Synthesis and fungicidal activities of derivatives of 2-alkylthio-3-amino- 4H-imidazol-4-one

Article abstract of DOI:10.1080/10426500490484977

2-Alkylthio-3-phenylamino-5-arylmethylene-4H-imidazol-4-ones 5 were synthesized by S-alkylation of 3-phenylamino-2-thioxo-4-imidazolidinones 4, which were obtained via cyclization of isothiocyanates 2 with phenylhydrazine in presence of solid potassium ca

Full text of DOI:10.1080/10426500490484977

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Phosphorus, Sulfur, and Silicon
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SYNTHESIS AND FUNGICIDAL
ACTIVITIES OF DERIVATIVES
OF 2-ALKYLTHIO-3-AMINO-4H-
IMIDAZOL-4-ONE
Ming-Wu Ding a , Yun-Feng Chen a & Nian-Yu Huang a
a Key Laboratory of Pesticide & Chemical Biology,
Ministry of Education, College of Chemistry, Central
China Normal University, Wuhan, P. R. China
Published online: 16 Aug 2010.
To cite this article: Ming-Wu Ding , Yun-Feng Chen & Nian-Yu Huang (2004):
SYNTHESIS AND FUNGICIDAL ACTIVITIES OF DERIVATIVES OF 2-ALKYLTHIO-3-AMINO-4H-
IMIDAZOL-4-ONE, Phosphorus, Sulfur, and Silicon and the Related Elements, 179:11,
2287-2296
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Phosphorus, Sulfur, and Silicon, 179:2287–2296, 2004
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Copyright Taylor & Francis Inc.
ISSN: 1042-6507 print / 1563-5325 online
DOI: 10.1080/10426500490484977
SYNTHESIS AND FUNGICIDAL ACTIVITIES
OF DERIVATIVES OF
2-ALKYLTHIO-3-AMINO-4H-IMIDAZOL-4-ONE
Ming-Wu Ding, Yun-Feng Chen, and Nian-Yu Huang
Key Laboratory of Pesticide & Chemical Biology, Ministry of
Education, College of Chemistry, Central China Normal
University, Wuhan, P. R. China
(Received February 25, 2004; accepted May 7, 2004)
2-Alkylthio-3-phenylamino-5-arylmethylene-4H-imidazol-4-ones 5
were synthesized by S-alkylation of 3-phenylamino-2-thioxo-4-imidazo-
lidinones 4, which were obtained via cyclization of isothiocyanates 2
with phenylhydrazine in presence of solid potassium carbonate. Com-
pound 5 exhibited fungicidal activity.
Keywords: 4H-Imidazol-4-one; aza-Wittig reaction; fungicidal activi-
ties; synthesis
INTRODUCTION
Many 4H-imidazol-4-ones have shown biological and pharmaceutical
activities, especially some 2-alkylthioimidazolones.1−3 Since a new imi-
dazolone (Fenamidone; Figure 1) was found to show high fungicidal ac-
tivities, many other 2-alkylthio-3-aminoimidazolones were synthesized
to evaluate their fungicidal activities.4−7
Most of the 2-alkylthio-3-aminoimidazolones reported are 5,5-
disubstituted types. They were generally synthesized from correspond-
ing amino acetic acid6,7 (Scheme 1). Unfortunately, 5-arylmethylene-
2-alkylthio-3-aminoimidazolones cannot be prepared by this general
method because corresponding starting materials needed are unsta-
ble vinyl amino acetic acids. Recently, we became interested in the
We gratefully acknowledge financial support of this work by the National Key Project
for Basic Research (2003CB114400, 2003CB114406) and the National Natural Science
Foundation of China (Project No. 20102001).
Address correspondence to Ming-Wu Ding, Key Laboratory of Pesticide & Chemical
Biology, Ministry of Education, College of Chemistry, Central China Normal University,
Wuhan 430079, P. R. China. E-mail: ding5229@yahoo.com.cn
2287

