3-Amino-4-(α-nitroalkyl-ONN-azoxy)furazans and some of their derivatives

Article abstract of DOI:10.1007/s11172-012-0049-y

Synthetic procedures towards 3-amino-4-(a-nitroalkyl-ONN-azoxy)furazans and their derivatives involving nucleophilic displacement of the nitro group of 3-nitro-4-(a-nitroalkyl-ONN-azoxy)furazans on treatment with ammonia, primary and secondary amines, including diamines, were developed.

Full text of DOI:10.1007/s11172-012-0049-y

Russian Chemical Bulletin, International Edition, Vol. 61, No. 2, pp. 355—359, February, 2012
355
3ꢀAminoꢀ4ꢀ(ꢀnitroalkylꢀONNꢀazoxy)furazans and some of their derivatives
O. A. Luk´yanov, V. V. Parakhin, G. V. Pokhvisneva, and T. V. Ternikova
N. D. Zelinsky Institute of Organic Chemistry, Russian Academy of Sciences,
47 Leninsky prosp., 119991 Moscow, Russian Federation.
Fax: +7 (499) 135 5328. Eꢀmail: L120@ioc.ac.ru
Synthetic procedures towards 3ꢀaminoꢀ4ꢀ(ꢀnitroalkylꢀONNꢀazoxy)furazans and their
derivatives involving nucleophilic displacement of the nitro group of 3ꢀnitroꢀ4ꢀ(ꢀnitroalkylꢀ
ONNꢀazoxy)furazans on treatment with ammonia, primary and secondary amines, including
diamines, were developed.
Key words: furazans, (ꢀnitroalkylꢀONNꢀazoxy)furazans, 3ꢀaminoꢀ4ꢀ(ꢀnitroalkylꢀONNꢀ
azoxy)furazans, nitrofurazans, aminofurazans, nucleophilic substitution.
Earlier,1 we have developed method for the synthesis
of bis(ꢀnitroalkylꢀONNꢀazoxy)furazans and their derivꢀ
atives by the reaction of 3,4ꢀdiaminofurazan with geminal
nitronitroso compounds in the presence of dibromoisoꢀ
cyanuric acid (DBI). Despite the moderate yields (20—55%)
of the aforesaid compounds and stability of the intermediꢀ
ates, 3ꢀaminoꢀ4ꢀ(ꢀnitroalkylꢀONNꢀazoxy)furazans, the
latter were not obtained in preparative yields even after
changing the reaction conditions. Since the compounds
of this type are of interest and could be used as halfꢀprodꢀ
ucts towards other energetic compounds, in the present
work we suggest another strategy for their synthesis. The
approach involved the nucleophilic displacement known
for the furazans2—4, namely, the displacement of the nitro
group on the furazan ring by Nꢀnucleophiles. It was found
that 3ꢀnitroꢀ4ꢀ(ꢀnitroalkylꢀONNꢀazoxy)furazans and
some of their derivatives (compounds 1—3) reacted rather
smoothly with ammonia at room temperature in the inert
solvents to give target 3ꢀaminoꢀ4ꢀ(ꢀnitroalkylꢀONNꢀ
azoxy)furazans 4—7 (Scheme 1).
On going from ammonia to methylamine, the reaction
(performed in H2O—CH2Cl2) proceeded more readily. It
is of note that disubstitution products 8—9 were predomiꢀ
nantly formed in the reactions with diamines carried out
even with the large excess of the latter (Scheme 2).
Scheme 2
R = H (8); R + R = (CH2)2 (9)
However, we were not able to extend this procedure on
the aromatic amines (the reactions were carried out on the
example of pꢀtoluidine); no formation of the substitution
product was observed.
Scheme 1
In our opinion, these results indicate that electronic
effect (electronꢀwithdrawing or electronꢀreleasing) of the
ꢀnitroalkyl substituent at the ONNꢀazoxy group does not
affect the nucleophilic substitution of the nitro group on
the furazan ring. It is true only when the substituent is
stable upon the nucleophilic attack or transforms into
stable structural fragment.
Thus, no individual products of the reaction of 3ꢀ(diꢀ
bromonitromethylꢀONNꢀazoxy)ꢀ4ꢀnitrofurazan and 3ꢀ(2ꢀ
hydroxyꢀ1ꢀhydroxymethylꢀ1ꢀnitroethylꢀ1ꢀONNꢀazoxy)ꢀ
4ꢀnitrofurazan with ammonia were isolated, although in
R = Me (1, 4); R + R = (CH2)5 (2, 5), CH2OCMe2OCH2 (3, 6, 7);
R´ = H (4—6); Me (7)
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 2, pp. 353—357, February, 2012.
1066ꢀ5285/12/6102ꢀ355 © 2012 Springer Science+Business Media, Inc.

