Synthesis of 4-(hydroxyphenyl)-1,2,4-triazoles

Full text of DOI:10.1134/S1070363206010312

ISSN 1070-3632, Russian Journal of General Chemistry, 2006, Vol. 76, No. 1, pp. 158 160.
Original Russian Text V.N. Elokhina, A.S. Nakhmanovich, T.I. Yaroshenko, Z.V. Stepanova, L.I. Larina, 2006, published in Zhurnal Obshchei Khimii,
006, Vol. 76, No. 1, pp. 161 163.
Pleiades Publishing, Inc., 2006.
2
LETTERS
TO THE EDITOR
Synthesis of 4-(Hydroxyphenyl)-1,2,4-triazoles
V. N. Elokhina, A. S. Nakhmanovich, T. I. Yaroshenko,
Z. V. Stepanova, and L. I. Larina
Favorskii Irkutsk Institute Khimii, Siberian Branch, Russian Academy of Sciences,
ul. Favorskogo 1, Irkutsk, 664033 Russia
e-mail: k301@irioch.irk.ru
Received July 7, 2005
DOI: 10.1134/S1070363206010312
Derivatives of 1,2,4-triazole are potential ligands
while 4-substituted 1,2,4-triiazoles exhibit radiopro-
tective activity [14, 15].
for the synthesis of magnetoactive coordination com-
pounds possessing optoelectronic, electrochemical,
electrophysical, and thermochemical properties [1 7].
Certain 1,2,4-triazoles are applied as drugs [8 10],
herbicides, pesticides, and growth regulators [11 13],
In the present work we developed a procedure for
preparing previously unknown 4-substituted 1,2,4-
triazoles, specifically 4-(o-,m-,p-hydroxyphenyl)-1,2,4-
triazoles, and studied their azo coupling with phenyl-
diazonium chloride.
H
5
3
6
5
1N
2H2O 2N
HN
O
O
4
N
1
4
R
NH +
R
2
HN
2
3
OH
OH
H
Ia Id
II
IIIa IIId
+
5
3
6
5
o
m
PhN Cl 1N
4
N
6 7
N= N
2
1
4
i
p
2N
2
3
OH
IVa, IVb
-OH (Ia, IIIa, IVa), 3-OH (Ib, IIIb, IVb), 4-OH (Ic, IIIc); R = H (Ia Ic, IIIa IIIc); 2-OH; R = NO 3 (Id, IIId).
2
2
4
-Substituted 1,2,4-triazoles were prepared by
fusing diformylhydrazine (II) with amino phenols I at
14 170 C. Triazoles III are stable crystalline sub-
ture of 8.8 g of diformylhydrazone (II), 10.9 g of
o-aminophenol (Ia), and a little hydroquinone was
heated at 145 150 C for 0.5 h under argon and then
cooled to 70 C, and 20 ml of ethanol. The mixture
was stirred for 5 min, cooled to 20 C, diluted with
1
stances with high melting points and soluble in etha-
nol, DMSO, and aqueous ethanol (1:1).
1
00 ml of absolute ether, and left to stand overnight
Treatment of solutions of compounds IIIa and IIIb
in a refrigerator. The precipitate that formed was
filtered off and recrystallized from aqueous ethanol
in methanol (aniline, NaNO , conc. HCl) gave azo
2
derivatives IVa and IVb, respectively.
(
1:1). Yield 6.65 g (46%), grayish yellow crystals, mp
1
4-(o-Hydroxyphenyl)-1,2,4-triazole (IIIa). A mix-
214 216 C. IR spectrum, , cm : 3400 (OH), 3100
158

