Oxidation of alkylcyanohydrazines to azo-bis nitriles using Oxone-potassium bromide in aqueous medium

Article abstract of DOI:10.1081/SCC-120014980

Azo-bis nitriles were prepared in good yields and high purity by oxidation of corresponding 1,2-bis-dialkylcyano hydrazines using oxone-potassium bromide in aqueous medium.

Full text of DOI:10.1081/SCC-120014980

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OXIDATION OF ALKYLCYANOHYDRAZINES TO AZO-
BIS NITRILES USING OXONE®–POTASSIUM BROMIDE IN
AQUEOUS MEDIUM
a
b
a
a
c
B. V. Tamhankar , Uday V. Desai , R. B. Mane , P. P. Kulkarni & P. P. Wadgaonkar
a
Department of Chemistry, Shivaji University, Kolhapur, 416 004, India
b
Department of Chemistry, Shivaji University, Kolhapur, 416 004, India
c
Polymer Division, National Chemical Laboratory, Pune, 411 008, India
Published online: 16 Aug 2006.
To cite this article: B. V. Tamhankar , Uday V. Desai , R. B. Mane , P. P. Kulkarni & P. P. Wadgaonkar (2002) OXIDATION
OF ALKYLCYANOHYDRAZINES TO AZO-BIS NITRILES USING OXONE®–POTASSIUM BROMIDE IN AQUEOUS MEDIUM, Synthetic
Communications: An International Journal for Rapid Communication of Synthetic Organic Chemistry, 32:23, 3643-3646, DOI:
0.1081/SCC-120014980
1
To link to this article: http://dx.doi.org/10.1081/SCC-120014980
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SYNTHETIC COMMUNICATIONS
Vol. 32, No. 23, pp. 3643–3646, 2002
OXIDATION OF
ALKYLCYANOHYDRAZINES TO AZO-BIS
Õ
NITRILES USING OXONE –POTASSIUM
BROMIDE IN AQUEOUS MEDIUM
1
1,
1
B. V. Tamhankar, Uday V. Desai, * R. B. Mane,
1
P. P. Kulkarni, and P. P. Wadgaonkar
2
1
Department of Chemistry, Shivaji University,
Kolhapur-416 004, India
2
Polymer Division, National Chemical Laboratory,
Pune-411 008, India
ABSTRACT
Azo-bis nitriles were prepared in good yields and high purity
by oxidation of corresponding 1,2-bis-dialkylcyano hydra-
zines using oxone-potassium bromide in aqueous medium.
The chemistry of azo-bis nitriles, a useful class of organic compounds,
has been the subject of intensive studies. Commercially they are not only
used as initiators for free radical polymerisation of common vinyl mono-
[
1]
mers like styrene, vinyl chloride, vinyl acetate, alkyl methacrylates, etc.,
but are also used as blowing agents for the production of polymer foams.
[
2]
*
Corresponding author. E-mail: uprabhu_desai@rediffmail.com
643
3
DOI: 10.1081/SCC-120014980
Copyright & 2002 by Marcel Dekker, Inc.
0039-7911 (Print); 1532-2432 (Online)
www.dekker.com

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3
644
TAMHANKAR ET AL.
Scheme 1.
Routinely, symmetrical azo-bis nitriles are produced by the reaction
between a ketone and hydrazine to form an azine, which on reaction with
hydrogen cyanide yields the intermediate 1,2-bis-dialkylcyano hydrazine (I)
which is then oxidised to symmetrical azo-bis nitrile (II) (Sch. 1).
The oxidation of intermediate hydrazino compound (I) to azo-bis nitrile
[
3]
has been achieved earlier using conventional oxidising agents like chlorine,
[5]
[4]
[6]
bromine,
potassium dichromate,
sodium dichromate,
potassium
[8]
permanganate and also by using oxidants like oxygen–ozone mixture,
[7]
[
9]
sodium hypochlorite salt solution and by using hydrogen peroxide in
10]
[
combination with bromine compound and sulphuric acid.
However,
some of these oxidants are not acceptable from the viewpoint of environ-
mental concerns.
Õ
Oxone is a stable ternary composite of KHSO , KHSO and K SO
2
5
4
4
in 2: 1 : 1 molar ratio and its utility has been demonstrated for a variety of
We have recently reported bromination of
[11,12]
organic transformations.
Õ[11]
activated arenes using alkali metal bromide and Oxone
0
and also the
Õ
oxidation of hydrazides to N,N -diacyl hydrazines using Oxone in
[12]
Õ
aqueous medium. In continuation of our work on Oxone –KBr reagent
system, we wish to report here its usefulness for the oxidation of 1,2-bis-
dialkylcyano hydrazines (I) to azo-bis nitriles (II) (Sch. 1).
A variety of 1,2-bis-dialkylcyano hydrazines were smoothly oxidised
Õ
using Oxone –KBr reagent system to the corresponding azo-bis nitriles in
good yields except for levulinic acid-based hydrazino compound in which
case the yield was low. (Entry 6, Table 1).
Õ
In summary, Oxone –KBr reagent system constitutes an useful
and complimentary method for the oxidation of 1,2-bis-dialkylcyano hydra-
zines to the corresponding azo-bis nitriles.
EXPERIMENTAL
OxoneÕ (M/s Lancaster), potassium bromide and hydrazine sulphate
E.Merck), cyclohexanone, acetone, ethyl methyl ketone (Sd Fine Chem.)
(
levulinic acid, cyclopentanone and methyl propyl ketone (Fluka) were used
as received. All 1,2-bis dialkylcyano hydrazines were prepared by the
standard procedure.
[2,4]

