T. Rische, L. Bärfacker, P. Eilbracht
FULL PAPER
1
(
3.32 g). Ϫ H NMR (400 MHz, CDCl
3
, 20°C): δ ϭ 0.89/0.94 (2
(m, 1 H), 1.63 (m, 1 H), 1.85 (m, 1 H), 2.04/2.08 (2 s, 3 H), 2.89
(s, 3 H), 3.02Ϫ3.45 (m, 6 H), 6.58Ϫ6.70 (m, 3 H), 7.17Ϫ7.26 (m,
3
3
d, J ϭ 6.7 Hz, 3 H), 1.11/1.17 (2 t, J ϭ 7.1 Hz, 3 H), 1.29 (m, 1
H), 1.56 (m, 1 H), 1.89 (m, 1 H), 2.07/2.10 (2 s, 3 H), 2.34 (m, 2 2 H). Ϫ C NMR (100 MHz, CDCl
H), 2.40 (m, 4 H), 3.03Ϫ3.40 (m, 4 H), 3.69 (t, J ϭ 4.6 Hz, 4 H). 17.2/17.4 (CH
1
3
3
, 20°C): δ ϭ 12.5/13.6 (CH
), 29.7/30.5 (CH), 30.6/30.7 (CH
), 40.5/43.4 (NCH ), 50.4/50.5 (NCH
), 112.0/112.1 (2 PhH), 115.8/116.2 (PhH), 129.0/129.1
3
),
3
3
), 21.3/21.8 (CH
), 16.7/ 37.97/37.99 (NCH
), 39.8/ 54.4 (NCH
3
2
),
13
Ϫ
C NMR (100 MHz, CDCl
6.8 (CH ), 20.6/21.1 (CH ), 29.4/29.9 (CH), 30.1/30.3 (CH
2.5 (NCH ), 49.7/53.5 (NCH ), 53.0 (2 NCH ), 55.7/56.0 (NCH
6.1 (2 CH O), 169.2/169.4 (Cq, CϭO). Ϫ GC MS (EI, 70 eV);
3
, 20°C): δ ϭ 11.8/12.9 (CH
3
3
2
2
), 50.5/
1
4
6
3
3
2
2
2
2
2
2
), (2 PhH), 148.98/149.03 (Cq), 170.1/170.3 (Cq, CϭO). Ϫ GC MS
ϩ
2
(EI, 70 eV); m/z (%): 262 [M ] (14), 120 (100), 104 (7), 77 (7), 58
ϩ
Ϫ1
m/z (%): 243 [M ϩ 1] (38), 211 (3), 156 (22), 112 (8), 100 (100),
(14). Ϫ IR (NaCl/film): ν˜ ϭ 3092 cm (w), 3059 (w), 3024 (w),
7
2
(
0 (14), 58 (19). Ϫ IR (NaCl/film): ν˜ ϭ 2958 cmϪ1 (s), 2931 (s), 2964 (s), 2930 (s), 2874 (m), 1645 (vs), 1600 (vs), 1574 (m), 1507
870 (m), 2854 (m), 2807 (m), 1647 (vs), 1456 (s), 1447 (s), 1424
s), 1377 (m), 1360 (m), 1274 (m), 1133 (m), 1118 (vs). Ϫ (m), 1121 (m), 1034 (m), 749 (s), 693 (m). Ϫ C16
C H N O
13 26 2 2
(vs), 1480 (m), 1444 (s), 1425 (s), 1372, 1272 (m), 1255 (m), 1193
O (262.4):
calcd. C 73.2, H 10.0, N 10.7; found C 72.7, H 9.7, N 10.6.
26 2
H N
(242.4): calcd. C 64.4, H 10.8, N 11.6; found C 64.2,
H 10.5, N 11.7.
