Synthesis and selected transformations of 1-(5-methyl-1-aryl-1H-1,2,3- triazol-4-yl)ethanones and 1-[4-(4-R-5-methyl-1H-1,2,3-triazol-1-yl)phenyl] ethanones

Article abstract of DOI:10.1134/S1070363209020248

By cycloaddition of arylazides to acetylacetone are obtained derivatives of 1,2,3-triazole. In the reaction of 1-[5-methyl-1-(R-phenyl)-1H-1,2,3-triazol-4- yl] ethanones (IIa-IIe) and 1-[4-(4-R-5-methyl-1H-1,2,3-triazol-1-yl)phenyl] ethanones (VIIa-VIIe)

Full text of DOI:10.1134/S1070363209020248

ISSN 1070-3632, Russian Journal of General Chemistry, 2009, Vol. 79, No. 2, pp. 309–314. © Pleiades Publishing, Ltd., 2009.
Original Russian Text © N.T. Pokhodylo, R.D. Savka, V.S. Matiichuk, N.D. Obushak, 2009, published in Zhurnal Obshchei Khimii, 2009, Vol. 79, No. 2,
pp. 320–325.
Synthesis and Selected Transformations
of 1-(5-methyl-1-aryl-1H-1,2,3-triazol-4-yl)ethanones
and 1-[4-(4-R-5-methyl-1Н-1,2,3-triazol-1-yl)phenyl]ethanones
N. T. Pokhodylo, R. D. Savka, V. S. Matiichuk, and N. D. Obushak
Ivan Franko Lviv National University
ul. Kirilla i Mefodiya 6, Lviv, 79005 Ukraine
e-mail: obushak@in.lviv.ua
Received July 8, 2008
Abstract―By cycloaddition of arylazides to acetylacetone are obtained derivatives of 1,2,3-triazole. In the
reaction of 1-[5-methyl-1-(R-phenyl)-1H-1,2,3-triazol-4-yl] ethanones (ІІа–IIe) and 1-[4-(4-R-5-methyl-1H-
1,2,3-triazol-1-yl)phenyl] ethanones (VIІа–VIIe) with isatin are obtained 2-[1-(R-phenyl)-5-methyl-1H-1,2,3-
triazol-4-yl]-4-quinolinecarboxylic acids (IIIа–IIIe) and 2-[4-(4-R-5-methyl-1H-1,2,3-triazol-1-yl)phenyl] -4-
quinolinecarboxylic acids (IХа, IXb), respectively. We found that 1-[5-methyl-1-(R-phenyl)-1H-1,2,3-triazol-
4-yl] ethanones (ІІа–ІІe) readily transform into [5-methyl-1-(R-phenyl)-1H-1,2,3-triazol-4-yl] acetic acids
(IVа–IVc) by the method of Wilgerodt–Kindler. The (5-methyl-1-phenyl-1H-1,2,3-triazol-4-yl)acetic acid
reacts with 5-phenyl-4-amino-4H-1,2,4-triazol-3-thiol affording 6-[(5-methyl-1-phenyl-1H-1,2,3-triazol-4-yl)
methyl]-3-phenyl[1,2,4] triazolo[3,4-b] [1,3,4] thiadiazole (VI).
DOI: 10.1134/S1070363209020248
In this study we investigated possibility of
application of 1-(5-methyl-1-aryl-1H-1,2,3-triazol-4-
yl)ethanones (ІІа–ІІe) and 1-[4-(4-R-5-methyl-1H-
1,2,3-triazol-1-yl)phenyl] ethanones (VIІа–VIIe) in
some reactions that proceed under rigid conditions.
Derivatives of 1,2,3-triazole is an important class of
heterocyclic compounds [1–3]. They are applied as
pharmaceutical preparations with cytostatic [4],
antiviral [5] and antiproliferative [6] action and as γ-
aminobutyric acid antagonists [7, 8]. They are used as
intermediates at the synthesis of antibiotics [9, 10, 11],
antigistamine preparations [12] and neuroleptics [13],
muscarin antagonists [14], nucleozides [15, 16],
rotaxanes [17] and chemiluminescent compounds
[18, 19]. The derivatives of 1,2,3-triazole also are
applied as insecticides [20], fungicides [21], plant
growth regulators [22, 23], corrosion inhibitors [24]
and photostabilizers [25]. Therefore in the last two
decades the chemistry of 1,2,3-triazole derivatives was
developed intensively. Many publications are denoted
to the development of new synthetic methods and
improving existing ones [1–3]. Much less were studied
transformations of functionalized 1,2,3-triazoles. The
triazole ring is known as enough labile and can exert
both thermal and photochemical destruction [26].
