Synthesis and properties of novel imidazolone derivatives containing a sulfur atom

Article abstract of DOI:10.1080/10426500601088762

Novel 5-(2-chlorophenylmethylidene)-2-thio-4-imidazolinones 3 and 2-Alkythio-5-(2-chlorophenylmethylidene)-4H-imidazolin-4-ones 4 have been synthesized via a tandem aza-Wittig reaction to develop more imidazolinones that may possess biological activities.

Full text of DOI:10.1080/10426500601088762

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Synthesis and Properties of
Novel Imidazolone Derivatives
Containing a Sulfur Atom
Xiaobo Huang a b , Zhaojie Liu a , Fengling Yang a c
Mingwu Ding a
&
a College of Chemistry , Central China Normal
University , Wuhan, P. R. China
b College of Chemistry, Department of Chemistry
and Material Science , Wenzhou University ,
Wenzhou, P. R. China
c College of Chemistry, Department of Chemistry ,
Xuchang University , Xuchang, P. R. China
Published online: 19 Apr 2007.
To cite this article: Xiaobo Huang , Zhaojie Liu , Fengling Yang & Mingwu Ding (2007)
Synthesis and Properties of Novel Imidazolone Derivatives Containing a Sulfur Atom,
Phosphorus, Sulfur, and Silicon and the Related Elements, 182:5, 939-950, DOI:
10.1080/10426500601088762
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Phosphorus, Sulfur, and Silicon, 182:939–950, 2007
Copyright © Taylor & Francis Group, LLC
ISSN: 1042-6507 print / 1563-5325 online
DOI: 10.1080/10426500601088762
Synthesis and Properties of Novel Imidazolone
Derivatives Containing a Sulfur Atom
Xiaobo Huang
College of Chemistry, Central China Normal University, Wuhan,
P. R. China; and College of Chemistry, Department of Chemistry
and Material Science, Wenzhou University, Wenzhou, P. R. China
Zhaojie Liu
College of Chemistry, Central China Normal University, Wuhan,
P. R. China
Fengling Yang
College of Chemistry, Central China Normal University, Wuhan,
P. R. China; and College of Chemistry, Department of Chemistry,
Xuchang University, Xuchang, P. R. China
Mingwu Ding
College of Chemistry, Central China Normal University, Wuhan,
P. R. China
Novel 5-(2-chlorophenylmethylidene)-2-thio-4-imidazolinones 3 and 2-Alkythio-5-
(2- chlorophenylmethylidene)-4H-imidazolin-4-ones 4 have been synthesized via a
tandem aza-Wittig reaction to develop more imidazolinones that may possess bi-
ological activities. The target compounds were identified by GC-MS, IR, and 1H
NMR spectroscopies, and element analysis, and, in the case of 4k, its structure was
established by single crystal X-ray diffraction. They showed not only fungicidal
activities against Gibberella zeae, Cercospora beticola, Fusarium oxysporium, Rhi-
zoctonia solani, and Botryosphaeria berengeriana, but also growth inhibition of
Barnyard grass and Cole root and stalk.
Keywords aza-Wittig reaction; crystal structure; fungicidal activities; herbicidal activ-
ities; Imidazolinone derivatives; vinyliminophosphorane
Received August 29, 2006; accepted October 6, 2006.
The authors acknowledge financial support by the National Science Foundation of
China (Grant No. 20102001), New Century Excellent Talents in Universities of Henan
Province (Grant No. 2005HANCET-17), and the Scientific Research Fund of Zhejiang
Provincial Education Department (Grant No. 20051292).
Address correspondence to Xiaobo Huang, Department of Chemistry and Materi-
als Science, Wenzhou University, Wenzhou, 325027, P. R. China. E-mail: xiaobhuang@
hotmail.com
939

940
X. Huang et al.
INTRODUCTION
Imidazolinone derivatives exhibit various biological properties. Some
of them have been reported to posses a broad spectrum of pharmaco-
logical actions, which are reflected by their use as anticonvulsant.1−3
antiviral,4 antitumor,5 antibacterial,6 anti-inflammatory7 and hypoten-
sive agents.8 Some have been found to possess fungicidal activi-
ties; for example, 5-methyl-2- methylthio-5-phenyl-3-phenylamine-3,5-
dihydro-imidazolin-4-one (RPA407213) shows high fungicidal activity.9
And the literature also reveals that a number of imidazolinones are se-
lective herbicides,10 which inhibit acetolactate synthase11−12or acetohy-
droxyacid synthase.13 In view of these facts, we have synthesized a va-
riety of imidazolinones via a tandem aza-Wittig reaction and evaluated
their biological activities.14−18 Now we report the synthesis and biolog-
ical activities of some new 2-alkylthio-5-(2-chlorophenyl-methylidene)-
4H-imidazolin-4-ones.
