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SIZOVA et al.
Scheme.
H N
NH2
2
NHCOOEt EtOOCHN
EtOOCHN
EtOOCHN
NHCOOEt
NHCOOEt
N
N
O
IV
NH
NH
N
N
O
X
3-furazanylamine providing the corresponding derivatives
(DMSO-d ), δ, ppm: 1.20 t (6H, CH , J 10.5 Hz), 1.95 d
6 3
VIII and IX in quantitative yields.
(3H, CH , J 42.1 Hz), 4.05 q (4H, CH , J 5.5 Hz), 4.95–
3
2
5
.95 m (2H, CH), 6.70–7.90 m (2H, NH). Found, %:
The reaction of monoacetoxy derivative IV with
equiv of diaminofurazane gave rise instead of expected
monosubstituted product to disubstituted compound X in
C 44.47; H 6.87; N 12.37. C H N O . Calculated, %:
C 44.70; H 6.64; N 12.03.
1
13 23
3
8
high yield (91%) (see scheme).
1,2-Di(acetylamino)-1,2-bis(ethoxycarbonyl-
amino)ethane (V). mp 240–241°C (240°C [1]).
In contrast to 1,2-diacetoxy-1,2-bis(acylamino)ethanes
[
(
1] 1,2-diacetoxy-1,2-bis(ethoxycarbonyl-amino)ethane
III) does not form with diaminofurazan the correspond-
1-Acetylamino-1,2,2-tris(ethoxycarbonylamino)-
ethane (VI). mp 237–239°C (decomp.). H NMR spec-
1
ing bicyclic compound. In the course of reaction a gradual
tarring was observed, and we succeeded in separation
of only a little of 1,1,2,2-tetrakis(ethoxycarbonyl-
amino)ethane (VII) (10%).
trum (DMSO-d ), δ, ppm: 1.20 t (6H, CH , J 10.5 Hz),
6
3
1.80 s (3H, CH3), 4.00 d (6H, CH2, J 10.5 Hz), 4.75–
.50 m (2H, CH), 6.05–7.20 m (3H, NH), 7.80 s (1H,
NH). Found, %: C 44.21; H 6.34; N 15.89. C H N O .
5
13 24
4
7
Calculated, %: C 44.82; H 6.94; N 16.08.
Initial 1,2-dihydroxy-1,2-bis(ethoxycarbonylamino)-
ethane (I) and 1-hydroxy-1,2,2-tris(ethoxycarbonyl-
amino)ethane (II) were prepared by procedure [2] in
1
,1,2,2-Tetrakis(ethoxycarbonylamino)ethane
(
VII). mp 277–279°C (276–278°C [2], 274–276°C [3]).
H NMR spectra of compounds V and VII are identical
1
4
1 and 53% yield respectively. Their physicochemical
to the published ones [1–3].
1
characteristics and H NMR spectra are in agreement
with the published data [2].
General procedure of condensation of 1,2-di-
acetoxy-1,2-bis(ethoxycarbonylamino)ethane (I)
and 1-acetoxy-1,2,2-tris(ethoxycarbonylamino)-
ethane (II) with diaminofurazan and 4-phenyl-3-
furazanylamine. To a solution of 0.01 mol of compound
I or II in 15 ml of acetonitrile was added at room
temperature 0.01 mol of diaminofurazan or 0.02 mol of
General procedure of condensation of 1,2-di-
acetoxy-1,2-bis(ethoxycarbonylamino)ethane (I)
and 1-acetoxy-1,2,2-tris(ethoxycarbonylamino)-
ethane (II) with acetamide and urethane. Athorough-
ly ground in a mortar mixture of 0.1 mol of compound I
or II and 0.4 mol of acetamide or urethane was melted
at 100–110°C, then 0.005 mol of p-toluenesulfonic acid
was added to the melt, and the mixture was stirred at the
same temperature for 20 min. The reaction mixture was
cooled, and the residue was washed from excess
acetamide with acetone or from urethane with ether.
4-phenyl-3-furazanylamine, and 0.001 mol of p-toluene-
sulfonic acid. The reaction mixture was stirred at room
temperature for 8 h, the precipitate was filtered off,
O
washed with boiling ethanol, and dried at 50–60° C.
1
,2-Bis(4-phenyl-3-furazanylamino)-1,2-di-
(
ethoxycarbonylamino)ethane (VIII). mp 234–237°C.
H NMR spectrum (DMSO-d ), δ, ppm: 1.20 t (6H, CH ,
1
,2-Diacetoxy-1,2-bis(ethoxycarbonyl-amino)-
1
6
3
1
ethane (III). mp 155–156°C. H NMR spectrum
J 10.5 Hz), 4.00 q (4H, CH , J 5.5 Hz), 6.45 s (2H, CH),
2
(
DMSO-d ), δ, ppm: 1.20 t (6H, CH , J 10.5 Hz), 1.95 s
6 3
6.30 s (2H, NH), 6.70–7.10 m (2H, NH), 7.50– 7.60 m
(6Harom), 7.65–7.80 m (4Harom). Found, %: C 55.57;
H 4.99; N 21.88. C H N O . Calculated, %: C 55.17;
(
6H, CH ), 4.05 q (4H, CH , J 5.5 Hz), 6.20 d (2H, CH,
3
2
J 12.0 Hz), 7.95 s (2H, NH). Found, %: C 44.87; H 6.74;
24
26
8
6
N 8.47. C H N O . Calculated, %: C 45.00; H 6.29;
H 5.02; N 21.44.
1
2
20
2
8
N 8.75.
2
-(4-Phenyl-3-furazanylamino)-1,1,2-tris(ethoxy-
1
-Diacetoxy-1,2,2-tris(ethoxycarbonyl-
carbonylamino)ethane (IX). mp 213–215°C (decomp.).
1
1
amino)ethane (IV). mp 172–174°C. H NMR spectrum
H NMR spectrum (DMSO-d ), δ, ppm: 1.10– 1.25 m
6
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 43 No. 2 2007