4-Hydroxy-3-(α-nitroalkyl-ONN-azoxy)furazans and some their O-derivatives

Article abstract of DOI:10.1007/s11172-013-0071-8

Methods for the synthesis of 4-hydroxy- and 4-alkoxy-3-(a-nitroalkyl-ONN- azoxy)furazans and difurazanyl ethers were developed. The methods involve displacement of the nitro group from 4-nitro-3-(α-nitroalkyl-ONN-azoxy) furazans under the action of aqueous solutions of alkalis, mono- and diatomic alcohols (in the presence of inorganic bases), and sodium carbonate in anhydrous acetonitrile.

Full text of DOI:10.1007/s11172-013-0071-8

Russian Chemical Bulletin, International Edition, Vol. 62, No. 2, pp. 516—520, February, 2013
516
4ꢀHydroxyꢀ3ꢀ(ꢀnitroalkylꢀONNꢀazoxy)furazans and some their Oꢀderivatives*
V. V. Parakhin and O. A. Luk´yanov
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
Methods for the synthesis of 4ꢀhydroxyꢀ and 4ꢀalkoxyꢀ3ꢀ(ꢀnitroalkylꢀONNꢀazoxy)furazans
and difurazanyl ethers were developed. The methods involve displacement of the nitro group
from 4ꢀnitroꢀ3ꢀ(ꢀnitroalkylꢀONNꢀazoxy)furazans under the action of aqueous solutions of
alkalis, monoꢀ and diatomic alcohols (in the presence of inorganic bases), and sodium carbonꢀ
ate in anhydrous acetonitrile.
Key words: furazans, (ꢀnitroalkylꢀONNꢀazoxy)furazans, 4ꢀhydroxyꢀ3ꢀ(ꢀnitroalkylꢀONNꢀ
azoxy)furazans, 4ꢀalkoxyꢀ3ꢀ(ꢀnitroalkylꢀONNꢀazoxy)furazans, 3,3´ꢀbis(ꢀnitroalkylꢀONNꢀ
azoxy)difurazanyl ethers, nitrofurazans, hydroxyfurazans, nucleophilic substitution.
Scheme 1
Earlier, the syntheses of 4ꢀaminoꢀ3ꢀ(ꢀnitroalkylꢀ
ONNꢀazoxy)furazans1 and their highꢀenergy derivatives
(including new oxidants 3ꢀ(polynitromethylꢀONNꢀazoxy)ꢀ
4ꢀnitraminofurazans) have been reported.2 As a next step
in those investigations, here we studied nucleophilic subꢀ
stitution of the nitro group in a series of 4ꢀnitroꢀ3ꢀ
(ꢀnitroalkylꢀONNꢀazoxy)furazans under the action of
Oꢀnucleophiles. The goal of the present work was to obꢀ
tain 4ꢀhydroxyꢀ3ꢀ(ꢀnitroalkylꢀONNꢀazoxy)furazans that
could serve as intermediate products in the synthesis of
highꢀenergy compounds with potential attractive properties.
Results and Discussion
R = Me (1, 4); R + R = (CH2)5 (2, 5)
Nitrofurazans are known to undergo nucleophilic subꢀ
stitution in reactions with aqueous solutions of alkalis3 to
give hydroxyfurazans. We found that 4ꢀnitroꢀ3ꢀ(ꢀnitroꢀ
alkylꢀONNꢀazoxy)furazans 1—3 react with alkalis in waꢀ
ter and a waterꢀmiscible organic solvent (acetone or aceꢀ
tonitrile) even at 0—3 C and that the nitro group directly
bound to the furazan ring is replaced by a hydroxy group in
0.5 h. Treatment of the reaction mixture with HCl gives
the desired products 4ꢀhydroxyꢀ3ꢀ(ꢀnitroalkylꢀONNꢀ
azoxy)furazans 4—6 (Schemes 1 and 2).
Scheme 2
With substrate 3, the above transformation is compliꢀ
cated by hydrolysis of the 2,2ꢀdimethylꢀ5ꢀnitroꢀ1,3ꢀdiꢀ
oxanꢀ5ꢀyl substituent upon the treatment with HCl, yieldꢀ
ing triol 6 (see Scheme 2).
