1070-4272/02/7504-0669 $27.00 C 2002 MAIK [Nauka/Interperiodica]
Russian Journal of Applied Chemistry, Vol. 75, No. 4, 2002, pp. 669!671. Translated from Zhurnal Prikladnoi Khimii, Vol. 75, No. 4, 2002,
Original Russian Text Copyright + 2002 by Svetlakov, Nikitin, Orekhova.
Oxidation of Tetrahydrofuran and 1,4-Butanediol
with Nitric Acid
N. V. Svetlakov, V. G. Nikitin, and A. O. Orekhova
Kazan State Technological University, Kazan, Tatarstan, Russia
Received August 13, 2001; in final form, January 2002
Abstract-Preparation of succinic acid by oxidation of tetrahydrofuran and 1,4-butanediol with nitric acid
One of practically important aliphatic dicarboxylic
acids is succinic acid (SA). Owing to its unique bio-
logical properties, this acid is widely used in medi-
cine and agriculture [1, 2].
Succinic acid is prepared in industry  by reduc-
tion of maleic and fumaric acids. The production pro-
cess is being constantly improved [4, 5]. A promising
procedure for preparing SA is oxidation of butadiene
rubber with ozone . Oxidation of tetrahydrofuran
(THF) with nitric acid  is also of practical interest.
However, this procedure is poorly studied.
Tetrahydrofuran was oxidized with nitric acid of
various concentrations (97330%) at a temperature
lower than 25oC. THF vigorously reacts with concen-
(80397%) with liberation of nitrogen
oxides and heat. Already 30340 min after mixing
of the reactants, crystalline SA starts to precipitate.
The oxidation is complete in 334 h after mixing
the reactants. The SA yield is 80385%. An addi-
tional amount of SA is precipitated after prolonged
storage of the filtrate. The total yield exceeds 90%.
Oxidation of THF with 40360% nitric acid is less
exothermic. The liberation of nitrogen oxides, whose
composition was not studied, is less vigorous. Oxida-
tion of THF with 30% HNO
continues for several
days. The SA yield was 40345%, which is due to
losses with spent nitric acid.
Nitric acid with a concentration higher than 70%
contains nitronium cation, which is a strong electro-
phile . We suggested that, in concentrated HNO
nitronium cation must cleave the C3O bond of THF
to form 1,4-butanediol dinitrate (BDN). To confirm
this assumption, we performed the reaction of THF
with fuming nitric acid at temperatures lower than
0oC. After reaction completion, the reaction mixture
was diluted with water and extracted with chloroform.
As determined by elemental and spectral analysis,
the isolated liquid product was BND.
1,4-Butanediol dinitrate thus obtained is converted
into SA by treatment with nitric acid at 25330oC.
These results suggest that SA can also be prepared
by oxidation of 1,4-butanediol (BD) with nitric acid.
1,4-Butanediol was oxidized with 30397% HNO
25330oC. At nitric acid concentration higher than
80%, vigorous liberation of heat and nitrogen oxides
was observed. In 334 h, precipitation of crystalline
SA from the reaction mixture and liberation of nitro-
gen oxides were complete.
The yield of SA prepared by oxidation with 80%
is as high as 90%. When 60340% nitric acid
is used, the SA yield decreases to 40360%. This is
due to dissolution of SA in spent HNO
. The SA loss
can be decreased if the spent nitric acid is recycled
by mixing with concentrated HNO
Since alcohols are O-nitrated readily and fast ,
BDN is apparently the intermediate of BD oxidation
with concentrated nitric acid.
It is known than BDN can be prepared by esteri-
fication of BD with a mixture of sulfuric and nitric
acid at temperatures below 0oC. At higher tempera-
tures BDN is unstable . BDN was oxidized to
SA by the above procedure. The SA yield was 85%.
Nitrogen oxides evolved in BD oxidation probably
affect the oxidation. For example, N
, NO, and