The Journal of Organic Chemistry
Article
2-(Fluoromethyl)isouronium-2,4,6-trinitrobenzenesulfo-
nate (5a). Reagent 4 (100 mg, 309 μmol) was dissolved in
acetonitrile (1.5 mL) and added dropwise to a solution of urea
(18.6 mg, 309 μmol) in acetonitrile (5 mL). The resulting solution
was stirred overnight, and the solvent was removed in vacuo. The
crude product was recrystallized from a dichloromethane/acetoni-
trile mixture (5 mL/0.3 mL). The mixture was centrifuged, and the
solvent was decanted. The remaining solid was dried in vacuo,
yielding 95 mg of a white solid. Yield: 80%. Tmp: 180 °C. Tdec: 200
MHz): δ −14.9 (s, 2N), −22.7 (s, 1N), −230.9 (s, 1N). IR (ATR):
3095 (m), 3041 (w), 2997 (m), 2904 (w), 1723 (m), 1607 (m),
1542 (s), 1443 (w), 1403 (w), 1353 (s), 1314 (m), 1269 (s), 1236
(s), 1187 (w), 1164 (w), 1120 (m), 1056 (m), 1035 (m), 1004
(m), 991 (s), 937 (w), 924 (w), 912 (w), 902 (w), 844 (m), 825
ν
̃
(w), 749 (s), 732 (m), 718 (s), 632 (s). Raman: ν 3095 (w), 3039
̃
(w), 3025 (w), 3972 (m), 1722 (w), 1602 (m), 1554 (w), 1431
(w), 1381 (m), 1358 (s), 1071 (m), 827 (m), 349 (w), 319 (w),
268 (m), 231 (m), 168 (w), 151 (m). Anal. Calcd for
C10H11FN4O10S: C, 30.16; H, 2.78; N, 14.07; S, 8.05. Found: C,
30.01; H, 2.93; N, 14.23; S, 7.82.
1
°C. H NMR (CD3CN, 400 MHz): δ 8.57 (s, 2H), 7.49 (d, 4H, J =
136.0 Hz), 5.80 (d, 2H, J = 50.2 Hz). 13C{1H} NMR (CD3CN, 101
1
MHz): δ 162.2, 150.8, 149.3, 137.8, 122.1, 99.9 (C−F, JC−F
=
Ammonium-2,4,6-trinitrobenzenesulfonate (6a). From the
filtrate of the synthesis of 5a, the solvent was slowly removed under
reduced pressure, yielding 3.5 mg of colorless crystals. Tdec: 254.8
229.0 Hz). 19F{1H} NMR (CD3CN, 376 MHz): δ −156.5 (s). 19F
2
NMR (CD3CN, 376 MHz): δ −156.5 (CH2F, JF−H = 50.2 Hz).
15N{1H} NMR (acetone-d6, 29 MHz): δ −15.6 (s, 2N), −22.6 (s,
1
°C. H NMR (CD3CN, 400 MHz): δ 8.54 (s, 2H), 5.96 (t, 4H, J =
50.2 Hz). 13C{1H} NMR (CD3CN, 101 MHz): δ 121.8. 14N{1H}
NMR (CD3CN, 29 MHz): δ −15.2 (s, 2N), −22.4 (s, 1N), −360.1
1N), −298.3 (s, 1N). IR (ATR): ν 3419 (m), 3393 (m), 3352 (m),
̃
3247 (m), 3183 (m), 3162 (m), 3113 (m), 3085 (m), 1703 (s),
1643 (w), 1603 (w), 1556 (s), 1544 (s), 1531 (s), 1414 (w), 1349
(s), 1282 (w), 1235 (s), 1188 (w), 1168 (m), 1121 (m), 1095 (w),
1072 (m), 1026 (s), 934 (w), 926 (w), 912 (w), 892 (m), 826 (w),
749 (m), 731 (m), 719 (s), 637 (s), 564 (m), 547 (s), 526 (m),
(s, 1N). IR (ATR): ν 3462 (w), 3208 (s), 3072 (s), 2895 (w), 1842
̃
(w), 1658 (w), 1600 (w), 1532 (s), 1415 (s), 1350 (s), 1249 (s),
1227 (s), 1120 (s), 1072 (s), 1032 (s), 983 (m), 936 (m), 918 (s),
827 (w), 749 (s), 733 (s), 714 (s), 663 (m), 633 (s), 559 (s), 520
483 (m), 451 (m), 441 (s). Raman: ν 3084 (w), 1602 (m), 1567
̃
(m), 479 (m), 454 (s), 435 (m). Raman: ν 3078 (w), 1602 (m),
̃
(m), 1547 (m), 1377 (m), 1351 (s), 1187 (w), 1075 (m), 1030
(w), 893 (m), 826 (m), 529 (w), 454 (w), 442 (m), 352 (m), 318
(w), 276 (w), 238 (w), 207 (s), 172 (s). HRMS (ESI) m/z: M+
calcd for C2H6FN2O+, 93.0459; found, 93.0459. Anal. Calcd for
C8H8FN5O10S: C, 24.94; H, 2.09; N, 18.18; S, 8.32. Found: C,
24.94; H, 2.38; N, 18.34; S, 8.03.
