Construction of C(sp2)-S and C(sp2)-Se bonds via a silver(i)-mediated coupling reaction of heterocyclic ketene aminals with diaryl dichalcogenides

Article abstract of DOI:10.1039/c4ra02519a

A novel silver(i)-mediated direct coupling reaction using heterocyclic ketene aminals (HKAs) and diaryl dichalcogenides for the construction of C(sp²)-S and C(sp²)-Se bonds was reported. The transformation involves a variety of functionalized substrates, leading to α-arylthio and α-phenylselanyl HKAs in a mild, facile and efficient way with high regioselectivity and excellent yields. The broad scope of the starting materials enhanced the chemo-diversity of the target materials, thus affording a number of potential applications in the synthesis of heterocycles and its relevant medicinal chemistry.

Full text of DOI:10.1039/c4ra02519a

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Construction of C(sp2)–S and C(sp2)–Se bonds via a
silver(I)-mediated coupling reaction of heterocyclic
ketene aminals with diaryl dichalcogenides†
Cite this: RSC Adv., 2014, 4, 26389
a
a
a
a
ab
*
*
Xiu-Yang Jiang, Zhi-Cheng Liu, Li Fang, Sheng-Jiao Yan and Jun Lin
A novel silver(I)-mediated direct coupling reaction using heterocyclic ketene aminals (HKAs) and diaryl
dichalcogenides for the construction of C(sp2)–S and C(sp2)–Se bonds was reported. The transformation
involves a variety of functionalized substrates, leading to a-arylthio and a-phenylselanyl HKAs in a mild,
facile and efficient way with high regioselectivity and excellent yields. The broad scope of the starting
materials enhanced the chemo-diversity of the target materials, thus affording a number of potential
applications in the synthesis of heterocycles and its relevant medicinal chemistry.
Received 22nd March 2014
Accepted 27th May 2014
DOI: 10.1039/c4ra02519a
www.rsc.org/advances
This leads to higher electron density of the a-carbon (C3) than
that of the secondary amino groups (N1 and N5). Consequently,
Introduction
the substituted targets of the a-carbon have been obtained with
high selectivity via alkylation,20 acylation,21 glycosation,22 halo-
genations,23 and nitration reactions.24 However, to the best of
our knowledge, no information is available on the formation of
C–chalcogen bonds via the coupling reaction of HKAs with
chalcogen. Herein, we report the rst example of an AgOAc-
mediated direct coupling reaction of HKAs 1 with diaryl
A transition-metal-catalyzed coupling reaction for the formation
of carbon–heteroatom bonds is one of the most active
contemporary topics in modern synthetic chemistry.1 The
development of concise and sustainable procedures, as well as
the discovery of novel and efficient transition-metal catalysts,
have been a driving force in the construction of selective
synthetic methods. Among the plethoric formalism of carbon–
heteroatom bonds, in particular, the sp2 hybrid carbon–chal-
cogen bonds2 have enjoyed prominent standing in elds such as
total synthesis,3 medicinal chemistry,4 organometallic chem-
istry,5 chemical biology,6 and supramolecular chemistry.7
Despite remarkable progress in direct transition-metal-cata-
lyzed coupling reactions of aromatic systems with chalcogen,8
olen systems with chalcogen have been hardly explored.9
In the past few decades, stereoselective and regioselective
synthesis focusing on heterocycles frequently found in natural
products, pharmaceuticals, and dyes has played a signicant
role in many chemical branches, leading to the rapid develop-
ment of widely used synthons. For example, there is a lot of
research effort focused on concise and efficient access of HKAs
to highly functionalized target materials.10–19 The structure of
HKAs is shown as Fig. 1. Due to the conjugation of electro-
donating amino groups and the electron-withdrawing carbonyl
group, the double bond (C]C) of HKAs is highly polarized.19
dichalcogenides
2
that leads to the regioselective
aKey Laboratory of Medicinal Chemistry for Natural Resource (Yunnan University),
Ministry of Education, School of Chemical Science and Technology, Yunnan
University, Kunming, 650091, P. R. China. E-mail: yansj@ynu.edu.cn; linjun@ynu.
edu.cn; Fax: +86 871 65033215
bState Key Laboratory of Elemento-Organic Chemistry, Nankai University, Tianjin,
30071, P. R. China
† Electronic supplementary information (ESI) available. CCDC 949284 (3g). For
ESI and crystallographic data in CIF or other electronic format see DOI:
10.1039/c4ra02519a
Fig. 1 Regioselective reactions of the a-carbon of HKAs.
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functionalization of the a-carbon with excellent yields (83–98%) and 0.3 mol%, but the yields of 4a were nearly the same as that
by a facile post-treatment protocol. The scope of the reaction with 1.0 mol%, or even sacriced. Therefore, the results showed
encompasses HKAs and diaryl dichalcogenides bearing that AgOAc (1.0 mol%) was the best (Table 1, entries 14–17).
different sized rings, substitution patterns, and functional Further screening of solvents (toluene, DMF, EtOH, and
groups, which suggests that these novel synthons will be suit- CH3CN) indicated that the prospective product could be
able for further synthesis of diverse heterocyclic architectures. obtained with the highest yield (91%) (Table 1, entries 18–21) in
toluene, but for the purposes of concise post-treatment and
higher yield, 1,4-dioxane remained the most suitable reaction
medium. Encouraged by these results, other silver salts,
Results and discussion
including AgNO3, AgCO3 and AgOTf, were checked (Table 1,
entries 22–24). Hence, the optimum conditions included HKAs
1 (1.0 mol) and diaryl dichalcogenides 2 (1.0 mol) in 1,4-dioxane
(10 mL) at reux temperature for 4 hours with AgOAc (1.0 mol%)
as the catalyst (Table 1, entries 4).
Initially, we screened the optimum conditions for the coupling
reaction to synthesize 1-phenyl-2-(phenylthio)-2-(tetrahy-
dropyrimidin-2(1H)-ylidene)ethan-1-one 4a using HKA 1g and
1,2-di-phenyl disulfane 2a as the model substrates (Table 1). No
reaction occurred without the addition of a catalyst at room
temperature or reuxing temperature even aer 24 hours
(Table 1, entries 1 and 2). However, when AgOAc (1.0 mol%) was
added to reuxed 1,4-dioxane, the yield of 4a reached 95%
(Table 1, entries 3 and 4). Subsequently, trials with PdCl2, as
well as other basic (t-BuOK, Cs2CO3, K2CO3, piperidine, and
Et3N) or acidic (p-MBSA, TFA, and HAc) catalysts were screened,
but the results demonstrated that only PdCl2 could slightly
promote the reaction (Table 1, entries 5–13). We also attempted
to change the AgOAc loading to 1.3 mol%, 0.7 mol%, 0.5 mol%,
With the optimized reaction conditions in hand, we focused
on the evaluation of the substrate scope (Table 2). A wide range
of substituted HKAs 1a–p with three distinctively sized dia-
zaheterocycles were employed to react with diaryl disuldes 2a–
f or diphenyl diselenide 2g separately under the optimized
conditions to afford the corresponding a-arylthio or a-phenyl-
selanyl HKAs 3–5 in good yields. At rst, we examined the scope
of substrates 1. It was observed that the substituent group (Ar)
on the HKAs had a certain inuence on the yields. The system
with an electron-donating group (OMe or Me) on the aryl ring
reacted faster and gave higher yields than those with no
substituent (H) or an electron-withdrawing group (F or Cl) (e.g.
Table 2, entries 1–6). Notably, the reaction involving substrates
with ortho-Cl always showed the lowest yield, which could be
attributed to the electronic effect and steric hindrance (Table 2,
entries 6, 22, and 33). On the other hand, as the diazahetero-
cycle is far away from the reactive a-position, the size of it (n)
almost has no distinct effect on the yields of target materials
(e.g. Table 2, entries 1, 17, and 34). Moreover, further explora-
tion of the substrate scope referred to diaryl dichalcogenides 2
that mainly examined the impact of hetero-atoms (Z) and the
substituent group (Ar1) on the yields of target molecules.
