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H. Möhrle - J. Mehrens • Cyclisierungen über Enamin-Zwischenstufen bei Amindehydrierungen
Hg(II)-EDTA-Dehydrierung von 4'-(Perhydroazepin-1-
yl)acetophenon (9a)
26.02/25.86 (CH3); 31.88 / 26.46 / 25.41 / 24.83 / 24.73
(C-3"-7").
Nach AV 1 [13]: 1.00 g (4.61 mmol) 9a in 40 ml Was- C26H30N2O2 (402.5)
ser/Ethanol (1+1); 5 h. Hg-Abscheidung: 0.49 g (53%
bez. auf 2 Ox.-Äq.). SC: 721 mg (72%) 9a; 81 mg (8%)
12a (Kieselgel, Länge 25 cm, Durchmesser 2 cm, Chlo-
roform).
6-(4-Acetylphenylamino)hexanal (12a): Gelbliches
Öl; wurde mit Dianilinoethan [15] in 79-proz. Ausbeute
überführt in
4'-[5-(l,3-Diphenyl-2-imidazolidinyl)pentylamino]-
acetophenon: Weiße Kristalle. Schmp. 128 - 130 °C. -
IR (KBr): 3310; 3030; 1655; 1600 cm“ 1. - MS (130 °C):
m/z(%) = 223 (10); 119(34); 104 (15); 91 (100); 77 (45).
- 'H-NMR (CDC13): 6 (ppm) = 7.78 ('d', 2H, 2’-H + 6'-H,
7' = 8.8); 7.37 - 7.05 (m, 4H, 2- Ph 3/5-H); 6.84 - 6.58
(m, 6H, 2-Ph 2/4/6-H); 6.44 (d, 2H, 3’-H + 5'-H, 'J' =8.8);
5.42 ('t', 1H, N-CH-N,V = 3.3); 4.10-3.90 (m, 1H, NH,
aust.); 3.75 - 3.48 (m, 4H, N-CH2-CH2-N); 3.10 - 2.90
(m, 2H, 1"-H2); 2.47 (s, 3H, CH3); 2.10 - 1.75 (m, 2H,
5"-H2); 1.70- 1.10 (m, 6H, 2”-4"-H2).
Ber. C 77.58 H7.51 N 6.96%,
Gef. C 77.53 H 7.52 N 6.76%.
4',4"-[3,3'-Methylendi( 1,4,5,6-tetrahydro-1-pyridyl)]-
diacetophenon (19a): Rosafarbenes Pulver. - IR (KBr):
2920; 2850; 1650; 1595 cm-1. - MS (120 °C): m/z(%) =
414 (32; M+); 413 (14); 214 (56); 213 (100); 207 (21);
200 (29); 148 (38); 146 (33); 119 (21); 91 (41); 77 (39);
Strukturen der Fragmente [12]. - 'H-NMR (CDC13): 6
(ppm) = 7.88 (’d', 4H, 2-[2-H + 6 -H, arom.], 7' = 9.0);
6.85Cd’, 4H, 2-[3-H + 5-H, arom.],7' = 9.0); 6.52 (s, 2H,
2-2-H, Pip); 3.57 - 3.40 (m, 4H, 2-6-H2, Pip); 2.78 (s, 2H,
Brücken-CH,); 2.52 (s, 6 H, 2-CH3); 2.05 - 1.90 (m, 8H,
2 [4-H2 + 5-H2, Pip]).
C27H30N2O2 (414.5).
Hg(ll)-EDTA-Dehydrierung von 4-Piperidinobenzonitril
(10 b)
QgH^N^O (426.6)
Nach AV 1 [13]: 1.00 g (5.38 mmol) 10b [16]; 4 h. De-
hydrierung und Aufarbeitung unter Lichtausschluß! Hg-
Abscheidung: 2.00 g (186% bez. auf 2 Ox.-Äq.). SC:
185 mg (19%) 10b; 94 mg (9%) 16b; 90 mg (9%) 19b
(Kieselgel, Länge 50 cm, Durchmesser 3 cm, Chloro-
form).
Ber. C 78.65 H 7.78 N 9.83%,
Gef. C 78.86 H 7.70 N 9.92%.
Hg(II)-EDTA-Dehydrierung von 4'-Piperidinoaceto-
phenon (10a)
Nach AV 1 [13]: 1.00 g (4.93 mmol) 10a; 1 h. Dehy-
drierung und Aufarbeitung unter Lichtausschluß! Hg-Ab-
scheidung: 0.93 g (94% bez. auf 2 Ox.-Äq.). SC: 138 mg
(14%) 10a; 460 mg (46%) 16a; 4 mg (0.4%) 19a (Kiesel-
gel, Länge 55 cm, Durchmesser 3 cm, Chloroform).