4ꢀHydroxyꢀ3ꢀ(ꢀnitroalkylꢀONNꢀazoxy)furazans 5
and 6 are yellow oils, while product 4 is a white crystalline
solid with m.p. 85.0—87.0 C. Hydroxyfurazans 4 and 5
can form metal salts by exchanging the OH proton. For
instance, treatment of compound 4 with EtONa in diethyl
ether affords the sodium salt Na[4].
The reaction in methanol in the presence of inorganic
bases proceeds even more violently than that in aqueous
* Dedicated to Academician of the Russian Academy of Sciences
S. M. Aldoshin on the occasion of his 60th birthday.
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 2, pp. 0514—0518, February, 2013.
1066ꢀ5285/13/6202ꢀ0516 © 2013 Springer Science+Business Media, Inc.

4ꢀHydroxyꢀ3ꢀ(ꢀnitroalkylꢀONNꢀazoxy)furazans
Russ.Chem.Bull., Int.Ed., Vol. 62, No. 2, February, 2013
517
solutions of alkalis. Although nitrofurazans 1—3 do not
react even with boiling methanol when it is used alone,
addition of K2CO3 or KOH promotes nucleophilic disꢀ
placement of the nitro group from the furazan ring by
a methoxy group. The reaction at 20 C is completed in
0.5 h to give the corresponding 4ꢀmethoxyꢀ3ꢀ(ꢀnitroꢀ
alkylꢀONNꢀazoxy)furazans 7—9 (Scheme 3). Note that
the use of K2CO3 ensures higher yields of the reacꢀ
tion products than does KOH (e.g., 92 against 81% for
compound 9).
ment of both the nitro groups, thus producing 4ꢀmethoxyꢀ
3ꢀ(ꢀmethoxyalkylꢀONNꢀazoxy)furazans 10 and 11, reꢀ
spectively (Scheme 4).
The structures of the methoxy and dimethoxy derivaꢀ
1
tives 7—11 were confirmed by H, 13C, and 14N NMR
spectra. Comprehensive assignment of the signals in the
13C NMR spectra of these compounds was performed usꢀ
ing 2D NMR experiments ({1H—13C} HMBC).
Methoxyfurazans 7—9 and 11 are white crystalline
compounds. Interestingly, the replacement of the nitro
group in the (ꢀnitroalkylꢀONNꢀazoxy) fragment by the
methoxy group lowers the melting point (from 78.5—79.0
and 72.5—73.0 C for 9 and 7, respectively, to 48.0—49.5 C
for dimethoxy derivative 11). Compound 10 is entirely
liquid at room temperature.
Scheme 3
Like other nitrofurazans,4 4ꢀnitroꢀ3ꢀ(ꢀnitroalkylꢀ
ONNꢀazoxy)furazans react with glycols in the presence of
bases to give glycol monoꢀ and diethers. For instance,
a reaction of an excess of compound 3 with ethylene glyꢀ
col in acetonitrile in the presence of K2CO3 at 20 C takes
96 h, affording diether 12 (Scheme 5). Monoether 13 is
also formed as a byꢀproduct (7%), even when nitrofuraꢀ
zan 3 is employed in more than a twofold excess.
4ꢀNitroꢀ3ꢀ(ꢀnitroalkylꢀONNꢀazoxy)furazans also reꢀ
act with weak bases in anhydrous media, which is typical
of nitrofurazans.5,6 Treatment of compound 3 with
Na2CO3 in anhydrous acetonitrile (60—65 C, 5 h) gives
difurazanyl ether 14 in 63% yield (Scheme 5). This prodꢀ
uct is a white crystalline solid with m.p. 99.0—100.0 C.
R = Me (1, 7); R + R = (CH2)5 (2, 8); R + R = CH2OCMe2OCH2 (3, 9)
Reactions of 4ꢀnitroꢀ3ꢀ(ꢀnitroalkylꢀONNꢀazoxy)ꢀ
furazans 1 and 3 with such a strong nucleophile as MeONa
in methanol at 20 C unexpectedly resulted in replaceꢀ
Scheme 4
R = Me (1, 10); R + R = CH2OCMe2OCH2 (3, 11)
Scheme 5

518
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Parakhin and Luk´yanov
In contrast to NNOꢀazoxyfurazans,3,6 which eliminate
4ꢀHydroxyꢀ3ꢀ(1ꢀmethylꢀ1ꢀnitroethylꢀONNꢀazoxy)furazan,
sodium salt (Na[4]). Metallic sodium (0.012 g, 0.506 mmol) was
dissolved in EtOH (0.25 mL). The solution was added at 5—10 C
to a stirred solution of compound 4 (0.100 g, 0.460 mmol) in
Et2O (4.0 mL). The resulting mixture was kept at 20 C for 1 h.
