C. Goꢀmez et al. / Tetrahedron 62 (2006) 9832–9839
9837
4.3.2.7. [Chloromethoxy(phenyl)methyl]benzene (1o).
Yield: 88%. Yellowish oil; tR¼14.3 min; n (film) 3062,
3030 (]CH), 1109 (C–O) cmꢁ1; dH (400 MHz) 5.48 (2H,
s, CH2), 5.92 (1H, s, CH), 7.29–7.35 (10H, m, 10ꢃArH);
dC (100 MHz) 80.0 (CH2), 80.8 (CH), 127.5, 128.1, 128.5
(ArCH), 139.7 (ArC); m/z 234 (M++2, 4%), 232 (M+,
12%), 168 (16), 167 (100), 166 (13), 165 (35), 152 (16);
HRMS calcd for C14H13OCl 232.0655, found 232.0660.
(ArCH2), 63.5 (CH2O), 126.7, 128.0 (ArCH), 137.9, 138.2
(ArC); m/z 150 (M+, 45%), 120 (41), 119 (100), 106 (10),
105 (27), 91 (21), 77 (10).
4.4.5. 2-(4-tert-Butylphenyl)ethanol (2f).28 Colourless liq-
uid; tR¼11.3 min; n (film) 3346 (OH), 3055 (]CH) cmꢁ1
;
dH (300 MHz) 1.31 (9H, s, 3ꢃCH3), 2.83 (2H, t, J¼6.6,
ArCH2), 3.84 (2H, t, J¼6.6, CH2O), 7.16 (2H, d, J¼8.2,
2ꢃArH), 7.34 (2H, d, J¼8.2, 2ꢃArH); dC (75 MHz) 31.3
(CH3), 34.4 [C(CH3)3], 38.6 (ArCH2), 63.6 (CH2O), 125.4,
128.7 (ArCH), 135.3, 149.2 (ArC); m/z 178 (M+, 21%),
164 (21), 163 (100), 149 (41), 147 (15), 117 (18), 105
(12), 91 (20).
4.4. DTBB-catalysed lithiation of chloromethyl ethers 1.
Preparation of compounds 2. General procedure
To a cooled green suspension of lithium (49 mg, 7 mmol)
and DTBB (13 mg, 0.05 mmol) in THF (2 mL) at 0 ꢀC (or
at ꢁ40 ꢀC for 1g–j,l and ꢁ78 ꢀC for 1k) was added the
corresponding chloromethyl ether (1 mmol). The resulting
mixture was stirred for 1 h at the same temperature and
then it was hydrolysed with water (5 mL) allowing the tem-
perature to rise to 20 ꢀC. The resulting mixture was extracted
with ethyl acetate (3ꢃ5 mL), and the organic layer was dried
over anhydrous MgSO4 and evaporated (15 Torr). The
resulting residue was then purified by vacuum distillation
in a Kugelrohr apparatus (ca. 0.01 Torr for 2a–f,h–j,m,n)
or after column chromatography (silica gel, hexane/ethyl
acetate for 2g,k,l,o) to give the title compounds. Compound
2a was characterised by comparison of its spectroscopic and
chromatographic data with those of the commercially avail-
able (Aldrich) authentic sample. Yields are given in Table 1;
physical, analytical spectroscopic data, as well as literature
references for the known compounds, follow.
4.4.6. 2-(4-Phenylphenyl)ethanol (2g).29 White solid; mp
91 ꢀC (hexane/ethyl acetate); tR¼15.1 min; n (KBr) 3249
(OH), 3030 (]CH) cmꢁ1; dH (400 MHz) 2.92 (2H, t,
J¼6.5, ArCH2), 3.92 (2H, m, CH2O), 7.30–7.36 (3H, m,
2ꢃArH), 7.41–7.46 (2H, m, 2ꢃArH), 7.54–7.59 (4H, m,
2ꢃArH); dC (100 MHz) 38.8 (ArCH2), 63.6 (CH2O),
127.0, 127.3, 128.7, 129.4 (ArCH), 139.5, 140.9 (ArC);
m/z 198 (M+, 36%), 168 (19), 167 (100), 165 (24), 152 (13).
4.4.7. 2-(2-Methoxyphenyl)ethanol (2h).30 Colourless oil;
tR¼10.4 min; n (film) 3384 (OH) cmꢁ1; dH (300 MHz)
2.90 (2H, t, J¼6.5, ArCH2), 3.79–3.85 (5H, m, CH2O,
CH3), 6.85–6.93 (2H, m, 2ꢃArH), 7.14–7.27 (2H, m,
2ꢃArH); dC (75 MHz) 34.0 (ArCH2), 55.2 (CH3), 62.8
(CH2O), 110.4, 120.6, 127.7, 130.8 (ArCH), 127.0, 157.6
(ArC); m/z 152 (M+, 58%), 122 (31), 121 (100), 92 (10),
91 (98), 77 (12), 65 (13).
4.4.1. 2-(2-Methylphenyl)ethanol (2b).25 Colourless liq-
uid; tR¼9.3 min; n (film) 3354 (OH), 3063, 3017 (]CH)
cmꢁ1; dH (300 MHz) 2.32 (3H, s, CH3), 2.87 (2H, t,
J¼6.9, ArCH2), 3.80 (2H, t, J¼6.9, CH2O), 7.12–7.18
(4H, m, 4ꢃArH); dC (75 MHz) 19.4 (CH3), 36.3 (ArCH2),
62.5 (CH2O), 126.0, 126.5, 129.6, 130.4 (ArCH), 136.5,
140.1 (ArC); m/z 136 (M+, 39%), 118 (10), 117 (13), 106
(33), 105 (100), 103 (13), 91 (23), 79 (14), 77 (15).
