N-substituted tetrahydro-1,3-oxazines and -oxazolidines. 2. Nitration of N-(ω-acylamino-β,β-dinitroalkyl)tetrahydro-1,3-oxazines and -oxazolidines

Article abstract of DOI:10.1007/s11172-009-0287-9

Nitration of N-(ω-acylamino0-β,β-dinitroalkyl)tetrahydro-1, 3-oxazines and N-(ω-acylamino-β,β-dinitroalkyl)oxazolidines resulted in O-nitrates bearing amide, dinitromethylene, and nitroamine groups. It was found that nitration can be accompanied by N-hydr

Full text of DOI:10.1007/s11172-009-0287-9

Russian Chemical Bulletin, International Edition, Vol. 58, No. 10, pp. 2103—2108, October, 2009
2103
NꢀSubstituted tetrahydroꢀ1,3ꢀoxazines and ꢀoxazolidines.
2.* Nitration of Nꢀ(ωꢀacylaminoꢀβ,βꢀdinitroalkyl)tetrahydroꢀ1,3ꢀoxazines
and ꢀoxazolidines
A. G. Korepin,a P. V. Galkin,a E. K. Perepelkina,a N. M. Glushakova,a I. L. Eremenko,b and L. T. Eremenkoa†
aInstitute of Problems of Chemical Physics, Russian Academy of Sciences,
1 prosp. Akad. Semenova, 142432 Chernogolovka, Moscow Region, Russian Federation.
Fax: +7 (496) 515 3588. Eꢀmail: agkor@icp.ac.ru
bN. S. Kurnakov Institute of General and Inorganic Chemistry, Russian Academy of Sciences,
31 Leninsky prosp., 119991 Moscow, Russian Federation.
Fax: +7 (495) 952 1279. Eꢀmail: ilerem@igic.ras.ru
Nitration of Nꢀ(ωꢀacylaminoꢀβ,βꢀdinitroalkyl)tetrahydroꢀ1,3ꢀoxazines and Nꢀ(ωꢀacylamiꢀ
noꢀβ,βꢀdinitroalkyl)oxazolidines resulted in Oꢀnitrates bearing amide, dinitromethylene, and
nitroamine groups. It was found that nitration can be accompanied by Nꢀhydroxymethylation
of the amide group. Three nitrates synthesized were tested for, and exhibited good level of,
cardioprotection.
Key words: Cꢀ and Oꢀaminomethylation, (acylamino)dinitroalkanes, Nꢀ(ωꢀacylaminoꢀβ,βꢀ
dinitroalkyl)tetrahydroꢀ1,3ꢀoxazines and Nꢀ(ωꢀacylaminoꢀβ,βꢀdinitroalkyl)oxazolidines, nitraꢀ
tion, Oꢀnitrates, acute toxicity, cardioprotection.
In our laboratories, we have previously found2 that
nitration of Nꢀsubstituted tetrahydroꢀ1,3ꢀoxazines, which
are the aminomethylation products of some NH acids (for
example, isatin and succinimide), furnished amino alcoꢀ
hol nitrates (Scheme 1).
In continuation of the research in chemistry of Nꢀsubꢀ
stituted tetrahydroꢀ1,3ꢀoxazines and oxazolidines,2 which
may be regarded as sources of potential bioactive comꢀ
pounds,3 we set a goal in the present work to synthesize
(acylamino)dinitroalkane derivatives by Cꢀ and Oꢀaminoꢀ
methylation and subsequent nitration of the resulting comꢀ
pounds (Scheme 2).
Scheme 1
In recent decades, the role of nitric oxide in vital activꢀ
ity of organisms was discovered, and, as a result, the sigꢀ
nificance of the Cꢀ, Nꢀ and Oꢀnitro compounds, as promꢀ
ising exogenous NO donors, greatly increased. The range
of nitro compounds that could play a role of NO donors
R is NH acid residue
Scheme 2
R = Me, Ph; n = 1, 2; m = 2, 3
* For Part 1, see Ref. 1.
† Deceased.
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 10, pp. 2040—2044, October, 2009.
1066ꢀ5285/09/5810ꢀ2103 © 2009 Springer Science+Business Media, Inc.

