Unusual reaction of 3,4-bis(3-nitrofurazan-4-yl) furoxan with ammonia, primary amines and hydrazine

Article abstract of DOI:10.2478/s11532-012-0020-7

The nucleophilic displacement of two nitro groups in 3,4-bis(3- nitrofurazan-4-yl)furoxan with ammonia, primary aliphatic amines and hydrazine leads to formation of a novel heterocyclic system, 7H-tris[ 1,2,5]oxadiazolo[3, 4-b:3',4'-d:3'',4''-f]azepine. The reaction of compound 1 with secondary aliphatic amines proceeds in a typical way for nitrofurazans when the nitro-group in the starting compound is substituted by RR'N-group. Versita Sp. z o.o.

Full text of DOI:10.2478/s11532-012-0020-7

Cent. Eur. J. Chem. • 10(4) • 2012 • 1087-1094
DOI: 10.2478/s11532-012-0020-7
Central European Journal of Chemistry
Unusual reaction of 3,4-bis(3-nitrofurazan-4-yl)
furoxan with ammonia, primary amines
and hydrazine
Research Article
Alexander A. Astrat’ev, Dmitry V. Dashko, Andrei I. Stepanov*
Special Design and Construction Bureau SDCB “Technolog”,
Saint Petersburg 192076, Russia
Received 25 August 2011; Accepted 12 January 2012
The nucleophilic displacement of two nitro groups in 3,4-bis(3-nitrofurazan-4-yl)furoxan with ammonia, primary aliphatic amines
and hydrazine leads to formation of a novel heterocyclic system, 7H-tris[ 1,2,5]oxadiazolo[3,4-b:3’,4’-d:3’’,4’’-f]azepine.
The reaction of compound 1 with secondary aliphatic amines proceeds in a typical way for nitrofurazans when the nitro-group in the
starting compound is substituted by RR’N-group.
Abstract:
Keywords: 1,2,5-oxadiazole • Furazan • Furoxan • Azepine • 3,4-bis(3-nitrofurazan-4-yl)furoxan
© Versita Sp. z o.o.
1. Introduction
addition, the nitro group has been successfully replaced
by chlorine[16].
Derivativesof1,2,5-oxadiazole(furazan)1,2,5-oxadiazole-
It was also demonstrated that the nucleophilic
2-oxide (furoxan) have generated appreciable interest displacement of the nitro group at the furazan ring with
due to the variety of their chemical transformations [1], ammonia [10] or primary and secondary amines [17,18]
their important biological activity [2]; the 1,2,5-oxadiazole provides an efficient approach to the synthesis of
ring has been found to be an important substructure for aminofurazanes derivatives.
the design of new high density, high energy materials
Recently synthesized [19,20] 3,4-bis(3-nitrofurazan-
[3]. Nucleophilic displacement reactions are widely used 4-yl)furoxan 1 (Scheme 1) was suggested as novel
for the modification of 1,2,5-oxadiazole compounds [2]. high density energetic compound [21,22], and its
The use of halogen derivatives of 1,2,5-oxadiazoles in physical-chemical properties were examined [23,24],
this reaction [4-6] is restricted due to difficulty in their but its chemical properties have never been discussed.
preparation. In contrast, 3-nitro-4-R-1,2,5-oxadiazoles Meanwhile the latter compound in concordance with
are much more synthetically accessible and may be above cited should be rather sensitive to nucleophilic
obtained in scaled-up quantities [7,8] by the oxidation of agents. The main purpose of our presented research is
3-amino-1,2,5-oxadiazoles [9].
to fulfill a lack in this field.
Due to the electron withdrawing character of the
furazan ring, a nitro group bound to the furazan ring
is rather mobile in nucleophilic substitution reactions; 2. Experimental procedure
therefore, nitrofurazanes can be used as versatile
building-blocks for the synthesis of various furazan CAUTION! The dinitro compound 1 is highly explosive
derivatives. It was shown [10,11] that the nitro group at and maybe sensitive to shock, friction or heating and
the furazan ring is more mobile than the chlorine atom.
