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L. B. Krivdin et al.
N-(2-piperidino-2-butenylidene)methanamine (3) was pre-
pared as a mixture (1 : 1.5) of EZ- and EE-isomers by the reac-
tion of 2-piperidino-2-butenal with methylamine hydrochlo-
ride at the present of K2CO3, as described elsewhere.23 1H
chemical shifts, CDCl3 (υ, ppm): EZ-isomer: 1.45–1.60 (m,
6H, ꢁCH2ꢂ3); 1.91 (d, J D 7.3, 3H, CH3); 2.60–2.75 (m, 4H,
NꢁCH2ꢂ2); 3.31 (d, J D 1.4, 3H, NMe); 5.47 (q, J D 7.3, 1H,
CH ); 7.69 (q, J D 1.4, 1H, CH N); EE-isomer: 1.45–1.60
(m, 6H, ꢁCH2ꢂ3); 1.87 (d, J D 7.3, 3H, CH3); 2.60–2.75
(m, 4H, NꢁCH2ꢂ2); 3.43 (d, J D 1.7, 3H, NMe); 5.08 (q,
J D 7.3, 1H, CH ); 8.05 (q, J D 1.7, 1H, CH N); 13C
chemical shifts, CDCl3 (υ, ppm): EZ-isomer: 12.98 (CH3);
51.33 (C˛ piperidine); 26.67 (Cˇ piperidine); 24.25 (Cꢆ piperi-
dine); 47.91 (NMe); 124.96 (CH ); 148.50 ( C–N); 163.03
(C N); EE-isomer: 12.31 (CH3); 51.33 (C˛ piperidine); 25.76
(Cˇ piperidine); 24.28 (Cꢆ piperidine); 48.37 (NMe); 111.44
(CH ); 147.80 ( C–N); 158.60 (C N).
N-(2-bromo-3-phenyl-2-propenylidene)-N-(trimethylsilyl)
amine (7) was prepared by the reaction of 2-bromo-3-phenyl-
2-propenal with hexamethyldisilazane according to Ref. 26
1H chemical shifts, CDCl3 (υ, ppm): 0.24 (s, 9H, SiMe3);
7.25–7.45 (m, 3H, arom.); 7.54 (s, 1H, CH ); 7.85–7.90 (m,
2H, arom.); 8.22 (s, 1H, CH N); 13C chemical shifts, CDCl3
(υ, ppm): 1.91 (SiMe3); 122.69 ( C–Br); 129.36, 129.77, 130.25,
134.52 (C arom.); 141.51 (CH ); 158.68 (CH N).
Acknowledgements
Authors are grateful to Dr George E. Salnikov (Novosibirsk Institute
of Organic Chemistry, Russia) for providing the most recently
compiled versions of DALTON and GAMESS. Financial support
from the Russian Foundation for Basic Research, Grant No. 05-03-
32231, and from the Russian Ministry of Education and Science,
Grant No. EZN-AGTA-2005, are gratefully acknowledged.
REFERENCES
N-(2-ethoxy-2-propenylidene)butanamine (4) was synthe-
sized as reported earlier.24 1H chemical shifts, CDCl3 (υ,
ppm): 0.54 (t, J D 7.5, 3H, CH3); 0.90–1.00 (m, 2H, CH2); 1.05
(t, J D 7.0, 3H, CH3); 1.20–1.30 (m, 2H, CH2); 3.13 (t, J D 7.0,
2H, NCH2); 3.50 (q, J D 7.0, 2H, OCH2); 4.18 (d, J D 10.8,
CH2 ); 7.28 (s, 1H, CH N); 13C chemical shifts, CDCl3 (υ,
ppm): 12.84 (CH3 n-Bu); 13.24 (CH3); 60.22 (C˛ n-Bu); 31.74
(Cˇ n-Bu); 19.43 (Cꢆ n-Bu); 62.42 (OCH2); 92.30 (CH2 );
156.71 ( C–O); 156.75 (C N).
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N-[2-(butylsulfanyl)-3-phenyl-2-propenylidene]methanamine
(5) was prepared as follows: 2-Butylsulfanyl-3-phenyl-2-
propenal (1.5 g, 6.8 mmol) was added to methylamine
hydrochloride (3.5 g, 52 mmol) in benzene at room tem-
perature (rt). The reaction mixture left out for 24 h. After
filtration solvent was removed under reduced pressure, the
residue was distilled as a mixture of EZ and EE isomers. 1H
chemical shifts, CDCl3 (υ, ppm): EZ-isomer: 0.77 (t, J D 7.4,
3H, CH3); 1.20–1.30 (m, 2H, CH2); 1.40–1.50 (m, 2H, CH2);
2.80 (t, J D 7.4, 3H, CH3); 3.46 (s, 3H, NMe); 7.13 (s, 1H,
CH ); 7.15–7.40 (m, 3H, arom.); 7.70–7.80 (m, 2H, arom.);
7.95 (s, 1H, CH N); EE-isomer: 0.91 (t, J D 7.4, 3H, CH3);
1.40–1.50 (m, 2H, CH2); 1.63–1.73 (m, 2H, CH2); 2.80 (t,
J D 7.4, 3H, CH3); 3.40 (s, 3H, NMe); 6.83 (s, 1H, CH );
7.15–7.40 (m, 3H, arom.); 7.70–7.80 (m, 2H, arom.); 8.22 (s,
1H, CH N); 13C chemical shifts, CDCl3 (υ, ppm): EZ-isomer:
13.58 (CH3); 21.82, 30.25, 32.70 (CH2); 47.92 (NMe); 135.65
(Ci.); 130.35 (Co ); 128.13 (Cm.); 127.52 (Cp ); 131.01 (CH );
.
.
134.07 ( C–S), 164.11 (C N); EE-isomer: 13.71 (CH3); 22.25,
30.72, 31.78 (CH2); 48.05 (NMe); 136.09 (Ci.); 129.30 (Co );
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.
128.37 (Cm.); 128.58 (Cp ); 131.26 (CH ); 137.28 ( C–S);
.
159.63 (C N).
N-(2-chloro-3,3-diphenyl-2-propenylidene)-N-cyclohexyl-
amine (6) was prepared starting from 2-chloro-3,3-diphenyl-
propenal and trimethylsilylcyclohexylamine according to
the reported procedure.25 1H chemical shifts, CDCl3 (υ,
ppm): 1.20–1.30 (m, 2H); 1.55–1.70 (m, 8H); 3.00–3.10 (m,
1H); 7.20–7.40 (m, 10H); 8.02 (s, 1H); 13C chemical shifts,
CDCl3 (υ, ppm): 69.47 (C˛ cyclohexyl); 34.07 (Cˇ cyclohexyl);
24.82 (Cꢆ cyclohexyl); 25.49(Cυ cyclohexyl); 139.33, 140.46
(Ci); 129.64, 130.42(Co); 128.05, 128.35(Cm); 128.27, 128.54(Cp);
129.92 ( CCl); 148.76 (Ph2C ); 155.10 (CH N).
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Copyright 2005 John Wiley & Sons, Ltd.
Magn. Reson. Chem. 2006; 44: 178–187