D. Guieysse et al. / Tetrahedron: Asymmetry 14 (2003) 317–323
321
(-OC
168.40 (C
6
H2-), 128.72 (×2), 128.84 (×2), 129.28, 135.97,
OO). Elemental anal. calcd for C16H23O2Br:
C9H9O2Br: C, 47.19; H, 3.96. Found: C, 47.60; H,
4.38%.
6
C, 58.72; H, 7.08. Found: C, 58.91; H, 6.90%.
4.4.8. ( )-2-Bromo-m-tolyl ethyl acetate, 3. Yield: 8.40 g
(75%). IR (neat) 1750 and 1730 (wCꢀO), 1600 and 1475
(wCꢀC), 1280–1140 (wCꢁO) cm−1. 1H NMR (CDCl3), l
4.4.3. ( )-2-Bromo-o-tolylacetic acid, 9. Yield: 5.39 g
(39%). IR (KBr, neat) 3300–2800 (wO-H), 1710 (wCꢀO),
1600 (wCꢀC), 1310–1240 (wCꢁO) cm−1. 1H NMR (d,
1.24–1.31 (t, J=7 Hz, 3H, -OCH2CH3
ArCH3), l 4.17–4.26 (qd, J=3.2 and 7 Hz, 2H,
-OCH2CH3), l 5.32 (s, 1H, -CHBr), l 7.17–7.36 (m,
4H, ArH H3),
). 13C NMR (CDCl3), l 13.99 (-CH2C
21.40 (ArCH3), 47.10 (-CHBr), 62.55 (-OCH2CH3),
125.76, 128.76, 129.30, 130.13, 135.80, 136.67, 168.42
(COO). Elemental anal. calcd for C11H13O2Br: C, 51.38;
6 ), l 2.36 (s, 3H,
6
DMSO), l 2.35 (s, 3H, ArCH
l 7.20–7.51 (m, 4H, ArH), l 13.24 (s, 1H, COOH
NMR (d, DMSO), l 18.74 (ArCH3), 47.39 (-CHBr),
126.420, 128.59, 128.81, 130.66, 135.39, 138.16, 169.06
(COOH). Elemental anal. calcd for C9H9O2Br: C,
6
3), l 5.95 (s, 1H, -CH
6 Br),
6
6
); 13C
6
6
6
6
6
6
6
6
6
47.19; H, 3.96. Found: C, 47.69; H, 3.58%.
6
H, 5.10. Found: C, 51.46; H, 4.89%.
4.4.4. ( )-2-Bromo-o-tolyl ethyl acetate, 2. Yield: 8.70 g
(78%). IR (neat) 1750 and 1730 (wCꢀO), 1600 and 1475
(wCꢀC), 1280–1140 (wCꢁO) cm−1. 1H NMR (CDCl3), l
4.4.9. ( )-2-Bromo-m-tolyl benzyl acetate, 6. Yield:
10.01 g (72%). IR (neat) 1750 and 1730 (wCꢀO), 1600 and
1
1475 (wCꢀC), 1280–1140 (wCꢁO) cm−1. H NMR (CDCl3),
1.24–1.31 (t, J=7 Hz, 3H, -OCH2CH3
3H, ArCH3), l 4.19–4.31 (qd, J=3.2–7 Hz, 2H,
-OCH2CH3), l 5.63 (s, 1H, -CHBr), l 7.19–7.26 (m,
3H, ArH), l 7.59–7.64 (m, 1H, ArH
); 13C NMR
(CDCl3), l 14.05 (-CH2CH3), 19.36 (ArCH3), 44.83
(-CHBr), 62.68 (-OCH2CH3), 126.90, 128.79, 129.25,
130.87, 134.48, 136.13, 168.30 (COO). Elemental anal.
6 ), l 2.41 (s,
l 2.35 (s, 3H, ArCH
-OCH2ph), l 5.39 (s, 1H, -CH
ArH
). 13C NMR (CDCl3), l 21.41 (ArC
(-CHBr), 68.09 (-OCH2ph), 125.85, 128.29 (×2), 128.58
(×2), 128.66, 128.80, 129.34, 130.21, 135.08, 135.61,
138.72, 168.23 (COO). Elemental anal. calcd for
6
3), l 5.21–5.24 (d, J=4.8 Hz, 2H,
Br), l 7.17–7.36 (m, 9H,
H3), 46.95
6
6
6
6
6
6
6
6
6
6
6
6
6
6
6
6
calcd for C11H13O2Br: C, 51.38; H, 5.10. Found: C,
51.40; H, 4.98%.
C16H15O2Br: C, 60.21; H, 4.74. Found: C, 60.59; H,
4.72%.
