Chemistry of Heterocyclic Compounds 2016, 52(2), 133–139
3116 (w), 3027 (w), 2935 (m), 2858 (m), 1748 (C=O, s),
(m), 1487 (m), 1451 (m), 1418 (w), 1362 (w), 1270 (w),
1217 (s), 1166 (vs), 1155 (vs), 1117 (m), 1029 (w), 1005
(w), 935 (w), 898 (w), 745 (m), 697 (m), 638 (w), 615 (w),
1675 (C=O, s), 1636 (m), 1589 (m), 1551 (w), 1489 (w),
1465 (w), 1456 (w), 1358 (w), 1317 (w), 1253 (m), 1239
(m), 1204 (s), 1164 (s), 1133 (m), 1078 (m), 1018 (w), 914
(w), 891 (w), 795 (w), 737 (m), 656 (w). 1H NMR
spectrum, δ, ppm: 1.11–1.30 (5H, m) and 1.54–1.76 (5H,
m, 5CH2); 3.39–3.40 (1H, m, CH); 6.38 (1H, br. s, NH);
7.99 (1H, br. s, NH); 11.02 (1H, s, NH). 13C NMR
spectrum, δ, ppm (J, Hz): 25.0, 25.6, 33.3 (5 CH2); 48.8
(CH); 116.4 (q, 1JCF = 286.5, CF3); 156.5 (C=O); 156.9 (q,
2JCF = 35.5, CF3C=O). 19F NMR spectrum, δ, ppm: –73.7
(3F, s, CF3). Mass spectrum (ESI+), m/z (Irel, %): 276
[M+Na]+ (100), 254 [M+H]+ (25). Mass spectrum (ESI–),
m/z (Irel, %): 252 [M–H]– (100). Found, m/z: 253.1028 [M]+.
C9H14F3N3O2. Calculated, m/z: 253.1033.
1
526 (m). H NMR spectrum, δ, ppm: 7.18–7.46 (5H, m, H
Ph); 9.75 (2H, br. s, 2NH); 11.52 (1H, br. s, NH). 13C NMR
spectrum, δ, ppm (J, Hz): 116.8 (q, 1JCF = 291.7, CF3); 125.6
2
(C-1 Ph); 128.7, 139.4 (C Ph); 155.8 (q, JCF = 30.0,
CF3C=O); 179.9 (C=S). 19F NMR spectrum, δ, ppm: –73.6
(s, CF3). Mass spectrum (ESI+), m/z (Irel, %): 286 [M+Na]+
(100), 264 [M+H]+ (75). Mass spectrum (ESI–), m/z (Irel, %):
262 [M–H]– (100). Found, m/z: 263.0342 [M]+. C9H8F3N3OS.
Calculated, m/z: 263.0334.
N-(4-Fluorophenyl)-2-(trifluoroacetyl)hydrazinecarbo-
thiamide (6h). Yield 415 mg (74%), colorless crystals, mp
138–139°C. IR spectrum, ν, cm–1: 3238 (3N–H, br., s),
3148 (w), 3063 (m), 1726 (C=O, m), 1616 (w), 1559 (m),
1518 (m), 1416 (w), 1362 (m), 1304 (w), 1249 (w), 1208
(m), 1191 (m), 1170 (m), 1126 (w), 1097 (w), 918 (w), 830
2-(Difluoroacetyl)-N-phenylhydrazinecarboxamide (6e).
Yield 410 mg (90%), colorless crystals, mp 172–174°C.
