T. M. Klapçtke et al.
was added B2O3 (225 mg, 3.23 mmol) at ambient temperature under care-
ful exclusion of moisture. After stirring the colorless mixture for 7 h at
458C, the reaction mixture was decanted to remove unreacted boron
oxide/acid. Removing the solvent in vacuo left a colorless solid. Crystalli-
zation of the product from dichloromethane yielded 2 (1.66 g, 83%) as
colorless crystals. Raman: n˜ =3017 (11), 2966 (38), 2895 (3), 1612 (12),
1588 (20, nasNO2), 1456 (12), 1393 (20), 1359 (33), 1320 (17), 1248 (11),
1180 (3), 1115 (5), 1069 (13), 1019 (6), 1003 (6), 930 (14), 882 (4), 854
(100, nCN), 807 (1), 768 (9), 705 (1), 536 (8), 423 (25), 382 (23), 361 (28),
309 (6), 287 (2), 267 (3), 213 (19), 192 cmÀ1 (18); IR (ATR): n˜ =3015 (w),
2963 (w), 2897 (w), 1589 (vs, nasNO2), 1457 (s), 1435 (s), 1413 (vs), 1382
(s), 1337 (s), 1310 (vs), 1261 (m), 1243 (s), 1194 (s), 1115 (s), 1068 (s),
magnesium sulfate. After removing the solvent in vacuo, the pale brown-
ish oil was distilled (418C at 6 mbar) yielding 5 (6.02 g, 51%) as a color-
less oil. Raman: n˜ =3006 (5), 2955 (18), 2877 (3), 1591 (13, nasNO2), 1448
(11), 1385 (14), 1356 (28), 1326 (10), 1234 (2), 1090 (9), 1001 (4), 916 (4),
852 (100, nCN), 801 (2), 756 (2), 570 (3), 516 (5), 423 (12), 381 (45), 318
(2), 282 (3), 190 cmÀ1 (17); IR (ATR): n˜ =3355 (w), 2953 (w), 2908 (w),
1586 (vs, nasNO2), 1446 (m), 1381 (w), 1353 (m), 1314 (s), 1231 (m), 1079
(s), 1002 (m), 917 (m), 878 (w), 850 (m, nCN), 798 (vs), 759 (m),
691 cmÀ1 (m); 1H NMR (CDCl3): d=4.66 (dd, 3JHÀF =15.3 Hz, 2H,
4
OCH2), 2.80 ppm (t, JHÀF =1.6 Hz, 1H, HO); 13C{1H} NMR (CDCl3): d=
120.8 (d, 1JCÀF =290.2 Hz,
(NO2)2F), 61.6 ppm (d, 2JCÀF =21.3 Hz,
CACHTUNGRTNEGNU
3
OCH2); 15N NMR (CDCl3): d=À22.7 ppm (dt, 2JNÀF =15.0 Hz, JNÀH
=
1.3 Hz, NO2); 19F NMR (CDCl3): d=À111.9 ppm (m, br, FC); MS
(CI+): m/z (%): 155 (100) [M++H]; MS (EI+): m/z (%): 155 (0.3) [M+
H]+, 62 (100) [MÀ2NO2]+, 46 (89) [NO2]+; elemental analysis calcd (%)
for C2H3FN2O5 (154.05): C 15.59, H 1.96, N 18.18; found: C 15.81, H
1.94, N 18.11; DTA (Tonset, 58C minÀ1): 2158C (boiling point); sensitivities
(liquid): impact: 30 J, friction: 240 N.
1
1002 (m), 927 (m), 884 (w), 850 (s, nCN), 800 (vs), 760 cmÀ1 (s); H NMR
(CD3OD): d=4.63 ppm (d, 3JHÀF =18.1 Hz, 6H, OCH2); 11B NMR
(CD3OD): d=18.1 ppm (br); (CDCl3): d=17.8 ppm (br); 13C{1H} NMR
2
(CD3OD): d=123.6 (d, 1JCÀF =289.3 Hz, C
C
=
19.8 Hz, OCH2); 14N NMR (CDCl3): d=À24 ppm (s, NO2); 15N NMR
(CD3OD): d=À21.3 ppm (d, 2JNÀF =15.0 Hz, NO2); 19F NMR (CD3OD):
d=À114.5 ppm (m, br, FC); (CDCl3): d=À111.8 ppm (m, br, FC); ele-
mental analysis calcd (%) for C6H6BF3N6O15 (469.95): C 15.33, H 1.29, N
17.88; found: C 14.89, H 1.60, N 16.65; DTA (Tonset, 58C minÀ1): 2098C
(decomposition); sensitivities (grain size: <100 mm): impact: 18 J, fric-
tion: >360 N, electrostatic: 1.0 J.
