4-formylsydnonimine derivatives

Article abstract of DOI:10.1007/s11172-009-0346-2

The procedure for the synthesis of 4-formylsydnonimine derivatives based on the reaction of 4-lithiosydnonimines with (methoxymethylidene)dimethylammonium methyl sulfate was proposed.

Full text of DOI:10.1007/s11172-009-0346-2

Russian Chemical Bulletin, International Edition, Vol. 58, No. 12, pp. 2474—2477, December, 2009
2474
4ꢀFormylsydnonimine derivatives
I. A. Cherepanov, L. H. Kusaeva, I. A. Godovikov, and V. N. Kalinin
A. N. Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences,
28 ul. Vavilova, 119991 Moscow, Russian Federation.
Fax: +7 (499) 135 5085. Eꢀmail: vkalin@ineos.ac.ru
The procedure for the synthesis of 4ꢀformylsydnonimine derivatives based on the reaction of
4ꢀlithiosydnonimines with (methoxymethylidene)dimethylammonium methyl sulfate was proposed.
Key words: sydnonimines, 1,2,3ꢀoxadiazoliumꢀ5ꢀamidines, metallation, (methoxyꢀ
methylidene)dimethylammonium methyl sulfate.
Sydnonimines (1,2,3ꢀoxadiazoliumꢀ5ꢀamidines) are
tive charge. It was confirmed indirectly by the facts that
N(6)ꢀderivatives of sydnonimine form salts with strong
acids and quaternary ammonium salts at the exocyclic
nitrogen atom under the action of strong electrophiles (for
example, methyl iodide).9 The coordination of an electroꢀ
phile to the N(6) atom results in a decrease in the electron
density of the aromatic ring of the mesoionic compound
and prevents electrophilic substitution reaction. An addiꢀ
tional argument is that sydnonimines do not undergo
nitration and sulfonation in acidic medium unlike their
oxygen analogs, sydnones.10,11
Earlier,12 we have shown that N(6)ꢀderivatives of
sydnonimines unsubstituted on С(4) atom 1 smoothly
undergo metallation under the action of BuLi to produce
the corresponding 4ꢀlithio derivatives. Unfortunately, this
kind of lithio derivatives possess low nucleophilicity
and are thermally unstable. Our attempt to introduce
4ꢀlithio derivatives of sydnonimines into the reaction with
dimethylformamide has lead only to decomposition prodꢀ
ucts of mesoionic compound. This problem could be
solved by using (methoxymethylidene)dimethylammoꢀ
nium methyl sulfate (2) as the electrophilic agent, which
is applied in the cases of organometallic compounds with
low reactivity.13—15
The choice of this reagent is caused by its high elecꢀ
trophilicity. It should also be noted that in its reaction
with sydnonimine organolithium derivative intermediate
3 should form, which is stable against the secondary
attack by the organometallic reagent; hydrolysis of 3
affords the target 4ꢀformyl derivative 4 (Scheme 1).
Sydnonimines containing various substituents in both
the position N(3) of the mesoionic ring and the exocyclic
atom N(6) were introduced into this reaction. The results
obtained are presented in Table 1.
one of the most examined representatives of mesoionic
heterocyclic compounds.1,2 Studies on the synthesis and
properties study of sydnonimines are of great interest
mainly due to the wide spectrum of their pharmacological
activities.2 Currently it was shown that sydnonimines are
effective exogenous donors of nitric oxide (NO), which is
an unique intracellular metabolism regulator.3—5
At present, there exists virtually one procedure for the
synthesis of sydnonimines, viz., cyclization of properly
substituted Nꢀnitrosoaminoacetonitrile derivatives. This
considerably limits the range of the representatives of this
promising class of heterocyclic compounds for subsequent
studies.
The aim of the present work is the development of
the procedure for the synthesis of hitherto unknown
4ꢀformylsydnonimine derivatives. The presence of such a
highly reactive fragment as the formyl group in a mesoionic
compound opens wide possibilities for the synthesis of
various, previously unavailable sydnonimine derivatives.
