Nucleophilic substitution in the furazan series. Reactions of nitrofurazans with ammonia

Article abstract of DOI:10.1023/A:1020931511013

The reactions of 3-nitro-4-R-furazans with ammonia were studied. The effect of the substituent R on the specific features of the nucleophilic substitution reaction observed was considered. The nitro group attached to the furazan ring can act as both the l

Full text of DOI:10.1023/A:1020931511013

Russian Chemical Bulletin, International Edition, Vol. 51, No. 8, pp. 1533—1539, August, 2002
1533
Nucleophilic substitution in the furazan series.
Reactions of nitrofurazans with ammonia
ꢀ
A. B. Sheremetev, V. O. Kulagina, I. A. Kryazhevskikh, T. M. Melnikova, and N. S. Aleksandrova
N. D. Zelinsky Institute of Organic Chemistry, Russian Academy of Sciences,
47 Leninsky prosp., 119991 Moscow, Russian Federation.
Fax: +7 (095) 135 5328. Eꢀmail: sab@ioc.ac.ru
The reactions of 3ꢀnitroꢀ4ꢀRꢀfurazans with ammonia were studied. The effect of the
substituent R on the specific features of the nucleophilic substitution reaction observed was
considered. The nitro group attached to the furazan ring can act as both the leaving group
and the activating group facilitating the displacement of the second substituent (for example,
OR´ or N(NO2)R´).
Key words: furazans, nitrofurazans, aminofurazans, nitramines, alkoxyfurazans, nucleoꢀ
philic substitution.
Scheme 1
In 1968, the first publication appeared pointing to the
expediency of using nitrofurazans as explosives.1 This
circumstance stimulated the development of the chemisꢀ
try and research into the properties of these compounds.2,3
Thus nitrofurazans were demonstrated to be fairly effiꢀ
cient as components of various energetic composiꢀ
tions.4—15 It is noteworthy that the furazan ring itself is
an explosophoric fragment. Therefore, even aminoꢀ, azoꢀ,
and azoxyfurazans containing no nitro groups are also of
interest as components of energetic compositions.16—22
Study of the chemical stability and targeted modifiꢀ
cation of nitrofurazans are topical tasks. It has been shown
previously that the nitro group in the furazan ring is
easily displaced on treatment with nucleophiles. Thus
the corresponding products have been obtained in the
reactions with Oꢀ6,23—29 and Sꢀnucleophiles;30 in addiꢀ
tion, the nitro group has been successfully replaced by
chlorine.31
This study represents further development of our reꢀ
search into the nucleophilic substitution in the furazan
series and deals with the reaction of nitrofurazans with
ammonia.
Previously, we reported that an aqueous solution of
ammonia reacts with 3,4ꢀdinitrofurazan (1) to give a
mixture of aminoꢀ and hydroxyfurazans.27 It is also known
that anhydrous ammonia taken as a solution in MeCN is
capable of displacing the nitro group in 3ꢀaminoꢀ4ꢀnitroꢀ
furazan (2) under a high pressure.32 We found that selecꢀ
tive displacement of one nitro group in compound 1
proceeds smoothly on treatment with an excess of a satuꢀ
rated solution of ammonia in anhydrous CHCl3 or CCl4
(Scheme 1). The change in the reaction temperature
from –10 °C to the boiling temperature has virtually no
influence on the yield of amine 2, which equals 95—100%
(GLC data, preparative yield 85—90%). Note that the
displacement of one nitro group in 3,4ꢀdinitrofurazan
Nꢀoxide (3,4ꢀdinitrofuroxan) on treatment with ammoꢀ
nia proceeds smoothly only at –15 to –20 °C; at higher
temperatures, the reaction is complicated by side proꢀ
cesses.33,34
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 8, pp. 1411—1417, August, 2002.
1066ꢀ5285/02/5108ꢀ1533 $27.00 © 2002 Plenum Publishing Corporation

1534
Russ.Chem.Bull., Int.Ed., Vol. 51, No. 8, August, 2002
Sheremetev et al.