SYNTHESIS OF 4-(HYDROXYPHENYL)-1,2,4-TRIAZOLES
159
(
(
(
CH), 1600 (C=N), 1520, 1475, 1440 (C=Carom), 1285
4-(2-Hydroxy-4-phenylazophenyl)-1,2,4-triazole
(IVa). To a cold (0 C) solution of 1.61 g of 4-(o-
hydroxyphenyl)-1,2,4-triazole (IIIa) in 20 ml of
methanol, a cold (0 C) solution of phenyldiazonium
1
C N). H NMR spectrum, , ppm: 7.32 7.81m
3
,5
CH ), 9.20 s (2H, C H), 10.92 br.s (1H, OH).
arom
1
3
2
C NMR spectrum, , ppm: 150.53 (C ), 143.17
C
3
,5
5
4
1
chloride (2 g of aniline and 1.65 g of NaNO in 6 ml
2
(C ), 129.79 (C ), 125.63 (C ), 121.71 (C ), 119.70
of conc. HCl and 50 ml of water) was added. After
3
6
15
(
C ), 119.95 (C ). N NMR spectrim, N, ppm:
2
5
-min stirring, a saturated solution of sodium acetate
4
1,2
03.5 (N ), 62.0 (N ). Found, %: C 59.62; H 3.95;
was added until turbidity, and the mixture was left to
stand overnight. The precipitate that formed was
filtered off, washed on the filter with cold water, and
dried in a vacuum. Yield 1.56 g (60%), bright yellow
N 26.12. C H N O. Calculated, %: C 59.63; H 4.38;
N 26.07.
8
7
3
4-(m-Hydroxyphenyl)-1,2,4-triazole (IIIb) was
crystals, mp 235 237 C (from DMF). IR spectrum,
prepared similarly to IIIa from 4.4 g of compound II
and 5.5 g of m-aminophenol at 114 115 C, reaction
temperature 1 h. Yield 4.37 g (54%), grayish yellow
1
,
cm : 3440 (OH), 3100 (CH), 1610, 1595 (N=N,
C=N), 1530, 1500, 1425 (C=Carom), 1205 (C N).
1
H NMR spectrum, , ppm: 7.27 8.01 m (3H, C H ),
crystals, mp 230 231 C (from ethanol). IR spectrum,
6
3
1
3,5
13
,
cm : 3410 (OH), 3100 (CH), 1605 (C=N), 1520,
7.54 7.85 m (5H, C H ), 8.93 (2H, C H). C NMR
6 5
spectrum, , ppm: 153.81 (C ), 151.81 (C ), 144.88
C i
(C ), 143.00 (C ), 131.05 (C ), 129.40 (C ), 124.38
1
6
1
490, 1440 (C=Carom), 1220 (C N). H NMR spec-
trum, , ppm: 6.85 7.33 m (CHarom), 9.05 s (2H,
3
3,5
p
m
3
,5
13
C H), 10.01 s (1H, OH). C NMR spetrum, C,
ppm: 158.87 (C ), 141.71 (C ), 135.19 (C ), 131.25
(
NMR spectrum, , ppm: 193.8 (N ), 59.7 (N ).
Found, %: C 59.58; H 4.30; N 25.92. C H N O.
Calculated, %: C 59.63; H 4.38; N 26.07.
4
1
2
5
(C ), 122.27 (C , C ), 120.21 (C ), 117.22 (C ).
3
3,5
1
o
15
4
N NMR spectrum,
, ppm: 200.8 (N ), 125.5
5
6
4
2
15
N
C ), 115.42 (C ), 112.02 (C ), 108.60 (C ).
N
6
7
1,2
(N ), 121.5 (N ), 57.7 (N ). Found, %: C 63.25;
4
1,2
N
H 4.29; N 26.18. C H N O. Calculated, %: C 63.38;
14 11 5
8
7
3
H 4.17; N 26. 40.
-(3-Hydroxy-4-phenylazophenyl)-1,2,4-triazole
4
4-(p-Hydroxyphenyl)-1,2,4-triazole (IIIc) was
(IVb) was prepared similarly to IVa from 1.73 g of
4-(m-hydroxyphenyl)-1,2,4-triazole (Ib), 2.0 g of
prepared similarly to IIIc from 4.4 g of compound II
and 5.5 g p-aminophenol at 165 170 C, reaction time
0
2
3
(
6
aniline, 1.65 g of NaNO , 1.65 g of sodium acetate at
2
.5 h. Yield 4.82 g (64%), grayish yellow crystals, mp
0 C. Yield 1.51 g (58%), bright yellow crystals, mp
1
1
85 286 C (from ethanol). IR spectrum, , cm :
274 276 C. IR spectrum, , cm : 3430 (OH), 3105
400 (OH), 3090 (CH), 1590 (C=N), 1520, 1480
(CH), 1610, 1585 (N=N, C=N), 1535, 1510, 1410
(C=Carom), 1205 (C-N). 1H NMR spectrum, , ppm:
7.00 7.66 m (3H, C H ), 7.48 7.85 m (5H, C H ),
1
C=Carom), 1230 (C N). H NMR spectrum, , ppm:
3
,5
.90 17.45 m (C
), 8.92 s (2H, C ), 9.85 s (1H,
arom
6
3
6
5
1
3
4
3,5
13
OH). C NMR spectrum,
1
, ppm: 157.43 (C ),
8.85 s (C H), 10.96 br.s (1H, OH). C NMR spec-
C
3
,5
1
2 ,
3
41.82 (C ), 125.85 (C ), 123.33 (C 6 ), 116.30
trum,
, ppm: 162.26 (C ), 152.38 (C ), 144.30
C
i
3
,5
15
, ppm: 194.4 (N4),
3,5
4
1
(C
). N NMR spectrum,
(C ), 137.49 (C ), 135.17 (C ), 131.32 (C ), 129.55
p
N
1
,2
5
6
5
9.7 (N ). Found, %: C 59.48; H 4.25; N 26.02.
(
(
C ), 122.75 (C ), 118.27 (C ), 117.04 (C ), 112.12
m o
C ). N NMR spectrum, N, ppm: 199.3 (N ),
20.4 (N ), 116.0 (N ), 58.1 (N ). Found, %:
C 63.38; H 4.22; N 26.12. C H N O. Calculated, %:
C H N O. Calculated, %: C 59.63; H 4,38; N 26.07.
2
15
4
8
7
3
7
6
1,2
1
4-(2-Hydroxy-4-nitrophenyl)-1,2,4-triazole (IIId)
was prepared similarly to IIIa from 4.4 g of com-
pound II and 7.7 g of 2-amino-5-nitrophenol at 175
14 11
5
C 63.38; H 4.17; N 26.40.
1
80 C, reaction time 1 h. Yield 6.68 g (68%), black
The IR spectra were obtained on a Specord IR-75
1
crystals, mp 360 365 C. IR spectrum, , cm : 3410
1
13
instrument in KBr. The H and C NMR spectra were
recorded at 20 C on a Bruker-400 spectrometer
(400.13 and 100.62 MHz, respectively) in DMSO-d6,
internal reference HMDS.
(
(
OH), 3105 (CH), 1590 (C=N), 1520, 1495, 1425
C=Carom), 1360, 865 (NO ), 1210 (C N). H NMR
1
2
spectrum, , ppm: 7.72 7.83 m (3H, C H ), 8.95 s
6
3
3
,5
13
(
2H, C H), 14.33 br.s (1H, OH). C NMR spectrum,
C, ppm: 151.36 (C ), 147.93 (C ), 143.41 (C ),
2
4
3,5
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1
6
5
3
1
27.69 (C ), 126.55 (C ), 115.29 (C ), 111.92 (C ).
1
5
4
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2
2
2
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