2288
M.-W. Ding et al.
SCHEME 1
synthesis of biologically active imidazolones via a tandem aza-Wittig
reaction.8–10 We wish to report a new efficient synthesis of unre-
ported 5-arylmethylene-2-alkylthio-3-aminoimidazolones 5 from the
stable vinyliminophosphorane 1.
RESULTS AND DISCUSSION
The easily accessible vinyliminophosphorane 1 reacted with carbon
disulfide to give vinyl isothiocyanates 2, which were allowed to re-
act with phenylhydrazine in presence of catalytic solid potassium car-
bonate to give the 3-phenylamino-2-thioxo-4-imidazolidinones 4 at 40–
50◦C. The formation of 4 can be rationalized in terms of an initial nucle-
ophilic addition of phenylhydrazine to give the intermediates 3, which
cyclize to give 4, catalyzed by potassium carbonate (Scheme 2). Since
the direct reaction of isothiocyanates 2 with phenylhydrazine often give
a mixture of intermediates 3 and imidazolidinones 4, the presence of
catalytic solid potassium carbonate is necessary for the cyclization to
occur completely.
S-Alkylation of 4 with alkyl halides in the presence of potas-
sium carbonate provided 2-alkylthio-3-phenylamino-5-arylmethylene-
4H-imidazol-4-ones 5 in satisfactory yields (Scheme 3). With alkylating
Fenamidone
FIGURE 1

Alkylthio-3-Amino-4 H-imidazol-4-one
2289
SCHEME 2
SCHEME 3
reagents such as RI and BrCH2COR, the alkylation could be carried out
at room temperature; with other reagents the alkylation had to be car-
ried out at 50◦C (See Table I).
The structures of 5 have been characterized spectroscopically. For ex-
ample, the 1H NMR spectral data in 5a show the signals for SCH3 and
NH at δ 2.68 and δ 6.36 as singlets. The signals of alkenyl hydrogen
were overlapped with the signals of Ar (δ 8.20–6.76). In the IR spectral
data of 5a, the stretching resonance peak of N H appears at 3344 cm−1
.
The strong stretching resonance peak of imidazolone C O appears at
1725 cm−1. The stretching of C C shows relatively strong absorbtion at
about 1638 cm−1 due to resonance effect. The MS spectrum of 5a shows
a molecule ion peak at m/z 309 with 20% abundance.
The biological activities of 5 were investigated, and the results
showed that they exhibited fungicidal activities, especially against
Botrytis Cinerea Pers. For example, 5l showed 91% inhibition of Botrytis
Cinerea Pers in 50 mg/l (See Table II).

2290
M.-W. Ding et al.
TABLE I Preparation of 2-Thioxo-4-imidazolidinones 4
and 4H-Imidazol-4-ones 5
Ar
RX
Condition
Yield (%)∗
4a
4b
5a
5b
5c
5d
5e
5f
5g
5h
5i
5j
5k
5l
Ph
4-Cl-C6H4
Ph
Ph
Ph
Ph
Ph
Ph
Ph
Ph
Ph
Ph
Ph
2 h/40–50◦C
3 h/40–50◦C
2 h/rt
76
72
87
65
83
86
70
71
81
82
75
86
80
74
85
68
73
87
77
83
CH3I
EtBr
n-PrBr
n-BuBr
n-C6H13Br
PhCH2Cl
ClCH2CN
PhCOCH2Br
ClCH2CONH2
ClCH2COOEt
BrCH2COOMe
BrCH(Me)COOEt
CH3I
5 h/50◦C
3 h/50◦C
3 h/50◦C
3 h/50◦C
2 h/50◦C
2 h/50◦C
2 h/rt
2 h/50◦C
2 h/50◦C
2 h/rt
Ph
3 h/50◦C
2 h/rt
5m 4-Cl-C6H4
5n
5o
5p
5q
5r
4-Cl-C6H4
4-Cl-C6H4
4-Cl-C6H4
4-Cl-C6H4
4-Cl-C6H4
EtBr
n-PrBr
n-BuBr
PhCH2Cl
5 h/50◦C
3 h/50◦C
3 h/50◦C
2 h/50◦C
3 h/50◦C
ClCH2COOEt
∗Isolated yields of 4 or 5 based on iminophosphosphorane 1 or
imidazolidinone 4, respectively.
EXPERIMENTAL
Melting points were uncorrected. MS were measured on a Finnigan
Trace MS spectrometer. IR were recorded on a PE-983 infrared spec-
trometer as KBr pellets with absorption in cm−1. NMR were recorded
in CDCl3 or dimethylsulfoxide (DMSO)-d6 on a Varian Mercury 400
spectrometer, and resonances are given in ppm (δ) relative to tetram-
ethyl silane (TMS). Elementary analyses were taken on a Vario EL III
elementary analysis instrument.
Preparation of 3-Phenylamino-2-thioxo-4-
imidazolidinones 4
To a solution of vinyliminophosphorane 110 (5 mmol) in dry methylene
chloride (15 ml) was added excess carbon disufide (5 ml). After the re-
action mixture was refluxed for 28 h, the solvent was removed under
reduced pressure, and ether/petroleum ether (1:2, 20 ml) was added to
precipitate triphenylphosphine sulfide, which was removed by filtra-
tion. The filtrate was evaporated to give isothiocyanate 2, which was