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Luk´yanov et al.
the latter case the target product of the displacement of
the nitro group (i.g., compound 10) is rather stable and
was prepared by solvolysis of aminofurazan 6 (Scheme 3).
ammonolysis) by treatment of 3ꢀnitroꢀ4ꢀ(trinitromethylꢀ
ONNꢀazoxy)furazan (13) with ammonia.
Treatment of salt 12ꢀNH4 with gaseous HCl in MeOH
afforded low stable crystalline 3ꢀnitroꢀ4ꢀ(dinitromethylꢀ
ONNꢀazoxy)furazan (12) with m.p. 85—87.5 C
(decomp.).
Scheme 3
Likewise ammonia, methylamine reacted with 11. In
this reaction due to the higher reactivity of methylamine
with respect to ammonia, after methylammonium salt forꢀ
mation bearing the dinitromethyl group, a product of subꢀ
stitution of the methylamino group for the nitro group
immediately formed. Treatment of this product with HCl
resulted in 3ꢀ(Nꢀmethylamino)ꢀ4ꢀ(dinitromethylꢀONNꢀ
azoxy)furazan (14). For purification and unambiguous
identification, furazan 14 was converted into more stable
potassium salt 14ꢀK by treatment with KOH in MeOH
(Scheme 5).
Reaction of 3ꢀ(dinitromethylꢀONNꢀazoxy)ꢀ4ꢀnitroꢀ
furazan (11) with ammonia proceeded in two steps. In
CH2Cl2 after 2 min of the reaction, ammonium salt
11ꢀNH4 was formed in 90% yield. This salt also formed on
bubbling of NH3 through a solution of 11 in MeCN and
then within 2.5 h transformed into ammonium salt of
3ꢀaminoꢀ4ꢀ(dinitromethylꢀONNꢀazoxy)furazan (12ꢀNH4)
in 95% yield (Scheme 4). Compound 12ꢀNH4 was obꢀ
tained in a yield of 78% in two steps also (denitration and
Compound 11 reacted with ethylenediamine similarly
but with lower rate to give (after acidification) a product
at both the amino group of ethylnediamine, N,N´ꢀbisꢀ
[4ꢀ(dinitromethylꢀONNꢀazoxy)furazanꢀ3ꢀyl]ethylenediꢀ
Scheme 4
Scheme 5

3ꢀAminoꢀ4ꢀ(ꢀnitroalkylꢀONNꢀazoxy)furazans
Russ.Chem.Bull., Int.Ed., Vol. 61, No. 2, February, 2012
357
114.56 (C—NO2), 148.34 (C—NH2), 154.16 (C—N=NO).
amine (15). For identification, diamine 15 as in the case
of compound 11 was converted into dipotassium salt
15ꢀ2K, however, the latter turned to be highly hygroscopꢀ
ic and was transformed into dichloro derivative 16 by treatꢀ
ment with gaseous chlorine (see Scheme 5).
In summary, in the present work synthetic procedure
towards 3ꢀaminoꢀ4ꢀ(ꢀnitroalkylꢀONNꢀazoxy)furazans
and some of their derivatives by displacement of the nitro
groups of 3ꢀnitroꢀ4ꢀ(ꢀnitroalkylꢀONNꢀazoxy)furazans on
treatment with ammonia, primary and secondary amines,
and diamines as well, was developed. In the case of
(ꢀnitroalkylꢀONNꢀazoxy)furazans, no nucleofuge activꢀ
ity was observed.
14N NMR (22 MHz, CDCl3), : –45.6 (NO,  = 97 Hz);
0.5
–2.6 (NO2, 0.5 = 85 Hz). 14N NMR (22 MHz, acetoneꢀd6), :
–43.7 (NO, 0.5 = 83 Hz); 1.2 (NO2, 0.5 = 76 Hz).
B. To a solution of 1 (3.50 g, 14.2 mmol) in MeCN (70 mL),
25% NH4OH (11 mL) was added at 20 C. The mixture was kept
at 20 C for 24 h, the solvent was removed in vacuo, the residue
was washed with water to give compound 4 (2.52 g, 82%). The
physicochemical parameters of the sample are in agreement with
those of the compound obtained by the method A.
