Derivatives of 1,1,2,2-tetraaminoethane: I. Condensation of 1,2-diacetoxy-1,2-bis(acylamino)ethanes with nitrogen-containing nucleophiles

Article abstract of DOI:10.1134/S1070428007020029

Reaction of 1,2-diacetoxy-1,2-bis(acylamino)ethanes with acetamide and urethane gave rise to 1,2-bis(acetylamino)-1,2-bis(acylamino)ethanes and 1,2-bis(acylamino)-1,2-bis(ethoxycarbonylamino)ethanes respectively. Condensation products were isolated of rea

Full text of DOI:10.1134/S1070428007020029

ISSN 1070-4280, Russian Journal of Organic Chemistry, 2007, Vol. 43, No. 2, pp. 170−175. © Pleiades Publishing, Ltd. 2007.
Original Russian Text © E.V. Sizova, V.V. Sizov, M.P. Zelenov, I.V. Tselinskii, 2007, published in Zhurnal Organicheskoi Khimii, 2007, Vol. 43, No. 2,
pp. 178−183.
Derivatives of 1,1,2,2-Tetraaminoethane: I. Condensation
of 1,2-Diacetoxy-1,2-bis(acylamino)ethanes
with Nitrogen-Containing Nucleophiles
E. V. Sizova, V. V. Sizov, M. P. Zelenov, and I. V. Tselinskii
St. Petersburg State Technological Institute, St. Petersburg, 190013 Russia
e-mail: vvsizov@list.ru
Received May 11, 2006
Abstract—Reaction of 1,2-diacetoxy-1,2-bis(acylamino)ethanes with acetamide and urethane gave rise to 1,2-bis-
(acetylamino)-1,2-bis(acylamino)ethanes and 1,2-bis(acylamino)-1,2-bis(ethoxycarbonylamino)ethanes respec-
tively. Condensation products were isolated of reactions between 1,2-diacetoxy-1,2-bis-(acylamino)ethanes with
acetonitrile, diaminofurazan, and 4-phenylfurazan-3-ylamine.
DOI: 10.1134/S1070428007020029
Nowadays the information on acyclic derivatives of
1,1,2,2-tetraaminoethane is very poor notwithstanding the
simplicity of their structure. 1,1,2,2-Tetraaminoethane
proper and also its N,N',N'',N'''-tetraalkyl derivatives were
not described in the literature. Only three representatives
are known of this class compounds: 1,1,2,2-tetrakis(nitro-
amino)ethane (I) obtained by hydrolysis of 1,3,4,6-
tetranitroglycoluril [1–3], N,N',N'',N'''-tetrabenzyl-1,1,2,2-
tetrakis-(acetylamino)ethane (II) isolated in 4% yield as
a result of N,N',N'',N'''-tetrabenzyl-2,4,6,8-tetraaza-
bicyclo[3,3,0]octane hydrogenation [4], and 1,1,2,2-
tetrakis(ethoxycarbonylamino)ethane (III) prepared by
urethane condensation with glyoxal [5, 6].
nucleophiles with 1,2-bis(acylamino)-1,2-ethanediols IV
that are easily obtained from primary and secondary
amides and glyoxal in a weakly basic medium [7–11]
(Scheme 1).
Scheme 1.
R
OH
R
R
OR'
OR'
RH + OHC CHO
R
OH
_
_
IVа IVf
IVа IVe, VI
O
O
(c),
(d),
IV, V, R = NHAc (a), NHBz (b),
N
N
One of the possible synthetic routes to 1,1,2,2-tetra-
aminoethane is the condensation of nitrogen-containing
O
NHCOPr-i(е), R' = Ac; VI, R = NHCOCH(CH3)2, R' = Me.
Ac
Ac
It was noted that whereas in a weakly basic media
diols IV were formed in good yield, in the acid medium it
was impossible to isolate the condensation products [7,
9]. Urethane is an exception for its heating with aqueous
glyoxal in a 10% hydrochloric acid leads to the formation
both of 1,1,2-tris(ethoxycarbonylamino)ethan-2-ol and
1,1,2,2-tetrakis(ethoxycarbonylamino)ethane (III). The
latter formed in 30% yield [6].
H
H
O2N N
N NO2
Bn
Bn
N
N Bn
O2N N
H
N NO2
H
N
N Bn
Ac
Ac
I
II
H
H
EtOOC N
N COOEt
The procedure used for condensation of urethane with
glyoxal is not suitable for the most amides due to their
low hydrolytic stability in the hydrochloric acid. Therefore
we studied the reaction of primary amides (acetamide,
EtOOC N
H
N COOEt
H
III
170

DERIVATIVES OF 1,1,2,2-TETRAAMINOETHANE: I.
