Russian Journal of Organic Chemistry, Vol. 38, No. 2, 2002, pp. 290 291. Translated from Zhurnal Organicheskoi Khimii, Vol. 38, No. 2, 2002,
pp. 312 313.
Original Russian Text Copyright
2002 Svetlakov, Nikitin, Ruziev.
SHORT
COMMUNICATIONS
Reaction of Octyl Ether with Nitric Acid and its Mixtures
N. V. Svetlakov, V. G. Nikitin, and F. F. Ruziev
Kazan State Technological University, Kazan, 420015, Russia
Received March 16, 2001
We reported previously that alkanes reacted at
15 20 C with a mixture HNO3 (CH3CO)2O to afford
mononitrates of secondary alcohols [1]. To outline
the application range of the process we studied a
reaction between octyl ether and the mixture of nitric
acid with acetic anhydride. It was presumed that the
reaction could proceed at the carbon hydrogen bond
in the aliphatic moiety or at the carbon oxygen bond
or in both directions.
HNO3 (CH3CO)2O
HNO3 H2SO4
HNO3
[CH3(CH2)7]2O
CH3(CH2)7ONO2
HNO3
CH3(CH2)6COOH
(1) To 85 g (1.35 mol) of 97.5% nitric acid was
added 37.8 g (0.37 mol) of acetic anhydride at
temperature not exceeding 25 C. To the acid mixture
was added at 5 10 C while stirring 14.5 g (0.06 mol)
of octyl ether, and the resulting reaction mixture was
maintained at 20 C for 30 min. The reaction mixture
was poured into cold water, the organic part was
extracted with chloroform (3 50 ml), the extract was
washed with water, 3% solution of sodium carbonate,
again with water, and was dried on sodium sulfate.
The solvent was distilled off, and the reaction pro-
ducts were distilled in a vacuum. We obtained 11.6 g
(56%) of octyl nitrate, bp 91 92 C (17 mm Hg),
The octyl ether was added while stirring at 10
15 C to the mixture HNO3 (CH3CO)2O, and the
reaction was carried out for 30 min at temperature no
higher than 20 C. The reaction is accompanied by
heat evolution and nitrogen oxides liberation. The
reaction products were purified by vacuum distilla-
1
tion. The H NMR and IR spectra indicated that the
reaction product was 1-octyl nitrate with up to 3% of
carbonyl-containing impurities.
Alongside the octyl nitrate we isolated a fraction
with a wide boiling temperature interval. It is pre-
sumably a mixture of oxidized compounds formed
from the primary reaction product, octyl nitrate, since
the components of the mixture contain both carbonyl
and nitroxyl groups.
d2n0 0.9510, n2D0 1.4246. IR spectrum ( , cm ): 875,
1
1630 (ONO2). The IR spectrum contains a weak
1
absorption band at 1730 cm (C=O) evidencing the
1
presence of a carbonyl-containing impurity. H NMR
spectrum ( , ppm): 0.98 t (3H, CH3), 1.4 1.8 m
(12H, 6CH ), 4.0 t, 4.4 t [2H, HACHB ONO2,
J(HA,HB) 142 Hz], the signal 7.9 s (CHO) indicates
the presence of aldehyde traces. Found, %: C 54.79;
H 9.90; N 8.64. MRD 47.81. C8H17NO3. Calculated,
%: C 54.85; H 9.71; N 8.00. MRD 47.31.
The reaction of the octyl ether with a mixture of
nitric and sulfuric acids was vigorous and accompani-
ed with nitrogen oxides liberation. Vacuum distilla-
tion of the reaction products provided two fractions.
1
As show H NMR and IR spectra the first fraction
contains 1-octyl nitrate with caprylic acid as impurity,
and the second fraction consists of caprylic acid
apparently formed by oxidation of the octyl nitrate.
The concentrated nitric acid reacts with octyl nitrate
in a similar way.
The second fraction (4 g) was separated at 115
130 C (17 mm Hg). In the IR spectrum appear
absorption bands at 875, 1630 (ONO2) and 1730 cm
(C=O). This fraction presumably consists of the
substances arising at octyl nitrate decomposition.
1
Thus under the applied conditions aliphatic moiety
virtually does not undergo nitroxylation, and the
reaction takes as the main course the rupture of the
carbon oxygen bond to afford octyl nitrate and its
oxidation products.
(2) To a mixture of 41.5 g (0.4 mol) of technical
grade concn. sulfuric acid and 85 g (1.35 mol) of
97.5% nitric acid was added at temperature not
exceeding 15 C 14.5 g (0.06 mol) of octyl ether, and
the resulting reaction mixture was kept for 30 min.
1070-4280/01/3802-290$27.00 2002 MAIK Nauka/Interperiodica