8260
E. M. MacKenzie et al. / Bioorg. Med. Chem. 16 (2008) 8254–8263
2.28 (t, J = 2.7 Hz, 1H, CH2C„CH); 13C NMR (CDCl3): d 142.85
(CH@N), 138.22, 137.24 (phenyl C-1, C-3), 129.61, 128.46 (phenyl
C-2, C-5), 127.86 (phenyl C-4), 125.86 (phenyl C-6), 72.13 (C„CH),
60.30 (C„CH), 39.10 (CH2C„CH), 38.91 (CH2CH@N), 21.36 (CH3);
(Z)-8f isomer: 1H NMR (CDCl3): d 7.05–7.13 (m, 4H, phenyl hydro-
gens), 6.81 (t, J = 5.4 Hz, 1H, CH2CH@N), 5.08 (br s, 1H, NH), 3.99 (d,
J = 2.4 Hz, 2H, CH2C„CH), 3.43 (d, J = 5.4 Hz, 2H, CH2CH@N), 2.36
(s, 3H, CH3), 2.30 (t, J = 2.4 Hz, 1H, CH2C„CH); 13C NMR (CDCl3):
d 142.85 (CH@N), 138.22, 137.24 (phenyl C-1, C-3), 129.32,
128.73 (phenyl C-2, C-5), 127.28 (phenyl C-4), 125.59 (phenyl C-
6), 72.13 (C„CH), 60.30 (C„CH), 40.45 (CH2C„CH), 33.22
(CH2CH@N), 21.36 (CH3).
(phenyl C-4, C-6), 72.29 (C„CH), 61.00 (C„CH), 38.92 (CH2C„CH),
38.54 (CH2CH@N); (Z)-8h isomer: 1H NMR (CDCl3): d 7.10–7.31 (m,
4H, phenyl hydrogens), 6.80 (t, J = 5.1 Hz, 1H, CH2CH@N), 5.10 (br s,
1H, NH), 4.03 (d, J = 1.8 Hz, 2H, CH2C„CH), 3.48 (d, J = 5.1 Hz, 2H,
CH2CH@N), 2.35 (t, J = 1.8 Hz, 1H, CH2C„CH); 13C NMR (CDCl3): d
141.23 (CH@N), 139.44 (phenyl C-1), 134.35 (phenyl C-3), 130.04
(phenyl C-5), 128.70 (phenyl C-2), 126.99, 126.72 (phenyl C-4, C-
6), 71.87 (C„CH), 61.00 (C„CH), 40.44 (CH2C„CH), 32.81
(CH2CH@N).
5.3.9. (E)- and (Z)-N-(2-Propynyl)-2-(3-fluorophenyl)ethyli-
dene]hydrazines [(E)-8i and (Z)-8i, ratio 5.2:1]
Yellow oil separated using petroleum ether–ethyl acetate (93:7,
v/v) as eluant; yield, 22%; IR (liquid film): 3294 (C„CH), 1703
(CH@N) cmÀ1; (E)-8i isomer: 1H NMR (CDCl3): d 7.21–7.31 (m,
1H, phenyl H-5), 7.09 (t, J = 6.0 Hz, 1H, CH2CH@N), 6.90–7.14 (m,
3H, phenyl H-2, H-4, H-6), 5.10 (br s, 1H, NH), 3.91 (d, J = 2.4 Hz,
2H, CH2C„CH), 3.56 (d, J = 6.0 Hz, 2H, CH2CH@N), 2.28 (t, J = 2.4
5.3.7. (E)-N-Bis-(2-propynyl)-2-(3-methoxyphenyl)ethyidene]-
hydrazine [(E)-7g], and (E)- and (Z)-N-(2-Propynyl)-2-(3-
methoxyphenyl)ethylidene]hydrazines [(E)-8g and (Z)-8g]
(E)-7g: Yellow oil separated using petroleum ether–ethyl ace-
tate as eluant (95:5, v/v); yield, 12%; IR (liquid film): 3301 (C„CH),
1709 (CH@N) cmÀ1; 1H NMR (CDCl3): d 7.22 (t, J = 7.3 Hz, 1H, phe-
nyl H-5), 7.04 (t, J = 5.7 Hz, 1H, CH2CH@N), 6.76–6.84 (m, 3H, phe-
nyl H-2, H-4, H-6), 3.97 (d, J = 2.4 Hz, 4H, CH2C„CH), 3.80 (s, 3H,
OCH3), 3.59 (d, J = 5.7 Hz, 2H, CH2CH@N), 2.26 (t, J = 2.4 Hz, 2H,
CH2C„CH); 13C NMR (CDCl3): d 157.21 (phenyl C-3), 141.99
(CH@N), 139.22 (phenyl C-1), 129.45 (phenyl C-5), 121.21 (phenyl
C-6), 114.49 (phenyl C-2), 112.04 (phenyl C-5), 73.47 (C„CH),
61.30 (C„CH), 55.21 (OCH3), 42.23 (CH2C„CH), 39.56 (CH2CH@N).
