Bis(nitroxymethyl)dinitrobutanediol dinitrate
Russ.Chem.Bull., Int.Ed., Vol. 64, No. 8, August, 2015
1969
Table 1. Crystallographic parameters for compound 1
stirring at 10 C to a mixture of compound 5 (15.1 g, 0.1 mol) and
acetone (50 mL, 0.68 mol). The reaction mixture was stirred for
10 min and poured into a mixture (100 mL) of a saturated potasꢀ
sium carbonate solution and ice. Then the reaction mixture was
stirred until the ice disappeared. The precipitate that formed was
filtered off, washed with cold water, and dried in air. Compound 2
was obtained in a yield of 13.5 g (71%), m.p. 132—134 C (aceꢀ
tone) (cf. lit. data5: m.p. 133—134 C). According to the TLC
data and the IR spectrum, this compound is identical to the
product prepared by a method described earlier.5 Rf = 0.67 (ethyl
acetate—hexane, 1 : 1, as the eluent). IR (KBr), /cm–1: 3427,
3002, 2949, 2893, 1542, 1443, 1386, 1352, 1319, 1266, 1251,
1206, 1149, 1091, 1061, 1027, 825, 732, 568, 518. 1H NMR
(300 MHz, CDCl3), : 1.42 (s, 3 H, CH3); 1.44 (s, 3 H, CH3);
2.08—2.19 (br.s, 1 H, OH); 3.99—4.43 (m, 4 H, CH2O); 4.06
(s, 2 H, CH2OH).
Parameter
Data
of this work
published1
Molecular formula
Molecular weight
С6Н8N6O16
420.18
С6Н8N6O16
420.18
Т/К
150
103
Crystal system
Space group
Monoclinic
P21/n
Monoclinic
P21/n
Unit cell parameters
a/Å
b/Å
c/Å
/deg
8.1377(8)
23.113(2)
8.5220(9)
90.0
8.1228(6)
23.0560(16)
8.5072(6)
90.0
/deg
113.872(10)
90.0
1465.7(3)
4
113.950(10)
90.0
1465.01(18)
4
5,5´ꢀBis(2,2ꢀdimethylꢀ5ꢀnitroꢀ1,3ꢀdioxane) (3). A. Comꢀ
pound 2 (3.22 g, 0.02 mol) was added with stirring to a solution
of NaOH (0.96 g, 0.024 mol) in water (32 mL). The suspension
was heated to 60 C and stirred for 40 min. The wineꢀcolored
solution was cooled to 20 C, bromine (1.76 g, 0.011 mol) was
dosed at this temperature, and the reaction mixture was stirred
for 30 min. Then ethanol (4 mL) was added, and the mixture was
refluxed for 10 h, the pH value of the reaction mixture being
maintained equal to 12 by adding an aqueous NaOH solution.
After the completion of the reaction, the mixture was cooled to
10 C and diluted with water (10 mL). The precipitate was filꢀ
tered off and successively washed with a 5% NaOH solution
(2×10 mL) and water (2×15 mL). Compound 3 was obtained in
/deg
V/Å3
Z
dcalc/g cm–3
Absorption coefficient
(Mо)/mm–1
1.904
0.194
1.917
0.195
(~20 C), the density of 1 should be lower because the unit
cell parameters increase with an increase in the temperaꢀ
ture. Actually, we found that the density of compound 1 at
20 C measured by the flotation method for the crystals,
which were obtained from a dichloromethane—hexane
mixture, is 1.856 g cm–3, for the crystals obtained from
isopropyl alcohol, the density is 1.823 g cm–3 (the differꢀ
ence in the flotation densities is due to the different number
of inclusions in the crystals and the sizes of the resulting
crystals). Oxley et al.,6 who have repeated the synthesis of
compound 1, obtained a similar result ( = 1.8238 g cm–3).
a yield of 0.55 g (17.2%), m.p. 128—129 C (cf. lit. data1,2
:
m.p. 129—130 C). During TLC, the product gives one spot with
Rf = 0.88 (ethyl acetate—hexane, 1 : 1, as the eluent). IR (KBr),
/cm–1: 3002, 2945, 2886, 1570, 1382, 1338, 1202, 1123, 1081,
952, 828, 581, 527. 1H NMR (300 MHz, CDCl3), : 1.35 (s, 6 H,
CH3); 1.41 (s, 6 H, CH3); 4.29—4.49 (m, 8 H, CH2O). Accordꢀ
1
ing to the TLC data, the IR spectrum, and the H NMR specꢀ
trum, this compound is identical to that prepared by a method
described earlier.12
B. Dimethyl sulfoxide (10 mL) was placed in a flask equipped
with a stirrer, a thermometer and a reflux condenser, and then
compound 2 (3.22 g, 0.02 mol) was added with stirring. At
20—25 C, a solution of NaOH (0.8 g, 0.02 mol) in water (1.2 mL)
was dosed. The wineꢀcolored solution was stirred at 25—30 C
for 40 min, and CCl4 (2.4 mL, 3.85 g, 0.025 mol) was added.
Then the reaction mixture was warmed to 55 C and stirred at
this temperature for 8 h. The content of the flask was cooled to
15 C and diluted with water (30 mL). The yellow precipitate
that formed was filtered off and successively washed with a 10%
NaOH solution (3×15 mL) and water (3×15 mL) until a neutral
reaction of the wash water. Compound 3 was obtained in a yield
of 1.36 g (42.5%), m.p. 129—131 C (ethanol). According to the
TLC data, the IR spectrum, and the 1H NMR spectrum, this
compound is identical to that prepared by the method A.
C. Compound 2 (64 g, 0.33 mol) was added with stirring at
20 C to a solution of NaOH (26.8 g, 0.67 mol) in water (0.5 L).
The reaction mixture was warmed to 60 C for 1 h and then
cooled to 20 C. Solid sodium persulfate (159.5 g, 0.67 mol) was
added in one portion. The resulting mixture was stirred at 20 C
for 4 h and allowed to stand at room temperature for two days,
during which a white precipitate of compound 3 formed. Then
pH of the reaction mixture was adjusted to >11 by adding
Experimental
The 1H, 13C, and 15N NMR spectra were recorded on Bruker
AMꢀ300 spectrometers at 300.13, 75.7, and 30.4 MHz, respecꢀ
tively, in CDCl3 or CD3CN. The IR spectra were measured on
a Specord M80 spectrometer as KBr pellets. The mass spectra
were obtained on a Finnigan MAT INCOSꢀ50 instrument using
a direct inlet system at an electron ionization energy of 70 eV.
The elemental analysis was carried out on a PerkinꢀElmer
C,H,NꢀAnalyser instrument. Analytical TLC was performed on
Merck TLC Silica gel 60 F254 plates. The melting points were
measured in a capillary. The TGA and DTA thermograms (therꢀ
mal analysis curves) were obtained on a Diamond TG/DTA
Perkin Elmer Thermal Analysis instrument. The heating rate
was 5 C min–1 in the range of 20—240 C. The Xꢀray diffraction
study of the reaction product was performed on a SMART APEX
2 CCD diffractometer (graphite monochromator, (MoꢀK) raꢀ
diation, ꢀ and ꢀscanning technique, max = 27, 150 K).
Nitroisobutylglycerol was prepared by a known procedure.11
The other compounds used in this study are commercially available.
2,2ꢀDimethylꢀ5ꢀhydroxymethylꢀ5ꢀnitroꢀ1,3ꢀdioxane (2). Phosꢀ
phorus pentoxide (5 g, 0.035 mol) was added in one portion with