N-(4-Butylamino-2-methylbutyl)-N-ethylacetamide (10f): Obtained
from 9a and n-butylamine (2j) as a colourless oil in 62% yield (2.03
N-Ethyl-N-(2-methyl-4-piperidin-1-ylbutyl)acetamide (10b): Ob-
1
3
g). Ϫ H NMR (400 MHz, CDCl
6.7 Hz, 3 H), 0.91 (t, J ϭ 7.4 Hz, 3 H), 1.10 /1.16 (2 t, J ϭ 7.1
3
, 20°C): δ ϭ 0.88/0.93 (2 d, J ϭ
tained from 9a and piperidine (2b) as a colourless oil in 82% yield
3
3
1
(
2.85 g). Ϫ H NMR (400 MHz, CDCl
3
, 20°C): δ ϭ 0.87/0.92 (2
3
3
Hz, 3 H), 1.33 (m, 3 H), 1.52 (m, 3 H), 1.92 (m, 1 H), 2.07/2.10 (2
d, J ϭ 6.7 Hz, 3 H), 1.10/1.16 (2 t, J ϭ 7.1 Hz, 3 H), 1.27 (m, 1
1
3
s, 3 H), 2.54Ϫ2.74 (m, 4 H), 3.03Ϫ3.40 (m, 4 H). Ϫ C NMR (100
MHz, CDCl , 20°C): δ ϭ 11.9/13.1 (CH ), 13.4 (CH ), 16.8/17.0
CH ), 19.9 (CH ), 20.8/21.3 (CH ), 29.3/30.2 (CH), 31.7 (CH
4.1 (CH ), 40.0/43.0 (NCH ), 47.2 (NCH ), 49.19/49.23 (NCH
0.2/53.9 (NCH
H), 1.42 (m, 1 H), 1.61 (m, 6 H), 1.85 (m, 1 H), 2.07/2.10 (2 s, 3
H), 2.25 (m, 2 H), 2.38 (m, 4 H), 3.01Ϫ3.49 (m, 4 H). Ϫ 1 C NMR
3
3
3
3
(
3
5
3
2
3
2
),
),
(
2
3
100 MHz, CDCl
3
, 20°C): δ ϭ 12.4/13.5 (CH
), 24.21/24.23 (CH ), 25.8 (2 CH
), 40.4/43.2 (NCH ), 50.5/54.2 (NCH
), 170.0/170.1 (Cq, CϭO). Ϫ GC MS
3
), 17.3/17.4 (CH
), 30.3/31.0 (CH),
), 54.44/54.45
3
),
1.3/21.7 (CH
1.2/31.3 (CH
3
2
2
2
2
2
2
2
), 169.5/169.7 (Cq, CϭO). Ϫ GC MS (EI, 70 eV);
2
2
2
ϩ
m/z (%): 229 [M ϩ 1] (100), 156 (9), 140 (4), 112 (14), 100 (7), 58
(18). Ϫ IR (NaCl/film): ν˜ ϭ 3306 cm (m), 2959 (s), 2930 (s), 2873
(
(
8
(
2 NCH
EI, 70 eV); m/z (%): 241 [M ϩ 1] (30), 154 (3), 112 (8), 98 (100),
4 (8), 70 (8), 58 (11). Ϫ IR (NaCl/film): ν˜ ϭ 2932 cmϪ1 (s), 2874
m), 2853 (m), 1648 (vs), 1442 (s), 1424 (s), 1377 (m), 1356 (w),
271 (m). Ϫ C14 O (240.4): calcd. C 69.9, H 11.8, N 11.7;
2
), 56.8/57.1 (NCH
2
Ϫ1
ϩ
(s), 2814 (m), 1644 (vs), 1457 (s), 1425 (s), 1379 (s), 1366 (m), 1271
(
28 2
m), 1126 (m), 1096 (m), 1033 (m), 732 (m). Ϫ C13H N O (228.4):
calcd. C 68.4, H 12.4, N 12.3; found C 68.1, H 12.2, N 12.5.
1
28 2
H N
found C 69.5, H 11.5, N 11.8.