171
benzamide, chloroacetamide), and also of urethane with
1,2-bis(acylamino)-1,2-diols IV and their acetoxy
derivatives V in anhydrous environment.
diacetoxyethylenediamides Vd and Ve under more rigid
conditions (150–160°C); no expected derivatives of
tetraaminoethane were obtained, and only gradual tarring
was observed under the given conditions.
The corresponding condensations performed in aprotic
solvents (acetonitrile, DMF) under acid catalysis with
p-toluenesulfonic acid only in a single case of diacetoxy
derivative Va resulted in isolation of 1,1,2,2-tetrakis-
(acetylamino)ethane (VIIa), although in a very low yield
(5%). The higher acidity of the reaction system or
increased temperature led only to fast tarring both in this
and all other cases.
N-Alkyl-substituted amides are known to be obtained
by Ritter reaction of aliphatic, aromatic, and heterocyclic
nitriles with secondary and tertiary alcohols in the presence
of strong acids (85–100% sulfuric acid, phosphoric acid,
benzenesulfonic acid, 90% formic acid, perchloric acid)
[12–14].
We demonstrated that diol IVe in the presence of 90%
sulfuric acid at 0–5°C reacted with acetonitrile forming
target compound VIIe in 85% yield (Scheme 3). The
attempts to involve into the Ritter reaction diols IVa–IVc
under similar conditions failed to give the corresponding
tetraacylaminoethanes VIIa–VIIc apparently due to the
hydrolysis of initial and/or intermediate compounds.
At the same time the use as solvent excess amide (or
urethane) made it possible to synthesize the derivatives
of tetraaminoethane VII and VIII in yields from 30 to
70%.
It was established that the condensation of 1,2-di-
acetoxy-1,2-bis(acylamino)ethanes Va–Vc with acet-
amide and urethane occurred successfully at heating
without solvent for 30 min at 100–110°C under acid
catalysis with p-toluenesulfonic acid (Scheme 2). The
introducing into the reaction dimethoxy derivative VI
under analogous conditions permitted isolation of com-
pounds VIIf and VIIIf in respective yields 42 and 56%.
We established that a reaction in 100% sulfuric acid
with diacetoxy derivatives Va–Vc instead of diols IVa–
IVc provided target compounds VIIa–VIIc in 70–80%
yield. In the course of these studies we found that the
reagents ratio H2SO4(100%)/CH3CN essentially affected
the yield of the final tetrakis(acylamino) derivatives VIIa–
VIIc : By increasing the ratio H2SO4(100%)/CH3CN
from 1:15 to 2:3 (by volume) the yield of compounds
VIIa–VIIc as expected grew (from 50 to 80%).
The study of the effect of the process parameters on
the yield of compounds VII and VIII revealed that raising
the temperature by 20–30°C sharply decreased the yield
of target products because of the fast tarring. The increase
than twice in the amount of catalyst used more resulted
in significant reduction in the yield of derivatives VII and
VIII by the same reason.
The investigation of the reactivity of diacetoxy
derivatives V with respect to other nitrogen-containing
nucleophiles revealed the ease of compounds V
condensation with low-basic amines from a furazan seies
similar in the basicity to the acetamide and urethane.
We failed to carry out the condensation of compounds
Va–Vc with chloroacetamide and benzamide, less basic
than acetamide and urethane, and also to involve into the
reaction with acetamide and urethane less active
The reaction of compounds Va–Vc with diamino-
furazan under mild conditions (at room temperature
in acetonitrile in the presence of a catalytic quantity
of p-toluenesulfonic acid) provided cyclic derivatives
of tetraaminoethane Xa–Xc in quantitative yield
(Scheme 4). Diacetoxy derivatives Va–Vc under ana-
logous conditions reacted with 4-phenylfurazan-3-
ylamine giving the corresponding disubstituted compounds
IXa–IXc in nearly 90% yield.
Scheme 2.
R
R
NHAc
NHAc
AcNH2
_
TsOH
_
VIIа VIIc, VIIf
R
Vа Vc, VI
_
Consequently, the application of a stepwise procedure
to the preparation of tetraaminoethane derivatives
100 110oC
NHCOOEt
NH2COOEt
Scheme 3.
R
NHCOOEt
_
R
R
NHAc
NHAc
VIIIа VIIIc, VIIIf
CH3CN/H2SO4 (90 or 100%)
_
O
IVe, Vа Vc
_
0 5oC
(c),
VII, VIII, R = NHAc (a), NHBz (b),
NHCOPr-i (f).
