PAPER
Synthesis of N-Tetrachloroallylidene-N¢-arylhydrazines
2931
1H NMR (200 MHz, DMSO-d6): d = 10.85 (br s, 1 H, NH), 7.72 [d,
J = 8.7 Hz, 2 H, Ph(H-3,5)], 7.39 [d, J = 8.7 Hz, 2 H, Ph(H-2,6)].
13C NMR (50 MHz, DMSO-d6): d = 146.9 (CNH), 133.9 [2 C,
Ph(C-3,5)], 125.1, 124.8 (2 C, Cl2C=CCl), 119.6 (C=N), 116.2
(CN), 114.5 [Ph(C-2,6)], 103.2 [Ph(C-4)].
1H NMR (200 MHz, DMSO-d6): d = 11.74 (br s, 1 H, NH), 8.15 (s,
1 H, CH=N), 8.14 [d, J = 9.2 Hz, 2 H, Ph(H-3,5)], 7.11 [d, J = 9.2
Hz, 2 H, Ph(H-2,6)].
13C NMR (50 MHz, DMSO-d6): d = 149.6 (CNH), 140.0 (CNO2),
133.6 (CH=N), 128.0 (CCl), 126.3 [2 C, Ph(C-3,5)], 121.8 (CCl2),
112.3 [2 C, Ph(C-2,6)].
EIMS: m/z (%) = 306 (M+) (55), 271 (M+ – Cl) (18), 236 (M+ – 2
Cl) (5), 116 (PhN+) (100).
N-(1-Organylamino-2,3,3-trichloroallylidene)-N¢-(4-nitrophen-
yl)hydrazines (15–19); General Procedure
HRMS (EI): m/z calcd for C10H5Cl4N3 (M+): 306.9238; found:
306.9238.
To a suspension of hydrazone 8 (500 mg, 1.52 mmol) in MeOH (20
mL) was added with stirring a solution of the corresponding amine
(3.19 mmol) in MeOH (5 mL) at 0 °C over 10 min. The resulting re-
action mixture was stirred for 3–8 h at r.t. Subsequently, the super-
natant liquid was concentrated in vacuo to a volume of about 10 mL
and treated with dilute HCl (30 mL). The precipitate was isolated,
washed with H2O (3 × 50 mL), PE (3 × 10 mL), and finally dried
under reduced pressure.
N-(1,2,3,3-Tetrachloroallylidene)-N¢-(4-trifluoromethylphen-
yl)hydrazine (13)
Synthesized according to the typical procedure with a reaction time
of 3 d at 40 °C. Yield: 50%; viscous oil; Rf 0.40 (PE–EtOAc, 3:1).
IR (NaCl): 3334, 1618, 1528, 1418, 1325, 1271, 1126, 1065, 966,
880, 836, 705 cm–1.
1H NMR (200 MHz, CDCl3): d = 8.20 (br s, 1 H, NH), 7.56 [d,
J = 8.6 Hz, 2 H, Ph(H-3,5)], 7.19 [d, J = 8.6 Hz, 2 H, Ph(H-2,6)].
13C NMR (50 MHz, CDCl3): d = 144.7 (CNH), 126.8 [Ph(C-3,5)],
126.1 (C=N), 125.5 (CCl), 124.1 [Ph(C-4)], 121.6 (CCl2), 120.5
( 1JC,F = 270.4 Hz, CF3), 113.5 [Ph(C-2,6)].
N-(1-Pyrrolidino-2,3,3-trichloroallylidene)-N¢-(4-nitrophen-
yl)hydrazine (15)
Yield: 80%; mp 73–75 °C.
IR (KBr): 3291, 2970, 2867, 1597, 1576, 1498, 1461, 1300, 1272,
1174, 1110, 946, 897, 836, 751 cm–1.
1H NMR (200 MHz, CDCl3): d = 8.11 [d, J = 9.3 Hz, 2 H, Ph(H-
3,5)], 6.96 (br s, 1 H, NH), 6.90 [d, J = 9.3 Hz, 2 H, Ph(H-2,6)],
3.30–3.50 (m, 4 H, NCH2), 1.95–2.05 (m, 4 H, CH2).
EIMS: m/z (%) = 349 (M+) (20), 314 (M+ – Cl) (8), 279 (M+ – 2 Cl)
(5), 159 [Ph(CF3)N+] (100).
HRMS (EI): m/z calcd for C10H5Cl4F3N2 (M+): 349.9159; found:
349.9159.
13C NMR (50 MHz, CDCl3): d = 151.2 (C=N), 146.4 (CNH), 138.5
(CNO2), 126.1 [2 C, Ph(C-3,5)], 125.2 (CCl), 119.0 (CCl2), 110.9
[2 C, Ph(C-2,6)], 46.9 (2 C, NCH2), 25.0 (2 C, CH2).
N-(2,3,3-Trichloroallylidene)-N¢-(4-nitrophenyl)hydrazine (14)
Method A
EIMS: m/z (%) = 362 (M+) (12), 326 (M+ – HCl) (9), 292 (M+ – 2
To a suspension of NaBH4 (38 mg, 1.0 mmol) in EtOH (20 mL) was
added hydrazone 8 (329 mg, 1.0 mmol) portionwise with stirring.