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Russ.Chem.Bull., Int.Ed., Vol. 58, No. 10, October, 2009
Korepin et al.
Scheme 3
2
R
n
a
Me
2
b
Me
1
с
Ph
1
3
R
n
a
Me
2
b
Me
1
c
Me
1
d
Ph
1
e
Ph
1
m
2
3
2
2
3
includes Oꢀnitro compounds, Cꢀ and Nꢀnitro derivatives4
nitration of the aminomethylation products of (acylꢀ
amino)dinitroalkanes with conc. HNO3 resulted excluꢀ
sively in Nꢀnitro derivatives. In this case, no formation of
ammonium nitrates was observed (Scheme 4 and 5).
This finding could undoubtedly be explained by lower
basicity of the amine nitrogen due to the electronꢀwithꢀ
drawing effect of the dinitromethylene group, which is
enhanced by the neighboring amide group with the inducꢀ
tive (–M)ꢀeffect. The CH acids used in the present work
are stronger acids than the NH acids. For example, pKa of
succinimide is 9.66,10 while pKa of 1,1ꢀdinitroalkanes are
about 5.21—5.53 (see Ref. 11).
The nitration at low or room temperatures resulted in
Nꢀhydroxymethylation of the amide group along with degꢀ
radation and nitration. In our opinion, multistep transforꢀ
mations of tetrahydrooxazines and oxazolidines 3 in
HNO3 should begin from the protonation of the ring niꢀ
trogen and cleavage of the N—C bond of the N—C—O
fragment. The mechanism of Nꢀhydroxymethylation of
the amide group, which could involve either formaldeꢀ
and extends continuously.5,6
Results and Discussion
The starting CH acids, acylamino dinitroalkanes 2a—c,
were synthesized from trinitromethane by the known meꢀ
thods.7—9
Used in nitration previously unknown Nꢀ(ωꢀacylamiꢀ
noꢀβ,βꢀdinitroalkyl)tetrahydroꢀ1,3ꢀoxazines and Nꢀ(ωꢀ
acylaminoꢀβ,βꢀdinitroalkyl)oxazolidines 3a—e were preꢀ
pared under conditions similar to those for a 1,1ꢀdinitroꢀ
ethane derivative2 (Scheme 3).
The Cꢀ and Oꢀaminomethylation proceeded smothly
in water or in aqueous ethanol at room temperature and
completed in a few hours. The IR, 1H NMR spectral data
and elemental analysis data of the compounds synthesized
are given in Table 1.
In contrast to nitration of the compounds synthesized
by aminomethylation of the NH acids (see Scheme 1),
Scheme 4
a
2
2
b
1
3
c
1
2
n
m
Scheme 5
m = 2 (a, d), 3 (b, e)

Nitration of N,Oꢀheterocycles
Russ.Chem.Bull., Int.Ed., Vol. 58, No. 10, October, 2009
2105
ences. The signals were assigned using the data obtained previꢀ
ously for the related compounds.1,2 The starting compounds
2a—c were synthesized in accordance with the known methꢀ
ods.7—9 Freshly distilled HNO3 (d = 1.51 g•cm–3) was used for
nitration.
hyde formation from the oxazacycle followed by its reacꢀ
tion with the amide group or intermediate A, was not studꢀ
ied. However, an attempt to
confirm the first pathway, viz.,
to effect Nꢀhydroxymethylaꢀ
Spectral data and elemental analysis data of the compounds
synthesized are listed in Tables 1 and 2.
tion by adding formaldehyde
to a solution of compound 2b
Synthesis of compounds 3a—e (general procedure). An (acylꢀ
amino)dinitroalkane (10 mmol) was suspended in water (or
CH2Cl2) or dissolved in MeOH. To the resulting suspension or
solution, the solution of an amino alcohol (10 mmol) in water
and formaldehyde (20 mmol, as a 30% solution in water) were
added with stirring at 10—14 °C. The reaction mixture was kept
at 18—22 °C for 4 h. The products were isolated either by filtraꢀ
tion of the resulting precipitate or by extraction with CH2Cl2.
Solid compounds were recrystallized from appropriate solvents.