Therefore chemical behavior of compounds that
include triazole fragment remains unknown for many
reactions.
In the reaction of arylazides Іа–Ie with
acetylacetone we prepared a series of 1-(5-methyl-1-
aryl-1H-1,2,3-triazol-4-yl)ethanones IIa–IIe. We found
that 1,2,3-triazole derivatives IIa–IIe are formed in a
high yield when this reaction is conducted at room
temperature in methanol with sodium methylate as a
base. Reaction is completed in a week, yield of
compounds IIa–IIe was 37–77%. Attempted accelera-
tion of this reaction by heating led to tarring of the
reaction mixture. With softer bases and at reflux in
methanol the degree of conversion of the parent
arylazides Ia–Ie also diminished.
Note that only restricted data on the reaction of
arylazides with acetylacetone has been published [27–
30]. The procedure developed by us makes available
substituted triazoles IIa–IIe that can be used as reagents
for further application.
309

310
POKHODYLO et al.
We used 4-acetyltriazoles IIa–IIe in the syntheses
Ketones IIa–IIe also readily react with sulfur and
morpholine under the conditions of Wilgerodt-Kindler
reaction affording triazolylacetic acid trimorpholides
IVa–IVc in high yield (78–86%). By hydrolysis of the
latter we obtained triazolylacetic acids Va–Vc which
can be used as reagents for the creation of combinatory
libraries. On one example (compound VI) we showed
that acids V react with 4-amino-1,2,4-triazol-3-thiols
to form [1, 2, 4] triazolo[3,4-b] [1,3,4] thiadiazoles
[31–33].
of quinoline derivatives along Pfitzinger reaction and
of 1,2,3-triazolylacetic acids by the method of
Wilgerodt–Kindler. We found that compounds IIa–IIe
readily react with isatin in strong alkaline medium with
construction of quinoline ring. Yields of substituted 4-
quinolinecarboxylic acids IIIa–IIIe achieve 78–90%,
except that of compound IIIb, and reaction is fast due
to significant acceptor properties of triazole ring that
activates acetyl fragment.
OH
O
Me
O
O
N
NH2
N3
O
N
N
Me
acac
MeONa
(1) HCl
NaNO2
N
N
H
N
MeOH
(2) NaN3
KOH
EtOH/H2O
N
Me
R
R
N
R
Ia_Ie
IIa_IIe
S
R
IIIa_IIIe
O
HN
O
N
OH
O
N
S
N
N
SH
N
N
N
N
N
N
N
S
N
N
N
NH2
POCl3
Me
N
N
Me
(1) KOH
(2) HCl
N
Me
R
IVa_IVc
Va_Vc
R
VI
I, II, III: R = H (a), 2-Me (b), 3-Me (c), 4-Me (d), 4-Сl (e); IV, V: R = H (a), 4-Me (b), 4-Сl (c).
Using procedures described in [34] we synthesized
When a decarboxylated ketone phenylhydrazone VIII
is used occurs tarring that is explainable by the lability
of hydrogen atom in 4 position.
1-aryl-1H-1,2,3-triazolylethanones VII and VIII con-
taining acetyl group in the aryl ring. We found that
these compounds also react with isatin, the result of
this reaction is formation of 4-quinolinecarboxylic
acids IХа, IXb in high yield.
Thus, we elaborated general methodology for the
synthesis in high yield of 1,2,3-triazole derivatives by
cycloaddition of arylazides to acetylacetone. We
showed that 1-(5-methyl-1-aryl-1H-1,2,3-triazol-4-yl)-
ethanones IIa–IIe readily react with isatin in strong
alkaline medium, therewith are formed 2-(1-aryl-5-
methyl-1H-1,2,3-triazol-4-yl)-4-quinolinecarboxylic
acids IIIa–IIIe. We also elaborated a procedure for the
At the study of ketone phenylhydrazones VII and
VIII in the syntheses of pyrazoles was forund that at
the action of Wilsmeier–Haak complex the final
pyrazole X is formed only when the parent ketone VII
contains carboxy group in 4 position of triazole ring.