The resulting mixture was kept for 3 d at r.t. Then the solution was
neutralized by the addition of dilute HCl at 0 °C. After evaporation
of the solvent, the residue was removed by suction filtration,
washed with H2O (2 × 10 mL), PE (2 × 10 mL), and then dried in
vacuo. The crude product was purified by column chromatography
(PE–EtOAc, 4:1). The substituted hydrazine (E/Z)-14 was isolated
as an orange solid; yield: 206 mg (70%), mp 229–232 °C.
HCl) (92), 70 (100).
HRMS (EI): m/z calcd for C13H13Cl3N4O2 (M+): 362.0104; found:
362.0104.
Anal. Calcd for C13H13Cl3N4O2 (363.63): C, 42.94; H, 3.60; N,
15.41. Found: C, 42.43; H, 3.43; N, 15.14.
N-(1-Morpholino-2,3,3-trichloroallylidene)-N¢-(4-nitrophen-
yl)hydrazine (16)
Yield: 90%; mp 145–147 °C.
IR (KBr): 3336, 3258, 1733, 1596, 1500, 1300, 1276, 1109, 841,
801, 751 cm–1.
1H NMR (200 MHz, DMSO-d6): d = 11.77 (br s, 1 H, NH, Z), 9.66
(br s, 1 H, NH, E), 8.20 (m, 6 H), 7.72 [d, J = 8.9 Hz, 2 H, Ph(H-
2,6), E], 7.15 [d, J = 8.9 Hz, 2 H, Ph(H-2,6), Z].
13C NMR (50 MHz, CDCl3): d = 149.6 (CNH, Z), 145.9 (CNH, E),
141.7 (CNO2, E), 140.0 (CNO2, Z), 133.6 (CH=N, Z), 128.8
(CH=N, E), 128.0 (CCl, Z), 126.3 [Ph(C-3,5), Z], 125.9 (CCl, E),
125.3 [2 C, Ph(C-3,5), E], 125.2 (CCl2, E), 121.8 (CCl2, Z), 118.1
[2 C, Ph(C-2,6), E], 112.3 [2 C, Ph(C-2,6), Z].
EIMS: m/z (%) = 293 (M+) (82), 258 (M+ – Cl) (93), 212 (M+ – Cl
– NO2) (67), 64 (100).
HRMS (EI): m/z calcd for C9H6Cl3N3O2 (M+): 292.9526; found:
292.9526.
IR (KBr): 3252, 2843, 1599, 1532, 1498, 1475, 1316, 1302, 1277,
1252, 1109, 938, 893, 837, 752.3 cm–1.
1H NMR (200 MHz, CDCl3): d = 8.13 [d, J = 9.2 Hz, 2 H, Ph(H-
3,5)], 7.22 (br s, 1 H, NH), 6.96 [d, J = 9.2 Hz, 2 H, Ph(H-2,6)],
3.75–3.85 (m, 4 H, CH2O), 3.25–3.35 (m, 4 H, CH2N).
13C NMR (50 MHz, CDCl3): d = 150.4 (C=N), 145.0 (CNH), 139.4
(CNO2), 126.8 (CCl), 126.1 [2 C, Ph(C-3,5)], 117.5 (CCl2), 111.3
[2 C, Ph(C-2,6)], 66.2 (2 C, CH2O), 46.3 (2 C, CH2N).
EIMS: m/z (%) = 378 (M+) (6), 343 (M+ – Cl) (2), 308 (M+ – 2 Cl)
(2), 86 (100).
HRMS (EI): m/z calcd for C13H13Cl3N4O3 (M+): 378.0053; found:
378.0053.
N-[1-(N-Benzyl-N-methylamino)-2,3,3-trichloroallylidene]-N¢-
(4-nitrophenyl)hydrazine (17)
Yield: 70%; mp 115–116 °C.
Method B
A mixture of trichloroacrolein (0.50 g, 3.14 mmol) and 4-nitrophen-
ylhydrazine (0.43 g, 2.82 mmol) in MeOH (20 mL) was refluxed for
6 h. After cooling to r.t., the solid product formed was removed by
suction filtration, washed with H2O (3 × 10 mL), MeOH
(3 × 10 mL), and acetone (3 × 10 mL). The solvents were removed
under reduced pressure to afford (Z)-14 as an orange solid; yield:
0.66 g (80%); mp 238–239 °C.
IR (KBr): 3268, 1595, 1578, 1522, 1493, 1472, 1458, 1392, 1297,
1274, 1223, 1176, 1112, 1087, 893, 840, 748 cm–1.
1H NMR (200 MHz, CDCl3): d = 8.11 [d, J = 9.3 Hz, 2 H, Ph(H-
3,5)], 7.32 (m, 5 H, Bn), 7.09 (br s, 1 H, NH), 6.91 [d, J = 9.3 Hz, 2
H, Ph(H-2,6)], 4.56 (d, J = 15.3 Hz, 1 H, CH2), 4.44 (d, J = 15.3 Hz,
1 H, CH2), 2.90 (s, 3 H, CH3).
IR (KBr): 3252, 1593, 1497, 1302, 1275, 1108, 838, 799, 750 cm–1.
Synthesis 2006, No. 17, 2927–2933 © Thieme Stuttgart · New York