(E)-8g and (Z)-8g (ratio 3:1): Yellow oil separated using petro-
leum ether–ethyl acetate (93:7 v/v) as eluant; yield, 18%; IR (liquid
film): 3301 (C„CH), 1595 (CH@N) cmÀ1; (E)-8g isomer: 1H NMR
(CDCl3): d 7.25 (t, J = 7.3 Hz, 1H, phenyl H-5), 7.16 (t, J = 6.0 Hz,
1H, CH@N), 6.77–6.84 (m, 3H, phenyl H-2, H-4, H-6), 5.08 (br s,
1H, NH), 3.90 (d, J = 2.7 Hz, 2H, CH2C„CH), 3.80 (s, 3H,OCH3),
1
Hz, 1H, CH2C„CH); 13C NMR (CDCl3): d 164.54 (d, JC,F = 246.1 Hz,
phenyl C-3), 141.38 (CH@N), 140.01 (phenyl C-1), 129.94 (d,
4
3JC,F = 8.75 Hz, phenyl C-5), 124.43 (d, JC,F = 2.19 Hz, phenyl C-6),
2
2
115.73 (d, JC,F = 22.0 Hz, phenyl C-2), 113.45 (d, JC,F = 20.90 Hz,
phenyl C-4), 72.25 (C„CH), 60.10 (C„CH), 38.95 (CH2C„CH),
38.62 (CH2CH@N); (Z)-8i isomer: 1H NMR (CDCl3): d 7.21–7.31
(m, 1H, phenyl H-5), 6.90–7.14 (m, 3H, phenyl H-2, H-4, H-6),
6.78 (t, J = 4.8 Hz, 1H, CH2CH@N), 5.10 (br s, 1H, NH), 3.98 (d,
J = 2.1 Hz, 2H, CH2C„CH), 3.46 (d, J = 4.8 Hz, 2H, CH2CH@N), 2.30
(t, J = 2.1 Hz, 1H, CH2C„CH); 13C NMR (CDCl3): d 164.54 (d,
1JC,F = 246.1 Hz, phenyl C-3), 141.95 (CH@N), 140.01 (phenyl C-1),
3
4
130.30 (d, JC,F = 8.75 Hz, phenyl C-5), 124.22 (d, JC,F = 3.30 Hz,
2
phenyl C-6), 115.75 (d, JC,F = 21.96 Hz, phenyl C-2), 113.78 (d,
2JC,F = 20.90 Hz, phenyl C-4), 71.91 (C„CH), 60.10 (C„CH), 40.45
(CH2C„CH), 32.94 (CH2CH@N).
3.55 (d, J = 6.0 Hz, 2H, CH2CH@N), 2.27 (t,
J 8 2.7 Hz, 1H,
CH2C„CH); 13C NMR (CDCl3): d 159.78 (phenyl C-3), 142.44
(CH@N), 138.92 (phenyl C-1), 129.51 (phenyl C-5), 121.15 (phenyl
C-6), 114.46 (phenyl C-2), 112.08 (phenyl C-4), 72.15 (C„CH),
61.30 (C„CH), 55.17 (OCH3) 39.02 (CH2C„CH), 39.00 (CH2CH@N);
(Z)-8g isomer: 1H NMR (CDCl3): d 7.25 (t, J = 7.3 Hz, 1H, phenyl H-
5), 6.70–6.84 (m, 4H, phenyl H-2, H-4, H-6, CH@N), 5.08 (br s, 1H,
NH), 3.99 (d, J = 2.4 Hz, 2H, CH2C„CH), 3.81 (s, 3H, OCH3), 3.44 (d,
J = 4.8 Hz, 2H, CH2CH@N), 2.30 (t, J = 2.4 Hz, 1H, CH2C„CH); 13C
NMR (CDCl3): d 159.78 (phenyl C-3), 142.99 (CH@N), 138.92 (phe-
nyl C-1), 129.69 (phenyl C-5), 120.88 (phenyl C-6), 114.27 (phenyl
C-2), 112.23 (phenyl C-4), 71.81 (C„CH), 61.30 (C„CH), 55.17
(OCH3) 40.42 (CH2C„CH), 33.32 (CH2CH@N).
