REACTION OF 4-AMINO-4,5-DIHYDRO-1H-1,2,4-TRIAZOL-5-ONES WITH 2,5-DIMETHOXYTETRAHYDROFURAN

Full text of DOI:10.1135/cccc19940731

New Compounds
731
REACTION OF 4-AMINO-4,5-DIHYDRO-1H-1,2,4-TRIAZOL-5-ONES
WITH 2,5-DIMETHOXYTETRAHYDROFURAN
Aykut A. IKIZLER and Haydar YUKSEK
Department of Chemistry,
Karadeniz Technical University, 61080 Trabzon, Turkey
Received April 9, 1993
Accepted May 25, 1993
A number of studies involving some reactions of 4-amino-4,5-dihydro-1H-1,2,4-triazol-
5-ones have been made in recent years1 – 6. On the other hand, the reactions of some
N-aminoheteroaryls with 1,4-diketones or 1,4-dialdehydes to give N,N′-linked bi-
heteroaryls have also been reported7 – 10. In the present study, a series of 3-alkyl-4-
amino-4,5-dihydro-1H-1,2,4-triazol-5-ones I were condensed in good yields with the
succinaldehyde equivalent, 2,5-dimethoxytetrahydrofuran to give N,N′-bis(3-alkyl-4,5-
dihydro-1H-1,2,4-triazol-5-on-4-yl)-1,4-butanediimines II or 1-(3-alkyl-4,5-dihydro-
1H-1,2,4-triazol-5-on-4-yl)pyrroles III in nitrobenzene or acetic acid medium,
respectively. To obtain more information on type II compounds, 3-methyl-4-ethyliden-
amino-4,5-dihydro-1H-1,2, 4-triazol-5-one (IV) was synthesized.
EXPERIMENTAL
Melting points were determined on a Büchi oil heated melting point apparatus and are uncorrected.
Experimental data for compounds II, III and IV are given in Table I. Infrared spectra (given in cm−1
)
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Ikizler, Yuksek:
TABLE I
Experimental data for compounds II, III and IV
Calculated/Found
% H
M.p., °C
Yield, %
Formula
M.w.
Compound
% C
% N
IIa
IIb
IIc
225a
63
C10H14N8O2
278.3
43.16
42.94
5.07
5.13
40.27
40.00
221a
69
C12H18N8O2
306.3
47.05
46.79
5.92
5.95
36.58
36.74
228a
78
C22H22N8O2
430.5
61.38
61.25
5.15
5.12
26.03
25.94
IId
IIe
247a
65
C24H26N8O2
458.5
62.87
62.60
5.71
5.77
24.44
24.14
250a
63
C22H20Cl2N8O2
499.4
52.91
52.86
4.04
4.22
22.44
22.29
IIf
265a
79
C22H20N10O6
520.5
50.77
50.66
3.87
3.90
26.91
26.86
IIg
IIh
IIIa
IIIc
IIId
IIIe
IIIg
IV
230b
71
C20H18N8O2
402.4
59.69
59.40
4.51
4.78
27.84
27.60
307c
83
C22H22N8O2
430.5
61.38
61.10
5.15
5.09
26.03
25.73
135b
76
164d
C7H8N4O
164.2
51.21
51.34
4.91
4.87
34.13
34.41
64.98
64.76
66.12
66.00
5.03
5.10
5.55
5.50
23.32
23.37
22.04
21.85
C13H12N4O
290.3
88
190d
89
C14H14N4O
254.3
191e
86
C13H11ClN4O
274.7
56.84
57.13
4.03
4.08
20.39
20.56
204b
91
C12H10N4O
226.2
63.70
63.42
4.46
4.28
24.77
24.50
126e
41
C5H8N4O
140.1
42.85
42.60
5.75
5.85
39.98
39.96
a
b
c
d
e
Crystallized from: Ethanol; benzene–petroleum ether (1 : 1); DMSO–H2O (1 : 3); water; benzene.
Collect. Czech. Chem. Commun. (Vol. 59) (1994)