N
_
VIIа VIIc, VIIe
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SIZOVA et al.
172
Scheme 4.
(through an intermediate isolation of the products of
glyoxal condensation with amides followed by their
reaction with nitrogen-containing nucleophiles in anhydrous
medium) made it possible to obtain a wide range of
previously inaccessible polyfunctional compounds.
NH2
Ph
O
N
N
N
N
N
R
R
NH
N
Ph
Ph
O
The structure and composition of all first synthesized
1
compounds were confirmed by H NMR and IR
NH
spectroscopy, and also by elemental analyses
(physicochemical characteristics are reported in
EXPERIMENTAL).
O
N
_
_
NH2
Vа Vc
H2N
IXа IXc
H
N
N
N
R
R
EXPERIMENTAL
O
O
IR spectra of compounds synthesized were recorded
on a spectrometer Shimadzu FTIR 8400 (from films or
N
N
H
1
_
pellets with KBr). H NMR spectra were registered on
Xа Xc
Bruker WM-400 instrument (400 MHz), internal
reference HMDS. Elemental analysis was carried out
on a CHN-analyzer Hewlett Packard 185B.
CH2), 6.05 s (2H, CH), 6.40 s (2H, OH). Found, %:
C 47.03; H 4.97; N 11.08. C10H12N2O6. Calculated, %:
C 46.88; H 4.72; N 10.93.
1,2-Bis(acylamino)-1,2-ethanediols IV. General
procedure [7, 11]. To 0.5 mol of 40% aqueous glyoxal
was added 1 mol of amide (solid or dissolved in 50–
100 ml of water), pH of the reaction mixture was adjusted
to 8–9 by adding solid Na2CO3 or 20% solution of NaOH,
and the mixture was stirred at room temperature for
several days. The separated precipitate was filtered off,
washed with a little water, and dried at 70–80°C.
1,2-Bis(chloroacetylamino)-1,2-ethanediol (IVe).
1
Yield 92%, mp 138–144°C (decomp.) (DMF). H NMR
spectrum (DMSO-d6), δ, ppm: 4.06 q (4H, CH2,
J 8.0 Hz), 4.97 d (2H, CH, J 6.1 Hz), 6.90–7.55 m (2H,
OH), 8.45 d (2H, NH, J 6.9 Hz). Found, %: C 29.87;
H 4.62; N 11.58. C6H10Cl2N2O4.Calculated, %: C 29.41;
H 4.11; N 11.43.
1,2-Bis(isobutyrylamino)-1,2-ethanediol (IVf).
yield 87%, mp 145–146°C (ethanol–water). H NMR
1,2-Bis(acetylamino)-1,2-ethanediol (IVa). Yield
91%, mp 165–166°C (ethanol–water). H NMR
1
1
spectrum (DMSO-d6), δ, ppm: 1.00–1.15 m (12H, CH3),
2.25–2.45 m [2H, CH(CH3)2], 4.98–5.40 m (2H, CH),
5.50–6.40 m (2H, OH), 6.70–8.50 m (2H, NH). Found,
%: C 51.34; H 9.05; N 12.36. C10H20N2O4. Calculated,
%: C 51.71; H 8.68; N 12.06.
spectrum (DMSO-d6), δ, ppm: 1.85 s (6H, CH3), 5.04 d
(2H, CH, J 4.2 Hz), 5.60 s (2H, OH), 7.80 d (2H, NH,
J 4.2 Hz). Found, %: C 40.67; H 7.16; N 15.59.
C6H12N2O4. Calculated, %: C 40.91; H 6.87; N 15.90.
1,2-Bis(benzoylamino)-1,2-ethanediol (IVb).
1
Yield 89%, mp 168–169°C (ethanol–water). H NMR
Acylation of 1,2-bis(acylamino)-1,2-ethanediols
IVa–d. General procedure. To a mixture of 0.8 mol of
triethylamine or pyridine and 0.4 mol of acetic anhydride
was carefully added at vigorous stirring 0.1 mol of diol
IVa–IVd maintaining the temperature below 50–60°C.
After short stirring at this temperature the reaction mixture
was cooled and left overnight in a refrigerator. The
separated precipitate was filtered off, washed with cold
ethanol, and dried at 70–80°C.
spectrum (DMSO-d6), δ, ppm: 5.35–5.60 m (2H, CH),
7.35–7.60 m (6Harom), 7.75–8.05 m (4Harom), 8.50–
8.75 m (2H, NH). Found, %: C 63.53; H 5.84; N 9.67.
C16H16N2O4. Calculated, %: C 63.99; H 5.37; N 9.93.