N(6)ꢀAcyl, ꢀsulfonyl, and other N(6) derivatives of
sydnonimines unsubstituted at the C(4) atom of the
mesoionic ring undergo fairly smooth electrophilic subꢀ
stitution. They are brominated under the action of molecuꢀ
lar bromine in the absence of a catalyst6 and mercurated
under the action of mercury salts.7 However, no data on
the direct formylation of sydnonimines under the action
of the Vilsmeier reagent are available. Our attempt to carry
out the direct formylation of N(6)ꢀbenzoylꢀ3ꢀisopropylꢀ
sydnonimine under the action of the Vilsmeier reagent
prepared from dimethylformamide and oxalyl chloride
to produce the desired product, i.e., the corresponding
4ꢀformylderivative, failed. This reaction resulted in a mixꢀ
ture of saltꢀlike products that were difficult to identify.
We explain this result firstly by the fact that the elecꢀ
trophilic reagent attacks the exocyclic nitrogen atom of
the sydnonimine fragment bearing a considerable negaꢀ
As follows from these data, the method is of rather
general character and can be applied to both N(6)ꢀacetyl,
N(6)ꢀbenzoyl, and N(6)ꢀarylsulfonyl derivatives of sydnonꢀ
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 12, pp. 2395—2398, December, 2009.
1066ꢀ5285/09/5812ꢀ2474 © 2009 Springer Science+Business Media, Inc.

4ꢀFormylsydnonimine derivatives
Russ.Chem.Bull., Int.Ed., Vol. 58, No. 12, December, 2009 2475
Scheme 1
Experimental
All reactions with organometallic compounds were carried
out under dry argon in anhydrous solvents. All commercially
available reagents (Aldrich, Acros) were used without additional
purification. Column chromatography was carried out using
Merck Silica gel (40—60 μm). 1H NMR spectra were recorded
on a Bruker WMꢀ400 spectrometer with an operating frequency
of 400 MHz.
The starting reagents and sydnonimines were prepared
MeOCH
according to the known procedures: 1c,16 1d,16 1i,16 1e,17
3ꢀmethylsydnonimine and 3ꢀethylsydnonimine hydrochlorides18
,
3ꢀisopropylsydnonimine and 3ꢀdimethylaminosydnonimine
hydrochlorides16, (2ꢀmethoxyethylamino)acetonitrile19, (methoxyꢀ
methylidene)dimethylammonium methyl sulfate13
.
N(6)ꢀBenzoylꢀ3ꢀmethylsydnonimine (1a). 3ꢀMethylsydnonꢀ
imine hydrochloride (5 g, 0.037 mol) was added to a solution
of benzoyl chloride (5.1 mL, 0.044 mol) in dichloromethane
(70 mL) and then triethylamine (11.8 mL, 0.085 mol) was added
over 15 min at –20 °С. The mixture was kept for 16 h, then
water (50 mL) was added, the aqueous layer was extracted with
dichloromethane (3×50 mL). The combined extract was dried
with sodium sulfate, filtered through a layer of Al2O3 (2×3 cm)
using dichloromethane as the eluent. The solvent was evapoꢀ
rated in vacuo, the residue was recrystallized from isopropyl
alcohol. Compound 1a was obtained in a yield of 4.6 g (61%),
m.p. 224—225 °С. Found (%): C, 59.07; H, 4.51; N, 20.61.
C10H9N3O2. Calculated (%): C, 59.11; H, 4.46; N, 20.68.
1H NMR (CDCl3), δ: 4.20 (s, 3 Н, Me); 7.38—7.51 (m, 3 Н,
m,pꢀH, Ph); 8.19 (s, 1 Н, Н(4)); 8.26—8.30 (m, 2 Н, oꢀH, Ph).
N(6)ꢀBenzoylꢀ3ꢀethylsydnonimine (1b) was prepared analoꢀ
gously to 1a from benzoyl chloride (12 mL, 0.10 mol), 3ꢀethylꢀ
sydnonimine hydrochloride (12.7 g, 0.085 mol) and triethylꢀ
amine (27 mL, 0.20 mol) in dichloromethane (150 mL).
