Synthesis and biological activities of novel 1,3- bis[substitutedpyridyl(thiazolyl)methyl]-2-substitutedmethylideneimidazolidines

Article abstract of DOI:10.1002/jhet.5570450415

(Chemical Equation Presented) A series of novel 1,3- dissubstitutedpyridyl(thiazolyl)methyl-2-substituted-methylideneimidazolidine derivatives 2 and 4 were designed and synthesized via the N-alkylation of the disubstituted heterocyclic ketene aminal derivative 1. When 1 (R = CN, R ¹ = COOC₂H₅) was used as the starting materials, mono N-alkylated reaction can take place in good yields owing to the presence of the intramolecular hydrogen bond. However, as for 1 (R = R ¹ = CN), it is difficult to obtain pure mono N-alkylated product. The structures of the target compounds were confirmed by IR, ¹H NMR, EI-MS and elemental analyses, and, in the case of 2c, by single crystal X-ray diffraction. The preliminary bioassay indicated that some of the title compounds possess moderate fungicidal and insecticidal activity.

Full text of DOI:10.1002/jhet.5570450415

Jul-Aug 2008
1045
Synthesis and Biological Activities of Novel 1,3-bis[substituted-
pyridyl(thiazolyl)methyl]-2-substitutedmethylideneimidazolidines
Man Yan, Zai-Gang Luo, Xiao-fei Zhu and De-Qing Shi*
Key Laboratory of Pesticide and Chemical Biology of Ministry of Education, College of Chemistry, Central
China Normal University, Wuhan 430079, Hubei, P. R. China
Address correspondence to: Prof. Dr. De-Qing Shi;
e-mail: chshidq@mail.ccnu.edu.cn
Received May 24, 2007
Revised March 26, 2008
NaH/DMF
NH
R'
HN
R
N
Het
N
R
Het
ClCH2Het
R'
2
1
1
N
NaH/DMF
ClCH2Het
HN
Het
NH
CN
HN
C2H5O2C
CN
C2H5O2C
3a-3b
S
S
N
Cl
N
Cl
N
HN
N
NaH/DMF
Cl
N
N
C2H5O2C
CN
C2H5O2C
CN
Cl
CH2Cl
N
3b
4
A series of novel 1,3-dissubstitutedpyridyl(thiazolyl)methyl-2-substituted-methylideneimidazolidine
derivatives 2 and 4 were designed and synthesized via the N-alkylation of the disubstituted heterocyclic
ketene aminal derivative 1. When 1 (R = CN, R' = COOC2H5) was used as the starting materials, mono N-
alkylated reaction can take place in good yields owing to the presence of the intramolecular hydrogen
bond. However, as for 1 (R = R' = CN), it is difficult to obtain pure mono N-alkylated product. The
structures of the target compounds were confirmed by IR, 1H NMR, EI-MS and elemental analyses, and, in
the case of 2c, by single crystal X-ray diffraction. The preliminary bioassay indicated that some of the title
compounds possess moderate fungicidal and insecticidal activity.
J. Heterocyclic Chem., 45, 1045 (2008).
INTRODUCTION
activities [5-8], as well as low toxicity toward mammals.
Some mono N-substituted heterocyclic ketene aminal
derivatives have also been reported [9-11]. However, there
are only a few reports on the synthesis and biological
activities of 1,3-bis substituted imidazolidine derivatives. As
a continuation of our search for new biologically active
compounds [12-13], we designed and synthesized a series of
novel 1,3-bis substituted pyridyl (thiazolyl)methyl-2-
substituted-methylidene imidazolidine derivatives via the N-
alkylation of the disubstituted heterocyclic ketene aminal
derivative 1 in mild condition, which is similar to
imidacloprid in the chemical structure.