3ꢀAminoꢀ4ꢀ(1ꢀnitrocyclohexylꢀONNꢀazoxy)furazan (5). NH3
was bubbled through a stirred solution of 2 (0.180 g, 0.629 mmol)
in CH2Cl2 (8.00 mL) for 4 h at 20 C. The mixture was kept in
refrigerator for 24 h, the solvent was removed in vacuo. Purificaꢀ
tion of the residue by preparative TLC (silica gel, elution with
benzene—acetone, 5 : 1) afforded compound 5 (0.130 g, 81%),
yellowish crystals, m.p. 81.0—83.0 C (from H2O—PriOH). MS
(ESI), m/z: 257.1003 [M + H]+; calculated for C8H12N6O4,
[M + H]+, m/z: 257.0993. IR (KBr), /cm–1: 3454 (s, NH2),
3334 (s, NH2), 1626 (v.s, NH2), 1561 (v.s, C—NO2), 1504 (v.s,
N=NO), 1325 (s, C—NO2), 1256 (m, N=NO). 1H NMR
(CDCl3), : 1.62 (m, 2 H, CH2(CH2CH2)2); 1.77 (m, 4 H,
CH2(CH2CH2)2); 2.73 (m, 4 H, (CH2)2CNO2); 4.53 (s, 2 H, NH2).
13C NMR (75 MHz, acetoneꢀd6), : 22.92 (CH2(CH2CH2)2),
23.83 (CH2(CH2CH2)2), 33.50 ((CH2)2CNO2), 116.99
((CH2)2CNO2), 148.45 (C—NH2), 154.25 (C—N=NO).
Experimental
The course of the reactions was monitored by TLC on the
Silufol UVꢀ254 plates. IR spectra were recorded on a Bruker
1
Alpha instrument. H, 13C, and 14N NMR spectra were run on
a Bruker AMꢀ300 instrument. High resolution mass spectra with
electrospray ionization were obtained on a Bruker micrOTOF II
mass spectrometer.5 Melting points were determined on a Koefꢀ
fler apparatus. The starting compounds 3ꢀaminoꢀ4ꢀnitrofurazan,6
1ꢀnitroꢀ1ꢀnitrosocyclohexane,7 DBI,8 3ꢀ(dibromonitromethylꢀ
ONNꢀazoxy)ꢀ4ꢀnitrofurazan,9 3ꢀ(2ꢀhydroxyꢀ1ꢀhydroxymethylꢀ
1ꢀnitroethylꢀ1ꢀONNꢀazoxy)ꢀ4ꢀnitrofurazan,9 compounds 1,9 3,9
11,9 and 139 were synthesized by the known procedures.
3ꢀNitroꢀ4ꢀ(1ꢀnitrocyclohexylꢀONNꢀazoxy)furazan (2). To
a stirred solution of 1ꢀnitroꢀ1ꢀnitrosocyclohexane (1.01 g,
6.39 mmol) in anh. CH2Cl2 (50.0 mL), DBI (2.20 g, 7.67 mmol)
and 3ꢀaminoꢀ4ꢀnitrofurazan (0.83 g, 6.39 mmol) were added at
20 C. The suspension was stirred at 20 C for 24 h, the precipiꢀ
tate was filtered off, the mother liquor was concentrated in vacuo,
purification of the residue by column chromatography (silica
gel, elution with benzene—hexane, 1 : 4) afforded compound 2
(1.13 g, 62%), yellowish oil. Found (%): C, 33.71; H, 3.71; N, 29.55.
C8H10N6O6. Calculated (%): C, 33.57; H, 3.50; N, 29.37.
IR (KBr), /cm–1: 1573 (v.s, C—NO2); 1542 (s, C—NO2);
1506 (v.s, N=NO); 1373 (s, C—NO2); 1351 (s, C—NO2);
1306 (m, N=NO). 1H NMR (CDCl3), : 1.65 (m, 2 H,
CH2(CH2CH2)2); 1.81 (m, 4 H, CH2(CH2CH2)2); 2.77 (m, 4 H,
(CH2)2CNO2). 13C NMR (75 MHz, acetoneꢀd6), : 22.80
(CH2(CH2CH2)2), 23.71 (CH2(CH2CH2)2), 33.57 ((CH2)2CNO2),
117.90 ((CH2)2CNO2), 149.91 (C—NO2), 156.47 (C—N=NO).
14N NMR (22 MHz, acetoneꢀd6), : –35.86 (NO, NO2,
0.5 = 36 Hz); –2.94 ((CH2)2CNO2, 0.5 = 138 Hz).
14N NMR (22 MHz, acetoneꢀd6), : –46.41 (NO, 
= 86 Hz); –0.21 (NO2, 0.5 = 92 Hz).
=
0.5
3ꢀAminoꢀ4ꢀ(2,2ꢀdimethylꢀ5ꢀnitroꢀ1,3ꢀdioxanꢀ5ꢀylꢀONNꢀ
azoxy)furazan (6). A. NH3 was bubbled through a stirred solution
of 3 (0.900 g, 2.83 mmol) in CH2Cl2 (30.0 mL) for 4 h at 20 C.
