Dicarboxylic acids with nitrate groups
Russ.Chem.Bull., Int.Ed., Vol. 63, No. 5, May, 2014
1123
1
3
ꢀaminopropanol was used in the reaction instead of monoꢀ
oil pump to obtain compound 6 (6.7 g) as a dense oil. H NMR
3
ethanolamine. The reaction product was filtered off, dried in air,
and subjected to nitration reaction.
(DMSOꢀd , SiMe ), : 1.53 (q, 4 H, CH , J
= 6.5 Hz);
CH,CH
6
4
2
3
2.31 (s, 4 H, CH C(O)); 3.11 (dt, 4 H, NHCH , JCH,CH
2
2
3
3
N,N´ꢀBis(2ꢀhydroxyethyl)oxysuccindiamide (7). Malic acid
J
5.7 Hz); 3.40 (dt, 4 H, CH OH, JCH,CH 5.7,
CH,NH
2
3
3
(
6.7 g, 0.05 mol) was added to ethanol (75 mL) at 0—50 C with
JCH,OH 5.0 Hz); 4.43 (t, 2 H, OH, J
5.0 Hz); 7.96
OH,CH
3
stirring, followed by addition of concentrated H SO (4.5 mL).
(br.t, 2 H, NH, J 5.7 Hz). Then, this oil was treated
2
4
NH,CH
After mixing the reagents, the reaction mixture was heated to
00 C and allowed to stand at this temperature with stirring for
with a mixture of conc. H SO (24 mL) and conc. HNO (8 mL)
2 4 3
8
and allowed to stand at 50 C with stirring for 3.5 h. The content
of the flask was poured into a mixrure ice—water (200 mL),
neutralized with KOH to pH 7—7.5, and extracted with ethyl
acetate (3×50 mL). The combined extracts were dried with
another 2 h. The azeotropic mixture of ethanol—water (15 mL)
was distilled off in vacuo, followed by addition of ethanol (15 mL)
into the reaction flask and heating for another 1 h. Then, the
reaction mixture was cooled to room temperature and poured
into a mixrure ice—water (120 mL), neutralized with К CO ,
MgSO . Compound 9 (4.75 g) was obtained after evaporation of
4
1
ethyl acetate at reduced pressure, m.p. and H NMR spectrum
2
3
and extracted with dichloroethane (DCE) (2×70 mL). The comꢀ
are given in Table 2.
bined extracts were dried with MgSO , DCE was evaporated
in vacuo using a waterꢀaspirator pump. Malic acid diethyl ester
N,N´ꢀBis(2ꢀnitroxyethyl)oxysuccindiamide (10). N,N´ꢀBis(2ꢀ
hydroxyethyl)oxysuccindiamide (7) (4.2 g, 19.07 mmol) was addꢀ
4
(
5.94 g) was obtained in the residue as an oil, to which monoꢀ
ed to 75% aqueous HNO (21 mL) at 18—20 C. After mixing
3
ethanolamine (2.5 g) was added. After mixing the reagents, the
reaction mixture was heated to 85—90 C and allowed to stand at
this temperature for 1 h. The reaction mixture crystallized durꢀ
ing standing. Diethyl ether (20 mL) was added into the flask, the
crystalline substance formed was triturated, colorless crystalline
precipitate was filtered off. The yield of product 7 was 4.08 g
the reagents, the reaction mixture was stirred for 1.5—2 h at this
temperature and poured into a mixrure ice—water, neutralized
with NaHCO , and extracted with ethyl acetate (5×15 mL). The
3
extracts were combined and dried with MgSO . Compound 10
4
(3.3 g, 55.9%) was obtained after usual treatment, m.p. 90—91 C
(from DCE). Found (%): C, 30.84; H, 5.14; N, 18.11. C H N O .
8
14
4 9
1
(
91% calculated on ethanolamine), m.p. 119.5—121.0 C. IR,
Calculated (%): C, 30.97; H, 5.42; N, 18.06. H NMR spectrum
is given in Table 2.
–
1
8
1
1
3
/cm : 683.6 w, 691.5 w, 758.2 m, 811.1 w, 829.4 w, 854 w,
29.3 m, 854.1 m, 896 m, 962.2 w, 1051.3 s, 1087.5 s, 1094 s,
1.86 s, 12.18 m, 12.87 m, 1323 m,13.51 m, 1379 w, 14.42 m,
5.47 s, 17.35 m, 2033 w, 2886 w, 2941 w, 2972.6 w, 3003 w,
N,N´ꢀBis(2ꢀnitroxyethyl)nitroxysuccindiamide (11). N,N´ꢀ
Bis(2ꢀhydroxyethyl)oxysuccindiamide 7 (5 g, 23.78 mmol) was
added in portions to HNO (20 mL, d = 1.51) at room temperaꢀ
3
1
13913 s, 3652.4 w, 3759 w, 3781.4 w. H NMR (DMSOꢀd ,
ture with stirring. After mixing the reagents, the reaction mixꢀ
ture was stirred for 3 h, then poured onto crushed ice. A colorless
precipitate formed was filtered off, washed with iceꢀcold water, and
dried in air to obtain nitrate 11 (5.24 g, 62%), m.p. 108—109 C.