1,2-Bis(2-oxopyrrolidin-1-yl)-1,2-ethanediol
1
(IVc). Yield 90%, mp 190–191°C (ethanol–water). H
NMR spectrum (DMSO-d6), δ, ppm: 1.80–2.10 m (4H,
CH2), 2.10–2.35 m (4H, CH2), 3.35–3.55 m (4H, CH2),
5.20 s (2H, OH), 5.80 s (2H, CH). Found, %: C 52.98;
H 7.36; N 12.05. C10H16N2O4. Calculated, %: C 52.62;
H 7.07; N 12.27.
1,2-Bis(acetylamino)-1,2-diacetoxyethane (Va).
Yield 86%, mp 175–177°C (ethanol–water). IR spectrum,
cm–1: 3269 (NH), 3069 (CN, CH3), 1751 (C=O), 1676
(C=O), 1558 (CN, NH), 1375 (CH3), 1330 (CH), 1243
(CNH, CO), 692 (NH). 1H NMR spectrum (DMSO-
d6), δ, ppm: 1.94 d (12H, CH3, J 19.2 Hz), 6.40 d (2H,
1,2-Bis(2,5-dioxopyrrolidin-1-yl)-1,2-ethanediol
(IVd). Yield 80%, mp 182–183°C (ethanol–water).
1H NMR spectrum (DMSO-d6), δ, ppm: 2.65 s (8H,
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DERIVATIVES OF 1,1,2,2-TETRAAMINOETHANE: I.
173
CH, J 7.7 Hz), 8.50 d (2H, NH, J 7.7 Hz). Found, %:
C 45.93; H 6.40; N 10.42. C10H16N2O6. Calculated, %:
C 46.15; H 6.20; N 10.76.
in 50 ml of methanol was added 5.0 g (0.02 mol) of diol
IVf, the reaction mixture was heated at reflux for 1 h,
cooled, left overnight in a refrigerator, and the separated
precipitate was filtered off. Yield 4.2 g (75%), mp 172–
174°C (2-propanol). IR spectrum, cm–1: 3269 (NH), 3069
(CN, CH3), 2966 (OCH3), 1652 (C=O), 1552 (CN, NH),
1464 (CH3), 1386 (CH3), 1320 (CH), 1232 (CNH, CO),
1174 (CH3), 1115 (COC), 725 (NH). 1H NMR spectrum
(DMSO-d6), δ, ppm: 1.00–1.15 m (12H, CH3), 2.30–
2.50 m [2H, CH(CH3)2], 3.20 s (6H, OCH3), 4.90 d (2H,
CH, J 7.7 Hz), 7.80 d (2H, NH, J 7.7 Hz). Found, %:
C 55.59; H 8.96; N 10.83. C12H24N2O4. Calculated, %:
C 55.36; H 9.29; N 10.76.
1,2-Diacetoxy-1,2-bis(benzoylamino)ethane
(Vb). Yield 84%, mp 153–155°C (ethane). IR spectrum,
cm–1: 3292 (NH), 3063 (CN, CH3), 1740 (C=O), 1661
(C=O), 1603 (C=C), 1534 (CN, NH), 1490 (C=C), 1372
(CH3), 1330 (CH), 1221 (CNH, CO), 804 (CH), 694 (NH).
1H NMR spectrum (DMSO-d6), δ, ppm: 1.85– 2.05 m
(6H, CH3), 6.65–6.85 m (2H, CH), 7.45–7.55 m (6Harom),
7.80–8.00 m (4Harom), 8.80–9.35 m (2H, NH). Found,
%: C 62.76; H 5.84; N 7.62. C20H20N2O6. Calculated,
%: C 62.49; H 5.24; N 7.29.
Condensation of 1,2-diacetoxy-1,2-bis(acyl-
amino)ethanes Va–Vc and 1,2-bis(isobutyrylamino)-
1,2-dimethoxyethane (VI) with acetamide and
urethane. General procedure. A mixture of 0.1 mol
of compound Va–Vc (or VI) and 0.4 mol of acetamide
(or urethane) preliminary thoroughly ground in a mortar
was melted at 100–110°C, then 0.005 mol of p-toluene-
sulfonic acid was added to the melt, and the mixture was
stirred at the same temperature for 30 min. The reaction
mixture was cooled, and the residue was washed from
excess acetamide with acetone or from urethane with
ether.