RESULTS AND DISCUSSION
The synthetic pathway for the title compounds 4 is shown in Scheme 1.
The intermediate vinyliminophosphorane 1 was prepared according
the literature method.19 3-(2-Chlorophenyl)-2-isothiocyanato acrylic
acid ethyl ester 2 can be synthesized from vinyliminophosphorane 1
with carbon disulfide via a tandem aza-Wittig reaction. Intramolec-
ular cyclocondensation of the intermediate 2 in situ with R1NH2
SCHEME 1

Novel Imidazolone Derivatives
941
at r.t. gave the previously unreported 5-(2-chlorophenylmethylidene)-
2-thio-4-imidazolinones 3, which reacted with R2X (X = Cl, Br, I)
in the presence of K2CO3 (s) to give 4 in 56–79%. When R1X is
CH3I, the S-alkylation reaction could be carried out at r.t. When
R1X is BrCH2COOEt or PhCH2Cl, the S-alkylation reaction required
heating. Twelve novel 5-(2-chlorophenylmethyllidene)-4H-imidazolin-
4-ones were synthesized and identified by GC-MS, IR, elemental anal-
ysis, and 1H NMR spectroscopies.
A single crystal of 4k was grown from CH2Cl2, and ether (1:1, v/v) was
confirmed by X-ray diffraction analysis as shown in Figure 1. Diffrac-
tion measurements were carried out on a Bruker APEX area-detector
diffractometer (graphite-monochromatized Mo-Kα radiation, λ =
˚
0.71073 A). The hydrogen atoms were added according to the theoretical
models. The structure was refined by full-matrix least-squares method
on F2 with anisotropic thermal parameters for all non-hydrogen atoms.
The programs for structure solution and refinement are SHELXS-9720
and SHELXL-97,21 respectively. Crystal data are summarized in Table
I. The crystallographic data was deposited at CCDC.22 Compounds 4
may exist in (Z)- or (E)-isomeric forms with respect to the exocyclic C C
double bond. We had reported that the configuration of 2-alkylamino-
3-aryl-5-phenylmethylene-3,5-dihydro-4H-imidazo-4-lones could be
FIGURE 1 The molecular structure of 4k, with the atom-numbering scheme.
Displacement ellipsoids are drawn at the 50% probability level.

942
X. Huang et al.
TABLE I Crystal Data and Summary of Data Collection and
Structure Refinement of 4k
Formal
C21H21ClN2OS
Temperature (K)
Wavelength (A)
298(2)
0.71073
˚
Crystal system
Space group
Monoclinic
P 21/c
5.8814(5)
20.843(2)
16.6068(15)
90
104.594(4)
90
˚
a (A)
˚
b (A)
˚
c (A)
α(◦)
β(◦)
γ (◦)
3
˚
Volume (A )
1970.1(3)
Z
4
Calculated density (Mg mm−3
)
1.298
0.312
808
Absorption coefficient (mm−1
F(000)
)
Crystal size (mm)
0.32 × 0.16 × 0.13
θ Range for data collection (o)
Limiting indices
1.60–25.02
−5 ≤ h ≤ 6, −24 ≤ k ≤ 24, −19 ≤ l ≤ 19
10288/3461 [R(int) = 0.0559]
100.0%
Semi-empirical from equivalents
Full-matrix least-squares on F2
1.465
Reflections collection/unique
Completeness to θ = 25.19◦
Absorption correction
Refinement method
Goodness-of fit on F2
Final R indices [I >2σ (I)]
R1= 0.1056, wR2 = 0.2258
Largest diffusion peak and hole (e A−3
)
1.030 and −1.275
determined as in (Z)-form by analyzing its 13C NMR spectrum.23 Now
the X-ray crystal structure of 4k indicates the compounds exist as (Z)-
form.
