T. M. Klapçtke et al.
(23), 1632 (5), 1610 (24), 1586 (7), 1567 (10), 1455 (16), 1434 (9), 1400
(11), 1348 (38), 1306 (8), 1283 (64), 1138 (4), 1102 (10), 1014 (4), 991
(10), 945 (7), 933 (2), 891 (54), 871 (8), 858 (100), 806 (4), 789 (5), 769
(3), 723 (7), 670 (3), 641 (15), 611 (8), 555 (10), 445 (4), 432 (23), 388
(30), 364 (54), 345 (8), 283 cmꢀ1 (24); MS (DEI+): m/z (%): 312 (<1)
[M+H]+, 266 (2) [MꢀOC2H5]+, 238 (14) [MꢀCOOC2H5]+, 219 (13)
[Mꢀ2NO2]+, 173 (11) [Mꢀ3NO2]+, 147 (23) [H5C2OOCCH2NNO2]+, 145
(16) [Mꢀ3NO2ꢀC2H4]+, 119 (8) [HOOCCH2NNO2]+, 46 (90) [NO2]+, 29
(100) [C2H5]+; sensitivities: impact: >40 J, friction: 192 N, grain size:
<100 mm.
d=5.46 (s, 2H; NCH2CACHTUNGTER(UNNG NO2)3), 4.61 ppm (s, 2H; COCH2N);
13C{1H} NMR (CDCl3): d=173.4 (CO), 122.0 (br; C
ACHTUNGTRENNUNG
53.9 ppm (CH2); 14N NMR (CDCl3): d=ꢀ36 (br; C
ACHTUNGTRENNUNG
OCNNN), ꢀ149 (br; OCNNN), ꢀ254 ppm (br; OCNNN); IR: n˜ =3015
(vw), 2972 (vw), 2862 (vw), 2248 (w), 2196/2129 (m, n N3), 1734 (vw),
1703 (s), 1604 (s), 1583 (s), 1563 (s), 1436 (w), 1397 (m), 1359 (w), 1330
(w), 1278 (vs), 1229 (vw), 1183 (vs), 1096 (w), 1075 (vw), 1009 (vw), 940
(m), 876 (vw), 861 (m), 854 (m), 806 (s), 786 (w), 774 (s), 750 (vw), 722
(w), 675 cmꢀ1 (vw); Raman: n˜ =3017 (34), 2984 (71), 2973 (3), 2873 (4),
2245 (4), 2188 (18), 2127 (7), 1709 (44), 1623 (18), 1608 (5), 1588 (4),
1566 (8), 1434 (19), 1397 (13), 1345 (41), 1299 (20), 1280 (52), 1135 (7),
1099 (5), 941 (4), 926 (61), 878 (10), 855 (100), 806 (3), 787 (7), 749 (25),
725 (5), 676 (5), 643 (9), 604 (3), 548 (14), 504 (13), 451 (3), 430 cmꢀ1
(40); MS (DEI+): m/z (%): 309 (<1) [M+H]+, 262 (<1) [MꢀNO2]+, 238
2-(Nitro-(2,2,2-trinitroethyl)amino)acetic acid (3): Compound 3 was pre-
pared according to a literature procedure.[3a]
1H NMR (CD3CN): d=5.64 (s, 2H; NCH2C
ACTHNUGTRNEG(UN NO2)3), 4.61 ppm (s, 2H;
COCH2N); 13C{1H} NMR (CD3CN): d=168.1 (COO), 55.4/54.9 ppm
(30) [CH2N
(NO2)C
E
(CH2); 14N NMR (CD3CN): d=ꢀ32 (br; NNO2), ꢀ34 ppm (C
ACHTUGNRTNE(NUNG NO2)3);
AHCTUNGTRENNUNG
(NO2)2]+, 70 (20) [OCNCH2N]+, 56 (32) [OCNCH2]+, 46 (100) [NO2]+, 30
1H NMR ([D6]DMSO): d=5.99 (s, 2H; NCH2C
ACTHNUGTRNEG(UN NO2)3), 4.64 ppm (s, 2H;
(100) [NO]+, 28 (50) [N2]+; sensitivities: impact: <1 J, friction: 48 N,
ESD: 0.03 J, grain size: 100–500 mm.
