¨
D. Donnecke, W. Imhof / Tetrahedron 59 (2003) 8499–8507
8506
3
3JHH¼5.0 Hz, 1H, vCH), 6.43 (d, JHH¼5.0 Hz, 1H,
vCH), 7.17–7.56 (m, 10H, Ph). 13C NMR (CDCl3,
298 K, 50.32 MHz) [ppm]: d¼13.96 (CH3), 22.45 (CH2),
24.58 (CH2), 31.96 (CH2), 38.53 (CH2), 45.73 (CH2), 57.90
(C), 114.06 (CH), 126.69 (CH), 126.99 (CH), 127.68 (CH),
127.81 (CH), 128.48 (CH), 128.75 (CH), 130.79 (CH),
136.79 (C), 140.16 (C), 179.68 (CvO).
3JHC¼5.0 Hz, 3JHH¼4.9 Hz, 1H, vCH), 7.16–7.51 (m, 5H,
Ph). 13C NMR (CDCl3, 298 K, 50.32 MHz) [ppm]: d¼9.25
(CH3), 28.96 (CH2), 31.38 (NCH3), 58.16, (d, 1JCC¼48 Hz,
C), 113.19 (d, 2JCC¼3 Hz, CH), 126.78 (CH), 126.97 (CH),
2
128.40 (CH), 132.56 (d, JCC¼9 Hz, CH), 139.99 (C),
179.93 (13CvO).
4.1.11. 1-Methyl-2-ethyl-3-phenyl-pyrrole (4e). C13H15N
GC–MS: m/z (%): 185 (Mþ, 100), 170 (Mþ2CH3, 93); IR
(KBr disk, neat) [cm21]: n¼3067 m, 3038 w, 2975 s, 2947 s,
2891 m, 1603 m, 1501 vs, 1416 m, 1352 s, 1247 s, 931 w,
762 m, 695 vs. 1H NMR (CDCl3, 298 K, 200 MHz) [ppm]:
4.1.6. 1-Benzyl-2-pentyl-3-phenyl-pyrrole (4c, n-isomer).
1H NMR (CDCl3, 298 K, 200 MHz) [ppm]: d¼6.35 (d,
3
3JHH¼2.9 Hz, 1H, vCH), 6.64 (d, JHH¼2.9 Hz, 1H,
vCH).
3
3
d¼1.25 (t, JHH¼7.5 Hz, 3H, CH3), 2.74 (q, JHH¼7.4 Hz
3
4.1.7. 1,3-Dihydro-1-benzyl-3-hexyl-3-phenyl-2H-
pyrrol-2-one (3d). HRMS calcd for C23H27NO (Mþ)
333.2091; found 333.2084, D¼0.7 mmu; MS (EI): m/z
(%): 333 (Mþ, 40), 249 (Mþ2C6H12, 53), 248 (Mþ2C6H13,
48), 91 (C7Hþ7 , 100); IR (KBr disk, neat) [cm21]: n¼3086
w, 3062 m, 3029 m, 2954 m, 2929 m, 2857 m, 1698 s, 1605
m, 1495 m, 1454 m, 1394 m, 1357 m, 1269 m, 1077 w, 1030
w, 698 s. 1H NMR (CDCl3, 298 K, 400 MHz) [ppm]:
2H, CH2), 3.62 (s, 3H, NCH3), 6.23 (d, JHH¼2.8 Hz, 1H,
3
vCH), 6.57 (d, JHH¼2.8 Hz, 1H, vCH), 7.15–7.41 (m,
5H, Ph). 13C NMR (CDCl3, 298 K, 100.65 MHz) [ppm]:
d¼14.83 (CH3), 17.89 (CH2), 33.74 (NCH3), 107.31 (CH),
120.83 (C), 121.79 (CH), 125.13 (CH), 127.89 (CH), 128.27
(CH), 131.21 (C), 137.65 (C).
