Synthesis of 4,4-bis(dichloroamino) and 4,4-bis(chloroamino)-3,3-azo furazans, the first representatives of dichloroamino and chloroaminofurazans

Article abstract of DOI:10.1007/s11172-013-0198-7

First representatives of dichloroamino- and chloroaminofurazans, viz., 4,4-bis(di- chloroamino)- and 4,4-bis(chloroamino)-3,3-azofurazans, were synthesized by the chlorina- tion of 4,4-diamino-3,3-azofurazan with sodium hypochlorite in the CH2Cl2-H2O mixt

Full text of DOI:10.1007/s11172-013-0198-7

1
388
Russian Chemical Bulletin, International Edition, Vol. 62, No. 6, pp. 1388—1390, June, 2013
Synthesis of 4,4´ꢀbis(dichloroamino)ꢀ and 4,4´ꢀbis(chloroamino)ꢀ3,3´ꢀazoꢀ
furazans, the first representatives of dichloroaminoꢀ and chloroaminofurazans
L. V. Batog, L. S. Konstantinova, A. S. Kulikov, and N. N. Makhova
N. D. Zelinsky Institute of Organic Chemistry, Russian Academy of Sciences,
4
7 Leninsky prosp., 119991 Moscow, Russian Federation.
Fax: +7 (499) 135 5328. Eꢀmail: mnn@ioc.ac.ru
First representatives of dichloroaminoꢀ and chloroaminofurazans, viz., 4,4´ꢀbis(diꢀ
chloroamino)ꢀ and 4,4´ꢀbis(chloroamino)ꢀ3,3´ꢀazofurazans, were synthesized by the chlorinaꢀ
tion of 4,4´ꢀdiaminoꢀ3,3´ꢀazofurazan with sodium hypochlorite in the CH Cl —H O mixture.
2
2
2
Key words: 4,4´ꢀbis(dichloroamino)ꢀ3,3´ꢀazofurazan, 4,4´ꢀbis(chloroamino)ꢀ3,3´ꢀazofurꢀ
azan, 4,4´ꢀdiaminoꢀ3,3´ꢀazofurazan, 4,4´ꢀdinitroꢀ3,3´ꢀazofurazan, NaOCl, AcOCl, oxidation.
Over the years, the scientific interest of our research
were carried out in an organic solvent—water mixture
(MeCN—H O or AcOEt—H O), whereas the reaction
group is focused on the development of methods for the
synthesis and studies of reactivity of 1,2,5ꢀoxadiazole deꢀ
rivatives, viz., furazans and furoxans. These substances are
of interest as potential highꢀenergy and biologically active
compounds.1—6 In particular, earlier7—9 we have shown
that 4,4´ꢀdiaminoꢀ3,3´ꢀazofurazan 1 treated with hypoꢀ
halites (NaOBr, NaOCl, AcOBr, AcOCl), dibromoisocyꢀ
anurate (DBI) and mixtures of Pb(OAc) with Bu NBr,
2
2
with DBI and with the mixtures based on Pb(OAc) , in
4
organic solvents (CH Cl , MeCN, or AcOEt).
2
2
The present work is devoted to the studies of the reacꢀ
tion of 4,4´ꢀdiaminoꢀ3,3´ꢀazofurazan 1 with hypohalites
(NaOCl, AcOCl) in the twoꢀphase system CH Cl —H O
2
2
2
(1 : 1 v/v). The reaction was initially carried out with
NaOCl. It turned out that the use of a 40ꢀfold molar exꢀ
cess of NaOCl per 1 mol of diaminoazofurazan 1 and the
reaction temperature of 5—10 C (similarly to the known7
method for the synthesis of macrocycles 2) led to a draꢀ
matic change in the reactivity of compound 1. The earlier
unknown 4,4´ꢀbis(dichloroamino)ꢀ3,3´ꢀazofurazan 3, the
4
4
Br , or NaBr form macrocyclic compounds 2a—c. In this
2
case, compound 2a containing 4 azofurazan units was
the major isomer, whereas isomers 2b,c with 6 and 8
azofurazan units were formed in the insignificant
amounts (Scheme 1). The reactions of 1 with hypohalites
product of the exhaustive chlorination of both NH groups
2
in the starting compound 1, was unexpectedly isolated as
the reaction product (Scheme 2). Under this conditions,
compound 3 was formed in almost quantitative yield within
Scheme 1
3
0 min. Its structure was established based on elemental
13
analysis data, C NMR spectroscopy and mass spectroꢀ
metry. The TLC showed that neither products of oxidative
cyclocondensation of 2a—c, nor any other products were
formed under these conditions even in the minor amounts.
