X. Xu et al. / Journal of Fluorine Chemistry 121 (2003) 51–54
53
The infrared (IR) spectra were recorded on a Nicolet 470
infrared Fourier transform spectrometer using potassium
bromide pellets. The proton nuclear magnetic resonance
(1H NMR, 500 MHz) spectra were recorded on Bruker
WP-500SY spectrometers with CD3Cl as the solvent and
TMS as internal standard. High resolution mass spectra were
obtained on MicroMass GCT CA 055 spectrometers. Ana-
lytical thin-layer chromatography (TLC) was carried out on
precoated plated (silica gel 60 F254), and spots were visua-
lised with ultraviolet light. All chemicals or reagents were
purchased from standard commercial suppliers.
(100.00), 77 (C6H5) (67.83), HRMS Calcd. for C14H10ClFN2-
OS 308.0186. Found: 308.0189.
3.1.3. Syntheses of N-(3-chloro-4-fluorophenyl) -N0-
(2,4,5-trifluoro-3-methoxylbenzoyl)thiourea (5c)
Yield 64%, mp 162–163 8C. 1H NMR (CD3Cl, 500 MHz):
d 4.09 (s, 3H, –OCH3), 7.17 (t, 1H, J56 ¼ 8:6, J45 ¼ 8:8 Hz,
H-5), 7.51 (m, 1H, H-6), 7.59 (o, 1H, JFðoÞÀH ¼ 11:7 Hz,
JFðmÞÀH ¼ 8:4 Hz, H-60), 7.84 (dd, 1H, J24 ¼ 6:5 Hz,
J26 ¼ 2:7 Hz, H-2), 9.53 (d, 1H, J ¼ 14:5 Hz, C¼SNH),
12.29 (s, 1H, C¼ONH). IR (KBr): n ¼ 3400, 1680, 1550,
1500, 1460, 1370, 1270, 1200, 1100, 1040, 870, 830, 780,
680 cmÀ1. MS (EI, 70 eV): m/z (%): 392 (Mþ) (17.35), 205
(C8H6F3NO2) (19.45), 189 (C8H4F3O2) (100.00), 161
(C7H4F3O) (20.00), 129 (C6H3ClF) (18.51), 92 (C6H6N)
(14.36). HRMS Calcd. for C15H9ClF4N2O2S 392.0009.
Found: 392.0016.
3.1. General procedure
Fluorine-containing benzoic acid (10 mmol) and thionyl
chloride (20–50 mmol) were refluxed for 5 h, thionyl chlor-
ide was removed under reduced pressure. Benzoyl chloride
was used in next reaction without purification. Powered
ammonium thiocyanate (15 mmol), appropriate benzoyl
chloride (10 mmol), PEG-400 (0.18 g, 3% with respect to
ammonium thiocyanate) and methylene dichloride (25 ml)
were placed in a dried round-bottomed flask containing a
magnetic stirrer bar and stirred at room temperature for 1 h
or so, then appropriate amine (10 mmol) was added, and the
mixture was stirred for 8–12 h. The mixture was filtered off
to remove inorganic salts and the filtrate was concentrated
under reduced pressure. The resulting solid was recrystal-
lised from anhydrous ethanol to give respond as benzo-
lylthiourea.
3.1.4. Syntheses of N-(2-fluoro-4-chlorophenyl)-N0-
(2,4,5-trifluoro-3-methoxybenzoyl)thiourea (5d)
Yield 83.3%, mp 155–56 8C. 1H NMR (CD3Cl, 500 MHz):
d 4.09 (s, 3H, –OCH3), 7.19 (m, 2H, H-3, H-5), 7.63 (o, 1H,
JFðoÞÀH ¼ 11:7 Hz, JFðmÞÀH ¼ 8:4 Hz, H-60), 8.41 (t, 1H,
J56 ¼ 8:6 Hz, J26 ¼ 8:1 Hz, H-6), 9.57 (d, 1H, J ¼
14:5 Hz, C¼SNH), 12.44 (s, 1H, C¼ONH). IR (KBr):
n ¼ 3050, 1680, 1600, 1540, 1510, 1470, 1370, 1220,
1150, 1100, 1050, 910, 820, 780, 760, 600 cmÀ1. MS (EI,
70 eV): m/z (%): 392 (Mþ) (29.37), 205 (C8H6F3NO2) (18.13),
189 (C8H4F3O2) (100.00), 161 (C7H4F3O) (13.51), 146
(C6HF3O) (11.68). HRMS Calcd. for C15H9ClF4N2O2S
392.0009. Found: 392.0013.
3.1.1. Syntheses of N-(4-hydroxylphenyl)-N0-(2,4,5-
trifluoro-3-methoxylbenzoyl)thiourea (5a)
Yield 78%, mp 182–83 8C. 1H NMR (CD3Cl, 500 MHz):
d 4.09 (s, 3H, –OCH3), 5.15 (s, 1H, –OH), 6.85 (d, 2H,
J ¼ 6:8 Hz, H-3, H-5), 7.49 (d, 2H, J ¼ 6:8 Hz, H-2, H-6),
7.58 (o, 1H, JFðoÞÀH ¼ 11:7 Hz, JFðmÞÀH ¼ 8:4 Hz, H-60),
9.49 (d, 1H, J ¼ 14:0 Hz, C¼SNH), 12.13 (s, 1H, C¼ONH).
