V.A. D’yakonov et al. / Tetrahedron xxx (2013) 1e11
7
(15). Anal. Calcd for C18H32N2O2: C, 70.09; H, 10.46. Found: C, 69.91;
H, 10.44.
C(2,3,12,13)H2), 2.01e2.17 (m, 8H, C(4,7,8,11)H2), 2.38 (t, 8H,
C(16,19,21,24)H2), 2.81 (s, 2H, C(15,20)H2), 2.92 (s, 2H, C(15,20)H2),
3.69 (t, 8H, C(17,18,22,23)H2, J¼4 Hz) ppm. 13C NMR (CDCl3,
6.2.22. 1,10-(2Z,6Z)-2,7-Dimethyl-3,6-dideuteroocta-2,6-diene-1,8-
diyldimorpholine (4l). Yield¼80% (1.24 g), as a pale yellow oil.
Rf¼0.50 (hexane/EtOAc 5:1). IR: 2957, 2893, 2851, 2175 (CeD),1454,
100 MHz): d 14.1 (C(1,14)), 22.5, 22.9 (C(2,13)), 27.9, 28.0, 28.7, 35.6
(C(4,7,8,11)), 53.7 (C(16,19,21,24)), 57.4, 65.6 (C(15,20)), 67.2
(C(17,18,22,23)), 128.1, 128.0 (t, C(6,9), JC,D¼22.5 Hz), 136.1, 136.4
(C(5,10)) ppm. Anal. Calcd for C24H42D2N2O2: C, 73.05; H, 10.73; D,
1.02. Found: C, 72.91; HþD, 11.69.
1291, 1117, 1008, 866 cmꢁ1. 1H NMR (CDCl3, 400 MHz):
d
ꢁ1.72 (s,
6H, C(1,8)H3), 2.08 (m, 4H, C(4,5) H2), 2.34 (t, 8H, C(10,13,15,18)H2,
J¼4.8 Hz), 2.89 (s, 4H, C(9,14)H2), 3.68 (t, 8H, C(11,12,16,17)H2,
J¼4.8 Hz), 5.33 (t, 2H, C(3,6)H, J¼7 Hz) ppm. 13C NMR (CDCl3,
6.2.27. 1,10-(3Z,7Z)-Deca-3,7-diene-1,10-diyldimorpholine (3o). Yield¼
85% (1.31 g), as a pale yellow oil. Rf¼0.50 (hexane/EtOAc 5:1). IR: 3016,
2834, 2862, 1384, 1218, 1115, 1066, 923, 754, 667, 628 cmꢁ1. 1H NMR
100 MHz):
d 22.8 (C(1,8)), 28.0 (C(4,5)), 53.6 (C(10,13,15,18)), 59.0
(C(9,14)), 67.1 (C(11,12,16,17)), 128.6 (t, C(3,6), JC,D¼22.5 Hz), 132.0
(C(2,7)) ppm. Anal. Calcd for C18H30D2N2O2: C, 69.64; H, 9.74; D,
1.29. Found: C, 69.49; HþD, 10.98.
(CDCl3, 400 MHz):
d
ꢁ2.11 to 2.13 (m, 4H, C(5,6)H2), 2.37 (t, 4H, C(1,10)