Potassium 1,1,3,3-tetranitropropane-1,3-diide (6): Into a suspension of 4
(1.35 g, 7.75 mmol) in water (6 mL) was added 1m sulfuric acid until a
pH value of 4 was achieved (ca. 2 mL). After stirring the yellow solution
for 1 h, the color had changed to red and a saturated potassium hydrox-
ide solution was added at 08C. The precipitated product was filtered and
washed with cold water and diethylether (each 2ꢂ2 mL). Drying on air
at room temperature yielded 6 (0.74 g, 63%) as yellow-orange crystals.
Raman: n˜ =3010 (1), 2976 (6), 1520 (1), 1490 (12, nasNO2), 1422 (2), 1403
(1), 1380 (8), 1348 (25), 1321 (10), 1220 (51), 1153 (7), 1146 (6), 1111 (6),
1085 (44), 1061 (2), 984 (29), 893 (3), 861 (54), 851 (100, nCN), 778 (14),
743 (3), 721 (1), 704 (1), 661 (4), 627 (2), 620 (4), 484 (49), 455 (5), 436
(5), 376 (18), 286 (4), 271 (6), 2458 cmÀ1 (6); IR (ATR): n˜ =3007 (w),
2975 (w), 1498 (m, nasNO2), 1470 (m), 1380 (m), 1355 (m), 1334 (m), 1321
(m), 1232 (s), 1206 (s), 1195 (s), 1153 (s), 1142 (s), 1103 (vs), 1081 (vs),
1031 (s), 983 (m), 891 (m), 860 (m, nCN), 776 (m), 742 (m), 718 (m),
698 cmÀ1 (s); 1H NMR ((CD3)2SO): d=4.57 ppm (d, 2H, CH2);
Synthesis of tris(2,2,2-trinitroethyl) borate (3): Into a solution of 2,2,2-tri-
nitroethanol (3.45 g, 19.1 mmol) of dry acetonitrile (3 mL) was added
B2O3 (290 mg, 4.14 mmol) at ambient temperature under careful exclu-
sion of moisture. After stirring the colorless mixture for 7 h at 408C, the
reaction mixture was decanted to remove unreacted boron oxide/acid.
Removing the solvent in vacuo left a colorless solid. Crystallization of
the product from dichloromethane yielded 3 (2.65 g, 88%) as colorless
crystals. Raman: n˜ =3009 (18), 2970 (33), 2910 (3), 1612 (19), 1599 (21,
nasNO2), 1456 (6), 1445 (6), 1426 (3), 1395 (12), 1376 (5), 1355 (36), 1310
(30), 1278 (12), 1180 (1), 1150 (3), 1100 (4), 1075 (7), 1019 (5), 1006 (6),
883 (8), 858 (100, nCN), 824 (2), 809 (5), 782 (6), 762 (3), 722 (3), 652 (5),
566 (2), 542 (15), 418 (37), 402 (44), 378 (62), 340 (4), 306 (10), 261 (10),
233 (7), 205 cmÀ1 (19); IR (ATR): n˜ =3009 (w), 2966 (w), 2893 (w), 1586
(vs, nasNO2), 1455 (m), 1439 (m), 1419 (m), 1373 (m), 1330 (m), 1306 (m),
1297 (s), 1274 (m), 1259 (m), 1243 (m), 1199 (m), 1148 (m), 1089 (s),
1059 (m), 1005 (m), 941 (w), 881 (m), 856 (m, nCN), 803 (vs), 779 (s),
712 cmÀ1 (m); 1H NMR (CD3OD): d=4.92 ppm (s, 6H, OCH2);
11B NMR (CD3OD): d=18.1 ppm (br); (CDCl3): d=17.6 ppm (br);
13C{1H} NMR ((CD3)2SO): d=131.7 (br, C
ACHTUNGRTNE(UNG NO2)2), 29.6 ppm (s, CH2);
14N NMR ((CD3)2SO): d=À24 ppm (s, NO2); MS (FAB+): m/z (%): 39
(100) [K]+; MS (FABÀ): m/z (%): 223 (100) [(NO2)2CCH2C
(NO2)2+H]À;
ACHTUNGTRENNUNG
elemental analysis calcd (%) for C3H2K2N4O8 (300.27): C 12.00, H 0.67,
N 18.66; found: C 12.07, H 0.70, N 18.57.