The latest class of chemical insecticides with outstanding
economical impact on the agrochemical industry comprises
the neonicotinoid insecticides, which act agonistically and
show high selectivity to insect nicotinic acetylcholine
receptor. Imidacloprid [1-(6-chloro-3-pyridyl)methyl-N-
nitro imidazolidinimine, see Figure 1] is the first commer-
cially and widely used neonicotinoid insecticide with
relatively low human toxicity [1,2], and thiamethoxam (see
Figure 1) is a second generation neonicotinoid insecticide
with more active insecticidal activity. It was found that most
of the biologically active neonicotinic compounds contain
the aminomethylpyridine or aminomethylthiazole moiety
[3,4]. Moreover, in the study of pharmaceuticals and
agrochemicals, the introduction of pyridine or thiazole ring
into parent compounds may improve the properties and
biological activities of compounds, and many pyridyl and
1,3-thiazolyl-containing compounds are also known to
possess a wide range of biological and pharmacological
O
N
N
CH3
NO2
Thiamethoxam
NH
N
N
S
N
N
NO2
Cl
N
Cl
Imidacloprid
Figure 1

1046
M. Yan, Z.-G. Luo, X.-F. Zhu and D.-Q. Shi
Vol 45
under the reaction condition, compounds 3 all have E-
configuration, which is due to the presence of an intra
molecular hydrogen bond between the N-H and the ester
group as indicated by the downfield shift of the N-H
signal to 8.75 ppm in the 1H NMR spectra and
bathochromic shift of the carbonyl absorption (1680-1660
cm-1) in the IR spectra, which is consistent to the
reference [11]. It is noteworthy that even when excess 3-
(chloromethyl)pyridine (2 equimolecular) was used as the
alkylation agent, no double only mono substituted product
was obtained; as for 2-chloro-5-(chloromethyl)thiazole, in
order to obtain the pure mono substituted derivative, the
molecular ratio of 1 and alkyl halide has to be 1:1,
otherwise, the mixtures of the mono and double
substituted imidazolidines were formed, which are very
difficult to purify due to their similar polarity. On the
other hand, for 1 (R = R' = CN), it is difficult to obtain
pure mono alkylated derivatives even in excess 1 due to
the absence of an intra molecular hydrogen bond between
N-H and CN group.
RESULTS AND DISCUSSION
Various disubstituted heterocyclic ketene aminal 1
reacted with 2-chloro-5-(chloromethyl)pyridine or 2-chlo-
ro-5-(chloromethy)thiazole to give 1,3-bis N-alkylated
products 2 in satisfactory yields in the presence of
NaH/DMF system. However, when excess anhydrous
K2CO3 was used, the reaction takes place very slowly, and
the higher reaction temperature required results in many
by-products and difficult purification (Scheme 1).
Scheme 1
NaH/DMF
NH
R'
HN
R
N
Het
N
R
Het
ClCH2Het
R'
1
2
R, R' = CN, CO2C2H5, O,O-diethylphosphonyl
Het = 6-chloropyridin-3-yl, 2-chlorothiazol-5-yl
The disubstituted heterocyclic ketene aminal 1 (When
R = CN, COOC2H5) reacts with 2-chloro-5-(chloro-
methyl)thiazole, or 3-(chloromethyl)pyridine under basic
reaction condition (NaH/DMF) to give the mono N-
alkylated product 3. The alkylation reaction between
compound 1 and chloromethylpyridine (thiazole) takes
place on the N atom at the opposite position of ester group
(E) 1-(2-Chlorothiazol-5-yl)methyl-2-[(cyano)(ethoxy-
carbonyl)methylidene] imidazolidine (3b) can easily react
with 2-chloro-5-(chloromethyl)pyridine to provide asym-
metric double substituted imidazolidine derivative 4.
(Scheme 2). The reaction condition is listed in Table 1.
1
All products were fully characterized by IR, H NMR,
EI-MS and elemental analysis. All the spectral data were
Scheme 2
NH
CN
N
NaH/DMF
ClCH2Het
HN
HN
Het
3a: Het = pyridin-3-yl
3b: Het = 2-chlorothiazol-5-yl
C2H5O2C
C2H5O2C
CN
3a-3b
1
(E-configuration)
S
S
N
Cl
N
N
Cl
HN
N
NaH/DMF
Cl
N
N
C2H5O2C
CN
C2H5O2C
CN
Cl
CH2Cl
N
3b
4
Table 1 Reaction conditions of the target compounds
Compd.