4'-(12-Acetyl-l,3,4,4a,4b,5,6,7,8,13b-decahydro-2H-
benzo[h]pyrido[2.1-f][1.6]naphthyridin-l -yl)-
acetophenon (16a): Hellbeiges Pulver aus Tolu-
ol/Petrolether 40/60 °C. Schmp. 157 - 159 °C. - IR (KBr):
3050; 2930; 2855; 1660; 1590 cm“ 1. - MS (150 °C):
m/z(%) = 402 (2; M+); 373 (0.1); 226 (100); 148 (6); 43
(21); Strukturen der Fragmente [12], - 'H-NMR (CDC13):
6 (ppm) = 7.89 (dd, 2H, 2’-H + 6’-H, V = 7.3, 4J = 1.9);
7.78 (dd, 1H, 11"-H, 3i = 8.8, V = 2.2); 7.61 - 7.60 (m,
4-(12-Cyan-l,3,4,4a,4b,5,6,7,8,13b-decahydro-2H-
benzo[h]-pyrido[2.1-f][1.6Jnaphthyridin-1-yl)benzo-
nitril (16b): Hellbeiges Pulver. Schmp. 110 - 115 °C. -
IR (KBr): 2930; 2850; 2210; 1600 cm "1. - MS (180 °C):
m/z(%) =368 (6 ; M+); 339 (0.2); 209 (100); 131 (13); 102
(9); Strukturen der Fragmente [12], - 1H-NMR (CDC13):
6 (ppm) = 7.60 - 7.08 (m, 4H, 2-H, 6-H, 1l’-H, 13'-H);
6.95 - 6.60 (m, 3H, 3-H, 5-H, 10'-H); 5.03 (d, 1H, 13b’-H,
-V = 5.1); 4.20 - 3.55 (m, 2 H, 2’-Heq, 8’-Heq); 3.25 - 2.75
(m, 3H, 2’-Hax, 4b'-Hax, 8'-Hax); 2.15-1.20 (m, 11H, 3’-
7'-H2 + 4a'-H).
C24H24N4 (368.5).
4,4'-[3,3 '-Methylendi(1,4,5,6-tetrahydro-1-pyridyl)]-
1H, 13"-H); 6.93 (dd, 2H, 3'-H + 5'-H, V = 7.3, 4J = dibenzonitril (19b): Hellrosa Kristalle. Schmp. 199 -
1.9); 6.75 (d, 1H, 10"-H, 3/ = 8.8); 5.18 (d, 1H, 13b"- 201 °C (Isopropanol). - IR (KBr): 2960; 2930; 2890;
H, 37 = 5.1); 4.13 ('d', 1H, 8"-Heq?, 2J = 13.9); 3.80 ('d',
1H, 2"-Heq?, 2J = 13.4); 3.14 - 2.92 (m, 3H, 2"-Hax, 8"-
Hax, 4b"-H); 2.52/2.34 (2s, 2-3H, 2-CH3); 2.02 - 1.39 (m,
11H, 3"-7"-H2 + 4a"-H). - ,3C-NMR (CDC13, DEPT):
6 (ppm) = 196.14/196.07 (CO); 154.41 (C-4'); 148.75
(C-9a"); 130.92 (C-2’ + C-6’); 129.53 (C-l3"); 128.35
(C-l 1"); 126.78 (C-l’); 125.94 (C-12"); 118.93 (C-13aM);
112.56 (C-3’ + C-5’); 110.83 (C-10”); 63.16 (C-13b");
53.12 (C-4b"); 48.74 (C-8"); 41.85 (C-2"); 38.04 (C-4a");
2870; 2210; 1655; 1590cm "'.-M S (220°C): m/z(%) =
380* (31; M+); 379 (12); 197 (40); 196* (100); 190(37);
183(14); 131 (26); 129* (50); 102* (67);91 (14); 77 (14);
* Hochauflösungen; Strukturen der Fragmente [12]. D O -
MS (NH3): m/z(%) = 398 ([M+NH4]+); 381 ([M+H]+). -
1H-NMR (CDCI3): 6 (ppm) = 7.48 ('d', 4H, 2-[2-H + 6-H,
arom.], 7' = 9.1); 6.85 ('d', 4H, 2-[3-H + 5-H, arom.], 7' =
9.1); 6.47 (s, 2H, 2-2-H, Pip); 3.48 (T, 4H, 2-6-H2, Pip,
7' = 5.5); 2.78 (s, 2H, Brücken-CH2); 2.05-1.95 (m, 8H,
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