The mixture was kept in refrigerator for 24 h, the solvent was
removed in vacuo. Purification of the residue by column chroꢀ
matography (silica gel, elution with benzene) afforded compound 6
(0.650 g, 80%), bright yellow crystals, m.p. 150.0—152.0 C (from
CHCl3). Found (%): C, 33.43; H, 4.03; N, 29.18. C8H12N6O6.
Calculated (%): C, 33.33; H, 4.17; N, 29.17. IR (KBr), /cm–1
:
3465 (s, NH2), 3347 (v.s, NH2), 1629 (v.s, NH2), 1575 (v.s,
C—NO2), 1506 (v.s, N=NO), 1385 (s, C—NO2), 1301
(m, N=NO). 1H NMR (acetoneꢀd6), : 1.45, 1.53 (both s,
6 H, 2 Me); 4.96 (m, 4 H, CH2); 6.00 (s, 2 H, NH2). 13C NMR
(75 MHz, acetoneꢀd6), : 21.12 (Me), 25.01 (Me), 62.68 (CH2),
100.75 (C(Me)2), 107.14 (C—NO2), 148.04 (C—NH2), 154.48
(C—N=NO). 14N NMR (22 MHz, acetoneꢀd6), : –55.87
(NO, 0.5 = 81 Hz); –10.58 (NO2, 0.5 = 86 Hz).
B. To a solution of compound 3 (0.5 g, 1.6 mmol) in CH2Cl2
(30 mL), 25% NH4OH (2 mL) was added at 20 C. The mixture
was stirred at 20 C for 24 h, the aqueous layer was separated,
25% NH4OH (2 mL) was added to the organic phase, and the
mixture was stirred at 20 C for 6 days. The organic phase was
separated, washed with water (3×5 mL), dried with MgSO4, the
solvent was removed in vacuo, the residue was washed with
hexane—diethyl ether to give compound 6 (0.327 g, 73%). The
physicochemical parameters of the sample are in agreement with
those of the compound obtained by the method A.
3ꢀAminoꢀ4ꢀ(1ꢀmethylꢀ1ꢀnitroethylꢀ1ꢀONNꢀazoxy)furazan
(4). A. NH3 was bubbled through a solution of 1 (1.04 g,
4.23 mmol) in CH2Cl2 (35.0 mL) for 4 h at 20 C, the mixture
was kept in refrigerator for 24 h, and the solvent was removed
in vacuo. Purification of the residue by column chromatography
(silica gel, elution with benzene) afforded compound 4 (0.800 g,
88%), yellowish crystals, m.p. 89.5—91.0 C (from CHCl3—hexꢀ
ane). Found (%): C, 27.94; H, 3.86; N, 38.43. C5H8N6O4. Calꢀ
3ꢀ(NꢀMethylamino)ꢀ4ꢀ(2,2ꢀdimethylꢀ5ꢀnitroꢀ1,3ꢀdioxanꢀ5ꢀ
ylꢀONNꢀazoxy)furazan (7). To a 0 C solution of MeNH2 (0.1 g,
3.23 mmol) in water (10.0 mL), a solution of compound 3 (0.2 g,
0.629 mmol) in CH2Cl2 (10.0 mL) was added with vigorous stirꢀ
ring. Emulsion was stirred at 20 C for 1.5 h, diluted with water
(10 mL), the products were extracted with CH2Cl2 (4×10 mL),
culated (%): C, 27.78; H, 3.70; N, 38.89. IR (KBr), /cm–1
:
3464 (s, NH2); 3328 (s, NH2); 1624 (v.s, NH2); 1576
(v.s, C—NO2); 1504 (v.s, N=NO); 1380 (s, C—NO2); 1268
1
(s, N=NO). H NMR (CDCl3), : 2.29 (s, 6 H, 2 Me); 4.53
(s, 2 H, NH2). 13C NMR (75 MHz, acetoneꢀd6), : 24.69 (Me),

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Luk´yanov et al.
the organic layer was separated, washed with water (3×10 mL),
5% aqueous HCl (3×10 mL), 5% aqueous Na2CO3 (3×10 mL),
and water (3×10 mL), the organic phase was dried with MgSO4.
Removal of the solvent in vacuo and purification of the residue
by preparative TLC (silica gel, elution with benzene—acetone,
5 : 1) afforded compound 7 (0.152 g, 80%), bright yellow crysꢀ
tals, m.p. 50.0—52.0 C. MS (ESI), m/z 303.1048 [M + H]+;
calculated for C9H14N6O6, [M + H]+, m/z: 303.1048. IR (KBr),
/cm–1: 3432 (m, NH), 1612 (v.s, N—H), 1576 (v.s, C—NO2),
1508 (v.s, N=NO), 1380 (s, C—NO2), 1296 (s, N=NO).