Obviously, compounds 2, which have an electronegative
element (S), gave higher yields than the relatively electropositive
one (Se) (e.g. Table 2, entries 1 and 12). The substituents on the
diaryl disuldes 2a–f exhibited trend in terms of the yields of
target products, i.e., p-OMe z p-Me > p-H > p-Cl > m-F > m-diCl
(e.g. Table 2, entries 17 and 23–27). Similarly, the inuence of
substrates 2 can be explained by the electronic and the steric
effect. In brief, these results conrmed that the substituent
groups (Ar and Ar1) and the heteroatoms (Z) were the most
signicant inuencing factors for this type of direct coupling
reaction, which can be used to synthesize a-arylthio or a-phe-
nylselanyl HKAs 3–5.
Table 1 Optimization of the reaction conditionsa
Entry
Cat. [concn/mol%]
Solvent
t (ꢀC)
Yieldb (%)
1c
2c
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
—
—
1,4-Dioxane
1,4-Dioxane
1,4-Dioxane
1,4-Dioxane
1,4-Dioxane
1,4-Dioxane
1,4-Dioxane
1,4-Dioxane
1,4-Dioxane
1,4-Dioxane
1,4-Dioxane
1,4-Dioxane
1,4-Dioxane
1,4-Dioxane
1,4-Dioxane
1,4-Dioxane
1,4-Dioxane
Toluene
r. t.
Reux
r. t.
N. R.
N. R.
32
95
61
N. R.
N. R.
N. R.
N. R.
N. R.
N. R.
N. R.
N. R.
95
87
79
68
91
77
72
51
N. R.
90
AgOAc (1.0)
AgOAc (1.0)
PdCl2 (1.0)
t-BuOK (1.0)
Cs2CO3 (1.0)
K2CO3 (1.0)
Piperidine (1.0)
Et3N (1.0)
Reux
Reux
Reux
Reux
Reux
Reux
Reux
Reux
Reux
Reux
Reux
Reux
Reux
Reux
Reux
Reux
Reux
Reux
Reux
Reux
Reux
p-MBSA (1.0)
TFA (1.0)
HAc (1.0)
AgOAc (1.3)
AgOAc (0.7)
AgOAc (0.5)
AgOAc (0.3)
AgOAc (1.0)
AgOAc (1.0)
AgOAc (1.0)
AgOAc (1.0)
AgNO3 (1.0)
Ag2CO3 (1.0)
AgOTf (0.5)
Finally, the scope of this synthetic protocol was evaluated for
other HKAs (1q–r). The results are shown in Scheme 1 and
demonstrate that 1q–r are also good substitutes in this synthetic
procedure.
It is also worth noting that the purication for all of the
target products only required recrystallization rather than
column chromatography. This easy post-treatment protocol
makes this methodology facile, practical, and rapid to execute.
DMF
EtOH
CH3CN
1,4-Dioxane
1,4-Dioxane
1,4-Dioxane
93
a
Reactions were carried out using 1g (1.0 mmol), 2a (1.0 mmol),
b
catalyst, and solvent (10 mL) for 4 hours. Isolated yield, N. R. ¼ no
reaction. c Prolonged the duration of the reaction to 24 hours.
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Table 2 Substrate scope of silver(I)-mediated coupling reaction of
HKAs 1a–p with diaryl dichalcogenides 2a–ga
Scheme 1 Preparation of a-arylthio-substituted HKAs.
Entry
1 (n/Ar)
2 (Z/Ar1)
Product
Yieldb (%)
1
2
3
4
5
6
7
8
1a (1/Ph)
2a (S/Ph)
2a (S/Ph)
2a (S/Ph)
2a (S/Ph)
2a (S/Ph)
2a (S/Ph)
2b (S/p-OMePh)
2c (S/p-MePh)
2d (S/p-ClPh)
2e (S/m-diClPh)
2f (S/m-FPh)
2g (Se/Ph)
2g (Se/Ph)
2g (Se/Ph)
2g (Se/Ph)
2g (Se/Ph)
2a (S/Ph)
3a
3b
3c
3d
3e
3f
3g
3h
3i
94
97
94
93
89
85
94
95
90
84
88
91
93
91
87
88
95
98
96
92
90
87
95
96
93
85
92
92
95
94
90
86
83
92
93
90
87
96
95
91
83
88
90
93
86
85
1b (1/p-OMePh)
1c (1/p-MePh)
1d (1/p-FPh)
1e (1/p-ClPh)
1f (1/o-ClPh)
1a (1/Ph)
1a (1/Ph)
1a (1/Ph)
1a (1/Ph)
1a (1/Ph)
Fig. 2 ORTEP view of the molecular structure of 3g (thermal ellipsoids
are drawn at 30% probability).
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
3j
3k
3l
1a (1/Ph)
1b (1/p-OMePh)
1c (1/p-MePh)
1d (1/p-FPh)
1e (1/p-ClPh)
1g (2/Ph)
1h (2/p-OMePh)
1i (2/p-MePh)
1j (2/p-FPh)
1k (2/p-ClPh)
1l (2/o-ClPh)
1g (2/Ph)
3m
3n
3o
3p
4a
4b
4c
4d
4e
4f
4g
4h
4i
4j
4k
4l
4m
4n
4o
4p
4q
5a
5b
5c
5d
5e
5f
5g
5h
5i
5j
5k
5l
2a (S/Ph)
2a (S/Ph)
2a (S/Ph)
2a (S/Ph)
2a (S/Ph)
Scheme 2 Plausible mechanism for the synthesis of target materials
3–5.
2b (S/p-OMePh)
2c (S/p-MePh)
2d (S/p-ClPh)
2e (S/m-diClPh)
2f (S/m-FPh)
2g (Se/Ph)
2g (Se/Ph)
2g (Se/Ph)
2g (Se/Ph)
2g (Se/Ph)
2g (Se/Ph)
2a (S/Ph)
1g (2/Ph)
1g (2/Ph)
1g (2/Ph)
1g (2/Ph)
All compounds were characterized by IR, 1H NMR, 13C NMR
spectroscopies as well as HRMS. The outcome of the regiose-
lective direct coupling reaction was conrmed by X-ray diffrac-
tion analysis of selected single crystal of 3g (Fig. 2).
In combination with known facts,25 a plausible mechanism
for this reaction is depicted in Scheme 2. Initially, the Ag+
derived from AgOAc coordinates with equivalent chalcogens of
diaryl dichalcogenides 2 to give 6. Subsequently, the coupling
reaction of the a-carbon of HKAs 1 with the non-complexed
heteroatom of 6 contributes to C-Z (S or Se) bond formation and
affords target materials 3–5 and 7. The outcome of the coupling
reaction is the direct synthesis of a sp2 hybrid carbon-chalcogen
bond in situ.
1g (2/Ph)
1h (2/p-OMePh)
1i (2/p-MePh)
1j (2/p-FPh)
1k (2/p-ClPh)
1l (2/o-ClPh)
1m (3/Ph)
1n (3/p-MePh)
1o (3/p-FPh)
1p (3/p-ClPh)
1m (3/Ph)
2a (S/Ph)
2a (S/Ph)
2a (S/Ph)
2b (S/p-OMePh)
2c (S/p-MePh)
2d (S/p-ClPh)
2e (S/m-diClPh)
2f (S/m-FPh)
2g (Se/Ph)
2g (Se/Ph)
2g (Se/Ph)
2g (Se/Ph)
1m (3/Ph)
1m (3/Ph)
1m (3/Ph)
1m (3/Ph)
1m (3/Ph)
1n (3/p-MePh)
1o (3/p-FPh)
1p (3/p-ClPh)
Conclusions
5m
In conclusion, we have developed the rst protocol for the direct
coupling reaction of HKAs with diaryl dichalcogenides in a
remarkably mild, facile, and efficient way that covers a wide
range of functionalized substrates, thus allowing in situ trans-
formation of a variety of HKAs to a-arylthio and a-phenylselanyl
target compounds in excellent yields with high regioselectivity.
a
Reaction conditions: 1 (1.0 mmol) and 2 (1.0 mmol) were added in 1,4-
dioxane (10 mL) in the presence of AgOAc (1.0 equiv.), and then reuxed
in a round-bottom ask for 4 hours. b Isolated yield.