H2, J¼7.2 Hz), 2.47 (t, 8H, C(11,14,15,18)H2, br s), 3.73 (t, 8H,
C(12,13,16,17)H2, J¼4.4 Hz), 5.37e5.45 (m, 2H, C(3,4,7,8)H) ppm. 13
C
6.2.23. 1,10-(3Z,7Z)-3,8-Dimethyldeca-3,7-diene-1,10-diyldimorpho-
line (3m). Yield¼84% (1.41 g), as a pale yellow oil. Rf¼0.51 (hexane/
EtOAc 5:1). IR: 2961, 2931, 2857, 2807, 1726, 1454, 1345, 1290, 1117,
NMR (CDCl3, 100 MHz): d 24.6 (C(2,9)), 27.3 (C(5,6)), 53.6
(C(11,14,15,18)), 58.7 (C(1,10)), 66.8 (C(12,13,16,17)), 127.3 (C(3,8)),
130.4 (C(4,7)) ppm. MS m/z (EI, 70 eV): 308 [M]þ (3), 100 (100), 56
(11), 101 (10), 70 (5), 102 (4). Anal. Calcd for C18H32N2O2: C, 70.09; H,
10.46. Found: C, 68.08; H, 9.25.
1006, 909, 865, 734 cmꢁ1. 1H NMR (CDCl3, 400 MHz):
d
ꢁ0.99 (t, 6H,
C(1,10)H3, J¼4.8 Hz), 2.08 (t, 4H, C(5,6)H2, J¼7.2 Hz), 2.35 (t, 8H,
C(12,15,17,20)H2, J¼4.8 Hz), 2.91 (s, 4H, C(11,16)H2), 3.68 (t, 8H,
C(13,14,18,19)H2, J¼16 Hz), 5.33 (t, 2H, C(4,7)H, J¼6.4 Hz) ppm. 13
C
6.2.28. 1,10-(3Z,7Z)-4,7-Dideuterodeca-3,7-diene-1,10-diyldimorpho-
line (4o). Yield¼83% (1.29 g), as a pale yellow oil. Rf¼0.50 (hexane/
EtOAc 5:1). IR: 3016, 2833, 2862, 2175 (CeD), 1385, 1216, 1116, 1065,
NMR (CDCl3, 100 MHz): d 12.8, 12.9, 13.2 (C(1,10)), 21.9 (C(2,9)), 28.6
(C(5,6)), 53.6 (C(12,15,17,20)), 57.5 (C(11,16)), 67.1 (C(13,14,18,19)),
127.1, 127.20 (C(4,7)), 137.5, 134.5 (C(3,8)) ppm. MS m/z (EI, 70 eV)
m/z (%): 336 [M]þ (26), 133 (100), 162 (69), 100 (65), 87 (40), 152
(29), 86 (28), 55 (27), 147 (24), 167 (23), 154 (22), 56 (21), 67 (19), 41
(18), 57 (17), 93 (16), 250 (15), 134 (14), 120 (11). Anal. Calcd for
922, 755, 669, 627 cmꢁ1. 1H NMR (CDCl3, 400 MHz):
d
ꢁ2.16 (t, 4H,
C(5,6)H2, J¼7.6 Hz), 2.30 (t, 4H, C(1,10)H2, J¼7.2 Hz), 2.39 (t, 8H,
C(11,14,15,18)H2, br s), 3.65 (t, 8H, C(12,13,16,17)H2, J¼4.4 Hz), 5.31
(t, 2H, C(3,8)H, J¼6.4 Hz) ppm. 13C NMR (CDCl3, 100 MHz):
d 24.6
C
20H36N2O2: C, 71.38; H, 10.78. Found: C, 71.09; H, 10.57.
(C(2,9)), 27.1 (C(5,6)), 53.6 (C(11,14,15,18)), 58.7 (C(1,10)), 66.8
(C(12,13,16,17)), 127.1 (C(3,8)), 130.0 (t, C(4,7), JC,D¼23 Hz) ppm.
Anal. Calcd for C18H30D2N2O2: C, 69.63; H, 9.74; D, 1.30. Found: C,
69.04; HþD, 10.94.
6.2.24. 1,10-(3Z,7Z)-3,8-Dimethyl-3,6-dideuterodeca-3,7-diene-1,10-
diyldimorpholine (4m). Yield¼82% (1.39 g), as a pale yellow oil.
Rf¼0.51 (hexane/EtOAc 5:1). IR: 2961, 2931, 2857, 2808, 2170 (CeD),
1726, 1454, 1345, 1290, 1116, 1006, 909, 866, 734 cmꢁ1
.
