My PhD dissertation - Institut Fresnel

78
C12H12BrN (250.13) calcd. C 57.62% H 4.84%
found C 57.63% H 4.72%.
(+)-(1R)-2-Bromo-N-(1-phenylethyl)pyrrole (R-17): Analogously prepared from
(-)-(1S)-N-(1-phenylethyl)pyrrole (9; 43 g, 0.25 mol) and N-bromosuccinimide (44 g,
20
20
0.25 mol); colorless needles; m.p. -24 to -20 °C; n = 1.5761; d = 1.329; [ α ] = +22.0
(c = 1.2, acetone); yield: 43.0 g (69%).
(-)-(1S)-2-Chloro-N-(1-phenylethyl)pyrrole (S-20): N-Chlorosuccinimide (42 g, 0.30 mol)
was added portionwise to a solution of (+)-(1S)-N-(1-phenylethyl)pyrrole (14; 51 g, 0.30 mol)
in toluene (0.50 L) at 25 °C. Once the reagent was completely dissolved, the solvent was
removed and the pale yellow oil was suspended in diethyl ether (0.20 L). The solid (21) was
collected by filtration. Gas chromatography (30 m, DB-1, 175 °C) of the ethereal mother
liquor revealed the presence of 20% of pyrrole (21). After evaporation of the solvent, the
yellow residue was distilled under reduced pressure to afford a colorless liquid; b.p. 78 -
20
20
80 °C/0.3 Torr; n = 1.563; = 1.134;
(74%).
D
d [ ] 20
4
D
D
4
α = -13.7 (c = 1.11, acetone); yield: 46.4 g
1 H NMR: δ = 7.31 (tt, J = 6.4, 1.3 Hz, 2 H), 7.25 (tt, J = 7.4, 1.3 Hz, 1 H), 7.1 (m,
2 H), 6.74 (dd, J = 3.2, 1.6 Hz, 1 H), 6.16 (t, J = 3.5 Hz, 1 H), 6.08 (dd, J = 3.5,
1.6 Hz, 1 H), 5.52 (q, J = 7.0 Hz, 1 H), 1.80 (d, J = 7.0 Hz, 3 H) ppm.
13 C NMR: δ = 142.3, 128.6, 127.4, 126.2, 117.4, 116.0, 108.0, 106.7, 54.9,
21.7 ppm.
MS: 205 (18%, M + ), 105 (100%), 106 (76%).
C12H12ClN (205.68) calcd. C 70.07% H 5.88%
found C 70.02% H 5.93%.
(+)-(1R)-2-Chloro-N-(1-phenylethyl)pyrrole (R-20): Analogously prepared from
(-)-(1S)-N-(1-phenylethyl)pyrrole (14; 51 g, 0.30 mol) and N-chlorosuccinimide (42 g, 0.30
20
20
mol); colorless liquid; b.p 86 - 88 °C/0.4 Torr; n = 1.560; d = 1.133; [ α
] = +11.0
(c = 1.11, acetone); yield: 48.9 g (79%).
D
4
20
D
20
D