The same reaction carried out in dinitrofurazan 1
solutions in DMSO, MeCN, glyme, or benzene results
in a lower yield of compound 2. For example, in anhyꢀ
drous MeCN at –10 °C and at a 1 : NH3 ratio of 1 : 2,
the yield of 2 is only 17%, the reaction giving also 3ꢀhydrꢀ
oxyꢀ4ꢀnitrofurazan (3) (35%) and its ammonium salt 4
(40%). A twofold increase in the amount of ammonia
increases the yield of amine 2 to 48% and only salt 4
(37%) is isolated as a side product. The formation of the
hydroxy derivative is a consequence of participation of
the nitrite ion,35 capable of functioning as an Oꢀnucleoꢀ
phile in a dipolar solvent. In the presence of moisture,
the hydroxy derivatives are formed in even higher yields.
Note that the presence of hydroxy derivatives formed as
side products appreciably increases the solubility of
amine 2 in water, which entails loss of the product durꢀ
ing isolation.
It is noteworthy that for an equimolar ratio of comꢀ
pound 1 and ammonia, the reaction is complicated, irreꢀ
spective of the solvent, by the formation of not only
hydroxyfurazans but also other side products. This is due
to diazotization of compound 2 and subsequent transꢀ
formations of the intermediate diazonium salt; these proꢀ
cesses normally accompany reactions with nitro group
displacement.36,37
Amino nitro ether 6 is a fairly interesting compound
from the practical standpoint. However, the reaction of
4,4´ꢀdinitrodifurazanyl ether (5) with ammonia in CHCl3
or CH2Cl2 involves only the ether bond, while the nitro
groups remain intact (see Scheme 1). This results in the
quantitative formation of amine 2, and the leaving group
is liberated quantitatively as salt 4 (the latter precipitates
during the reaction). No even traces of the asymmetrical
ether 6 (GLC and TLC data) are found in the reaction
medium. A similar outcome is observed in anhydrous
MeCN; however, due to the solubility of salt 4 in this
solvent, the product separation becomes more difficult.
Note that complete transformation of ether 5 into amine
2 takes a ∼4 times longer period than the synthesis of 2
from nitro compound 1 under analogous conditions. The
ability of the furazanoxy group to act as a leaving group
has also been noted in our previous publication.38
The reaction of nitramine 7 with ammonia in CHCl3
proceeds slowly and gives the same amine 2. The possiꢀ
bility of cleavage of nitramines on treatment with nuꢀ
cleophiles has been noted in the literature.39 In MeCN,
the displacement of the nitramine fragment proceeds
rapidly, and amine 2 can be isolated in 54% yield (in
relation to one furazan ring) as soon as 0.5 h after the
beginning of the reaction (Scheme 2). Note that under
these conditions, both the yields and the rates of formaꢀ
tion of amine 2 from nitramine 7 and ether 5 are similar.
As in the case of ether 5, no product resulting from
replacement of the nitro group attached to the furazan
ring, e.g., such as compound 8, was detected. The atꢀ
tempts to isolate the substances formed from the elimiꢀ
nated nitramine fragment of the initial molecule failed.
Scheme 2
Thus, the nitramino group bound to the furazan ring
can be displaced on treatment with nucleophiles, like
NO2, N(O)NR, Cl, F,40 SO2R, and furazanoxy groups.3
4,4ꢀDinitroazofurazan (9) reacts with ammonia in anꢀ
hydrous CHCl3 as readily as compound 1. However, this
may give both monoamine 10 and diamine 11 (Scheme 3).
Salt 12 formed as a minor impurity (yield 1—7%) can be
easily washed out by water and the corresponding hyꢀ
droxy derivative can be isolated upon acidification. In
the case of compound 9, predominant formation of a
definite product can be attained by changing the reactant
ratio or temperature. For instance, diamine 11 is the
major product (yield 86%) with a 10ꢀfold excess of NH3
and a temperature of 35—45 °C. Evidently, the reaction
proceeds as successive displacement of both nitro groups.
Indeed, under similar conditions, monoamine 10 is conꢀ
verted almost quantitatively (yield 96%) into diamine 11.
The use of a 1.25 N solution of NH3 in CHCl3 at
∼20 °C and a 9 : NH3 ratio of 1 : 2 affords monoamine 10
in 79% yield; in this case, diamine 11 is formed in 13%
yield. The formation of diamine 11 cannot be avoided
completely even when the reaction is carried out at –5 °C.
It is worth noting that the synthesis of monoamine 10 by
oxidation of diamine 11 is a very laborious procedure
resulting in a low product yield,41,42 whereas the use of
readily available dinitro compound 9 permits the prepaꢀ
ration of rather large amounts of this product.