1H NMR
6.2.29. 1,10-(4Z,8Z)-Dodeca-4,8-diene-1,12-diyldimorpholine (3p).
Yield¼81% (1.36 g), as a pale yellow oil. Rf¼0.50 (hexane/EtOAc 5:1).
(CDCl3, 400 MHz):
d
ꢁ0.98 (t, 6H, C(1,10)H3, J¼4.8 Hz), 2.07 (t, 4H,
C(5,6)H2, J¼7.2 Hz), 2.34 (t, 8H, C(12,15,17,20)H2, J¼4.8 Hz), 2.91 (s,
IR: 3019, 2831, 2865,1382, 1215,1116, 1067, 927, 756, 669, 627 cmꢁ1
.
4H, C(11,16)H2), 3.67 (t, 8H, C(13,14,18,19)H2, J¼16 Hz) ppm. 13C
1H NMR (CDCl3, 400 MHz):
2.01e2.11 (m, 8H, C(3,10)H2), 2.31 (t, 4H, C(1,12)H2, J¼7 Hz), 2.41 (t,
8H, C(13,16,17,20)H2, J¼7 Hz), 3.68 (t, 8H, C(14,15,18,19)H2, J¼5 Hz),
5.29e5.34 (m, 4H, C(4,5,8,9)H) ppm. 13C NMR (CDCl3, 100 MHz):
d
ꢁ1.45 to 1.56 (m, 4H, C(2,11)H2),
NMR (CDCl3, 100 MHz):
d
12.8,12.9,13.2 (C(1,10)), 22.0 (C(2,9)), 28.7
(C(5,6)), 53.7 (C(12,15,17,20)), 57.5, 57.6 (C(11,16)), 67.1
(C(13,14,18,19)), 127.2, 126.9 (t, C(3,6), JC,D¼22.5 Hz), 137.5, 134.5
(C(3,8)) ppm. Anal. Calcd for C20H34 D2N2O2: C, 70.96; H, 10.12; D,
1.19. Found: C, 70.80; HþD, 11.19.
d
25.0 (C(2,11)), 26.3 (C(3,10)), 27.3 (C(6,7)), 53.6 (C(13,16,17,20)),
58.5 (C(1,12)), 66.8 (C(14,15,18,19)), 129.5 (C(4,9)), 129.7
(C(5,8)) ppm. MS m/z (EI, 70 eV) m/z (%): 336 [M]þ (15), 100 (100),
138 (14), 72 (12), 56 (11), 168 (10). Anal. Calcd for C20H36N2O2: C,
71.38; H, 10.78. Found: C, 70.02; H, 9.65.
6.2.25. 1,10-(3Z,7Z)-1,5-Dimethyltetradeca-5,9-diene-1,14-diyldimor-
pholine (3n). Yield¼82% (1.61 g), as a pale yellow oil. Rf¼0.51 (hex-
ane/EtOAc 5:1). IR: 2956, 2929, 2856, 2806, 2763, 1678, 1454, 1396,
1378, 1345, 1290, 1269, 1240, 1118, 1005, 911, 867, 798, 733 cmꢁ1. 1H
6.2.30. 1,10-(4Z,8Z)-5,8-Dideuterododeca-4,8-diene-1,12-diyldimor-
pholine (4p). Yield¼79% (1.34 mg), as a pale yellow oil. Rf¼0.50
(hexane/EtOAc 5:1). IR: 3018, 2831, 2864, 2170 (CeD), 1382, 1216,
NMR (CDCl3, 400 MHz):
d
ꢁ0.91 (t, 3H, C(1,14)H3, J¼7 Hz), 0.92 (t, 3H,
C(1,14)H3, J¼7 Hz), 1.29e1.38 (m, 8H, C(2,3,12,13)H2), 2.00e2.17 (m,
8H, C(4,7,8,11)H2), 2.36 (t, 8H, C(16,19,21,24)H2), 2.81 (s, 2H, C(15,20)
H2), 2.91 (s, 2H, C(15,20)H2), 3.69 (t, 8H, C(17,18,22,23)H2, J¼4 Hz),
1116, 1067, 926, 756, 669, 628 cmꢁ1 1H NMR (CDCl3, 400 MHz):
.
