G. Herv e´ et al. / Tetrahedron 61 (2005) 6743–6748
6747
3
˚
7
60.67(7) A ; ZZ4; total reflections collected: 3814;
dichloromethane. A white solid product was yielded
1
independent reflections: 1341 (947F O4s(F )); a
hemisphere of data was collected up to a 2Qmax value of
9.968 (100% coverage). Number of variables: 124; R Z
(31%). Mp 129 8C; H NMR (acetone) dZ9.67 (s, broad).
o
o
1
3
14
C NMR (acetone) dZ121.0, 155.9 ppm. N NMR
(acetone) dZ K279 (broad, NH ), K27 (C–NO ), K23
4
1
2
2
0
density 0.328 e A
.0549, wR Z0.1391, SZ1.046; highest residual electron
(N–NO ). IR (KBr) 3388, 3253, 1637, 1623, 1599, 1578,
2
2
K3
K1
C
˚
.
1509, 1384, 1264, 1103, 791 cm . MS (CI , NH ): m/zZ
3
K
2
45 (7), 170 (8); MS (CI , NH ): m/zZ226 (100).
3
Crystallographic data for the structural analysis have been
deposited at the Crystallographic Data Centre, CCDC
4.2.4. 1-Amino-1-N-acetylamino-2,2-dinitroethene 11.
DADNE (0.74 g, 5 mmol) was introduced in refluxing
acetyl chloride. Hafnium trifluoro-methanesulfonate
(0.19 g, 0.25 mmol) was added. The mixture was stirred
3 h and became dark red, filtrated and evaporated to dryness
under vacuum. The crude product was purified by
2
64136–264137 for compounds 6 and 11. Copies of this
information may be obtained free of charge from the
Cambridge Crystallographic Data Centre, CCDC, 12 Union
chromatography on silica gel (Et O). The product was
2
then crystallised with acetone/hexane (10:80, v/v) to afford
a yellow solid product (0.170 g, 24% yield). Mp 132–
4
.2. Caution
1
1
33 8C; H NMR (acetone) dZ2.44 (s, 3H) 9.45 (s, 1H),
1
3
All polynitro compounds described in this paper are
explosive and sensitive to shocks, frictions and sparkles.
Certain compounds are unstable and may decompose at
ambient temperature. Proper shielding is strongly
recommended.
10.40 (s, 1H), 11.28 (s, 1H). C NMR (acetone) dZ132.6,
152.6, 175.1, 25.8 ppm. N NMR (acetone) dZK24
14
(NO ). IR (KBr) 3365, 3237, 1764, 1713, 1632, 1570,
1527, 1463, 1371, 1239, 1201, 1167, 1046, 787, 750, 660,
2
K1
568 cm . MS (EI): m/zZ190 (6), 147 (8), 144 (10), 43
C
(
100); MS (CI , NH ): m/zZ191 (12), 208 (100), 225 (5).
3
4
5
.2.1. 1-Chloro-1,1-dinitro-2-(N-chloroamidino)-ethane
. DADNE (0.50 g, 3.4 mmol) was placed in methanol
4.2.5. 1,1,1-Trinitro-2-N-nitramidinoethene 8. Trifluoro-
acetic acid (16 mL) was introduced drop wise in nitric acid
(8.88 g) at 0 8C. Trifluoroacetic anhydride (24 mL) was
added drop wise at 0 8C. The mixture was stirred 10 min and
reached K5 8C. DADNE (1.600 g, 10.8 mmol) was added
in one portion. The mixture was stirred until the temperature
reached 5 8C. The mixture was cool (K5 8C) and filtrated.