N-Ethyl-N-(4-isopropylamino-2-methylbutyl)acetamide (10g): Ob-
tained from 9a and isopropylamine (2k) as a colourless oil in 64%
N-Ethyl-N-(2-methyl-4-pyrrolidin-1-ylbutyl)acetamide (10c): Ob-
1
yield (1.98 g). Ϫ H NMR (400 MHz, CDCl
3
, 20°C): δ ϭ 0.88/
tained from 9a and pyrrolidine (2h) as a colourless oil in 90% yield
3
3
0
.93 (2 d, J ϭ 6.6 Hz, 3 H), 1.05 (d, J ϭ 7.3 Hz, 3 H), 1.06 (d,
1
(
2.92 g). Ϫ H NMR (400 MHz, CDCl
3
, 20°C): δ ϭ 0.89/0.94 (2
3
3
J ϭ 7.3 Hz, 3 H), 1.11/1.16 (2 t, J ϭ 7.1 Hz, 3 H), 1.27 (m, 1 H),
.53 (m, 1 H), 1.82 (m, 1 H), 2.07/2.10 (2 s, 3 H), 2.53Ϫ2.80 (m, 3
3
3
d, J ϭ 6.7 Hz, 3 H), 1.10/1.16 (2 t, J ϭ 7.1 Hz, 3 H), 1.32 (m, 1
H), 1.62 (m, 1 H), 1.77 (m, 4 H), 1.90 (m, 1 H), 2.07/2.10 (2 s, 3
H), 2.43 (m, 2 H), 2.48 (m, 4 H), 3.03Ϫ3.42 (m, 4 H). Ϫ 1 C NMR
1
1
3
H), 3.03Ϫ3.40 (m, 4 H). Ϫ C NMR (100 MHz, CDCl
δ ϭ 12.3/13.4 (CH ), 17.1/17.3 (CH ), 21.2/21.6 (CH ), 22.61/22.70
CH ), 22.74/22.78 (CH ), 29.7/30.6 (CH), 34.7/34.8 (CH ), 40.3/
3.3 (NCH ), 44.96/44.99 (NCH ), 48.5 (NCH), 50.5/54.2 (NCH ),
69.9/170.1 (Cq, CϭO). Ϫ GC MS (EI, 70 eV); m/z (%): 215 [M
3
, 20°C):
3
3
3
3
(
2
(
5
100 MHz, CDCl
1.2/21.6 (CH ), 23.05 (CH
CH ), 40.3/43.2 (NCH ), 50.4/53.5 (NCH
3.9 (2 NCH ), 169.9/170.1 (Cq, CϭO). Ϫ GC MS (EI, 70 eV);
3
, 20°C): δ ϭ 12.3/13.4 (CH
), 23.07 (CH ), 30.1/30.8 (CH), 33.3
), 53.84/54.02 (NCH ),
3 3
), 17.2/17.2 (CH ),
(
3
3
2
3
2
2
4
1
2
2
2
ϩ
2
2
2
2
2
ϩ 1] (100), 171 (4), 156 (21), 126 (8), 112 (47), 100 (11), 84 (10),
ϩ
m/z (%): 227 [M ] (39), 140 (3), 112 (6), 84 (100), 70 (3), 58 (6). Ϫ
IR (NaCl/film): ν˜ ϭ 2961 cm (vs), 2931 (vs), 2873 (s), 2855 (s),
Ϫ1
7
2
1
2 (17), 58 (75). Ϫ IR (NaCl/film): ν˜ ϭ 3305 cm (w), 2965 (s),
Ϫ1
930 (s), 2873 (m), 1645 (vs), 1456 (s), 1444 (s), 1425 (s), 1379 (m),
363 (m), 1272 (m), 1033 (m). Ϫ C12H N O (214.4): calcd. C 67.2,
26 2
2805 (s), 1643 (vs), 1480 (m), 1456 (vs), 1425 (vs), 1379 (m), 1361
(m), 1274 (m), 1118 (s), 1033 (m).
H 12.2, N 13.1; found C 66.9, H 11.9, N 13.2.
N-(4-Diethylamino-2-methylbutyl)-N-ethylacetamide (10d): Ob-
N-(4-Benzamino-2-methylbutyl)-N-ethylacetamide (10h): Obtained
from 9a and benzylamine (2d) as a yellow oil in 80% yield (3.00 g).