1H NMR (CDCl3), : 1.48, 1.52 (both s, 6 H, Me); 3.05 (s, 3 H,
Me); 4.39 (s, 1 H, NH); 4.78 (s, 4 H, CH2). 13C NMR (75 MHz,
acetoneꢀd6), : 21.10 (C—Me), 24.99 (C—Me), 29.32 (NHMe),
62.63 (CH2), 100.73 (C(Me)2), 107.05 (C—NO2), 147.45
(C—NHMe), 155.72 (C—N=NO). 14N NMR (22 MHz,
C, 38.22; H, 4.46; N, 26.75. IR (KBr), /cm–1: 1571 (v.s,
C—NO2), 1519 (v.s, N=NO), 1382 (s, C—NO2), 1279
1
(m, N=NO). H NMR (CDCl3), : 1.50, 1.52 (both s, 12 H,
Me); 3.63 (s, 8 H, CH2N); 4.79 (s, 8 H, (CH2)2CNO2). 13C NMR
(75 MHz, acetoneꢀd6), : 22.12 (C—Me), 23.94 (C—Me), 47.75
((CH2)2N), 62.64 ((CH2)2CNO2), 100.95 (C(Me)2), 107.46
(C—NO2), 148.34 (C—N(CH2)2), 156.64 (C—N=NO).
14N NMR (22 MHz, acetoneꢀd6), : –11.5 (NO, 
= 162 Hz), –55.6 (NO2, 0.5 = 92 Hz).
=
0.5
3ꢀAminoꢀ4ꢀ(2ꢀhydroxyꢀ1ꢀhydroxymethylꢀ1ꢀnitroethylꢀ1ꢀONNꢀ
azoxy)furazan (10). To a suspension of 6 (0.320 g, 1.11 mmol) in
MeOH (4.0 mL), AcCl (1.20 mL, 1.26 g, 16.1 mmol) was added
dropwise at 20 C. The mixture was stirred at 20 C for 0.5 h, the
solvent was removed in vacuo. Purification of the residue by
preparative TLC (silica gel, elution with benzene—acetone,
1.5 : 1) and further trituration of the oily product with diethyl
ether—hexane gave compound 10 (0.243 g, 88%), yellowish crysꢀ
tals, m.p. 110.0—112.5 C. Found (%): C, 24.48; H, 3.38;
N, 33.57. C5H8N6O6. Calculated (%): C, 24.19; H, 3.23;
N, 33.87. IR (KBr), /cm–1: 3480 (v.s, NH2), 3376 (v.s, NH2),
1628 (v.s, NH2), 1588 (v.s, C—NO2), 1496 (v.s, N=NO), 1360
(s, C—NO2), 1264 (m, N=NO). 1H NMR (acetoneꢀd6), :
4.66 (s, 4 H, CH2); 5.24 (s, 2 H, OH); 5.88 (s, 2 H, NH2).
13C NMR (75 MHz, acetoneꢀd6), : 61.18 (CH2), 115.05 (C—NO2),
148.20 (C—NH2), 154.14 (C—N=NO). 14N NMR (22 MHz,
acetoneꢀd6), : –56.69 (NO,  = 73 Hz); –10.98 (NO2,
0.5
0.5 = 86 Hz).
N,N´ꢀBis[4ꢀ(2,2ꢀdimethylꢀ5ꢀnitroꢀ1,3ꢀdioxanꢀ5ꢀylꢀONNꢀ
azoxy)furazanꢀ3ꢀyl]ethylenediamine (8). To a 0 C solution of
H2NCH2CH2NH2 (0.04 g, 0.667 mmol) and NaHCO3 (0.05 g,
0.6 mmol) in water (2.0 mL), a solution of compound 3 (0.17 g,
0.535 mmol) in CH2Cl2 (2.0 mL) was added with vigorous stirꢀ
ring. The emulsion was stirred at 20 C for 48 h, the precipitate
formed was filtered, washed with water to give 0.07 mg of comꢀ
pound 8. The mother liquor was diluted with water (10 mL), the
product was extracted with CH2Cl2 (4×10 mL), the organic layꢀ
er was separated, washed with water (3×10 mL), 5% aqueous
HCl (3×10 mL), 5% aqueous Na2CO3 (3×10 mL), and water
(3×10 mL), and dried with MgSO4. Removal of the solvent
in vacuo and purification of the residue by preparative TLC (silꢀ
ica gel, elution with benzene—acetone, 4 : 1) afforded 0.05 g of
compound 8. Total yield was 0.120 g (75%), bright yellow crysꢀ
tals, m.p. 187.0—189.0 C (from PriOH). Found (%): C, 35.92;
H, 4.38; N, 27.74. C18H26N12O12. Calculated (%): C, 35.88; H,
4.32; N, 27.91. IR (KBr), /cm–1: 3400 (s, NH), 1604 (v.s,
N—H), 1576 (v.s, C—NO2), 1504 (v.s, N=NO), 1380 (s,