The biological activities of all compounds 4a–l were investigated.
The method of testing adopted was taken from the literature.18 The
results are summarized in Tables II and Table III. The results of Table
II show that some compounds exhibited good fungicidal activities. For
example, in 50 µg/mL, 4i exhibited 86.6% inhibition of Gibberella zeae
and 90.0% inhibition of Cercospora beticol, while 4e showed 93.3% in-
hibition of Rhizoctonia solani. The best one was compound 4c, which
exhibited more than 86% inhibition of G. zeae, C. beticola, and Fusarium
oxysporium, respectively.
The studies of the biological activities of 5-arylmethylimidazolinone
derivatives were focused on fungicidal activities in the literatures.24−26
In our previous research, we found 2,3,5-trisubstituted imidazolinones

Novel Imidazolone Derivatives
943
TABLE II The Fungicidal Activity of Compounds 4a–4l (50 µg/mL,
Inhibition %)
Gibberella
zeae
Cercospora
beticola
Fusarium
oxysporium
Rhizoctonia Botryosphaeria
Entry
solani
berengeriana
4a
4b
4c
4d
4e
4f
4g
4h
4i
86.6
13.0
86.6
46.7
46.7
66.7
0
66.7
86.6
86.6
26.7
66.7
75.0
16.7
90.0
75.0
75.0
25.0
60.0
90.0
90.0
50.0
75.0
80.0
19.2
8.6
76.6
6.7
66.7
77.5
46.7
66.7
20.0
26.7
25.0
46.7
33.3
20.0
46.7
0
92.3
19.2
53.8
42.3
41.2
42.3
65.4
53.8
80.7
23.1
50.0
76.6
93.3
53.3
6.3
60.0
66.7
36.7
73.3
53.3
4j
4k
4l
with heterocyclic substituent group at 5-position showed herbicidal ac-
tivities to some extent.18 The results of Table III show that compounds 4
with 2-chlorophenyl group at 5-position also exhibited herbicidal activ-
ities. For example, in 100 µg/mL, 4b, 4d, and 4k showed 80.0%, 86.5%,
and 91.9% inhibition of Barnyard grass (Echinochloa crusgalli) root,
respectively, and 4b also exhibited 83.6% inhibition of Cole ( Brassica
campestris) root.
TABLE III Herbicidal Activity of Compounds 4a–4l
(Inhibition %)
Cole
Barnyard grass
100 µg/mL
10 µg/mL
100 µg/mL
10 µg/mL
Entry (Root/Stalk)
(Root/Stalk)
(Root/Stalk)
(Root/Stalk)
4a
4b
4c
4d
4e
4f
4g
4h
4i
52.2/38.6
83.6/44.4
37.2/12.3
65.5/35.1
40.0/14.3
25.5/30.9
45.8/29.4
60.2/22.8
19.2/72.2
46.7/28.6
76.1/31.6
56.6/21.1
45.1/31.6
51.7/8.9
31.8/12.3
53.9/21.1
7.8/14.3
23.3/16.7
28.1/27.9
45.1/22.8
18.2/38.9
34.4/14.3
34.5/24.6
38.9/15.8
45.9/32.4
80.0/4.5
51.4/37.8
86.5/37.8
2.0/40.0
16.3/33.3
54.0/50.0
67.6/29.7
40.0/41.7
18.4/40.0
91.9/45.9
54.1/43.2
43.2/27.0
62.5/0
48.6/35.1
45.9/27.0
32.6/50.0
18.4/36.7
50.0/39.6
59.5/24.3
32.0/30.5
38.8/36.7
27.0/27.0
37.8/37.8
4j
4k
4l

944
X. Huang et al.
In summary, novel 2-Alkythio-5-(2-chlorophenylmethylidene)-4H-
imidazolin-4-ones 4 have been synthesized via a tandem aza-Wittig re-
action and were identified by GC-MS, IR, and 1H NMR spectroscopies,
and element analysis. X-ray structure analysis of 4k showed that the
configuration of the target compounds is in (Z)-form. The results of
bioassay indicated that some of the target compounds possessed signi-
fication fungicidal activities. Especially A few of them exhibited good
herbicidal activities. It is worthwhile to optimize the structures.