4.4.10. ( )-2-Bromo-m-tolyl octyl acetate, 12. Yield:
10.25 g (69%). IR (neat) 1750 and 1730 (wCꢀO), 1600 and
4.4.5. ( )-2-Bromo-o-tolyl benzyl acetate, 5. Yield: 14.16
g (74%). IR (neat) 1750 and 1730 (wCꢀO), 1600 and 1475
1
1460 (wCꢀC), 1280–1140 (wCꢁO) cm−1. H NMR (CDCl3),
1
(wCꢀC), 1280–1140 (wCꢁO) cm−1. H NMR (CDCl3), l 2.4
l 0.85–0.91 (t, J=6.5 Hz, 3H, -CH2CH3
10H, CH2), l 1.64 (m, 2H, CH2), l 2.36 (s, 3H,
ArCH3), l 4.13–4.21 (td, J=1 and 6.5 Hz, -OCH2
), l 5.32 (s, 1H, -CHBr), l 7.12–7.36 (m, 4H, ArH
NMR (CDCl3), l 14.16 (-CH2C
22.69, 25.77, 28.41, 29.17, 29.17, 31.79, 47.20 (-C
66.63 (-OCH2-), 125.76, 128.73, 129.29, 130.11, 135.84,
136.64, 166.46 (COO). Elemental anal. calcd for
6 ), l 1.26 (s,
(s, 3H, ArCH3
-OCH2ph), l 5.71 (s, 1H, -CH
ArH), l 7.34–7.36 (m, 5H, ArH
ArH
); 13C NMR (CDCl3), l 19.38 (ArC
(-CHBr), 68.21 (-OCH2ph), 126.92, 128.34 (×2), 128.60
(×2), 128.68, 128.95, 129.33, 130.91, 134.30, 135.07,
136.18, 168.16 (COO). Elemental anal. calcd for
6
), l 5.17–5.32 (2H, d, J=12.2 Hz,
Br), l 7.18–7.27 (m, 3H,
), l 7.60–7.64 (m, 1H,
H3), 44.71
6
6
6
6
6
6
CH2-
6
6
6
6
). 13C
6
6
6
H3), 21.40 (ArC
6 H3),
6
6
6
HBr),
6
6
C16H15O2Br: C, 60.21; H, 4.74. Found: C, 60.58; H,
4.62%.
6
C17H25O2Br: C, 59.83; H, 7.38. Found: C, 60.20; H,
7.21%.
4.4.6. ( )-2-Bromo-o-tolyl octyl acetate, 10. Yield: 13.87
g (68%). IR (neat) 1750 and 1730 (wCꢀO), 1600 and 1460
(wCꢀC), 1280–1140 (wCꢁO) cm−1. 1H NMR (CDCl3), l
4.4.11. ( )-2-Bromo-p-tolylacetic acid, 13. Yield: 5.10 g
(37%). IR (KBr, neat) 3300–2800 (wO-H), 1710 (wCꢀO),
1600 (wCꢀC), 1310–1240 (wCꢁO
(CD3COCD3), l 2.31 (s, 3H, ArCH3
-CHBr), l 7.18–7.54 (2d, 2+2H, ArH
(CD3COCD3), l 21.21 (ArCH3), 48.04 (-C
(×2), 130.16 (×2), 134.75, 139.93, 169.62 (C
)
cm−1. 1H NMR
0.85–0.91 (t, J=6.8 Hz, 3H, -CH2CH3
CH2), l 1.63 (m, 2H, CH2), l 2.41 (s, 3H, ArCH3
4.15–4.22 (t, J=6.8 Hz, -OCH2CH2-), l 5.63 (s, 1H,
-CHBr), l 7.18–7.25 (m, 3H, ArH), l 7.60 (m, 1H,
ArH H3), 19.37
); 13C NMR (CDCl3), l 14.16 (-CH2C
(ArCH3), 22.69, 25.74, 28.42, 29.13, 29.17, 31.78, 44.85
(-CHBr), 66.75 (-OCH2-), 126.87, 128.88, 129.21,
130.82, 134.51, 136.05, 168.36 (COO). Elemental anal.
6
), l 1.25 (s, 10H,
6
), l 5.61 (s, 1H,
). 13C NMR
HBr), 129.56
OOH). Ele-
6
6
6
), l
6
6
6
6
6
6
6
6
6
6
mental anal. calcd for C9H9O2Br: C, 47.19; H, 3.96.
Found: C, 47.51; H, 3.81%.
6
6
6
6
calcd for C17H25O2Br: C, 59.83; H, 7.38. Found: C,
60.20; H, 7.36%.
4.4.12. ( )-2-Bromo-p-tolyl ethyl acetate, 4. Yield: 8.47
g (78%). IR (neat) 1750 and 1730 (wCꢀO), 1600 and 1475
(wCꢀC), 1280–1140 (wCꢁO) cm−1. 1H NMR (CDCl3), l
1.23–1.31 (t, J=7 Hz, 3H, -OCH2CH3
ArCH3), l 4.17–4.29 (qd, J=3 and 7 Hz, 2H,
-OCH2CH3), l 5.33 (s, 1H, -CHBr), l 7.15–7.46 (2d,
2+2H, ArH H3),
). 13C NMR (CDCl3), l 14.00 (-CH2C
21.30 (ArCH3), 46.97 (-CHBr), 62.50 (-OCH2CH3),
128.61 (×2), 129.57 (×2), 132.97, 139.41 168.44 (COO).
6 ), l 2.34 (s, 3H,
4.4.7. ( )-2-Bromo-m-tolylacetic acid, 11. Yield: 5.79 g
(42%). IR (KBr, neat) 3300–2800 (wO-H), 1710 (wCꢀO),
6
cm−1. 1H NMR
6
6
1600 (wCꢀC), 1310–1240 (wCꢁO
(CD3COCD3), l 2.33 (s, 3H, ArCH3
-CHBr), l 7.15–7.44 (m, 4H, ArH), l 13.19 (s, 1H,
COOH H3),
). 13C NMR (CD3COCD3), l 21.31 (ArC
48.21 (-CHBr), 126.70, 129.47, 130.13, 130.62, 137.65,
139.19 169.55 (COOH). Elemental anal. calcd for
)
6
6
6
), l 5.59 (s, 1H,
6
6
6
6
6
6
6
Elemental anal. calcd for C11H13O2Br: C, 51.38; H,
5.10. Found: C, 51.35; H, 5.00%.
6
6