IR spectrum, ν, cm–1: 3366 (N–H, br., s), 3300 (N–H, br.,
s), 3199 (N–H, br., s), 3099 (m), 3039 (m), 2926 (w), 2857
(w), 1946 (w), 1929 (w), 1717 (C=O, vs), 1693 (C=O, vs),
1600 (vs), 1564 (s), 1498 (s), 1444 (s), 1383 (w), 1320 (m),
1254 (m), 1218 (m), 1174 (m), 1151 (w), 1109 (s), 973 (w),
1
(w), 803 (w), 743 (w), 691 (w). H NMR spectrum, δ, ppm:
7.17–7.20 (2H, m, H Ar); 7.45 (2H, m, H Ar); 9.85 (2H,
br. s, 2NH); 11.53 (1H, br. s, NH). 13C NMR spectrum, δ, ppm
1
(J, Hz): 116.0, 115.5 (C Ar); 116.9 (q, JCF = 289.5, CF3);
1
2
906 (w), 837 (w), 745 (s), 692 (m), 645 (m). H NMR
136.1 (C-1 Ar); 157.3 (q, JCF = 35.7, F3CC=O); 158.1 (d,
1
spectrum, δ, ppm (J, Hz): 6.32 (1H, t, JCF = 52.1, CHF2);
1JCF = 237.1, C-4 Ar); 178.1 (C=S). 19F NMR spectrum,
δ, ppm: –117.3 (1F, s, CF); –73.4 (3F, s, CF3). Mass spectrum
(ESI+), m/z (Irel, %): 282 [M+H]+ (100). Mass spectrum
(ESI–), m/z (Irel, %): 280 [M–H]– (100). Found, m/z:
281.0243 [M]+. C9H7F4N3OS+. Calculated, m/z: 281.0240.
N-(4-Methoxyphenyl)-2-(trifluoroacetyl)hydrazinecarbo-
thiamide (6i). Yield 401 mg (68%), colorless crystals, mp
140–141°C. IR spectrum, ν, cm–1: 3214 (3N–H, br., s),
3046 (w), 2966 (w), 2943 (w), 2918 (w), 2845 (w), 1716
(C=O, m), 1613 (w), 1589 (w), 1545 (m), 1516 (m), 1469
(w), 1357 (m), 1302 (w), 1240 (m), 1215 (m), 1187 (m),
1168 (m), 1130 (w), 1101 (w), 1028 (m), 925 (m), 841 (w),
6.96–6.98 (1H, m, H Ph); 7.25–7.27 (2H, m, H Ph); 7.43–
7.45 (2H m, H Ph); 8.39 (1H, br. s, NH); 8.89 (1H, br. s,
NH); 10.64 (1H, br. s, NH). 13C NMR spectrum, δ, ppm
1
(J, Hz): 108.4 (t, JCF = 244.5, CHF2), 118.8, 122.2, 128.8
(C Ph); 139.0 (C-1 Ph); 154.7 (C=O); 161.9 (t, 2JCF = 25.2,
CHF2C=O). 19F NMR spectrum, δ, ppm (J, Hz): –126.5
(2F, d, 2JFH = 52.1, CHF2). Mass spectrum (ESI+), m/z (Irel, %):
252 [M+Na]+ (100). Mass spectrum (ESI–), m/z (Irel, %):
228 [M–H]– (100). Found, m/z: 229.0664 [M]+. C9H9F2N3O2.
Calculated, m/z: 229.0657.
N-Cyclohexyl-2-(difluoroacetyl)hydrazinecarboxamide
(6f). Yield 442 mg (94%), colorless crystals, mp 178–179°C.