EXPERIMENTAL
The 1H NMR spectrum (CDCl3) was recorded on a Varian XL-300 spec-
trometer with TMS as an internal standard, and IR spectrum was
recorded on a Pekin-Elmer-1600 FT infrared spectrometer in KBr Pel-
lets (ν in cm−1). Mass spectra were recorded on a Finnigen TRACE
GC-MS spectrometer. Elemental analyses were taken on a PE-2400-
CHN elemental analysis instrument. Melting points were determined
on an X4 microscopic melting apparatus (uncorrected).
General Preparation of 5-(2-Chlorophenylmethylidene)-2-
thio-4-imidazolinones 3
To a solution of vinyliminophosphorane 1 (2.43 g, 5 mmol) in dry
dichloromethane was added carbon disulfide (3.80 g, 50 mmol), and the
mixture was refluxed for 29 h under nitrogen. The solvent was removed
under reduced pressure, and 20 mL ether and petroleum ether (1:2, v/v)
was added to precipitate triphenylphosphine oxide. The solution was fil-
tered, and the filtrate was condensed in vacuo keeping the temperature
less 40◦C to give 3-(2-chlorophenyl)-2- isothiocyanato acrylic acid ethyl
ester 2, which was used without purification. To a solution of 2 in 20 mL
dry CH3CN was added R1NH2 (if R1 = n-Pr, 0.30 g, 5 mmol). The mix-
ture was allowed to stand 3 h, and then a yellow solid precipitated from
it. The solution was filtered, and the residue was recrystallized from
dichloromethane/petroleum ether to give intermediate 3.
3-Propyl-5-(2-chlorophenylmethylidene)-2-thio-4-
imidazolidinone (3a)
Appearance: yellow crystal; yield 52%; m.p. 129–130◦C; IR
(KBr)ν/cm−1: 3217 (NH), 1743 (C O), 1671 (C C), 1613, 1487, 1435
1
(Ar), 1226 (C=S); H NMR (300 MHz, CDCl3, pm): δ = 8.46 (brs, 1H,
NH), 7.46–7.32 (m, 4H, Ar), 6.93 (s, 1H, CH), 3.87 (t, 2H, J = 7.6 Hz,
2H, NCH2), 1.80–1.72 (m, 2H, NCH2CH2), 0.98 (t, 3H, J = 7.2 Hz, CH3).
MS (EI, m/z, %): 280 (M+, 55), 245 (74), 203 (100), 151 (56), 115 (53);

Novel Imidazolone Derivatives
945
calcd. for C13H13ClN2OS (%): C, 55.61; H, 4.67; N, 9.98; found (%): C,
55.69; H, 4.71; N, 9.90.
3-i-Propyl-5-(2-chlorophenylmethylidene)-2-thio-4-
imidazolidinone (3b)
Appearance: brown crystal; yield 55%; m.p. 113–115◦C; IR
(KBr)ν/cm−1: 3217 (NH), 1704 (C O), 1643 (C C), 1585, 1487, 1452
1
(Ar), 1228 (C=S); H NMR (300 MHz, CDCl3, ppm): δ = 8.48 (brs, 1H,
NH), 7.45–7.32 (m, 4H, Ar), 6.87(s, 1H, CH), 4.96–4.90 (m, 1H, NCH),
1.55 (d, J = 7.5 Hz, 6H, 2CH3); MS (EI, m/z, %): 280 (M+, 42), 245 (51),
203 (100), 151 (40), 115 (34); calcd. for C13H13ClN2OS (%): C, 55.61; H,
4.67; N, 9.98; found (%): C, 55.77; H, 4.19; N, 9.78.
3-Butyl-5-(2-chlorophenylmethylidene)-2-thio-4-
imidazolidinone (3c)
Appearance: yellow crystal; yield 66%; m.p. 129–130◦C; IR (KBr)
ν/cm−1: 3234 (NH), 1744 (C O), 1670 (C C), 1612, 1488, 1436 (Ar),
1223 (C S); 1H NMR (300 MHz, CDCl3, ppm): δ = 8.84 (brs, 1H, NH),
7.55–7.32 (m, 4H, Ar), 6.93 (s, 1H, CH), 3.90 (t, 2H, J = 7.8 Hz, NCH2),
1.75–1.66 (m, 2H, NCH2CH2), 1.45–1.34 (m, 2H, NCH2CH2CH2), 0.97
(t, 3H, J = 7.4 Hz, CH3); MS (EI, m/z, %): 294 (M+, 70), 259 (93), 203
(100), 151 (68), 115 (68); calcd. for C14H15ClN2OS (%): C, 57. 04; H, 5.13;
N, 9.50; found (%): C, 57.22; H, 5.19; N, 9.55.