4.1.12. 1-Methyl-2-ethyl-3-phenyl-pyrrole (4e 13C
labeled). 13C1C13H15N GC MS: m/z (%): 186 (Mþ, 100),
171 (Mþ2CH3, 93); IR (KBr disk, neat) [cm21]: n¼3059
m, 3028 w, 2966 s, 2930 s, 2873 m, 1601 m, 1503 vs, 1412
m, 1352 s, 1245 s, 929 w, 766 m, 699 vs. 1H NMR (CDCl3,
3
d¼0.83 (t, JHH¼6.7 Hz, 3H, CH3), 1.19 (m, 8H, 4CH2),
1.98 (m, 2H, CH2), 4.60 (m, 2H, CH2Ph), 5.63 (d,
3
3JHH¼5.0 Hz, 1H, vCH)), 6.42 (d, JHH¼5.0 Hz, 1H,
vCH)), 7.13–7.48 (m, 10H, Ph). 13C NMR (CDCl3, 298 K,
100.65 MHz) [ppm]: d¼14.05 (CH3), 22.52 (CH2), 24.86
(CH2), 29.44 (CH2), 31.61 (CH2), 38.54 (CH2), 45.70
(CH2), 57.89 (C), 114.07 (CH), 126.67 (CH), 126.99 (CH),
127.67 (CH), 127.79 (CH), 128.48 (CH), 128.74 (CH),
130.77 (CH), 136.75 (C), 140.11 (C), 179.8 (CvO).
3
298 K, 200 MHz) [ppm]: d¼1.2 (dt, JHC¼4.9 Hz,
2
3
3JHH¼7.5 Hz, 3H, CH3), 2.69 (dq, JHC¼6 Hz, JHH
¼
3
7.5 Hz, 2H, CH2), 3.58 (d, JHC¼2.5 Hz, 3H, NCH3), 6.19
3
3
(dd, JHC¼5.9 Hz, JHH¼2.8 Hz, 1H, vCH), 6.53 (dd,
3JHC¼5.3 Hz, 3JHH¼2.8 Hz, 1H, vCH), 7.10–7.38 (m, 5H,
Ph). 13C NMR (CDCl3, 298 K, 100.65 MHz) [ppm]:
2
1
4.1.8. 1-Benzyl-2-hexyl-3-phenyl-pyrrole (4d, n-isomer).
1H NMR (CDCl3, 298 K, 200 MHz) [ppm]: d¼6.29 (d,
d¼14.81 (d, JCC¼1.5 Hz, CH3), 17.87 (d, JCC¼51 Hz,
2
CH2), 33.73 (NCH3), 107.31 (d, JCC¼2 Hz, CH), 120.81
3JHH¼2.9 Hz, 1H, vCH), 6.59 (d, JHH¼2.9 Hz, 1H,
(d, 2JCC¼7.3 Hz, CH), 121.72 (d, 1JCC¼69.8 Hz, C), 125.12
(CH), 127.88 (CH), 128.26 (CH), 131.2 (13C), 137.65 (d,
2JCC¼4 Hz, C).
3
vCH).
4.1.9. 1,3-Dihydro-1-methyl-3-ethyl-3-phenyl-2H-
pyrrol-2-on (3e). HRMS calcd for C13H15NO (Mþ)
201.1182; found 201.1168, D¼1.4 mmu; MS (EI): m/z
(%): 201 (Mþ, 100), 172 (Mþ2C2H5, 91); IR (KBr disk,
neat) [cm21]: n¼3088 m, 3059 m, 3024 m, 2967 s, 2934 s,
2877 m, 1697 vs, 1610 m, 1495 m, 1456 m, 1386 s, 1316 s,
1266 m, 1071 m, 1055 m, 769 m, 697 s. 1H NMR (CDCl3,
4.1.13. 1,5-Dihydro-1-methyl-4-phenyl-5-hydroxy-5-
ethyl-pyrrol-2-one (E). C13H15NO2 MS: m/z (%): 217
(Mþ,8), 188 (Mþ2C2H5, 100); IR (KBr pellet) [cm21]:
n¼3171 br, 3054 w, 2972 m, 2935 w, 2878 w, 2831 w, 1686
vs, 1665 s, 1434 s, 1095 s, 1042 m, 857 m, 777 s, 698 m. 1H
NMR (CDCl3, 298 K, 400 MHz) [ppm]: d¼0.48 (t,
3JHH¼7.5 Hz, 3H, CH3), 2.01 (m, 2H, CH2), 2.50 (s, 1H,
OH), 2.88 (s, 3H, NCH3), 6.33 (s, 1H, vCH), 7.41(m, 3H,
Ph), 7.79 (m, 2H, Ph). 13C NMR (CDCl3, 298 K,
100.65 MHz) [ppm]: d¼7.31 (CH3), 23.06 (NCH3), 27.19
(CH2), 93.84 (C), 121.63 (CH), 127.38 (CH), 128.87 (CH),
130.12 (CH), 130.99 (C), 157.78 (C), 168.86 (CvO).