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 79 No. 2 2009

SYNTHESIS AND SELECTED TRANSFORMATIONS
311
synthesis of [5-methyl-1-(R-phenyl)-1H-1,2,3-triazol-
4-yl] acetic acids Va–Vc. We studied transformation
of 1-[4-(4-R-5-methyl-1H-1,2,3-triazol-1-yl)phenyl]-
ethanones VII and VIII into the derivatives of 4-
quinolinecarboxylic acids IXа and IXb and pyra-
zolecarbaldehyde X.
O
Me
O
OH
O
O
N
N
N
N
H
(1) PhNHNH2
O
KOH
EtOH/H2O
(2) POCl3
DMF
N
Me
HO
N
N
N
N
Me
O
VII
Me
HO
N
N
N
N
R
O
Δ
O
IXa, IXb
O
X
O
N
Me
Me
H
(1) PhNHNH2
KOH
EtOH/H2O
(2) POCl3
DMF
N
N
N
VIII
IХ: R = H (a), COOН (b).
amount of product was extracted. The product was
purified by recrystallization from aqueous ethanol.
Compound ІІа, yield 58%, mp 99–100ºС; ІIb, yield
37%, oily substance; ІІc, yield 67%, mp 74–75ºС; ІІd,
yield 74%, mp 108–109ºС; ІІe, yield 77%, mp 93–
94ºС.
EXPERIMENTAL
The 1Н NMR spectra of the synthesized compounds
were registered on a Varian Mercury 400 instrument
with operating frequency 400 MHz, solvent DMSO-d6,
internal reference TMS.
Compounds Iа–Ie and 1-(4-azidophenyl)ethanone
for the synthesis of compound VІI are prepared along
the procedures in [35], yields 46–84% on the parent
anilines: Іа, yield 63%, bp 52–53ºС (10 mm Hg); Іb,
yield 46%, bp 62ºС (10 mm Hg); Іc, yield 67%, bp
78ºС (10 mm Hg); Іd, yield 70%, bp 70ºС (10 mm
Hg); Іe, yield 84%, mp 21–22ºС; 1-(4-azidophenyl)
ethanone, yield 76%, mp 46–48ºС [34].
Compounds VІI and VІII were prepared along the
procedures in [34] and recrystallized from ethanol:
VІI, yield 85%, mp 198–199ºС; VІII, yield 63%, mp
113–114ºС.
Synthesis of cynchonic acids ІIIa–IIIe and ІХа,
IXb. At heating 1.47 g of isatin was dissolved in 25 ml
of 8 M solution of KOH, then 0.1 mol of ketone ІІ,
VІI or VІII was added and ethanol was added until the
mixture became homogenous. The mixture was boiled
under reflux for 2 h, then cooled and 10 ml of water
was added to it, then it was acidified with АсОН to
рН ≈ 6–7 and filtered. The products were
recrystallized from ethanol.
1-(5-Methyl-1-aryl-1H-1,2,3-triazol-4-yl)ethanones
(IIa–IIe). A solution of sodium methoxide is prepared
from 3 g of sodium and 70 ml of methanol. To the
solution at vigorous stirring was added10 g of acetyl-
acetone and 0.1 mol of arylazide. The mixture was
stirred at room temperature until precipitate was
formed. The precipitate was filtered off, to the filtrate
was added a few milliliters of water and additional
2-(1-Phenyl-5-methyl-1H-1,2,3-triazol-4-yl)-4-
quinolinecarboxylic acid (IIIа). Yield 88%, mp 294–
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 79 No. 2 2009

312
POKHODYLO et al.
1
295ºС. The H NMR spectrum, δ, ppm: 2.88 s (3Н,
Ме), 7.59–7.69 m (6Н, Ph + 6-H quinoline ), 7.75 t
2-[4-(5-Methyl-1H-1,2,3-triazol-1-yl)phenyl]-4-
quinolinecarboxylic acid (IХа). Yield 79%, mp 233–
3
1
(1Н, 7-H quinoline, J = 7.6 Hz), 8.07 d (1Н, 5-
234ºС. The H NMR spectrum, δ, ppm: 2.45 s (3Н,
3
H quinoline, J = 8.4 Hz), 8.79 s (1Н, 3-H quinoline),
Ме), 7.61 s (1Н, triazole), 7.67 t (1Н, 6-H quinoline, 3J =
3
3
8.80 d (1Н, 8-H quinoline, J = 8.4 Hz), 13.55 br.s
(1Н, СООН). Found, %: C 68.91; H 4.14; N 16.84.