When the reaction time with NaOCl in a CH Cl —H O
2
2
2
mixture was increased from 30 min to 24 h, another comꢀ
pound, rather than bis(dichloroamino) derivative 3, was
formed containing only two chlorine atoms according to
the elemental analysis and mass spectrometry data. Based
1
on this data and the H NMR spectrum (a singlet with the
chemical shift at  8.77), the structure of 4,4´ꢀbisꢀ
(
chloroamino)ꢀ3,3´ꢀazofurazan (4) was assigned to the
13
compound obtained. A C NMR spectrum of the isolated
product could provide an additional evidence of the strucꢀ
ture of this compound, however, during recording the specꢀ
2
: n = 1 (a); 3 (b); 5 (c)
Reagents and conditions: NaOCl, MeCN—H O or AcOEt—H O,
2
2
5
—10 C.
trum in acetoneꢀd , compound 4 transformed into an unꢀ
6
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 6, pp. 1388—1390, June, 2013.
066ꢀ5285/13/6206ꢀ1388 © 2013 Springer Science+Business Media, Inc.
1

Dichloraminoꢀ and monochloraminoazofurazans
Russ.Chem.Bull., Int.Ed., Vol. 62, No. 6, June, 2013
1389
Scheme 2
3ꢀaminoꢀ4ꢀnitrofurazan 5 only with potassium permanꢀ
ganate.
1
0,11
Scheme 3
Reagents and conditions: i. NaOCl, CH Cl —H O (1 : 1), 5—10 C,
2
2
2
ii. 30 min, iii. 24 h.
Reagents and conditions: i. NaOCl, CH Cl —H O (1 : 1), 5—10 C.
2
2
2
identified orange crystalline product, which sublimed at
75 C. The TLC showed that compound 3 was also
formed when AcOCl was used under the same conditions.
However, in this case, besides compound 3, macrocycle 2a
and, apparently, macrocycles with higher molecular
weights, were formed. Therefore, we did not use AcOCl as
the reagent in our further studies.
In conclusion, the studies conducted in this work reꢀ
sulted in the first synthesis of monoꢀ and dichloroamines
of the furazan series and in the first time oxidation of
1
3
ꢀaminoꢀ4ꢀnitrofurazan 5 to 4,4´ꢀdinitroꢀ3,3´ꢀazofurꢀ
azan 7 by the chlorinating agents.
Experimental
Compounds 3 and 4 are, respectively, orange and bright
yellow crystalline substances with m.p. 85—86 C and
1
67—169 C, they are well soluble in most organic solꢀ
IR spectra were recorded on a Specord Mꢀ80 spectrometer
in KBr pellets. NMR spectra were recorded on Bruker WMꢀ250
vents and insoluble in water. These compound are fairly
stable in the crystalline state, whereas their solutions in
CH Cl , AcOEt, and MeCN are unstable. Lability of comꢀ
pounds 3 and 4 depends on the nature of the solvent, time
of their contact with the solvent and drying agent (MgSO ).
1
13
(
H, 250 MHz) and Bruker AMꢀ300 ( C, 75.5 MHz) spectroꢀ
meters, chemical shifts are given in  scale relative to the interꢀ
2
2
nal standard Me Si. Mass spectra were recorded on a Varian
4
MAТ CHꢀ6 instrument. Thinꢀlayer chromatography was carꢀ
ried out on Silufol UVꢀ254 plates with visualizing under a UV
4
When tetrachloride 3 was allowed to stand in CH Cl over
2
2
lamp. Melting points were determined on a Boetius heating stage.
the drying agent during several days, it converted to diꢀ
aminoazofurazan 1 practically quantitatively. Practically
pure cyclic tetramer 2a was formed from tetrachloride 3 in
the solution in MeCN. In other solvents (according to the
TLC), complex mixtures of different compositions were
formed containing, besides other components, amine 1
and macrocycle 2a.
The behavior of 3ꢀaminoꢀ4ꢀnitrofurazan (5) containꢀ
ing one amino group was also studied under conditions
selected for the preparation of tetrachloride 3. Monitoring
of the reaction by chromatography showed the formation
of a compound with R 0.28 (C H ), which possibly was
Nꢀchloro derivative 6. However, attempted isolation and
characterization of this compound failed because of its
rapid conversion to 4,4´ꢀdinitroꢀ3,3´ꢀazofurazan (7),
which was isolated in 62% yield (Scheme 3). It is interꢀ
esting that the preparation of compound 7 by this reacꢀ
tion is the first example of its synthesis by the oxidation
of 3ꢀaminoꢀ4ꢀnitrofurazan 5 by chlorination agents.
