J. Chil. Chem. Soc., 55, Nº 1 (2010)
Table 1: structure and physicochemical properties of chalcone derivatives.
H), 7.19 (d, J=7.9Hz, 2H, 2” , 6” -H), 7.56 (s, 1H, –CH=CH–), 7.90 (s, 1H, –
CH=CH–), IR (KBr/cm-1): 3244 (–OH), 1732, 1716 (–CO), 1683 (–CH=CH–),
1577, 1540 (aromatic), 834 (p-disubstituted benzene).
4-(2-fluorophenyl)-1-[1-(2-hydroxyphenyl)-3-phenylallylidene]
semicarbazide (4)
Mp
(°C)
yield
(%)
Rf
value
com
R1
R2
Mol for
3a
3b
3c
H
H
H
H
C15H12O2
C15H12O3
C16H14O3
89
85
85
85
0.80
0.83
0.82
1H-NMR (δ/ppm in CDCl3): 4.70 (s, 1H, 2-OH), 7.30-7.70 (m, J=8.26 Hz,
13H, Ar-H) 7.91 (s, 1H, –CH=CH–), 8.32 (s, 1H, –CH=CH–), 6.56 (s, 1H,
ArNH, D2O exchangeable), 9.78 (s, 1H, CONH, D2O exchangeable); IR (KBr/
cm-1): 3431 (NH), 3478(–OH), 3315–3235 (CONH), 1674 (–CH=CH–),1599
(C-N), 1613, 1560 (aromatic), 755, 698 (monosubstituted benzene); MS,
m/z 374; Elemental analysis cal/fou (%) C (70.39/70.32), H (4.83/4.68), N
(11.19/10.98).
4”-OH
4”-OCH3
164
135
4”-
N(CH3)2
3d
3e
3f
H
C17H17NO2
C15H12O4
155
216
174
85
90
90
0.78
0.85
0.81
4’-
OH
4’-
6”-OH
Synthesis of 2-flouro- phenyl urea (1)
4”-
N(CH3)2
C17H17NO3
2-flouro aniline (0.1mol) was dissolved in 20 ml of glacial acetic acid and
10 ml of water. To this, 0.1 mol of sodium cyanate (6.5 g) in 80 ml of warm
water was added with continuous stirring. The reaction mixture was allowed to
stand for 30 min and then cooled in ice. The resultant crude solid was filtered
with suction, dried and recrystallized with boiling water to yield 1. m.p 218°C,
1H-NMR (δ/ppm in CDCl3): 7.12-7.64 (m, J = 8.3 Hz, 3H, Ar-H) , 8.02 (s,
1H, imine-H), 8.34 (s, 1H, ArNH, D2O exchangeable), 9.42 (s, 2H, CONH,
D2O exchangeable); IR (KBr/cm-1) 3260, 3040, 2850, 1710, 1600-1540, 1240.
Synthesis of 2-flourophenyl semicarbazide(2)
OH
3g
3h
3i
H
6”-OH
6”-OH
C15H12O3
C15H12O4
C15H12O4
C16H14O4
166
218
208
152
85
85
85
85
0.86
0.84
0.87
0.79
5’OH
5’OH
5’OH
4”-OH
3j
4”-OCH3
Spectral analysis of some selected compounds:
Equimolar quantities (0.05 mol) of above fluorophenyl urea (1) (9.2 g)
and hydrazine hydrate (2.5 ml, x mmol) in ethanol were refluxed for 27 h with
continuous stirring. The two-third volume of alcohol was distilled by vacuum
distillation unit. Then the remaining reaction mixture was poured into ice. The
resultant precipitate was filtered, washed with water and dried. The obtained
1
(3a) H-NMR (δ/ppm in CDCl ): 5.0 (s, 1H, 2’ -OH), 7.14 (dd, J = 7.9,
1.8Hz, 1H, 4” -H), 7.21 (d, J = 7.9 3Hz, 2H, 3” , 5 –H”), 7.30 (d, J = 7.9Hz,
2H, 2” , 6” -H), 7.56 (s, 1H, –CH= CH–), 7.64 (m, J = 8.3 Hz, 4H, Ar-H), 7.90
(s, 1H, –CH=CH–). IR (KBr/cm-1): 3480 (–OH), 1748—1716 (–CO), 1670 (–
CH=CH–), 1616, 1558 (aromatic), 754, 697 (monosubstituted benzene).