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The developed method can be applied to sp2 hybrid carbon–
chalcogen bond formation reactions in several other olen
systems. We are currently exploring the biological activity of the
recently generated compounds as well as their potential appli-
cation in the synthesis of novel heterocycles.
2-(Imidazolidin-2-ylidene)-2-(phenylthio)-1-(p-tolyl)etha-
none (3c). White solid, yield 94%; mp 213–214 ꢀC; IR (KBr):
3416, 3285, 1579, 1531, 1365, 1298, 744 cmꢁ1 1H NMR (500
;
MHz, CDCl3): d ¼ 2.28 (s, 3H, CH3), 3.57 (t, J ¼ 8.8 Hz, 2H,
NCH2), 3.91 (t, J ¼ 8.8 Hz, 2H, NCH2), 5.72 (br, 1H, NH), 7.02 (d,
J ¼ 7.8 Hz, 2H, ArH), 7.06–7.33 (m, ArH, 7H), 9.94 (br, 1H, NH);
13C NMR (125 MHz, CDCl3): d ¼ 21.8, 42.6, 45.8, 75.9, 124.7,
124.9, 127.5, 128.4, 129.3, 139.1, 139.7, 141.0, 168.7, 194.1;
HRMS (TOF ES+): m/z calcd for C18H18N2NaOS [(M + Na+)],
333.1032; found, 333.1027.
Experimental section
General information
All compounds were fully characterized by spectroscopic data.
The NMR spectra were recorded on a Bruker DRX500 (1H: 500
MHz, 13C: 125 MHz) or DRX400 (1H: 400 MHz, 13C: 100 MHz);
chemical shis (d) are expressed in ppm, J values are given in
Hz, and deuterated CDCl3 was used as the solvent. IR spectra
were recorded on a FT-IR Thermo Nicolet Avatar 360 using KBr
pellets. The reactions were monitored by thin layer chroma-
tography (TLC) using silica gel GF254. The melting points were
determined on an XT-4A melting point apparatus and are
uncorrected. HRMS was performed on an Agilent LC/Msd TOF
instrument. All chemicals and solvents were used as received
without further purication unless otherwise stated. The raw
material 1 was synthesised according to the literature.26 The
materials 3a–g were purchased from Aldrich Corporation
Limited.
1-(4-Fluorophenyl)-2-(imidazolidin-2-ylidene)-2-(phenylthio)-
ethanone (3d). White solid, yield 93%; mp 182–183 ꢀC; IR (KBr):
3305, 1580, 1532, 1370, 1303, 743 cmꢁ1 1H NMR (500 MHz,
;
CDCl3): d ¼ 3.50–3.57 (m, 2H, NCH2), 3.85–3.89 (m, 2H, NCH2),
5.80 (br, 1H, NH), 6.84–7.41 (m, 9H, ArH), 9.86 (br, 1H, NH); 13
C
NMR (125 MHz, CDCl3): d ¼ 42.6, 45.8, 75.9, 114.5 (d, J ¼ 20.0
Hz), 124.6, 125.1, 129.4, 129.7, 138.6, 140.7, 163.4 (d, J ¼ 245.0
Hz), 168.7, 192.7; HRMS (TOF ES+): m/z calcd for
C
17H15FN2NaOS [(M + Na+)], 337.0781; found, 337.0783.
1-(4-Chlorophenyl)-2-(imidazolidin-2-ylidene)-2-(phenylthio)-
ethanone (3e). White solid, yield 89%; mp 200–202 ꢀC; IR (KBr):
3413, 3267, 1579, 1532, 1370, 1306, 742 cmꢁ1 1H NMR (500
;
MHz, CDCl3): d ¼ 3.56 (t, J ¼ 8.9 Hz, 2H, NCH2), 3.90 (t, J ¼ 8.9
Hz, 2H, NCH2), 5.80 (br, 1H, NH), 7.06–7.34 (m, 9H, ArH), 9.85
(br, 1H, NH); 13C NMR (125 MHz, CDCl3): d ¼ 42.6, 45.8, 76.0,
124.6, 125.2, 127.9, 129.0, 129.4, 134.9, 140.6, 140.9, 168.7,
192.6; HRMS (TOF ES+): m/z calcd for C17H15ClN2NaOS [(M +
Na+)], 353.0486; found, 353.0486.
General procedure for the synthesis of 3–5
To a 25 mL round-bottomed ask, HKAs 1 (1 mmol), 1,2-
diphenyldiselane 2 (1 mmol), AgOAc (1 mmol) in dioxane (15
mL) were added. The resulting mixture was heated to reux and
stirred until all starting diphenyldiselane was consumed, as
monitored by TLC. Aer cooling to room temperature, the solid
AgOAc was removed by ltration. The organic layer was then
concentrated under reduced pressure to yield crude product.
The crude compound was then puried by recrystallization with
ethyl acetate and petroleum ether to afford compounds 3–5 as a
white solid.
2-(Imidazolidin-2-ylidene)-1-phenyl-2-(phenylthio)ethanone
(3a). White solid, yield 94%; mp 202–204 ꢀC; IR (KBr): 3194,
1573, 1482, 1373, 1299, 735 cmꢁ1; 1H NMR (500 MHz, CDCl3): d
¼ 3.53 (t, J ¼ 8.8 Hz, 2H, NCH2), 3.88 (t, J ¼ 8.8 Hz, 2H, NCH2),
5.78 (br, 1H, NH), 7.06–7.39 (m, ArH, 10H), 9.91 (br, 1H, NH);
13C NMR (125 MHz, CDCl3): d ¼ 42.6, 45.8, 76.1, 124.7, 125.0,
127.4, 127.7, 129.1, 129.3, 141.0, 142.6, 168.7, 194.1; HRMS (TOF
ES+): m/z calcd for C17H16N2NaOS [(M + Na+)], 319.0876; found,
319.0874.
1-(2-Chlorophenyl)-2-(imidazolidin-2-ylidene)-2-(phenylthio)-
ethanone (3f). White solid, yield 85%; mp 194–195 ꢀC; IR (KBr):
3193, 1582, 1540, 1482, 1381, 1299, 747 cmꢁ1 1H NMR (500
;
MHz, CDCl3): d ¼ 3.58 (t, J ¼ 8.9 Hz, 2H, NCH2), 3.92 (t, J ¼ 8.9
Hz, 2H, NCH2), 5.80 (br, 1H, NH), 7.05–7.30 (m, 9H, ArH), 9.74
(br, 1H, NH); 13C NMR (125 MHz, CDCl3): d ¼ 42.5, 45.7, 125.1,
126.3, 127.6, 129.0, 129.5, 130.6, 140.2, 142.2, 168.0, 192.1;
HRMS (TOF ES+): m/z calcd for C17H15ClN2NaOS [(M + Na+)],
353.0486; found, 353.0485.
2-(Imidazolidin-2-ylidene)-2-((4-methoxyphenyl)thio)-1-phe-
nylethanone (3g). White solid, yield 94%; mp 218–220 ꢀC; IR
1
(KBr): 3403, 3304, 1589, 1533, 1482, 1367, 1298, 700 cmꢁ1; H
NMR (500 MHz, CDCl3): d ¼ 3.55 (t, J ¼ 8.9 Hz, 2H, NCH2),
3.70 (s, 3H, CH3), 3.88 (t, J ¼ 8.9 Hz, 2H, NCH2), 5.82 (br, 1H,
NH), 6.78–7.40 (m, 9H, ArH), 9.87 (br, 1H, NH); 13C NMR (125
MHz, CDCl3): d ¼ 42.6, 45.8, 55.8, 115.1, 126.4, 127.1, 127.4,
127.7, 129.1, 131.6, 142.7, 157.9, 168.8, 194.1; HRMS (TOF ES+):
m/z calcd for C18H19N2O2S [(M + H+)], 327.1162; found,
327.1168.