Compound 1b was obtained in a yield of 9.3 g (50.4%),
m.p. 175—176 °С. Found (%): C, 60.95; H, 5.42; N, 19.29.
C11H11N3O2. Calculated (%): C, 60.82; H, 5.10; N, 19.34.
1H NMR (CDCl3), δ: 1.69 (t, 3 Н, Me, J = 7.4 Hz); 4.49 (q,
2 Н, СН2, J = 7.4 Hz); 7.37—7.5 (m, 3 Н, m,pꢀH, Ph); 8.16
(s, 1 Н, Н(4)); 8.22—8.30 (m, 2 Н, оꢀH, Ph).
3ꢀIsopropylꢀN(6)ꢀtosylsydnonimine (1f). A solution of
triethylamine (19.2 mL, 138 mmol) in dichloromethane
(50 mL) was added with vigorous stirring over 1 h to a mixture
of 3ꢀisopropylsydnonimine hydrochloride (15 g, 92 mmol) and
pꢀtoluenesulfonyl chloride (19.3 g, 101 mmol) in dichloroꢀ
methane (150 mL) at –20 °C. The mixture was stirred at room
temperature for 30 min and kept for 16 h. The precipitate was
filtered off and washed with dichloromethane. The solution
obtained was washed with water (50 mL) and 5% solution of
К2СО3, dried with sodium sulfate, concentrated in vacuo, filtered
through the a layer of Al2O3 (2×3 cm) using chloroform as the
eluent. The solution obtained was concentrated in vacuo, the
residue was recrystallized from a mixture of isopropyl alcohol
and petroleum ether (1 : 1.2). Compound 1f was obtained in a
yield of 18.5 g (72%), m.p. 106—108 °С. Found (%): C, 51.56;
H, 5.61; N, 14.82. C12H15N3O3S. Calculated (%): C, 51.23;
H, 5.37; N, 14.94. 1H NMR (CDCl3), δ: 1.7 (d, 6 Н, СН(СН3)2,
J = 6.8 Hz); 2.40 (s, 3 Н, С6Н4СН3); 4.80—4.90 (m, 1 Н,
СНMe2); 7.27 (d, 2 Н, mꢀH, C6Н4, J = 8.0 Hz); 7.52 (s, 1 Н,
Н(4)); 7.87 (d, 2 Н, oꢀH, C6H4, J = 8.0 Hz).
Table 1. Synthesis of 4ꢀformylsydnonimine derivatives
1
R
R´
Yield 4 (%)
a
b
c
d
e
f
g
h
i
Me
CH2Me
CH2Me
CHMe2
CHMe2
CHMe2
(CH2)2OMe
(CH2)2OMe
NMe2
COPh
COPh
COMe
COMe
COPh
61
64
45
64
91
83
38
10
41
64
62
SO2C6H4Me
COPh
SO2C6H4Me
COMe
SO2C6H4Me
COCF3
j
k
NMe2
CHMe2
imines. N(6)ꢀTrifluoroacetyl group also does not prevent
the normal course of the reaction and aldehyde 4k is
produced in satisfactory yield. The method is applicable
for the synthesis of 4ꢀformylsydnonimines containing both
alkyl and dialkylamino groups at the atom N(3). It should
be particularly noted that the presence of the 2ꢀmethoxyꢀ
ethyl group at the atom N(3) of the sydnonimine ring (1g,
1h) reduces considerably the yields of aldehydes; the reacꢀ
tion mixtures contain great amount of decomposition prodꢀ
ucts of sydnonimine organolithium derivative. We explain
this fact by the possibility of the intramolecular chelation
in such 4ꢀlithioorganic derivatives of sydnonimines.
This type of chelation should considerably decrease
the reactivity of sydnonimine organolithium derivative
and lead to the prevalence of sydnonimine ring decompoꢀ
sition over the reaction with an electrophile.
However, the yields in the reaction under study are
satisfactory, and it can be considered as a general procedure
for the synthesis of 4ꢀformylsydnonimine derivatives.

2476
Russ.Chem.Bull., Int.Ed., Vol. 58, No. 12, December, 2009
Cherepanov et al.