C19H14N4O2. Calculated, %: C 69.08; H 4.27; N 16.96.
7.6 Hz), 7.76 d (2Н, 3,5-Н С6Н4, J = 8.8 Hz), 7.82 t
3
(1Н, 7-H quinoline, J = 7.6 Hz), 8.16 d (1Н, 5-
H quinoline, 3J = 8.4 Hz), 8.51 d (2Н, 2,6-Н С6Н4, 3J =
8.8 Hz), 8.53 s (1Н, 3-H quinoline), 8.78 d (1Н, 8-
2-[1-(2-Methylphenyl)-5-methyl-1H-1,2,3-triazol-
4-yl]-4-quinolinecarboxylic acid (IIIb). Yield 52%,
mp >300ºС. The H NMR spectrum, δ, ppm: 2.09 s
(3Н, Ме), 2.68 s (3Н, Ме), 7.39–7.58 m (4Н, С6Н4),
7.63 pseudo-t (1Н, 6-H quinoline ), 7.77 pseudo-t (1Н,
7-H quinoline), 8.07 d (1Н, 5-H quinoline, 3J =
8.4 Hz), 8.78 d (1Н, 8-H quinoline, 3J = 8.4 Hz), 8.79 s
(1Н, 3-H quinoline), 13.69 br.s (1Н, СООН). Found,
%: C 69.87; H 4.61; N 16.18. C20H16N4O2. Calculated,
%: C 69.76; H 4.68; N 16.27.
3
H quinoline, J = 8.4 Hz). Found, %: C 68.92; H 4.40;
N 16.81. C19H14N4O2. Calculated, %: C 69.08; H 4.27;
N 16.96.
1
2-[4-(4-Carboxy-5-methyl-1H-1,2,3-triazol-1-yl)-
phenyl]-4-quinolinecarboxylic acid (IХb). Yield 83%,
1
mp >300ºС. The H NMR spectrum, δ, ppm: 2.46 s
(3Н, Ме), 7.68 pseudo-t (1Н, 6-H quinoline ), 7.78 d
3
(2Н, 3,5-Н С6Н4, J = 8.8 Hz), 7.81 pseudo-t (1Н, 7-
3
H quinoline), 8.16 d (1Н, 5-H quinoline, J = 8.4 Hz),
3
8.54 d (2Н, 2,6-Н С6Н4, J = 8.8 Hz), 8.54 s (1Н, 3-
2-[1-(3-Methylphenyl)-5-methyl-1H-1,2,3-triazol-
4-yl]-4-quinolinecarboxylic acid (IIIc). Yield 78%,
mp 285–286ºС. The 1H NMR spectrum, δ, ppm: 2.50 s
3
H quinoline), 8.79 d (1Н, 8-H quinoline, J = 8.4 Hz).
Found, %: C 64.08; H 3.54; N 14.85. C20H14N4O4.
Calculated, %: C 64.17; H 3.77; N 14.97.
3
(3Н, Ме), 2.86 s (3Н, Ме), 7.39 d (2Н, С6Н4, J =
7.2 Hz), 7.44 s (1Н, 2-Н С6Н4), 7.51 pseudo-t (1Н, 5-
Н С6Н4), 7.61 pseudo-t (1Н, 6-H quinoline), 7.75
pseudo-t (1Н, 7-H quinoline), 8.07 d (1Н, 5-H quinoline,
3J = 8.0 Hz), 8.78 s (1Н, 3-H quinoline ), 8.79 d (1Н,
8-H quinoline, J = 8.4 Hz). Found, %: C 69.52; H
4.59; N 16.36. C20H16N4O2. Calculated, %: C 69.76; H
4.68; N 16.27.
Synthesis of [5-methyl-1-aryl-1H-1,2,3-triazol-4-
yl]-1-(morpholin-4-yl)ethanethiones
(Wilgerodt–
Kindler reaction) (IVa–IVc). A mixture of 0.1 mol of
ketone II, 6.4 g of sulfir and 17.4 g of morpholine was
heated for 5 h in oil bath (the bath temperature 135ºС)
with reflux condenser. Warm mixture was carefully
poured into 50 ml of hot ethanol and triturated to the
beginning of crystallization. The mixture was left
overnight in a freezer, then the product was filtered
off, washed with little amount of cold ethanol and
dried in air. IVa, yield 78%, mp 148–149ºС; IVb,
yield 83%, mp 140–141ºС. IVc, yield 86%, mp 149–
150ºС.