1ꢀAcetylaminoꢀ3,3ꢀdinitroꢀ4ꢀ(oxazolidinꢀ3ꢀyl)butane (3a). To
compound 2a (1.91 g, 10 mmol), 2ꢀaminoethanol (0.61 g,
10 mmol), formaldehyde (2 g, 20 mmol), CH2Cl2 (20 mL), and
water (4 mL) were added. The organic layer was separated, exꢀ
tracted with CH2Cl2, the combined organics was washed with
water, dried with MgSO4 and treated with charcoal. Evaporaꢀ
tion of the solvent afforded the title compound 3a as a colorless
oil (2.34 g, 85%), nD20 1.5002.
1ꢀAcetylaminoꢀ2,2ꢀdinitroꢀ3ꢀ(tetrahydroꢀ1,3ꢀoxazinꢀ3ꢀyl)ꢀ
propane (3b) was synthesized from 2b (1.77 g, 10 mmol),
3ꢀaminopropanol (0.75 g, 10 mmol), and formaldehyde (2 g,
20 mmol) in CH2Cl2 (4 mL) and water (6 mL). Recrystallization
from dichloroethane—ethyl acetate mixture furnished compound
3b in the yield of 2.1 g (76%), m.p. 144—145 °C (decomp.).
1ꢀAcetylaminoꢀ2,2ꢀdinitroꢀ3ꢀ(oxazolidinꢀ3ꢀyl)propane (3c)
was synthesized from 2b (1.77 g, 10 mmol), 2ꢀaminoethanol
(0.61 g, 10 mmol), and formaldehyde (2 g, 20 mmol) in water
(8 mL). Recrystallization from carbon tetrachloride—chloroꢀ
form afforded compound 3c (1.88 g, 72%), m.p. 114—115 °C.
1ꢀBenzoylaminoꢀ2,2ꢀdinitroꢀ3ꢀ(oxazolidinꢀ3ꢀyl)propane (3d)
was synthesized from 2c (2.39 g, 10 mmol), 2ꢀaminoethanol
(0.61 g, 10 mmol), and formaldehyde (2 g, 20 mmol) in water—carꢀ
bon tetrachloride—benzene mixture. Recrystallization from carꢀ
bon tetrachloride—chloroform yielded compound 3d (2.24 g,
69%), m.p. 117—118 °C.
in HNO3, failed; the starting
2b was recovered.
Nitration of compounds 3d,e proceeded not only at
the N and O atoms, but also at the C atoms of the benzene
ring. The Cꢀnitration at low temperature proceeded selecꢀ
tively in the position 3. However, with an increase in the
tempetature, other positions became involved to yield
a mixture of Cꢀnitro isomers; no individual compounds
were isolated.
Structures of all synthesized compounds 3—6 were esꢀ
tablished on the basis of IR and NMR spectroscopy and
elemental analysis.
In our opinion, both series of the compounds syntheꢀ
sized, i.e., tetrahydroꢀ1,3ꢀoxazines and oxazolidines as
well as their nitration products, are of interest due to poꢀ
tential biological activity. Three selected nitrates, 4c, 5a,
and 5c, were subjected to the primary trials. As a reference
compound, Nꢀ(2ꢀnitroxyethyl)nicotinamide (Nicoranꢀ
dil12), a modern effective pharmaceutical used in cardiolꢀ
ogy, was used. Acute toxicity (LD50, mg kg–1) on the gray
mice was determined at the Laboratory of Experimental
Chemotherapy of Tumors, Institute of Problems of Chemꢀ
ical Physics, Russian Academy of Sciences. Cardiological
activity was determined at the AllꢀRussian Scientific Cenꢀ
ter for Safety of Biologically Active Substances (by adꢀ
ministrating a dose of a compound to white rats suffered
from the induced myocardial infarction with subsequent
mearsurment of necrosis zone in relation to ischemia
zone). The LD50 values and necrosisꢀtoꢀischemia zone
ratios were found to be 575 and 48.4; 475 and 39.0; 820
and 40.3; 475 and 42.0 for compounds 4c, 5a, 5c, and
Nicorandil, respectively. Thus, compounds 4c and 5c demꢀ
onstrated lower toxicity as compared with Nicorandil,
while compounds 5a and 5c showed higher of cardioproꢀ
tective activity.