R
R’
Het
Condition
Yield (%)*
2a
2b
2c
2d
2e
2f
3a
3b
4
CN
CN
COOEt
COOEt
CN
COOEt
COOEt
COOEt
COOEt
CN
CN
CN
CN
6-chloro-pyridin-3-yl
2-chloro-thiazol-5-yl
6-chloro-pyridin-3-yl
2-chloro-thiazol-5-yl
6-chloro-pyridin-3-yl
6-chloro-pyridin-3-yl
pyridin-3-yl
r.t./5 hr
r.t./6 hr
r.t./6 hr
r.t./6 hr
r.t./6 hr
r.t./5 hr
r.t./5 hr
r.t./5 hr
r.t./5 hr
86
75
78
66
77
72
87
69
70
O,O-diethylphosphonyl
O,O-diethylphosphonyl
CN
CN
CN
2-chloro-thiazol-5-yl
Yields of isolated products based on 2-substituted-methylene imidazolidine 1 or 3b

Jul-Aug 2008
Synthesis and Biological Activities
1047
1
in accordance with the anticipated structures. In the H
NMR spectra of 2, the CH2CH2 fragment in the
imidazolidine moiety displayed a singlet with a chemical
shifts of 3.5, while the protons of the CH2 linking with the
pyridine or thiazole ring is shifted downfield to 4.7.
However, for compounds 3 and 4, the CH2CH2 fragment
in the imidazolidine moiety displayed two resonances
with different chemical shifts as a result of their different
chemical environments. In order to confirm their
molecular structure absolutely, a single crystal of 2c was
obtained from absolute ethanol and the molecular
structure was determined by X-ray diffraction [14].
Compounds 2, 3, 4 were tested for insecticidal activities
against aphides at the concentration of 250 mg/L
according to a previously reported method [15]. The result
is listed in Table 2, which indicated that some of the title
compounds possess moderate insecticidal activity.
mono substituted derivatives. The results of the preliminary
bioassays indicated that some of the title compounds possess
moderate fungicidal and insecticidal activity.
EXPERIMENTAL
Melting points were determined with a WRS-1B digital
1
melting point apparatus and are uncorrected. H NMR spectra
was recorded with a Varian MERCURY-PLUS400 spectrometer
with TMS as the internal reference and CDCl3 as the solvent,
while mass spectra were obtained with
TRACEMS2000 spectrometer using the EI method. IR spectra
were measured by Nicolet NEXUS470 spectrometer.
a
Finnigan
a
Elemental analyses were performed with an Elementar Vario
ELIII CHNSO elementary analyzer. All of the solvents and
materials were reagent grade and purified as required. 2-
Substituted methylidene imidazolidines (1) were synthesized
according to the reported methods [16-19].
Table 2 Insecticidal activity of compound 2, 3 and 4 against aphides:
(250 mg/L, inhibitory rate %)
Compd.
2a
2b
2c
2d
2e
2f
3a
3b
4
Inhibitory 17.2
rate
56.0
8.4
28.5
42.4
39.3
36.0
11.0
45.1
General Procedure for the Preparation of 1,3-disub-
The fungicidal activities of the target compounds 2, 3, 4
were tested at a concentration of 50 mg/L. The five fungi
used, Fusarium oxysporium, Rhizoctonia solani, Botrytis
cinereapers, Gibberella zeae, Colletotrichum gossypii,
belong to the group of field fungi and were isolated from
corresponding crops. The activity data were listed in
Table 3. The preliminary bioassay indicated that some of
the title compounds possess moderate fungicidal activity,
for example, compounds 2c and 3b show 72.5% and
67.6% inhibitory activity against Botrytis cinereapers
fungus, respectively.
stitutedpyridyl(thiazolyl)methyl-2-substitued-methylidene-
imidazolidines (2). Under N2 atmosphere, the solution of of 2-
substituted methylidene imidazolidine (1) (0.01 mol) dissovled
in DMF (5 mL) was added dropwise to a mixture of NaH (0.02
mol) and anhydrous DMF (10 mL) at 0~5 °C for 0.5 h until no
more bubble was evolved. The solution of 2-chloro-5-
(chloromethyl)-pyridine or 2-chloro-5-(chloromethyl)-thiazole
(0.02 mol) in DMF (5 mL) was added dropwise to the flask
while cooling in an ice-bath. After the addition was complete,
the mixture was stirred at room temperature until the reaction
completed (monitored by TLC). The solution was concentrated
Table 3 The fungicidal activity of compounds 2, 3 and 4 (50 mg/L, inhibitory rate %)
Fusarium
oxysporium
Gibberella
zeae
Colletotrichum
gossypii
Compd.
