Synthesis and nitration of N,N-bis(3-R-furoxan-4-yl) methylenediamines

Article abstract of DOI:10.1007/s11172-010-0363-1

A Mannich reaction of 4-amino-3-R-furoxans with paraformaldehyde in 10% aqueous H₂SO₄ led to the high yields of N,N′-bis(3-R-furoxan-4-yl)methylenediamines, whose structure (using R = Me as an example) was confirmed by X-ray diffract

Full text of DOI:10.1007/s11172-010-0363-1

Russian Chemical Bulletin, International Edition, Vol. 59, No. 11, pp. 2108—2113, November, 2010
2108
Synthesis and nitration of N,N´ꢀbis(3ꢀRꢀfuroxanꢀ4ꢀyl)methylenediamines
A. O. Finogenov,a M. A. Epishina,a A. S. Kulikov,a N. N. Makhova,a I. V. Anan'ev,b and V. A. Tartakovskya
aN. D. Zelinsky Institute of Organic Chemistry, Russian Academy of Sciences,
47 Leninsky prosp., 119991 Moscow, Russian Federation.
Fax: +7 (499) 135 5328. Eꢀmail: mnn@ioc.ac.ru
bA. N. Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences,
28 ul. Vavilova, 119991 Moscow, Russian Federation.
Fax: +7 (499) 135 5085. Eꢀmail: kostya@xrlab.ineos.ac.ru
A Mannich reaction of 4ꢀaminoꢀ3ꢀRꢀfuroxans with paraformaldehyde in 10% aqueous
H2SO4 led to the high yields of N,N´ꢀbis(3ꢀRꢀfuroxanꢀ4ꢀyl)methylenediamines, whose strucꢀ
ture (using R = Me as an example) was confirmed by Xꢀray diffraction study. The N,N´ꢀbisꢀ
(3ꢀRꢀfuroxanꢀ4ꢀyl)methylenediamines obtained were nitrated to N,N´ꢀdinitroꢀN,N´ꢀbisꢀ
(3ꢀRꢀfuroxanꢀ4ꢀyl)methylenediamines upon the action of 100% HNO3 in acetic or trifluoroꢀ
acetic anhydride.
Key words: 4ꢀaminoꢀ3ꢀRꢀfuroxans, paraformaldehyde, hydroxymethylation, the Mannich
reaction, 4ꢀhydroxymethylaminoꢀ3ꢀRꢀfuroxans, N,N´ꢀbis(3ꢀRꢀfuroxanꢀ4ꢀyl)methylenediꢀ
amines, Nꢀnitration, N,N´ꢀdinitroꢀN,N´ꢀbis(3ꢀRꢀfuroxanꢀ4ꢀyl)methylenediamines.
Derivatives of methylenebisamines are widely used in
synthetic organic chemistry, for example, as aminomethꢀ
ylating agents,1 while methylenedinitramine fragments are
a part of highꢀenergy compounds, in particular, hexogene
and octogene. The most common and convenient method
for the synthesis of methylenediamine derivatives is conꢀ
densation of 2 moles of amines with 1 mole of formaldeꢀ
hyde by the Mannich reaction. Conditions for this reacꢀ
tion vary within a wide range and depend, in particular, on
the basicity of amines used.2 This approach was used for
the synthesis of derivatives of various heterocyclic amines
and their N,N´ꢀdinitro derivatives, including those derived
from aminofurazans, i.e., N,N´ꢀbis(furazanyl)methyleneꢀ
diamines and N,N´ꢀdinitroꢀN,N´ꢀbis(furazanyl)methylꢀ
enediamines.3—7
nich bases from aminofuroxans and their further transforꢀ
mations are not described in the literature by now, which
is due, by all accounts, to the fact that aminofuroxans with
suitable substituents at the second C atom are not easily
available. 3ꢀAminofuroxans, except their 4ꢀaryl derivaꢀ
tives,9 are virtually unavailable. However, in the last years
new fairly convenient methods for the preparation of funcꢀ
tionally substituted 4ꢀaminofuroxans were developed,10—12
that allowed one to start an extensive study of their reꢀ
activity.
