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Helvetica Chimica Acta Vol. 88 (2005)
(s); 47.2 (t); 62.6 (t); 66.8 (t); 77.1 (t); 80.4 (s); 122.4 (d); 126.9 (d); 127.0( d); 129.4 (br. d); 137.8 (s); 152.5 (s);
153.7 (s). Anal. calc. for C21H30N4O3 (386.49): C 65.25, H 7.82, N 14.50; found: C 65.5, H 7.9, N 14.3.
2.3. 5-(3,3-Dimethyl-2-phenylbut-1-enyl)-1-(4-nitrophenyl)-1H-1,2,3-triazole (4a). A soln. of 3a (340mg,
0.78 mmol) in 50% aq. AcOH (40 ml) was heated under reflux. When a homogeneous soln. had formed, it was
cooled to 08 whereupon an orange solid appeared. Precipitation was completed by addition of H2O (10ml), and
the solid was filtered off. Recrystallization from MeCN gave 4a (220mg, 81%). Deep-red needles. M.p. 117 8. IR
(KBr): 1590s, 1485s, 1340vs, 1255m, 1070s, 965s, 850vs. 1H-NMR (CDCl3): 1.16 (s, t-Bu); 6.28 (s, 1 H, CH); 6.36
3
(s, 1 H, CH); 7.08 (m, 3 arom. H); 7.41 (m, 2 arom. H); 7.76, 8.45 (AA'BB', J 8.9, NO2ÀC6H4). 13C-NMR
(CDCl3): 29.0( q); 37.2 (s); 108.3 (d); 124.7 (d); 125.7 (d); 127.6 (d); 128.3 (d); 128.5 (d); 132.7 (d, J 198, C(4));
134.7 (d, J 15, C(5)); 138.6 (s); 141.1 (s); 147.5 (s); 159.4 (s). Anal. calc. for C20H20N4O2 (348.40): C 68.95, H
5.79, N 16.08; found: C 69.0, H 5.9, N 16.3.
2.4. 5-(3,3-Dimethyl-2-phenylbut-1-enyl)-1-phenyl-1H-1,2,3-triazole (4d). A soln. of 1 (361 mg, 1.33 mmol)
and phenyl azide (2d; 159 mg, 1.33 mmol) in CHCl3 (2 ml) was stirred at r.t. for 24 h. The solvent was evaporated
and the residue purified by CC (Lobar column, Et2O/petroleum ether 6 :4). Crystallization from Et2O yielded
4d (255 mg, 63%). Colorless needles. M.p. 1018. IR (KBr): 2950s, 1590s, 1490vs, 1450m, 1350s, 1255s, 1200s,
1125m, 1090s, 1065s, 970s, 835s. 1H-NMR (CDCl3): 1.11 (s, t-Bu); 6.16 (s, 1 H, CH); 6.33 (s, 1 H, CH); 7.07
(m, 2 arom. H); 7.39 7.58 (m, 8 arom. H). 13C-NMR (CDCl3): 29.1 (q); 37.1 (s); 109.2 (d); 125.5 (d); 127.6 (d);
128.6 (d, 2 coinciding signals); 129.3 (d, 2 coinciding signals); 132.0( d, J 197, C(4)); 132.6 (d, J 15, C(5));
136.2 (s); 139.2 (s); 157.7 (s). Anal. calc. for C20H21N3 (303.41): C 79.17, H 6.98, N 13.85; found: C 79.3, H 7.1, N
13.7.
2.5. N-(4,4-Dimethyl-1-morpholino-3-phenylpent-2-enylidene)-4-methylbenzenesulfonamide (5). A soln. of
4-methylbenzenesulfonyl azide (2c; 350mg, 1.77 mmol) in benzene (20ml) was added dropwise into a soln. of
1
(480mg, 1.77 mmol) in benzene (20ml). After keeping the stirred mixture at r.t. for 15 h, the solvent was
evaporated and the residue crystallized from Et2O: 5 (425 mg, 56%). Pale-yellow microcrystals. M.p. 1838. IR
(KBr): 2950s, 1620m, 1590m, 1455s (br.), 1420s, 1270vs, 1255s, 1135vs, 1105s, 1080vs, 860vs. 1H-NMR (CDCl3):
1.22 (s, t-Bu); 2.41 (s, MeC6H4); 3.27 3.35 (m, 8 H, CH2N, CH2O); 6.43 (s, CH); 7.24 7.30( m, 7 H, Ph, Ts);
7.85 (AA' of AA'BB', 3J 8.1, 2 Htosyl, Ts). 13C-NMR (CDCl3): 21.4 (q); 29.3 (q); 37.3 (s); 44.1 (t, CH2N); 47.6 (t,
CH2N); 65.8 (t, CH2O); 66.4 (t, CH2O); 116.0( d); 126.3 (d); 127.6 (d); 127.7 (d); 128.5 (d); 129.0( d); 138.1 (s);
141.2 (s); 141.8 (s); 157.3 (s); 163.9 (s). Anal. calc. for C24H30N2O3S (426.58): C 67.58, H 7.09, N 6.57; found: C
67.1, H 7.1, N 6.4.
