Gꢀrard Cahiez et al.
FULL PAPERS
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0.4 mmHg). H NMR (400 MHz, CDCl3): d=4.04 (ddd, J=
J=6.9 Hz, 1H), 3.79 (s, 3H), 1.84 (d, J=6.9 Hz, 3H);
13C NMR (101 MHz, CDCl3): d=170.76, 53.01, 39.77, 21.70;
[a]D: À17 (c 1, CH2Cl2) (Lit.[19] [a]D: À18); MS (EI): m/z=
167 (M+).
15.2, 7.7, 5.4 Hz, 1H), 1.89–1.73 (m, 4H), 1.64–1.22 (m,
10H), 0.92 (t, J=7.1 Hz, 3H), 0.92–0.87 (t, J=7.1 Hz, 3H);
13C NMR (101 MHz, CDCl3): d=59.04, 39.14, 38.90, 31.26,
29.75, 27.26, 22.53, 22.18, 14.03, 13.99; MS (EI): m/z=221
(M+).
Ethyl 5-bromododecanoate (23): Colorless oil. It was pre-
pared in THF from the corresponding benzenesulfonate in
75% yield. 1H NMR (400 MHz, CDCl3): d=4.14 (q, J=
7.1 Hz, 2H), 4.02 (ddd, J=12.8, 7.5, 5.3 Hz, 1H), 2.33 (dd,
J=8.9, 5.3 Hz, 2H), 1.96–1.69 (m, 6H), 1.62–1.19 (m, 13H),
0.88 (t, J=6.9 Hz, 3H); 13C NMR (101 MHz, CDCl3): d=
173.28, 60.37, 57.84, 39.11, 38.33, 33.59, 31.78, 29.14, 28.99,
27.54, 23.00, 22.63, 14.25, 14.09; MS (EI): m/z=307 (M+);
HR-MS (EI, 70 eV): m/z=306.1186; calcd. for (M+À1):
306.1194.
Methyl 3-bromo-2-(R)-methylpropanoate (41): Colorless
oil. It was prepared in THF from the corresponding alcohol
1
via a mesylate in 83% yield. H NMR (400 MHz, CDCl3):
d=3.74 (s, 3H), 3.64–3.43 (m, 2H), 3.02–2.78 (m, 1H), 1.30
(d, J=7.0 Hz, 3H); 13C NMR (101 MHz, CDCl3): d=173.84,
52.13, 42.08, 34.08, 16.32; MS (EI): m/z=181 (M+).
Benzyl
3-bromo-2-(N-tert-butoxycarbonylamino)propa-
noate (43): It was prepared in THF from the corresponding
alcohol via a mesylate in 97% yield. 1H NMR (400 MHz,
CDCl3): d=7.48–7.31 (m, 5H), 5.43 (d, J=7.6 Hz, 1H), 5.22
(q, J=12.2 Hz, 2H), 4.79 (dt, J=6.9, 3.3 Hz, 1H), 3.78 (ddd,
J=52.2, 10.5, 3.3 Hz, 2H), 1.45 (s, 9H); 13C NMR
(101 MHz, CDCl3): d=169.15, 154.98, 134.87, 128.65 (2C),
128.46 (3C), 80.53, 67.91, 53.97, 34.11, 28.26 (3C). The enan-
tiomeric purity (95%) was determined, after reduction to al-
cohol with LiAlH4, then derivatization with the (S)-acetoxy-
1-Bromo-4-(3-bromobutyl)benzene (25): Colorless oil. It
was prepared in THF from the corresponding tosylate in
65% yield. 1H NMR (400 MHz, CDCl3): d=7.41 (d, J=
8.4 Hz, 2H), 7.08 (d, J=8.4 Hz, 2H), 4.04 (dqd, J=9.1, 6.7,
4.3 Hz, 1H), 2.76 (dddd, J=16.1, 13.9, 8.7, 6.3 Hz, 2H),
2.17–1.93 (m, 2H), 1.72 (d, J=6.7 Hz, 3H); 13C NMR
(101 MHz, CDCl3): d=139.83, 131.53 (2C), 130.28 (2C),
119.85, 50.52, 42.39, 33.36, 26.51; MS (EI): m/z=292 (M+).
(2-Bromoethyl)benzene (27): Colorless oil. It was pre-
pared in THF from the corresponding mesylate in 94%
yield. 1H NMR (400 MHz, CDCl3): d=7.58–6.86 (m, 5H),
3.56 (dd, J=10.1, 5.2 Hz, 2H), 3.16 (dd, J=9.8, 5.5 Hz, 2H);
13C NMR (101 MHz, CDCl3): d=138.92, 128.69 (2C),
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propionyl chloride[20], by H NMR and GC on a Lipodexꢃ-
E column (lengh: 50 m, internal diameter: 0.25 mm, film
width: 0.2 mm). This product was not suitable for GC/MS
(EI, 70 eV). HR-MS (EI, 70 eV): m/z=357.0582; calcd. for
(M+): 357.0576.
6-Chlorotridecane (45): Colorless oil. It was prepared in
THF from the corresponding benzenesulfonate or mesylate
in, respectively, 83% and 81% yield. The purification was
performed by distillation (bp 1248C/2 mmHg). 1H NMR
(400 MHz, CDCl3): d=3.95–3.83 (m, 1H), 1.78–1.62 (m,
4H), 1.59–1.46 (m, 2H), 1.46–1.20 (m, 14H), 0.88 (t, J=
6.6 Hz, 6H); 13C NMR (101 MHz, CDCl3): d=64.58, 38.67
(2C), 31.87 (2C), 29.01 (2C), 26.62 (2C), 22.75 (2C), 14.23
128.65ACHTUNGTRENNUNG
(2C), 126.96, 39.45, 32.98; MS (EI): m/z=185 (M+).