1,2-Diacetoxy-1,2-bis(2-oxopyrrolidin-1-yl)-
ethane (Vc). Yield 65%, mp 138–144°C. IR spectrum,
cm–1: 2990 (CH2), 2900 (CH), 1755 (C=O), 1680 (C=O),
1417 (CH2, CH3), 1370 (CH, CH3), 1227 (CO), 804
1
(CH). H NMR spectrum (DMSO-d6), δ, ppm: 1.80–
2.00 m (4H, CH2), 2.05 d (6H, CH3, J 13.3 Hz), 2.15–
2.25 m (4H, CH2), 3.25–3.45 m (4H, CH2), 6.55 d (2H,
CH, J 13.3 Hz). Found, %: C 53.47; H 6.29; N 9.02.
C14H20N2O6. Calculated, %: C 53.84; H 6.45; N 8.97.
1,2-Diacetoxy-1,2-bis(2,5-dioxopyrrolidin-1-yl)-
ethane (Vd). Yield 72%, mp 255–258°C (decomp.). IR
spectrum, cm–1: 2995 (CH2), 2937 (CH), 1759 (C=O),
1716 (C=O), 1429 (CH2, CH3), 1367 (CH, CH3), 1217
(CO), 818 (CH). 1H NMR spectrum (DMSO-d6), δ,
ppm: 2.05 d (6H, CH3, J 26.7 Hz), 2.65 d (8H, CH2,
J 26.7 Hz), 7.05 d (2H, CH, J 53.3 Hz). Found, %:
C 49.76; H 4.91; N 8.54. C14H16N2O8. Calculated, %:
C 49.41; H 4.74; N 8.23.
1,1,2,2-Tetrakis(acetylamino)ethane (VIIa). Yield
30%, mp > 300°C (water). IR spectrum, cm–1: 3284
(NH), 3132 (CN), 3030 (CH3), 1664 (C=O), 1570 (CN,
NH), 1446 (CH3), 1371 (CH3), 1273 (CNH), 750 (NH).
1H NMR spectrum (CF3COOD), δ, ppm: 1.75 s (12H,
CH3), 5.75 s (2H, CH), 7.70 s (2H, NH). Found, %:
C 46.83; H 7.16; N 21.73 C10H18N4O4. Calculated, %:
C 46.50; H 7.03; N 21.69.
1,2-Diacetoxy-1,2-bis(chloroacetylamino)ethane
(Ve). To 50 ml of acetic anhydride was added 5 g
(0.02 mol) of diol IVe and several drops of sulfuric acid,
the reaction mixture was heated at 50–60°C and stirred
at this temperature for 1 h, then it was cooled and poured
into water. The separated precipitate was filtered off,
washed with water, and dried at 70–80°C. Yield 5.6 g
(83%), mp 160–161°C (decomp.) (DMF). IR spectrum,
cm–1: 3223 (NH), 3074 (CN), 2883 (CH), 1680 (C=O),
1562 (CN, NH), 1421 (CH2Cl, CH3), 1352 (CH, CH3),
1280 (CH2Cl), 1230 (CO), 1217 (CNH), 689 (NH).
1H NMR spectrum (DMSO-d6), δ, ppm: 2.05 s (6H,
CH3), 4.05 s (4H, CH2), 6.45 d (2H, CH, J 14.3 Hz).
Found, %: C 36.78; H 4.68; N 8.61. C10H14Cl2N2O6.
Calculated, %: C 36.49; H 4.29; N 8.51.
1,2-Bis(acetylamino)-1,2-bis(benzoylamino)-
ethane (VIIb). Yield 30%, mp > 300°C (water). IR
spectrum, cm–1: 3273 (NH), 3115 (CN, CH3), 1740
(C=O), 1649 (C=O), 1603 (C=C), 1556 (CN, NH), 1491
(C=C), 1436 (CH3), 1371 (CH3), 1340 (CH), 1226 (CNH,
1
CO), 802 (CH), 716 (NH). H NMR spectrum (DMSO-
d6), δ, ppm: 1.85–2.00 m (6H, CH3), 5.50– 5.95 m (2H,
CH), 7.40–7.60 m (6Harom), 7.70–8.10 m (4Harom), 8.35–
8.70 m (2H, NH). Found, %: C 62.68; H 5.48; N 14.17.
C20H22N4O4. Calculated, %: C 62.82; H 5.80; N 14.65.
1,2-Bis(acetylamino)-1,2-bis(2-oxopyrrolidin-1-
yl)ethane (VIIc). Yield 63%, mp 281–283°C. IR
spectrum, cm–1: 3300 (NH), 3061 (CN), 2968 (CH2), 2898
(CH), 1663 (C=O), 1547 (CN, NH), 1433 (CH2, CH3),
1364 (CH, CH3), 1286 (CNH), 794 (CH), 680 (NH).