COCH2N); 13C{1H} NMR ([D6]DMSO): d=168.1 (COO), 123.8 (br; C-
(NO2)3), 55.1/53.7 ppm (CH2); 14N NMR ([D6]DMSO): d=ꢀ33 ppm (br;
ACHTUNGTRENNUNG
2,2,2-Trinitroethyl 2-(nitro-(2,2,2-trinitroethyl)amino)acetate (6): 2,2,2-
Trinitroethanol (0.75 g, 4.1 mmol) and compound 4 (1.00 g, 3.32 mmol)
were dissolved in boiling CCl4 (10 mL). Dry aluminumACTHNUTRGNE(NUG III) chloride
(0.5 g, 3.7 mmol) was added slowly to prevent extensive gas evolution
and the reaction mixture was heated at reflux for 1 h. Then, the mixture
was filtered, washed with cold hydrochloric acid (2m, 50 mL) and water
(50 mL), and dried in vacuo to afford compound 6 as a colorless solid
(0.72 g, 49% yield).
NO2); IR: n˜ =3011 (w), 2970 (w), 2866 (w), 2650 (vw), 2584 (vw), 2362
(vw), 2336 (vw), 1729 (s), 1609 (vs), 1591 (s), 1566 (vs), 1447 (m), 1428
(m), 1391 (m), 1345 (vw), 1276 (s), 1267 (s), 1198 (vw), 1138 (vw), 1098
(vw), 1016 (vw), 945 (w), 897 (w), 878 (vw), 866 (w), 854 (w), 804 (w),
787 (vw), 770 (w), 714 cmꢀ1 (vw); Raman: n˜ =3030 (11), 3013 (27), 2990
(63), 2973 (28), 2859 (4), 1662 (3), 1617 (46), 1584 (3), 1568 (10), 1452
(6), 1429 (18), 1393 (25), 1385 (6), 1346 (55), 1319 (9), 1300 (19), 1275
(49), 1138 (7), 1098 (4), 1016 (3), 998 (8), 945 (11), 894 (41), 880 (23), 855
(100), 806 (4), 789 (6), 771 (5), 724 (6), 669 (3), 627 (16), 607 (9), 558
(11), 466 (3), 451 (8), 436 (27), 389 (63), 365 (23), 348 (10), 288 (29), 247
(18), 235 cmꢀ1 (9); MS (DCI+): m/z (%): 284 (1) [M+H]+, 220 (1)
[MꢀOHꢀNO2]+, 178 (2) [MꢀCH2COOHꢀNO2]+, 146 (8) [MꢀCOOHꢀ2
NO2]+, 99 (61) [Mꢀ4NO2]+; MS (DEI+): m/z (%): 238 (8) [MꢀCOOH]+,
193 (18) [MꢀCO2ꢀNO2]+, 147 (10) [MꢀCO2ꢀ2NO2]+, 118 (10) [CH2C-
1H NMR ([D6]DMSO): d=6.06 (s, 2H; CH2C
CH2C
(NO2)3), 4.89 ppm (s, 2H; COCH2N); 13C{1H} NMR ([D6]DMSO):
d=164.9 (CO), 124.3 (br; C(NO2)3), 61.3 (OCH2C(NO2)3), 55.0 (CH2),
ACHTUGNTRENUN(NG NO2)3), 5.97 (s, 2H;
AHCTUNGTRENNUNG
A
ACHTUNGTRENNUNG
53.8 ppm (CH2); 14N NMR ([D6]DMSO): d=ꢀ31 (br; NO2), ꢀ34 ppm
(br; NO2); IR: n˜ =3020 (vw), 2978 (vw), 2890 (vw), 1772 (m), 1613 (s),
1590 (vs), 1576 (vs), 1435 (w), 1392 (m), 1366 (vw), 1326 (vw), 1294 (s),
1276 (vs), 1195 (s), 1139 (vw), 1099 (vw), 1035 (vw), 1011 (vw), 939 (w),
915 (vw), 878 (vw), 863 (m), 854 (w), 805 (s), 780 (m), 768 (w), 727 (vw),
711 (vw), 664 cmꢀ1 (vw); Raman: n˜ =3009 (27), 2964 (51), 2864 (3), 1786
(15), 1625 (24), 1603 (7), 1576 (3), 1563 (3), 1525 (2), 1440 (12), 1396
(20), 1374 (13), 1347 (35), 1302 (15), 1277 (28), 1217 (2), 1186 (5), 1131
(3), 1095 (10), 1054 (14), 1020 (3), 997 (6), 954 (7), 923 (14), 881 (26), 857
(100), 807 (7), 780 (4), 755 (4), 722 (4), 671 (4), 649 (2), 600 (5), 546 (11),
457 (4), 433 (22), 378 (53), 360 (13), 329 (6), 304 (6), 282 (27), 240 (13),
220 cmꢀ1 (2); MS (EI+): m/z (%): 399 (<1) [MꢀNO2ꢀH]+, 354 (1)
A
sitivities: impact: 15 J, friction: 144 N, grain size: 100–500 mm.