2-(Imidazolidin-2-ylidene)-1-(4-methoxyphenyl)-2-(phenyl-
2-(Imidazolidin-2-ylidene)-1-phenyl-2-(p-tolylselanyl)etha-
none (3h). White solid, yield 95%; mp 196–197 ꢀC; IR (KBr):
ꢀ
thio)ethanone (3b). White solid, yield 97%; mp 176–177 C; IR
(KBr): 3366, 3269, 1576, 1369, 1241, 732 cmꢁ1 1H NMR (500
;
3424, 3318, 1578, 1359, 1298, 702 cmꢁ1 1H NMR (500 MHz,
;
MHz, CDCl3): d ¼ 3.57 (t, J ¼ 8.9 Hz, 2H, NCH2), 3.75 (s, 3H,
CH3), 3.90 (t, J ¼ 8.9 Hz, 2H, NCH2), 5.72 (br, 1H, NH), 6.74 (t, J
¼ 8.6 Hz, 2H, ArH), 7.06–7.26 (m, 5H, ArH), 7.45 (t, J ¼ 8.6 Hz,
2H, ArH), 9.95 (br, 1H, NH); 13C NMR (125 MHz, CDCl3): d ¼
42.6, 45.8, 55.6, 75.6, 112.9, 124.6, 125.0, 129.3, 129.6, 134.9,
141.0, 160.6, 168.9, 193.2; HRMS (TOF ES+): m/z calcd for
CDCl3): d ¼ 2.29 (s, 3H, ArCH3), 3.49–3.53 (m, 2H, NCH2), 3.85–
3.88 (m, 2H, NCH2), 5.77 (br, 1H, NH), 7.01–7.41 (m, 9H, ArH),
9.91 (br, 1H, NH); 13C NMR (125 MHz, CDCl3): d ¼ 21.3, 42.6,
45.8, 76.4, 124.8, 127.4, 127.7, 129.1, 130.1, 134.7, 137.4, 142.7,
168.7, 194.0; HRMS (TOF ES+): m/z calcd for C18H19N2OS [(M +
H+)], 311.1213; found, 311.1216.
C
18H18N2NaO2S [(M + Na+)], 349.0981; found, 349.0971.
26392 | RSC Adv., 2014, 4, 26389–26397
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2-((4-Chlorophenyl)selanyl)-2-(imidazolidin-2-ylidene)-1-
RSC Advances
1-(4-Fluorophenyl)-2-(imidazolidin-2-ylidene)-2-(phenyl-
ꢀ
phenylethanone (3i). White solid, yield 90%; mp 211–213 ꢀC; IR selanyl)ethanone (3o). White solid, yield 87%; mp 167–169 C;
(KBr): 3200, 1581, 1377, 1299, 705 cmꢁ1 1H NMR (500 MHz, IR (KBr): 3412, 3312, 1575, 1525, 1367, 1298, 726 cmꢁ1; 1H NMR
;
CDCl3): d ¼ 3.58 (t, J ¼ 8.7 Hz, 2H, NCH2), 3.91 (t, J ¼ 8.7 Hz, 2H, (500 MHz, CDCl3): d ¼ 3.53–3.58 (m, 2H, NCH2), 3.90–3.94 (m,
NCH2), 5.73 (br, 1H, NH), 7.03–7.37 (m, 9H, ArH), 9.90 (br, 1H, 2H, NCH2), 5.81 (br, 1H, NH), 6.85–6.90 (m, 2H, ArH), 7.14–7.15
NH); 13C NMR (125 MHz, CDCl3): d ¼ 42.6, 45.8, 75.8, 126.0, (m, 1H, ArH), 7.22–7.37 (m, 6H, ArH), 9.96 (br, 1H, NH); 13C
127.3, 127.7, 129.2, 129.3, 130.7, 139.6, 142.4, 168.6, 194.2; NMR (125 MHz, CDCl3): d ¼ 42.5, 46.0, 73.7, 114.5 (d, J ¼ 20.0
HRMS (TOF ES+): m/z calcd for C17H16ClN2OS [(M + H+)], Hz), 126.0, 127.4, 129.6, 129.6, 135.5, 139.6, 163.2 (d, J ¼ 246.3
331.0666; found, 331.0663.
2-((3,5-Dichlorophenyl)selanyl)-2-(imidazolidin-2-ylidene)-1- [(M + H+)], 363.0406; found, 363.0412.
phenylethanone (3j). White solid, yield 84%; mp 213–214 ꢀC; IR
1-(4-Chlorophenyl)-2-(imidazolidin-2-ylidene)-2-(phenyl-
Hz), 168.6, 192.9; HRMS (TOF ES+): m/z calcd for C17H16FN2OSe
(KBr): 3208, 1575, 1377, 1300, 793 cmꢁ1 1H NMR (500 MHz, selanyl)ethanone (3p). White solid, yield 88%; mp 184–186 C;
;
ꢀ
CDCl3): d ¼ 3.55–3.61 (m, 2H, NCH2), 3.89–3.94 (m, 2H, NCH2), IR (KBr): 3405, 3263, 1576, 1528, 1369, 1305, 736 cmꢁ1; 1H NMR
5.76 (br, 1H, NH), 6.95–7.34 (m, 8H, ArH), 9.89 (br, 1H, NH); 13
NMR (125 MHz, CDCl3): d ¼ 42.6, 45.8, 74.7, 122.7, 125.2, 127.2, 2H, NCH2), 5.77 (br, 1H, NH), 7.13–7.28 (m, 9H, ArH), 9.95 (br,
127.8, 129.3, 135.8, 142.2, 145.3, 168.3, 194.1; HRMS (TOF ES+): 1H, NH); 13C NMR (125 MHz, CDCl3): d ¼ 42.5, 46.0, 73.7, 126.0,
m/z calcd for C17H15Cl2N2OS [(M + H+)], 365.0277; found, 127.3, 127.8, 128.9, 129.6, 134.7, 135.4, 141.9, 168.6, 192.8;
C
(500 MHz, CDCl3): d ¼ 3.56–3.60 (m, 2H, NCH2), 3.91–3.96 (m,
365.0258.
HRMS (TOF ES+): m/z calcd for C17H16ClN2OSe [(M + H+)],
2-(Nitro(phenylthio)methylenꢀe)imidazolidine (3q). White
1H NMR (500 solid, yield 88%; mp 163.5–164 C; IR (KBr): 3350, 3256, 1576,
2-((3-Fluorophenyl)selanyl)-2-(imidazolidin-2-ylidene)-1-phe- 379.0111; found, 379.0103.
nylethanone (3k). White solid, yield 88%; mp 204–205 ꢀC; IR
(KBr): 3423, 3305, 1581, 1367, 1299, 733 cmꢁ1
;
MHz, CDCl3): d ¼ 3.53 (t, J ¼ 8.8 Hz, 2H, NCH2), 3.88 (t, J ¼ 8.8 1392, 1335, 738 cmꢁ1; 1H NMR (500 MHz, CDCl3): d ¼ 3.75–3.79
Hz, 2H, NCH2), 5.79 (br, 1H, NH), 6.73–7.36 (m, 9H, ArH), 9.89 (m, 2H, NCH2), 3.95–4.00 (m, 2H, NCH2), 5.83 (br, 1H, NH),
(br, 1H, NH); 13C NMR (125 MHz, CDCl3): d ¼ 42.6, 45.8, 75.5, 7.13–7.17 (m, 3H, ArH), 7.24–7.28 (m, 2H, ArH), 8.83 (br, 1H,
111.5 (d, J ¼ 23.7 Hz), 111.9 (d, J ¼ 21.3 Hz), 112.0, 120.3, 127.3, NH); 13C NMR (125 MHz, CDCl3): d ¼ 43.1, 45.6, 98.4, 125.6,
127.8, 129.2, 130.6, 144.0, 163.2 (d, J ¼ 245.0 Hz), 168.5, 194.1; 125.9, 129.1, 136.1, 163.3; HRMS (TOF ES+): m/z calcd for
HRMS (TOF ES+): m/z calcd for C17H16FN2OS [(M + H+)],
C
10H11N3NaO2S [(M + Na+)], 260.0464; found, 260.0462.