3ꢀ(2ꢀMethoxyethyl)sydnonimine hydrochloride. A solution of
sodium nitrite (23 g, 0.33 mol) in water (100 mL) was added
over 30 min with stirring and cooling to –5 °С to a solution
of Nꢀ(2ꢀmethoxyethyl)aminoacetonitrile (36 g, 0.32 mol) and
11 М HCl (29 mL, 0.32 mol) in water (100 mL). After 30 min,
diethyl ether (100 mL) was added to the reaction mixture, the
aqueous layer was extracted with diethyl ether (3×70 mL). The
organic phase was dried with potassium carbonate, filtered
through the a layer of Al2O3. Hydrogen chloride (12.8 g,
0.35 mol) was passed through the obtained solution at –20 °С
with stirring. The mixture was stirred for 2 h at 0 °С, the
precipitate was filtered off and recrystallized from isopropyl
alcohol. 3ꢀ(2ꢀMethoxyethyl)sydnonimine hydrochloride was
obtained in a yield of 45.4 g (79%), m.p. 137—139 °С. Found (%):
C, 33.47; H, 5.63; N, 23.38. C5H10ClN3O2. Calculated (%):
C, 33.44; H, 5.61; N, 23.40. 1Н NMR (DMSOꢀd6), δ: 3.28 (s,
3 Н, MeО); 3.87 (t, 2 Н, СН2N, J = 4.8 Hz); 4.87
(t, 2 Н, MeОСН2, J = 4.8 Hz); 8.10 (s, 1 Н, Н(4)); 10.01 (br.s,
2 Н, NН2).
N(6)ꢀBenzoylꢀ3ꢀ(2ꢀmethoxyethyl)sydnonimine (1g) was preꢀ
pared analogously to 1a from benzoyl chloride (3.9 mL, 0.034 mol),
3ꢀ(2ꢀmethoxyethyl)sydnonimine hydrochloride (5 g, 0.028 mol),
and triethylamine (8.9 mL, 0.064 mol) in methylene chloride
(50 mL). Compound 1g was obtained in a yield of 4.5 g (65%),
m.p. 86—87 °С. Found (%): C, 58.35; H, 5.48; N, 16.86.
C12H13N3O3. Calculated (%): C, 58.29; H, 5.30; N, 16.99.
1H NMR (CDCl3), δ: 3.44 (s, 3 Н, СН3); 3.89 (t, 2 Н, СН2N,
J = 4.8 Hz); 4.62 (t, 2 Н, MeОСН2, J = 4.8 Hz); 7.43—7.54
(m, 3 Н, m,pꢀH, Ph); 8.29 (s, 1 Н, Н(4)); 8.28—8.31 (m, 2 Н,
oꢀH, Ph).
3ꢀ(2ꢀMethoxyethyl)ꢀN(6)ꢀtosylsydnonimine (1h) was preꢀ
pared analogously to 1f from 3ꢀ(2ꢀmethoxyethyl)sydnonimine
hydrochloride (5 g, 0.028 mol), pꢀtoluenesulfonyl chloride (5.9 g,
0.031 mol), and triethylamine (5.8 mL, 0.042 mol) in dichloroꢀ
methane (50 mL). Compound 1h was obtained in a yield of 2.8 g
(34%), m.p. 104—106 °С. Found (%): C, 48.75; H, 5.37;
N, 14.25. C12H15N3O4S. Calculated (%): C, 48.48; H, 5.08;
N, 14.13. 1H NMR (CDCl3), δ: 2.4 (s, 3 Н, СН3Ph); 3.38 (s,
3 Н, СН3О); 3.84 (t, 2 Н, СН2N, J = 4.8 Hz); 4.59 (t, 2 Н,
MeОСН2, J = 4.8 Hz); 7.27 (d, 2 Н, mꢀH, C6Н4, J = 8.5 Hz);
7.61 (s, 1 Н, Н(4)); 7.83 (d, 2 Н, оꢀH, C6Н4, J = 8.5 Hz).