C—NO2), 1300 (m, N=NO). 1H NMR (acetoneꢀd6), : 1.48,
1.53 (both s, 12 H, Me); 3.64 (s, 4 H, CH2NH); 4.94 (m, 8 H,
(CH2)2CNO2); 6.35 (s, 2 H, NH). 1H NMR (CDCl3), : 1.26
(s, 12 H, Me); 3.70 (s, 4 H, CH2NH); 4.78 (s, 8 H, (CH2)2CNO2);
4.86 (s, 2 H, NH). 1H NMR (DMSOꢀd6), : 1.48, 1.53 (both s,
12 H, Me); 3.48 (s, 4 H, CH2NH); 4.86 (m, 8 H, (CH2)2CNO2);
7.04 (s, 2 H, NH). 13C NMR (75 MHz, acetoneꢀd6), : 21.31
(C—Me), 24.78 (C—Me), 42.91 (CH2NH), 62.62 ((CH2)2CNO2),
100.78 (C(Me)2), 107.16 (C—NO2), 147.59 (C—NH), 154.97
(C—N=NO). 14N NMR (22 MHz, acetoneꢀd6), : –55.8
(NO, 0.5 = 138 Hz), –9.7 (NO2, 0.5 = 158 Hz).
1,4ꢀBis[4ꢀ(2,2ꢀdimethylꢀ5ꢀnitroꢀ1,3ꢀdioxanꢀ5ꢀylꢀONNꢀazoxy)ꢀ
furazanꢀ3ꢀyl]piperazine (9). To a 0 C solution of piperazine
(0.060 g, 0.698 mmol) and NaHCO3 (0.050 g, 0.595 mmol) in
water (2.0 mL), a solution of compound 3 (0.160 g, 0.503 mmol)
in CH2Cl2 (2.0 mL) was added with vigorous stirring. The emulꢀ
sion was stirred at 20 C for 48 h, diluted with water (10 mL), the
product was extracted with CH2Cl2 (4×10 mL), the organic layꢀ
er was separated, washed with water (3×10 ml), 5% aqueous HCl
(3×10 mL), 5% Na2CO3 (3×10 mL), and water (3×10 mL), and
dried with MgSO4. Removal of the solvent in vacuo and purificaꢀ
tion of the residue by preparative TLC (silica gel, elution with
benzene—acetone, 10 : 1) afforded compound 9 (0.100 g, 63%),
yellowish crystals, m.p. 192.0—194.0 C (from PriOH). Found (%):
C, 38.35; H, 4.50; N, 26.77. C20H28N12O12. Calculated (%):
acetoneꢀd6), : –51.8 (NO,  = 117 Hz), –8.5 (NO2,
0.5
0.5 = 114 Hz).
Ammonium salt of 3ꢀ(dinitromethylꢀONNꢀazoxy)ꢀ4ꢀnitroꢀ
furazan (11ꢀNH4). NH3 was bubbled through a stirred solution
of 11 (0.052 g, 0.198 mmol) in CH2Cl2 (3.0 mL) at 20 C for
2 min. The precipitate formed was filtered, washed with CH2Cl2,
and vacuum dried. Salt 11ꢀNH4 was obtained in the yield of
0.050 g (91%), bright yellow crystals, m.p. 129.0 C (decomp.).
Found (%): C, 12.97; H, 1.46; N, 39.43. C3H4N8O8. Calculated
(%): C, 12.86; H, 1.44; N, 40.00. IR (KBr), /cm–1: 3228
(m, NH4+), 1576 (v.s, C—NO2), 1528 (s, C—NO2), 1500
(v.s, N=NO), 1352 (s, C—NO2), 1288 (m, N=NO). 1H NMR
(acetoneꢀd6), : 7.57 (br.s, 4 H, NH4+).
Ammonium salt of 3ꢀaminoꢀ4ꢀ(dinitromethylꢀONNꢀazoxy)ꢀ
furazan (12ꢀNH4). A. NH3 was bubbled through a stirred soluꢀ
tion of compound 11 (0.100 g, 0.380 mmol) in MeCN (5.0 mL)
at 20 C for 2.5 h. Removal of the solvent in vacuo and purificaꢀ
tion of the residue by preparative TLC (silica gel, elution with
benzene—acetone, 1 : 2) afforded salt 12ꢀNH4 (0.090 g, 95%),
yellowish crystals, m.p. 115.0—117.0 C (decomp.). Found (%):
C, 14.39; H, 2.33; N, 44.49. C3H6N8O6. Calculated (%):
C, 14.40; H, 2.40; N, 44.80. IR (KBr), /cm–1: 3468 (s, NH2),
3320 (v.s, NH2), 3245 (m, NH4+), 1632 (m, NH2), 1576 (v.s,
C—NO2), 1484 (v.s, N=NO), 1368 (s, C—NO2), 1320
(m, N=NO). 1H NMR (acetoneꢀd6), : 5.64 (s, 2 H, NH2);
8.06 (br.s, 4 H, NH4+).