The present work is devoted to the study of behavior of
isomeric 4ꢀ and 3ꢀaminofuroxans in the Mannich reacꢀ
tion with formaldehyde in order to obtain N,N´ꢀbis(furꢀ
oxanyl)methylenediamines and their nitration to N,N´ꢀdiꢀ
nitro derivatives. The study was started from 4ꢀaminoꢀ3ꢀ
Rꢀfuroxans 1a—f with substituents of different types at the
C(3) atom of the ring (Scheme 1). Initially, in the syntheꢀ
sis of target N,N´ꢀbis(3ꢀRꢀfuroxanꢀ4ꢀyl)methylenediꢀ
Though, compounds derived from N,N´ꢀbis(furoxanꢀ
yl)methylenedinitramines can be of interest for the prepaꢀ
ration of potentially highꢀenergy compounds,8 the Manꢀ
Scheme 1
R = Me (a), Ph (b), Ac (c), COOMe (d), CONH2 (e), CON3 (f)
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 11, pp. 2054—2059, November, 2010.
1066ꢀ5285/10/5911ꢀ2108 © 2010 Springer Science+Business Media, Inc.

N,N´ꢀBis(3ꢀRꢀfuroxanꢀ4ꢀyl)methylendiamines
Russ.Chem.Bull., Int.Ed., Vol. 59, No. 11, November, 2010 2109
O(2)
amines 2a—f we used conditions for the preparation of
similar furazan derivatives. According to the literature
data,4—7 N,N´ꢀbis(4ꢀRꢀfurazanꢀ3ꢀyl)methylenediamines 5
were synthesized by the reaction of aminofurazans with
formaldehyde, as a rule, in weakly acidic medium (HCOOH
in MeCN, 0.5% aq. HCl or 1% aq. H2SO4). 3ꢀAminoꢀ4ꢀ
nitrofurazan4 was successfully involved into this reaction
only in 80% aq. H2SO4, which, obviously, is due to the
extremely low basicity of the compound under considerꢀ
ation because of strong electronꢀwithdrawing effect of the
nitrofurazanyl fragment.
N(2)
O(1)
N(1)
C(1A)
C(2A)
N(3A)
C(4)
C(3)
O(2)
C(3A)
N(3)
C(1)
N(1A)
O(1A)
N(2A)
O(2A)
Fig. 1. General view of compound 2a. Nonhydrogen atoms are
given as probability ellipsoids of thermal vibrations (p = 50%).
Conditions for the preparation of N,N´ꢀbis(3ꢀRꢀfurꢀ
oxanꢀ4ꢀyl)methylenediamine derivatives 2 were optimized
using 3ꢀacetylꢀ4ꢀaminofuroxan 1c and 4ꢀaminoꢀ3ꢀazidoꢀ
carbonylfuroxan 1f as examples. The reaction progress was
methylfuroxanꢀ4ꢀyl)methylenediamine is in particular
position and is placed on the second order axis passing
through the C(4) atom. Distribution of bond distances in
the compound is expected for aminofuroxans, the bond
between the furoxan ring and the amino group is shortꢀ
ened and its length approximates to that of a multiple
bond, that is also common for this class of compounds
(C(3)—N(3) 1.3618(12) Å, cf. with C—NH2, 1.344 Å in
4ꢀaminoꢀ3ꢀmethylfuroxan13). The N(3) nitrogen atom of
the NH group comes out of the plane of the C(3), C(4),
and H(3N) atoms by 0.175(7) Å. Such an arrangement of
substituents on the nitrogen atom has been also found
earlier for the symmetric methylenediamine derivatives
containing aryl or heteroaryl substituents (see, for examꢀ
ple, Ref. 14). The electron pair on the amine nitrogen
atom is antiperiplanar to the C(4)—N(3A) bond, that alꢀ
lows one to suggest a possibility of stereoelectronic interꢀ
action between the lone pair of electrons mentioned and
the antibonding orbital of the C(4)—N(3A) bond (n—σ*ꢀ
interaction). Apparently, the very existence of the anoꢀ
meric effect leads to the pyramidalization of the fragment
involving the NH nitrogen atom, despite significant douꢀ
bleꢀbond character of the C(3)—N(3) bond.