3ꢀDimethylaminoꢀN(6)ꢀtosylsydnonimine (1j) was prepared
analogously to 1f from 3ꢀN,Nꢀdimethylaminosydnonimine
hydrochloride (2 g, 0.012 mol), pꢀtoluenesulfonyl chloride
(2.7 g, 0.013 mol), and triethylamine (2.5 mL, 0.018 mol) in
dichloromethane (50 mL). Compound 1j was obtained in a yield
of 2.5 g (72%), m.p. 81—82 °С. Found (%): C, 46.97; H, 5.29;
N, 19.68. C11H14N4O3S. Calculated (%): C, 46.80; H, 5.00;
N, 19.85. 1H NMR (CDCl3), δ: 2.37 (s, 3 Н, СН3С6Н4); 3.20
(s, 6 Н, NMe2); 7.22 (d, 2 Н, mꢀH, C6Н4, J = 8.5 Hz); 7.44 (s,
1 Н, Н(4)); 7.83 (m, 2 Н, оꢀH, C6Н4, J = 8.5 Hz).
3ꢀIsopropylꢀN(6)ꢀtrifluoroacetylsydnonimine (1k). Trifluoroꢀ
acetic anhydride (10.4 mL, 0.074 mol) was added with stirring
to a solution of 3ꢀisopropylsydnonimine hydrochloride (10 g,
0.062 mol) in dichloromethane (200 mL). Then triethylamine
(20.5 mL, 0.15 mol) was added with stirring at –20 °С over
30 min. The reaction mixture was kept for 16 h. Water (150 mL)
was added, the solution was saturated with potassium carbonate,
the layers were separated, the aqueous layer was extracted with
dichloromethane (3×30 mL). The combined extract was dried
with sodium sulfate, filtered through a layer of silica gel and
concentrated in vacuo. The residue was recrystallized from a
mixture of isopropyl alcohol and petroleum ether (1 : 2).
Compound 1k was obtained in a yield of 12.1 g (88%) 1k,
m.p. 103—104 °С. Found (%): C, 37.71; H, 3.69; N, 18.71.
C7H8F3N3O2. Calculated (%): C, 37.68; H, 3.61; N, 18.83.
1H NMR (CDCl3), δ: 1.77 (d, 6 Н, СН(СН3)2, J = 6.8 Hz);
4.99—5.10 (m, 1 Н, СНMe2); 7.28 (s, 1 Н, H(4)).
N(6)ꢀBenzoylꢀ4ꢀformylꢀ3ꢀmethylsydnonimine
(4a).
N(6)ꢀBenzoylꢀ3ꢀmethylsydnonimine (1a) (0.5 g, 2.46 mmol)
and THF (50 mL) were placed in a threeꢀneck flask (100 mL).
The solution was cooled to –90 °С and 2.5 М solution of BuLi
in hexane (1.1 mL, 2.71 mmol) was added. The mixture was
stirred for 40 min at –90 °С, then (methoxymethylidene)ꢀ
dimethylammonium methyl sulfate (2) (0.61 g, 2.96 mmol) was
added. The reaction mixture was warmed to room temperature
and a saturated solution of sodium hydrogencarbonate (1 mL)
was added. The mixture obtained was dried with sodium sulfate,
filtered through a layer of Al2O3 (2×3 cm) using a mixture of
chloroform and ethyl acetate (5 : 1) as the eluent, the solvent
was evaporated in vacuo. The residue was chromatographed on a
column with SiO2 (30×2 cm, eluent, chloroform—ethyl acetate,
5 : 1) and recrystallized from a mixture of isopropyl alcohol
and petroleun ether (1 : 10). Compound 4a was obtained in a
yield of 0.35 g (61%), m.p. 171—172 °С. Found (%): С, 57.06;
Н, 3.88; N, 18.09. C11H9N3O3. Calculated (%): C, 57.14;
H, 3.92; N, 18.17. 1H NMR (CDCl3), δ: 4.48 (s, 3 Н, Me);
7.35—7.60 (m, 3 Н, m,pꢀH, Ph); 8.22—8.30 (m, 2 Н, oꢀH, Ph);
10.28 (s, 1 Н, СНО).