3-i-Butyl-5-(2-chlorophenylmethylidene)-2-thio-4-
imidazolidinone (3d)
Appearance: Yellow crystal; Yield 54%; m.p. 133–135◦C; IR
(KBr)ν/cm−1: 3217 (NH), 1739 (C O), 1668 (C C), 1604, 1491, 1437
1
(Ar), 1223 (C S); H NMR (300 MHz, CDCl3, ppm): δ = 8.47 (brs, 1H,
NH), 7.55–7.32 (m, 4H, Ar), 6.93 (s, 1H, CH), 3.73 (d, 2H, J = 7.2Hz,
NCH2), 1.59–1.54 (m, 1H, NCH2CH), 0.97 (d, 6H, J = 6.6 Hz, 2CH3);
MS (EI, m/z, %) : 294 (M+, 8), 259 (38), 203 (100), 151 (16), 115 (15);
calcd. for C14H15ClN2OS (%): C, 57.04; H, 5.13; N, 9.50; Found (%): C,
57.34; H, 5.03; N, 9.28.
3-t-Butyl-5-(2-chlorophenylmethylidene)-2-thio-4-
imidazolidinone (3e)
Appearance: yellow crystal; yield 50%; m.p. 144–146◦C; IR
(KBr)ν/cm−1: 3233 (NH), 1724 (C O), 1650 (C C), 1585, 1483, 1444
(Ar), 1268 (C S); 1H NMR (300 M Hz, CDCl3, ppm): δ = 8.52 (brs, 1H,
NH), 7.46–7.34 (m, 4H, Ar), 6.89 (s, 1H, CH), 1.85 (s, 9H, 3CH3); MS
(EI, m/z, %): 294 (M+, 70), 259 (67), 203 (100), 151 (56), 115 (58); calcd.

946
X. Huang et al.
for C14H15ClN2OS (%): C, 57.04; H, 5.13; N, 9.50; found (%): C, 56.99;
H, 5.20; N, 9.63.
General Preparation of 2-Alkythio-5-
(2-chlorophenylmethylidene)-4H-imidazolin-4-ones 4
A mixture of 3 (if R1 = n-Pr, 0.22 g, 0.77 mmol) in 40 mL dry acetonitrile,
alkyl halide (if R2X = CH3I, 0.22 g, 1.54 mmol), and solid K2CO3(0.18 g,
1.3 mmol) was stirred for 3 h at r.t. or 50–70◦C and then filtered. The
filtrate was concentrated under reduced pressure, and the residue was
recrystallized from a mixture of dichloromethane, ether, and petroleum
ether to give 2-Alkythio-5-(2-chlorophenylmethylidene)-4H-imidazolin-
4-ones 4.
2-Methylthio-3-propyl-5-(2-chlorophenylmethylidene)-
4H-imidazoli-4-one (4a)
Appearance: light yellow crystal; yield, 69%; m.p.: 101–103◦C; IR
(KBr)ν/cm−1: 1711 (C O), 1633 (C C), 1579 (C=N), 1558, 1490, 1438
(Ar).1H NMR (300 MHz, CDCl3, ppm): δ = 8.85 (d, 1H, J = 8.7 Hz,
=CH), 7.41–7.24 (m, 4H, Ar), 3.57 (t, 2H, J = 7.4 Hz, NCH2), 2.73 (s, 3H,
SCH3), 1.75–1.67 (m, 2H, NCH2CH2), 0.96 (t, 3H, J = 7.4 Hz, CH2CH3);
MS (EI, m/z, %): 294 (M+, 87), 259 (99), 217 (100), 150 (37); calcd. for
C14H15ClN2OS (%): C, 57.04; H, 5.13; N, 9.50; found (%): C, 57.50; H,
5.02; N, 9.44.