B. NH3 was bubbled through a stirred solution of comꢀ
pound 13 (0.100 g, 0.325 mmol) in MeCN (5.0 mL) at 20 C for
3 h. Removal of the solvent in vacuo and purification of the
residue by preparative TLC (silica gel, elution with benzꢀ
ene—acetone, 1 : 2) afforded salt 12ꢀNH4 (0.063 g, 78%). Physiꢀ
cochemical parameters of the sample are in agreement with those
of compound 12ꢀNH4 obtained by the method A.
3ꢀAminoꢀ4ꢀ(dinitromethylꢀONNꢀazoxy)furazan (12). HCl
was bubbled through a stirred 0 C solution of 12ꢀNH4 (0.090 g,
0.360 mmol) in MeOH (10.0 mL) for 20 min. The solvent was

3ꢀAminoꢀ4ꢀ(ꢀnitroalkylꢀONNꢀazoxy)furazans
Russ.Chem.Bull., Int.Ed., Vol. 61, No. 2, February, 2012
359
removed in vacuo, the residue was extracted with Et2O (3×10 mL),
and the organic layer was dried with MgSO4. Removal of
the solvent in vacuo afforded compound 12 (0.065 g, 81%),
bright yellow crystals, m.p. 85.0—87.5 C (decomp.) (from hexꢀ
ane—CH2Cl2). H NMR (CDCl3), : 4.60 (s, 2 H, NH2); 7.71
(s, 1 H, CH).
N,N´ꢀBis[4ꢀ(chlorodinitromethylꢀONNꢀazoxy)furazanꢀ3ꢀ
yl]ethylenediamine (16). Cl2 was bubbled through a stirred soluꢀ
tion of compound 15ꢀ2K (0.100 g, 0.176 mmol) in MeCN
(15.0 mL) at 20 C for 2 min. The precipitate formed was filtered
off, the mother liquor was concentrated in vacuo, purification of
the residue by preparative TLC (silica gel, elution with benzꢀ
ene—acetone, 5 : 1) afforded compound 16 (0.084 g, 85%), bright
orange crystals, m.p. 147.5—149.0 C (from CCl4—CH2Cl2). MS
1
Potassium salt of 3ꢀ(Nꢀmethylamino)ꢀ4ꢀ(dinitromethylꢀONNꢀ
azoxy)furazan (14ꢀK). To a 0 C solution of MeNH2 (0.143 g,
4.61 mmol) in water (7.0 mL), a solution of 11 (0.100 g,
0.380 mmol) in CH2Cl2 (4.0 mL) was added with vigorous stirꢀ
ring. The emulsion was stirred at 20 C for 20 min, diluted with
water (10 mL), washed with CH2Cl2 (3×5 mL), 33% HCl
(0.45 mL, 4.74 mmol) was added to the aqueous layer, the product
was extracted with CH2Cl2 (4×10 mL), the organic phase was
dired with MgSO4. Removal of the solvent in vacuo afforded
compound 14 (0.089 g, 95%), orange oil. 1H NMR (CDCl3), :
3.56 (s, 3 H, Me); 4.41 (s, 1 H, NH); 7.71 (s, 1 H, CH). To
a solution of compound 14 (0.089 g, 0.360 mmol) in MeOH
(2.0 mL), a solution of KOH (0.021 g, 0.375 mmol) in MeOH
(2.0 mL) was added, the solvent was removed in vacuo. Purificaꢀ
tion of the residue by preparative TLC (silica gel, elution with
benzene—acetone, 1 : 2) and subsequent washing with Et2O afꢀ
forded potassium salt 14ꢀK (0.080 g, 78%), light orange crystals,
m.p. 186.0—187.5 C (decomp.). Found (%): C, 16.61; H, 1.01;
N, 34.37. C4H4KN7O6. Calculated (%): C, 16.84; H, 1.40;
N, 34.39. IR (KBr), /cm–1: 3425 (m, NH), 1614 (m, N—H),
1589 (s, C—NO2), 1514 (v.s, N=NO), 1387 (s, C—NO2), 1294
(s, N=NO). 1H NMR (acetoneꢀd6), : 2.90 (s, 3 H, Me); 3.53
(s, 1 H, NH).