3
298 K, 200 MHz) [ppm]: d¼0.82 (t, JHH¼7.4 Hz, 3H,
CH3), 2.02 (q, 3JHH¼7.4 Hz 2H, CH2), 3.01 (s, 3H, NCH3),
3
3
5.64 (d, JHH¼5.0 Hz, 1H, vCH), 6.48 (d, JHH¼5.0 Hz,
1H, vCH), 7.21–7.52 (m, 5H, Ph). 13C NMR (CDCl3,
298 K, 50.32 MHz) [ppm]: d¼9.12 (CH3), 28.78 (CH2),
31.25 (NCH3), 58.00 (C), 113.00 (CH), 126.65 (CH), 126.82
(CH), 128.27 (CH), 132.46 (CH), 139.88 (C), 179.76
(CvO).
4.1.14. 1,3-Dihydro-1-methyl-3-propyl-3-phenyl-2H-
pyrrol-2-one (3f, mixture of n/iso isomers 56/44).
HRMS calcd for C14H17NO (Mþ) 215.1330; found
215.1320, D¼1.0 mmu; MS (DI, H2O): m/z (%): 215 (Mþ,
58), 172 (Mþ2C3H7, 100) 42 (OCNþ 66); IR (KBr disk,
neat) [cm21]: n¼3087 w, 3060 w, 3024 w, 2961 s, 2934 m,
2873 m, 1699 vs, 1610 m, 1495 m, 1446 m, 1386 s, 1307 m,
4.1.10. 1,3-Dihydro-1-methyl-3-ethyl-3phenyl-2H-
pyrrol-2-one (3e 13C labeled). HRMS calcd for
13C1C12H15NO (Mþ) 202.1211; found 202.1199,
D¼1.2 mmu; MS (EI): m/z (%): 202 (Mþ, 60), 173
(Mþ2C2H5, 100); IR (KBr disk, neat) [cm21]: n¼3088
m, 3059 m, 3024 m, 2968 s, 2934 s, 2878 m, 1652 vs, 1610
m, 1495 m, 1456 m, 1384 s, 1314 s, 1266 m, 1071 m, 1052
m, 768 m, 698 s. 1H NMR (CDCl3, 298 K, 200 MHz) [ppm]:
d¼0.80 (t, 3JHH¼7.4 Hz, 3H, CH3), 2.00 (m, 3JHC¼4.2 Hz,
3JHH¼7.4 Hz, 2H, CH2), 3.01 (d, 3JCH¼2.8 Hz, 3H, NCH3),
5.63 (dd, 3JHC¼6.9 Hz, 3JHH¼4.9 Hz, 1H, vCH), 6.49 (dd,
1
1272 m, 1080 m, 969 w, 969 w, 765 m, 698 s. H NMR
(CDCl3, 298 K, 200 MHz) [ppm]: d¼0.75 (d, 3JHH¼6.8 Hz,
3
3H, CH3), 0.84 (d, JHH¼6.8 Hz, 3H, CH3), 0.86 (t,
3JHH¼6.6 Hz, 3H, CH3), 1.17 (m 2H, CH2), 1.95 (m 2H,
CH2), 2.46 (m 1H, CH), 2.96 (s, 3H, NCH3), 3.00 (s, 3H,
NCH3), 5.64 (d, JHH¼5.0 Hz, 1H, vCH), 5.66 (d,
3