1ꢀBenzoylaminoꢀ2,2ꢀdinitroꢀ3ꢀ(tetrahydroꢀ1,3ꢀoxazinꢀ3ꢀ
yl)propane (3e) was synthesized from 2c (2.39 g, 10 mmol),
3ꢀaminopropanol (0.75 g, 10 mmol), and formaldehyde (2 g,
20 mmol) in a water—carbon tetrachloride—benzene mixture.
Recrystallization from carbon tetrachloride—benzene mixture
afforded compound 3e in the yield of 2.43 g (72%), m.p. 84—85 °C.
Synthesis of compounds 4—6 (general procedure). To HNO3
(250 mmol), the corresponding compound 3a—e (10 mmol) was
added with stirring at 0—4 °C. The reaction mixture was kept at
10 °C for 2 h (method A) or at 60 °C for 0.5 h (method B). The
resulting mixture was poured onto ice, the precipitate that formed
was filtered off, washed with water, dried and reecrystallized
from an appropriate solvent.
In summary, the synthetic method toward novel Cꢀ,
Nꢀ, Oꢀnitro compounds has been developed. Low toxicity
and cardioprotective activity of the obtained compounds
reflected the importance of the synthesis of new nitro comꢀ
pounds, which could serve as a source of pharmaceuticals.
Experimental
7ꢀ[(Acetyl)(hydroxymethyl)amino]ꢀ3,5,5ꢀtrinitroꢀ1ꢀnitroxyꢀ
3ꢀazaheptane (4a) was synthesized by the method A from comꢀ
pound 3a (2.76 g). Recrystallization from CHCl3—PriOH mixꢀ
ture afforded 4a in the yield of 2.0 g (52%), m.p. 102—103 °C
(decomp.).
The IR spectra were recorded on a Specord M82 spectroꢀ
photometer (KBr pellets). The 1H NMR spectra were meaꢀ
sured on an NMR spectrometer with superconducting magnet
(294 MHz), which was developed and constructed at the Instiꢀ
tute of Problems of Chemical Physics, Russian Academy of Sciꢀ
7ꢀ[(Acetyl)(hydroxymethyl)amino]ꢀ4,6,6ꢀtrinitroꢀ1ꢀnitroxyꢀ
4ꢀazaheptane (4b) was synthesized by the method A from

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Korepin et al.
Tables 1. Physicochemical and spectral data of Nꢀ((ωꢀacylꢀβ,βꢀdinitroalkyl)tetrahydroꢀ1,3ꢀoxazines and ꢀoxazolidines
Comꢀ
pound
Found
Calculated
Molecular
formula
IR, ν/cm–1
1H NMR (δ, J/Hz)*
(%)
C
H
N
3a
3b
3c
3d
39.20 6.00
39.13 5.84
20.32
20.28
С9Н16N4O6
С9Н16N4O6
С8Н14N4O6
—
1.94 (s, 3 H, CH3CO); 2.86 (m, 2 H, CH2CH2C(NO2)2);
3.00 (t, 2 H, NCH2CH2); 3.32 (m, 2 H, NHCH2);
3.70 (t, 2 H, CH2CH2O, 3JCH,CH = 6.7);
3.75 (s, 2 H, (NO2)2CCH2N); 4.22 (s, 2 H, NCH2O);
7.38 (br.t, 1 H, NH, 3JNH,CH = 6.0)
39.39 6.09
39.13 5.84