The nitro group in the furazan ring is easily displaced
must be handled with appropriate precautions.
Melting points were determined on a Koffler stage. IR
upon treatment with S - and O-nucleophiles[12-15]; in spectra were recorded with a spectrometer FSM-1201
* E-mail: stepanoff@pisem.net
1087

Unusual reaction of 3,4-bis(3-nitrofurazan-4-yl)furoxan
with ammonia, primary amines and hydrazine
O
O
N+
N
O
O
N+
N
N
N
N
N
H2O2
NH2
H2N
NO2
O2N
H2SO4 or TFAA
N
N
N
N
O
O
O
O
1
2a
Scheme 1. Oxidation of 3,4-bis(3-aminofurazan-4-yl)furoxan (2a) to 3,4-bis(3-nitrofurazan-4-yl)furoxan 1.
1
(KBr pellets). NMR H and 13C spectra were taken on was heated under reflux in presence of a few drops of
a Bruker DRX-500 instrument in DMSO-d6 with HMDS AcOH for one hour. After cooling at room temperature
as internal standard. Mass spectra were registered on the precipitate was filtered off and recrystallized from
Varian MAT CH_6 and Varian MAT CH_111 instruments AcOH-EtOH. The yield of the title compound was 90%.
(70 eV). The elemental analysis for C, H, N was carried
out on a Perkin-Elmer C, N, O analyzer.
7 - ( N - A c e t y l a c e t a m i d o ) - 7 H - t r i s [ 1 , 2 , 5 ]
oxadiazolo[3,4-b:3‘,4‘-d:3‘‘,4‘‘-f]azepine 1-oxide 5
1.25 g (0,01 mol) of compound 3f in 10 mL Ac2O
3,4-Bis(3-aminofurazan-4-yl)furoxan 2a and 3,4-
bis(3-nitrofurazan-4-yl)furoxan
1
were prepared was heated under reflux in presence of 0.5 g (6mmol)
according to known methods [19,20,23]. Assignment of NaOAc for one hour. The mixture was cooled to room
the NMR signals of the carbon atoms in fused 1,2,5- temperature and poured into 50 mL of H2O. The
oxadiazole were made according to [25].
precipitate was filtered off and recrystallized from AcOH-
EtOH. The yield of N,N-diacetyl compound 5 was 80%.
7-Amino-7H-tris[1,2,5]oxadiazolo[3,4-b:3’,4’-
d:3’’,4’’-f]azepine 1-oxide 3a by diazotization of
compound 3f
A saturated aqueous solution of NaNO2 (0,9 g,
0,013 mol) was added dropwise to a suspension
of 2.5 g (0.01 mol) of compound 3f in 30 mL of glacial
acetic acid at 5-10oC. The resulting mixture was
evaporated in vacuo, diluted by water and the precipitate
was filtered off and recrystallized from water. Compound
3a was obtained in 85% yield.
2.1. Generalprocedureforreactionof3,4-bis(3-
nitrofurazan-4-yl)furoxan 1 with aliphatic
amines and hydrazine (compounds 2b-2e,
3a-3f)
To stirred solution of 3.12 g, (0.01 mol) of compound
1 in dry acetonitrile (20 mL) the solution of at least
0.03 mol of appropriate primary amine* or 0.04 mol
of secondary amine in 20 mL acetonitrile was slowly
added with additional cooling such that the temperature
did not exceed 5-10oC. The mixture was maintained at
this temperature for additional hour, then heated to 40oC
and stirred for 30 minutes. About 2/3 of the acetonitrile 3. Results and discussion
was evaporated in vacuo, and the residue was diluted
with 50 mL of cold water. An oil (2b-2e) or solid Our experiments have shown that both nitro groups of
(3a-3f) was separated and recrystallized from Et2O- 3,4-bis(3-nitrofurazan-4-yl)furoxan 1 readily undergo
CCl4 (compounds 2b-2e) or MeOH-DMF (compounds nucleophilic substitution with amines. Acetonitrile was
3b-3f) and MeOH-H2O (compound 3a). Average yield used as a solvent, and the reaction proceeds at 5-10оС
was about 70%** (see Table 1).
and is accompanied by a significant exotherm. However,
*) in the case of NH3 and CH3NH3 (compounds 3a, reactions with primary and secondary amines leads to
3b) 25-30% solutions in water were used; hydrazine different products.