Found (%): C, 30.48; H, 3.92; N, 18.11. C H N O . Calculatꢀ
6
SiMe ), : 2.30 (s, 4 H, CH C(O)); 3.10 (dt, 4 H, NHCH ,
4
2
2
3
3
3
JCH,CH J
5.7 Hz); 3.37 (dt,
4
H, CH OH,
CH,NH
2
3
JCH,CH 5.7 Hz, JCH,OH 5.0 Hz); 4.61 (t, 2 H, OH,
3J
5.0 Hz); 7.79 (br.t, 2 H, NH, J
3
5.7 Hz).
OH,CH
NH,CH
8
13
5
11
1
N,N´ꢀBis(2ꢀnitroxyethyl)succindiamide (8). N,N´ꢀ(2ꢀHydrꢀ
oxyethyl)succindiamide 5 (7 g, 34.27 mmol) was added to a mixꢀ
ed (%): C, 30.05; H, 3.69; N, 19.71. H NMR spectrum is given
in Table 2.
ture of conc. H SO (28 mL) and conc. HNO (14 mL) at 0—5 C,
NꢀNitroxymethylsuccinimide (19). NꢀHydroxymethylsuccinꢀ
2
4
3
then, the reaction mixture was allowed to stand for another 6 h
at 0—5 C and poured onto crushed ice (250 mL), neutralized
with potassium hydroxide, and extracted with ethyl acetate
imide11 (1 g, 7.74 mmol) was added to a mixture of Ac O (1.1 mL)
2
and HNO (0.5 mL, d = 1.5) at 10—15 C with stirring. The
3
reaction mixture was allowed to stand at 15 C for 2 h with
stirring, then poured onto crushed ice. A colorless precipitate
formed was filtered off and dried in air to obtain colorless crysꢀ
tals (1.05 g) with m.p. 111.5—112.5 C. Found (%): C, 34.06;
H, 3.15; N, 15.84. C H N O . Calculated (%): C, 34.5; H, 3.47;
(
5×25 mL). The extracts were combined and dried with MgSO4.
Compound 8 (6.82 g, 68.1%) was obtained after evaporation of
ethyl acetate at reduced pressure, m.p. 100—101.5 C (chloroꢀ
form). Found (%): C, 32.50; H, 4.82; N, 19.16. C H N O .
8
16
4
8
5
6
2
5
1
Calculated (%): C, 32.65; H, 4.76; N, 19.04.
N, 16.09. H NMR spectrum is given in Table 2.
N,N´ꢀBis(3ꢀnitroxypropyl)succindiamide (9). Succinic acid
Nꢀ(2ꢀNitroxyethyl)succinimide (20). Nꢀ(2ꢀHydroxyethyl)ꢀ
succinimide 17 (6 g, 41.92 mmol) was added to a solution of
HNO (15 mL) in CH Cl (55 mL) at 15—20 C with stirring.
(
5.9 g, 0.05 mol) was added to a solution of conc. H SO (4.5 mL)
2
4
in ethanol (75 mL) at 0—50 C with stirring. The reaction mixꢀ
ture was heated to 80 C and allowed to stand at this temperature
for 3 h. The azeotropic mixture (ethanol—water, 15 mL) was
distilled off in vacuo using a waterꢀaspirator pump, followed by
addition of ethanol (15 mL) to the mixture and heating for anꢀ
other 1 h. Then, the content of the flask was poured into a mixrure
ice—water (120 mL), neutralized with dry Na CO to pH 8—9,
3
2
2
After mixing the reagents, the reaction mixture was stirred for 2 h,
then poured onto crushed ice, and neutralized with К CO to
2
3
pH = 7.2—7.0. The solution obtained was extracted with ethyl
acetate (3×15 mL). The extracts were combined and dried with
MgSO . Compound 20 (6.8 g, 86%) was obtained after evaporaꢀ
4
tion of the solvent in vacuo, white crystals, m.p. 61.5—62.5 C
2
3
1
and extracted with DCE (2×75 mL). The combined extracts
(DCE). H NMR spectrum is given in Table 2.
were dried with MgSO , DCE was separated, and the solvent
Nꢀ(3ꢀNitroxypropyl)succinimide (21). Nꢀ(3ꢀHydroxypropyl)ꢀ
succinimide (18) (1 g, 6.21 mmol) was added to a mixture of
HNO (2 mL) and H SO (6 mL) at –5—0 C with stirring and
4
was evaporated in vacuo using a waterꢀaspirator pump to obtain
an oily precipitate (6 g), which without purification was used in
the subsequent reaction. Namely, 3ꢀaminopropanol (3 g) was
added to this oily precipitate, the reaction mixture was heated to
3
2
4
the reaction mixture was stirred for 5 h at 0 C, then neutralized
with K CO , and extracted with ethyl acetate (3×15 mL). The
2
3
9
0 C and allowed to stand at this temperature for 2 h with
combined extracts were dried with MgSO . The usual treatment
4
stirring. The reaction mixture obtained was evacuated using an
gave Nꢀ(3ꢀnitroxypropyl)succinimide 21 (0.91 g, 70.8%) with