Rhizoctonia solani
Botrytis
cinereapers
2a
2b
2c
2d
2e
2f
11.8
35.0
11.8
23.5
-17.7
5.9
0
11.4
25.0
2.1
8.6
21.9
11.8
72.5
41.6
46.9
56.3
32.1
67.6
23.5
15.6
38.8
25.0
19.2
40.6
31.2
57.9
42.8
23.1
21.4
15.79
17.9
21.2
7.1
13.7
28.6
23.3
12.6
29.0
40.9
30.1
25.0
36.5
24.5
15.8
3a
3b
4
under vacuum. The residue was washed with brine, extracted
with CHCl3 (3ꢀ30 mL) and dried over anhydrous MgSO4,
respectively. The filtrate was evaporated and the residue was
In conclusion, we designed and synthesized a series of
novel 1,3-bis substituted pyridyl(thiazolyl)methyl-2-sub-
stituted-methylideneimidazolidine derivatives including two

1048
M. Yan, Z.-G. Luo, X.-F. Zhu and D.-Q. Shi
Vol 45
temperature until the reaction finished (monitored by TLC) and
the mixture was concentrated under vacuum. The residue was
washed with brine, extracted with CHCl3 (3ꢀ30 mL) and dried
over anhydrous MgSO4, respectively. The filtrate was evapo-
rated and the residue was purified by column chromatography
on silica gel (CH2Cl2:CH3OH (v/v) =15~10:1), giving the
corresponding imidazolines 3a-3b in 69-87% yields.
purified by flash column chromatography on silica gel
(CH2Cl2:CH3OH (v/v) =15~10:1), giving the corresponding 2 in
66~86% yields.
1,3-Bis-(6-chloropyridin-3-ylmethyl)-2-(bis-cyanomethyl-
idene)imidazolidine (2a). White crystals, mp 187-188º; ir: CN
1
2202, 2171, CO 1710 cm-1; H nmr: ꢀ 3.67 (s, 4H, CH2CH2),
4.84 (s, 4H, CH2N), 7.42 (d, J = 7.6 Hz, 2H, H-C(5) of pyridine),
7.74 (d, J = 6.8 Hz, 2H, H-C(4) of pyridine), 8.36 (s, 2H, H-
C(2) of pyridine); ms: m/z 386 (36), 384 (M+, 66), 258 (62), 232
(22), 126 (100), 98 (21), 90 (26), 62 (10). Anal. Calcd. for
C18H14Cl2N6: C, 56.12; H, 3.66; N, 21.81. Found: C, 55.96; H,
3.58; N, 21.57.
(E) 1-(pyridin-3-ylmethyl)-2-[(ethoxycarbonyl)(cyano)-
methylidene]-3H-imidazoline (3a). white crystals, mp 126-
1
128º; ir: N-H 3250, CN 2195, CO 1665 cm-1; H nmr: ꢀ 1.32 (t,
3H, CH3), 3.55-3.57 (m, 2H, CH2CH2), 3.63-3.65 (m, 2H,
CH2CH2), 4.21 (q, 2H, CH2CH3), 5.00 (s, 2H, NCH2), 7.38 (s,
1H, H-C(2) of pyridine), 7.81 (d, 1H, H-C(5) of pyridine), 8.58
(d, J = 7.6Hz, 1H, H-C(4) of pyridine), 8.75(s, 1H, H-C(6) of
pyridine), 8.75 (s, 1H, NH); ms: m/z 274 (13), 272 (M+, 77), 227
(49), 197 (62), 159 (76), 133 (28), 92 (100), 65 (28). Anal.
Calcd. for C14H16N4O2: C, 61.75; H, 5.92; N, 20.58. Found: C,
61.67; H, 5.81; N, 20.69.