20.48
20.28
3252, 3214 (NH);
1.60 (br.m, 2 H, CH2); 1.90 (s, 3 H, CH3CO);
1665 (С=O); 1577; 2.91 (t, 2 H, NCH2, 3JCH,CH = 5.4); 3.78 (t, 2 H, CH2O,
1552, 1328 (NO2);
1052 (C—O—C)
3JCH,CH = 5.0); 3.85 (s, 2 H, C(NO2)2CH2N); 4.20 (s, 2 H,
NCH2O); 4.30 (d, 2 H, NHCH2C(NO2)2, 3JCH,NH = 6.6);
6.80 (br.s, H, NH)
36.53 5.39
36.64 5.38
21.30
21.37
3254, 3218 (NH);
1.93 (s, 3 H, CH3CO); 2.99 (t, 2 H, NCH2,
1667 (C=O); 1577, 3JCH,CH = 5.7); 3.68 (t, 2 H, CH2O, 3JCH,CH = 5.7);
1559, 1337 (NO2);
1022 (C—O—C)
3.70 (s, 2 H, C(NO2)2CH2N); 4.20 (s, 2 H, NCH2O);
4.40 (d, 2 H, NHCH2C(NO2)2, 3JCH,CH = 6.0); 6.69
(t, H, NH, 3JNH,CH = 6.0)
3.02 (t, 2 H, NCH2, 3JCH,CH ≅ 6.3); 3.65 (t, 2 H,OCH2,
48.54 5.20
48.15 4.97
17.00
17.28
С13Н16N4O6 3345, 1515 (NH);
1650 (C=O); 1600, 3JCH,CH ≅ 6.3); 3.80 (s, 2 H, C(NO2)2CH2N); 4.23
1580, 1485, 1445
(s, 2 H, NCH2O); 4.59 (d, 2 H, NHCH2C(NO2)2,
(C—C); 1565, 1335 3JCH,CH = 6.3); 7.38 (br.s, H, NH); 7.40—7.80
(NO2); 1185, 1150, (m, 5 H, CH)
1140 (C—N); 1085,
1065, 1015 (C—O)
3e
49.32 5.51
49.70 5.36
16.27
16.56
С14Н18N4O6 3389, 3339 (NH);
1.66 (br.m, 2 H, CCH2C); 2.98 (t, 2 H, NCH2,
1652 (C=O); 1601, 3JCH,CH = 5.0); 3.80 (t, 2 H, OCH2, 3JCH,CH = 5.0);
1580, 1487 (C—C); 3.91 (s, 2 H, C(NO2)2CH2N); 4.24 (s, 2 H, NCH2O);
1559, 1340 (NO2);
1094, 1052, 1037,
995 (C—O)
4.52 (d, 2 H, NHCH2C(NO2)2, 3JCH,CH = 6.4);
7.34 (br.s, H, NH); 7.43—7.80 (m, 5 H, CH)
* SiMe4, DMSOꢀd6—CCl4.
Table 2. Physicochemical and spectral data of nitrates 4—6
Comꢀ
pound
Found
Calculated
Molecular
formula
IR, ν/cm–1
1H NMR (δ, J/Hz)*
(%)
C
H
N
4a
27.75 4.25 22.27 С9Н16N6O11 3395 (OH); 1650 (C=O); 2.06 (s, 3 H, CH3CO); 2.86 (m, 2 H, CH2C(NO2)2)2,
3
28.13 4.20 21.87
1640, 1625, 1265 (ONO2); JCH,CH ≅ 6.9); 3.49 (m, 2 H, NCH2, 3JCH,CH ≅ 6.9);
1575, 1325 (CNO2); 1540, 4.07 (br.t, 1 H, CH2OH, 3JOH,CH = 6.7); 4.25 (t, 2 H,
1295 (NNO2); 1045
N(NO2)CH2, 3JCH,CH = 4.4); 4.70 (d, 2 H, NCH2OH,
(C—OH); 850 (O—NO2) 3JCH,CH = 6.7); 4.72 (t, 2 H, CH2ONO2, 3JCH,CH = 4.4);
5.00 (s, 2 H, C(NO2)2CH2NNO2)
4b
4c
28.45 4.30 22.26 С9Н16N6O11 3332 (OH); 1650 (C=O); 2.07 (m, 2 H, CH2, 3JCH,CH = 6.0); 2.14 (s, 3 H, CH3CO);
28.13 4.20 21.87
1637, 1628, 1274 (ONO2); 3.95 (m, 2 H, NCH2CH2, 3JCH,CH = 6.0); 6.25 (br.s, H,
1547,1577, 1337, 1322
(CNO2); 854 (O—NO2)
OH); 4.60 (t, 2 H, CH2ONO2, 3JCH,CH = 6.0);