Alkylthio-3-Amino-4 H-imidazol-4-one
2291
TABLE II Fungicidal Activities of 4H-imidazol-4-ones 5 (50 mg/l, Relative
Inhibition of Growth %)
Fusarium
oxysporum
Pyricularia
oryzae
Botrytis
Cinerea Pers.
Gibberella
zeae
Cercospora
beticola Sacc.
Compound
5a
5b
5c
5d
5e
5f
5g
5h
5i
5j
5k
5l
5m
5n
5o
5p
37
34
43
40
29
26
43
40
54
57
29
54
34
19
23
46
31
35
100
53
47
55
60
38
43
53
45
64
68
43
77
47
38
31
53
47
50
81
47
61
73
45
55
64
66
64
77
84
64
91
55
52
45
77
84
84
85
14
22
43
49
0
39
44
51
41
54
34
41
49
56
78
51
61
54
32
26
46
52
39
11
22
32
27
43
38
30
49
38
43
31
41
43
40
100
5q
5r
Carbendazim
used directly without further purification. To a solution of the crude
2 in CH3CN (15 ml) was added phenylhydrazine (0.54 g, 5 mmol) and
solid potassium carbonate (0.05 g). The mixture was stirred for 2–3 h
at 40–50◦C and was filtered. The filtrate was condensed, and the resid-
ual was recrystallized from methylene chloride/petroleum ether to give
3-phenylamino-2-thioxo-4-imidazolidinones 4.
3-Phenylamino-5-phenylmethylene-2-thioxo-4-
imidazolidinone (4a)
Yellow crystals, m.p. 195–196◦C. 1H NMR (CDCl3, 400 MHz); δ 8.87
(s, 1H, NH), 7.50–6.86 (m, 11H, Ar H and CH), 6.54 (s, 1H, NHPh).
IR (cm−1); 3330 and 3209 (NH), 1734 (C O), 1653, 1466, 1266. MS
(m/z, %): 295 (M+, 100), 262 (7), 234 (11), 160 (54), 77 (88). Elemental
Anal. Calcd. for C16H13N3OS: C, 65.06; H, 4.44; N, 14.23. Found: C,
65.12; H, 4.35; N, 14.27.
3-Phenylamino-5-(4-chlorophenylmethylene)-2-thioxo-4-
imidazolidinone (4b)
Yellow crystals, m.p. 231–232◦C. 1H NMR (CDCl3, 400 MHz); δ 8.84
(s, 1H, NH), 7.49–6.84 (m, 10H, Ar H and CH), 6.51 (s, 1H, NHPh). IR
(cm−1); 3294 and 3212 (NH), 1722 (C O), 1651, 1460, 1263. MS (m/z,