1H NMR spectrum (DMSO-d6), δ, ppm: 1.45–1.65 m
1,2-Bis(isobutyrylamino)-1,2-dimethoxyethane
(VI). To a solution of 5.4 g (0.04 mol) of dimethyl sulfate
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SIZOVA et al.
174
(4H, CH2), 1.65–2.00 m (6H, CH3), 2.05–2.30 m (4H,
CH2), 3.15–3.50 m (4H, CH2), 5.60–6.00 m (2H, CH),
7.60–8.45 m (2H, NH). Found, %: C 54.25; H 6.85;
N 17.93. C14H22N4O4. Calculated, %: C 54.18; H 7.14;
N 18.05.
3292 (NH), 2980 (CN, CH3, CH2), 1697 (C=O), 1666
(C=O), 1554 (CN, NH), 1446 (CH3, CH2), 1371 (CH3),
1334 (CH), 1248 (CNH, CO), 783 (CH), 691 (NH).
Found, %: C 49.81; H 8.23; N 15.80. C16H30N4O6.
Calculated, %: C 51.32; H 8.08; N 14.96.
1,2-Bis(acetylamino)-1,2-bis(isobutyrylamino)-
ethane (VIIf). Yield 42%, mp > 300°C (water), insoluble
in DMSO. IR spectrum, cm–1: 3287 (NH), 3132 (CN,
CH3), 1663 (C=O), 1566 (CN, NH), 1470 (CH3), 1373
(CH3), 1323 (CH), 1238 (CNH, CO), 1176 (CH3), 732
(NH). Found, %: C 55.63; H 8.02; N 16.98. C14H26N4O4.
Calculated, %: C 55.49; H 8.34; N 17.42.
1,1,2,2-Tetrakis(acylamino)ethanes VIIa–e.
Ritter reaction. a. To 20 ml of acetonitrile was slowly
added 20 ml of 90% sulfuric acid maintaining the
temperature below 0–5°C.At the end of addition into the
reaction mixture was introduced 0.020 mol of diol IVd or
IVe, the mixture was stirred for 1.5 h at 0–5°C, and then
it was poured on ice. The separated precipitate was
filtered off and thoroughly washed with water.
1,2-Bis(acetylamino)-1,2-bis(ethoxycarbonyl-
amino)ethane (VIIIa). Yield 53%, mp 240°C (ethanol–
water). IR spectrum, cm–1: 3292 (NH), 3122 (CN), 2984
(CH3, CH2), 1693 (C=O), 1655 (C=O), 1558 (CN, NH),
1528 (C=O), 1437 (CH3, CH2), 1371 (CH3), 1329 (CH),
1,2-Bis(acetylamino)-1,2-bis(chloroacetyl-
amino)ethane (VIIe). Yield 84%, mp >300°C (DMF).
IR spectrum, cm–1: 3288 (NH), 3122 (CN), 3028 (CH3),
2958 (CH2), 1668 (C=O), 1558 (CN, NH), 1419 (CH2),
1373 (CH3), 1261 (CNH, CH2Cl), 694 (NH). 1H NMR
spectrum (DMSO-d6), δ, ppm: 1.80 s (6H, CH3), 4.05 s
(4H, CH2), 5.60–5.70 m (2H, CH), 8.05–8.20 m (2H,
NH), 8.25–8.40 m (2H, NH). Found, %: C 36.40; H 4.63;
N 16.89 C10H16Cl2N4O4.Calculated, %: C 36.71; H 4.93;
N 17.12.
1
1260 (CNH), 1176 (CO), 802 (CH), 736 (NH). H NMR
spectrum (DMSO-d6), δ, ppm: 1.15–1.25 m (6H, CH3),
1.80 s (6H, CH3), 3.90–4.05 m (4H, CH2), 5.20– 5.45 m
(2H, CH), 6.90 s (2H, NH), 7.75 s (2H, NH). Found, %:
C 45.11; H 5.97; N 17.22 C12H22N4O6. Calculated, %:
C 45.28; H 6.97; N 17.60.
b. To 15 ml of acetonitrile at 0–5°C was slowly added
while stirring 10 ml of 100% sulfuric acid. At the end of
addition into the reaction mixture cooled to –5°C was
introduced 0.015 mol of diol Va–Vc. The solution obtained
was left overnight in a refrigerator, then it was poured on
ice. The separated precipitate was filtered off and
thoroughly washed with water. Yields of compounds, %:
81 (VIIa), 70 (VIIb), 67 (VIIc).