N(6)ꢀBenzoylꢀ3ꢀethylꢀ4ꢀformylsydnonimine (4b) was preꢀ
pared analogously to 4a from N(6)ꢀbenzoylꢀ3ꢀethylsydnonimine
(1b) (0.5 g, 2.30 mmol), 2.5 М solution of BuLi in hexane
(1.0 mL, 2.53 mmol), and (methoxymethylidene)dimethylꢀ
ammonium methyl sulfate (2) (0.57 g, 2.76 mmol). Compound
4b was obtained in a yield of 0.36 g (64%), m.p. 131—132 °С.
Found (%): С, 59.02; Н, 4.51; N, 17.28. C12H11N3O3. Calculꢀ
ated (%): C, 58.77; H, 4.52; N, 17.13. 1H NMR (CDCl3), δ:
1.67 (t, 3 Н, СН2СН3, J = 7.4 Hz); 4.88 (q, 2 Н, СН2Me,
J = 7.4 Hz); 7.39—7.58 (m, 3 Н, m,pꢀH, Ph); 8.21—8.29 (m,
2 Н, oꢀH, Ph); 10.2 (s, 1 Н, СНО).
N(6)ꢀAcetylꢀ3ꢀethylꢀ4ꢀformylsydnonimine (4c) was prepared
analogously to 4a from N(6)ꢀacetylꢀ3ꢀethylsydnonimine (1с)
(0.5 g, 3.23 mmol), 2.5 М solution of BuLi in hexane (1.4 mL,
3.55 mmol), and compound 2 (0.79 g, 3.87 mmol). Comꢀ
pound 4c (yellow oil) was obtained in a yield of 0.27 g (45%).
Found (%): С, 45.82; Н, 50.5; N, 21.74. C7H9N3O3. Calculꢀ
ated (%): C, 45.90; H, 4.95; N, 22.94. 1H NMR (CDCl3), δ:
1.60 (t, 3 Н, СН2СН3, J = 7.4 Hz); 2.21 (s, 3 Н, COMe); 4.85
(q, 2 Н, СН2Me, J = 7.4 Hz); 10.0 (s, 1 Н, СНО).
N(6)ꢀAcetylꢀ4ꢀformylꢀ3ꢀisopropylsydnonimine (4d) was preꢀ
pared analogously to 4a from N(6)ꢀacetylꢀ3ꢀisopropylsydnonꢀ
imine (1d) (0.5 g, 2.96 mmol), 2.5 М solution of BuLi in hexane
(1.3 mL, 3.26 mmol), and compound 2 (0.73 g, 3.55 mmol).
Compound 4d was obtained in a yield of 0.37 g (64%),
m.p. 31—32 °С. Found (%): С, 48.82; Н, 5.52; N, 21.52.
C8H11N3O3. Calculated (%): C, 48.73; H, 5.62; N, 21.31.
1H NMR (CDCl3), δ: 1.69 (d, 6 Н, СН(СН3)2, J = 6.8 Hz); 2.27
(s, 3 Н, СОMe); 5.60 (m, 1 Н, СНMe2); 9.98 (s, 1 Н, СНО).
N(6)ꢀBenzoylꢀ4ꢀformylꢀ3ꢀisopropylsydnonimine (4e) was
prepared analogously to 4a from N(6)ꢀbenzoylꢀ3ꢀisopropylꢀ
sydnonimine (1e) (0.5 g, 2.16 mmol), 2.5 М solution of BuLi
in hexane (0.95 mL, 2.38 mmol), and compound 2 (0.53 g,

4ꢀFormylsydnonimine derivatives
Russ.Chem.Bull., Int.Ed., Vol. 58, No. 12, December, 2009 2477
2.60 mmol). Compound 4e was obtained in a yield of 0.51 g
(91%), m.p. 112—113 °С. Found (%): С, 60.33; Н, 4.94;
N, 16.34. C13H13N3O3. Calculated (%): C, 60.23; H, 5.05;
N, 16.21. 1H NMR (CDCl3), δ: 1.69 (d, 6 Н, СН(СН3)2,
J = 6.8 Hz); 5.74 (m, 1 Н, СНMe2); 7.41—7.51 (m, m,pꢀH, Ph);
8.24—8.26 (m, 2 Н, оꢀH, Ph); 10.12 (s, 1 Н, СНО).