2-Allylthio-3-propyl-5-(2-chlorophenylmethylidene)-
4H-imidazoli-4-one (4b)
Appearance: orange crystal; yield 76%; m.p. 113–114◦C; IR
(KBr)ν/cm−1: 1705 (C O), 1630 (C C), 1582 (C N), 1486, 1466, 1434
(Ar);1H NMR (300 MHz, CDCl3, ppm): δ = 8.83 (d, 1H, J = 9.0 Hz,
=CH), 7.39–7.21 (m, 4H, Ar), 6.06– 5.96 (m, 1H, SCH2CH=), 5.42–5.22
(dd, 2H, J = 9.9 Hz, J
= 17.1 Hz, CH2), 3.98 (d, 2H, J = 6.6 Hz,
cis
SCH2), 3.55 (t, 2H, J = t7ra.4nsHz, NH2), 1.73–1.66 (m, 2H, CH2CH3), 0.95
(t, 3H, J = 7.4 Hz, CH3); MS (EI, m/z, %): 320 (M+, 99), 285 (100), 244
(99), 150 (99); calcd. for C16H17ClN2OS (%): C, 59.90; H, 5.34; N, 8.73;
found (%): C, 60.01; H, 5.55; N, 8.97.
2-Ethoxycarbomethylenethio-3-propyl-5-
(2-chlorophenylmethylidene)-4H-imidazoli-4-one (4c)
Appearance: light yellow crystal; yield 62%; m.p 92–94◦C; IR
(KBr)ν/cm−1: 1730, 1715 (C O), 1631 (C C), 1572 (C N), 1496, 1471,
1435 (Ar);1H NMR (300 MHz, CDCl3, ppm): δ = 8.76 (d, 1H, J = 9.3 Hz,
=CH), 7.41–7.23 (m, 4H, Ar), 4.23 (q, 2H, J = 7.4 Hz, OCH2), 4.08 (s, 2H,

Novel Imidazolone Derivatives
947
SCH2), 3.58 (t, 2H, J = 7.2 Hz, NCH2), 1.76–1.68 (m, 2H, NCH2CH2),
1.28 (t, 3H, J = 7.4 Hz, OCH2CH3), 0.96 (t, 3H, J = 7.4 Hz, CH3);
MS (EI, m/z, %): 366 (M+, 66), 331 (100), 279 (64), 150 (74); calcd. for
C17H19ClN2O3S (%): C, 55.66; H, 5.22; N, 7.64; found (%): C, 55.44; H,
5.10; N, 7.82.
2-Benzylthio-3-propyl-5-(2-chlorophenylmethylidene)-
4H-imidazoli-4-one (4d)
Appearance: light yellow crystal; yield 72%; m.p. 102–103◦C; IR
(KBr)ν/cm−1: 1709 (C O), 1632 (C C), 1579 (C N), 1485, 1476, 1437
1
(Ar); H NMR (300 MHz, CDCl3, ppm): δ = 8.85 (d, 1H, J = 8.7 Hz,
CH2), 7.46–7.4 (m, 5H, Ph), 7.39–7.23 (m, 4H, Ar), 4.56 (s, 2H, SCH2),
3.54 (t, 2H, J = 7.2 Hz, NCH2), 1.74–1.61 (m, 2H, NCH2CH2), 0.93 (t,
3H, J = 7.4 Hz, CH3); MS (EI, m/z, %): 370 (M+, 12), 335 (9), 279 (6),
150 (11), 91 (100); calcd. for C20H19ClN2OS (%): C, 64.77; H, 5.16; N,
7.55; found (%): C, 64.62; H, 5.30; N, 7.91.
2-Ethoxycarbomethylenethio-3-i-propyl-5-
(2-chlorophenylmethylidene)-4H-imidazoli-4-one (4e)
Appearance: light yellow crystal; yield 70%; m.p. 98–100◦C; IR
(KBr)ν/cm−1: 1739, 1706 (C O), 1631 (C C), 1585 (C N), 1552, 1495,
1436 (Ar);1H NMR (300 MHz, CDCl3, ppm): δ = 8.74 (d, 1H, J = 8.4 Hz,
CH2), 7.40–7.20 (m, 4H, Ar), 4.29–4.19 (m, 1H, NCH), 4.23 (q, 2H, J =
7.2 Hz, OCH2), 4.06 (s, 2H, SCH2), 1.51 (d, 6H, J = 6.6 Hz, CH(CH3)2),
1.29 (t, 3H, J = 7.2 Hz, CH2CH3); MS (EI, m/z, %): 366 (M+, 19), 289
(31), 331 (100), 279 (17), 150 (35); calcd. for C17H19Cl N2O3S (%): C,
55.66; H, 5.22; N, 7.64; found (%): C, 55.70; H, 5.25; N, 7.73.