3
2-[1-(4-Methylphenyl)-5-methyl-1H-1,2,3-triazol-
4-yl]-4-quinolinecarboxylicа acid (IIId). Yield 83%,
mp 262–263ºС. The 1H NMR spectrum, δ, ppm: 2.46 s
(3Н, Ме), 2.87 s (3Н, Ме), 7.43 d (2Н, 3,5-Н С6Н4,
3
3J = 7.2 Hz), 7.50 d (2Н, 2,6-Н С6Н4, J = 7.2 Hz),
7.62 pseudo-t (1Н, 6-H quinoline), 7.76 pseudo-t (1Н,
7-H quinoline), 8.07 d (1Н, 5-H quinoline, 3J =
8.4 Hz), 8.78 d (1Н, 8-H quinoline, 3J = 8.4 Hz), 8.79 s
(1Н, 3-H quinoline ). Found, %: C 69.64; H 4.56; N
16.14. C20H16N4O2. Calculated, %: C 69.76; H 4.68; N
16.27.
Synthesis of (5-methyl-1-aryl-1H-1,2,3-triazol-4-
yl)acetic acids (Va–Vc). To a mixture of 80 g of 50%
aqueous solution of KOH and 140 ml of ethanol was
added 0.1 mol of crude thiomorpholide IVa–IVc. The
mixture was refluxed for 6 h and then poured to water
and acidified. The solution was cooled, the precipitate
formed was filtered off. The acid was recrystallized
from aqueous ethanol.
2-[1-(4-Chlorophenyl)-5-methyl-1H-1,2,3-triazol-
4-yl]-4-quinolinecarboxylic acid (IIIe). Yield 90%,
mp 261–262ºС. The 1H NMR spectrum, δ, ppm: 2.88 s
(3Н, Ме), 7.60–7.73 m (5Н, С6Н4 + 6-H quinoline),
7.77 pseudo-t (1Н, 7-H quinoline), 8.08 d (1Н, 5-
(5-Methyl-1-phenyl-1H-1,2,3-triazol-4-yl)acetic
1
3
acid (Vа). Yield 61%, mp 149–150ºС. The H NMR
H quinoline, J = 8.4 Hz), 8.77 s (1Н, 3-H quinoline),
3
spectrum δ, ppm: 2.28 s (3Н, Ме), 3.73 s (2Н, СН2),
7.57–7.68 m (5Н, Ph), 12.63 br.s (1Н, СООН). Found,
%: C 60.69; H 5.23; N 19.42. C11H11N3O2. Calculated,
%: C 60.82; H 5.10; N 19.34.
8.79 d (1Н, 8-H quinoline, J = 8.4 Hz), 13.69 br.s
(1Н, СООН). Found, %: C 62.70; H 3.45; N 15.31.
C19H13ClN4O2. Calculated, %: C 62.56; H 3.59; N
15.36.
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 79 No. 2 2009

SYNTHESIS AND SELECTED TRANSFORMATIONS
313
spectrum, δ, ppm: 2.62 s (3Н, Ме), 7.40 pseudo-t (1Н,
4-Н Ph), 7.55 pseudo-t (2Н, 3,5-Н Ph), 7.71 d (2Н,
[5-Methyl-1-(4-methylphenyl)-1H-1,2,3-triazol-4-
yl]acetic acid (Vb). Yield 65%, mp 196–197ºС. The
1H NMR spectrum, δ, ppm: 2.26 s (3Н, Ме), 2.44 s
(3Н, Ме), 3.63 s (2Н, СН2), 7.36 d (2Н, 3,5-Н С6Н4,
3
3
3,5-Н С6Н4, J = 8.4 Hz), 8.01 d (2Н, 2,6-Н Рh, J =
3
8.0 Hz), 8.25 d (2Н, 2,6-Н С6Н4, J = 8.4 Hz), 9.40 s
3
3J = 8.4 Hz), 7.39 d (2Н, 2,6-Н С6Н4, J = 8.4 Hz)
(1Н, СНО), 10.06 s (1Н, pyrazole). Found, %: C
64.20; H 4.21; N 18.64. C20H15N5O3. Calculated, %: C
64.34; H 4.05; N 18.76.
12.40 br.s (1Н, СООН). Found, %: C 62.19; H 5.52; N
18.11. C12H13N3O2. Calculated, %: C 62.33; H 5.67; N
18.17.
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1
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