1
monitored by TLC and H NMR spectroscopy analyzing
samples of the reaction mixtures. When 1—3% aq. H2SO4
was used, the reaction mixture contained the starting
aminofuroxans 1c,f and small amount of intermediates,
apparently, hydroxymethylaminofuroxans 3c,f. When the
concentration of H2SO4 was increased to 5—6%, the startꢀ
ing aminofuroxans completely disappeared and the reacꢀ
tion mixture contained comparable amounts of interꢀ
mediates 3c,f and target compounds 2c,f. The Rf values
for the intermediates were significantly lower than those
for the final reaction products 2c,f, while 1H NMR specꢀ
tra of the reaction mixture contained signals in the region
δ 7.7—8.4 related to the intermediates and signals for
the NH groups of the final products 2c,f in the region
δ 7.0—7.2. The optimum conditions for the preparation
of compounds 2c,f are the stirring a suspension of the
starting components at room temperature in 10—12%
aq. H2SO4 for 24 h. After the reaction reached compleꢀ
tion, compounds 2a—f were filtered off and isolated in
virtually pure form in high yields (see Scheme 1).
From the mechanism of the Mannich reaction2 and
obtained results on the synthesis of compounds 2, it folꢀ
lows that the first step of the process, i.e., the formation of
Nꢀmethylol derivatives 3, proceeds in less acidic medium
than subsequent steps, i.e., formation of iminium cations
4 and their reaction with the second molecule of 4ꢀaminoꢀ
furoxan 1.
Analysis of crystal packing of 2a (Fig. 2) showed that
the oxygen atom of the Nꢀoxide group is involved into the
formation of both the weak intermolecular hydrogen bond
with the NH fragment (H...O is 2.06 Å, N...O is 2.932(2) Å,
The structure of synthesized N,N´ꢀbis(3ꢀRꢀfuroxanꢀ
4ꢀyl)methylenediamines 2a—f was established based on
the combination of elemental analysis data and spectral
characteristics; the structure of N,N´ꢀbis(3ꢀmethylfurꢀ
oxanꢀ4ꢀyl)methylenediamine 2a was confirmed by Xꢀray
diffraction study. The mass spectra of all the compounds
obtained are characterized by the presence of highly inꢀ
tensive peaks, which correspond to the fragments formed
upon the CH2—N bonds cleavage in their molecules. Only
the mass spectra of compounds 1a and 1c contained peaks
of low intensities corresponding to the molecular ions.
The Xꢀray diffraction data on monocrystals of comꢀ
pound 2a (Fig. 1) show that the molecule of N,N´ꢀbis(3ꢀ
N(3)
N(2)
O(1)
N(3)
O(1)
Fig. 2. Fragment of crystal packing of 2a.

2110
Russ.Chem.Bull., Int.Ed., Vol. 59, No. 11, November, 2010
Finogenov et al.
the N—H...O angle is 168°) and the CH...O contact with
the methyl substituent of the furoxan ring (H...O is
2.66—2.70 Å, C...O is 3.10—3.68 Å). It is probable that
the hydrogen bonds mentioned, together with stereoelecꢀ
tronic interactions, affect geometry of the amine nitrogen
atom involved into the intermolecular bonding. Together
with the Hꢀbonds, the molecules in the crystal are inꢀ
volved into the strong enough stackingꢀinteractions, which
combine them in dimers (3.36 Å). In turn, such dimers are
bound with each other by the N—πꢀinteraction between
the N(2) nitrogen atom and the πꢀsystem of the furoxan
ring (N...C is 3.17 Å) (see Fig. 2).
The N,N´ꢀbis(3ꢀRꢀfuroxanꢀ4ꢀyl)methylenediamines
2a—f synthesized were studied in the nitration reaction in
order to obtain N,N´ꢀdinitroꢀN,N´ꢀbis(3ꢀRꢀfuroxanꢀ4ꢀ
yl)methylenediamines 6. The nitration of compounds 2a—f
with the mixture of 100% HNO3—Ac2O under conditions
similar to those described in the works on the preparation of
furazan derivatives4,5,7 (in CCl4 at 0 °C), allowed us to obꢀ
tain only N,N´ꢀdinitro derivatives 6b,e,f (Scheme 2). These
dinitro derivatives are poorly soluble in the HNO3—Ac2O
mixture. They precipitated and were easily separated by
filtration. Variation in the ratio HNO3 : Ac2O virtually
produces no change in the yield of the reaction products.
2a,c,d were soluble in the nitrating HNO3—Ac2O mixꢀ
ture, but no any products were isolated from the solution
after the reaction was completed.
