2096
B. R. Steele et al. / Tetrahedron Letters 47 (2006) 2093–2097
A similar procedure was used for the following:
J 7.3, ArH), 6.88 (1H, d, J 7.3, ArH); 13C NMR (CDCl3,
75 MHz): d 12.1, 14.4, 19.4, 22.4, 28.1, 28.9, 41.7, 121.4,
124.4, 126.2, 127.9, 138.9, 151.9; MS (EI) m/z (relative
intensity %): 220 (M+, 19%), 191 (100), 163 (39), 149
(9), 121 (12), 105 (4), 91 (7).
3.1.2. 2,6-Bis(1-ethylpropyl)phenol 2. Bp 78–80 ꢁC/
1
0.1 mbar. H NMR (CDCl3, 300 MHz): d 0.90 (12H, t,
J 7.3, CH3), 1.70 (4H, m, CH2), 1.81 (4H, m, CH2),
2.79 (2H, m, CH), 4.80 (1H, s, OH), 7.01 (3H, m,
ArH); 13C NMR (CDCl3, 75 MHz): d 12.2, 28.5, 42.0,
120.6, 124.6, 130.6, 152.3; MS (EI) m/z (relative inten-
sity %): 234 (M+, 20%), 205 (100), 177 (55), 147 (7),
128 (5), 107 (6).
3.1.9. B: 3-(1-Ethylpropyl)phenol 6. The procedure de-
scribed above was followed except that no Mg(OCH2-
CH2OEt)2 was added and the reaction time was
extended to 40 h.20 Compound 7 was formed in 44%
yield. 1H NMR (CDCl3, 300 MHz): d 0.80 (6H, t, J
7.3, CH3), 1.6 (4H, m, CH2), 2.28 (1H, m, CH), 5.4
(1H, br s, OH), 6.7 (3H, m, ArH), 7.2 (1H, m, ArH);
13C NMR (CDCl3, 75 MHz): d 12.2, 29.2, 49.6, 112.9,
114.7, 120.7, 129.4, 148.1, 155.2; MS (EI) m/z (relative
intensity %): 164 (M+, 39%), 136 (71), 107 (100), 91
(10), 77 (13).
3.1.3. 2-(1-Ethylpropyl)-4-methylphenol 3. Mp 70–
1
71 ꢁC. H NMR (CDCl3, 300 MHz): d 0.83 (6H, t, J
7.5, CH(CH2Me)2), 1.80–1.52 (4H, m, CH(CH2Me)2),
2.28 (3H, s, Me), 2.80–2.65 (1H, m, CHEt2), 4.54 (1H,
s, OH), 6.67 (1H, d, J 8.0, ArH), 6.87 (1H, dd, J 8.0
and 2.0, ArH), 6.90 (1H, d, J 2.0, ArH); 13C NMR
(CDCl3, 75 MHz): d 12.1, 20.7, 28.1, 41.6, 115.0,
126.8, 128.3, 129.8, 130.9, 151.4; m/z (EI) 178 (M+,
29%), 149 (70), 133 (5), 121 (100), 91 (13).
The following were prepared in a similar fashion:
3.1.10. 2,3-Dipropylphenol 8. Bp 95–98 ꢁC/1 mbar.
Spectroscopic data were in agreement with those
reported.12
3.1.4. 2,6-Bis(1-ethylpropyl)-4-methylphenol 4. Bp 80–
81 ꢁC/0.1 mbar. 1H NMR (CDCl3, 300 MHz): d 0.83
(12H, t, J 7.5, CH(CH2Me)2), 1.82–1.50 (8H, m,
CH(CH2Me)2), 2.27 (3H, s, Me), 2.65–2.60 (2H, m,
CHEt2), 4.50 (1H, s, OH), 6.73 (2H, s, ArH); 13C
NMR (CDCl3, 75 MHz): d 12.1, 21.0, 28.5, 41.9,
125.1, 129.1, 130.4, 149.8; m/z (EI) 248 (M+, 19%),
220 (16), 219 (100), 192 (6), 191 (52), 161 (10), 149
(14), 147 (5), 121 (17), 105 (6), 91 (6).