4.4.8. 2-(3-Methoxyphenyl)ethanol (2i).30 Colourless oil;
tR¼10.7 min; n (film) 3384 (OH) cmꢁ1; dH (300 MHz)
2.83 (2H, t, J¼6.6, ArCH2), 3.79 (3H, s, CH3), 3.84 (2H, t,
J¼6.6, CH2O), 6.76–6.82 (3H, m, 3ꢃArH), 7.20–7.25 (1H,
m, ArH); dC (75 MHz) 39.2 (ArCH2), 55.1 (CH3), 63.5
(CH2O), 111.7, 114.7, 121.3, 129.5 (ArCH), 140.1, 159.7
(ArC); m/z 152 (M+, 82%), 122 (65), 121 (100), 109 (15),
108 (11), 107 (16), 91 (47), 78 (16), 77 (21), 65 (11).
4.4.2. 2-(3-Methylphenyl)ethanol (2c).26 Colourless liquid;
tR¼9.0 min; n (film) 3346 (OH), 3023 (]CH) cmꢁ1; dH
(400 MHz) 2.33 (3H, s, CH3), 2.81 (2H, t, J¼6.6, ArCH2),
3.82 (2H, t, J¼6.6, CH2O), 7.00–7.03 (3H, m, 3ꢃArH),
7.17–7.21 (1H, m, ArH); dC (100 MHz) 21.3 (CH3), 39.0
(ArCH2), 63.6 (CH2O), 126.0, 127.1, 128.4, 129.8 (ArCH),
138.1, 138.3 (ArC); m/z 136 (M+, 49%), 106 (52), 103
(13), 105 (100), 91 (33), 79 (14), 77 (16).
4.4.9. 2-(4-Methoxyphenyl)ethanol (2j).21 Colourless liq-
uid; tR¼10.7 min; n (film) 3373 (OH), 3040 (]CH) cmꢁ1
;
dH (400 MHz) 2.81 (2H, t, J¼6.5, ArCH2), 3.79 (3H, s,
CH3), 3.82 (2H, t, J¼6.6, CH2O), 6.86 (2H, d, J¼8.5,
2ꢃArH), 7.15 (2H, d, J¼8.5, 2ꢃArH); dC (75 MHz) 38.2
(ArCH2), 55.2 (CH3), 63.8 (CH2O), 114.0, 129.9 (ArCH),
158.2 (ArC); m/z 152 (M+, 22%), 121 (100).
4.4.3. 2-(4-Methylphenyl)ethanol (2d).21 Colourless liq-
uid; tR¼8.9 min; n (film) 3345 (OH), 3048, 3020 (]CH)
cmꢁ1; dH (300 MHz) 2.39 (3H, s, CH3), 2.88 (2H, t,
J¼6.6, ArCH2), 3.87 (2H, t, J¼6.6, CH2O), 7.16–7.19
(4H, m, 4ꢃArH); dC (75 MHz) 20.9 (CH3), 38.6 (ArCH2),
63.7 (CH2O), 128.8, 129.2, (ArCH), 135.3, 135.9 (ArC);
m/z 136 (M+, 34%), 106 (24), 105 (100), 91 (13), 79 (11),
77 (12).
4.4.10. 2-(4-Fluorophenyl)ethanol (2k).31 Colourless liq-
uid; tR¼8.1 min; n (film) 3355 (OH), 3040 (]CH) cmꢁ1
;
dH (300 MHz) 2.84 (2H, t, J¼6.6, ArCH2), 3.84 (2H, t,
J¼6.6, CH2O), 7.00 (2H, t, J¼8.6, 2ꢃArH), 7.16–7.26 (2H,
m, 2ꢃArH); dC (75 MHz) 38.3 (ArCH2), 63.6 (CH2O),
115.2, 115.5, 130.3, 130.4 (ArCH), 134.1, 134.2, 160.1,
163.3 (ArC); m/z 140 (M+, 22%), 110 (29), 109 (100), 83(14).
4.4.11. 2-(1-Naphthyl)ethanol (2l).32 White solid; mp
59 ꢀC (hexane/ethyl acetate); tR¼13.5 min; n (KBr) 3290
(OH), 3046 (]CH) cmꢁ1; dH (300 MHz) 3.34 (2H, t,
J¼6.6, ArCH2), 3.98 (2H, t, J¼6.6, CH2O), 7.36–7.54
(4H, m, 2ꢃArH), 7.75 (1H, d, J¼8.0, ArH), 7.85–7.88
(1H, m, ArH), 8.05 (1H, d, J¼8.6, ArH); dC (75 MHz)
4.4.4. 2-(3,5-Dimethylphenyl)ethanol (2e).27 Colourless
liquid; tR¼10.0 min; n (film) 3354 (OH), 3013 (]CH)
cmꢁ1; dH (300 MHz) 2.25 (6H, s, 2ꢃCH3), 2.76 (2H, t,
J¼6.7, ArCH2), 3.78 (2H, t, J¼6.7, CH2O), 6.83 (2H, s,
ArCH), 6.85 (1H, s, ArCH); dC (75 MHz) 21.1 (CH3), 38.9