The precipitate that formed was filtered off and thoroughly
washed with Et2O. The yield of salt Na[4] was 0.058 g (53%),
light yellow crystals. 1H NMR (acetoneꢀd6), : 2.26 (s, 6 H,
Me). Acidification of salt Na[4] released free hydroxyfurazan 4
identical in physicochemical characteristics with that obtained
as described above.
the azoxy group in reactions with bases, the ONNꢀazoxy
group in (ꢀnitroalkylꢀONNꢀazoxy)furazans does not act
as a nucleofuge under similar conditions.
In our opinion, the results obtained suggest that
the electronic effect of the ꢀnitroalkyl substituent at the
ONNꢀazoxy group, as with Nꢀnucleophilic substitution in
this series,1 has minor influence on the possibility of
nucleophilic substitution of the nitro group directly bound
to the furazan ring.
4ꢀHydroxyꢀ3ꢀ(1ꢀnitrocyclohexꢀ1ꢀylꢀONNꢀazoxy)furazan (5).
A solution of compound 2 (0.108 g, 0.378 mmol) in acetone
(0.8 mL) was added at 0—3 C to a stirred solution of NaOH (0.076 g,
1.89 mmol) in water (1.0 mL). The resulting solution was stirred
at 0—3 C for 0.5 h, diluted with water (60.0 mL), and washed
with CH2Cl2 (4×15 mL). Then 33% aqueous HCl (0.20 mL,
2.11 mmol) was added, and the product was extracted with Et2O
(7×10 mL). The combined extracts were dried with MgSO4 and
concentrated in vacuo. The residue was washed with hexane.
The yield of compound 5 was 0.085 g (88%), yellow oil.
MS (ESI), m/z: 280.0654 [M + Na]+; calculated for C8H11N5O5:
[M + Na]+ 280.0652. IR (KBr), /cm–1: 1608 (vs, furazan);
1570 (vs, asymm., NO2); 1506 (vs, N=NO); 1332 (m, symm.,
NO2); 1247 (m, N=NO). 1H NMR (acetoneꢀd6), : 1.62
(m, 2 H, CH2(CH2CH2)2); 1.77 (m, 4 H, CH2(CH2CH2)2);
2.76 (m, 4 H, (CH2)2CNO2); 11.65 (br.s, 1 H, OH). 13C NMR
(75 MHz, acetoneꢀd6), : 21.8 (CH2(CH2CH2)2), 22.8
(CH2(CH2CH2)2), 32.5 ((CH2)2CNO2), 116.0 ((CH2)2CNO2),
147.3 (C—N=NO); 159.1 (C—OH). 14N NMR (22 MHz,
To sum up, we developed a method for the synthesis of
4ꢀhydroxyꢀ and 4ꢀalkoxyꢀ3ꢀ(ꢀnitroalkylꢀONNꢀazoxy)ꢀ
furazans and difurazanyl ethers by nucleophilic displaceꢀ
ment of the nitro group from 4ꢀnitroꢀ3ꢀ(ꢀnitroalkylꢀ
ONNꢀazoxy)furazans under the action of aqueous soluꢀ
tions of alkalis, monoꢀ and diatomic alcohols (in the presꢀ
ence of inorganic bases), and sodium carbonate in anꢀ
hydrous acetonitrile. The ONNꢀazoxy group shows no
nucleofugacity in reactions with nucleophilic reagents. In
addition, we were the first to notice that the nitro group of
the (ꢀnitroalkylꢀONNꢀazoxy) fragment act as a nucleoꢀ
fuge when (ꢀnitroalkylꢀONNꢀazoxy)furazans are treated
with alkali metal alkoxides.
Experimental
The course of the reactions was monitored by TLC on Siluꢀ
fol UVꢀ254 plates. IR spectra were recorded on a Bruker Alpha
instrument. NMR spectra were recorded on Bruker AMꢀ300
and Bruker AMꢀ600 instruments. Chemical shifts are referꢀ
acetoneꢀd6), : –43.2 (NO,  = 81 Hz); –1.72 (NO2,
0.5
0.5 = 78 Hz).