315.0962; found, 315.0965.
1-Phenyl-2-(phenylthio)-2-(tetrahydropyrimdin-2(1H)-yli-
2-(Imidazolidin-2-ylidene)-1-phenyl-2-(phenylselanyl)etha- dene)ethanone (4a). White solid, yield 95%; mp 167–169 ꢀC; IR
none (3l). White solid, yield 91%; mp 161–163 ꢀC; IR (KBr): (KBr): 3352, 3279, 1586, 1344, 1205, 742 cmꢁ1 1H NMR (500
;
3409, 3310, 1573, 1368, 1297, 728 cmꢁ1
;
1H NMR (500 MHz, MHz, CDCl3): d ¼ 1.79–1.82 (m, 2H, NCH2), 3.27–3.43 (m, 4H,
CDCl3): d ¼ 3.48–3.52 (m, 2H, NCH2), 3.86–3.90 (m, 2H, NCH2), NCH2), 6.49 (br, 1H, NH), 7.04–7.08 (m, 3H, ArH), 7.15–7.18 (m,
5.78 (br, 1H, NH), 7.11–7.34 (m, 10H, ArH), 9.98 (br, 1H, NH); 4H, ArH), 7.24–7.28 (m, 2H, ArH); 13C NMR (125 MHz, CDCl3): d
13C NMR (125 MHz, CDCl3): d ¼ 42.5, 46.0, 73.9, 125.8, 127.3, ¼ 20.4, 38.8, 39.5, 78.4, 124.7, 125.0, 126.8, 127.7, 128.5, 129.2,
127.5, 127.6, 128.9, 129.5, 135.7, 143.7, 168.5, 194.2; HRMS (TOF 141.0, 143.9, 160.8, 193.0; HRMS (TOF ES+): m/z calcd for
ES+): m/z calcd for C17H16N2NaOSe [(M + Na+)], 367.0320; found,
C
18H19N2OS [(M + H+)], 311.1213; found, 211.1209.
367.0315.
1-(4-Methoxyphenyl)-2-(phenylthio)-2-(tetrahydropyrimidin-
2-(Imidazolidin-2-ylidene)-1-(4-methoxyphenyl)-2-(phenyl- 2(1H)-ylidene)ethanone (4b). White solid, yield 98%; mp 177–
selanyl)ethanone (3m). White solid, yield 93%; mp 144–146 ꢀC; 178 ꢀC; IR (KBr): 3364, 3050, 1585, 1344, 1241, 735 cmꢁ1
;
1H
IR (KBr): 3309, 1603, 1347, 818, 737 cmꢁ1; H NMR (500 MHz, NMR (500 MHz, CDCl3): d ¼ 1.93–1.96 (m, 2H, CH2), 3.30–3.35
CDCl3): d ¼ 3.57–3.61 (m, 2H, NCH2), 3.78 (s, 3H, OCH3), 3.93– (m, 2H, NCH2), 3.43–3.49 (m, 2H, NCH2), 3.74 (s, 3H, OCH3), 6.49
3.96 (m, 2H, NCH2), 5.77 (br, 1H, NH), 6.75–7.43 (m, 9H, ArH), (br, 1H, NH), 6.71 (d, J ¼ 7.3 Hz, 2H, ArH), 7.08–7.26 (m, 5H,
10.04 (br, 1H, NH); 13C NMR (125 MHz, CDCl3): d ¼ 42.6, 46.0, ArH), 7.33 (d, J ¼ 7.3 Hz, 2H, ArH), 12.05 (br, 1H, NH); 13C NMR
55.6, 73.5, 112.9, 125.8, 127.4, 129.5, 129.6, 135.8, 135.9, 160.5, (125 MHz, CDCl3): d ¼ 20.4, 38.8, 39.5, 55.5, 112.9, 124.6, 125.0,
168.7, 193.5; HRMS (TOF ES+): m/z calcd for C18H19N2O2Se [(M + 128.9, 129.3, 136.3, 141.1, 160.0, 160.9, 192.4; HRMS (TOF ES+):
1
H+)] 375.0606; found, 375.0601.
m/z calcd for C19H21N2O2S [(M + H+)], 341.1318; found, 341.1316.
2-(Phenylthio)-2-(tetrahydropyrimidin-2(1H)-ylidene)-1-(p-
2-(Imidazolidin-2-ylidene)-2-(phenylselanyl)-1-(p-tolyl)-etha-
none (3n). White solid, yield 91%; mp: 205–207 ꢀC; IR (KBr): tolyl)ethanone (4c). White solid, yield 96%; mp 175–177 C; IR
ꢀ
3391, 3252, 1572, 1529, 1366, 1300, 733 cmꢁ1 1H NMR (500 (KBr): 3330, 3052, 1584, 1339, 1164, 746 cmꢁ1 1H NMR (500
; ;
MHz, CDCl3): d ¼ 2.12 (s, ArCH3), 3.55–3.66 (m, 2H, NCH2), MHz, CDCl3): d ¼ 1.88–1.92 (m, 2H, NCH2), 2.26 (s, 3H, ArCH3),
3.88–3.95 (m, 2H, NCH2), 5.74 (br, 1H, NH), 6.74 (d, J ¼ 8.6 Hz, 3.25–3.29 (m, 2H, NCH2), 3.40–3.47 (m, 2H, NCH2), 6.48 (br, 1H,
2H, ArH), 7.12–7.27 (m, 5H, ArH), 7.39 (d, J ¼ 8.6 Hz, 2H, ArH), NH), 6.98 (d, J ¼ 7.6 Hz, 2H, ArH), 6.97–7.12 (m, 3H, ArH), 7.22–
10.02 (br, 1H, NH); 13C NMR (125 MHz, CDCl3): d ¼ 42.6, 46.0, 7.25 (m, 4H, ArH); 13C NMR (125 MHz, CDCl3): d ¼ 20.4, 21.8,
55.6, 67.5, 112.8, 125.8, 127.4, 129.5, 129.6, 135.8, 135.9, 160.5, 38.8, 39.5, 78.2, 124.6, 125.0, 127.0, 128.3, 129.2, 138.3, 141.1,
168.7, 193.5; HRMS (TOF ES+): m/z calcd for C18H19Na2OSe [(M + 160.8, 193.0; HRMS (TOF ES+): m/z calcd for C19H21N2OS, [(M +
H+)], 359.0657; found, 359.0661.
H+)], 325.1369; found, 325.1365.
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Paper
1-(4-Fluorophenyl)-2-(phenylthio)-2-(tetrahydropyrimidin-
2-((3,5-Dichlorophenyl)selanyl)-1-phenyl-2-(tetrahydropyr-
2(1H)-ylidene)ethanone (4d). White solid, yield 92%; mp 122– imidin-2(1H)-ylidene)ethanone (4j). White solid, yield 85%; mp
1
124 ꢀC; IR (KBr): 3322, 3060, 1586, 1343, 1210, 746 cmꢁ1; H 223–225 ꢀC; IR (KBr): 3276, 3067, 1596, 1334, 1214, 786 cmꢁ1; 1H
NMR (400 MHz, CDCl3): d ¼ 1.93–1.99 (m, 2H, CH2), 3.39–3.43 NMR (500 MHz, CDCl3): d ¼ 1.96–2.01 (m, 2H, CH2), 3.34–3.38
(m, 4H, NCH2), 6.51 (br, 1H, NH), 6.83–7.32 (m, 9H, ArH), 11.92 (m, 2H, NCH2), 3.46–3.50 (m, 2H, NCH2), 6.35 (br, 1H, NH),
(br, 1H, NH); 13C NMR (100 MHz, CDCl3): d ¼ 20.0, 39.0, 39.0, 6.94–7.27 (m, 8H, ArH), 11.89 (br, 1H, NH); 13C NMR (125 MHz,
77.9, 114.1 (d, J ¼ 26.3 Hz), 124.2, 124.7, 128.6 (d, J ¼ 8.0 Hz), CDCl3): d ¼ 20.3, 38.8, 39.6, 122.7, 125.2, 126.7, 127.8, 128.7,
128.9, 139.4, 140.3, 160.4, 162.5 (d, J ¼ 245.0 Hz), 191.3; HRMS 135.8, 143.5, 145.3, 160.5, 193.4; HRMS (TOF ES+): m/z calcd for
(TOF ES+): m/z calcd for C18H17FN2NaOS [(M + Na+)], 351.0938;
C
18H17Cl2N2OS [(M + H+)], 379.0433; found, 379.0437.
found, 351.0637.