(compound 3f) was used as hydrazine-hydrate.
Reactions with secondary amine resulted in the
**) in case of aqueous solutions of ammonia and expected product of the substitution of both nitro groups
methylamine (compounds 3a, 3b) the yield was much by the secondary amino groups (Scheme 2).
smaller due to partial hydrolysis of 1 (see Table 1).
(E)-N-Benzylidene-7H-tris[1,2,5]oxadiazolo[3,4- 4-yl)furoxan 2b; N(C2H5)2,
b:3’,4’-d:3’’,4’’-f]azepine-7-amine 1-oxide 4
furazan-4-yl)furoxan 2c; N(C2H4)2NCH3, 3,4-bis(3-N-
HNR2=(N(CH2CH2)2O,3,4-bis(3-N-morfolinofurazan-
3,4-bis(3-diethylamino-
The mixture of 1.25 g (0.005 mol) of N-amine 3f (4-methylpiperazino)furazan-4-yl)furoxan 2d; N(CH2)5,
with 0.6 g (0.0057 mol) of benzaldehyde in 30 mL EtOH 3,4-bis(3-N-piperidinofurazan-4-yl)furoxan 2e.
1088

A. A. Astrat’ev, D. V. Dashko, A. I. Stepanov
Table 1. Spectral data of 3,4-bis(3- RRN-furazan-4-yl)furoxans 2 and 7H-tris[1,2,5]oxadiazolo[3,4-b:3‘,4‘-d:3‘‘,4‘‘-f]azepine 1-oxide derivatives
(3-5).
Compound No;
R; yield,
NMR-13C, δ, ppm,
NMR-1H, δ,
MS, m/e
IR, ν, cm-1
Elemen.
analysis,
C H N
ppm.
C(1)-
C(6)
R
%; m.p.,oC.
calc. /
found
1;
NO2;
85[23]; 109-
111[lit.109-
110[19]).
160.40;
137.60;
103.90;
143.20;
139.90;
160.00.
[M]312(17); 282(20),
M – NO; 130(10);
100(21); 88(9);
78(20); 60(100);
46(87); 38(11) [23]
1640; 1584; 1564; 1516;
1448; 1356; 1316; 1284;
1176; 1000; 964; 912;
880.
23.08; 0.00; 35.90 /
23.12; 0.03; 35.76.
-
-
-
156.30;
133.50;
104.60;
147.00;
136.30;
155.30.
[M]252(85); 222(75),
M-NO; 192(100),
M-2NO; 58(25), [NH2-
C=N-O]+; 30(30),
[NO]+.
2178; 2150 (N3); 1600;
1583; 1425; 1385
(furazan); 1630; 1532;
1463; 1230 (furoxan).
2a;
NH2;
74[23]; 167-
168(lit.168.2[21])
6,62 (NH2);
6,57(NH2).
28.57; 1.58; 44.44 /
28.40; 1.75; 44.31
[M]392(5); 375(22),
M– OH;362(2), M –
NO; 328(6); 86(39),
[O(CH2CH2)2N]+;
69(33), 86 - OH;
56(92), [C2H2NO]+;
45(100).
2980; 2960; 2860;1625;
1590; 1545; 1530; 1470;
1450; 1370; 1260; 1210;
1160; 1120; 1070; 1020;
990; 965; 913; 890; 807;
720; 550.
2b;
N(C2H4)2O;
75;
119(lit. 118-
120[18]).
159.60;
134.30;
105.50;
145.10;
138.00;
159.50.