4.63 (s, 2 H, C(NO2)2CH2N); 5.08 (s, 2 H,
NHCH2C(NO2)2); 4.75 (br.s, 2 H, NCH2OH)
26.40 3.90 22.22 С8Н14N6O11 3218 (OH); 1650 (C=O); 2.13 (s, 3 H, CH3CO); 4,25 (t, 2 H, NCH2CH2,
3
25.95 3.81 22.70
1640, 1271 (ONO2); 1568, JCH,CH = 5.0); 4.7 (s, 2 H, C(NO2)2CH2N);
1322 (CNO2); 1544, 1270 4.76 (d, 2 H, NCH2OH, 3JCH,OH = 6.0); 4.8 (t, 2 H,
(NNO2); 860 (O—NO2)
H2CH2ONO2, 3JCH,CH = 5.0); 5.1 (s, 2 H,
(NO2)2CH2N(NO2); 6.26 (br.t, H, OH, 3JOH,CH = 6.0)
(to be continued)

Nitration of N,Oꢀheterocycles
Table 2 (continued)
Russ.Chem.Bull., Int.Ed., Vol. 58, No. 10, October, 2009
2107
Comꢀ
pound
Found
Calculated
Molecular
formula
IR, ν/cm–1
1H NMR (δ, J/Hz)*
(%)
C
H
N
5a
5b
5c
26.72 4.10 23.62 С8Н14N6O10 3300, 1545 (NH); 1665
1.84 (s, 3 H, CH3CO); 2.82 (t, 2 H, H2C(NO2)2,
27.13 3.98 23.72
(C=O); 1640, 1265
3JCH,CH = 6.6); 3.31 (dt, 2 H, NHCH2, 3JCH,CH
=
(ONO2); 1580, 1330
(CNO2); 1580, 1295
(NNO2); 860 (O—NO2)
= 3JCH,NH = 6.6); 4.25 (t, 2 H, N(NO2)CH2, 4.77 (t, 2 H,
CH2ONO2, 3JCH,CH = 4.5); 3JCH,CH = 4.5); 5.01 (s, 2 H,
C(NO2)2CH2N(N)2)); 6.62 (br.s, 1 H, C(O)NH)
27.00 4.07 23.42 С8Н14N6O10 3328 (NH); 1673 (C=O); 1.94 (s, 3 H, CH3CO); 2.12 (m, 2 H, CH2, 3JCH,CH = 6.9,
3
27.13 3.98 23.72
1631, 1280 (ONO2); 1565, JCH,CH = 5.7); 3.92 (t, 2 H, NCH2, 3JCH,CH = 6.9);
1333 (CNO2); 1541, 1268 4.39 (d, 2 H, NHCH2C(NO2)2, 3JCH,NH = 6.0);
(NNO2); 845 (O—NO2)
4.55 (t, 2 H, CH2ONO2, 3JCH,CH = 5.7);
4.96 (s, 2 H, C(NO2)2CH2NNO2); 6.93 (br.s, H, NH)
1.95 (s, 3 H, CH3CO); 4.26 (t, 2 H, NCH2, 3JCH,CH = 4.7);
4.40 (d, 2 H, NHCH2C(NO2)2, 3JCH,NH = 6.6); 4.27 (t, 2 H,
25.00 3.67 24.36 С7Н12N6O10 3425, 1514 (NH); 1688
24.71 3.56 24.70 (C=O); 1637, 1271
(ONO2); 1571, 1559, 1331 CH2ONO2, 3JCH,CH = 4.7); 5.00 (s, 2 H, C(NO2)2CH2N);
(CNO2); 1532, 1271
6.90 (br.s, H, NH)
(NNO2); 857 (O—NO2)
6a
6b
32.28 3.33 21.00 С13Н15N7O13 1640, 1268 (ONO2); 1630 4.30 (t, 2 H, N(NO2)CH2, 3JCH,CH = 4.5); 4.35 (t, H, OH,
32.71 3.17 20.54
(C=O); 1616, 1487, 1445
(C—C); 1568, 1292
(NNO2); 1552, 1319,
1535, 1352 (CNO2); 857
(O—NO2); 767 (CH)
3JOH,CH = 6.0); 4.72 (d, 2 H, NCH2OH, 3JCH,OH = 6.0);
4.79 (t, 2 H, СH2ONO2, 3JCH,CH = 4.5); 4.92 (s, 2 H,
NCH2C(NO2)2); 5.12 (s, 2 H, C(NO2)2CH2NNO2);
7.72 (t, H, C(3)H, 3J3ꢀ4, 3ꢀ2 = 7.6); 7.89 (d, H, C(2)H,
3J2,3 = 7.6); 8.35 (d, H, C(4)H, 3J4,3 = 7.6);
8.38 (s, H, C(6)H)