IR (KBr): n ¼ 3300, 3240, 1680, 1540, 1500, 1470, 1440,
1370, 1230, 1210, 1190, 1160, 1100, 1050, 720 cmÀ1. MS
(EI, 70 eV): m/z (%): 357 (Mþ þ 1) (4.74), 356 (Mþ)
(27.39), 205 (C8H6F3NO2) (19.71), 189 (C8H4F3O2)
(100.00), 161 (C7H4F3O) (10.39), 151 (C7H5NOS)
(69.54), 146 (C6HF3O) (8.46), 109 (C6H7NO) (6.85), HRMS
Calcd. for C15H11F3N2O3S 356.0442. Found: 356.0430.
3.1.5. Syntheses of N-(2-fluoro-4-chlorophenyl)-N0-
benzoylthiourea (5e)
Yield 91.9%, mp 133–134 8C. 1H NMR (CD3Cl,
500 MHz): d 7.15 (m, 1H, H-3, H-5), 7.49 (t, 2H,
J6 5 ¼ J2 3 ¼ 8:0 Hz, H-30, H-50), 7.61 (t, 1H, J ¼ 7:4 Hz,
0
0
0 0
H-40), 7.85 (d, 2H, J5 6 ¼ J3 2 ¼ 8:0 Hz, H-20, H-60), 8.34 (t,
1H, J56 ¼ 8:6 Hz, J26 ¼ 8:2 Hz, H-6), 9.11 (s, 1H, C¼SNH),
12.64 (s, 1H, C¼ONH). IR (KBr): n ¼ 3240, 1680, 1600,
1550, 1530, 1350, 1260, 1210, 1150, 880, 800, 690 cmÀ1. MS
(EI, 70 eV): m/z (%): 308 (Mþ) (4.74), 273 (Mþ À Cl) (6.14),
186 (C7H3ClFNS) (83.11), 145 (C6H5ClFN) (9.23), 121
(C6H5CONH2) (8.20), 105 (C6H5C¼O) (100.00), 77 (C6H5)
(32.56), HRMS Calcd. for C14H10ClFN2OS 308.0186. Found:
308.0189.
0
0
0 0
3.1.2. Syntheses of N-(3-chloro-4-fluorophenyl)-N0-
benzoylthiourea (5b)
Yield 92.2%, mp 152–153 8C. 1H NMR (CD3Cl,
500 MHz): d 7.19 (t, 1H, J ¼ 8:6, H-5), 7.57 (m, 3H, H-
30, H-50, H-6), 7.68 (t, 1H, H-40), 7.89 (m, 3H, H-2, H-20, H-
60), 9.12 (s, 1H, C¼SNH), 12.58 (s, 1H, C¼ONH). IR (KBr):
n ¼ 3125 (NH), 3000, 2950, 2800 (C–H), 1660, 1620, 1570,
1530, 1490, 1350, 1260, 1160, 870, 810, 690 þcmÀ1. MS (EI,
70 eV): m/z (%): 308 (Mþ þ 2) (6.42), 308 (M ) (18.59), 273
(Mþ À Cl) (6.14), 187 (C7H4ClFNS) (55.24), 145 (C6H5-
ClFN) (6.07), 121 (C6H5CONH2) (9.02), 105 (C6H5C¼O)
3.1.6. Syntheses of N-(2-fluoro-4-chlorophenyl)-N0-
(2,4-dichloro-3-nitro-5-fluorobenzoyl)thiourea (5f)
Yield 74.9%, mp 220–221 8C. 1H NMR (CD3Cl,
500 MHz): d 7.16 (m, 1H, H-3, H-5), 7.68 (d, 1H,
J ¼ 7:8 Hz, H-60), 8.31 (t, 1H, J56 ¼ 8:6 Hz, J26 ¼ 8:2 Hz,
H-6), 9.18 (s, 1H, C¼SNH), 12.02 (s, 1H, C¼ONH). IR
(KBr): n ¼ 3200, 3050, 1690, 1590, 1560, 1540, 1450,
1400, 1350, 1230, 1160, 890, 800, 720 cmÀ1. MS (EI,
70 eV): m/z (%): 439 (Mþ) (1.16), 408 (Mþ þ 4-Cl)