3.61 and 3.53 (m,
8Н, 2О(CH2)2);
3.23(m, 4H,
65.61 and
65.59;
49.41 and
48.81.
42.86; 4.08; 28,57 /
42.73; 4.23; 28.35
C1N(CH2)2);
3.11(m, 4H ,
C6N(CH2)2).
[M]364(0.1); 234(6);
167(84); 83(7); 73(8);
157.70;
136.50;
107.40;
146.70;
137.40;
157.60.
2985; 2940; 2880; 2860;
2470; 2405;1625; 1570;
1540; 1470; 1460; 1385; 46,15; 5,49; 30,77 /
1360; 1290; 1225; 1200;
1045; 990; 960; 860; 810.
3.28(q, 4H,
2c;
N(C2H5)2;
65;
44.76 and
41.70; 12.48
and 11.36.
C1N(CH2)2); 2.85(q, 72(5); 69(7); 58(39);
4H, C6N(CH2)2);
1.17-1.06(m, 12H,
2CH3).
56(31); 55(16); 44(7);
43(8); 42(17); 41(7);
30(100), [NO]+;
45.91; 5.62; 30.42.
94(lit. 82-84[18]).
29(81), [C2H5]+.
[M]418(3); 124(6);
123(51); 99(8); 98(6);
97(17); 86(11); 83(6);
72(5); 71(24); 70(29);
58(14); 57(27);
3,16(bs,
8H, 4CH2);
2970; 2940; 2852; 2800;
2770; 1620; 1540; 1530;
1450; 1375; 1300; 1290;
1280; 1210; 1145; 1080;
1005; 995; 970; 910; 815;
785.
159.57;
134.50;
105.30;
145.00;
138.00;
159.54.
2d;
53.82 and
53.75;
49.19 and
48.76;
3,10(bs, 3H)
and 2,35(bs,3H)
- 3CH2; 2,28;
2,25; 2,21m,
overlapping (10H,
2CH2, 3CH3).
N(C2H4)2NMe;
60;
118.
56(34); 55(6); 54(8);
44(25); 43(100),
45.93; 5.26; 33.49 /
45.56; 5.60; 33.24.
[CH2NH=CH2]+;
42(78),
46.06
[CH2NH=CH2]+;
41(7); 40(5); 32(59);
30(16), [NO]+; 29(8).
[M]388(0.2); 372(2),
M-O; 371(12),
M-OH; 177(13);
125(10); 109(26);
84(12) [(CH2)5N]+;
83(9); 82(12); 69(34);
68(12); 67(12);
159.90;
134.50;
105.40;
145.20;
138.10;
159.80.
3.17(m, 4H,
C1N(CH2)2);
3.04(m, 4H,
C6N(CH2)2);
1.52(m, 8H);
1.45(m, 4H).
2940(CH2as;2860(CH2s);
2e;
N(CH2)5;
70;
50.40; 49.90;
24.80; 24.74;
23.31.
1630; 1590; 1445; 1385; 49.48; 5.15; 28.86 /
1280; 1260;1220; 1160; 49.67; 5.50; 28.24.
1140; 1110; 1010; 990;
56(12); 55(85);
94.
54(15); 53(10); 43(11)
[CH2NH=CH2]+;
42(60)
965; 900; 810; 715; 600.
[CH2=N=CH2]+;
41(100); 39(17);
30(27), [NO]+; 29(33).
3570 (as NH); 3500 (s
NH); 3000, 2850, 2760
(assoc. NH); 1620
(furazan +C=N→O); 1600, 30.87; 0.71; 41.33.
1570, 1530 (furoxan);
1500; 1470; 1360; 1150;
152.40;
135.80;
106.40;
145.60;
138.10;
152.00.
[M]235(100); 205(26),
M – NO; 175(30),
M – 2NO; 145(11),
(M - 3NO); 53(63),
[C2HN2]+.
3a;
H;
45;
227.
30.63; 0.43; 41.70 /
-
12.4(s, NH).