The solid product was washed twice with very small
amounts of cold dichloromethane (K20 8C). The product
was poured into 100 mL of cold ethyl acetate (K20 8C). The
organic layer was washed with 30 mL of cold water (0 8C),
dried over sodium sulphate and concentrated under vacuum
(TZ20 8C). A yellow oil (2.63 g) was yielded. The product
was purified by chromatography on silica gel (CHCl3/
MeCN, 20:12). 1.53 g of pale brown oil was yielded (60%
yield). Acetonitrile traces remained even after evaporation
under good vacuum. Decomposition temp. 50 8C (8 8C/min
(
30 mL). The yellow suspension was stirred at 20 8C and
then N-chlorosuccinimide was quickly added (0.90 g,
.8 mmol). The mixture was stirred 3 h until it was
colourless and limpid. Dichloromethane was added
120 mL) and the organic layer was washed six times with
0 mL, 0.4 M sodium hydrogenocarbonate solution. 0.46 g
6
(
3
1
of white solid (75% yield) was yielded. Mp 90 8C; H NMR
(
1
3
CDCl ) dZ5.87 (s, broad). C NMR (CDCl ) dZ118.1,
3
3
1
4
15
1
53.7 ppm. N NMR (CDCl ) dZK27 (NO ). N NMR
3 2
(CDCl ) dZK304 (NH ), K158 (C]N), K27 (NO ) ppm.
IR (KBr) 3435, 3327, 1647, 1605, 1384, 1348, 1300, 1055,
9
1
elemental analysis calcd (%): C 11.1, H 0.9, N 25.8, O
2
3 2 2
K1
57, 834, 792, 776, 623, 452 cm . MS (EI): m/zZ216 (3),
C
70 (8); MS (CI , NH ): m/zZ217 (5), 171 (100);
3
9.5, Cl 32.7; found: C 12.0, H 1.0, N 25.5, O 27.7, Cl 33.8.
1
3
14
4
7
7
.2.2. 1-Bromo-1,1-dinitro-2-(N-bromooamidino)-ethane
. The same procedure as above was used. 53% yield. Mp
DSC); C NMR (acetone) dZ125.3, 151.0 ppm. N NMR
(acetone) dZK34 (C–NO ), K22 (N–NO ). IR (KBr)
1628, 1586, 1577, 1508, 1459, 1326, 1285, 1252, 846,
2
2
1
13
1 8C; H NMR (acetone) dZ7.59 (s, broad). C NMR
1
4
K1
(acetone) dZ113.0, 157.6 ppm. N NMR (acetone) dZ
K24 (NO ). IR (KBr) 3430, 3328, 1634, 1595, 1384, 1325,
1
804 cm
.
2
K1
296, 1025, 925, 829, 786, 753, 676, 623, 444 cm . MS
4.2.6. Reaction of 1,1,1-triamino-2-N-nitramidinoethene
8 with ammonia. 1,1,1-Triamino-2-N-nitramidinoethene
(0.36 g, 1.5 mmol) was dissolved in acetonitrile (6 mL). A
low stream of ammonia slowly bubbled into the mixture. It
was stirred for 3 h at ambient temperature. It became deep
yellow and a white solid (110 mg, 70% yield) was filtered
C
(
(
CI , NH ): m/zZ343 (6), 341 (12), 339 (6), 326 (11), 324
21), 322 (11); MS (CI , NH ): m/zZ307 (12) 305 (23),
3
K
3
3
03 (12), 225 (62).
4
.2.3. 1-Chloro-1,1-dinitro-2-(N-nitramidino)-ethane 6.
1
In a 50 mL round stirred flask containing nitric acid
1.50 g), acetic acid (1.34 g) was added drop wise at
–5 8C. Acetic anhydride (2.08 g) was then slowly added
and washed four times with acetone (3 mL). Mp 210 8C; H
1
3
(
0
NMR (DMSO) dZ7.64 (s, broad), 11.54 (s, 1H). C NMR
14
(DMSO) dZ160.8 ppm. N NMR (DMSO) dZK12
drop wise at 0–5 8C. 1-Chloro-1,1-dinitro-2-(N-chloro-
amidino)-ethane (0.400 g) was introduced by small portions
within 15 min at 0 8C. The mixture was stirred, maintained
between 0 and 5 8C for 1 h and finally poured into ice (60 g).
When the mixture reached 20 8C, it was filtered. The filtrate
was evaporated to dryness under vacuum. The residual solid
was dried over P O , washed several times with
(NO ). IR (KBr) 3452, 3397, 3345, 3279, 3201, 1665,
1637, 1527, 1407, 1302, 1151, 1044, 743, 724, 644, 568,
476 cm ; UV lmax 265 nm.
2
K1
The yellow filtrate was concentrated and ammonium
nitroformate 9 was purified by chromatography on silica
gel (CHCl /MeCN, 2:1). A yellow solid was yielded (70%).
3
2
5