(ESI), m/z: 560.9733 [M + H]+; calculated for C8H6Cl2N14O12
,
[M + H]+, m/z: 560.9739. IR (KBr), /cm–1: 3374 (v.s, NH),
1609 (v.s, br, N—H and C—NO2), 1514 (v.s, N=NO), 1364
(s, C—NO2), 1287 (s, N=NO). 1H NMR (CDCl3), : 3.64
(s, 4 H, CH2); 6.55 (s, 2 H, NH). 13C NMR (75 MHz, acetoneꢀd6),
: 42.68 (CH2NH), 127.05 (C(NO2)2Cl), 147.37 (C—NH),
155.22 (C—N=NO). 14N NMR (22 MHz, acetoneꢀd6), :
–71.78 (NO, 0.5 = 69 Hz), –31.26 (NO2, 0.5 = 24 Hz).
References
1. O. A. Luk´yanov, G. V. Pokhvisneva, T. V. Ternikova, N. I.
Shlykova, Izv. Akad. Nauk, Ser. Khim., 2011, 358 [Russ.
Chem. Bull., Int. Ed., 2012, 61, 360].
2. A. M. Churakov, S. L. Ioffe, Yu. A. Strelenko, V. A. Tartaꢀ
kovsky, Tetrahedron Lett., 1996, 37, 8577.
3. A. B. Sheremetev, V. O. Kulagina, I. A. Kryazhevskii, M. M.
Mel´nikova, N. S. Aleksandrova, Izv. Akad. Nauk, Ser. Khim.,
2002, 1411 [Russ. Chem. Bull., Int. Ed., 2002, 51, 1533].
4. A. B. Sheremetev, V. G. Andrianov, E. V. Mantseva, E. V.
Shatunova, N. S. Aleksandrova, I. L. Yudin, D. E. Dmitriev,
B. B. Averkiev, M. Yu. Antipin, Izv. Akad. Nauk, Ser. Khim.,
2004, 569 [Russ. Chem. Bull., Int. Ed., 2004, 53, 596].
5. P. A. Belyakov, V. I. Kadentsev, A. O. Chizhov, N. G. Koloꢀ
tyrkina, A. S. Shashkov, V. P. Ananikov, Mendeleev Comꢀ
mun., 2010, 20, 125.
Dipotassium salt of N,N´ꢀbis[4ꢀ(dinitromethylꢀONNꢀazoxy)ꢀ
furazanꢀ3ꢀyl]ethylenediamine (15ꢀ2K). To a 0 C solution of
H2NCH2CH2NH2 (0.027 g, 0.456 mmol) and NaHCO3 (0.140 g,
1.67 mmol) in water (3.0 mL), a solution of compound 11
(0.200 g, 0.760 mmol) in CH2Cl2 (2.0 mL) was added with vigorꢀ
ous stirring. The emulsion was stirred at 20 C for 7 days, diluted
with water (10 mL), washed with CH2Cl2 (3×5 mL), 33% HCl
(0.17 mL, 1.82 mmol) was added to the aqueous layer, the prodꢀ
uct was extracted with CH2Cl2 (4×10 mL), the organic phase
was dried with MgSO4. Removal of the solvent in vacuo affordꢀ
ed compound 15 (0.103 g, 55%), light orange crystals, m.p.
6. 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].
7. S. S. Nametkin, Zh. Rus. Fiz.ꢀKhim. Oꢀva [J. Russ. Phys.ꢀ
Chem. Soc.], 1910, 42, 585 (in Russian).
1
8. W. Gottardi, Monatsh. Chem., 1968, 99, 815.
131.0—133.0 C. H NMR (acetoneꢀd6), : 3.64 (s, 4 H, CH2);
9. O. A. Luk´yanov, G. V. Pokhvisneva, T. V. Ternikova, N. I.
Shlykova, M. E. Shagaeva, Izv. Akad. Nauk, Ser. Khim., 2011,
1678 [Russ. Chem. Bull., Int. Ed., 2011, 60, 1703].
6.34 (s, 2 H, NH); 9.20 (s, 2 H, CH). To a solution of compound
15 (0.103 g, 0.209 mmol) in MeOH (2.0 mL), a solution of KOH
(0.012 g, 0.214 mmol) in MeOH (2.0 mL) was added, the solvent
was removed in vacuo. Purification of the residue by preparative
TLC (silica gel, elution with benzene—acetone, 1 : 2) affordꢀ
ed salt 15ꢀ2K (0.115 g, 97%), orange crystals (hygroscopic).
1H NMR (acetoneꢀd6), : 3.10 (s, 4 H, CH2); 3.68 (s, 2 H, NH).
The structure of compound 15 was confirmed by the conversion
of the latter into dichloride 16.
Received April 5, 2011;
in revised form September 9, 2011