1000; 970; 830.
1089

Unusual reaction of 3,4-bis(3-nitrofurazan-4-yl)furoxan
with ammonia, primary amines and hydrazine
ContinuedTable 1. Spectral data of 3,4-bis(3- RRN-furazan-4-yl)furoxans 2 and 7H-tris[1,2,5]oxadiazolo[3,4-b:3‘,4‘-d:3‘‘,4‘‘-f]azepine 1-oxide
derivatives (3-5).
Compound No;
R; yield,
NMR-13C, δ, ppm,
NMR-1H, δ,
MS, m/e
IR, ν, cm-1
Elemen.
analysis,
C H N
ppm.
C(1)-
C(6)
R
%; m.p.,oC.
calc. /
found
154.40;
135.40;
100.60;
145.30;
137.50;
154.10.
[M]249(92); 233(1),
M – O; 219(15), M
– NO; 189(100), M
– 2NO; 159(16), M –
3NO; 105(18); 83(33);
67(44).
3400, 1650 (furoxan);
1610; 1600; 1560; 1540;
1350; 1130; 1050; 990;
970; 850.
3b;
CH3;
50;
33.73; 1.20; 39.36 /
33.55; 1.54; 39.18.
38.47
3.72(s, CH3).
198.
154.00;
135.60;
106.20;
145.60;
137.70;
153.70.
3065; 3032; 2920; 1650;
1310; 1590; 1560; 1530;
1480; 1455; 1432; 1390;
1360; 1230; 1160; 1020;
990; 900; 830.
3c;
CH2Ph;
71;
Ar: 134.4;
128.9; 128.2;
127.6; 55.2
(CH2).
[M]325(2.7); 309(1),
M – O; 91(100),
5.41(s, CH2);
7,53 and 7,28 (m.,
2Н, m, 3H, Ar).
48.00; 2.15; 30.15 /
47.85; 2.42; 29.87.
[PhCH2]+, 65(16);
39(56); 30(23), [NO]+.
174.
[M]279(19); 249(6.5),
M – NO; 248(13), M
– CH2 – OH; 236(65), 2920(νsCH2); 1640; 1610;
3550(OH); 2980(νasCH2);
154.00;
135.40;
106.00;
145.30;
137.60;
153.60.
3d;
4,29(t, 2H); 3,79(t, M – CH2=CH-O or M 1590; 1570; 1520; 1480;
CH2CH2OH;
50;
34.41; 1.79; 35.12 /
34.09; 1.97; 34.86.
56.0; 53.8.
2H); 5,0-4,7(s,
1H,OH).
– HNCO; 205(8), 236
– NO – H; 189(24),
M – 3NO; 176(15),
236 – 2NO; 45(100),
[CH2CH2OH]+.
1350; 1200; 1160; 1070
(νasC-C-O); 1020; 980;
970; 900; 840.
193.
[M]331(1.4); 98(82),
C7H14; 97(88),
C7H13; 96(24); 81(7);
153.50;
136.10;
105.90;
145.30;
138.20;
153.00.
4,62m (1H, C-H);
2,38m (2H, CH2);
2930; 2855; 1650; 1620;
1585; 1555; 1525; 1475;
3e;
cyclo-C7H13;
63;
66.82; 30.17;
27.74;
1,87m (2H, CH2); 69(14); 67(13); 56(8); 1390; 1350; 1330; 1230; 47.13; 3.93; 29.61 /
1,70m (2H, CH2);
1,69-1,59m (6H,
CH2CH2CH2).
55(100); 54(8);
53(13); 43(16); 42(8); 890; 850; 825; 790; 720;
41(69); 40(5); 39(27);
30(91), [NO]+; 29(30).
1160; 1010; 990; 970;
46.90; 4.11; 29.43.
25.79.
219.
680; 590; 545.
[M]250(100);
220(0.8), M – NO;
190(75), M – 2NO;
160(4), M – 3NO;
101(30); 68(54),
[C2N2O]+.
relative intensity
[M+1]/[M] = 9,5%
(calc. 9,7%); [M+2]/
[M] = 1% (calc.