4ꢀFormylꢀ3ꢀisopropylꢀN(6)ꢀtosylsydnonimine (4f) was preꢀ
pared analogously to 4a from 3ꢀisopropylꢀN(6)ꢀtosylsydnonꢀ
imine (1f) (0.5 g, 1.78 mmol), 2.5 М solution of BuLi in
hexane (0.78 mL, 1.96 mmol), and compound 2 (0.44 mL,
2.14 mmol). Compound 4f was obtained in a yield of 0.46 g
(83%), m.p. 139—140 °С. Found (%): С, 50.58; Н, 4.91;
N, 13.65. C13H15N3O4S. Calculated (%): C, 50.48; H, 4.89;
N, 13.58. 1H NMR (CDCl3), δ: 1.67 (d, 6 Н, СН(СН3)2,
J = 6.8 Hz); 2.44 (s, 3 Н СН3С6Н4); 5.67 (m, 1 Н, СНMe2);
7.33 (d, 2 Н, mꢀH, C6Н4, J = 8.5 Hz); 7.97 (d, 2 Н, oꢀH, C6Н4,
J = 8.5 Hz); 9.68 (s, 1 Н, СНО).
N(6)ꢀBenzoylꢀ4ꢀformylꢀ3ꢀ(2ꢀmethoxyethyl)sydnonimine (4g)
was prepared analogously to 4a from N(6)ꢀbenzoylꢀ3ꢀ
(2ꢀmethoxyethyl)sydnonimine (1g) (0.3 g, 1.22 mmol), 2.5 М
solution of BuLi in hexane (0.54 mL, 1.34 mmol), and comꢀ
pound 2 (0.30 g, 1.46 mmol). Compound 4g was obtained in a
yield of 0.13 g (38%), m.p. 76—77 °С. Found (%): С, 56.31;
Н, 4.82; N, 15.33. C13H13N3O4. Calculated (%): C, 56.72;
H, 4.76; N, 15.27. 1H NMR (CDCl3), δ: 3.35 (s, 3 Н, ОMe);
3.85 (t, 2 Н, NСН2, J = 4.5 Hz); 5.0 (t, 2 Н, СН2O, J = 4.5 Hz);
7.37—7.56 (m, 3 Н, 2 m,pꢀH, Ph); 8.19—8.29 (m, 2 Н, oꢀH,
Ph); 10.2 (s, 1 Н, СНО).
4ꢀFormylꢀ3ꢀ(2ꢀmethoxyethyl)ꢀN(6)ꢀtosylsydnonimine (4h)
was prepared analogously to 4a from 3ꢀ(2ꢀmethoxyethyl)ꢀ
N(6)ꢀtosylsydnonimine (1h) (0.5 g, 1.68 mmol), 2.5 М solution
of BuLi in hexane (0.74 mL, 1.85 mmol), and compound 2
(0.42 g, 2.02 mmol). Compound 4h (yellow oil) was obtained
in a yield of 0.057 g (10%). Found (%): C, 47.85; H, 4.71;
N, 12.84. C13H15N3O5S. Calculated (%): C, 47.99; H, 4.65;
N, 12.92. 1H NMR (CDCl3), δ: 1.2 (s, 3 Н, С6Н4СН3); 3.30 (s,
3 Н, ОСН3); 3.82 (t, 2 Н, NСН2, J = 4.5 Hz); 4.94 (t, 2 Н,
СН2O, J = 4.5 Hz); 7.27 (d, 2 Н, mꢀH, C6Н4, J = 8.5 Hz); 7.97
(d, 2 Н, oꢀH, C6Н4, J = 8.5 Hz); 9.70 (s, 1 Н, СНО).