When compound 13 is treated with a CHCl3 solution
of ammonia, the ether bond is the first to be cleaved (as
in ether 5), resulting in precipitation of salt 12 (see
Scheme 3). However, as in the case of azo compound 9,
the nitro group in the resulting amino nitro compound
10 is substituted to give diamine 11. Nevertheless, at 0 °C
and at a 13 : NH3 ratio of 1 : 2.5, the yield of monoamine
10 can reach 85%. It is noteworthy that although nitro
compound 1 and ether 5 differ appreciably in reactivity,
compounds 9 and 13 differ only slightly in this respect.
An interesting result was obtained in the reaction of
ammonia with 4ꢀnitroꢀ4´ꢀchloroazofurazan (14) in
CHCl3. Even with a large excess of ammonia, only the
nitro group was displaced (Scheme 4). A manyꢀday stirꢀ

Reaction of nitrofurazans with ammonia
Russ.Chem.Bull., Int.Ed., Vol. 51, No. 8, August, 2002
1535
Scheme 3
Scheme 5
ring of amino chloro derivative 15 in a 1.25 N solution of
NH3 in CHCl3 did not result in chlorine displacement.
Note that displacement of only the nitro group was obꢀ
served in a previous study29 for reactions of 4ꢀ(4ꢀ
chlorofurazanꢀ3ꢀN(O)Nꢀazoxy)ꢀ3ꢀnitrofurazan with Oꢀ
and Cꢀnucleophiles.
Scheme 4
Both nitro groups in bisꢀ and trisꢀazo compounds 16
and 17 are readily substituted on treatment with ammoꢀ
nia in CHCl3 both at room temperature and at lower
temperatures (Scheme 5). When excess ammonia was
used, diamines 18 and 19 were formed in almost quantiꢀ
tative yields (91—94%). The attempts to prepare monoꢀ
substituted products using a nitro compound to ammoꢀ
nia ratio of 1 : 2 proved unsuccessful. The reaction gave
a complex mixture of products (according to TLC, more
than six products), from which no individual compounds
could be isolated. Evidently, in this case, too, the nitrite
ion evolved upon displacement of the nitro group inꢀ
duces side processes.
Treatment of 4,4´ꢀdinitroꢀ3,3´ꢀbifurazan (20) with
ammonia in CHCl3 gives mainly diamino derivative 22,
in addition to monoamine 21 (Scheme 6). Even at –30 °C
and a deficiency of ammonia, monoamine 21 can be
prepared in a yield of ≤35%, the reaction mixture conꢀ
taining both the initial compound 20 and diamine 22
n = 1 (16, 18), 2 (17, 19)
(the mixture was separated by preparative chromatograꢀ
phy). The side products resulting from the concomitant
reactions of the nitrite ion do not interfere much with
the isolation of compound 21.
Although the furazan ring is similar to the dinitroꢀ
phenyl fragment in electronꢀwithdrawing properties,43,44
nitrofurazans containing no strong electronꢀwithdrawꢀ
ing substituents are rather inert with respect to solutions
of ammonia. Thus 3ꢀnitroꢀ4ꢀphenylfurazan (23) reacts
with a CHCl3 solution of ammonia very slowly (a 10ꢀfold
excess of NH3, 20—60 °C). However, heating of comꢀ
pound 23 with an excess of ammonia as a benzene soluꢀ
tion in an autoclave at 120—130 °C for 3 h affords amine
24 in 89% yield (Scheme 7).

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Sheremetev et al.
side hydroxy derivatives35 and is also reactive toward
Nꢀnucleophiles.36,37
Scheme 6
Although displacement of the methoxy groups in
methoxy azofurazans 27—29 occurs at usual pressure,
this reaction is very slow. Conducting the reaction in an
autoclave at 120—130 °C provides efficient (30 min, yields
80—93%) synthesis of amines 11, 18, and 19, respecꢀ
tively (Scheme 9). It should be emphasized that the use
of the methoxy analogs instead of the nitro compounds
makes the synthesis of these amines safe.
Scheme 9
Scheme 7
A similar autoclave treatment of compound 2 affords
3,4ꢀdiaminofurazan (25) in 83% yield (Scheme 8). Moreꢀ
over, diamine 25 is formed in 65—85% yield upon a
similar autoclave treatment of any nitro derivative (comꢀ
pound 1, 5, or 7), which is converted into amine 2 under
mild conditions.
n = 0 (11, 27), 1 (18, 28), 2 (19, 29)
Dinitrotriazene 30 reacts with ammonia in CHCl3 at
∼20 °C to give salt 31, which is quantitatively precipiꢀ
tated and is not further converted. Heating of compound
30 with ammonia in glyme gives a mixture of amine 2
and azide 32 in ∼30% yields (Scheme 10).