2-(Nitro-(2,2,2-trinitroethyl)amino)acetyl chloride (4): In contrast to the
procedure reported in ref. [3a], compound 3 (2.73 g, 9.64 mmol) was dis-
solved in thionyl chloride (40 mL, 66 g, 550 mmol) and the mixture was
heated at reflux (80–858C) for 4.5 h. The volatile materials were removed
under reduced pressure and the residue was dissolved in refluxing CCl4
(10 mL), filtered whilst hot, and allowed to crystallize at 48C to obtain
compound 4 as colorless crystals (2.34 g, 80% yield).
[Mꢀ2NO2]+, 308 (<1) [Mꢀ3NO2]+, 238 (7) [CH2N
(NO2)3]+, 118
ACHUTGTNERN(NUG NO2)CACHTUTGNRENNUGN
1H NMR (CD3CN): d=5.66 (s, 2H; NCH2C
COCH2N); 13C{1H} NMR (CD3CN): d=170.4 (CO), 63.6 (OCCH2N),
54.4 ppm (NCH2C
ꢀ34 ppm (C
(NO2)3); 1H NMR ([D6]DMSO): d=6.01 (s, 2H; NCH2C-
(NO2)3), 4.65 ppm (s, 2H; COCH2N); 13C{1H} NMR ([D6]DMSO): d=
168.0 (CO), 123.8 (br; C
(NO2)3), 55.1 (CH2), 53.7 ppm (CH2); 14N NMR
ACHTUGNTRENUN(GN NO2)3), 5.09 ppm (s, 2H;
(29) [CH2CACTHNUTRGNEUNG
(NO2)2]+, 46 (100) [NO2]+; elemental analysis calcd (%) for
C6H6N8O16: C 16.2, H 1.4, N 25.1; found: C 16.5, H 1.1, N 24.4; sensitivi-
ties: impact: 3 J, friction: 64 N, ESD: 0.25 J, grain size: <100 mm.
ACHTUNGTRENNUNG
ACHTUNGTRENNUNG
ACHTUNGTRENNUNG
2,2,2-Trinitroethyl (nitro-(2,2,2-trinitroethyl)amino)methyl carbamate (7):
AHCTUNGTRENNUNG
2,2,2-Trinitroethanol (0.47 g, 2.6 mmol) and compound
1.6 mmol) were dissolved in dry CHCl3 (5 mL) and a catalytic amount of
anhydrous aluminum(III) chloride was added. The reaction mixture was
5 (0.50 g,
([D6]DMSO): d=ꢀ34 ppm (br; NO2); IR: n˜ =3008 (vw), 2964 (vw), 1785
(m), 1729 (vw), 1625 (m), 1594 (vs), 1576 (vs), 1427 (w), 1383 (w), 1350
(vw), 1297 (s), 1272 (vs), 1204 (w), 1135 (vw), 1100 (w), 967 (m), 952 (m),
926 (m), 878 (vw), 860 (m), 854 (m), 807 (s), 788 (s), 776 (s), 754 (m), 719
(vw), 670 cmꢀ1 (vw); Raman: n˜ =3009 (30), 2974 (55), 1797 (27), 1621
(15), 1606 (22), 1592 (6), 1573 (13), 1516 (3), 1428 (8), 1392 (20), 1351
(44), 1324 (15), 1302 (20), 1274 (56), 1207 (4), 1135 (4), 1102 (5), 999 (7),
969 (3), 927 (5), 879 (32), 855 (100), 808 (7), 793 (36), 759 (22), 721 (4),
673 (3), 633 (11), 613 (6), 552 (11), 461 (95), 447 (6), 425 (18), 409 (29),
388 (37), 373 (24), 289 (13), 266 (32), 246 (14), 222 cmꢀ1 (12); MS
(DCI+): m/z (%): 302 (11) [M+H]+, 266 (91) [MꢀCl]+, 238 (55)
[MꢀClꢀCO]+, 208 (6) [MꢀClꢀCOꢀNO]+, 193 (22) [MꢀClꢀCOꢀ
NO2+H]+, 117 (16) [Mꢀ4NO2]+, 99 (15) [HOOCCH2NCH2C]+; sensitivi-
ties: impact: 30 J, friction: 64 N, ESD: 0.17 J, grain size: 100–500 mm.