Earlier, azofurazan 7 was obtained by the oxidation of
4,4´ꢀDiaminoꢀ3,3´ꢀazofurazans 1,12 2a7, 4ꢀaminoꢀ3ꢀnitrofurꢀ
1
3
10,11
azan 5, and 4,4´ꢀdinitroꢀ3,3´ꢀazofurazan 7
were obtained
according to the known procedures.
4
,4´ꢀBis(dichloroamino)ꢀ3,3´ꢀazofurazan (3). Chlorine was
passed through a solution of NaOH (17.5 g, 0.42 mol) in water
135 mL) at 5—10 C until pH 7, followed by the addition of
,4´ꢀdiaminoꢀ3,3´ꢀazofurazan 1 (0.5 g, 2.5 mmol) and CH Cl
(
4
2
2
(
3
(
150 mL) with stirring, then the cooling bath was removed. After
0 min, the organic layer was separated, washed with water
2×10 mL), dried with MgSO4 for 20 min, and the solvent was
evaporated in vacuo to obtain compound 3 (0.76 g, 97%) as an
orange powder, m.p. 85—86 C, R 0.63 (C H —AcOEt, 5 : 1).
f
6
6
1
3
C NMR (acetoneꢀd6), : 155.08 (CNCl2), 158.99 (CN2). IR,
v/cm : 1585, 1550, 1450, 1390, 1350, 1240, 1040, 930, 880,
f
6
6
–
1
3
7
35 +
8
[
[
20, 745. MS, m/z (I (%)): 338 [M(3 Cl + Cl ] , (12), 336
rel
M(2 Cl + 2 Cl )]+ (49), 334 [M(Cl + 3 Cl35)]+ (100), 332
3
7
35
37
M(4 Cl35)] (76). Found (%): C, 14.82; N, 42.27; Cl, 33.06.
+
C N Cl O Calculated (%): C, 14.37; N, 42.51; Cl, 33.53.
4
8
4
2.
Precautions should be made while determining elemental
composition of compound 3, since this compound can explode
1
4
on heating. Dichloroamines are known to explode on rapꢀ
id heating.

1
390
Russ.Chem.Bull., Int.Ed., Vol. 62, No. 6, June, 2013
Batog et al.
4
,4´ꢀBis(chloroamino)ꢀ3,3´ꢀazofurazan (4) was obtained simꢀ
ilarly to azofurazan 3 from 4,4´ꢀdiaminoꢀ3,3´ꢀazofurazan (1)
0.1 g, 0.5 mmol) and NaOCl, the reaction time 24 h. The orꢀ
2. N. N. Makhova, T. I. Godovikova, Ros. Khim. Zh., 1997,
41, No. 2, 54 [Mendeleev Chem. J. (Engl. Transl.), 1997,
41, No. 2].
(
ganic layer was separated, dried with MgSO4 for 40 h, the solꢀ
vent was evaporated in vacuo. The residue was diluted with
3. V. Yu. Rozhkov, L. V. Batog, E. K. Shevtsova M. I. Struchꢀ
kova, Mendeleev Commun., 2004, 14, 76.
CH Cl2 (3 mL), a precipitate formed was filtered off to obtain
4. V. Yu. Rozhkov, L. V. Batog, M. I. Struchkova, Russ. Chem.
Bull. (Int. Ed.), 2005, 54, 1866 [Izv. Akad. Nauk, Ser. Khim.,
2005, 1923].
5. L. V. Batog, L. S. Konstantinova, V. Yu. Rozhkov, Russ.
Chem. Bull. (Int. Ed.), 2005, 54, 1859 [Izv. Akad. Nauk, Ser.
Khim., 2005, 1915].
2
compound 5 (0.14 g, 52%) as a bright yellow powder, m.p.
1
1
67—169 C, Rf 0.79 (C H —AcOEt, 5 : 1). H NMR (aceꢀ
6
6
–
1
toneꢀd ), : 8.77 (s). IR, v/cm : 3280 (NH), 3180 (NH), 1600,
6
1
[
500, 1435, 1350, 1245, 1040, 940, 800. MS, m/z (I (%)): 266
rel
M(Cl37 + Cl )] (65), 264 [M(2 Cl )] (100). Found (%):
35
+
35
+
C, 18.43; H, 0.90; Cl, 27.04; N, 41.97. C H Cl N O Calculatꢀ
ed (%): C, 18.11; H, 0.75; Cl, 26.79; N, 42.26.
6. V. Yu. Rozhkov, L. V. Batog, M. I. Struchkova, Mendeleev
Commun., 2008, 18, 161.