3. Cycloaddition with Dimorpholinobutadiene 7. 3.1. [(1E,3Z)-3-(Phenylmethylene)prop-1-ene-1,3-diyl]-
bis[morpholine] (7). a) A mixture of phenylbuta-1,3-diyne [29] (1.02 g, 8.09 mmol) and morpholine (710 mg,
8.15 mmol) was heated under reflux during 7 h. The product mixture was extracted with Et2O (5 Â 25 ml), and
the combined extract was evaporated: orange oil, which was identified as a 4 :3 mixture of (E/Z)-6 ((E)/(Z)
1:1.17) and 7 by 1H-NMR. Bulb-to-bulb distillation at 1608/0.002 mbar furnished rather impure (E/Z)-6
(725 mg, 42%) which could not be purified further. The residue of the distillation consisted of 7 (435 mg, 18%).
Data of 4-[(1E)-and (1 Z)-4-Phenylbut-1-en-3-ynyl)morpholine ((Z)/(E)-6): 1H-NMR (CDCl3): 2.91 (−t×,
3
3
4 H, CH2N); 3.61 (m, 4 H, CH2O); 4.21 (d, J 9.6, HÀC(2) of (Z)-6); 4.47 (d, J 13.8, HÀC(2) of (E)-6);
3
3
5.77 (d, J 9.6, HÀC(1) of (Z)-6); 6.49 (d, J 13.8, HÀC(1) of (E)-6); 7.10 7.52 ( m, 5 H). 13C-NMR: 48.1,
49.7 (2t, CH2N); 66.0, 66.6 (2t, CH2O); 77.6, 74.8 (2d, C(2)); 86.4, 89.9, 89.8 (3s, C(3), C(4)); 149.3, 144.5 (2d,
C(1)).
b) A mixture of phenylbuta-1,3-diyne [29] (1.15 g, 9.12 mmol) and morpholine (5.04 g, 57.8 mmol) was
heated at 1008 during 15 h. The excess of morpholine was evaporated at 0.005 mbar, the residue extracted with
Et2O (4 Â 25 ml), the combined extract evaporated, and the residue crystallized from Et2O/pentane 1:1: 7
(1.70g, 62%). Yellow crystals. M.p. 94 8. IR (KBr): 2835s, 1620vs, 1580s, 1435s, 1370s, 1245s, 1205s, 110vs, 1005s,
965s. 1H-NMR (CDCl3): 2.99 (m, 8 H, CH2N), 3.72 (−t×, J 4.8, 4 H, CH2O); 3.78 (−t×, J 4.6, CH2O); 5.25 (d,
3J 13.8, HÀC(2)); 5.44 (s, PhCHC); 6.50( d, 3J 13.8, HÀC(1)); 7.06 (t, 3J 7.4, 1 H); 7.24 (t, 3J 7.5, 2 H);
7.31 (d, 3J 7.4, 2 H). 13C-NMR (CDCl3): 49.0( t, CH2N); 51.5 (t, CH2N); 66.4 (t, CH2O); 67.5 (t, CH2O); 96.0
(dd, J 154, J 7.8, C(2)); 106.3 (d, J 152, PhCHC); 124.4 (d); 127.9 (d); 128.4 (d); 139.6 (s); 143.1 (d, J
165, C(1)); 149.5 (s, C(3)). Anal. calc. for C18H24N2O2 (300.40): C 71.97, H 8.05, N 9.33; found: C 71.8, H 7.7, N
9.0.
3.2. 4-{(1Z)-1-[1-(4-Nitrophenyl)-1H-1,2,3-triazol-4-yl]-2-phenylethenyl}morpholine (8). A soln. of 2a
(355 mg, 2.17 mmol) in CH2Cl2 (35 ml) was added dropwise to a soln. of 7 (320mg, 1.07 mmol) in CH 2Cl2
(25 ml). After 18 h, the solvent was evaporated, and the residue was filtered through a short column (silica gel
(20g), Et 2O/petroleum ether 8 :2). Evaporation and recrystallization from CH2Cl2/Et2O 2 :1 yielded 8 (245 mg,
61%). Violet crystals. M.p. 1438. IR (KBr): 1575m, 1505s, 1330vs, 1300s, 1265s, 1215vs, 1115s, 1055s, 1010s, 850s.