Reinvestigation of the Nitration of Trichloroethene
161.4 (C1), 151.8 (C5), 134.1 (C7), 130.8 (C9), 118.9 (C8), 115.3 139 (85). HRMS (ESI): m/z calcd. for C13H14Cl4N5O5 [M + H]+
(C6), 114.3 (C10), 101.0 (C2), 49.7 (2 NCH2), 49.2 (2 NCH2), 47.4
(2 NCH2), 47.1 (2 NCH2) ppm. EIMS: m/z (%) = 495 (1) [M+],
478 (25), 449 (2), 300 (7), 166 (100). HRMS (ESI): m/z calcd. for
C22H24Cl3N5O2Na [M + Na]+ 518.0893; found 518.0890.
459.9749; found 459.9747.
(1E,1ЈE)-Nitro(4-{(E)-nitro[(1,2,2-trichloro-2-nitroethoxy)imino]-
methyl}piperazin-1-yl)methanone O-(1,2,2-Trichloro-2-nitroethyl)
Oxime (22): The product was synthesized by following General Pro-
cedure II from azinate 9 (1.58 g, 5.00 mmol) and piperazine (0.47 g,
5.50 mmol). Pale yellow solid, 88% yield (1.35 g), m.p. 184–186 °C.
14 was also obtained by following General Procedure I from 8
(0.21 g, 1.00 mmol) and 1-(3-chlorophenyl)piperazine (1.02 g,
5.20 mmol) at –20 °C for 1 h, then 4 h at r.t. in 52% yield.
IR (ATR): ν = 3001, 2936, 1675, 1591, 1558, 1447, 1401, 1357,
˜
1332, 1285, 1204, 1092, 1007, 969, 892, 809, 758, 683, 621 cm–1. 1H
General Procedure II
1
NMR (600 MHz, [D6]DMSO): δ = 7.47 (s, JC,H = 187.7 Hz, 2 H,
CHCl), 3.44 (s, 8 H) ppm. 13C NMR (150 MHz, [D6]DMSO): δ
= 156.7 [=C(NR2)NO2], 110.9 (CCl2NO2), 96.8 (CHCl), 48.1 (4
CH2) ppm. 14N (43.4 MHz, CDCl3): δ = –12.1 (NO2), –19.5 (NO2),
–72.4 (C=N-O), –314.4 (NCH2) ppm. EIMS: m/z (%) = 612 (1)
[M+], 566 (1), 531 (2), 328 (4), 282 (7), 138 (100). HRMS (ESI): m/z
calcd. for C10H11Cl6N8O10 [M + H]+ 612.8729; found 612.8732.
(E)-Morpholino(nitro)methanone O-(1,2,2-Trichloro-2-nitroethyl)
Oxime (19): A solution of morpholine (0.96 g, 11.00 mmol) in
MeOH (5 mL) was added dropwise to a solution of azinate 9
(1.58 g, 5.00 mmol) in MeOH (10 mL) at –10 °C over 20 min. The
resulting reaction mixture was kept at the same temperature for an
additional 60 min with stirring. After 4 h at r.t. and subsequent
cooling to 0 °C the resulting precipitate was filtered, washed with
cold MeOH (5 mL), and then dried in vacuo to give 19 as a mixture
of E- and Z-isomers (94.4:5.6). Yellow solid, 78% yield (1.37 g),
1,3-Bis(4-chlorophenyl)-2-(1,2,2-trichloro-2-nitroethoxy)guanidine
(23): The product was synthesized by following General Procedure
II from azinate 9 (1.58 g, 5.00 mmol) and (2.81 g, 22 mmol) 4-chlo-
roaniline, reaction time 1 h at –10 °C and 14 h at r.t. Beige solid,
m.p. 108–109 °C. IR (KBr): ν = 2986, 2866, 1693, 1593, 1556, 1338,
˜
1269, 1113, 1090, 968, 890, 800, 714, 588 cm–1
.
1H NMR
65% yield (1.54 g), m.p. 141–142 °C. IR (ATR): ν = 3417, 1638,
˜
1
(400 MHz, CDCl3): Major isomer, δ = 6.67 (s, JC,H = 188.2 Hz, 1
H), 3.79–3.55 (m, 4 H, 2 OCH2), 3.37–3.30 (m, 4 H, 2 NCH2) ppm.