2-((4-Fluorophenyl)selanyl)-1-phenyl-2-(tetrahydropyrimidin-
1-(4-Chlorophenyl)-2-(phenylthio)-2-(tetrahydropyrimidin- 2(1H)-ylidene)ethanone (4k). White solid, yield 92%; mp 181–
2(1H)-ylidene)ethanone (4e). White solid, yield 90%; mp 180– 183 ꢀC; IR (KBr): 3283, 1590, 1342, 1210, 780 cmꢁ1; 1H NMR (500
1
181 ꢀC; IR (KBr): 3330, 3052, 1584, 1339, 1164, 746 cmꢁ1; H MHz, CDCl3): d ¼ 1.95–1.98 (m, 2H, CH2), 3.32–3.36 (m, 2H,
NMR (500 MHz, CDCl3): d ¼ 1.95–1.98 (m, 2H, CH2), 3.39–3.44 NCH2), 3.67–3.72 (m, 2H, NCH2), 6.43 (br, 1H, NH), 6.73–7.29
(m, 4H, NCH2), 6.52 (br, 1H, NH), 7.07–7.48 (m, 9H, ArH), 11.85 (m, 9H, ArH), 11.93 (br, 1H, NH); 13C NMR (125 MHz, CDCl3): d
(br, 1H, NH); 13C NMR (125 MHz, CDCl3): d ¼ 20.4, 39.1, 39.1, ¼ 20.4, 38.8, 39.5, 111.5 (d, J ¼ 23.8 Hz), 112.0 (d, J ¼ 21.3 Hz),
78.5, 124.6, 125.2, 127.9, 128.5, 129.3, 134.2, 140.6, 142.2, 160.8, 120.3, 123.1, 126.8, 127.7, 128.6, 130.5, 143.9, 160.7, 163.6 (d, J ¼
191.6; HRMS (TOF ES+): m/z calcd for C18H17ClN2NaOS [(M + 246.3 Hz), 164.8, 193.2; HRMS (TOF ES+): m/z calcd for
Na+)], 367.0642; found, 367.0637.
C
18H18FN2OS [(M + H+)], 329.1118; found, 329.1118.
1-(2-Chlorophenyl)-2-(phenylthio)-2-(tetrahydropyrimidin-
1-Phenyl-2-(phenylselanyl)-2-(tetrahydropyrimidin-2(1H)-yli-
2(1H)-ylidene)ethanone (4f). White solid, yield 87%; mp 163– dene)ethanone (4l). White solid, yield 92%; mp 162–164 ꢀC; IR
165 ꢀC; IR (KBr): 3261, 1593, 1341, 1210, 747 cmꢁ1; 1H NMR (400 (KBr): 3353, 1587, 1343, 741 cmꢁ1; 1H NMR (500 MHz, CDCl3): d
MHz, CDCl3): d ¼ 1.95–1.99 (m, 2H, CH2), 3.38–3.44 (m, 4H, ¼ 1.94–1.98 (m, 2H, CH2), 3.32–3.37 (m, 2H, NCH2), 3.46–3.50
NCH2), 7.00–7.28 (m, 9H, ArH); 13C NMR (100 MHz, CDCl3): d ¼ (m, 2H, NCH2), 6.57 (br, 1H, NH), 7.15–7.31 (m, 10H, ArH), 12.12
19.9, 38.7, 38.7, 79.5, 124.5, 124.7, 125.9, 126.9, 128.4, 128.6, (br, 1H, NH); 13C NMR (125 MHz, CDCl3): d ¼ 20.0, 38.5, 39.2,
129.1, 130.1, 139.7, 142.4, 160.0, 189.9; HRMS (TOF ES+): m/z 77.8, 125.3, 126.3, 126.8, 127.1, 127.7, 129.0, 135.3, 144.6, 160.1,
calcd for C18H17ClN2NaOS [(M + Na+)], 367.0642; found, 192.6; HRMS (TOF ES+): m/z calcd for C18H19N2OSe [(M + H+)],
367.0635.
2-((4-Methoxyphenyl)selanyl)-1-phenyl-2-(tetrahydropyr-
359.0657; found, 359.0668.
1-(4-Methoxyphenyl)-2-(phenylselanyl)-2-(tetrahydropyr-
imidin-2(1H)-ylidene)ethanone (4g). White solid, yield 95%; mp imidin-2(1H)-ylidene)ethanone (4m). White solid, yield 95%;
174–176 ꢀC; IR (KBr): 3368, 3187, 1592, 1354, 1232, 743 cmꢁ1; 1H mp 154–156 ꢀC; IR (KBr): 3353, 1581, 1344, 1240, 799 cmꢁ1; 1H
NMR (400 MHz, CDCl3): d ¼ 1.93–1.96 (m, 2H, CH2), 3.35–3.45 NMR (500 MHz, CDCl3): d ¼ 1.90–1.95 (m, 2H, CH2), 3.33–3.45
(m, 4H, NCH2), 3.76 (s, 3H, OCH3), 6.56 (br, 1H, NH), 6.78–7.31 (m, 4H, NCH2), 3.73 (s, 3H, OCH3), 6.53 (br, 1H, NH), 6.69–7.29
(m, 9H, ArH), 11.93 (br, 1H, NH); 13C NMR (100 MHz, CDCl3): d (m, 9H, ArH); 13C NMR (125 MHz, CDCl3): d ¼ 20.5, 39.2, 39.8,
¼ 20.1, 38.9, 38.9, 55.5, 79.2, 114.7, 125.8, 126.6, 127.3, 128.1, 55.5, 112.8, 125.8, 127.3, 128.8, 129.5, 135.9, 137.6, 159.9, 160.8,
131.4, 143.6, 157.5, 160.5, 192.6; HRMS (TOF ES+): m/z calcd for 192.5; HRMS (TOF ES+): m/z calcd for C19H21N2O2Se [(M + H+)],
C
19H21N2O2S [(M + H+)], 341.1318; found, 341.1319.
389.0763; found, 389.0768.
1-Phenyl-2-(tetrahydropyrimidin-2(1H)-ylidene)-2-(p-tolylse-
2-(Phenylselanyl)-2-(tetrahydropyrimidin-2(1H)-ylidene)-1-
ꢀ
lanyl)ethanone (4h). White solid, yield 96%; mp 213–214 ꢀC; IR (p-tolyl)ethanone (4n). White solid, yield 94%; mp 157–159 C;
(KBr): 3369, 1593, 1342, 1208, 800 cmꢁ1 1H NMR (500 MHz, IR (KBr): 3363, 3325, 1582, 1341, 1207, 742 cmꢁ1; 1H NMR (500
;
CDCl3): d ¼ 1.94–1.97 (m, 2H, CH2), 2.29 (s, 3H, ArCH3), 3.31– MHz, CDCl3): d ¼ 1.94–1.97 (m, 2H, CH2), 2.31 (s, 3H, ArCH3),
3.34 (m, 2H, NCH2), 3.45–3.49 (m, 2H, NCH2), 6.51 (br, 1H, NH), 3.34–3.47 (m, 4H, NCH2), 6.56 (br, 1H, NH), 7.01–7.30 (m, 9H,
6.99–7.32 (m, 9H, ArH), 11.97 (br, 1H, NH); 13C NMR (125 MHz, ArH), 12.17 (br, 1H, NH); 13C NMR (125 MHz, CDCl3): d ¼ 20.5,
CDCl3): d ¼ 20.4, 21.3, 38.8, 39.5, 78.7, 124.7, 126.9, 127.6, 128.4, 21.8, 39.0, 39.7, 78.1, 125.8, 126.9, 127.3, 128.3, 129.5, 135.9,
130.0, 134.7, 137.4, 143.9, 160.8, 193.0; HRMS (TOF ES+): m/z 138.0, 142.2, 160.7, 193.2; HRMS (TOF ES+): m/z calcd for
calcd for C19H21N2OS [(M + H+)], 325.1369; found, 325.1364.