IR spectrum, ν, cm–1: 3391 (N–H, br., m), 3351 (N–H, s),
3231 (N–H, s), 3104 (w), 3038 (w), 2935 (s), 2856 (m),
1731 (C=O, s), 1656 (C=O, vs), 1564 (vs), 1464 (w), 1454
(m), 1399 (w), 1370 (w), 1346 (w), 1320 (w), 1277 (w),
1258 (w), 1238 (m), 1190 (w), 1125 (s), 1095 (m), 1076
(m), 978 (w), 967 (w), 893 (w), 845 (w), 824 (w), 773 (w),
670 (w), 639 (w). 1H NMR spectrum, δ, ppm (J, Hz): 1.13–
1.28 (5H, m) and 1.65–1.76 (5H, m, 5CH2); 3.31–3.42 (1H,
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783 (w), 742 (w), 688 (w), 658 (w). H NMR spectrum, δ,
ppm: 3.77 (3H, s, CH3); 6.93–6.94 (2H m, H Ar); 7.26–
7.27 (2H, m, H Ar); 9.73 (1H, br. s, NH); 9.88 (1H, br. s,
NH); 11.47 (1H, br. s, NH). 13C NMR spectrum, δ, ppm
(J, Hz): 55.7 (OCH3); 114.0, 132.1 (C Ar); 127.8 (C-1 Ar);
2
2
116.4 (q, JCF = 286.5, CF3); 156.8 (q, JCF = 35.7,
CF3C=O); 157.5 (C-4 Ar); 181.9 (C=S). 19F NMR
spectrum, δ, ppm: –73.6 (3F, s, CF3). Mass spectrum
(ESI+), m/z (Irel, %): 294 [M+H]+ (100). Mass spectrum
(ESI–), m/z (Irel, %): 292 [M–H]– (100). Found, m/z:
293.0437 [M]+. C10H10F3N3OS. Calculated, m/z: 293.0440.
2-(Difluoroacetyl)-N-phenylhydrazinecarbothiamide
(6j). Yield 394 mg (80%), colorless crystals, mp 143–144°C.
IR spectrum, ν, cm–1: 3284 (N–H, br., s), 3163 (2N–H, br., vs),
3033 (m), 2886 (w), 1725 (C=O, vs), 1592 (w), 1523 (s),
1500 (s), 1452 (m), 1374 (w), 1335 (w), 1290 (w), 1241
(w), 1201 (m), 1150 (s), 1120 (m), 1090 (s), 1027 (w),
1004 (w), 970 (w), 935 (w), 911 (w), 820 (w), 742 (m), 697
1
m, CH); 6.26 (1H, t, JCF = 53.2, CHF2); 6.28 (1H, br. s,
NH); 7.88 (1H, br. s, NH); 10.44 (1H, br. s, NH). 13C NMR
spectrum, δ, ppm (J, Hz): 25.0, 25.7, 33.4 (5 CH2); 48.6
1
(CH); 108.6 (t, JCF = 244.2, CHF2); 156. 8 (C=O); 162.0
2
(t, JCF = 25.2, CHF2C=O). 19F NMR spectrum, δ, ppm
2
(J, Hz): –126.5 (2F, d, JFH = 53.2, CHF2). Mass spectrum
(ESI+), m/z (Irel, %): 258 [M+Na]+ (100), 236 [M+H]+ (50).
Mass spectrum (ESI–), m/z (Irel, %): 234 [M–H]– (100).
Found, m/z: 235.1133 [M]+. C9H15F2N3O2. Calculated, m/z:
235.1127.
1
(s), 668 (w), 636 (w), 616 (w). H NMR spectrum, δ, ppm
N-Phenyl-2-(trifluoroacetyl)hydrazinecarbothiamide
(6g). Yield 405 mg (77%), colorless crystals, mp 128–129°C
(mp 132.0–133.0°C15). IR spectrum, ν, cm–1: 3310 (N–H,
br., m), 3158 (2N–H, br., s), 3034 (m), 2891 (w), 1735
(C=O, vs), 1628 (w), 1594 (m), 1538 (s), 1520 (s), 1498
(J, Hz): 6.30 (1H, t, 2JCF = 50.8, CHF2); 7.19–7.43 (5H, m,
H Ph); 9.79 (2H, br. s, 2NH); 10.91 (1H, br. s, NH).
1
13C NMR spectrum, δ, ppm (J, Hz): 108.6 (t, JCF = 244.8,
CHF2); 125.8 (C-1 Ph); 128.7, 139.4 (C Ph); 162.3 (t,
2JCF = 25.0, CHF2C=O); 181.4 (C=S). 19F NMR spectrum,
137