4
2
2
8
2.
Orange crystals were formed in the NMR tube while recordꢀ
7. L. V. Batog, L. S. Konstantinova, O. V. Lebedev, L. I.
Khmel´nitskii, Mendeleev Commun., 1996, 6, 193.
8. L. V. Batog, V. Yu. Rozhkov, L. S. Konstantinova, V. E.
Eman, M. O. Dekaprilevich, Yu. T. Struchkov, S. E. Seꢀ
menov, O. V. Lebedev, L. I. Khmel´nitskii, Russ. Chem.
Bull. (Engl. Transl.), 1996, 45, 1189 [Izv. Akad. Nauk, Ser.
Khim., 1996, 1250].
ing 13C NMR spectrum of compound 4, subl.p. 175 C. IR,
–
1
v/cm : 3460, 3410, 3340, 2600, 2470, 2440, 1615, 1410, 1180,
1
040, 965, 770.
Transformation of 4,4´ꢀbis(dichloroamino)ꢀ3,3´ꢀazofurazan
(
3) to 4,4´ꢀdiaminoꢀ3,3´ꢀazofurazan (1). Calcined MgSO (2 g)
4
was added to a solution of tetrachloride 3 (0.67 g, 2 mmol) in
CH Cl (10 mL), and the reaction mixture was stirred for 3 days
9. V. E. Eman, M. S. Sukhanov, O. V. Lebedev, L. V. Batog,
L. S. Konstantinova, V. Yu. Rozhkov, L. I. Khmel´nitskii,
Mendeleev Commun., 1996, 6, 66.
2
2
at room temperature until compound 3 disappeared (TLC monꢀ
itoring, R 0.63 (C H —AcOEt, 5 : 1)). A precipitate was filtered
f
6
6
off, washed with CH Cl (3 mL), the solvent was evaporated to
dryness to obtain diaminoazofurazan 1 (0.38 g, 97%), m.p.
10. T. S. Novikova, T. M. Melnikova, O. V. Kharitonova, V. O.
Kulagina, N. S. Aleksandrova, A. B. Sheremetev, T. S. Piviꢀ
na, L. I. Khmel´nitskii, S. S. Novikov, Mendeleev Commun.,
1994, 4, 138.
2
2
3
24—326 C (cf. Ref. 12: 325 C). The spectroscopic characterꢀ
1
2
istics of compound 1 corresponded to the literature data.
Synthesis of 4,4´ꢀdinitroꢀ3,3´ꢀazofurazan (7) by the reaction
of 3ꢀaminoꢀ4ꢀnitrofurazan (5) with NaOCl in the CH Cl —H O
11. A. K. Zelenin, M. L. Trudell, R. D. Gilardi, J. Heterocycl.
Chem., 1998, 35, 151.
2
2
2
mixture. Chlorine was passed through a solution of NaOH (4.4 g,
.11 mol) in water (35 mL) at 5—10 C to pH 7, followed by the
addition of 3ꢀaminoꢀ4ꢀnitrofurazan 5 (0.16 g, 1.25 mmol) and
12. G. D. Solodyuk, M. D. Boldyrev, B. V. Gidaspov, V. D.
Nikolaev, Zh. Org. Khim., 1981, 17, 861 [J. Org. Chem. USSR
(Engl. Transl.), 1981, 17, 756].
0
CH Cl2 (40 mL) with stirring, the cooling bath was removed.
13. A. B. Sheremetev, V. O. Kulagina, I. A. Kryazhevskikh,
T. M. Melnikova, N. S. Aleksandrova, Russ. Chem. Bull.
(Int. Ed.), 2002, 51, 1533 [Izv. Akad. Nauk, Ser. Khim.,
2002, 1411].
14. R. E. Banks, J. H. Farhat, R. Fields, G. P. Robin, M. S.
Monamod, J. Fluorine Chem., 1985, 28, 325.
2
After 30 min, the organic layer was separated, washed with waꢀ
ter (2×10 mL), dried with MgSO4 for 20 min, the solvent
was evaporated in vacuo. The residue was recrystallized from
CH Cl —C H (1 : 1) to obtain compound 7 (77 mg, 62%) as
2
2
5
12
an orange powder, m.p. 53—54 C (cf. Ref. 13: 51—53 C). The
spectroscopic characteristics of compound 7 corresponded to
the literature data.13
References
1
. A. B. Sheremetev, N. N. Makhova, W. Friedrichsen, Adv.
Heterocycl. Chem., 2001, 78, 66.
Received December 28, 2012;
in revised form March 28, 2013