1558 (m), 1544 (m), 1371 (s), 1353 (s), 1078 (s), 827 (s), 770 (s),
561 (w), 523 (w), 455 (w), 436 (m), 356 (m), 321 (w), 275 (w),
240 (w), 215 (w), 177 (m), 128 (m). HRMS (ESI) m/z: M+ calcd
for C6H10N5O9S+, 328.0194; found, 328.0190.
Dimethylammonium-2,4,6-trinitrobenzenesulfonate (6b).
From either of the filtrates obtained during the syntheses of 5b or
5c, the solvent was slowly removed under reduced pressure, yielding
2 or 13 mg, respectively, of colorless crystals. Tdec: 189 °C. 1H
NMR (CD3CN, 400 MHz): δ 8.57 (s, 2H), 6.62 (t, 2H, J = 50.7
Hz), 2.65 (t, 6H, J = 5.7 Hz). 13C{1H} NMR (CD3CN, 101 MHz):
δ 150.8, 149.1, 138.6, 121.9, 36.1. 14N{1H} NMR (CD3CN, 29
MHz): δ −15.5 (s, 2N), −22.9 (s, 1N), −358.9 (s, 1N). IR (ATR):
Fluoromethyl-dimethylacetamidinium-2,4,6-trinitrobenze-
nesulfonate (5b). Reagent 4 (126 mg, 387 μmol) was dissolved in
acetonitrile (1.0 mL) and added dropwise to a solution of
dimethylacetamide (33.7 mg, 387 μmol) in acetonitrile (5 mL).
The yellowish solution was stirred for 18 h at room temperature.
After the solvent was removed in vacuo, the crude product was
recrystallized from a dichloromethane/acetonitrile mixture (10 mL/
0.3 mL). The mixture was centrifuged, and the solvent was
decanted. The remaining solid was dried in vacuo, yielding 143 mg
ν 3159 (m), 3099 (m), 1665 (w), 1607 (m), 1541 (s), 1467 (m),
̃
1354 (s), 1275 (m), 1223 (s), 1153 (m), 1122 (m), 1071 (m),
1034 (m), 984 (w), 926 (w), 911 (m), 901 (m), 883 (w), 823 (w),
1
of 5b as a colorless solid. Yield: 78%. Tmp: 175 °C. Tdec: 185 °C. H
749 (s), 732 (m), 719 (s). Raman: ν 3097 (w), 3051 (w), 2980
̃
NMR (CD3CN, 400 MHz): δ 8.53 (s, 2H), 5.95 (d, 2H, J = 49.7
Hz), 3.39 (s, 3H), 3.30 (s, 3H), 2.55 (s, 3H). 13C{1H} NMR
(CD3CN, 101 MHz): δ 175.9, 150.6, 148.9, 139.4, 121.7, 100.8
(m), 1604 (m), 1549 (m), 1533 (w), 1469 (w), 1370 (s), 1355 (s),
1189 (w), 1074 (s), 883 (w), 824 (m), 450 (w), 354 (m), 322 (m),
271 (m), 234 (s), 181 (s). HRMS (ESI) m/z: M+ calcd for
C10H18N5O9S+, 384.0820; found, 384.0819.
1
(C−F, JC−F = 231.3 Hz), 42.8, 40.8, 16.1. 19F{1H} NMR (CD3CN,
376 MHz): δ −154.7 (s). 19F NMR (CD3CN, 376 MHz): δ −154.7
2
Dimethylammonium-d2-2,4,6-trinitrobenzenesulfonate. Di-
methylacetamidinium-fluoromethyl-2,4,6-trinitrobenzenesulfonate (5
mg, 0.01 mmol) was introduced in an NMR tube under argon and
dissolved in D2O (0.6 mL). The resulting solution was monitored
(CH2F, JF−H = 49.7 Hz). 14N{1H} NMR (CD3CN, 29 MHz): δ
−15.2 (s, 2N), −22.4 (s, 1N), −232.9 (s, 1N). IR (ATR): ν 3090
̃
(m), 1686 (m), 1606 (m), 1535 (s), 1448 (w), 1395 (w), 1352 (s),
1263 (s), 1247 (s), 1190 (m), 1151 (w), 1122 (m), 1068 (m), 1050
(m), 1035 (s), 1005 (s), 936 (w), 917 (w), 902 (m), 826 (w), 766
(w), 749 (s), 733 (s), 718 (s), 631 (s), 586 (m), 559 (s), 528 (w),
1
1
by H NMR after 5 min. H NMR (D2O, 400 MHz): δ 8.93 (s,
2H), 2.74 (quint, 6H, J = 0.7 Hz).