2292
M.-W. Ding et al.
%): 331 (35), 329 (M+, 100), 238 (7), 194 (25), 151 (59), 93 (82). Elemental
Anal. Calcd. for C16H12ClN3OS: C, 58.27; H, 3.67; N, 12.74. Found: C,
58.16; H, 3.69; N, 12.81.
Preparation of 2-Alkylthio-3-phenylamino-5-
arylmethylene-4H-imidazol-4-ones 5
A mixture of 4 (4 mmol), alkyl halide (5 mmol), and solid potassium
carbonate (1.11 g, 8 mmol) in CH3CN (30 ml) was stirred for 2–5 h at
room temperature or 50◦C and was filtered. The filtrate was condensed,
and the residue was recrystallized from methylene chloride/petroleum
ether to give 2-alkylthio-3-phenylamino-5-arylmethylene-4H-imidazol-
4-ones 5.
2-Methylthio-3-phenylamino-5-phenylmethylene-4 H-
imidazol-4-one (5a)
Yellow crystals, m.p. 180–181◦C. 1H NMR (CDCl3, 400 MHz); δ 8.20–
6.76 (m, 11H, Ar H and CH), 6.36 (s, 1H, NH), 2.68 (s, 3H, SCH3).
IR (cm−1); 3344 (NH), 1725 (C O), 1638, 1499, 1240, 1140. MS (m/z,
%): 309 (M+, 20), 234 (7), 165 (11), 116 (66), 92 (100). Elemental Anal.
Calcd. for C17H15N3OS: C, 66.00; H, 4.89; N, 13.58. Found: C, 66.16; H,
4.81; N, 13.63.
2-Ethylthio-3-phenylamino-5-phenylmethylene-4 H-
imidazol-4-one (5b)
1
Light yellow crystals, m.p. 169–170◦C, H NMR (CDCl3, 400 MHz):
δ 8.13–6.71 (m, 11H, Ar H and CH), 6.18 (s, 1H, NH), 3.25 (q, 2H,
J= 7.2 Hz, SCH2), 1.44 (t, 3H, J= 7.2 Hz, CH3). IR (cm−1): 3282 (NH),
1719 (C O), 1638, 1497, 1244, 1142. MS (m/z, %): 323 (M+, 89), 295
(19), 262 (23), 234 (42), 179 (61), 92 (100). Elemental Anal. Calcd. for
C18H17N3OS: C, 66.85; H, 5.30; N, 12.99. Found: C, 66.91; H, 5.48; N,
12.92.
2-(n-Propylthio)-3-phenylamino-5-phenylmethylene-4 H-
imidazol-4-one (5c)
1
Light yellow crystals, m.p. 150–151◦C. H NMR (CDCl3, 400 MHz):
δ 8.12–6.69 (m, 11H, Ar H and CH), 6.24 (s, 1H, NH), 3.21 (t, 2H,
J= 7.2 Hz, SCH2), 1.84–1.78 (m, 2H, CH2), 1.03 (t, 3H, J= 7.2 Hz,
CH3). IR (cm−1): 3284 (NH), 1711 (C O), 1628, 1492, 1253, 1138. MS
(m/z, %): 337 (M+, 58), 295 (52), 262 (36), 234 (41), 193 (49), 92 (100).
Elemental Anal. Calcd. for C19H19N3OS: C, 67.63; H, 5.68; N, 12.45.
Found: C, 67.71; H, 5.69; N, 12.31.

