Cyclocondensation of nitromalonaldehyde sodium salt with substituted 1-amino-3-butanones

Article abstract of DOI:10.1023/A:1015616727964

Cyclocondensation of nitromalonaldehyde sodium salt with substituted 1-amino-3-butanones afforded 2-dimethyl-, diethylaminomethyl-4-nitrophenols and 2-piperidylo-, morpholylomethyl-4-nitrophenols.

Full text of DOI:10.1023/A:1015616727964

Russian Journal of Organic Chemistry, Vol. 38, No. 2, 2002, pp. 158 159. Translated from Zhurnal Organicheskoi Khimii, Vol. 38, No. 2, 2002,
pp. 178 179.
Original Russian Text Copyright
2002 by Belyaev, Dolzhenko, Zadov, Semichenko.
Cyclocondensation of Nitromalonaldehyde Sodium Salt
with Substituted 1-Amino-3-butanones
E. Yu. Belyaev , N. A. Dolzhenko, V. E. Zadov, and E. S. Semichenko
Siberian State Technological University, Krasnoyarsk, 660049 Russia
Received February 9, 2001
Abstract Cyclocondensation of nitromalonaldehyde sodium salt with substituted 1-amino-3-butanones
afforded 2-dimethyl-, diethylaminomethyl-4-nitrophenols and 2-piperidylo-, morpholylomethyl-4-nitro-
phenols.
At present N-substituted 2-aminomethyl-4-nitro-
phenols are synthesized either by Mannich reaction
from p-nitrophenol, formaldehyde, and an appropriate
amine [1 5] or by condensation of p-nitrophenol with
aminal [6, 7]. Yet a method is known for preparation
of 2- and 2,6-substituted p-nitrophenols by cyclo-
condensation of nitromalonaldehyde sodium salt with
aliphatic ketones [8].
R = Me (I); R = Et (II); NR2 = piperidyl (III);
We carried out a reaction between nitromalon-
NR2
= morpholyl (IV).
aldehyde sodium salt and N-substituted 1-amino-3-
butanones that in the aqueous alcohol in the presence
of bases gave rise to substituted 2-aminomethyl-4-
nitrophenols I IV in 15 30% yield.
In the IR spectra of compounds I IV appear ab-
1
sorption bands at 3400 3300 cm of O H stretching
1
vibrations and at 1300 1280 cm of C O stretching
Physical characteristics of compounds I IV are
given in the table. In the electronic spectra of com-
pounds I IV in 0.1 N NaOH an absorption peak is
present at 410 nm identical to the peak of p-nitro-
phenol in 0.1 N NaOH.
vibrations in agreement with the published data on
compound I [9]. The absorption bands at 1527 1510
1
cm correspond to symmetrical stretching vibrations
of N O bonds. Melting point of compounds I and II
are consistent with the literature data.
Yields, melting points, and spectral characteristics of substituted 2-(aminomethyl)-4-nitrophenols I IV
Compound
Yield, UVspectrum (0.1 N NaOH),
IR spectrum (KBr),
mp,
C
1
%
max, nm ( )
, cm
(publ. mp, C)
2-(Dimethylaminomethyl)- 20
4-nitrophenol (I)
410 (22500)
3300 3400 br (OH), 1510 s (N O),
1283 s (C O)
168
(168 170 [5])
2-(Diethylaminomethyl)
4-nitrophenol (II)
15
30
15
410 (25000)
410 (17000)
410 (11200)
3300 3400 br (OH), 1516 s (N O),
1292 m (C O)
128
(127 128 [7])
2-(Piperidylomethyl)
4-nitrophenol (III)
3400 3500 br (OH), 1515 s (N O),
1280 s (C O)
139 141
2-(Morpholylomethyl)
4-nitrophenol (IV)
3200 3400 br (OH), 1527 s (N O),
1281 s (C O)
125
Deceased.
1070-4280/01/3802-158$27.00 2002 MAIK Nauka/Interperiodica

CYCLOCONDENSATION OF NITROMALONALDEHYDE SODIUM SALT
159
EXPERIMENTAL
3. Salodar, W.E. and Green, M., J. Org. Chem., 1962,
vol. 27, no. 3, pp. 1077 1078.
4. US Patent, 3187049, 1965. Ref. Zh. Khim., 1966,
13N 170P.
5. Arct, J., Eckstein, Z., and Krzywicka, H., Przem.
Chem., 1964, vol. 43, no. 2, pp. 87 91.
6. Gun, Syun-tsi, Chzhan, Tsi-kai, Yaosyue, Syuebao,
Acta Pharmac. Sicina, 1958, vol. 6, no. 5, pp. 295
300. Ref. Zh. Khim., 1959.
Electronic spectra were recorded on SF-26 instru-
ment at cell thickness 1 cm and concentration 0.5
10 mol l in the region 200 400 nm. IR spectra
were measured on Impact-400 instrument. 1-Diethyl-
4
1
amino-3-butanone,
1-dimethylamino-3-butanone,
1-morpholyl-3-butanone, and 1-piperidyl-3-butanone
were prepared along procedures [10 12] respectively.
General procedure for preparation of 2-amino-
methyl-4-nitrophenols I IV. To a mixture of
0.00827 mol of 1-amino-3-butanone, 0.00719 mol of
nitromalonaldehyde sodium salt, 6.6 ml of ethanol,
and 9.4 ml of water was added 0.02 mol of NaOH as
20% water solution. The reaction mixture was
maintained at room temperature for 3 days and then
neutralized with 19% HCl and extracted with ethyl
ether (2 30 ml). On evaporating the ether the oily
residue was crystallized from ethanol. Spectral char-
acteristics, melting points, and yields of compounds
synthesized are listed in the table.
7. Kuliev, A.M., Mamedov, F.N., Mamedov, F.A., and
Mirzoeva, M.A., USSR Inventor,s Certificate 393267,
1973. SSSR Byull. Izobr., 1973, no. 33.
8. Belyaev, E.Yu., Tovbis, M.S., Suboch, G.A., Or-
lovskaya, N.F. and Astakhov, A.M., Zh. Org. Khim.,
1998, vol. 34, no. 9, pp. 1271 1281.
9. Kuliev, A.M., Salimov, M.A., Mamedov, F.N., and
Ibragimov, N.Yu., Dokl. Akad. Nauk SSSR, 1969,
vol. 184, no. 5, pp. 1141 1143.
10. Fieser, L. and Fieser, M., Reagents for Organic
Synthesis, New York, London, Sidney: Wiley and
Sons. Translated under the title Reagenty dlya
organicheskogo sinteza, Moscow: Mir, 1978,
11. Golovin, E.T., Peredreeva, M.A., and Bystrov, V.M.,
Izv. Vuzov, Ser. Khim. i Khim. Tekhnol., 1967,
vol. 10, no. 6, pp. 663 667.
REFERENCES
1. Starovskaya, V.I., Zh. Org. Khim., 1955, vol. 25,
no. 5, pp. 951 956.
12. Hahn, W.E. and Bartnik, R., Rocz. Chem., 1974,
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2. US Patent 2843519, 1959. Ref. Zh. Khim., 1960,
10605P.
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 38 No. 2 2002