N,N´ꢀDinitro derivatives with Me (6a), Ac (6c), and
COOMe (6d) substituents were successfully obtained in
high yields upon nitration of compounds 2a,c,d with the
100% HNO3—(CF3CO)2O mixture. Dinitramines 6a,d
under these conditions precipitated from the reaction mixꢀ
ture and were isolated in high yield. Compound 6c was
soluble in the nitrating mixture and isolated from the reꢀ
action mixture after evaporation of HNO3 and (CF3CO)2O
on a rotary evaporator at room temperature. Nitration of
methylenebisamines with the aminocarbonyl (2e) and aziꢀ
docarbonyl (2f) substituents with the HNO3—(CF3CO)2O
mixture led to the isolation of the same products 6e,f,
which were formed in the HNO3—Ac2O mixture. In this
case, their yield somewhat increased (by 3—4%), while
the nitration time half decreased.
Nitration of N,N´ꢀbis(3ꢀphenylfuroxanꢀ4ꢀyl)methylꢀ
enediamine 2b with the mixture of HNO3 and (CF3CO)2O
involves, besides the NH group, the phenyl fragment to
form N,N´ꢀdinitroꢀN,N´ꢀbis[3ꢀ(4ꢀnitrophenyl)furoxanꢀ4ꢀ
yl]methylenediamine (6j) (Scheme 3). Its structure was
confirmed by a combination of elemental analysis data
and spectral characteristics.
Scheme 2
Scheme 3
R = Ph (b), CONH2 (e), CON3 (f)
R = Me (a), Ph (b), Ac (c), COOMe (d), CONH2 (e), CON3 (f),
4ꢀNO2C6H4 (j)
However, only dinitro derivatives 6b,f were successꢀ
fully isolated in the analytically pure form and complꢀ
etely characterized. According to the TLC (Rf 0.36
(CHCl3—EtOAc, 1 : 1)) and 1H NMR spectroscopic data
(acetoneꢀd6, δ: 6.42 (s, 2 H, CH2), 7.64 (s, 2 H, NH2),
7.95 (s, 2 H, NH2)), the structure of compound 6e agreed
with the desired N,N´ꢀbis(3ꢀaminocarbonylfuroxanꢀ4ꢀyl)ꢀ
N,N´ꢀdinitromethylenediamine. However, it was imposꢀ
sible to obtain good 13C and 14N NMR spectra for this
compound, since signals for the products of its decompoꢀ
sition rapidly appeared in the spectrum of 6e on standing
in acetoneꢀd6 and DMSOꢀd6. The mass spectrum of this
compound has also proved poorly informative, it exhibitꢀ
ed only lowꢀweight fragment ions corresponding to the
deep disintegration of the starting molecule. Compounds
Behavior of 3ꢀaminofuroxans in the Mannich reaction
with formaldehyde was studied using 3ꢀaminoꢀ4ꢀphenylꢀ
furoxan 7 as an example. However, in aqueous H2SO4
of different concentrations (3.5, 10, 25, and 50%) for
24—150 h at 20 °C, in all the cases the starting furoxan 7
was isolated from the mixture. The same result was also
obtained when H2SO4 was replaced by HCOOH in MeCN.
When the reaction was carried out in weakly basic mediꢀ
um (рH = 8—9), decomposition of the starting furoxan 7
occurred after 48 h.
In conclusion, the study of behavior of aminofurꢀ
oxans in the Mannich reaction with formaldehyde showed
that only 4ꢀaminofuroxans can be involved into this reacꢀ

N,N´ꢀBis(3ꢀRꢀfuroxanꢀ4ꢀyl)methylendiamines
Russ.Chem.Bull., Int.Ed., Vol. 59, No. 11, November, 2010 2111
Table 1. Yields and some physicochemical characteristics of synthesized N,N´ꢀbis(3ꢀRꢀfuroxanꢀ4ꢀyl)methylenediꢀ
amines 2a—f and N,N´ꢀdinitroꢀN,N´ꢀbis(3ꢀRꢀfuroxanꢀ4ꢀyl)methylenediamines 6a—d,f,j
Comꢀ
pound
Yield
(%)
M.p.
