Chirale Ionische Flüssigkeiten in der homogenen Katalyse

51a
Experimenteller Teil
N-[1-(4-Brom-phenyl)-2-methylen-3-oxo-butyl]-4-methyl-benzensulfonamid
C18H18BrN2O5S, 374.41
1 H-NMR (300 MHz, [D6]-DMSO): = 2.35 (s, 3H, CH3), 2.61 (s, 3H, CH3), 5.33 (s, 1H, CH), 6.12 (s,
1H, C=CH2), 6.26 (s, 1H, C=CH2), 6.99 (d, 2H, J = 8.5 Hz, Ar), 7.26 (d, 2H, J = 8.5 Hz, Ar), 7.37 (d,
2H, J = 8.3 Hz, Ar), 7.50 (d, 2H, J = 8.3 Hz, Ar) ppm.
13 C-NMR (75.5 MHz, [D6]-DMSO): = 20.9 (CH3), 21.0 (CH3), 46.7 (CH), 121.2, 125.6, 126.3, 128.2,
128.9, 129.3, 131.1, 135.5, 137.8, 142.6, 197.8 (CO) ppm.
TLC: Rf = 0.37 (Laufmittel: Pentan/Ethylacetat = 2/1)
HPLC: Daicel Chiralcel OD-H, 223 nm, Heptan / Isopropanol = 85/15, Flußrate 0.5 ml/min,
t(S) = 31.4 min, t(R) = 35.1 min.
51b
4-Methyl-N-[2-methylen-1-(4-nitro-phenyl)-3-oxo-butyl]-benzensulfonamid
C18H18BrN2O5S, 374.41
1 H-NMR (300 MHz, CDCl3): = 2.09 (s, 3H, CH3), 2.34 (s, 3H, CH3), 5.26 (s, 1H, CH od. NH), 6.02 (s,
1H, C=CH2), 6.07 (s, 1H, C=CH2), 6.19 (s, 1H, CH od. NH), 6.73 (d, 2H, J = 8.3 Hz, Ar), 7.58 (d, 2H,
J = 8.3 Hz, Ar), 7.99 (d, 2H, J = 8.8 Hz, Ar), 8.12 (d, 2H, J = 8.8 Hz, Ar) ppm.
13 C-NMR (75.5 MHz, CDCl3): = 21.5 (CH3), 25.6 (CH3), 46.4 (CH), 115.5, 119.9, 123.6, 127.2, 127.9,
129.6, 129.7, 131.5, 135.7, 156.5, 198.8 (CO) ppm.
TLC: Rf = 0.24 (Laufmittel: Pentan/Ethylacetat = 2/1)
HPLC: Chiralpack IA, 223 nm, Heptan / Ethanol = 80/20, Fließrate 0.7 ml/min, t(S) = 39.6 min,
t(R) = 61.1 min.
51c
N-(2-Methylen-3-oxo-1-phenyl-butyl)-4-nitro-benzensulfonamid
C17H16N2O5S, 360.38
1 H-NMR (600 MHz, [D6]-DMSO): = 2.17 (s, 3H, CH3), 3.59 (m, 1H, NH) 5.49 (s, 1H, C=CH2), 6.07 (s,
1H, C=CH2), 6.29 (s, 1H, CH), 7.07 (d, 2H, J = 7.7 Hz, Ar), 7.16 (d, 2H, J = 7.7 Hz, Ar), 7.88 (d, 2H,
J = 8.9 Hz, Ar), 8.28 (d, 2H, J = 8.9 Hz, Ar), 8.41 (m, 1H, Ar) ppm.
13 C-NMR (150.9 MHz, [D6]-DMSO): = 26.4 (CH3), 55.9 (CH), 124.9, 125.1, 127.8, 128.7, 128.9,
129.4, 132.2, 139.9, 147.9, 150.1, 198.4 (CO) ppm.
128