Synthesis of Spiro Heterocyclic Compounds
57
Preparation of 3-phenacylidene -2-indolinones (IIIa-c
)
A mixture of 0.01 mole of compound (IIa-c), ethanol 25 mL and 50 mL of dilute HCl
solution (25%), was allowed to stand overnight, fine orange needles were formed.
Preparation of spiropyrazolines (IVa-c & Va-c
)
A mixture of 0.01 mole of compound (IIIa-c) and hydrazine hydrate (50 %) or phenyl
hydrazine (0.01 mole) in ethanol (50 mL ) and diethyl amine (1 mL ) was refluxed for 10-14
hours, then acetic acid (10 ml) was added to the cold solution. The precipitate formed after
concentration was filtered and washed with cold ethanol and recrystallised from acetic acid.
Preparation of spiropyrimidinethione (VI a-c
)
A mixture of 0.01 mole of (III a-c ), phenylthiourea (0.02 mol), KOH (2 g), ethanol (60 mL)
and water (10 mL) was refluxed for 10-14 hours. The heavy precipitate formed after
concentration and cooling was filtered, dried and recrystallised from ethanol.
Table 1. Physical and spectral data of compounds (II a-c – VI a-c
)
Compd.
No
M. p,
o C
127-9
Yield,
%
65
IR,
υ / Cm-1
1H NMR,
δ / ppm
1630( CO); 1705(CO)
3410(NH); 3500(OH)
1640(CO); 1685(CO)
3400(NH); 3440(OH)
1650(CO); 1710(CO)
1100(O-C); 3420(NH)
3500(OH)
3.7(s,2H,CH2); 6.0(b,1H,OH)
7.6(m,9H,Ar-H); 10.1(s,1H,NH)
3.5(s,2H,CH2); 5.7(s,1H,OH)
7.8(m,8H,Ar-H); 10.2(s,1H,NH)
3.3(s,2H,CH2); 4.6(s,3H,OCH3)
5.9(s,1H,OH); 7.4(m,8H,Ar-H)
10.0(s,1H,NH)
IIa
184-6
187-9
76
72
IIb
IIc
194-6
182-5
192-4
262-4
222-3
226-7
210-2
164-6
212-3
146-9
245-7
183-5
86
80
87
56
52
55
56
60
55
60
57
50
1590(C=C); 1630(CO)
1690(CO); 3400(NH)
1580(C=C); 1620(CO)
1675(CO); 3400(NH)
1580(C=C); 1640(CO)
1690(CO); 3400(NH)
7.6(s,1H,CH); 7.8(m,9H,Ar-H)
10.8(s,1H,NH)
IIIa
IIIb
IIIc
IVa
IVb
IVc
Va
7.5(s,1H,CH); 7.7(m,8H,A-H)
10.6(s,1H,NH)
4.6(s,3H,OCH3); 7.5(s,1H,CH)
7.8(m,8H,Ar-H);10.4(s,1H,NH)
1240(C-N); 1625(C=N) 3.8(s,2H,CH2); 7.7(m,9H,Ar-H)
1695(CO); 3300(NH) 10.1(s,2H,2NH)
1250(C-N); 1620(C=N) 3.6(s,2H,CH2); 7.8(m,8H,Ar-H)
1690(CO); 3400(NH) 10.1(s,2H,2NH)
1240(C-N); 1630(C=N) 3.8(s,2H,CH2); 4.4(s,3H,OCH3);
1690(CO); 3340(NH) 7.7(m,8H,Ar-H);10.2(s,2H,2NH)
1240(C-N); 1600(C=C) 6.6(s,1H,CH); 8.0(m,14H,Ar-H)
1700(CO); 3400(NH) 10.0(s,2H,2NH)
1250(C-N); 1605(C=C) 6.7(s,1H,CH); 7.9(m.13H,Ar-
1690(CO); 3390(NH) H)10.1(s,2H,2NH)
1245(C-N); 1590(C=C) 6.5(s,1H,CH); 4.4(s,3H,OCH3)
Vb
Vc
1695(CO); 3400(NH)
1240(CS); 1605(C=C)
1695(CO); 3400(NH)
1250(CS); 1580(C=C)
1695(CO); 3360(NH)
1240(CS); 1590(C=C)
1695(CO); 3400(NH)
8.0(m,13H,Ar-H);10.0(s,2H,2NH)
6.9(s,1H,CH); 8.0(m,13H,Ar-H)
10.0(s,2H,2NH)
VIa
VIb
VIc
6.8(s,1H,CH); 7.9(m,13H,Ar-H)
10.1(s,2H,2NH)
6.6(s,1H,CH); 4.6(s,3H,OCH3)
8.1(m,13H,Ar-H);10.1(s,2H,2NH)