/°C
Rf
(eluent)
Found
Calculated
Molecular formula
(%)
C
H
N
2a
2b
2c
2d
2e
2f
74
75
178—179
190—191
162—162.5
215—216
252—253
140
0.33
34.55
34.71
55.47
55.74
36.12
36.25
32.44
32.74
33.29
33.34
—
4.30
4.16
3.81
3.85
3.57
3.38
3.22
3.05
2.39
2.49
—
34.90
34.70
23.07
22.94
28.30
28.18
25.61
25.45
34.60
34.56
—
С7H10N6O4
С17H14N6O4
С9H10N6O6
С9H10N6O8
С9H8N8O6
С7H4N12O6
С7H8N8O8
С17H12N8O8
С9H8N8O10
С9H8N8O12
С7H2N14O10
(CHCl3—EtOAc, 1 : 1)
0.76
(CHCl3—EtOAc, 1 : 1)
93
0.64
(CHCl3—EtOAc, 3 : 1)
0.70
(CHCl3—EtOAc, 1 : 1)
0.36
91
95
(CHCl3—EtOAc, 1 : 1)
0.57
87
(decomp. with sparkling) (CHCl3—EtOAc, 4 : 1)
6a
6b
6c
6d
6f
86*
72**
89*
84*
91*, 88**
82*
129—130
136—137
Caramel
124—125
131
0.31
25.42
25.31
44.68
44.75
28.12
27.85
25.68
25.73
—
2.29
2.43
2.80
2.65
2.00
2.08
1.78
1.92
—
34.00
33.73
24.80
24.56
29.08
28.86
26.63
26.67
—
(CHCl3—EtOAc, 3 : 1)
0.53
(CHCl3—EtOAc, 8 : 1)
0.40
(CHCl3—EtOAc, 4 : 1)
0.38
(CHCl3—EtOAc, 3 : 1)
0.77
(decomp. with sparkling) (CHCl3—EtOAc, 3 : 1)
6j
96—97
0.77
37.50
37.37
1.76
1.84
25.49 С17H10N10O12
25.64
(CHCl3—EtOAc, 8 : 1)
* Nitrating mixture: 100% HNO3—(CF3CO)2O.
** Nitrating mixture: 100% HNO3—Ac2O.
tion. 3ꢀAminoꢀ4ꢀphenylfuroxan does not give the Mannich
reaction products. Based on 4ꢀaminofuroxans, the earlier
unknown N,N´ꢀbis(3ꢀRꢀfuroxanꢀ4ꢀyl)methylenediamines
2a—f were synthesized in high yields, conditions for their
nitration at the nitrogen atoms were found and the earlier
unknown N,N´ꢀdinitroꢀN,N´ꢀbis(3ꢀRꢀfuroxanꢀ4ꢀyl)ꢀ
methylenediamines 6a—j were also obtained.
Attention! Compounds 2f and 6f containing each two azidoꢀ
carbonyl groups in the molecule and two N—NO2 fragments
(compound 6f) are sensible to impact and require careful
handling.
The reaction conditions, yields, spectral and physicoꢀ
chemical characteristics of the synthesized compounds
2a—f and 6a—d,f—j are given in Tables 1 and 2.
1
Table 2. The IR and H, 13C, 14N NMR spectroscopic and mass spectrometric data for the synthesized N,N´ꢀbis(3ꢀRꢀfuroxanꢀ4ꢀ
yl)methylenediamines 2a—f and N,N´ꢀdinitroꢀN,N´ꢀbis(3ꢀRꢀfuroxanꢀ4ꢀyl)methylenediamines 6a—d,f,j
Comꢀ
pound
IR spectrum,
1H NMR, δ, J/Hz
[MS, m/z (Irel (%))]
13C NMR, δ,
ν/cm–1
[14N NMR, δ, Δν1/2/Hz]
2a
3272, 3152, 3048, 2964, 2924,
1688, 1624, 1568, 1524, 1436,
1380, 1292, 1264, 1116, 1032,
864, 716, 696
2.05 (s, 3 H, Me); 4.67 (s, 2 H, CH2);
7.48 (br.s, 2 H, 2 NH)
[242 [M]+ (2), 160 (9), 128 (100),
115 (70), 98 (62)]
7.08 (Me); 49.61 (CH2);
107.43 (C(3) in furoxan ring);
156.86 (C(4) in furoxan ring)
2b
3352, 3060, 2928, 1624, 1576,
1512, 1424, 1376, 1184, 1076,
1000, 956, 848, 780, 712, 692
4.77 (t, 2 H, CH2, 3J = 8.0); 7.17
(t, 2 H, 2 NH, 3J = 8.0); 7.55 (m, 6 H,
Ar); 7.73 (m, 4 H, Ar)
[262 (5), 188 (11), 177 (19), 129 (100),
117 (62), 103 (72)]
50.74 (CH2);
109.02 (C(3) in furoxan ring);
122.33, 127.90 (C(1), C(4), Ar);
128.98, 130.41 (C(3), C(2), Ar);
155.61 (C(4) in furoxan ring)
(to be continued)

2112
Russ.Chem.Bull., Int.Ed., Vol. 59, No. 11, November, 2010
Finogenov et al.