AHCTUNGTRENNUNG
heated at reflux under an inert atmosphere for 5 h. CH2Cl2 (10 mL) was
added and the reaction mixture was washed with HCl (2m, 5ꢂ100 mL)
and water (5ꢂ100 mL). The organic layer was dried with magnesium sul-
fate and concentrated under reduced pressure to give a mixture of a col-
orless solid and a yellow oil. Complete solidification was achieved by ul-
trasound treatment of the mixture in water. Carbamate 7 was obtained
after recrystallization from CCl4 as colorless crystals (0.45 g, 61% yield).
1H NMR ([D6]acetone): d=8.49 (br t, 1H; NH), 6.01 (s, 2H; OCH2C-
3
(NO2)3), 5.81 (s, 2H; NCH2C
E
N
NHCH2N); 13C{1H} NMR ([D6]acetone): d=155.1 (CO), 124.9 (br; C-
(NO2)3), 124.4 (br; (NO2)3), 62.0 (OCH2C(NO2)3), 59.6 (NCH2N),
54.0 ppm (CH2C
NO2); 1H NMR (CDCl3): d=6.31 (t, 3J
2H; OCH2C(NO2)3), 5.46 (s, 2H; NCH2C
NHCH2N); 13C{1H} NMR (CDCl3): d=154.4 (CO), 122.6 (br; C
62.4 (OCH2C(NO2)3), 58.3 (NCH2N), 52.9 ppm (CH2C
(NO2)3); 14N NMR
A
C
A
ACHTUNGTRENNUNG
AHCTUNGTRENNUNG
2-(Nitro-(2,2,2-trinitroethyl)amino)acetyl azide (5): Compound 5 was pre-
pared according to a literature procedure.[3a] Compound 5 must be han-
dled with extreme caution and further conversion is recommended,
owing to its high tendency for decomposition.
AHCTUNGTRENNUNG
A
ACHTUNGTRENNUNG
ACHTUNGTRENNUNG
A
ACHTUNGTRENNUNG
1H NMR ([D6]DMSO): d=6.00 (s, 2H; NCH2C
COCH2N); 13C{1H} NMR ([D6]DMSO): d=174.2 (CO), 123.6 (br; C-
(NO2)3), 56.8 (COCH2N), 53.6 ppm (NCH2C
(NO2)3); 1H NMR (CDCl3):
ACHTUGNTRENUN(GN NO2)3), 4.85 ppm (s, 2H;
(CDCl3): d=ꢀ35 (br; NO2), ꢀ36 ppm (br; NO2); IR: n˜ =3381 (w), 3002
(vw), 2963 (vw), 2886 (vw), 1745 (m), 1623 (m), 1604 (s), 1588 (vs), 1572
(vs), 1531 (s), 1444 (m), 1410 (w), 1397 (w), 1346 (vw), 1288 (vs), 1227
A
ACHTUNGTRENNUNG
&
10
&
ꢀ 2013 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Chem. Eur. J. 0000, 00, 0 – 0
ÝÝ
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