1
solid was recrystallized with 50 ml of 90% ethanol?. Mp 196°C H-NMR (δ/
1
(3b) H-NMR (δ/ppm in CDCl ): 5.0 (s, 1H, 2’ -OH), 5.1 (s, 1H, 4”
-OH), 6.68 (d, J = 7.9Hz, 2H, 3” , 5”3-H), 7.13 (d, J = 8.0Hz, 2H, 2” , 6” -H),
7.64—6.92 (m, J = 8.3 Hz, 4H, Ar-H), 7.56 (s, 1H, –CH=CH–), 7.90 (s, 1H,
–CH=CH–), IR (KBr/ cm-1 ): 3480, 3345 (–OH), 1771, 1732 (–CO), 1682 (–
CH=CH–), 1603, 1575 (aromatic), 834 (p-disubstituted benzene).
ppm in CDCl ): 5.46 (s, 2H, NH2, D2O exchangeable), 7.32-7.84 (m, J = 8.38
Hz, 3H, Ar-H3) , 8.32 (s, 1H, imine-H), 8.34 (s, 1H, ArNH, D2O exchangeable),
9.86 (s, 2H, CONH, D O exchangeable); IR (KBr/cm-1) 3245, 3047, 2837,
1743, 1618-1537, 1241.2
Generalmethodforthesynthesisof2-flourophenylchalconylsemicarbazone
(4-13)
To a solution of fluorophenyl semicarbazide (2) (0.005 mol, 1.175 g) in
25 ml of ethanol added an equimolar quantity of the appropriate chalcone
derivatives previously dissolved in 25 ml of ethanol. Then few drops of
concentrated hydrochloric acid were added. Continuous stirring was done
for 4-5 hr, then reaction mixture poured on ice. Immediate precipitation was
observed. The resultant precipitate was filtered, washed with sodium acetate
(0.005 mol, 0.41g) in 2ml water, dried and recrystallized with hot ethanol. The
physicochemical parametes of the synthesized compounds were given in table
2.
1
(3c) H-NMR (δ/ppm in CDCl3): 3.73 (s, 3H, 4” -OCH3), 5.0 (s, 1H, 2’
-OH), 6.72 (d, J = 7.9Hz, 2H, 3” , 5” -H), 7.19 (d, J = 7.9Hz, 2H, 2” ,6” -H),
7.56 (s, 1H, –CH=CH–), 7.64—6.92 (m, J = 8.1 Hz, 4H, Ar-H), 7.90 (s, 1H,
–CH=CH–), IR (KBr/ cm-1 ): 3480, 3446 (–OH), 1748, 1716 (–CO), 1670 (–
CH=CH–), 1605, 1575 (aromatic), 834 (p-disubstituted benzene).
1
(3d) H-NMR (δ/ppm in CDCl3): 2.8 (s, 6H, 4” -NMe2 ), 5.0 (s, 1H, 2’
-OH), 6.54 (d, J = 7.9 Hz, 2H, 3” , 5” -H), 7.12 (d, J = 8.0 Hz, 2H, 2” , 6” - H),
7.56 (s, 1H, –CH=CH–), 7.64—6.92 (m, J = 7.9 Hz, 4H, Ar-H), 7.90 (s, 1H,
–CH=CH–), IR (KBr/ cm-1 ): 3480, 3446 (–OH),1748, 1716 (–CO), 1670 (–
CH=CH–), 1621, 1558, 1521 (aromatic), 1312 (C–N stretching in Ar amines),
835 (p-disubstituted ben-zene).
Please to correct the NMR data as above.