C
19H21N2OSe [(M + H+)], 373.0814; found, 373.0817.
2-((4-Chlorophenyl)selanyl)-1-phenyl-2-(tetrahydropyrimidin-
1-(4-Fluorophenyl)-2-(phenylselanyl)-2-(tetrahydropyrimidin-
2(1H)-ylidene)ethanone (4i). White solid, yield 93%; mp 210– 2(1H)-ylidene)ethanone (4o). White solid, yield 90%; mp 139–
211 ꢀC; IR (KBr): 3360, 1588, 1344, 1210, 809 cmꢁ1; 1H NMR (500 140 ꢀC; IR (KBr): 3322, 1582, 1346, 1210, 740 cmꢁ1; 1H NMR (500
MHz, CDCl3): d ¼ 1.93–1.96 (m, 2H, CH2), 3.33–3.36 (m, 2H, MHz, CDCl3): d ¼ 1.93–1.98 (m, 2H, CH2), 3.40–3.47 (m, 4H,
NCH2), 3.44–3.47 (m, 2H, NCH2), 6.43 (br, 1H, NH), 7.00–7.27 NCH2), 6.59 (br, 1H, NH), 6.85–7.30 (m, 9H, ArH), 12.07 (br, 1H,
(m, 9H, ArH), 11.89 (br, 1H, NH). 13C NMR (125 MHz, CDCl3): d NH); 13C NMR (125 MHz, CDCl3): d ¼ 20.4, 39.6, 40.9, 78.5, 114.4
¼ 20.4, 38.8, 39.5, 78.1, 125.9, 126.7, 127.7, 128.6, 129.3, 130.7, (d, J ¼ 21.3 Hz), 125.9, 127.2, 128.9, 129.6, 135.6, 141.1, 160.7,
139.6, 143.7, 160.7, 193.1; HRMS (TOF ES+): m/z calcd for 163.8, 191.8; HRMS (TOF ES+): m/z calcd for C18H18FN2OSe [(M +
C
18H18ClN2OS [(M + H+)], 345.0823; found, 345.0829.
H+)], 377.0563; found, 377.0565.
26394 | RSC Adv., 2014, 4, 26389–26397
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1-(4-Chlorophenyl)-2-(phenylselanyl)-2-(tetrahydropyrimidin-
1-(4-Chlorophenyl)-2-(1,3-diazepan-2-ylidene)-2-(phenylthio)
2(1H)-ylidene)ethanone (4p). White solid, yield 86%; mp 176– ethanone (5d). White solid, yield 87%; mp 156–157 ꢀC; IR (KBr):
1
177 ꢀC; IR (KBr): 3319, 3057, 1581, 1345, 1205, 740 cmꢁ1; H 3325, 3053, 1594, 1349, 1202, 833, 744 cmꢁ1; 1H NMR (500 MHz,
NMR (500 MHz, CDCl3): d ¼ 1.91–1.94 (m, 2H, CH2), 3.36–3.41 CDCl3): d ¼ 1.68–1.81 (m, 4H, CH2CH2), 3.20–3.24 (m, 2H,
(m, 4H, NCH2), 6.58 (br, 1H, NH), 7.12–7.25 (m, 9H, ArH), 11.98 NCH2), 3.67–3.70 (m, 2H, NCH2), 6.56 (br, 1H, NH), 7.05–7.25
(br, 1H, NH); 13C NMR (125 MHz, CDCl3): d ¼ 20.4, 39.4, 39.4, (m, 9H, ArH), 12.06 (br, 1H, NH); 13C NMR (125 MHz, CDCl3): d
78.3, 126.0, 127.2, 127.8, 128.4, 129.6, 133.9, 135.5, 143.4, 160.6, ¼ 27.9, 28.2, 45.5, 46.3, 81.5, 124.7, 125.3, 127.8, 128.5, 129.4,
191.6; HRMS (TOF ES+): m/z calcd for C18H18ClN2OSe [(M + H+)], 134.4, 140.5, 142.2, 170.6, 192.7; HRMS (TOF ES+): m/z calcd for
393.0265; found, 393.0267.
C
19H20ClN2OS [(M + H+)], 359.0979; found, 359.0975.
1-(2-Chlorophenyl)-2-(imidazolidin-2-ylidene)-2-(phenyl-
2-(1,3-Diazepan-2-ylidene)-2-((4-methoxyphenyl)thio)-1-phe-
ꢀ
selanyl)ethanone (4q). White solid, yield 83%; mp 151–153 C; nylethanone (5e). White solid, yield 96%; mp 171–172 ꢀC; IR
IR (KBr): 3350, 1589, 1350, 1211, 747 cmꢁ1; 1H NMR (500 MHz, (KBr): 3316, 2930, 1600, 1342, 1238, 816 cmꢁ1 1H NMR (500
;
CDCl3): d ¼ 1.89–1.93 (m, 2H, CH2), 3.28–3.32 (m, 2H, NCH2), MHz, CDCl3): d ¼ 1.75–1.79 (m, 4H, CH2CH2), 3.19–3.23 (m, 2H,
3.41–3.45 (m, 2H, NCH2), 6.49 (br, 1H, NH), 6.99–7.24 (m, 9H, NCH2), 3.42–3.47 (m, 2H, NCH2), 3.76 (s, 3H, OCH3), 6.64 (br,
ArH), 11.78 (br, 1H, NH); 13C NMR (125 MHz, CDCl3): d ¼ 20.4, 1H, NH), 6.80 (d, J ¼ 8.5 Hz), 6.98 (d, J ¼ 8.5 Hz), 7.18–7.26 (m,
39.0, 39.6, 79.8, 125.9, 126.4, 127.7, 128.7, 129.4, 130.5, 134.9, 3H, ArH), 7.28–7.32 (m, 2H, ArH), 12.11 (br, 1H, NH); 13C NMR
144.0, 160.2, 190.1; HRMS (TOF ES+): m/z calcd for (125 MHz, CDCl3): d ¼ 28.0, 28.3, 45.5, 46.3, 55.8, 82.8, 115.1,
C
18H17ClN2NaOSe [(M + Na+)], 415.0087; found, 415.0083.
126.3, 126.9, 127.6, 128.6, 131.5, 144.0, 157.9, 170.8, 194.1;
2-(Nitro(phenylthio)methylene)hexahydropyrimidine (4r). HRMS (TOF ES+): m/z calcd for C20H23N2O2S [(M + H+)],
White solid, yield 90%; mp 152.5–153 ꢀC; IR (KBr): 3284, 1585, 355.1475; found, 355.147.
1356, 1200, 1127, 738 cmꢁ1
;
1H NMR (500 MHz, CDCl3): d ¼
2-(1,3-Diazepan-2-ylidene)-1-phenyl-2-(p-tolylthio)ethanone
1.93–1.98 (m, 2H, CH2), 3.42–3.47 (m, 4H, NCH2), 7.11–7.15 (m, (5f). White solid, yield 95%; mp 175–177 ꢀC; IR (KBr): 3334,
3H, ArH), 7.22–7.26 (m, 2H, ArH); 13C NMR (125 MHz, CDCl3): d 3046, 1600, 1345, 1200, 800 cmꢁ1; 1H NMR (500 MHz, CDCl3): d
¼ 19.0, 39.0, 39.0, 100.8, 125.5, 125.9, 129.1, 135.7, 155.7; HRMS ¼ 1.75–1.81 (m, 4H, CH2CH2), 2.30 (s, 3H, ArCH3), 3.19–3.23 (m,
(TOF ES+): m/z calcd for C11H13N3NaO2S [(M + Na+)], 274.0621; 2H, NCH2), 3.42–3.48 (m, 2H, NCH2), 6.58 (br, 1H, NH), 6.98 (d, J
found, 274.0619.