(E) 1-(2-Chlorothiazol-5-ylmethyl)-2-[(ethoxycarbonyl)-
(cyano)methylidene]-3H-imidazoline (3b). white crystals, mp
119-121º; ir: N-H 3302, CN 2180, CO 1680 cm-1; 1H nmr: ꢀ 1.30
(t, 3H, CH3), 3.61-3.72 (m, 2H, CH2CH2), 3.74-3.81 (m, 2H,
CH2CH2), 4.16-4.23 (m, 2H, CH2CH3), 5.06 (s, 2H, NCH2), 7.53
(s, 1H, thiazole-H), 8.72 (s, 1H, NH). Anal. Calcd. for
C12H13ClN4O2S: C, 46.08; H, 4.19; N, 17.91. Found: C, 45.91;
H, 4.08; N, 17.84.
Preparation of 1-(6-chloropyridin-3-ylmethyl)-3-(2-chloro-
thiazol-5-ylmethyl)-2-[(ethoxycarbonyl)(cyano)methylidene]-
imidazolidine (4). The solution of 3b (0.012 mol) in DMF
(5mL) was added dropwise to a mixture of NaH (0.012 mol) and
anhydrous DMF (10 mL) under N2 at 0~5 °C. After no more
bubble was evolved, the solution of 2-chloro-5-(chloromethyl)-
pyridine (0.01 mol) in DMF (5mL) was added dropwise to the
above solution while cooling in an ice-bath. After the addition
complete, the mixture was stirred at room temperature until the
reaction finished (monitored by TLC). The mixture was
concentrated under vacuum, washed with brine, extracted with
CHCl3 (3ꢀ30 mL) and dried over anhydrous MgSO4,
respectively. The filtrate was evaporated and the residue was
purified by column chromatography on silica gel (petroleum
1,3-Bis-(2-chlorothiazol-5-ylmethyl)-2-(bis-cyanomethylid-
ene)imidazolidine (2b). White crystals, mp 197-198º; ir: CN
1
2190, 2175 cm-1; H nmr: ꢀ 3.62 (s, 4H, CH2CH2), 4.89 (s, 4H,
2CH2N), 7.73 (s, 2H, thiazole-H). ms: m/z 398 (28), 396 (M+,
73), 237(65), 211 (34), 132 (100), 98 (21), 62 (15). Anal. Calcd.
for C14H10Cl2N6S2: C, 42.32; H, 2.54; N, 21.15. Found: C, 42.28;
H, 2.61; N, 21.37.
1,3-Bis-(6-chloropyridin-3-ylmethyl)-2-[(cyano)(ethoxycar-
bonyl)methylidene]imidazolidine (2c). White crystals, mp
1
172-174º; ir: CN 2182, CO 1692, 1678, 1540 cm-1; H nmr: ꢀ
1.29 (t, 3H, CH3), 3.49 (s, 4H, CH2CH2), 4.17 (q, 2H, CH2CH3),
4.67 (s, 4H, CH2N), 7.39 (d, J = 8.0 Hz, 2H, H-C(5) of pyridine),
7.82 (d, J = 6.8 Hz, 2H, H-C(4) of pyridine), 8.36 (s, 2H, H-
C(2) of pyridine). Anal. Calcd. for C20H19Cl2N5O2: C, 55.57; H,
4.43; N, 16.20. Found: C, 55.76; H, 4.18; N, 15.97.
1,3-Bis-(2-chlorothiazol-5-ylmethyl)-2-[(cyano)(ethoxycar-
bonyl)methylidene] imidazolidine (2d). yellow viscous solid;
ir: CN 2190, CO 1725 cm-1; 1H nmr: ꢀ 1.18 (t, 3H, CH3), 3.58 (s,
4H, CH2CH2), 4.06 (q, 2H, CH2CH3), 4.74 (s, 4H, CH2N), 7.70
(s, 2H, thiazole-H); ms: m/z 445 (30), 443 (M+, 72), 284 (64),
258 (22), 211(18), 132 (100), 109 (10). Anal. Calcd. for
C16H15Cl2N5O2S2: C, 43.25; H, 3.40; N, 15.76. Found: C, 43.48;
H, 3.31; N, 15.64.