4ꢀHydroxyꢀ3ꢀ(2ꢀhydroxyꢀ1ꢀhydroxymethylꢀ1ꢀnitroethylꢀONNꢀ
azoxy)furazan (6). A solution of compound 3 (0.100 g,
0.314 mmol) in acetone (0.8 mL) was added at 0—3 C to a stirred
solution of NaOH (0.063 g, 1.57 mmol) in water (1.0 mL). The
resulting solution was stirred at 0—3 C for 0.5 h, diluted with
water (60.0 mL), and washed with Et2O (4×15 mL). Then 33%
aqueous HCl (0.37 mL, 3.93 mmol) was added, and the product
was extracted with Et2O (7×10 mL). The combined extracts were
dried with MgSO4 and concentrated in vacuo. The residue was
washed with hexane. The yield of compound 6 was 0.063 g (81%),
yellow oil. Found (%): C, 24.35; H, 2.95; N, 28.42. C5H7N5O7
(M = 249.14). Calculated (%): C, 24.10; H, 2.81; N, 28.11.
IR (KBr), /cm–1: 1699 (vs, furazan); 1576 (vs, asymm., NO2);
1510 (vs, N=NO); 1362 (s, symm., NO2); 1239 (s, N=NO).
1H NMR (acetoneꢀd6), : 4.64 (s, 4 H, CH2); 5.26 (br.s, 2 H,
CH2OH); 11.58 (br.s, 1 H, OH). 1H NMR (DMSOꢀd6), : 4.82
(s, 4 H, CH2); 6.10 (br.s, 2 H, CH2OH); 12.20 (br.s, 1 H, OH).
13C NMR (75 MHz, acetoneꢀd6), : 60.5 (CH2), 114.5 (C—NO2),
147.4 (C—N=NO), 160.0 (C—OH). 14N NMR (22 MHz,
acetoneꢀd6), : –49.1 (NO, 0.5 = 92 Hz); –9.1 (NO2,
0.5 = 88 Hz).
enced to Me4Si (1H, 13C) or MeNO2 14N, the external stanꢀ
(
dard, highꢀfield chemical shifts are negative). Highꢀresolution
mass spectra were measured on a Bruker micrOTOF II inꢀ
strument. Melting points were determined on a Kofler hot stage.
The starting compounds 3ꢀ(1ꢀmethylꢀ1ꢀnitroethylꢀONNꢀazoxy)ꢀ
4ꢀnitrofurazan (1),1 3ꢀ(2,2ꢀdimethylꢀ5ꢀnitroꢀ1,3ꢀdioxanꢀ5ꢀ
ylꢀONNꢀazoxy)ꢀ4ꢀnitrofurazan (3),1 and 4ꢀnitroꢀ3ꢀ(1ꢀnitroꢀ
cyclohexꢀ1ꢀylꢀONNꢀazoxy)furazan (2)7 were prepared as deꢀ
scribed earlier.
4ꢀHydroxyꢀ3ꢀ(1ꢀmethylꢀ1ꢀnitroethylꢀONNꢀazoxy)furazan
(4). A solution of compound 1 (0.110 g, 0.447 mmol) in acetone
(0.8 mL) was added at 0—3 C to a vigorously stirred solution of
NaOH (0.090 g, 2.24 mmol) in water (1.0 mL). The resulting
solution was stirred at 0—3 C for 0.5 h, diluted with water
(60.0 mL), and washed with CH2Cl2 (4×15 mL). Then 33%
aqueous HCl (0.23 mL, 2.42 mmol) was added, and the product
was extracted with Et2O (7×10 mL). The combined extracts were
dried with MgSO4 and concentrated in vacuo. The residue was
washed with hexane. The yield of compound 4 was 0.092 g (95%),
white crystals, m.p. 85.0—87.0 C (from CH2Cl2—hexane). MS
(ESI), m/z: 240.0345 [M + Na]+; calculated for C5H7N5O5:
[M + Na]+ 240.0339. IR (KBr), /cm–1: 1607 (s, furazan); 1569
(vs, asymm., NO2); 1505 (vs, N=NO); 1377 (m, symm., NO2);
1234 (s, N=NO). 1H NMR (acetoneꢀd6), : 2.36 (s, 6 H, Me);
11.53 (br.s, 1 H, OH). 13C NMR (75 MHz, acetoneꢀd6), : 24.6
(Me); 114.5 (C—NO2); 148.2 (C—N=NO); 160.2 (C—OH).
14N NMR (22 MHz, acetoneꢀd6), : –39.7 (NO, 0.5 = 64 Hz);
0.2 (NO2, 0.5 = 54 Hz).