Table 2 (continued)
Comꢀ
pound
IR spectrum,
1H NMR, δ, J/Hz
[MS, m/z (Irel (%))]
13C NMR, δ,
ν/cm–1
[14N NMR, δ, Δν1/2/Hz]
2c
2d
2e
3408, 3384, 2976, 1684, 1600,
1524, 1376, 1350, 1272, 1112,
988, 948, 840, 720, 608
2.48 (s, 3 H, Me); 4.82 (t, 2 Н, CH2,
3J = 8.2); 7.13 (t, 2 Н, 2 NH, 3J = 8.2)
[298 [M]+ (2), 267 (1), 237 (1), 155 (87),
143 (94), 127 (16), 126 (48), 113 (100)]
28.21 (Me); 49.49 (CH2);
108.84 (C(3) in furoxan ring);
155.07 (C(4) in furoxan ring);
188.92 (СО)
3444, 2964, 2880, 1736, 1696,
1580, 1532, 1432, 1384, 1328,
1224, 1124, 1008, 808, 772,
732, 680
3.88 (s, 6 H, Me); 4.83 (t, 2 H, CH2,
3J = 8.2); 6.98 (t, 2 H, 2 NH, 3J = 8.2)
[172 (37), 159 (73), 142 (100), 129 (63),
112 (92), 101 (65)]
4.81 (t, 2 H, CH2,3J = 8.0); 7.12
(t, 2 H, 2 NH, 3J = 8.0); 7.71 (s, 2 H,
NH2); 8.50 (s, 2 H, NH2)
49.79 (CH2); 53.02 (Me);
103.03 (C(3) in furoxan ring);
154.88 (C(4) in furoxan ring);
157.00 (СО)
3360, 3188, 2880, 1680, 1628,
1580, 1532, 1392, 1340, 1256,
1168, 1116, 1028, 988, 852,
728, 644
49.50 (CH2);
104.25 (C(3) in furoxan ring);
155.94 (C(4) in furoxan ring);
157.26 (СО)
[265 (4), 241 (4), 231 (4), 156 (100),
144 (7), 127 (34), 114 (46)]
2f
3420, 3376, 2176, 1712, 1600,
1568, 1520, 1372, 1324, 1216,
1120, 1080, 960, 872, 820, 748,
732, 676
4.83 (t, 2 Н, СН2, 3J = 8.8); 7.02
(t, 2 Н, NH, 3J = 8.8)
[193 (3), 183 (12), 170 (24), 154 (25),
140 (24), 126 (7), 111 (32)]
49.83 (CH2);
104.53 (C(3) in furoxan ring);
154.61 (C(4) in furoxan ring);
161.80 (CO)
6a
3420, 3012, 2932, 2852, 1640,
1592, 1488, 1426, 1408, 1388,
1280, 1248, 1108, 1076, 1036,
968, 908, 856, 768, 748, 724,
688, 640, 632
2.45 (s, 6 H, Me); 6.74 (s, 2 H, CH2)
[173 (13), 128 (12), 127 (100), 101
(20), 97(44), 84 (33)]
7.52 (Me); 64.85 (CH2);
111.51 (C(3) in furoxan ring);
152.09 (C(4) in furoxan ring)
[–40.3 (NO2), Δν1/2 = 260]
6b
3420, 3012, 2924, 2852, 1624,
1576, 1508, 1464, 1424, 1408,
1364, 1316, 1280, 1208, 1120,
1092, 1040, 1004, 988, 976,
924, 904, 840, 792, 772, 744,
720, 700, 664, 640
6.96 (s, 2 H, CH2); 7.61 (m, 6 H, Ar);
7.75 (m, 4 H, Ar)
[204 (3), 201 (8), 189 (20), 178 (7),
173 (10), 172 (10), 132 (41), 129 (100),
119 (5), 116 (36), 102 (76)]
65.23 (CH2);
110.13 (C(3) in furoxan ring);
120.73, 126.45 (C(1), C(4), Ar);
129.57, 131.67 (C(3), C(2), Ar);