d
ꢁ1.43 to 1.55 (m, 4H, C(2,11)H2), 2.01e2.14 (m, 8H, C(3,10)H2),
5.28 (t, 2H, C(6,9)H, J¼7 Hz) ppm. 13C NMR (CDCl3, 100 MHz):
d
14.1
2.30 (t, 4H, C(1,12)H2, J¼7 Hz), 2.42 (t, 8H, C(13,16,17,20)H2, J¼7 Hz),
3.66 (t, 8H, C(14,15,18,19)H2, J¼5 Hz), 5.32 (t, 2H, C(4,9)H,
(C(1,14)), 22.5, 22.9 (C(2,13)), 27.9, 28.0, 28.7, 35.6 (C(4,7,8,11)), 53.7
(C(16,19,21,24)), 57.4, 65.6 (C(15,20)), 67.2 (C(17,18,22,23)), 128.1,
128.3 (C(6,9)), 136.1, 136.4 (C(5,10)) ppm. MS m/z (EI, 70 eV) m/z (%):
392 [M]þ (63),100 (100), 87 (54),166 (40),196 (37), 86 (35),152 (34),
55 (24), 67 (22), 195 (21), 69 (19), 58 (16), 180 (15), 89 (14), 68 (12),
197 (11). Anal. Calcd for C24H44N2O2: C, 73.42; H, 11.30. Found: C,
73.28; H, 11.21.
J¼6.4 Hz) ppm. 13C NMR (CDCl3, 100 MHz):
d 25.1 (C(2,11)), 26.3
(C(3,10)), 27.3 (C(6,7)), 53.6 (C(13,16,17,20)), 58.4 (C(1,12)), 66.8
(C(14,15,18,19)), 129.4 (C(4,9)), 129.5 (t, C(5,8), JC,D¼23 Hz) ppm.
Anal. Calcd for C16H26D2N2O2: C, 70.96; H, 10.12; D, 1.19. Found: C,
70.02; HþD, 11.31.
6.2.31. (2Z,6Z)-Octa-2,6-diene-1,8-diylbis(trimethylsilane)
Yield¼92% (1.17 g), as a colorless oil. Rf¼0.72 (hexane). IR: 3019,
2955, 1249, 1216, 853, 758 cmꢁ1 1H NMR (CDCl3, 400 MHz):
ꢁ0.049 (s, 18H, C(9e14)H3), 1.51 (d, 4H, C(1,8)H2, J¼8.4 Hz),
2.07e2.08 (m, 4H, C(4,5)H2), 5.32e5.34 (m, 2H, C(3,6)H, J¼4.8 Hz),
5.41e5.48 (m, 2H, C(2,7)H) ppm. 13C NMR (CDCl3, 100 MHz):
ꢁ1.7
(C(9,10,11,12,13,14)), 18.5 (C(1,8)), 27.3 (C(4,5)), 125.6 (C(2,7)), 127.2
(3q).
6.2.26. 1,10-(3Z,7Z)-1,5-Dimethyl-3,6-dideuterotetradeca-5,9-diene-
1,14-diyldimorpholine (4n). Yield¼82% (1.61 g), as a pale yellow oil.
Rf¼0.51 (hexane/EtOAc 5:1). IR: 2956, 2929, 2856, 2806, 2764, 2175
(CeD), 1678, 1454, 1396, 1378, 1345, 1290, 1269, 1240, 1117, 1005,
.
d
911, 868, 798, 734 cmꢁ1. 1H NMR (CDCl3, 400 MHz):
d
ꢁ0.91 (t, 3H,
d
C(1,14)H3, J¼7 Hz), 0.92 (t, 3H, C(1,14)H3, J¼7 Hz), 1.29e1.39 (m, 8H,