New Compounds
733
TABLE II
IR Data for compounds II, III and IV
Substituted
benzenoid ring
Compound
νNH
νC=O
νC=N
IIa
IIb
IIc
3 175
3 180
3 170
3 185
3 175
3 175
3 190
3 170
3 200
3 195
3 200
3 195
3 190
3 190
1 690
1 695
1 700
1 685
1 695
1 692
1 690
1 695
1 710
1 705
1 695
1 695
1 705
1 690
1 590
1 580
1 582
1 590
1 590
1 585
1 575
1 575
1 595
1 590
1 588
1 590
1 580
1 595
–
–
730, 695
810
IId
IIe
825
IIf
808
IIg
IIh
IIIa
IIIc
IIId
IIIe
IIIg
IV
760, 690
820
–
730, 690
800
815
765, 690
–
TABLE III
1H NMR Data for compounds II
Compound
2 CH3
CH2CH2
2 CH2
2 CH
2 NH
Aromatic H
IIa
IIb
IIc
IId
IIe
IIf
2.22 s
2.40 – 3.00 m
–
9.20 s
9.15 s
9.05 s
9.00 s
9.15 s
9.16 s
12.00 s
11.95 s
–
–
a
a
1.16 t
–
2.35 – 2.85 m
2.40 – 2.90 m
2.40 – 2.85 m
2.35 – 2.80 m
3.85 s
3.85 s
3.90 s
4.05 s
11.90 s 7.20 s, 10 H
11.90 s 7.10 s, 8 H
12.05 s 7.30 s, 8 H
12.18 s 7.60 d, 4 H
8.25 d, 4 H
2.20 s
–
–
IIg
IIh
–
2.40 – 3.05 m
2.30 – 2.80 m
–
–
9.16 s
9.05 s
12.20 s 7.40 – 8.20 m, 10 H
12.10 s 7.32 d, 4 H
7.76 d, 4 H
3.10 s
a
2.20 – 2.90 m, 8 H (4 CH2).
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Ikizler, Yuksek:
were run as potassium bromide pellets using a Perkin–Elmer 337 spectrophotometer (Table II).
1H NMR and 13C NMR spectra (given in δ, ppm) were recorded on a Varian A60 spectrometer or a
Bruker AC-200 FT instrument in (CD3)2SO. Combustion analyses were performed on a Carlo Erba
1
1106 elemental analyzer. H NMR Data are given in Tables III and IV. Mass spectrum of compound
IIa was run on a Kratos MS-50 instrument. The starting compounds I were synthesized by methods
described earlier2,11
.
N,N′-Bis(3-alkyl-4,5-dihydro-1H-1,2,4-triazol-5-on-4-yl)-1,4-butanediimines II.
General Procedure
3-Alkyl-4-amino-4,5-dihydro-1H-1,2,4-triazol-5-one (I, 0.01 mol) was treated with a solution of 2,5-
dimethoxytetrahydrofuran (1.3 ml, 0.01 mol) in nitrobenzene (20 ml), and the mixture was refluxed
for 2 h. After cooling, the precipitate formed was recrystallized from an appropriate solvent to give
compound II.
1-(3-Alkyl-4,5-dihydro-1H-1,2,4-triazol-5-on-4-yl)pyrroles III.
General Procedure
3-Alkyl-4-amino-4,5-dihydro-1H-1,2,4-triazol-5-one (I, 0.01 mol) was dissolved in acetic acid
(25 ml) and treated with 2,5-dimethoxytetrahydrofuran (1.3 ml, 0.01 mol). The mixture was refluxed
for 1.5 h and then evaporated at 50 – 55 °C under reduced pressure. Several recrystallizations of the
residue from an appropriate solvent afforded pure compound III.
Synthesis of 3-Methyl-4-ethylideneamino-4,5-dihydro-1H-1,2,4-triazol-5-one (IV)
3-Methyl-4-amino-4,5-dihydro-1H-1,2,4-triazol-5-one (Ia) (1.14 g, 0.01 mol) was dissolved in
ethanol (30 ml), and acetaldehyde (0.62 ml, 0.11 mol) was added to the solution. The mixture was
refluxed for 1 h and then evaporated at 25 – 30 °C under reduced pressure. The viscous residue
TABLE IV
1H NMR Data for compounds III and IV
Compound
CH3
CH3
CH2
CH
NH
Aromatic H
IIIa
IIIc
2.02 s
–
–
–
–
–
12.05 s
12.15 s
6.26 t, 2 H; 7.00 t, 2 H
6.20 t, 2 H; 6.90 t, 2 H
7.00 – 7.40 m, 5 H
6.30 t, 2 H; 6.95 t, 2 H
7.20 q, 4 H
–
3.95 s
IIId
IIIe
IIIg
IV a
2.34 s
–
3.85 s
–
12.25 s
12.20 s
12.40 s
12.30 s
–
–
–
–
3.90 s
–
–
6.20 t, 2 H; 6.90 t, 2 H
7.20 q, 4 H
–
–
6.30 t, 2 H; 7.10 t, 2 H;
7.30 – 7.60 m, 5 H
–
2.10 d
2.28 s
9.15 s
a
CDCl3.
Collect. Czech. Chem. Commun. (Vol. 59) (1994)

New Compounds
735
solidified in deep-freeze with 2 – 3 ml of ethyl acetate. Recrystallization of the product from benzene
gave pure compound IV. The 13C NMR data for compounds IIa and IIc are given below.
IIa: 158.88 (2 C, C=N), 151.24 (2 C, triazole C5), 143.87 (2 C, triazole C3), 28.77 (2 C, CH2CH2),
10.95 (2 C, CH3).
IIc: 158.72 (2 C, C=N), 151.30 (2 C, triazole C5), 145.87 (2 C, triazole C3), 135.69 (2 C, aryl ring
carbons), 128.66 (4 C, aryl ring carbons), 128.31 (4 C, aryl ring carbons), 126.60 (2 C, aryl ring
carbons), 30.91 (2 C, CH2), 28.25 (2 C, CH2CH2).
Molecular ion (M+) for compound IIa: 278.
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