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OXIDATION OF ALKYLCYANOHYDRAZINES
3645
Table 1. Oxidation of 1,2-bis-Dialkylcyanohydrazines to Azo-bis Nitriles Using
Õ
Oxone –KBr System
ꢀ
M.P. C
(Lit. M.P. C)
ꢀ
Entry
1
Substrate
Product
Yield (%)
66
CN
C
CN
CH3
CN
CN
102–103
(103–104)
H3C
NH NH
C
H C
C
N
CH3
N
N
N
C
CH3
CH3
3
[2]
CH3
CH3
CN
CN
CN
CN
C
C
2
64
52–55
(49–51)
H
3
C
C
C
NH NH C CH
H
3
H C
C
C
N
CH3
H
2 5
3
[2]
2
5
C
2
H
5
H
2
5
CN
CN
CN
C
CN
C CH3
3
4
71
89
71
(73–74.5)
H
3
C C NH NH C CH
3
H C
N
3
[
2]
C
3
H
7
C
3
H
7
C H
C H
3
7
3
7
CN
CN
CN
CN
82
83–84)
[
13]
(
NH NH
N
N
CN
NH NH
CN
CN
CN
5
6
75
26
114
(114–115)
[
2]
N
N
CN
CN
CN
H C C
CN
C
113–118
[1]
112–116)
H C C NH NH C CH3
N
2
N
CH3
3
3
(
CH
CH
CH
CH
COOH
CH
CH
2
2
2
2
2
CH2
CH2
COOH
COOH
COOH
0
Typical Procedure: 1,1 -Azo bis-1-Cyclohexanenitrile
To a stirred suspension of 1,2-di-1-(1-cyano)-cyclohexylhydrazine
2.46 g, 0.01 mol) in water (30 mL) was added potassium bromide (1.18 g,
(
Õ
0.01 mol) followed by the solution of Oxone (6.15 g, 0.01 mol) in water
(
20 mL) during a period of 30 min. The reaction mixture was stirred for
additional 3 h and the resultant product was filtered at pump, washed
with water and dried under vacuum. The crude product was recrystallized
from petroleum ether. Yield: 1.82g (75%).
ACKNOWLEDGMENTS
BVT thanks UGC, New Delhi for the award of fellowship under
Faculty Improvement programme.

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TAMHANKAR ET AL.
REFERENCES
1
. Sheppard, C.S.; Encyclopedia of Polymer Science and Engineering;
Mark, H.F., Bikales, N.M., Overberger, C.G., Menges, G., Eds.;
John Wiley and Sons: New York, 1985; Vol. 2, 143.
2. Overberger, C.G.; O’Shaughnessy, M.T.; Shalit, H. J. Am. Chem. Soc.
1949, 71, 2661.
3
. (a) Citron, J.D. J. Appl. Polym. Sci. 1974, 18, 3259; (b) Mishina, I.M.;
Bryuske, Ya.E.; Toropova, G.A.; Pirogova, L.V.; Ovchinnikov, A.A.;
Fashchilina, L.K.; Matvievskii, N.V.; Dolzhenko, V.N. USSR Patent;
6
76587; (Chem. Abstr. 1979, 91, 157308h).
. Overberger, C.G.; Huang, P.-T.; Berenbaum, M.B. Org. Synth. 1952,
2, 16.
. Dragutan, V.; Medvedic, C.; Caproiu, O.I. Rom. RO. 1986 89, 926,
Chem. Abstr. 1987, 107, 154 926w).
. Dragutan, V.; Dragutan, I.; Medvedic, C.; Caproiu, O.E. Rom. RO.
1, 888, 1987 (Chem. Abstr. 1988, 108, 132473q).
4
5
6
7
3
(
9
. Nasakin, O.E.; Lukin, P.M.; Sheverdov, V.P.; Tafeenko, V.A.; Bulai,
A.Kh.; Medvedev, S.V.; Sharbatyan, P.A. USSR S. U: 1, 699, 999,
1
991 (Chem. Abstr. 1992, 117, 26352a).
. Kawabe, N.; Esumi, Y.; Ono, M. JP 7115, 495, 1971 (Chem. Abstr.
971, 75, 8843f).
. Owari, E.; Honda, R.; Suda, S. JP 7440,692, 1974 (Chem. Abstr. 1975,
2, 139 434f).
0. (a) Dragutan, V.; Medvedic, C.; Caproiu, O.I. Rom. RO. 89, 673, 1986
Chem. Abstr. 1987, 107, 283879k); (b) Dragutan, I.; Dragutan, V.;
Condeiu, C. Rom. RO. 105, 694, 1992 (Chem. Abstr. 1998, 129, 4976c).
1. Tamhankar, B.V.; Desai, U.V.; Mane, R.B.; Bedekar, A.V.;
Wadgaonkar, P.P. Synth. Commun. 2001, 31, 81, and references
therein.
8
9
1
8
1
1
(
12. Kulkarni, P.P.; Desai, U.V.; Mane, R.B.; Kadam, A.J.; Wadgaonkar,
P.P. J. Chem. Res. (S) 2000, 184.
13. Overberger, C.G.; Berenbaum, M.B. J. Am. Chem. Soc. 1951, 73, 4883.
Received in the UK July 3, 2001