5.3.10. (E)-N-Bis-(2-propynyl)-2-(3-trifluoromethylphenyl)-
ethyidene]hydrazine [(E)-7j], and (E)- and (Z)-N-(2-propynyl)-2-
(3-trifluoromethylphenyl)ethylidene]hydrazines [(E)-8j and (Z)-
8j]
(E)-7j: Yellow oil separated using petroleum ether–ethyl ace-
tate as eluant (96:4, v/v); yield, 14%; IR (liquid film): 3294 (C„CH),
1736 (CH@N) cmÀ1 1H NMR (CDCl3): d 7.32–7.54 (m, 4H, phenyl
;
hydrogens), 7.02 (t, J = 5.7 Hz, 1H, CH2CH@N), 3.99 (d, J = 2.4 Hz,
4H, CH2C„CH), 3.68 (d, J = 5.7 Hz, 4H, CH2CH@N), 2.27 (t,
J = 2.4 Hz, 2H, CH2C„CH); 13C NMR (CDCl3): d 140.11 (CH@N),
138.73 (phenyl C-1), 132.60 (phenyl C-6), 130.56 (q,
2JC,F = 29.66 Hz, phenyl C-3), 128.84 (phenyl C-5), 125.57 (d,
1
5.3.8. (E)-N-Bis-(2-propynyl)-2-(3-chlorophenyl)ethyidene]-
hydrazine [(E)-7h], and (E)- and (Z)-N-(2-propynyl)-2-(3-
chlorophenyl)ethylidene]hydrazines [(E)-8h and (Z)-8h]
(E)-7h: Yellow oil separated using petroleum ether–ethyl ace-
tate as eluant (97:3, v/v); yield, 12%; IR (liquid film): 3301 (C„CH),
3JC,F = 3.24 Hz, phenyl C-2), 124.09 (q, JC,F = 272.46 Hz, CF3),
3
123.32 (d, JC,F = 3.32 Hz, phenyl C-4), 73.62 (C„CH), 61.50
(C„CH), 42.15 (CH2C„CH), 39.20 (CH2CH@N).
(E)-8j and (Z)-8j (ratio 6:1): Yellow oil separated using petro-
leum ether–ethyl acetate (90:10, v/v) as eluant; yield, 21%; IR (li-
quid film): 3301 (C„CH), 1736 (CH@N) cmÀ1; (E)-8j isomer: 1H
NMR (CDCl3): d 7.39–7.52 (m, 4H, phenyl hydrogens), 7.21 (t,
J = 5.4 Hz, 1H, CH2CH@N), 5.12 (br s, 1H, NH), 3.92 (d, J = 2.7 Hz,
2H, CH2C„CH), 3.63 (d, J = 5.4 Hz, 2H, CH2CH@N), 2.28 (t,
J = 2.7 Hz, 1H, CH2C„CH); 13C NMR (CDCl3): d 140.11 (CH@N),
138.73 (phenyl C-1), 132.60 (phenyl C-6), 130.56 (q,
2JC,F = 29.66 Hz, phenyl C-3), 128.86 (phenyl C-5), 125.57 (d,
1650 (CH@N) cmÀ1 1H NMR (CDCl3): d 7.08–7.32 (m, 4H, phenyl
;
hydrogens), 7.00 (t, J = 5.7 Hz, 1H, CH2CH@N), 3.99 (d, J = 2.4 Hz,
4H, CH2C„CH), 3.59 (d, J = 5.7 Hz, 2H, CH2CH@N), 2.28 (t, J = 2.4
Hz, 2H, CH2CCH); 13C NMR (CDCl3): d 141.23 (CH@N), 139.44 (phe-
nyl C-1), 134.35 (phenyl C-3), 129.73 (phenyl C-5), 128.93 (phenyl
C-2), 126.93, 126.73 (phenyl C-4, C-6), 72.30 (C„CH), 61.00
(C„CH), 42.26 (CH2C„CH), 38.54 (CH2CH@N).
(E)-8h and (Z)-8h (ratio 4.3:1): Yellow oil separated using
petroleum ether–ethyl acetate (93:7 v/v) as eluant; yield, 18%; IR
(liquid film): 3288 (C„CH), 1689 (CH@N) cmÀ1; (E)-8h isomer:
1H NMR (CDCl3): d 7.10–7.31 (m, 5H, phenyl hydrogens, CH2CH@N),
5.10 (br s, 1H, NH), 3.95 (d, J = 2.1 Hz, 2H, CH2C„CH), 3.58 (d,
J = 6.0 Hz, 2H, CH2CH@N), 2.33 (t, J = 2.1 Hz, 1H, CH2C„CH); 13C
NMR (CDCl3): d 141.23 (CH@N), 139.44 (phenyl C-1), 134.35 (phe-
nyl C-3), 129.73 (phenyl C-5), 128.93 (phenyl C-2), 126.99, 126.72
1
3JC,F = 3.24 Hz, C2 aryl), 124.08 (q, JC,F = 272.46 Hz, CF3), 123.32
3
(d, JC.F = 3.32 Hz, phenyl C-4), 73.62 (C„CH), 61.50 (C„CH),
42.15 (CH2C„CH), 39.20 (CH2CH@N); (Z)-8j isomer: 1H NMR
(CDCl3): d 7.39–7.52 (m, 4H, phenyl hydrogens), 6.77 (t, J = 5.1 Hz,
1H, CH2CH@N), 5.12 (br s, 1H, NH), 4.00 (d, J = 2.4 Hz, 2H,
CH2C„CH), 3.52 (d, J = 5.1 Hz, 2H, CH2CH@N), 2.30 (t, J = 2.4 Hz,
1H, CH2C„CH); 13C NMR (CDCl3): d 140.11 (CH@N), 138.73 (phe-
2
nyl C-1), 132.30 (phenyl C-6), 130.56 (q, JC,F = 29.66 Hz, phenyl