1,2-Bis(benzoylamino)-1,2-bis(ethoxycarbonyl-
amino)ethane (VIIIb). Yield 69%, mp 260–262°C
(ethanol–water). IR spectrum, cm–1: 3285 (NH), 2983
(CN, CH3, CH2), 1697 (C=O), 1647 (C=O), 1603 (C=C),
1550 (CN, NH), 1491 (C=C), 1458 (CH3, CH2), 1370
(CH3), 1344 (CH), 1256 (CNH, CO), 802 (CH), 694 (NH).
1H NMR spectrum (DMSO-d6), δ, ppm: 1.05–1.30 m
(6H, CH3), 3.90–4.10 m (4H, CH2), 5.55–5.95 m (2H,
CH), 6.55–7.10 m (2H, NH), 7.30–7.65 m (6Harom), 7.70–
7.95 m (4Harom), 8.40–8.50 m (2H, NH). Found, %:
C 60.07; H 5.59; N 12.85. C22H26N4O6. Calculated, %:
C 59.72; H 5.92; N 12.66.
Condensation of 1,2-diacetoxy-1,2-bis(acyl-
amino)ethanes Va–Vc with diaminofurazan and
4-phenylfurazan-3-ylamine. General procedure. To
a suspension of 0.01 mol of reagent Va–Vc in 15 ml of
acetonitrile was added at room temperature 0.01 mol of
diaminofurazan (or 0.02 mol of 4-phenylfurazan-3-
ylamine), 0.001 mol of p-toluenesulfonic acid, and 3 drops
of DMSO. The reaction mixture was vigorously stirred
for 36 h at room temperature, then the precipitate was
filtered off, washed with boiling ethanol, and dried at 50–
60°C.
1,2-Bis(2-oxopyrrolidin-1-yl)-1,2-bis(ethoxy-
carbonylamino)ethane (VIIIc). Yield 81%, mp 223–
225°C. IR spectrum, cm–1: 3233 (NH), 3064 (CN), 2987
(CH3, CH2), 1664 (C=O), 1560 (CN, NH), 1489 (C=O),
1439 (CH3, CH2), 1389 (CH3), 1366 (CH), 1234 (CNH),
1165 (CO), 783 (CH), 681 (NH). 1H NMR spectrum
(DMSO-d6), δ, ppm: 1.15–1.25 m (6H, CH3), 1.75–
2.00 m (4H, CH2), 2.05–2.30 m (4H, CH2), 3.25–3.50 m
(2H, CH2), 3.85–4.05 m (4H, CH2), 5.65 c (2H, CH),
7.65 C (2H, NH). Found, %: C 52.37; H 6.76; N 15.52.
C16H26N4O6. Calculated, %: C 51.88; H 7.08; N 15.13.
1,2-Bis(acetylamino)-1,2-bis(4-phenylfurazan-3-
ylamino)ethane (IXa). Yield 93%, mp 224–226°C
(decomp.). IR spectrum, cm–1: 3271 (NH), 3058 (CH3),
1656 (C=O, C=N, CH), 1593 (CH), 1519 (C=N, NH),
1472 (CC), 1448 (CH3), 1375 (CH3), 1263 (CNH), 800
(CH), 696 (NH). 1H NMR spectrum (DMSO-d6), δ,
ppm: 1.75–1.90 m (6H, CH3), 5.20–5.75 m (2H, CH),
1,2-Bis(isobutyrylamino)-1,2-bis(ethoxy-
carbonylamino)ethane (VIIIf). Yield 56%, mp 268–
269°C (water), insoluble in DMSO. IR spectrum, cm–1:
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 43 No. 2 2007

DERIVATIVES OF 1,1,2,2-TETRAAMINOETHANE: I.
175
6.30– 6.60 m (2H, NH), 7.50–7.65 m (6Harom), 7.65–
7.75 m (4Harom), 7.90–8.15 m (2H, NH). Found, %:
C 57.24; H 5.01; N 23.91. C22H22N8O4. Calculated, %:
C 57.14; H 4.79; N 24.23.
H 4.24; N 22.76. C18H16N6O3. Calculated, %: C 59.34;
H 4.43; N 23.06.