Scheme 8
Scheme 10
R = Me (a), Et (b), Pri (c), Bn (d), Ph (e)
It is of interest that heating in a autoclave of 3ꢀmethꢀ
oxyꢀ4ꢀnitrofurazan (26а) with ammonia results in the
displacement of both nitro and methoxy groups to give
3,4ꢀdiaminofurazan (25) in 78% yield (see Scheme 8).
Similar results were obtained by using alkoxyfurazans
26b—d and phenoxy derivative 26e (yields 75—81%).
Evidently, the reaction proceeds as a stepwise displaceꢀ
ment of substituents. Although the displacement of the
alkoxy group bound to the polynitrophenyl fragment is a
wellꢀstudied reaction,36 it is quite unusual for alkoxyꢀ
azoles. We would like to emphasize the importance of
the possibility of displacing the RO group attached to the
furazan ring. In some cases, it is necessary to exclude the
presence of the nitrite ion, which could give rise to
In conclusion, note that the nitro group bound to the
furazan ring can act as both a leaving and an activating
group, which facilitates the displacement of the second
substituent (for example, OR or N(NO2)R). The data

Reaction of nitrofurazans with ammonia
Russ.Chem.Bull., Int.Ed., Vol. 51, No. 8, August, 2002
1537
evaporated in vacuo. The crude product was recrystallized from
water to give 0.55 g (42%) of compound 2. The aqueous layer
was acidified with HCl and extracted with ether (3×30 mL).
The ethereal extract was dried with MgSO4 and concentrated
in vacuo to give 0.72 g (55%) of 3ꢀhydroxyꢀ4ꢀnitrofurazan (3) as
a thick oil. The spectroscopic characteristics corresponded to
published data.23,26,27
Reaction of 4,4´ꢀdinitrodifurazanyl ether (5) with NH3. A
1.25 N solution of NH3 in CHCl3 (10 mL) was added dropwise
with stirring to a solution of compound 5 (1.22 g, 5 mmol) in
CH2Cl2 (25 mL). The mixture was stirred for an additional 2 h,
the precipitate was filtered off, washed with CH2Cl2, and dried
in air to give 0.73 g (98%) of salt 4, m.p. 110—111 °C. The
filtrate was concentrated to dryness, and the residue was reꢀ
crystallized from water to give 0.63 g (97%) of compound 2,
m.p. 124—125 °C.
about the groups able to be displaced by nucleophiles are
exceptionally important for choosing the synthetic pathꢀ
ways to furazan derivatives. The use of OR or N(NO2)R
as the leaving groups in the furazan series can be recomꢀ
mended for efficient application in processes where the
presence of nitrite ions, supplied to the reaction medium
upon displacement of the nitro group, is undesirable.
Experimental
Melting points were determined on a Köffler stage. 1H,
13C, and 14N NMR spectra for natural isotope abundances
were recorded on a Bruker AMꢀ300 spectrometer operating at
300.13, 75.7, and 21.5 МHz, respectively. The 14N NMR chemiꢀ
cal shifts were determined in the δ scale relative to external
MeNO2. Mass spectra were registered on Varian MAT CHꢀ6
and Varian MAT CHꢀ111 instruments (70 eV). IR spectra were
measured on a Specord IRꢀ75 spectrometer (KBr pellets for
solids and thin films for liquids). The reactions were monitored
and the product purity was checked by TLC on Silufol UVꢀ254
plates; silica gel was used for preparative chromatography.
The starting nitrofurazans 1,41 5,23 7,45 9,41 13,24 14,31
16,6,46 17,47 19,41 23,41 26,41 and 30 28 were prepared by previꢀ
ously described procedures.
Reaction of methyleneꢀN,N´ꢀbis[(4ꢀnitrofurazanꢀ3ꢀyl)nitrꢀ
amine] (7) with NH3. Ammonia gas was passed for 0.5 h at
∼20 °C through a stirred solution of compound 7 (1.81 g,
5 mmol) in anhydrous MeCN (30 mL). The solvent was evapoꢀ
rated in vacuo. The residue was dissolved in CH2Cl2 (100 mL)
and washed with water (4×30 mL). The organic layer was dried
with MgSO4 and evaporated in vacuo, and the residue was
recrystallized from water to give 0.35 g (54%) of compound 2.