1,3-Bis-(6-chloropyridin-3-ylmethyl)-2-[(cyano)(O,O-dieth-
ylphosphonyl)methylidene]imidazolidine (2e). white crystals,
1
mp 117-118º; ir: CN 2164, P=O 1248, P-O-C 1103 cm-1; H
nmr: ꢀ 1.33 (t, 6H, CH2CH3), 3.43 (s, 4H, CH2CH2), 4.11 (q, 4H,
CH2CH3), 4.81 (s, 4H, CH2N), 7.37 (d, J = 7.6 Hz, 2H, H-C(5)
of pyridine), 7.92 (d, J = 6.8 Hz, 2H, H-C(4) of pyridine), 8.34
(s, 2H, H-C(2) of pyridine). Anal. Calcd. for C21H24Cl2N5O3P: C,
50.82; H, 4.87; N, 14.11. Found: C, 50.69; H, 4.80; N, 13.99.
1,3-Bis-(6-chloropyridin-3-ylmethyl)-2-[(ethoxycarbonyl)-
(O,O-diethylphosphonyl)methylidene]imidazolidine (2f).
white crystals, mp 143-145º; ir: CO 1720, P=O 1277, P-O-C)
1220, 1107 cm-1; 1H nmr: ꢀ 1.20-1.25 (m, 9H, CH3), 3.47 (s, 4H,
CH2CH2), 4.05-4.13 (m, 6H, CH2CH3), 4.70 (s, 4H, CH2N), 7.36
(d, J = 7.6 Hz, 2H, H-C(5) of pyridine), 7.92 (d, J = 7.2 Hz, 2H,
H-C(4) of pyridine), 8.32 (s, 2H, H-C(2) of pyridine). Anal.
Calcd. for C23H29Cl2N4O5P: C, 50.84; H, 5.38; N, 10.31. Found:
C, 50.96; H, 5.63; N, 10.25.
Preparation of (E) 1-substitued-2-[(ethoxycarbonyl)-
(cyano)methylidene]-3H-imidazolines 3. To a mixture of NaH
(0.012 mol) and unhydrous DMF (10 mL) in 50 mL three-
necked flask, was added dropwise the solution of 2-
substitutedmethylidene imidazolidine (2) (0.012 mol) in DMF (5
mL) under N2 at 0-5 °C. After no more bubble was evolved, the
solution of 2-chloro-5-(chloromethyl)-thiazole or 3-(chloro-
methyl)-pyridine (0.01 mol) in DMF (5 mL) was added
dropwise to the above solution while cooling in an ice-bath.
After the addition complete, the mixture was stirred at room
ether:acetone (v/v)
asymmetrical disubstituted imidazoline 4 in 70% yield. white
=
2:1), giving the corresponding
1
viscous solid; ir: CN 2190, CO 1728 cm-1; H nmr: ꢀ 1.26-1.34
(m, 3H, CH3), 3.45-3.53 (m, 2H, CH2CH2), 3.55-3.60 (m, 2H,
CH2CH2), 4.17-4.23 (m, 2H, CH2CH3), 4.68 (s, 2H, NCH2), 4.76
(s, 2H, NCH2), 7.38 (d, J = 8.0 Hz, 1H, H-C(5) of pyridine); 7.49
(s, 1H, H-C(2) of pyridine); 7.80 (d, J = 7.2 Hz, 1H, H-C(3) of
pyridine), 8.32 (s, 1H, thiazole-H); ms: m/z 440 (16), 438 (M+,
38), 312 (24), 306(18), 126 (100), 90 (70). Anal. Calcd. for
C18H17Cl2N5O2S: C, 49.32; H, 3.91; N, 15.98. Found: C, 49.27;
H, 3.76; N, 15.75.
Fungicidal activity testing. The fungicidal activity
measurement method was adapted from the one described by
Molina Torres et al. [20]. The synthesized target compounds were
dissolved in 0.5-1.0 mL of DMF to the concentration of 500 mg/L.
The solutions (1 mL) were mixed rapidly with thawed potato
glucose agar culture medium (9 mL) under 50 ºC. The mixtures
were poured into Petri dishes. After the dished were cooled, the
solidified plates were incubated with 4 mm mycelium disk,
inverted, and incubated at 28 ºC for 48 h. Distilled water was used
as the blank control. Three replicates of each test were carried out.
The mycelial elongation radius (mm) of fungi settlements was

Jul-Aug 2008
Synthesis and Biological Activities
1049
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Acknowledgement. The authors are grateful to the Natural
Science Foundation of China (grant No. 20302002) and the
Scientific Research Foundation for the Returned Overseas
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