34.00 3.39 19.30 С14Н17N7O13 3398 (OH); 1670 (C=O);
2.18 (quint, 2 H, CCH2C, 3JCH,CH ≅ 7.0); 4.03 (t, 2 H,
34.22 3.49 19.26
1646, 1277 (ONO2); 1590, N(NO2)CH2, 3JCH,CH ≅ 7.0); 4.33 (t, H, OH,
1481, 1454 (C—C); 1577, 3JCH,OH = 6.2); 4.59 (t, 2 H, CH2ONO2, 3JCH,CH ≅ 7.0);
1319, 1538, 1355 (CNO2); 4.73 (d, 2 H, NCH2OH, 3JCH,OH = 6.2); 4.90 (s, 2 H,
1570, 1290 (NNO2); 1049 NCH2C(NO2)2); 5.13 (s, 2 H, C(NO2)2CH2NNO2);
(C—OH); 875 (CH)
4.73 (t, H, C(3)H, 3J3ꢀ2, 3ꢀ4 = 7.4); 7.90 (d, H, C(2)H,
3J2,3 = 7.4); 8.38 (d, H, C(4)H, 3J4,3 = 7.4);
8.40 (s, H, C(6)H)
* SiMe4, DMSOꢀd6—CCl4.
compound 3b (2.76 g). Recrystallization from a dichloroꢀ
ethane—PriOH mixture furnished the title compound 4b (0.96 g,
25%), m.p. 113—114 °C (decomp.).
6ꢀ[(Acetyl)(hydroxymethyl)amino]ꢀ3,5,5ꢀtrinitroꢀ1ꢀnitrꢀ
oxyꢀ3ꢀazahexane (4c) was synthesized by the method A
from compound 3c (2.62 g). Recrystallization from dichloroetꢀ
hane afforded compound 4c (1.3 g, 35%), m.p. 114—115 °C
(decomp.).
7ꢀAcetylaminoꢀ3,5,5ꢀtrinitroꢀ1ꢀnitroxyꢀ3ꢀazaheptane (5a)
was synthesized by the method B from compound 3a (2.76 g).
Recrystallization from dichloroethane afforded 5a in the yield of
1.06 g (30%), m.p. 88—90 °C.
7ꢀAcetylaminoꢀ4,6,6ꢀtrinitroꢀ1ꢀnitroxyꢀ4ꢀazaheptane (5b)
was synthesized by the method B from compound 3b (2.76 g).
Recrystallization from dichloroethane furnished compound 5b
(0.74 g, 21%), m.p. 121—122 °C (decomp.).
6ꢀ[(Hydroxymethyl)(3ꢀnitrobenzoyl)amino]ꢀ3,5,5ꢀtrinitroꢀ1ꢀ
nitroxyꢀ3ꢀazahexane (6a) was synthesized by the method A
from compound 3d (3.24 g). Recrystallization from dichloroetꢀ
hane—ethyl acetate mixture yielded compound 6a (2.96 g, 62%),
m.p. 140—141 °C (decomp.).
7ꢀ[(Hydroxymethyl)(3ꢀnitrobenzoyl)amino]ꢀ4,6,6ꢀtrinitroꢀ1ꢀ
nitroxyꢀ4ꢀazaheptane (6b) was synthesized by the method A from
3e (3.38 g). Recrystallization from dichloroethane—ethyl aceꢀ
tate mixture yielded compound 6b (0.83 g, 17%), m.p. 110—111 °C
(decomp.).
References
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6ꢀAcetylaminoꢀ3,5,5ꢀtrinitroꢀ1ꢀnitroxyꢀ3ꢀazahexane (5c)
was synthesized by the method B from 3c (2.62 g). Recrystalliꢀ
zation from dichloroethane furnished compound 5c (0.82 g,
24%), m.p. 124—125 °C (decomp.).

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Received March 11, 2009;
in revised form July 29, 2009