Synthesis of salts of new arylamides of 2-hydroxy-5-nitroso-4,6- dimethylisophthalic acid

Full text of DOI:10.1134/S1070428013080241

ISSN 1070-4280, Russian Journal of Organic Chemistry, 2013, Vol. 49, No. 8, pp. 1236−1237. © Pleiades Publishing, Ltd., 2013.
Original English Text © N.A. Fedorova, D.G. Slaschinin, A.B. Lyubyashkin, I.V. Peterson, M.S. Tovbis, 2013, published in Zhurnal Organicheskoi Khimii,
2013, Vol. 49, No. 8, pp. 1250−1251.
SHORT
COMMUNICATIONS
Synthesis of Salts of New Arylamides
of 2-Hydroxy-5-nitroso-4,6-dimethylisophthalic Acid
N. A. Fedorovaa, D. G. Slaschinina, A. B. Lyubyashkina, I. V. Petersonb, and M. S. Tovbisa
aSiberian State Technologic University, Krasnoyarsk, 660049 Russia
e-mail: tovbis@bk.ru
bInstitute of Chemistry and Chemical Engineering, Siberian Branch,
Russian Academy of Sciences, Krasnoyarsk, Russia
Received January 30, 2013
DOI: 10.1134/S1070428013080241
Completely substituted nitrosophenols containing me-
thoxy-, ethoxy-, propoxy-, butoxycarbonyl substituents
in the ortho-position with respect to the hydroxy group
are obtained by the reactions of esters of acetonedicar-
boxylic acid with isonitrosacetylacetone [1–3]. Such
nitrosophenols are readily reduced to persubstituted
aminophenols [4] that at the modification of the amino
group afford the derivatives exhibiting the antiarrhythmic
action [5].
24 h by the procedure [6].
Compounds IIIа–IIId were obtained by cyclization
using the procedure applied in the reaction of isonitro-
soacetylacetone with dialkyl acetonedicarboxylate [2].
In 2 ml of anhydrous ethanol was dissolved 0.25 mmol
of potassium hydroxide and to the solution was added
0.25 mmol of isonitrosoacetylacetone (II) and 0.5 mmol
of arylamide of acetonedicarboxylic acid Iа–Id dissolved
in 0.5 ml of DMSO. The mixture was maintained for
some time at 18–20°С, therewith the color of the solution
changed from orange to green. Potassium phenolate was
isolated by adding anhydrous ethyl ether till the solution
turned turbid. The brght green crystals of precipitated
phenolate III were filtered off, recrystallized from etha-
nol, and dried in a vacuum over Na2SO4.
The aim of this study was the preparation of persub-
stituted nitrosophenols of analogous structure containing
arylamide groups instead of ester groups that would give
an opportunity to synthesize new biologically active
substances.
The cyclization of arylamides of acetonedicarboxylic
acid (I) dissolved in DMSO was carried out by the
reaction with isonitrosoacetylacetone (II) in anhydrous
ethanol containing potassium hydroxide. Nitrosophenols
were isolated as potassium salts III.
Potassium 2,6-bis(phenylcarbamoyl)-3,5-dimethyl-
4-nitrosophenolate (IIIа). Reaction duration 6 h. Yield
0.105 g (88%), green crystals. IR spectrum: 1642 cm–1
[ν(С=О)]. UV spectrum, λmax, nm (ε): 603 (73), 393
(16960). 1Н NMR spectrum, δ, ppm: 2.75 s (6H, 2CH3),
7.02 m (2Harom), 7.30 m (4Harom), 7.81 m (4Harom), 11.16
br.s (2H, NH). 13С NMR spectrum, δ, ppm: 17.2, 119.4,
The initial arylamides of acetonedicarboxylic acid (I)
were obtained by heating diethyl acetonedicarboxylate
with the corresponding anilines in a sealed ampule for
O
OK
O
O
O
O
O
O
NHR
RHN
H3C
KOH, C2H5OH
CH3
DMSO
+
H3C
RHN
NHR
CH3
NOH
NO
Iа_Id
II
IIIа_IIId
R = C6H5 (a), C6H4Cl-p(b), C6H4Br-p (c), C6H4CH3-p (d).
1236