1,02%).
155.94;
136.00;
105.50;
144.60;
133.90;
155.90.
3310(νasNH2);
3240(νsNH2); 1640; 1600; 28.80; 0.80; 44.80 /
1550; 1520; 1480; 1350;
1000; 970; 840; 790.
3f;
NH2;
70;
-
6,00(s, NH2).
28.63; 0.98; 44.61.
169-171.
339(4), [M+1]; [M]
338(22); 278(6);
235(13), M –C6H5CN;
205(23), M – C6H5CN
– NO; 145(7);
153.30;
134.90;
105.90;
145.10;
137.00;
152.90.
105(20); 104(99),
3085, 3030 (νAr-H); 1650;
1600; 1560; 1520; 1470; 46.15; 1.78; 33.14 /
1385; 1350; 1230; 1000;
970; 850; 790; 770; 700;
420.
4;
172.7
(N=CH);
133.9; 131.7;
129.7; 129.6.
[C6H5CH=N]+;
9.11(=CH);
8.03(m, 2H, Ar)
7.61(m, 3H, Ar).
N=CHPh;
90;
214.
103(21), [C6H5CN]+;
93(7); 90(20),
46.31; 1.97; 33.05.
[C7H6]+; 89(28);
78(22); 77(98),
[C6H5]+; 76(21);
63(12); 53(10);
51(68); 50(16);
30(100), [NO]+.
[M]334(1.5);
292(10), M –
CH2=C=O; 276(1),
292 – O;
3600(νasNH);
153.27;
134.70;
106.10;
144.80;
136.60;
152.88.
3530(νasNH); 3230 and
3080 (NH assoc.); 1650;
1600; 1590; 1550; 1520;
1460; 1370; 1300; 1270;
1220; 1000; 960; 890;
840; 790; 600; 590.
5;
NAc2;
80;
169.7
(C=O); 25.62
(CH3).
35.93; 1.80; 33.53 /
35.87; 1.94; 33.32.
2.50(COCH3).
250(2), M –
194.
2CH2=C=O; 43(100),
[CH3CO]+.
1090

A. A. Astrat’ev, D. V. Dashko, A. I. Stepanov
O
1
O
N+
N
O
O
N+
N
N
R
N
N
R
R2NH
NO2
O2N
N
N
R
R
6
5
2
1
4
3
CH3CN
N
N
N
N
N
O
O
O
O
2b-2e
Scheme 2. Reaction of 3,4-bis(3-nitrofurazan-4-yl)furoxan 1 with secondary aliphatic amines.
O
O
N
O
N+
N
N
N
5
N
CH3CN
6
1
NO2
O2N
4
3
H2N-R
O
N R
+
N+
2
N
N
N
N
O
O
O
1
N
3a-3f
O
Scheme 3. Synthesize 7H-tris[1,2,5]oxadiazolo[3,4-b:3’,4’-d:3’’,4’’-f]azepine 1-oxide derivatives.
(R = CH3), 3c (R = CH2Ph), 3d (R = CH2CH2OH),
3e(R=cyclo-C7H13)(Table1). ThesignaloftheNHgroup
in compound 3a (R = NH) is less shifted in comparison
to the chemical shifts of the NH2 groups [29] in 3,4-bis(3-
aminofurazan-4-yl)furoxan 2a (Scheme 1). It should
be noted that in the case of the formation of a linear
4,4’-diaminosubstituted product like compounds 2a-2e,
two terminal amino groups should be nonequivalent
in NMR-1H spectra, owing to the asymmetry of the
structure due to the influence of exocyclic N→O group
as it occurs in NMR-1H spectra of compounds 2a-2e. It
applies equally to chemical shifts of the carbon atoms
of joined N-alkyl group in NMR-13C spectra; the signals
of only single substituent R in cyclic compounds 3a-3e
were fixed though. There are six signals assigned to
two nonequivalent furazan and one furoxan [20] rings in
NMR-13C spectra of compounds obtained. The chemical
shift of carbons adjacent to exocyclic N→O carbon atom
lies in stronger field than signals of the rest of carbon
atoms in 1,2,5-oxadiazole rings system. The chemical
shits of C-1 and C-6 atoms in the seven-membered
structure are located in stronger field in comparison
with similar atoms in a linear structure (2a-2e). This
result can be explained by the participation of a lone-
electron pair of the nitrogen atom in π-electron system
of four member heterocyclic system and reallocation of
the electron density in molecule towards to concerning
nitrogen atom.