(4,5,6,7-Tetrahydro[1,2,5]oxadiazolo[3,4-b]-
pyrazine-5,6-diyl)dipyrrolidin-2-one (Xc). Yield 92%,
mp 168–171°C (decomp.) (ethanol–water). IR spectrum,
cm–1: 3317 (NH), 3062 (CH2), 1678 (C=O, C=N, CH),
1569 (CH, C=N, NH), 1488 (CC), 1419 (CH2), 1288
1,2-Bis(benzoylamino)-1,2-bis(4-phenylfurazan-
3-ylamino)ethane (IXb). Yield 91%, mp 215–218°C
(decomp.). IR spectrum, cm–1: 3285 (NH), 1641 (C=O,
C=N, CH), 1593 (CH), 1524 (C=N, NH), 1489 (CC),
1
(CNH), 837 (CH), 651 (NH). H NMR spectrum
1
1265 (CNH), 800 (CH), 692 (NH). H NMR spectrum
(DMSO-d6), δ, ppm: 1.60–2.00 m (4H, CH2), 2.05–2.35
m (4H, CH2), 2.80–3.50 m (4H, CH2), 5.45– 5.70 m (2H,
CH), 6.65–7.20 m (2H, NH). Found, %: C 46.61; H 6.21;
(DMSO-d6), δ, ppm: 6.00–6.20 m (2H, CH), 6.35–
6.60 m (2H, NH), 7.35–7.65 m (6Harom), 7.65–7.80 m
(4Harom), 8.50–8.70 m (2H, NH). Found, %: C 65.88;
H 4.79; N 19.40 C22H22N8O4. Calculated, %: C 65.52;
H 4.47; N 19.10.
.
N 27.19. C12H16N6O3 H2O. Calculated, %: C 46.45;
H 5.85; N 27.08.
REFERENCES
1,2-Bis(2-oxopyrrolidin-1-yl)-1,2-bis(4-phenyl-
furazan-3-ylamino)ethane (IXc). Yield 73%, mp 232–
235°C (decomp.). IR spectrum, cm–1: 3248 (NH), 3055
(CH2), 1664 (C=O, C=N, CH), 1593 (CH), 1548 (C=N,
NH), 1419 (CH2), 1290 (CNH), 773 (CH), 692 (NH).
1H NMR spectrum (DMSO-d6), δ, ppm: 1.80–2.00 m
(4H, CH2), 2.10–2.30 m (4H, CH2), 3.00–3.15 m (2H,
CH2), 3.40–3.55 m (2H, CH2), 5.80–5.85 m (2H, CH),
6.85– 7.25 m (2H, NH), 7.35–7.60 m (6Harom), 7.65–
7.75 m (4Harom). Found, %: C 61.10; H 4.95; N 22.03
C26H26N8O4. Calculated, %: C 60.69; H 5.09; N 21.78.
1. Zheng, Y., Zhou, J., Zhou, D., and Zhang, M., Binggong
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1965, vol. 30, p. 1195.
8. Currie, A.C., Dinwoodie, A.H., Fort, G., and Thomp-
son, J.M.C., J. Chem. Soc. C, 1967, p. 491.
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p. 391.
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ker, R.H., and La, M., US Patent 3579536, 1971; Chem.Abstr.,
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(4,5,6,7-Tetrahydro[1,2,5]oxadiazolo[3,4-b]-
pyrazine-5,6-diyl)diacetamide (Xa). Yield 83%, mp
165–166°C (decomp.). IR spectrum, cm–1: 3292 (NH),
3061 (CH3), 1660 (C=O, C=N), 1516 (C=N, NH), 1436
1
(CH3), 1375 (CH3), 1284 (CNH), 705 (NH). H NMR
spectrum (DMSO-d6), δ, ppm: 1.70–1.95 m (6H, CH3),
5.00–5.55 m (2H, CH), 6.30–6.90 m (2H, NH), 7.10–
8.25 m (2H, NH). Found, %: C 39.87; H 5.64; N 34.25.
C8H12N6O3. Calculated, %: C 40.00; H 5.04; N 34.98.
(4,5,6,7-Tetrahydro[1,2,5]oxadiazolo[3,4-b]-
pyrazine-5,6-diyl)dibenzamide (Xb). Yield 94%, mp
230–232°C (decomp.). IR spectrum, cm–1: 3323 (NH),
3030 (CH3), 1650 (C=O, C=N, CH), 1582 (CH), 1514
(C=N, NH), 1485 (CC), 1446 (CH3), 1334 (CH3), 1280
(CNH), 830 (CH), 711 (NH). 1H NMR spectrum
(DMSO-d6), δ, ppm: 5.45–6.25 m (2H, CH), 7.15–
7.55 m (6Harom), 7.55–7.80 m (4Harom), 7.80–8.00 m (2H,
NH), 8.45– 9.10 m (2H, NH). Found, %: C 59.02;
12. Ritter, J.J. and Kalish, J., J. Am. Chem. Soc., 1948, vol. 70,
p. 4048.
13. Benson, F.R. and Ritter, J.J., J. Am. Chem. Soc., 1949, vol. 71,
p. 4128.
14. Hartzel, L.W. and Ritter, J.J., J. Am. Chem. Soc., 1949, vol. 71,
p. 4130.
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 43 No. 2 2007