SYNTHESIS OF SALTS OF NEW ARYLAMIDES
1237
122.4, 125.0, 128.5, 131.6, 140.5, 160.3, 167.5, 177.0.
Mass spectrum, m/z (Irel, %): 93 (100), 66 (65), 39 (47),
32 (72).
were registered in acetone-d6 on a spectrometer Bruker
Avance III 600 at the Krasnoyarsk regional ceneter for
joint use of the Siberian Division of the RussianAcademy
of Sciences, mass spectra, on an instrument Finnigan
MAT 8200, UV spectra, on a spectrophotometer Helios
Omega in the measurement range 190–1100 nm in quartz
celle of 1 cm. Salt concn. in 0.1 N aqueous potassium
hydroxide 0.1·10–4 mol l−1 in the UV region, and in the
region of n-π* transition of the nitroso group (600–700
nm) concn. 0.1·10–2 mol l−1. IR spectra were recorded on
an IR microscope SpecTRA TECH InspectIR based on
an IR Fourier spectrophotometer Impact 400. The sample
of the substance was placed on a gold plate, adjusted
with a roller blade, placed on the microscope, and the
spectrum of partial internal reflection was recorded. De-
tector МСТ/А, lens Si Caplugs, range of wave numbers
4000–650 cm–1, resolution 1.928 cm–1, number of scans
64, software OMNIC 5.1 E.S.P. the reaction progress
was monitored and the homogeneity of the compounds
obtained was checked by TLC on Sorbfil PTSKh-AF-V
plates (Russia) with UV indicator, eluent toluene, spots
visualized under UV irradiation.
Potassium 2,6-bis[(4-chloroрphenyl)carbamoyl]-
3,5-dimethyl-4-nitrosophenolate (IIIb). Reaction
duration 24 h. Yield 0.087 g (70%), green crystals. IR
spectrum: 1634 cm–1 [ν(С=О)]. UV spectrum, λmax, nm
(ε): 612 (72), 392 (18390). 1Н NMR spectrum, δ, ppm:
3
2.75 s (6H, 2CH3), 7.32 d (4Harom, J 8.2 Hz), 7.84 d
(4Harom, 3J 8.2 Hz), 11.48 br.s (2H, NH). 13С NMR spec-
trum, δ, ppm: 17.0, 120.7, 120.8, 126.5, 128.4, 131.8,
139.4, 160.2, 167.5, 176.8. Mass spectrum, m/z (Irel, %):
127 (85), 92 (26), 65 (54), 44 (45), 32 (100).
Potassium 2,6-bis[(4-bromophenyl)carbamoyl]-
3,5-dimethyl-4-nitrosophenolate (IIIc). Reaction
duration 48 h. Yield 0.1 g (37%), green crystals. IR
spectrum: 1665 cm–1 [ν(С=О)]. UV spectrum, λmax, nm
(ε): 613 (73), 393 (20210). 1Н NMR spectrum, δ, ppm:
3
2.76 s (6H, 2CH3), 7.45 d (4Harom, J 8.7 Hz), 7.80 d
(4Harom, 3J 8.7 Hz), 11.58 br.s (2H, NH). 13С NMR spec-
trum, δ, ppm: 17.0, 113.9, 121.0, 121.2, 123.8, 131.3,
139.9, 160.8, 167.5, 176.7. Mass spectrum, m/z (Irel, %):
173 (13), 63 (31), 45 (19), 32 (100).
REFERENCES
Potassium 2,6-bis[(4-methylphenyl)carbamoyl]-
3,5-dimethyl-4-nitrosophenolate (IIId). Reaction
duration 24 ч. Yield 0.11 g (90%), green crystals. IR
spectrum: 1638 cm–1 [ν(С=О)]. UV spectrum, λmax, nm
(ε): 607 (66), 394 (13630). 1Н NMR spectrum, δ, ppm:
1. Belyaev, E.Yu., Tovbis, M.S., and El’tsov, A.V., Zh. Org.
Khim., 1978, vol. 14, p. 2375.
2. Semin, I.V., Sokolenko, V.A., and Tovbis, M.S., Zh. Org.
Khim., 2007, vol. 43, p. 545.
3. Slaschinin, D.G.,Alemasov, Yu.A., Tovbis, M.S., and Kirik,
S.D., J. Mol. Struct. 2011, vol. 985, p. 184.
4. Slaschinin, D.G., Tovbis, M.S., Root, E.V., Zadov, V.E., and
Sokolenko, V.A., Zh. Org. Khim., 2010, vol. 46, p. 527.
5. Eiden, F., Leister, H.P., and Mayer, D., Arz. Forsch. 1983,
vol. 33,p. 101.
2.30 s (6H, 2CH3), 2.75 s (6H, 2CH3), 7.12 d (4Harom
,
3J 8.4 Hz), 7.71 d (4Harom, J 8.4 Hz), 11.10 br.s (2H,
NH). 13С NMR spectrum, δ, ppm: 17.0, 19.9, 119.3,
119.4, 124.6, 128.9, 131.5, 138.1, 160.7, 167.4, 176.8.
Mass spectrum, m/z (Irel, %): 106 (65), 77 (23), 44 (36),
32 (100).
3
1Н (600.13 МHz) and 13С (151.91 МHz) NMR spectra
6. Besthorm, E. and Garden, E. Ber. 1903, vol. 33, p. 3435.
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 49 No. 8 2013