150.36 (C(4) in furoxan ring)
[–39.7 (NO2), Δν1/2 = 231]
6c
6d
6f
3112, 2932, 1708, 1604, 1552,
1532, 1460, 1424, 1348, 1312,
1280, 1224, 1176, 1040, 1016,
984, 876, 856, 800, 720, 624
2.61 (s, 6 H, Me); 6.23 (s, 2 H, CH2)
[179 (48), 167 (100), 148 (31), 137 (34),
120 (59), 112 (28), 101 (76), 95 (94)]
28.12 (Me); 66.34 (CH2);
109.64 (C(3) in furoxan ring);
149.22 (C(4) in furoxan ring);
186.96 (СО)
[–38.3 (NO2), Δν1/2 = 227]
3784, 3036, 2964, 1756, 1716,
1664, 1584, 1492, 1324, 1280,
1216, 1100, 1044, 1020, 900,
752, 712, 684
3.91 (s, 6 H, 2 Me); 6.50 (s, 2 H, CH2)
[217 (37), 183 (58), 171 (80), 111 (100)]
54.05 (Me); 65.71 (CH2);
104.52 (C(3) in furoxan ring);
148.81 (C(4) in furoxan ring);
155.31 (CO)
[–36.7 (NO2), Δν1/2 = 243]
3044, 2992, 2858, 2248, 2176,
1832, 1688, 1648, 1592, 1492,
1404, 1352, 1284, 1180, 1072,
1040, 988, 876, 776, 728, 704,
684, 628
6.65* (s, 2 H, CH2)
[264 (1), 228 (11), 194 (12), 182 (10),
154 (5), 111 (12), 101 (17), 54 (100)]
66.61* (CH2);
106.14 (C(3) in furoxan ring);
149.21 (C(4) in furoxan ring);
161.20 (CO)
[–43.0* (NO2), Δν1/2 = 78]
6j
3420, 2962, 2924, 2840, 1596,
1528, 1508, 1464, 1348, 1280,
1216, 1168, 1116, 1092, 980,
880, 856, 760, 708, 624
7.14* (s, 2 H, CH2); 8.14 (d, 2 H, Ar,
3J = 10.2); 8.46. (d, 2 H, Ar, 3J = 10.2)
[234 (7), 218 (19), 188 (22), 176 (41),
174 (89), 164 (28), 149 (48), 147 (86),
134 (24), 129 (62), 118 (37), 104 (59),
102 (100)]
65.72* (CH2);
111.53 (C(3) in furoxan ring);
116.79 (C(1), Ar);
124.96, 128.71 (C(2), C(3), Ar);
149.73 (С(4), Ar);
151.06 (C(4) in furoxan ring)
[–42.4* (NO2), Δν1/2 = 134]
* NMR spectra were recorded in (CD3)2CO.

N,N´ꢀBis(3ꢀRꢀfuroxanꢀ4ꢀyl)methylendiamines
Russ.Chem.Bull., Int.Ed., Vol. 59, No. 11, November, 2010 2113
2a—f (1 mmol) was added in portions at this temperature. The
reaction mixture was stirred for 2 h at 0—5 °C. A precipitate was
filtered off, washed with CCl4 (2×2 mL), and dried in a vacuum
desiccator over КOH.
Upon nitration of N,N´ꢀbis(3ꢀmethylfuroxanꢀ4ꢀyl)diaminoꢀ
methane (2a), a product fairly well soluble in the reaction mixꢀ
ture is formed. The yield of product 6a after filtration of a preꢀ
cipitate was 61%. After the mother liquor was concentrated on
a rotary evaporator at room temperature, 25% of compound 6a
was additionally isolated.
