.
The above procedure was repeated in the presence of air
without deoxygenating the reagents or solvent. Molecular
sieves were not added to this reaction. The reaction was
irradiated for 2 h with the same microwave settings as above,
and the title compound was isolated in 87% yield (0.15 g).
Preparation of 2-Tetrahydrofurfuryloxyanisole (Table
1, Entry 5): Method A. The general procedure was followed
using 2 (0.008 g, 4.1 µmol), 2-iodoanisole (0.11 g, 0.85 mmol),
crushed molecular sieves (0.5 g), and Cs2CO3 (0.55 g, 1.7
mmol). The test tube was evacuated and refilled with nitrogen
before addition of the tetrahydrofurfuryl alcohol (1.50 mL, 15.5
mmol). The reaction mixture was stirred at 110 °C for 15 h,
cooled to room temperature, and filtered through a short plug
of silica gel eluting with ethyl acetate. The excess tetrahydro-
furfuryl alcohol was removed under vacuum with gentle
heating. Purification of the residue by column chromatography
(silica: hexane/ethyl acetate 2:1) afforded 0.155 g (88%) of the
title compound as a dull yellow oil. Anal. Calcd for C12H16O3:
C, 69.23; H, 7.69. Found: C, 69.05; H, 7.91. 1H NMR (CDCl3,
25 °C): δ 6.89 (m, 4H, -C6H4OMe), 4.31 (m, 1H, -CH-), 3.97
(m, 3H, -CH2-), 3.83 (s, 3H, -C6H4OMe), 3.81 (m, 1H,
248 J. Org. Chem., Vol. 70, No. 1, 2005