4
3
5
N
N
2
6
O
1
N
7
8
H
Scheme 4. Structure of 1H-[1,2,5]-oxadiazole[3,4-c]azepine.
Unexpectedly, the reaction of 3,4-bis(3-nitrofurazan-
4-yl)furoxan 1 with ammonia or primary aliphatic
amines leads to the formation of an annelated azepine
structure, i.e., two nitro groups in the initial product are
replaced just by one amino group with 7-membered
cycle formation (Scheme 3).
R = (H, 7H-tris[1,2,5]oxadiazolo[3,4-b:3’,4’-d:3’’,4’’-f]
azepine 1-oxide (3a); CH3, 7-methyl-7H-tris[1,2,5]
oxadiazolo[3,4-b:3’,4’-d:3’’,4’’-f]azepine 1-oxide 3b;
CH2Ph,
7-benzyl-7H-tris[1,2,5]oxadiazolo[3,4-b:3’,4’-
d:3’’,4’’-f]azepine 1-oxide 3c; CH2CH2OH, 7-(2-
hydroxyethyl)-7H-tris-[1,2,5]oxadiazolo[3,4-b:3’,4’-
d:3’’,4’’-f]azepine 1-oxide 3d; cyclo-C7H13, 7-cyclo-
hepthyl-7H-tris[1,2,5]oxadiazolo[3,4-b:3’,4’-d:3’’,4’’-f]
azepine 1-oxide 3e; NH2, 7-amino-7H-tris[1,2,5]
oxadiazolo[3,4-b:3’,4’-d:3’’,4’’-f]azepine 1-oxide 3f)
The received heterocyclic systems are not described
intheliterature, frompossiblefourjoints1,2,5-oxadiazole
ring and azepine cycle only not numerous derivatives
1,2,5-oxadiazole[3,4-c]azepine (Scheme 4) are known
[26,27]. (For a review of furazanes fused to six- and
seven- membered heterocycles see [28]).
The formation of cyclic products has been
demonstrated by physical-chemical analysis (Table 1)
and confirmed by their chemical properties.
No signals corresponding to protons of an NH group
were detected in NMR-1H spectra of compounds 3b
The IR spectrum of azepine structures like 3a-3f also
differs from the IR spectrum of linear products 2a-2e
particularly in the field of skeleton ring system vibrations
at 1650-1500 cm-1.
Mass spectra of the obtained products 3a-3f include
peaks of the molecular ions assigned to the assumed
cyclic structure. The ion peak intensities with m/e [M+1]
1091

Unusual reaction of 3,4-bis(3-nitrofurazan-4-yl)furoxan
with ammonia, primary amines and hydrazine
O
O
N
N
N
N
N
N
O
N
N+
PhCHO
NH2
O
O
O
O
O
4
N
N
N
N
N
N
N
N
N
N
N
N
O
NAc2
5
O
Ac2O/ NaOAc
N+
N+
O
O
3f
NaNO2/AcOH
O
O
N
N
N
O
NH
N
N+
O
3a
N
Scheme 5. Some reactions of amino group of 7-amino-7H-tris[1,2,5]oxadiazolo[3,4-b:3’,4’-d:3’’,4’’-f]azepine 1-oxide 3f.