Experimental
IR spectra were recorded on a URꢀ20 spectrometer in KBr
pellets. NMR spectra were recorded on a Bruker WMꢀ250 (1H,
250 MHz) and Bruker AMꢀ300 spectrometers (13C, 75.5 MHz;
14N, 21.5 MHz) in DMSOꢀd6. Chemical shifts in the H and
1
13C NMR spectra were measured relatively to Me4Si as an interꢀ
nal standard, the 14N NMR spectra, relatively to MeNO2 as an
external standard. Mass spectra were obtained on a Varian MAT
CH 6 instrument (70 eV). Thinꢀlayer chromatography was perꢀ
formed on Silufol UVꢀ254 with visualization under the UV light.
4ꢀAminoꢀ3ꢀmethylfuroxan 1a,15 4ꢀaminoꢀ3ꢀphenylfuroxan 1b,9
3ꢀacetylꢀ4ꢀaminofuroxan 1c,10 4ꢀaminoꢀ3ꢀmethoxycarbonylꢀ
furoxan 1d,12 4ꢀaminoꢀ3ꢀaminocarbonylfuroxan (1e),12 and
4ꢀaminoꢀ3ꢀazidocarbonylfuroxan (1f)12 were obtained accordꢀ
ing to the known procedures.
Upon nitration of N,N´ꢀbis(3ꢀacetylfuroxanꢀ4ꢀyl)methylꢀ
enediamine (2c), the final product 6c forms no precipitate. It
was isolated by concentration of the reaction mixture on a rotary
evaporator at room temperature.
This work was partially financially supported by the
Division of Chemistry and Materials Science of the Russian
Academy of Sciences (Program for Development of Sciꢀ
entific Basis for Preparation of New Generation of Highꢀ
energetic Compounds).
Crystals of 2a are tetragonal (100 К), the space group is
Iꢀ42d, a = b = 12.240(6) Å, c = 13.608(7) Å, V = 2038.8(17) Å ,
Z = 8 (Z´ = 0.5), M = 242.21 g mol–1, dcalc = 1.578 g cm–3
3
,
μ(MoꢀKα) = 1.70 cm–1, F(000) = 1008. Intensities of 10837
reflections were measured on a Smart Apex II CCD diffractoꢀ
meter (λ(MoꢀKα) = 0.71072 Å, ωꢀscanning, 2θ < 60°), 1499 of
them were independent reflections (Rint = 0.0234), which were
used in the further refinement. The structure was solved by the
direct method and refined by the least squares method in anisoꢀ
tropic fullꢀmatrix approximation on F2hkl. Positions of the hyꢀ
drogen atoms of the NH group were found from differential
Fourierꢀsyntheses, positions of the rest of hydrogen atoms were
calculated starting from the geometrical assumptions and refined
with the fixed thermal parameters Uiso = 1.2Ciso in isotropic
approximation. The final value of the reliability factors for 2a:
R1 = 0.0251 (calculated on Fhkl for 1463 reflections with
References
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2a—f (general procedure). Aminofuroxan 1a—f (4.0 mmol) was
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Synthesis of N,N´ꢀdinitroꢀN,N´ꢀbis(3ꢀRꢀfuroxanꢀ4ꢀyl)ꢀ
methylenediamines 6b,e,f by nitration of compounds 2b,e,f with
100% HNO3 in Ac2O (general procedure). Concentrated HNO3
(1.0 mL, 24 mmol) and CCl4 (4 mL) were added to acetic anꢀ
hydride (2.5 mL, 26.5 mmol) at –2—0 °C over 5—10 min. After
15 min, finely triturated N,N´ꢀbis(3ꢀRꢀfuroxanꢀ4ꢀyl)diaminoꢀ
methane 2b,e,f (1 mmol) was added in portions at this temperaꢀ
ture. The reaction mixture was stirred for 6 h at 0—5 °C.
A precipitate was filtered off, washed with CCl4 (2×2 mL) and
dried in a vacuum desiccator over КOH.
Synthesis of N,N´ꢀdinitroꢀN,N´ꢀbis(3ꢀRꢀfuroxanꢀ4ꢀyl)ꢀ
methylenediamines 6a—f by nitration of compounds 2a—f with
100% HNO3 in (CF3CO)2O (general procedure). Concentrated
HNO3 (1.0 mL, 24 mmol) was added to trifluoroacetic anhydride
(4.0 mL, 28.8 mmol) at –2—0 °C over 5—10 min. After 15 min,
finely triturated N,N´ꢀbis(3ꢀRꢀfuroxanꢀ4ꢀyl)diaminomethane
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Received April 6, 2010;
in revised form October 22, 2010