Reaction of 4,4´ꢀdinitroazofurazan (9) with NH3. А. Amꢀ
monia gas was passed for 0.5 h through a stirred solution of
compound 9 (2.56 g, 10 mmol) in CHCl3 (60 mL) heated to
35—40 °C. The residue was filtered off and recrystallized from
DMSO to give 1.88 g (96%) of 4,4´ꢀdiaminoazofurazan (11)
as a yellow amorphous powder, m.p. 325—326 °C (dec.)
Caution! Most of nitrofurazans are explosive. The precauꢀ
tions recommended by the appropriate instructions must be
taken.
Reaction of 3,4ꢀdinitrofurazan (1) with NH3. A. A 1.25 N
solution of NH3 in CHCl3 (5—10 mL) was added dropwise
with stirring to a solution of compound 1 (1.6 g, 10 mmol) in
anhydrous CHCl3 (15 mL). The mixture was stirred until the
initial compound was no longer detected by TLC (elution with
a CCl4—CH2Cl2 mixture). The reaction mixture was evapoꢀ
rated to dryness in vacuo and the residue was recrystallized
from water to give 1.25 g (96%) of 3ꢀaminoꢀ4ꢀnitrofurazan (2)
as primroseꢀcolored crystals, m.p. 124—125 °C (cf. Ref. 48:
m.p. 122.5—123 °C, cf. Ref. 41: m.p. 125 °C). The spectroꢀ
scopic characteristics corresponded to the published data.
B. A solution of NH3 (0.68 g, 40 mmol) in anhydrous
MeCN (20 mL) was added dropwise at –10 °C to a solution of
compound 1 (1.6 g, 10 mmol) in anhydrous MeCN (15 mL).
After spontaneous heating of the reaction mixture to ∼20 °C,
the solvent was removed in vacuo. Extraction of the residue
with an ether—hexane mixture (10 : 1, 100 mL) gave comꢀ
pound 2, which was obtained in 48% yield after solvent evapoꢀ
ration and recrystallization from water. The residue insoluble
in the ether mixture was recrystallized from a CHCl3—AcOH
mixture (15 : 2) to give 0.55 g (37%) of the ammonium salt of
3ꢀhydroxyꢀ4ꢀnitrofurazan (4), m.p. 110—112 °C. Found (%):
C, 16.27; H, 2.71; N, 37.81. C2H4N4O4. Calculated (%):
C, 16.22; H, 2.72; N, 37.84. IR, ν/cm–1: 3350, 3250—2900,
1610, 1540, 1500, 1470, 1420, 1390, 1320, 1205, 1020, 910,
870. 14N NMR (DMSOꢀd6), δ: –23.6 (NO2); –359.4 (NH4+).
C. A solution of NH3 (0.68 g, 40 mmol, 25 mL) in anꢀ
hydrous glyme was added dropwise with stirring at ∼20 °C over
a period of 0.5 h to a solution of compound 1 (1.6 g, 10 mmol)
in the same solvent (15 mL). The mixture was stirred for an
additional 0.5 h and the solvent was evaporated in vacuo. The
residue was dissolved in CH2Cl2 (200 mL) and washed with
water (4×30 mL). The organic layer was dried with MgSO4 and
1
(cf. Ref. 48: m.p. 325 °C (dec.)). H NMR (DMSOꢀd6), δ: 6.89
(NH2). 13C NMR (DMSOꢀd6), δ: 150.7 (CNH2); 155.8 (CNN).
The other spectroscopic characteristics corresponded to pubꢀ
lished data.48
B. A 1.25 N solution of NH3 in CHCl3 (5 mL) was added
dropwise with stirring to a solution of compound 9 (2.56 g,
10 mmol) in anhydrous CHCl3 (45 mL). After 20 min of stirꢀ
ring, the reaction mixture was washed with water (3×15 mL),
dried with MgSO4, filtered through a thin silica gel layer, and
concentrated in vacuo. The residue was recrystallized from CCl4
to give 1.78 g (79%) of 4ꢀaminoꢀ4´ꢀnitroazofurazan (10) as orꢀ
ange crystals, m.p. 92—93 °C (cf. Ref. 41: m.p. 93 °C). The specꢀ
troscopic characteristics corresponded to published data.41,42
Reaction of 4,4´ꢀbis(4ꢀnitrofurazanꢀ3ꢀylazo)difurazanyl ether
(13) with NH3. A 1.25 N solution of NH3 in CHCl3 (7 mL) was
added with stirring at 0 °C to a solution of compound 13 (2.18 g,
5 mmol) in anhydrous CCl4 (50 mL). Then CH2Cl2 (50 mL)
was added and after stirring for 20 min at 0 °C, the reaction
mixture was allowed to warm up to ∼20 °C. The mixture was
washed with water (3×15 mL), dried with MgSO4, filtered
through a thin layer of silica gel, and concentrated in vacuo.