4ꢀMethoxyꢀ3ꢀ(1ꢀmethylꢀ1ꢀnitroethylꢀONNꢀazoxy)furazan
(7). Potassium carbonate (0.074 g, 0.536 mmol) was added at
20 C to a stirred solution of compound 1 (0.110 g, 0.447 mmol)
in MeOH (6.0 mL). The resulting suspension was stirred at 20 C
for 0.5 h and filtered. The mother liquor was concentratꢀ
ed in vacuo. The product was purified by preparative TLC
(chromatographed three times) on silica gel with ethyl acetꢀ
ate—hexane (1 : 5) as an eluent. The yield of compound 7 was

4ꢀHydroxyꢀ3ꢀ(ꢀnitroalkylꢀONNꢀazoxy)furazans
Russ.Chem.Bull., Int.Ed., Vol. 62, No. 2, February, 2013
519
0.098 g (95%), white crystals, m.p. 72.5—73.0 C (from hexane).
MS (ESI), m/z: 254.0488 [M + Na]+; calculated for C6H9N5O5:
[M + Na]+ 254.0496. IR (KBr), /cm–1: 1589 (vs, furazan);
1585 (vs, asymm., NO2); 1517 (s, N=NO); 1417 (s, symm.,
NO2); 1264 (m, N=NO). 1H NMR (acetoneꢀd6), : 2.36
(s, 6 H, C—Me); 4.19 (s, 3 H, O—Me). 13C NMR (75 MHz,
acetoneꢀd6), : 24.6 (C—Me), 59.9 (O—Me), 114.6 (C—NO2),
147.5 (C—N=NO), 162.4 (C—OMe). The signals in the specꢀ
trum were assigned using HMBC experiments. 14N NMR
4ꢀMethoxyꢀ3ꢀ(1ꢀmethoxyꢀ1ꢀmethylethylꢀONNꢀazoxy)furꢀ
azan (10). Metallic sodium (0.047 g, 2.04 mmol) was dissolved in
MeOH (2.0 mL), whereupon a solution of compound 1 (0.100 g,
0.407 mmol) in MeOH (1.0 mL) was added at 20 C with stirꢀ
ring. The resulting mixture was kept at 20 C for 0.5 h. The
solvent was removed in vacuo. The product was purified by preꢀ
parative TLC (chromatographed three times) on silica gel with
ethyl acetate—hexane (1 : 3) as an eluent. The yield of comꢀ
pound 10 was 0.088 g (80%), yellow oil. MS (ESI), m/z: 239.1841
[M + Na]+; calculated for C7H12N4O4: [M + Na]+ 239.1845.
IR (KBr), /cm–1: 1588 (vs, furazan); 1517 (s, N=NO); 1262
(m, N=NO). 1H NMR (acetoneꢀd6), : 2.18 (s, 6 H, C—Me);
2.84 (s, 3 H, C(NON)O—Me); 4.19 (s, 3 H, O—Me). 13C NMR
(75 MHz, acetoneꢀd6), : 24.8 (C—Me), 49.9 (C(NON)O—Me),
60.0 (O—Me), 109.7 (C(NON)O—Me), 148.0 (C—N=NO),
162.2 (C—OMe). The signals in the spectrum were assigned
using HMBC experiments. 14N NMR (22 MHz, acetoneꢀd6),
: –29.4 (NO, 0.5 = 165 Hz).
(22 MHz, acetoneꢀd6), : –40.0 (NO,  = 58 Hz); –0.8
0.5
(NO2, 0.5 = 51 Hz).
4ꢀMethoxyꢀ3ꢀ(1ꢀnitrocyclohexꢀ1ꢀylꢀONNꢀazoxy)furazan (8).
Potassium carbonate (0.058 g, 0.420 mmol) was added at 20 C
to a stirred solution of compound 2 (0.100 g, 0.350 mmol) in
MeOH (6.0 mL). The resulting suspension was stirred at 20 C
for 0.5 h and filtered. The mother liquor was concentrated
in vacuo. The product was purified by preparative TLC (chroꢀ
matographed four times) on silica gel with ethyl acetate—hexꢀ
ane (1 : 7) as an eluent. The yield of compound 8 was 0.081 g
(85%), white crystals, m.p. 57.5—58.0 C (from H2O—PriOH).