13C NMR (100 MHz, CDCl3): δ = 156.8 [=C(NR2)NO2], 110.8
(CCl2NO2), 96.9 (CHCl), 66.2 (2 OCH2), 48.4 (2 NCH2) ppm. 14N
(28.9 MHz, CDCl3): δ = –8.8 (NO2), –14.0 (NO2), –75.0 (C=N-O),
1584, 1532, 1490, 1431, 1299, 1345, 1137, 1088, 1014, 931, 829,
709, 663, 562 cm–1. 1H NMR (400 MHz, CDCl3): δ = 7.34–7.20
(m, 4 H), 7.14–7.08 (m, 4 H), 6.72 (s, 1 H, CHCl), 6.48 (br. s, 1 H,
NH), 5.43 (br. s, 1 H, NH) ppm. 13C NMR (100 MHz, CDCl3): δ
= 151.8 [=C(NAr2)2], 129.6 (2 CH), 129.4 (2 CH), 128.8 (2 CH),
128.5 (2 CH), 125.4 (Cq), 125. 6 (Cq), 120.5 (Cq), 120.3 (Cq), 111.5
(CCl2NO2), 97.1 (CHCl) ppm. EIMS: m/z (%) = 470 (5) [M+], 294
(10), 278 (12), 263 (8), 243 (6), 127 (100) [NH2C6H4Cl]. HRMS
(ESI): m/z calcd. for C15H12Cl5N4O3 [M + H]+ 470.9352; found
470.9358.
1
–313.3 (NCH2) ppm. Minor isomer, δ = 6.27 (s, JC,H = 184.8 Hz
1 H), 3.79–3.55 (m, 4 H, 2 OCH2 ), 3.41–3.36 (m, 4 H, 2
NCH2) ppm. 13C NMR (100 MHz, CDCl3): δ = 153.5 [=C(NR2)-
NO2], 110.7 (CCl2NO2), 100.9 (CHCl), 66.3 (2 OCH2), 48.3 (2
NCH2) ppm. EIMS: m/z (%) = 350 (2) [M+], 304 (8), 269 (2), 128
(20), 112 (100). HRMS (EI): m/z calcd. for C7H9Cl3N4O6 [M+]
349.9588; found 349.9580. The structure of E-oxime 19 was evi-
denced by single-crystal X-ray diffraction analysis (Figure 3).
1,3-Bis(4-bromophenyl)-2-(1,2,2-trichloro-2-nitroethoxy)guanidine
(24): The product was prepared by following General Procedure II
from azinate 9 (1.58 g, 5.00 mmol) and (3.78 g, 22 mmol) 4-bromo-
aniline, reaction time 1 h at –10 °C and 18 h at r.t. Beige solid, 70%
(E)-[3,4-Dihydroisoquinolin-2(1H)-yl](nitro)methanone O-(1,2,2-Tri-
chloro-2-nitroethyl) Oxime (20): The product was prepared by fol-
lowing General Procedure II from azinate 9 (1.58 g, 5.00 mmol) and
1,2,3,4-tetrahydroisoquinoline (1.47 g, 11 mmol). Pale yellow solid,
yield (1.97 g), m.p. 154–156 °C. IR (ATR): ν = 3413, 3396, 1640,
˜
1585, 1531, 1487, 1432, 1362, 1298, 1233, 1133, 1119, 1011, 930,
826, 713, 661, 539 cm–1. 1H NMR (400 MHz, CDCl3): δ = 7.48 (d,
J = 8.7 Hz, 2 H), 7.36 (d, J = 8.6 Hz, 2 H), 7.10–7.02 (m, 4 H),
6.72 (s, 1 H, CHCl), 6.48 (br. s, 1 H, NH), 5.41 (br. s, 1 H,
NH) ppm. 13C NMR (100 MHz, CDCl3): δ = 151.6 [=C(NAr2)2],
137.5 (Cq), 135.4 (Cq), 132.9 (2 CH), 132.0 (2 CH), 125.7 (2 CH),
120.8 (2 CH), 119.4 (Cq), 115.7 (Cq), 111.5 (CCl2NO2), 97.1
(CHCl) ppm. EIMS: m/z (%) = 558 (5) [M+], 382 (10), 366 (12),
354 (7), 287 (20), 171 (100). HRMS (ESI): m/z calcd. for
C15H12Br2Cl3N4O3 [M + H]+ 558.8342; found 558.8341.