The residue was recrystallized from CCl4 to give 0.96 g (85%)
of compound 10, m.p. 92—93 °C.
Reaction of 4ꢀnitroꢀ4´ꢀchloroazofurazan (14) with NH3. A
1.25 N solution of NH3 in CHCl3 (60 mL) was added to a
solution of compound 14 (0.49 g, 2 mmol) in anhydrous CHCl3
(10 mL) at ∼20 °C. The resulting solution was stirred for 2 h,
washed with water (3×60 mL), dried with MgSO4, filtered
through a thin layer of silica gel, and concentrated in vacuo.
The residue was recrystallized from CCl4 to give 0.37 g (86%)
of 4ꢀaminoꢀ4´ꢀchloroazofurazan (15) as orange crystals, m.p.

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Sheremetev et al.
121—122.5 °C. Found (%): C, 22.26; H, 1.00; Cl, 16.39;
N, 45.41. C4H2ClN7O2. Calculated (%): C, 22.29; H, 0.94;
Cl, 16.45; N, 45.49. MS, m/z: 215, 216 [M]+, 132, 131, 84. IR,
ν/cm–1: 3472, 3320, 1628, 1540, 1528, 1476, 1432, 1388, 1187,
1028, 1012, 765, 680. 13C NMR (DMSOꢀd6), δ: 141.6 (CCl);
149.2 (CNH2); 156.0 (CCNH2); 159.5.
Reaction of 3,4ꢀbis(4ꢀnitrofurazanꢀ3ꢀylazo)furazan (16) with
NH3. Ammonia gas was passed for 0.5 h at ∼20 °C through a
solution of compound 16 (3.52 g, 10 mmol) in a mixture of
CHCl3 (50 mL) and CCl4 (20 mL). The reaction mixture was
cooled to 0 °C and at this temperature, the product was filtered
off and washed with cold water. Recrystallization from PriOH
gave 2.66 g (91%) 4,4´ꢀbis(4ꢀaminofurazanꢀ3ꢀylazo)furazan (18)
as fine yellowꢀorange crystals, m.p. 205—207 °C. Found (%):
C, 24.71; H, 1.37; N, 57.51. C6H4N12O3. Calculated (%):
C, 24.67; H, 1.38; N, 57.53. MS, m/z: 292 [M]+, 208, 112. IR,
ν/cm–1: 3430, 3310, 1615, 1400, 1230, 1090, 1045. 13C NMR
(DMSOꢀd6), δ: 149.1 (CNH2); 156.1; 157.4 (CNN).
Reaction of 4,4´ꢀbis(4ꢀnitrofurazanꢀ3ꢀylazo)azofurazan (17)
with NH3. The reaction carried out as described above usꢀ
ing compound 17 (4.48 g, 10 mmol) gave 3.65 g (94%)
of 4,4´ꢀbis(4ꢀaminofurazanꢀ3ꢀylazo)azofurazan (19), m.p.
264—266 °C. Found (%): C, 24.78; H, 1.06; N, 57.72.
C8H4N16O4. Calculated (%): C, 24.75; H, 1.04; N, 57.73. MS,
m/z: 388 [M]+, 304, 208, 180. IR, ν/cm–1: 3344, 3232, 1630,
1610, 1580, 1490, 1410, 1290, 1110, 1040, 790. 13C NMR
(DMSOꢀd6), δ: 149.0 (CNH2); 155.9; 156.4; 158.3 (CNN).
Reaction of 4,4´ꢀdinitrobifurazan (20) with NH3. The reacꢀ
tion carried out as described in the previous procedure using
compound 20 (2.28 g, 10 mmol) gave 1.63 g (97%) of 4,4´ꢀdiꢀ
aminobifurazan (22), m.p. 300 °C (dec.) (cf. Ref. 49, 50: m.p.