13C{1H} NMR (CD3OD): d=128.3 (br, C
ACHTUNGRTNE(UNG NO2)3), 64.0 ppm (s, OCH2);
14N NMR (CDCl3): d=À33 ppm (s, NO2); 15N NMR (CD3OD): d=
À31.1 ppm (s, NO2); elemental analysis calcd (%) for C6H6BN9O21
(550.97): C 13.08, H 1.10, N 22.88; found: C 13.18, H 1.41, N 22.01; DTA
Acknowledgements
Financial support of this work by the Ludwig-Maximilian University of
Munich (LMU), the U. S. Army Research Laboratory (ARL) under
grant no. W911NF-09-2-0018, the Armament Research, Development
and Engineering Center (ARDEC) under grant no. W911NF-12-1-0467,
and the Office of Naval Research (ONR) under grant nos. ONR.N00014-
10-1-0535 and ONR.N00014-12-1-0538 is gratefully acknowledged. The
authors acknowledge collaborations with Dr. Mila Krupka (OZM Re-
search, Czech Republic) in the development of new testing and evalua-
tion methods for energetic materials. We would also like to thank Dr.
Jesse J. Sabatini (US Army RDECOM-ARDEC, USA) for many in-
spired discussions. Research students Katrin Fenzke, M.Sc., and Andreas
Ahlers, M.Sc., are thanked for their participation in this project.
(Tonset,
58C minÀ1): 1508C (decomposition); sensitivities (grain size:
<100 mm): impact: 8 J, friction: 144 N, electrostatic: 0.5 J.
Additional analytical data of potassium 2-hydroxy-1,1-dinitroethane-1-ide
(4): Raman: n˜ =3032 (13), 2976 (1), 2932 (5), 1498 (4, nasNO2), 1465 (2),
1449 (8), 1407 (7), 1387 (22), 1362 (15), 1326 (5), 1311 (9), 1286 (11),
1223 (51), 1133 (14), 1091 (23), 1005 (24), 934 (17), 847 (100, nCN), 778
(2), 766 (5), 745 (1), 738 (1), 675 (3), 662 (1), 484 (50), 455 (12), 434 (14),
363 (5), 292 (15), 218 cmÀ1 (2); IR (ATR): n˜ =3510 (w), 3031 (w), 2931
(w), 1470 (s, nasNO2), 1410 (m), 1356 (m), 1326 (m), 1288 (m), 1222 (m),
1134 (s), 1122 (vs), 1083 (s), 1006 (vs), 931 (s), 892 (m), 860 (m, nCN),
845 (s), 776 (m), 759 (s), 747 (m), 736 (m), 698 (m), 675 cmÀ1 (s);
1H NMR ((CD3)2SO): d=4.70 (d, 2H, OCH2), 4.44 ppm (t, 1H, HO);
13C{1H} NMR ((CD3)2SO): d=135.9 (br, C
ACHTUNGRTNE(UNG NO2)2), 57.0 ppm (s, OCH2);
14N NMR ((CD3)2SO): d=À22 ppm (s, NO2); MS (FAB+): m/z (%): 39
Moll, A. Penger, S. M. Sproll, R. J. F. Berger, S. A. Hayes, N. W.
Mitzel, Z. Naturforsch. 2013, 68b, 719–731.
(100) [K]+; MS (FABÀ): m/z (%): 135 (100) [HOCH2C
(NO2)2]À; ele-
ACHTUNGTRENNUNG
mental analysis calcd (%) for C2H3KN2O5 (174.15): C 13.79, H 1.74, N
16.09; found: C 13.70, H 1.66, N 16.17.
Synthesis of 2-fluoro-2,2-dinitroethanol (5): Into
a suspension of 4
[2] a) F. Zwicky, Astronautics (Easton. 1957-63) 1957, 2, 45–49/95–97;
[3] a) V. I. Burmistrov, L. M. Kozlov, T. F. Telkova (Chem. Technol.
Inst., Kazan), SU154243, 1963; b) L. M. Kozlov, V. I. Burmistrov,
T. F. Telkova, Izv. Vyssh. Uchebn. Zaved. Khim. Khim. Tekhnol.
(13.4 g, 77.0 mmol) in water (100 mL) was added Selectfluor fluorinating
reagent (30.0 g, 84.7 mmol) at 08C. After stirring the yellow mixture for
2 h at ambient temperature, the reaction mixture had become colorless.
The mixture was filtered to remove precipitated reaction residues, ex-
tracted with dichloromethane (5ꢂ120 mL) and dried over anhydrous
&
10
&
ꢀ 2013 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Chem. Eur. J. 0000, 00, 0 – 0
ÝÝ
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