71% yield (1.41 g), m.p. 85–87 °C. IR (KBr): ν = 2998, 1686, 1583,
˜
1562, 1497, 1443, 1394, 1329, 1251, 1101, 1048, 998, 953, 800, 756,
692 cm–1. 1H NMR (400 MHz, CDCl3): δ = 7.27–7.22 (m, 2 H),
7.20–7.16 (m, 1 H), 7.07–7.02 (m, 1 H), 6.70 (s, 1 H, CHCl), 4.52
(s, 2 H), 3.66–3.54 (m, 2 H), 3.05–3.00 (m, 2 H) ppm. 13C NMR
(100 MHz, CDCl3): δ = 157.2 [=C(NR2)NO2], 133.0 (Cq), 130.8
(Cq), 129.1 (CH), 127.3 (CH), 126.8 (CH), 126.1 (CH), 110.9
(CCl2NO2), 97.1 (CHCl), 49.7 (CH2), 46.4 (CH2), 28.6 (CH2) ppm.
EIMS: m/z (%) = 396 (1) [M+], 350 (1), 304 (1), 193 (5), 158 (48),
104 (100). HRMS (ESI): m/z calcd. for C12H12Cl3N4O5 [M + H]+
396.9873; found 396.9878.
1,3-Bis(4-fluorophenyl)-2-(1,2,2-trichloro-2-nitroethoxy)guanidine
(25): The product was synthesized by following General Procedure
II from azinate 9 (1.58 g, 5.00 mmol) and 4-fluoroaniline (2.44 g,
22 mmol), reaction time 1 h at –10 °C and 18 h at r.t. Beige solid,
(E)-[4-(3-Chlorophenyl)piperazin-1-yl](nitro)methanone O-(1,2,2-
Trichloro-2-nitroethyl) Oxime (21): The product was prepared by
following General Procedure II from azinate 9 (1.58 g, 5.00 mmol)
and 1-(3-chlorophenyl)piperazine (2.16 g, 11 mmol). Pale yellow
43% yield (0.95 g), m.p. 81–82 °C. IR (ATR): ν = 3416, 1640, 1586,
˜
1541, 1506, 1395, 1299, 1211, 1140, 1013, 933, 831, 710, 659, 608,
513 cm–1. 1H NMR (400 MHz, CDCl3): δ = 7.21–7.12 (br. m, 4 H),
7.10–7.01 (br. m, 2 H), 6.99–6.89 (br. m, 2 H), 6.71 (s, 1 H, CHCl),
6.46 (br. s, 1 H, NH), 5.29 (br. s, 1 H, NH) ppm. 13C NMR
solid, 79% yield (1.82 g), m.p. 131–132 °C. IR (KBr): ν = 2948,
˜
2834, 1690, 1592, 1556, 1453, 1400, 1334, 1315, 1219, 1148, 1118,
1
1015, 956, 869, 807, 731, 692, 632 cm–1
.
1H NMR (400 MHz,
(100 MHz, CDCl3): δ = 161.1 (d, JC,F = 242.8 Hz, CF), 159.2 (d,
CDCl3): δ = 7.25–7.18 (m, 1 H), 6.94–6.88 (m, 2 H), 6.82–6.78 (m, 1JC,F = 242.8 Hz, CF), 152.9 [=C(NAr2)2], 134.3 (Cq), 132.1 (Cq),
3
3
1 H), 6.69 (s, 1 H, CHCl), 3.52–3.46 (m, 4 H), 3.33–3.25 (m, 4 127.2 (d, JC,F = 8.4 Hz, 2 CH), 121.6 (d, JC,F = 8.4 Hz, 2 CH),
H) ppm. 13C NMR (100 MHz, CDCl3): δ = 156.9 [=C(NR2)NO2], 116.7 (d, 2JC,F = 23.4 Hz, 2 CH), 115.6 (d, 2JC,F = 23.4 Hz, 2 CH),
151.6 (Cq), 135.2 (Cq), 130.4 (CH), 121.0 (CH), 116.9 (CH), 114.9 111.6 (CCl2NO2), 97.3 (CHCl) ppm. EIMS: m/z (%) = 438 (5)
(CH), 110.9 (CCl2NO2), 97.1 (CHCl), 49.1 (2 CH2), 48.2 (2
[M+], 262 (20), 246 (19), 231 (12), 111 (100). HRMS (ESI): m/z
CH2) ppm. EIMS: m/z (%) = 459 (16) [M+], 331 (2), 221 (100),
calcd. for C15H11Cl3F2N4O3 [M + H]+ 438.9943; found 438.9946.
Eur. J. Org. Chem. 2015, 7763–7774
© 2015 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.eurjoc.org
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