298—299 °C, cf. Ref. 1: 305 °C (dec.)). The spectroscopic charꢀ
acteristics corresponded to published data.
reaction mixture was concentrated in vacuo to dryness and the
residue was washed with water and recrystallized from DMSO
to give 1.82 g (93%) of compound 11, m.p. 325—326 °C (dec.).
Reaction of 3,4ꢀbis(4ꢀmethoxyfurazanꢀ3ꢀylazo)furazan (28)
with NH3. The reaction carried out similarly to the previous
experiment using 3.22 g (10 mmol) of compound 28 gave 2.54 g
(87%) of compound 18, m.p. 205—207 °C.
Reaction of 4,4´ꢀbis(4ꢀmethoxyfurazanꢀ3ꢀylazo)azofurazan
(29) with NH3. The reaction carried out similarly to the previꢀ
ous experiment using compound 29 (4.18 g, 10 mmol) gave
3.1 g (80%) of 4,4´ꢀbis(4ꢀaminofurazanꢀ3ꢀylazo)azofurazan (19),
m.p. 264—266 °C.
Reaction of 1,3ꢀbis(4ꢀnitrofurazanꢀ3ꢀyl)triazene (30) with
NH3. A. A 1.25 N solution of NH3 in CHCl3 (10 mL) was
added dropwise with stirring to a solution of compound 30
(2.71 g, 10 mmol) in anhydrous CHCl3 (50 mL). Then ether
(50 mL) was added, the mixture was stirred for 20 min, and the
ammonium salt 31 was filtered off. Reprecipitation with ether
from MeCN at 0 °C gave 0.96 g (85%) of product 31 as yellow
crystals, m.p. 102—106 °C (dec.). Found (%): C, 16.59; H, 1.45;
N, 48.67. C4H4N10O6. Calculated (%): C, 16.67; H, 1.40;
N, 48.61. Acidification of salt 31 with HCl gave the initial
triazene 30, m.p. 96—97 °C (cf. Ref. 28: m.p. 95—96 °C).
B. Ammonia gas was passed for 0.5 h at 40—50 °C through
a stirred solution of compound 30 (2.71 g, 10 mmol) in anꢀ
hydrous glyme (30 mL). After stirring (1 h), the reaction mixꢀ
ture was concentrated to dryness. The residue was separated
on a chromatographic column (SiO2 40/100, elution with
CHCl3—MeCN, 7 : 1). The first fraction (0.36 g, yield 29%)
was 3ꢀazidoꢀ4ꢀaminofurazan (32), m.p. 85—86 °C (cf. Ref. 53:
m.p. 86.5—87.5 °C). The second fraction (0.4 g, yield 31%)
was compound 2, m.p. 124—125 °C.
This work was partially supported by NATO (grant
SSS.CLG.977566) and the International Technical Cenꢀ
ter (Project No. 1882).
Reaction of 3ꢀnitroꢀ4ꢀphenylfurazan (23) with NH3. A soluꢀ
tion of compound 23 (1.91 g, 10 mmol) in benzene (30 mL)
was placed into a 150 mL autoclave. The autoclave was purged
with nitrogen and evacuated, and NH3 gas was supplied up to a
pressure of 15 atm. The reaction mixture was stirred for 3 h at
120—130 °C. After cooling, the pressure was relieved and the
autoclave was purged with nitrogen. Ether (30 mL) was added,
the mixture was washed with water (3×30 mL), and the orꢀ
ganic layer was dried with MgSO4. After removal of the solꢀ
vent, the residue was recrystallized from 95% propanꢀ2ꢀol to
give 1.43 g (89%) of 3ꢀaminoꢀ4ꢀphenylfurazan (24) as lightꢀ
creamꢀcolored crystals, m.p. 97—98 °C (cf. Ref. 49, 51: m.p.
98—99 °C). The spectroscopic characteristics corresponded to
published data.
Reaction of 3ꢀmethoxyꢀ4ꢀnitrofurazan (26а) with NH3. The
reaction carried out as in the previous experiment with comꢀ
pound 26а (2.9 g, 20 mmol) gave 1.56 g (78%) 3,4ꢀdiaminoꢀ
furazan (25), m.p. 179—180 °C (cf. Ref. 52: m.p. 179—180 °C,
cf. Ref. 1: m.p. 180 °C). The spectroscopic characteristics corꢀ
responded to published data.
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Received April 1, 2002
in revised form May 23, 2002