Alkylthio-3-Amino-4 H-imidazol-4-one
2293
2-( n-Butylthio)-3-phenylamino-5-phenylmethylene-4 H-
imidazol-4-one (5d)
1
Light yellow crystals, m.p. 126–128◦C. H NMR (CDCl3, 400 MHz):
δ 8.20–6.76 (m, 11H, Ar H and CH), 6.29 (s, 1H, NH), 3.30 (t, 2H,
J= 7.2 Hz, SCH2), 1.86–1.49 (m, 4H, CH2CH2), 1.00 (t, 3H, J= 7.2 Hz,
CH3). IR (cm−1), 3278 (NH), 1711 (C O), 1637, 1497, 1252, 1141. MS
(m/z, %): 351 (M+, 29), 295 (17), 234 (6), 151 (19), 92 (100). Elemental
Anal. Calcd. for C20H21N3OS: C, 68.35; H, 6.02; N, 11.96. Found: C,
68.28; H, 6.14; N, 12.05.
2-( n-Hexylthio)-3-phenylamino-5-phenylmethylene-4 H-
imidazol-4-one (5e)
1
Light yellow crystals, m.p. 106–107◦C. H NMR (CDCl3, 400 MHz):
δ 8.20–6.76 (m, 11H, Ar H and CH), 6.31 (s, 1H, NH), 3.28 (t, 2H,
J= 7.2 Hz, SCH2), 1.87–1.35 (m, 8H, (CH2)4), 0.91 (t, 3H, J= 7.2 Hz,
CH3). IR (cm−1): 3325 (NH), 1733 (C O), 1637, 1493, 1245, 1143. MS
(m/z, %): 379 (M+, 37), 295 (41), 234 (8), 151 (24), 92 (100). Elemental
Anal. Calcd. for C22H25N3OS: C, 69.62; H, 6.64; N, 11.07. Found: C,
69.48; H, 6.67; N, 11.14.
2-Phenylmethylthio-3-phenylamino-5-phenylmethylene-
4 H-imidazol-4-one (5f)
1
Light yellow crystals, m.p. 200–201◦C. H NMR (CDCl3, 400 MHz):
δ 8.22–6.74 (m, 16H, Ar H and CH), 6.27 (s, 1H, NH), 4.54 (s, 2H,
SCH2). IR (cm−1): 3332 (NH), 1720 (C O), 1638, 1494, 1252, 1141. MS
(m/z, %): 385 (M+, 29), 295 (9), 236 (58), 116 (30), 91 (100). Elemental
Anal. Calcd. for C23H19N3OS: C, 71.66; H, 4.97; N, 10.90. Found: C,
71.73; H, 4.88; N, 10.95.
2-Cyanomethylthio-3-phenylamino-5-phenylmethylene-
4 H-imidazol-4-one (5g)
Light yellow crystals, m.p. 218–220◦C. 1H NMR (DMSO-d6, 400
MHz): δ 9.04 (s, 1H, NH), 8.33–6.70 (m, 11H, Ar H and CH), 4.41
(s, 2H, SCH2). IR (cm−1): 3272 (NH), 2246 (CN), 1718 (C O), 1637,
1499, 1258, 1139. MS (m/z, %): 334 (M+, 45), 295 (4), 236 (13), 116 (60),
92 (100). Elemental Anal. Calcd. for C18H14N4OS: C, 64.65; H, 4.22; N,
16.75. Found: C, 64.77; H, 4.39; N, 16.92.
2-Benzoylmethylthio-3-phenylamino-5-phenylmethylene-
4 H-imidazol-4-one (5h)
1
Light yellow crystals, m.p. 201–202◦C. H NMR (CDCl3, 400 MHz):
δ 8.14–6.82 (m, 16H, Ar H and CH), 6.26 (s, 1H, NH), 4.77 (s, 2H,
SCH2). IR (cm−1): 3312 (NH), 1722 and 1688 (C O), 1637, 1492, 1256,