2-Benzylthio-3-i-propyl-5-(2-chlorophenylmethylidene)-
4H-imidazoli-4-one (4f)
Appearance: light yellow crystal; yield 67%; m.p. 83–85◦C; IR
(KBr)ν/cm−1:1709 (C O), 1632 (C C), 1579 (C N), 1485, 1476, 1437
1
(Ar); H NMR (300 MHz, CDCl3, ppm): δ = 8.82 (d, 1H, J = 8.7 Hz,
CH), 7.46–7.36 (m, 5H, Ph), 7.34–7.27 (m, 4H, Ar), 4.56 (s, 2H, SCH2),
4.24–4.19 (m, 1H, NCH), 1.48(d, 6H, J = 7.5 Hz, CH(CH3)2); MS (EI,
m/z, %): 370 (M+, 29), 335 (12), 279 (21), 150 (16), 91 (100); calcd. for
C20H19ClN2OS (%): C, 64.77; H, 5.16; N, 7.55; found (%): C, 64.86; H,
4.98; N, 7.38.
2-Ethoxycarbomethylenethio-3-butyl-5-
(2-chlorophenylmethylidene)-4H-imidazoli-4-one (4g)
Appearance: light yellow crystal; yield 56%; m.p. 56–57◦C; IR
(KBr)ν/cm−1:1729, 1708 (C O), 1635 (C C), 1587 (C N), 1548, 1486,

948
X. Huang et al.
1438 (Ar); 1H NMR (300 MHz, CDCl3, ppm): δ = 8.72 (d, 1H, J = 9.9 Hz,
CH), 7.38–7.21 (m, 4H, Ar), 4.22 (q, 2H, J = 7.1 Hz, OCH2CH3),
4.06 (s, 2H, SCH2), 3.59 (t, 2H, J = 7.1 Hz, NCH2), 1.69–1.59 (m, 2H,
NCH2CH2), 1.41–1.33 (m, 2H, NCH2CH2CH2), 1.28 (t, 3H, J = 7.1 Hz,
OCH2CH3); 0.95 (t, 3H, J = 7.4 Hz, NCH2CH2CH2CH3); MS (EI, m/z,
%): 380 (M+, 19), 345 (100), 293 (12), 150 (35); calcd. for C18H21Cl N2O3S
(%): C, 56.76; H, 5.56; N, 7.35; found (%): C, 56.55; H, 5.39; N, 7.94.
2-Benzylthio-3-butyl-5-(2-chlorophenylmethylidene)-
4H-imidazoli-4-one (4h)
Appearance: light yellow crystal; yield 66%; m.p. 97–99◦C; IR
(KBr)ν/cm−1:1708 (C O), 1632 (C C), 1582 (C N), 1532, 1483, 1439
1
(Ar); H NMR (300 MHz, CDCl3, ppm): δ = 8.84 (d, 1H, J = 8.4 Hz,
CH), 7.46–7.40 (m, 5H, Ph), 7.34–7.24 (m, 4H, Ar), 4.56 (s, 2H, SCH2),
3.57 (t, 2H, J = 7.4 Hz, NH2), 1.65–1.57 (m, 2H, NCH2CH2), 1.38–1.30
(m, 2H, CH2CH3), 0.93 (t, 3H, J = 7.4 Hz, CH3); MS (EI, m/z,%): 384
(M+, 38), 351 (28), 293 (26), 150 (20), 91 (100); calcd. for C21H21ClN2OS
(%): C, 65.53; H, 5.50; N, 7.28; found (%): C, 65.17; H, 5.58; N, 7.70.