1
(3e) H-NMR (δ/ppm in CDCl ): 5.0 (s, 3H, 2’ , 4’ , 6” -OH), 6.68 (d,
J=7.9Hz, 2H, 3” , 5” -H), 7.13 (d, 3J=7.9Hz, 2H, 2” , 4” -H), 7.39 (s, 1H, –
CH=CH–), 7.47—6.39 (m, J=8.2 Hz, 3H, Ar-H), 8.17 (s, 1H, –CH=CH–), IR
(KBr/ cm-1 ): 3841 (–OH), 1732, 1698 (–CO), 1670 (–CH=CH–), 1616, 1558
(aromatic), 727, 652 (monosubstituted benzene).
1
(3f) H-NMR (δ/ppm in CDCl3): 2.85 (s, 6H, 4” -NMe2 ), 5.0 (s, 2H, 2’
, 4’ -OH), 6.54 (d, J=7.9Hz, 2H, 3” , 5” -H), 7.12 (d, J=7.9Hz, 2H, 2” , 6”
-H), 7.56 (s, 1H, –CH=CH–), 7.47—6.39 (m, J= 8.1 Hz, 3H, Ar-H), 7.90 (s,
1H, –CH=CH–), IR (KBr/ cm-1 ): 3480 (–OH), 1748, 1697 (–CO), 1670 (–
CH=CH–), 1616, 1540 (aromatic), 1316 (C–N stretching in Ar. amines), 824
(p-disubstituted benzene).
(3g) 1H-NMR (δ/ppm in CDCl3): 5.0 (s, 2H, 2’ , 6” -OH), 7.11—6.75 (m,
J=8.2 Hz, 4H, Ar-H), 7.14 (dd, J=7.9, 1.8Hz, 1H, 4” -H), 7.21 (d, J=7.9Hz,
2H, 3” , 5” -H), 7.30 (s, 1H, 2” -H), 7.56 (s, 1H, –CH=CH–), 7.90 (s, 1H,
–CH=CH–), IR (KBr/ cm-1 ): 3391, 3209 (–OH), 1748, 1698 (–CO), 1653 (–
CH=CH–), 1623, 1576 (aromatic), 728, 697 (monosubstituted benzene)s.
1
(3h) H-NMR (δ/ppm in CDCl3): 5.0 (s, 3H, 2’ , 5’ , 6” -OH), 6.68 (d,
J=7.9Hz, 1H, 3’ -H), 6.77 (dd, J=7.9, 1.8Hz, 1H, 6’ -H), 6.97 (dd, J=7.9, 1.8Hz,
1H, 4’ -H), 7.11—6.75 (m, J =8.3 Hz, 4H, Ar-H), 7.39 (s, 1H, –CH=CH–),
8.17 (s, 1H, –CH=CH–), IR (KBr/ cm-1): 3446 (–OH), 1748, 1698 (–CO),
1670, 1652 (–CH=CH–), 1616, 1540 (aromatic), 714, 673 (monosubstituted
benzene).
1
(3i) H-NMR (δ/ppm in CDCl ): 5.0 (s, 3H, 2’ , 5’ , 4” -OH), 6.68 (d,
J=7.9Hz, 2H, 3” , 5” -H), 7.11—36.75 (m, J=8.3 Hz, 3H, Ar-H), 7.13 (d,
J=7.9Hz, 2H, 2” , 6” -H), 7.56 (s, 1H, –CH=CH–), 7.90 (s, 1H, –CH=CH–), IR
(KBr/ cm-1): 3244 (–OH), 1732, 1698 (–CO), 1683 (–CH=CH–), 1646, 1557
(aromatic), 834 (p-disubstituted benzene).
(3j) 1H-NMR (δ/ppm in CDCl3): 3.73 (s, 3H, 4” -OCH3), 5.0 (s, 2H, 2’ , 5’
-OH), 6.72 (d, J =7.9 Hz, 2H, 3” , 5” -H), 7.11—6.75 (m, J=8.3 Hz, 3H, Ar-
104