3.1.11. 2-(1-Ethylpropyl)-5-propylphenol 10. Bp 85–
88 ꢁC/0.3 mbar. 1H NMR (CDCl3, 300 MHz): d 0.81
(6H, t, J 7.3, CH(CH2CH3)2), 0.94 (3H, t, J 7.3,
CH2CH2CH3), 1.5–1.7 (6H, m, CH2), 2.51 (2H, t, J
7.3, CH2), 2.70 (1H, m, CH), 4.64 (1H, s, OH), 6.59
(1H, s, ArH), 6.74 (1H, d, J 7.3, ArH), 7.00 (1H, d, J
7.3, ArH); 13C NMR (CDCl3, 75 MHz): d 12.1, 13.9,
24.3, 28.1, 37.5, 41.3, 115.3, 121.1, 127.5, 128.3, 141.3,
153.5; MS (EI) m/z (relative intensity %): 206 (M+,
26%), 177 (100), 149 (55), 133 (7), 107 (15).
3.1.5. 3-Propylphenol 5. Bp 88–90 ꢁC/2 mbar (lit.9 bp
93–95 ꢁC/2.3 mmHg). Spectroscopic data were in agree-
ment with those reported.15
3.1.6. 3-Methyl-2-propylphenol 7. Bp 90–93 ꢁC/2 mbar
(lit.11 mp 29–32 ꢁC). 1H NMR (CDCl3, 300 MHz): d
1.08 (3H, t, J 7.3, CH3), 1.64 (2H, m, CH2), 2.38
(3H, s, ArCH3), 2.60–2.63 (2H, dd, J 7.9, 8.0, CH2),
4.7 (1H, br s, OH), 6.67 (1H, d, J 7.7, ArH), 6.83 (1H,
d, J 7.7, ArH), 7.01 (1H, t, J 7.7, ArH); 13C NMR
(CDCl3, 75 MHz): d 14.5, 19.6, 22.4, 28.5, 113.0,
122.9, 126.3, 127.5, 138.0, 153.6; MS (EI) m/z (relative
intensity %): 150 (M+, 36%), 121 (100), 93 (7), 91 (22),
77 (17).
3.1.12. 6-(1-Ethylpropyl)-2,3-dipropylphenol 12. The
product co-distilled in the range 83–86 ꢁC/0.5 mbar with
1
11 and was not obtained analytically pure. H NMR
(CDCl3, 300 MHz): d 0.90 (6H, t, J 7.3, CH(CH2CH3)2),
1.07 (3H, t, J 7.3, CH2CH2CH3), 1.10 (3H, t, J 7.3,
CH2CH2CH3), 1.7 (4H, m, CH2), 1.8 (4H, m, CH2),
2.7 (5H, m, CH+2 · CH2), 4.77 (1H, s, OH), 6.82 (1H,
d, J 7.3, ArH), 6.95 (1H, d, J 7.3, ArH); 13C NMR
(CDCl3, 75 MHz): d 12.2, 14.4, 23.3, 24.5, 28.3, 28.7,
35.1, 41.9, 121.4, 124.4, 126.2, 127.9, 138.9, 151.9; MS
(EI) m/z (relative intensity %): 248 (M+, 15%), 219
(100), 191 (38), 161 (10), 149 (8), 121 (9).
3.1.7. 2-(1-Ethylpropyl)-5-methylphenol 9. Bp 78–
80 ꢁC/0.3 mbar. 1H NMR (CDCl3, 300 MHz): d 0.84
(6H, t, J 7.3, CH2CH3), 1.6–1.7 (4H, m, CH2), 2.30
(3H, s, ArCH3), 2.74 (1H, m, CH), 4.6 (1H, br s, OH),
6.60 (1H, s, ArH), 6.76 (1H, d, J 7.3, ArH), 7.01 (1H,
d, J 7.3, ArH); 13C NMR (CDCl3, 75 MHz): d 12.1,
21.0, 28.1, 41.2, 116.1, 121.7, 127.7, 128.2, 136.4,
153.6; MS (EI) m/z (relative intensity %): 178 (M+,
36%), 149 (95), 121 (100), 91 (13), 77 (9).
Acknowledgements
Funding of this work by the General Secretariat for
Research and Technology is gratefully acknowledged.
References and notes
3.1.8. 6-(1-Ethylpropyl)-3-methyl-2-propylphenol 11.
The product co-distilled in the range 83–86 ꢁC/0.5 mbar
with 12 and was not obtained analytically pure. 1H
NMR (CDCl3, 300 MHz): d 0.90 (6H, t, J 7.3,
CH(CH2CH3)2), 1.06 (3H, t, J 7.3, CH2CH2CH3), 1.6
(4H, m, CH2), 1.7 (2H, m, CH2), 2.32 (3H, s, ArCH3),
2.6 (3H, m, CH+CH2), 4.72 (1H, s, OH), 6.77 (1H, d,
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