and [M+2] did not contradict the natural isotope content of hydrazine with seven-membered ring formation. In
of elements in chemical composition of the synthesized case of successive substitution of nitro groups in the
compounds. The character of fragmentation is typical dinitro compound 1 by hydrazine, one should expect
for furoxan and furazan derivatives [30] (the loss of dihidrazino-substituted product formation as a result of
exocyclic atom O and consecutive loss of NO).
interaction of the second nitro group in mono hydrazino-
Compounds 3a, 3b, 3c, and 3e appeared to be inert substituted reaction intermediate with free hydrazine
towards reaction with acetic anhydride. In the case of owing to its major nucleophility.
compound 3a the result can be explained by the lower
The chemical properties of the obtained of
basicity of cyclic amino group due to strong electron 7-amino-7H-tris[1,2,5]oxadiazolo[3,4-b:3’,4’-d:3’’,4’’-f]
acceptor properties of the two furazan moieties. In the azepine 1-oxide 3f confirm its structure (Scheme 5).
othercases, thisconfirmstheabsenceoffreeN-Hgroups Thus, compound 3f with benzaldehyde gives the
(in case of formation a linear 4,4’-diaminosubstituted corresponding azomethine 4. The acylation of 3f results
product N-H groups should be acylated easily as it takes in N,N-diacetyl derivative 5 and the diazotization by
place in case of 3,4-bis(3-aminofurazan-4-yl)furoxan nitrous acid leads to removal of the N-amino group and
2a).
compound 3a formation (in case of linear structure one
Such behavior of 3,4-bis(3-nitrofurazan-4-yl)furoxan should expect the azido group formation).
1 towards primary amines might be explained by the
It should be noted that the result of interaction of
following: according to the X-ray diffraction analysis dinitro compound 1 with primary amines does not depend
[19,31] furazan rings of dinitro compound 1 are initially on the order of mixing reagents. The corresponding
located turned in with respect to each other which linear products of mono- or disubstitution of nitro group
creates favorable pre-conditions for ring structure by amine were not formed when amine was added to the
formation.
excess of the donator compound or donator compound
In this case, it can be assumed that the reaction was added to the excess of amine. The lack of amine
proceeds as intramolecular, two-step procedure with results in decrease of conversion ratio of 1 to 3a-3f and
elimination of two molecules of nitrous acid and favorable the formation of some side products. Hence, the leaving
seven-membered ring formation.
of two terminal nitro groups with the formation of two new
We have received additional proof of this assumption C-N bonds should occur simultaneously. Otherwise one
by studying the reaction of 3,4-bis(3-nitrofurazan-4-yl)- should expect formation of terminal diamino derivatives
furoxan 1 with hydrazine (Scheme 3, R = NH2). Both due to higher nucleophility of free amine in comparison
nitro groups of 1 were replaced by only one NH2 moiety to the amino group linked with the furazan cycle.
1092

A. A. Astrat’ev, D. V. Dashko, A. I. Stepanov
of 3,4-bis(3-nitrofurazan-4-yl)furoxan 1 with ammonia,
primary aliphatic amines and hydrazine reveals a new
applied approach for the synthesis of novel class of
seven-membered heterocyclic compounds containing
annelated three 1,2,5-oxadiazole rings. Such unusual
ring formation can be explained by highly preorganized
structure of dinitro compound 1 for a new ring formation.
These compounds may possess certain interest in the
chemistry of energetic materials and also have biological
activity. Their chemical properties will be studied in our
lab.
4. Conclusions
To summarize, we demonstrated that 3,4-bis(3-
nitrofurazan-4-yl)furoxan is quite sensitive to reaction
with nucleophiles, notably hydrazine, ammonia, primary
and secondary highly basic amines. The reaction of
3,4-bis(3-nitrofurazan-4-yl)furoxan 1 with secondary
aliphatic amines runs in a typical way typical of other
nitrofurazan compounds (see for example [18]) and
may be suggested as convenient synthetic method for
tertiary amino bis-furazanylfuroxans. The nucleophilic
displacement of the nitro groups at the furazan rings
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