4ꢀFormylꢀ3ꢀisopropylꢀN(6)ꢀtrifluoroacetylsydnonimine (4k)
was prepared analogously to 4a from N(6)ꢀtrifluoroacetylꢀ
3ꢀisopropylsydnonimine (1k) (0.5 g, 2.24 mmol), 2.5 М solution
of BuLi in hexane (0.99 mL, 2.47 mmol), and compound 2
(0.55 g, 2.69 mmol). Compound 4k was obtained in a yield of
0.35 g (62%), m.p. 78—79 °С. Found (%): С, 38.09; Н, 3.08;
N, 16.71. C8H8F3N3O3. Calculated (%): C, 38.26; H, 3.21;
N, 16.73. 1H NMR (CDCl3), δ: 1.75 (d, 6 Н, СН(СН3)2,
J = 6.8 Hz); 5.73—5.86 (m, 1 Н, СНMe2); 10.14 (s, 1 Н, СНО).
References
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4. V. G. Granik, N. B. Grigor´ev, Oksid azota (NO). Novyi
put´ k poisku lekarstv [Nitric oxide (NO). New way to the
search of medicines], Vuzovskaya kniga, Moscow, 2004, 360
(in Russian).
5. E. Yu. Khmel´nitskaya, V. I. Levina, L. A. Truhacheva,
N. B. Grigor´ev, V. N. Kalinin, I. A. Cherepanov, S. N.
Lebedev, V. G. Granik, Izv. Akad. Nauk, Ser. Khim., 2004,
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1957, 78, 707.
8. V. G. Yashunskii, L. E. Holodov, O. I. Samoilova, Chem.
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Obshch. Khim., 1964, 34, 2050 [J. Gen. Chem. USSR (Engl.
Transl.), 1964, 34].
10. E. E. Nifant´ev, V. S. Blagoveshchensky, A. M. Sokurenko,
L. S. Sklyarsky, Zh. Obshch. Khim., 1974, 44, 108 [J. Gen.
Chem. USSR (Engl. Transl.), 1974, 44].
11. V. G. Yashunskii, V. F. Vasil´eva, Yu. N. Sheinker, Zh.
Obshch. Khim., 1959, 29, 2712 [J. Gen. Chem. USSR (Engl.
Transl.), 1959, 29].
12. I. A. Cherepanov, N. V. Egorova, K. B. Martinovich, V. N.
Kalinin, Dokl. АN, 2000, 374, 64 [Dokl. Chem. (Engl.
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1984, 49, 1288.
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N(6)ꢀAcetylꢀ3ꢀdimethylaminoꢀ4ꢀformylsydnonimine (4i)
was prepared analogously to 4a from N(6)ꢀacetylꢀ3ꢀdimethylꢀ
aminosydnonimine (1i) (0.5 g, 2.94 mmol), 2.5 М solution of
BuLi in hexane (1.3 mL, 3.24 mmol), and compound 2 (0.72 g,
3.53 mmol). Compound 4i was obtained in a yield of 0.24 g
(41%), m.p. 60—61 °С. Found (%): С, 42.44; Н, 5.14; N, 28.36.
C7H10N4O3. Calculated (%): C, 42.42; H, 5.09; N, 28.27.
1H NMR (CDCl3), δ: 2.23 (s, 3 Н, СОMe); 3.23 (s, 6 Н,
NMe2); 9.80 (s, 1 Н, СНО).
3ꢀDimethylaminoꢀ4ꢀformylꢀN(6)ꢀtosylsydnonimine (4j) was
prepared analogously to 4a from 3ꢀdimethylaminoꢀN(6)ꢀtosylꢀ
sydnonimine (1j) (0.4 g, 1.42 mmol), 2.5 М solution of BuLi
in hexane (0.62 mL, 1.56 mmol), and compound 2 (0.35 mL,
1.70 mmol). Compound 4j was obtained in a yield of 0.30 g
(64%), m.p. 135—136 °С. Found (%): С, 46.42; Н, 4.52;
N, 18.06. C12H14N4O4S. Calculated (%): C, 46.45; H, 4.55;
1
N, 18.05. H NMR (CDCl3), δ: 2.40 (s, 3 Н, С6Н4СН3); 3.22
(s, 6 Н, NMe2); 7.39 (d, 2 Н, mꢀH, C6Н4, J = 8.5 Hz); 7.96 (d,
2 Н, oꢀH, C6Н4, J = 8.5 Hz); 9.60 (s, 1 Н, СНО).
Received March 12, 2009