tained from 9a and diethylamine (2c) as a colourless oil in 82%
1
yield (2.70 g). Ϫ H NMR (400 MHz, CDCl
3
, 20°C): δ ϭ 0.88/
1
3
Ϫ H NMR (400 MHz, CDCl
3
, 20°C): δ ϭ 0.86/0.90 (2 d, J ϭ
3
3
0
.93 (2 d, J ϭ 6.5 Hz, 3 H), 1.01 (t, J ϭ 6.5 Hz, 6 H), 1.11/1.17
2 t, J ϭ 7.1 Hz, 3 H), 1.23 (m, 1 H), 1.52 (m, 1 H), 1.84 (m, 1
3
6
.6 Hz, 3 H), 1.09/1.13 (2 t, J ϭ 7.1 Hz, 3 H), 1.27 (m, 1 H), 1.52
3
(
(
(
(
(
(
(
m, 1 H), 1.90 (m, 1 H), 2.04/2.08 (2 s, 3 H), 2.60 (m, 2 H), 2.83
m, 2 H), 3.01Ϫ3.37 (m, 4 H), 3.766/3.773 (2 s, 2 H), 7.22Ϫ7.31
H), 2.07/2.11 (2 s, 3 H), 2.35 (m, 2 H), 2.49 (m, 4 H), 3.02Ϫ3.38
(
m, 4 H). Ϫ 13C NMR (100 MHz, CDCl
3
, 20°C): δ ϭ 11.0 (2 CH
3
),
),
13
m, 5 H). Ϫ C NMR (100 MHz, CDCl
3
, 20°C): δ ϭ 12.3/13.5
), 29.7/30.4 (CH), 34.4
), 46.8/46.9 (NCH ), 50.5/54.2 (CH ), 53.9
Ph), 126.5/126.6 (PhH), 127.8 (2 PhH), 128.1 (2 PhH),
40.1/140.3 (Cq), 170.0/170.1 (Cq, CϭO). Ϫ GC MS (EI, 70 eV);
1
3
5
1.9/13.1 (CH
1.0 (CH ), 40.0/42.7 (NCH
0.0 (NCH
3
), 16.8/16.9 (CH
3
), 20.8/21.3 (CH
3
), 29.6/30.2 (CH),
CH
CH
3
), 17.1/17.3 (CH
), 40.4/43.3 (NCH
3 3
), 21.2/21.7 (CH
2
2
), 46.1 (2 NCH
), 49.9/53.9 (NCH
2 2
2
2
2
2
2
), 169.5/169.6 (Cq, CϭO). Ϫ GC MS (EI, 70 eV); m/z
NCH
2
ϩ
(%): 229 [M ϩ 1] (50), 156 (7), 112 (7), 86 (100), 72 (6), 58 (14).
1
Ϫ1
Ϫ IR (NaCl/film): ν˜ ϭ 2968 cm (vs), 2932 (s), 2873 (m), 2799
m), 1649 (vs), 1446 (s), 1424 (s), 1380 (m), 1272 (m), 1122 (w),
073 (w), 1033 (w). Ϫ C13 O (228.4): calcd. C 68.4, H 12.4,
ϩ
m/z (%): 263 [M ϩ 1] (33), 171 (11), 156 (10), 120 (7), 112 (28),
(
1
Ϫ1
9
1 (50), 84 (10), 65 (8), 58 (36). Ϫ IR (NaCl/film): ν˜ ϭ 3307 cm
w), 3061 (w), 3026 (w), 2965 (m), 2929 (m), 2873 (w), 1644 (vs),
478 (w), 1453 (m), 1425 (m), 1272 (w), 737 (w), 699 (w). Ϫ
O (262.4): calcd. C 73.2, H 10.0, N 10.7; found C 73.0,
H 9.8, N 10.7.
28 2
H N
(
1
N 12.3; found C 67.8, H 11.7, N 12.1.
16 26 2
C H N
N-(4-Benzylamino-2-methylbutyl)-N-ethylacetamide (10e): Ob-
tained from 9a and N-methylaniline (2i) as an orange oil in 86%
1
yield (3.25 g). Ϫ H NMR (400 MHz, CDCl
0
3
, 20°C): δ ϭ 0.93/ N-Ethyl-N-(2-methyl-4-phenylaminobutyl)acetamide (10i): Obtained
3
3
.98 (2 d, J ϭ 6.8 Hz, 3 H), 1.08/1.12 (2 t, J ϭ 7.0 Hz, 3 H), 1.34 from 9a and aniline (2e) as an orange oil in 92% yield (3.27 g). Ϫ
658 Eur. J. Org. Chem. 1999, 653Ϫ660