Dimethyl-2,4,6-trinitroaniline. A solution of 4 (3.61 g, 11.1
mmol) in acetonitrile (10 mL) was added while stirring to a
solution of dimethylamine (500 mg, 11.1 mmol) in acetonitrile (10
mL). The resulting deep red solution was stirred for 30 min at room
temperature, and the formed solid was filtered off. The solvent was
slowly removed from the filtrate in vacuo, yielding 2.10 g of
yellowish crystals. Yield: 73%. Tmp: 138 °C (lit.17 138 °C). Tdec: 250
513 (w), 482 (m), 455 (m), 440 (s). Raman: ν 3097 (m), 3029
̃
(w), 2962 (m), 1601 (w), 1558 (m), 1544 (m), 1381 (m), 1353
(s), 1265 (w), 1188 (w), 1070 (m), 827 (m), 725 (w), 352 (w),
322 (m), 234 (w), 212 (w), 173 (m), 116 (m). HRMS (ESI) m/z:
M+ calcd for C5H11FNO+, 120.0819; found, 120.0820. Anal. Calcd
for C11H13FN4O10S: C, 32.04; H, 3.18; N, 13.59; S, 7.78. Found: C,
31.83; H, 3.03; N, 13.40; S, 7.71.
1
°C. H NMR (CD3CN, 400 MHz): δ 8.69 (s, 2H), 2.90 (s, 6H).
Fluoromethyl-dimethylformamidinium-2,4,6-trinitrobenze-
nesulfonate (5c). Reagent 4 (358 mg, 1.10 mmol) was dissolved
in dichloromethane (5 mL), and dimethylformamide (80.5 mg, 1.10
mmol) was added. The yellowish solution was stirred for 24 h at
room temperature. After the precipitate was centrifuged, the solvent
was decanted and the crude product was washed with dichloro-
methane (3 × 5 mL). The remaining solid was dried in vacuo,
yielding 359 mg of 5c as a colorless solid. Yield: 82%. Tmp: 150 °C.
1H NMR (CD3CN, 400 MHz): δ 8.58 (septet, 1H, J = 0.9 Hz),
13C{1H} NMR (CD3CN, 101 MHz): δ 144.1, 142.9, 137.4, 126.8,
43.1. 14N{1H} NMR (CD3CN, 29 MHz): δ −14.2 (s, 2N), −20.1
(s, 1N). IR (ATR): ν 3062 (m), 2956 (w), 2924 (w), 2875 (w),
̃
2819 (w), 1857 (w), 1603 (m), 1575 (s), 1530 (s), 1505 (s), 1473
(s), 1456 (s), 1428 (m), 1411 (m), 1376 (m), 1359 (m), 1325 (m),
1302 (s), 1235 (s), 1179 (m), 1170 (m), 1131 (w), 1086 (m), 1063
(m), 953 (m), 930 (s), 821 (m), 760 (m), 748 (s), 732 (s), 708
(m), 662 (w), 624 (w), 545 (m), 517 (m), 430 (w). Raman: ν 2956
̃
8.54 (s, 2H), 5.96 (d, 2H, J = 49.2 Hz), 3.41 (s, 3H), 3.26 (s, 3H).
13C{1H} NMR (CD31CN, 101 MHz): δ 166.5, 150.8, 148.9, 138.9,
121.9, 104.6 (C−F, JC−F = 234.6 Hz), 43.1, 38.1. 19F{1H} NMR
(CD3CN, 376 MHz): δ −153.1 (s). 19F NMR (CD3CN, 376 MHz):
(w), 1607 (w), 1542 (w), 1476 (w), 1447 (w), 1422 (w), 1343
(m), 1328 (s), 1180 (w), 1088 (w), 934 (w), 823 (w), 761 (w),
667 (w), 331 (w), 195 (w). HRMS (DEI) m/z: M+ calcd for
C8H8N4O6, 256.0444; found, 256.0444. Anal. Calcd for C8H8N4O6:
C, 37.51; H, 3.15; N, 21.87. Found: C, 37.41; H, 3.26; N, 21.89.
2
δ −153.1 (CH2F, JF−H = 49.2 Hz). 14N{1H} NMR (CD3CN, 29
4428
J. Org. Chem. 2021, 86, 4423−4431