2-Propargylthio-3-i-butyl-5-(2-chlorophenylmethylidene)-
4H-imidazoli-4-one (4i)
Appearance: light yellow crystal; yield 70%; m.p. 120–121◦C; IR
C
(KBr) ν/cm−1: 3253 (
H), 2125 (C C), 1740 (C O), 1635 (C C), 1582
(C N), 1483, 1466, 1439 (Ar); 1H NMR (300 MHz, CDCl3, ppm): δ = 8.82
(d, 1H, J = 9.6 Hz, CH), 7.43–7.23 (m, 4H, Ar), 4.11 (s, 2H, SCH2),
C
3.38 (d, 2H, J = 7.5 Hz, NCH2), 2.32 (t, 1H, J = 2.7 Hz,
H), 2.12–2.07
(m, 1H, CH), 0.94 (d, 6H, J = 6.6Hz, 2CH3); MS (EI, m/z, %): 332 (M+,
100), 317 (10), 293 (40), 150 (61), calcd. for C17H17ClN2OS (%): C, 61.34;
H, 5.15; N, 8.42; found (%): C, 61.11; H, 5.13; N, 8.68.
2-Ethoxycarbomethylenethio-3-i-butyl-5-(2-
chlorophenylmethylidene)-4H-imidazoli-4-one
(4j)
Appearance: light yellow crystal; yield 59%; m.p. 93–94◦C; IR
(KBr)ν/cm−1: 1725, 1704 (C O), 1633 (C C), 1579 (C N), 1554, 1486,
1
1437 (Ar); H NMR (300 MHz, CDCl3, ppm): δ = 8.77 (d, 1H, J = 9.3
Hz, CH), 7.41–7.23 (m, 4H, Ar), 4.22 (q, 2H, J = 6.9 Hz, OCH2CH3),
4.07 (s, 2H, SCH2), 3.42 (d, 2H, J = 7.2Hz, NCH2), 2.18–2.08 (m, 1H,
NCH2CH), 1.28 (t, 3H, J = 7.4 Hz, OCH2CH3), 0.96 (d, 3H, J = 6.6
Hz, 2CH3); MS (EI, m/z, %): 380 (M+, 13), 345 (100), 293 (13), 150 (24),
calcd. for C18H21ClN2O3S (%): C, 56.76; H, 5.56; N, 7.35; found (%): C,
56.48; H, 5.65; N, 7.52.

Novel Imidazolone Derivatives
949
2-Benzylthio-3-i-butyl-5-(2-chlorophenylmethylidene)-
4H-imidazoli-4-one (4k)
Appearance: light yellow crystal; yield 63%; m.p. 105–107◦C; IR
(KBr)ν/cm−1: 1709 (C O), 1622 (C C), 1582 (C N), 1552, 1484, 1436
1
(Ar); H NMR (300 MHz, CDCl3, ppm): δ = 8.86 (d, 1H, J = 9.3 Hz,
CH), 7.46–7.37 (m, 5H, Ph), 7.34–7.24 (m, 4H, Ar), 4.56 (s, 2H, SCH2),
3.38 (d, 2H, J = 7.2 Hz, NCH2), 2.13–2.07 (m, 1H, CH), 0.94 (d, 6H,
J = 6.6 Hz, 2CH3). MS (EI, m/z, %): 384(M+, 38), 349 (55), 293 (67), 150
(56); calcd. for C21H21ClN2OS (%): C, 65.53; H, 5.50; N, 7.28; found (%):
C, 65.31; H, 5.06; N, 7.61.
2-Methylthio-3-t-butyl-5-(2-chlorophenylmethylidene)-
4H-imidazoli-4-one (4l)
Appearance: light yellow crystal; yield 79%; m.p. 128–129◦C; IR
(KBr)ν/cm−1:1709 (C O), 1629 (C C), 1582 (C N), 1552, 1484, 1443
1
(Ar); H NMR (300 MHz, CDCl3, ppm): δ = 8.81 (d, 1H, J = 9.0 Hz,
CH), 7.42–7.27 (m, 4H, Ar), 2.68 (s, 3H, SCH3), 1.69 (s, 9H, 3CH3);
MS (EI, m/z, %): 308 (M+, 18), 273 (14), 217 (100), 151 (40); calcd. for
C15H17ClN2OS (%): C, 58.34; H, 5.55; N, 9.07; found (%): C, 58.37; H,
5.64; N, 8.87.
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