MS (ESI), m/z: 294.0807 [M + Na]+; calculated for C9H13N5O5:
[M + Na]+ 294.0809. IR (KBr), /cm–1: 1588 (vs, furazan);
1567 (vs, asymm., NO2); 1499 (s, N=NO); 1425 (s, symm.,
NO2); 1261 (m, N=NO). 1H NMR (acetoneꢀd6), : 1.66 (m, 2 H,
CH2(CH2CH2)2); 1.80 (m, 4 H, CH2(CH2CH2)2); 2.78 (m, 4 H,
(CH2)2CNO2); 4.20 (s, 3 H, Me). 13C NMR (75 MHz, acetꢀ
oneꢀd6), : 23.0 (CH2(CH2CH2)2), 23.9 (CH2(CH2CH2)2),
33.7 ((CH2)2CNO2), 60.2 (Me), 117.2 ((CH2)2CNO2), 147.8
(C—N=NO), 162.5 (C—OMe). The signals in the spectrum
were assigned using HMBC experiments. 14N NMR (22 MHz,
4ꢀMethoxyꢀ3ꢀ(5ꢀmethoxyꢀ2,2ꢀdimethylꢀ1,3ꢀdioxanꢀ5ꢀylꢀ
ONNꢀazoxy)furazan (11). Metallic sodium (0.036 g, 1.57 mmol)
was dissolved in MeOH (2.0 mL), whereupon a solution of comꢀ
pound 3 (0.100 g, 0.314 mmol) in MeOH (1.0 mL) was added at
20 C with stirring. The resulting mixture was kept at 20 C for
0.5 h. The solvent was removed in vacuo. The product was puriꢀ
fied by preparative TLC (chromatographed three times) on
silica gel with ethyl acetate—hexane (1 : 3) as an eluent. The
yield of compound 11 was 0.086 g (87%), white crystals, m.p.
48.0—49.5 C (from hexane). MS (ESI), m/z: 311.0953 [M + Na]+;
calculated for C10H16N4O6: [M + Na]+ 311.0962. IR (KBr),
/cm–1
: 1592 (vs, furazan); 1501 (vs, N=NO); 1254
acetoneꢀd6), : –42.1 (NO,  = 64 Hz); –2.0 (NO2,
0.5 = 71 Hz).
(m, N=NO). 1H NMR (acetoneꢀd6), : 1.38, 1.46 (both s,
3 H, C—Me); 3.49 (s, 3 H, C(NON)O—Me), 4.15 (s, 3 H,
O—Me); 4.18, 4.62 (both d, 4 H, CH2, J = 13.20 Hz). 13C NMR
(75 MHz, acetoneꢀd6), : 22.3, 24.1 (both C—Me), 52.7
(C(NON)O—Me), 59.7 (O—Me), 62.9 (CH2), 99.7 (CMe2),
103.2 (C(NON)O—Me), 148.2 (C—N=NO), 161.9 (C—OMe).
The signals in the spectrum were assigned using HMBC experiꢀ
ments. 14N NMR (22 MHz, acetoneꢀd6), : –27.8 (NO,
0.5 = 180 Hz).
1,2ꢀBis[3ꢀ(2,2ꢀdimethylꢀ5ꢀnitroꢀ1,3ꢀdioxanꢀ5ꢀylꢀONNꢀazꢀ
oxy)furazanꢀ4ꢀyloxy]ethane (12). Potassium carbonate (0.045 g,
1.05 mmol) was added at 20 C to a stirred solution of compound 3
(0.100 g, 0.314 mmol) and HOCH2CH2OH (0.011 g, 0.173 mmol)
in dry MeCN (0.4 mL). The resulting suspension was stirred at
20 C for 96 h and filtered. The mother liquor was concentrated
in vacuo. The residue was separated into two fractions by preꢀ
parative TLC (chromatographed four times) on silica gel with
ethyl acetate—hexane (1 : 2) as an eluent. First fraction (Rf 0.85):
compound 12 (0.059 mg, 62%), yellow oil. MS (ESI), m/z:
605.1541 [M + H]+; calculated for C18H24N10O14: [M + H]+
605.1546. IR (KBr), /cm–1: 1594 (vs, furazan); 1576 (vs,
asymm., NO2); 1509 (s, N=NO); 1380 (s, symm., NO2); 1249
(m, N=NO). 1H NMR (acetoneꢀd6), : 1.48, 1.51 (both s,
6 H, Me); 4.91 (s, 8 H, (CH2)2CNO2); 4.94 (s, 4 H, CH2).
13C NMR (75 MHz, acetoneꢀd6), : 21.6, 24.3 (both Me), 62.6
((CH2)2CNO2), 71.3 (CH2), 100.9 (CMe2), 107.4 (C—NO2),
147.4 (C—N=NO), 161.6 (C—OCH2). The signals in the specꢀ
trum were assigned using HMBC experiments. 14N NMR
(22 MHz, acetoneꢀd6), : –50.5 (2 NO, 0.5 = 73 Hz); –11.6
(2 NO2, 0.5 = 86 Hz). Second fraction (Rf 0.35): compound 13
(0.007 mg, 7%).
0.5
3ꢀ(2,2ꢀDimethylꢀ5ꢀnitroꢀ1,3ꢀdioxanꢀ5ꢀylꢀONNꢀazoxy)ꢀ4ꢀ
methoxyfurazan (9). A. Potassium carbonate (0.052 g, 0.377 mmol)
was added at 20 C to a stirred solution of compound 3 (0.100 g,
0.314 mmol) in MeOH (6.0 mL). The resulting suspension was
stirred at 20 C for 0.5 h and filtered. The mother liquor was
concentrated in vacuo. The product was purified by preparative
TLC (chromatographed five times) on silica gel with ethyl acetꢀ
ate—hexane (1 : 5) as an eluent. The yield of compound 9 was
0.087 g (92%), white crystals, m.p. 78.5—79.0 C (from hexane).
MS (ESI), m/z: 326.0715 [M + Na]+; calculated for C9H13N5O7:
[M + Na]+ 326.0707. IR (KBr), /cm–1: 1593 (vs, furazan);
1576 (vs, asymm., NO2); 1501 (s, N=NO); 1377 (s, asymm.,
NO2); 1257 (m, N=NO). 1H NMR (acetoneꢀd6), : 1.49, 1.54
(both s, 3 H, C—Me); 4.20 (s, 3 H, O—Me); 4.94 (s, 4 H, CH2).
13C NMR (75 MHz, acetoneꢀd6), : 21.4, 24.5 (both C—Me),
60.0 (O—Me), 62.6 (CH2), 100.9 (CMe2), 107.4 (C—NO2),
147.3 (C—N=NO), 162.5 (C—OMe). The signals in the spectrum
were assigned using HMBC experiments. 14N NMR (22 MHz,
acetoneꢀd6), : –51.5 (NO,  = 64 Hz); –11.5 (NO2,
0.5
0.5 = 81 Hz).
B. Potassium hydroxide (0.023 g, 0.408 mmol) was added at
20 C to a solution of compound 3 (0.100 g, 0.314 mmol) in
MeOH (6.0 mL). The resulting solution was stirred at 20 C for
0.5 h and concentrated in vacuo. The product was purified
by preparative TLC (chromatographed five times) on silica gel
with ethyl acetate—hexane (1 : 5) as an eluent. The yield of
compound 9 was 0.077 g (81%). This sample is identical in
physicochemical characteristics with that obtained according to
procedure A.

520
Russ.Chem.Bull., Int.Ed., Vol. 62, No. 2, February, 2013
Parakhin and Luk´yanov
3ꢀ(2,2ꢀDimethylꢀ5ꢀnitroꢀ1,3ꢀdioxanꢀ5ꢀylꢀONNꢀazoxy)ꢀ
We are grateful to M. I. Struchkova, A. S. Shashkov,
E. D. Lubuzh, N. G. Kolotyrkina, V. I. Kadentsev, and
A. O. Chizhov for performing spectroscopic measureꢀ
ments.
4ꢀ(2ꢀhydroxyethoxy)furazan (13). MS (ESI), m/z: 334.0983
[M + H]+; calculated for C10H15N5O8: [M + H]+ 334.0993.