2294
M.-W. Ding et al.
1143; MS (m/z, %), 413 (M+, 4), 381 (13), 296 (4), 116 (17), 105 (100).
Elemental Anal. Calcd. for C24H19N3O2S: C, 69.71; H, 4.63; N, 10.16.
Found: C, 69.75; H, 4.51; N, 10.15.
2-Aminocarbonylmethylthio-3-phenylamino-5-
phenylmethylene-4 H-imidazol-4-one (5i)
Light yellow crystals, m.p. 182–184◦C, 1H NMR (DMSO-d6, 400 MHz)
δ 8.94 (s, 1H, NHPh), 7.81 and 7.32 (s, 2H, NH2), 8.28–6.69 (m, 11H,
Ar H and CH), 4.02 (s, 2H, SCH2); IR (cm−1), 3433 and 3327 (NH and
NH2), 1738 and 1661 (C O), 1639, 1493, 1260, 1143. MS (m/z, %), 352
(M+, 7), 295 (48), 207 (12), 116 (78), 92 (100). Elemental Anal. Calcd.
for C18H16N4O2S: C, 61.35; H, 4.58; N, 15.90. Found: C, 61.31; H, 4.64;
N, 15.74.
2-Ethoxycarbonylmethylthio-3-phenylamino-5-
phenylmethylene-4 H-imidazol-4-one (5j)
1
Light yellow crystals, m.p. 159–160◦C. H NMR (CDCl3, 400 MHz):
δ 8.15–6.80 (m, 11H, Ar H and CH), 6.28 (s, 1H, NH), 4.27 (q, 2H,
J= 7.2 Hz, OCH2), 4.06 (s, 2H, SCH2), 1.32 (t, 3H, J= 7.2 Hz, CH3). IR
(cm−1): 3270 (NH), 1737 and 1724 (C O), 1633, 1502, 1258, 1140. MS
(m/z, %): 381 (M+, 93), 353 (12), 336 (15), 295 (24), 262 (54), 191 (76),
92 (100). Elemental Anal. Calcd. for C20H19N3O3S: C, 62.98; H, 5.02; N,
11.02. Found: C, 62.84; H, 5.24; N, 10.06.
2-Methoxycarbonylmethylthio-3-phenylamino-5-
phenylmethylene-4 H-imidazol-4-one (5k)
1
Light yellow crystals, m.p. 136–138◦C. H NMR (CDCl3, 400 MHz):
δ 8.15–6.79 (m, 11H, Ar H and CH), 6.32 (s, 1H, NH), 4.05 (s, 2H,
SCH2), 3.82 (s, 3H, OCH3). IR (cm−1): 3283 (NH), 1744 and 1721 (C O),
1634, 1504, 1258, 1141. MS (m/z, %): 367 (M+, 7), 331 (100), 116 (81),
92 (84). Elemental Anal. Calcd. for C19H17N3O3S: C, 62.11; H, 4.66; N,
11.44. Found: C, 62.10; H, 4.85; N, 11.37.
2-(1-Ethoxycarbonylethylthio)-3-phenylamino-5-
phenylmethylene-4 H-imidazol-4-one (5l)
1
Light yellow crystals, m.p. 139–140◦C. H NMR (CDCl3, 400 MHz):
δ 8.16–6.78 (m, 11H, Ar H and CH), 6.29 (s, 1H, NH), 4.62 (q, 1H,
J= 7.6 Hz, SCH), 4.29–4.19 (m, 2H, OCH2), 1.73 (d, 3H, J= 7.6 Hz,
CH3), 1.29 (t, 3H, J= 7.2 Hz, COOCH2CH3). IR (cm−1): 3279 (NH),
1728 and 1711 (C O), 1635, 1495, 1254, 1139. MS (m/z, %): 395 (M+,
53), 350 (12), 295 (45), 262 (25), 151 (46), 92 (100). Elemental Anal.