1-Bromo-2-phenoxyethane (29): It was prepared in THF
from the corresponding benzenesulfonate in 94% yield.
1H NMR (400 MHz, CDCl3): d=7.34–7.26 (m, 2H), 7.03–
6.95 (m, 1H), 6.94–6.88 (m, 2H), 4.29 (t, J=6.3 Hz, 2H),
3.64 (t, J=6.3 Hz, 2H); 13C NMR (101 MHz, CDCl3): d=
158.09, 129.63 (2C), 121.47, 114.78 (2C), 67.80, 29.19; MS
(EI): m/z=201 (M+).
1-Iodo-2-phenoxyethane (30). It was prepared in THF
from the corresponding benzenesulfonate in 85% yield.
1H NMR (400 MHz, CDCl3): d=7.34–7.25 (m, 2H), 7.03–
6.94 (m, 1H), 6.94–6.86 (m, 2H), 4.25 (t, J=6.9 Hz, 2H),
3.42 (t, J=6.9 Hz, 2H): 13C NMR (101 MHz, CDCl3): d=
158.05, 129.75 (2C), 121.56, 114.95 (2C), 68.71, 1.37; MS
(EI): m/z=248 (M+).
(Z)-1-Bromo-3-nonene (32): Colorless oil. It was prepared
in THF from the corresponding mesylate in 96% yield.
1H NMR (400 MHz, CDCl3): d=5.47 (m, 1H), 5.29 (m,
1H), 3.30 (t, J=7.2 Hz, 2H), 2.68–2.47 (m, 2H), 2.03–1.89
(m, 2H), 1.35–1.15 (m, 6H), 0.82 (t, J=6.9 Hz, 3H);
13C NMR (101 MHz, CDCl3): d=132.21, 124.69, 31.60,
30.44, 29.81, 28.16, 26.36, 21.52, 13.03; MS (EI): m/z=205
(M+).
N-Benzyloxycarbonyl-2-bromoethylamine (35): It was
prepared in THF from the corresponding mesylate in 98%
yield. 1H NMR (400 MHz, CDCl3): d=7.44–7.28 (m, 5H),
5.19 (s, 1H), 5.12 (s, 2H), 3.61 (t, J=5.8 Hz, 2H), 3.48 (t,
J=5.8 Hz, 2H); 13C NMR (101 MHz, CDCl3): d=156.17,
136.26, 128.59, 128.27, 128.16, 67.02, 44.07, 42.86, 42.78,
32.47; MS (EI): m/z=258 (M+).
+A
(2C); MS (EI): m/z=183 [CH3ACHTUNRGTNENUG(CH2)4CH HCUTNGTREN(NUGN CH2)5CH3].
2-Chlorotridecane (47): Colorless oil. It was prepared in
THF from the corresponding benzenesulfonate in 81%
yield. 1H NMR (400 MHz, CDCl3): d=3.88–3.75 (m, 1H),
1.86–1.58 (m, 4H), 1.52–1.33 (m, 2H), 1.33–1.18 (m, 14H),
1.01 (t, J=7.3 Hz, 3H), 0.92–0.80 (m, 3H); 13C NMR
(101 MHz, CDCl3): d=66.06, 38.26, 32.07, 31.64, 29.76,
29.74, 29.68, 29.49, 29.36, 26.70, 22.84, 14.27, 11.10; MS (EI):
m/z=220 (M+).
3-Chloropentane (49): Colorless oil. It was prepared in
THF from the corresponding benzenesulfonate in 75%
yield. After extractions using kerosene as the organic phase
(until no trace of THF is detected through GC analysis,
about 30 times), the purification was performed by distilla-
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tion (bp 858C/760 mmHg). H NMR (400 MHz, CDCl3): d=
3.79 (tt, J=8.4, 4.5 Hz, 1H), 1.84–1.65 (m, 4H), 1.02 (t, J=
7.3 Hz, 6H); 13C NMR (101 MHz, CDCl3): d=67.63, 31.21
(2C), 11.12 (2C); MS (EI): m/z=106 (M+).
(R)-2-Chlorooctane (51): Colorless oil. It was prepared in
THF from the corresponding benzenesulfonate in 85%
yield. 1H NMR (400 MHz, CDCl3): d=4.04 (h, J=6.5 Hz,
1H), 1.79–1.62 (m, 2H), 1.51 (d, J=6.5 Hz, 3H), 1.44–1.22
(m, 8H), 0.96–0.86 (m, 3H); 13C NMR (101 MHz, CDCl3):
d=59.13, 40.55, 31.86, 28.95, 26.78, 25.51, 22.73, 14.21; MS
+A
(EI): m/z=113 [CH3CH CTHNGURTEN(NUG CH2)5CH3].
(2-Chloropropyl)benzene (53): Colorless oil. It was pre-
pared in THF from the corresponding benzenesulfonate in
60% yield. 1H NMR (400 MHz, CDCl3): d=7.34–7.10 (m,
5H), 4.19 (h, J=6.7 Hz, 1H), 3.05 (dd, J=13.9, 7.0 Hz, 1H),
Methyl 2-(R)-bromopropanoate (39): Colorless oil. It was
prepared in THF from the corresponding alcohol via a mesy-
late in 74% yield. H NMR (400 MHz, CDCl3): d=4.39 (q,
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ꢁ 2012 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Adv. Synth. Catal. 0000, 000, 0 – 0
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