IR (KBr), /cm–1: 3435 (m, OH); 1593 (vs, furazan); 1581 (vs,
asymm., NO2); 1509 (s, N=NO); 1381 (s, symm., NO2); 1253
(s, N=NO). 1H NMR (acetoneꢀd6), : 1.46, 1.52 (both s,
3 H, Me); 3.93 (m, 2 H, CH2OH); 4.19 (br.s, 1 H, OH); 4.52
(t, 2 H, CH2CH2OH, J = 4.50 Hz); 4.92 (q, 4 H, (OCH2)2CNO2,
J = 12.00 Hz). 13C NMR (75 MHz, acetoneꢀd6), : 21.6,
24.7 (both Me), 60.2 (CH2OH), 62.8 ((CH2)2CNO2),
75.7 (CH2CH2OH), 101.0 (CMe2), 107.7 (C—NO2), 147.6
(C—N=NO), 162.2 (C—OCH2). The signals in the spectrum
were assigned using HMBC experiments. 14N NMR (22 MHz,
References
1. O. A. Luk´yanov, V. V. Parakhin, G. V. Pokhvisneva, T. V.
Ternikova, Russ. Chem. Bull. (Int. Ed.), 2012, 61, 355 [Izv.
Akad. Nauk, Ser. Khim., 2012, 353].
2. O. A. Luk´yanov, V. V. Parakhin, Russ. Chem. Bull. (Int. Ed.),
2012, 61, 8 [Izv. Akad. Nauk, Ser. Khim., 2012, 1566].
3. A. B. Sheremetev, O. V. Kharitonova, E. V. Mantseva, V. O.
Kulagina, E. V. Shatunova, N. S. Aleksandrova, T. M. Melꢀ
nikova, E. A. Ivanova, D. E. Dmitriev, V. A. Eman, I. L.
Yudin, V. S. Kuzmin, Yu. A. Strelenko, T. S. Novikova, O. V.
Lebedev, L. I. Khmelnitskii, Zh. Org. Khim., 1999, 35, 1555
[Russ. J. Org. Chem. (Engl. Transl.), 1999, 35, 1525].
4. A. B. Sheremetev, E. V. Shatunova, B. B. Averkiev, D. E.
Dmitriev, V. A. Petukhov, M. Yu. Antipin, Heteroat. Chem.,
2004, 15, 131.
5. A. B. Sheremetev, O. V. Kharitonova, T. M. Melnikova, T. S.
Novikova, V. S. Kuzmin, L. I. Khmelnitskii, Mendeleev Comꢀ
mun., 1996, 141.
6. A. B. Sheremetev, S. E. Semenov, V. S. Kuzmin, Yu. A. Streꢀ
lenko, S. L. Ioffe, Chem. Eur. J., 1998, 4, 1023.
acetoneꢀd6), : –51.7 (NO,  = 90 Hz); –11.3 (NO2,
0.5
0.5 = 76 Hz).
Bis[3ꢀ(2,2ꢀdimethylꢀ5ꢀnitroꢀ1,3ꢀdioxanꢀ5ꢀylꢀONNꢀazoxy)ꢀ
furazanꢀ4ꢀyl] ether (14). Sodium carbonate (0.037 g, 0.345 mmol)
was added at 20 C to a stirred solution of compound 3 (0.100 g,
0.314 mmol) in dry MeCN (6.0 mL). The resulting solution was
kept at 65 C for 5 h and concentrated in vacuo. The product was
purified by preparative TLC (chromatographed four times)
on silica gel with ethyl acetate—hexane (1 : 4) as an eluent.
The yield of compound 14 was 0.055 g (63%), white crystals,
m.p. 99.0—100.0 C (from hexane). MS (ESI), m/z: 583.1111
[M + Na]+; calculated for C16H20N10O13: [M + Na]+ 583.1104.
IR (KBr), /cm–1: 1590 (s, furazan); 1577 (vs, asymm., NO2);
1484 (s, N=NO); 1379 (m, symm., NO2); 1258 (m, N=NO).
1H NMR (acetoneꢀd6), : 1.49, 1.52 (both s, 6 H, Me); 4.93
(s, 8 H, CH2). 13C NMR (75 MHz, acetoneꢀd6), : 21.8, 24.2
(both Me), 62.6 (CH2), 101.1 (CMe2), 107.9 (C—NO2), 147.8
(C—N=NO), 158.4 (C—O). The signals in the spectrum were
assigned using HMBC experiments. 14N NMR (22 MHz, acetꢀ
7. O. A. Luk´yanov, G. V. Pokhvisneva, T. V. Ternikova, N. I.
Shlykova, M. E. Shagaeva, Russ. Chem. Bull. (Int. Ed.), 2011,
60, 1703 [Izv. Akad. Nauk, Ser. Khim., 2011, 1678].
oneꢀd6), : –48.2 (2 NO,  = 134 Hz); –12.5 (2 NO2,
0.5 = 108 Hz).
Received November 19, 2012;
in revised form February 6, 2013
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