Alkylthio-3-Amino-4 H-imidazol-4-one
2295
Calcd. for C21H21N3O3S: C, 63.78; H, 5.35; N, 10.62. Found: C, 63.65;
H, 5.29; N, 10.74.
2-Methylthio-3-phenylamino-5-
(4-chlorophenylmethylene)-4 H-imidazol-4-one (5m)
Yellow crystals, m.p. 187–189◦C. 1H NMR (CDCl3, 400 MHz): δ 8.13–
6.76 (m, 10H, Ar H and CH), 6.33 (s, 1H, NH), 2.67 (s, 3H, SCH3). IR
(cm−1): 3359 (NH), 1714 (C O), 1626, 1488, 1248, 1139. MS (m/z, %):
345 (30), 343 (M+, 99), 296 (31), 268 (34), 150 (51), 92 (100). Elemental
Anal. Calcd. for C17H14ClN3OS: C, 59.39; H, 4.10; N, 12.22. Found: C,
59.33; H, 4.23; N, 12.14.
2-Ethylthio-3-phenylamino-5-(4-chlorophenylmethylene)-
4 H-imidazol-4-one (5n)
1
Light yellow crystals, m.p. 189–191◦C. H NMR (CDCl3, 400 MHz):
δ 8.12–6.75 (m, 10H, Ar H and CH), 6.33 (s, 1H, NH), 3.29 (q, 2H,
J= 7.2 Hz, SCH2), 1.50 (t, 3H, J= 7.2 Hz, CH3). IR (cm−1): 3330 (NH),
1713 (C O), 1635, 1486, 1250, 1144. MS (m/z, %): 359 (3), 357 (M+, 10),
150 (82), 92 (100). Elemental Anal. Calcd. for C18H16ClN3OS: C, 60.41;
H, 4.51; N, 11.74. Found: C, 60.56; H, 4.54; N, 11.64.
2-( n-Propylthio)-3-phenylamino-5-
(4-chlorophenylmethylene)-4 H-imidazol-4-one (5o)
1
Light yellow crystals, m.p. 171–173◦C. H NMR (CDCl3, 400 MHz):
δ 8.14–6.77 (m, 10H, Ar H and CH), 6.24 (s, 1H, NH), 3.28 (t, 2H,
J= 7.2 Hz, SCH2), 1.92–1.86 (m, 2H, CH2), 1.10 (t, 3H, J= 7.2 Hz,
CH3). IR (cm−1): 3282 (NH), 1715 (C O), 1634, 1493, 1251, 1143. MS
(m/z, %): 373 (10), 371 (M+, 28), 329 (16), 151 (30), 92 (100). Elemental
Anal. Calcd. for C19H18ClN3OS: C, 61.37; H, 4.88; N, 11.30. Found: C,
61.43; H, 4.72; N, 11.33.
2-( n-Butylthio)-3-phenylamino-5-
(4-chlorophenylmethylene)-4 H-imidazol-4-one (5p)
1
Light yellow crystals, m.p. 170–172◦C. H NMR (CDCl3, 400 MHz):
δ 8.14–6.77 (m, 10H, Ar H and CH), 6.23 (s, 1H, NH), 3.29 (t, 2H,
J= 7.2 Hz, SCH2), 1.86–1.50 (m, 4H, CH2CH2), 1.01 (t, 3H, J= 7.2 Hz,
CH3). IR (cm−1): 3286 (NH), 1716 (C O), 1637, 1494, 1252, 1144. MS
(m/z, %): 387 (18), 385 (M+, 46), 329 (25), 268 (8), 151 (46), 92 (100).
Elemental Anal. Calcd. for C20H20ClN3OS: C, 62.25; H, 5.22; N, 10.89.
Found: C, 62.31; H, 5.28; N, 10.75.

2296
M.-W. Ding et al.
2-Phenylmethylthio-3-phenylamino-5-
(4-chlorophenylmethylene)-4 H-imidazol-4-one (5q)
1
Light yellow crystals, m.p. 208–210◦C. H NMR (CDCl3, 400 MHz):
δ 8.15–6.76 (m, 15H, Ar H and CH), 6.22 (s, 1H, NH), 4.53 (s, 2H,
SCH2). IR (cm−1): 3283 (NH), 1722 (C O), 1632, 1492, 1258, 1139. MS
(m/z, %): 421 (3), 419 (M+, 8), 270 (18), 150 (13), 91 (100). Elemental
Anal. Calcd. for C23H18ClN3OS: C, 65.79; H, 4.32; N, 10.01. Found: C,
65.75; H, 4.24; N, 10.18.
2-Ethoxycarbonylmethylthio-3-phenylamino-5-
(4-chlorophenylmethylene)-4 H-imidazol-4-one (5r)
1
Light yellow crystals, m.p. 168–169◦C. H NMR (CDCl3, 400 MHz):
δ 8.09–6.80 (m, 10H, Ar H and CH), 6.29 (s, 1H, NH), 4.26 (q, 2H,
J= 7.2 Hz, OCH2), 4.04 (s, 2H, SCH2), 1.31 (t, 3H, J= 7.2 Hz, CH3). IR
(cm−1): 3342 (NH), 1743 and 1717 (C O), 1636, 1499, 1257, 1140. MS
(m/z, %): 417 (14), 415 (M+, 38), 267 (8), 191 (12), 150 (34), 92 (100).
Elemental Anal. Calcd. for C20H18ClN3O3S: C, 57.76; H, 4.36; N, 10.10.
Found: C, 57.88; H, 4.42; N, 10.03.
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