¼ 8.2 Hz, 2H, ArH), 7.06 (d, J ¼ 8.2 Hz, 2H, ArH), 7.17–7.32 (m,
2-(1,3-Diazepan-2-ylidene)-1-phenyl-2-(phenylthio)ethanone 5H, ArH), 12.14 (br, 1H, NH); 13C NMR (125 MHz, CDCl3): d ¼
(5a). White solid, yield 92%; mp 177–178 ꢀC; IR (KBr): 3363, 21.3, 28.0, 28.3, 45.5, 46.3, 81.9, 124.8, 126.9, 127.6, 128.6, 130.1,
1594, 1343, 1202, 742 cmꢁ1
;
1H NMR (500 MHz, CDCl3): d ¼ 134.8, 137.2, 143.9, 170.7, 194.1; HRMS (TOF ES+): m/z calcd for
1.75–1.81 (m, 4H, CH2CH2), 3.20–3.23 (m, 2H, NCH2), 3.45–3.48
(m, 2H, NCH2), 6.55 (br, 1H, NH), 7.08–7.31 (m, 10H, ArH),
C
20H23N2OS [(M + H+)], 339.1526; found, 339.1527.
2-((4-Chlorophenyl)thio)-2-(1,3-diazepan-2-ylidene)-1-phe-
12.14 (br, 1H, NH); 13C NMR (125 MHz, CDCl3): d ¼ 28.0, 28.3, nylethanone (5g). White solid, yield 91%; mp 200–202 ꢀC; IR
45.5, 46.3, 81.6, 124.8, 125.1, 126.9, 127.6, 128.7, 129.3, 140.9, (KBr): 3318, 1603, 1346, 1199, 803 cmꢁ1 1H NMR (500 MHz,
;
143.9, 170.7, 194.2; HRMS (TOF ES+): m/z calcd for C19H21N2OS CDCl3): d ¼ 1.74–182 (m, 4H, CH2CH2), 3.21–3.23 (m, 2H,
[(M + H+)], 325.1369; found, 325.1368.
NCH2), 3.45–3.48 (m, 2H, NCH2), 6.48 (br, 1H, NH), 7.00 (d, J ¼
2-(1,3-Diazepan-2-ylidene)-2-(phenylselanyl)-1-(p-tolyl)-etha- 8.6 Hz, 2H, ArH), 7.17–7.28 (m, 7H, ArH), 12.1 (br, 1H, NH); 13
C
none (5b). White solid, yield 93%; mp 157–158 ꢀC; IR (KBr): NMR (125 MHz, CDCl3): d ¼ 27.9, 28.2, 45.5, 46.3, 81.2, 126.0,
3317, 2932, 1605, 1349, 1200, 741 cmꢁ1 1H NMR (500 MHz, 126.7, 127.7, 128.8, 129.4, 130.8, 139.5, 143.7, 170.5, 194.2;
;
CDCl3): d ¼ 1.73–1.80 (m, 4H, CH2CH2), 2.29 (s, 3H, ArCH3), HRMS (TOF ES+): m/z calcd for C19H20 ClN2OS [(M + H+)],
3.18–3.20 (m, 2H, NCH2), 3.43–3.47 (m, 2H, NCH2), 6.54 (br, 1H, 359.0979; found, 359.0982.
NH), 7.01 (d, J ¼ 7.7 Hz, 2H), 7.00–7.13 (m, 3H, ArH), 7.24–7.27
2-(1,3-Diazepan-2-ylidene)-2-((3,5-dichlorophenyl)thio)-1-
(m, 3H, ArH), 12.20 (br, 1H, NH); 13C NMR (125 MHz, CDCl3): d phenylethanone (5h). White solid, yield 83%; mp 139–141 ꢀC; IR
¼ 21.8, 28.1, 28.3, 45.5, 46.3, 81.4, 124.8, 125.1, 127.1, 128.3, (KBr): 3308, 1561, 1348, 1206, 791 cmꢁ1
;
1H NMR (500 MHz,
128.3, 129.3, 138.6, 141.0, 170.8, 194.2; HRMS (TOF ES+): m/z CDCl3); d ¼ 1.79–1.84 (m, 4H, CH2CH2), 3.24–3.28 (m, 2H,
calcd for C20H23N2OS [(M + H+)], 339.1526; found, 339.1518.
NCH2), 3.47–3.50 (m, 2H, NCH2), 6.38 (br, 1H, NH), 6.91 (s, 2H,
2-(1,3-Diazepan-2-ylidene)-1-(4-uorophenyl)-2-(phenylthio) ArH), 7.04 (s, 1H, ArH), 7.20–7.27 (m, 5H, ArH), 12.07 (br, 1H,
ethanone (5c). White solid, yield 90%; mp 124–125 ꢀC; IR (KBr): NH); 13C NMR (125 MHz, CDCl3): d ¼ 27.8, 28.1, 45.4, 46.3, 80.0,
3331, 3060, 1591, 1348, 1207, 847, 740 cmꢁ1; 1H NMR (500 MHz, 122.7, 125.3, 126.6, 127.8, 128.9, 135.8, 143.5, 145.1, 170.1,
CDCl3); d ¼ 1.76–1.84 (m, 4H, CH2CH2), 3.22–3.26 (m, 2H, 194.3; HRMS (TOF ES+): m/z calcd for C19H19Cl2N2OS [(M + H+)],
NCH2), 3.46–3.50 (m, 2H, NCH2), 6.59 (br, 1H, NH), 6.85–6.91 393.0590; found, 393.0596.
(m, 2H, ArH), 7.09–7.14 (m, 3H, ArH), 7.25–7.29 (m, ArH, 2H),
2-(1,3-Diazepan-2-ylidene)-2-((4-uorophenyl)thio)-1-phenyl-
7.33–7.36 (m, ArH, 2H), 12.12 (br, 1H, NH); 13C NMR (125 MHz, ethanone (5i). White solid, yield 88%, mp 188–189 ꢀC; IR (KBr):
CDCl3): d ¼ 28.0, 28.2, 45.5, 46.3, 81.5, 114.4 (d, J ¼ 21.3 Hz), 3255, 1556, 1354, 1210, 776 cmꢁ1; 1H NMR (500 MHz, CDCl3): d
124.7, 125.2, 129.2, 129.4, 139.9, 140.6, 163.0 (d, J ¼ 245.0 Hz), ¼ 1.75–1.83 (m, 4H, CH2CH2), 3.19–3.23 (m, 2H, NCH2), 3.42–
170.7, 192.80; HRMS (TOF ES+): m/z calcd for C19H19FN2NaOS 3.47 (m, 2H, NCH2), 6.48 (br, 1H, NH), 6.74–6.86 (m, 3H, ArH),
[(M + Na+)], 365.1094; found, 365.1087.
7.15–7.83 (m, 6H, ArH), 12.09 (br, 1H, NH); 13C NMR (125 MHz,
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CDCl3): d ¼ 27.9, 28.2, 45.5, 46.3, 111.5 (d, J ¼ 23.8 Hz), 112.0 (d,
J ¼ 21.3 Hz), 120.4, 126.8, 127.3, 127.7, 128.7, 128.8, 130.6,
143.7, 163.8 (d, J ¼ 246.3 Hz), 170.4, 194.2; HRMS (TOF ES+): m/z
calcd for C19H20FN2OS [(M + H+)], 343.1275; found, 343.1271.
2-(1,3-Diazepan-2-ylidene)1-phenyl-2-(phenylselanyl)etha-
none (5j). White solid, yield 90%; mp 154–156 ꢀC; IR (KBr):
3347, 1593, 1342, 1202, 737 cmꢁ1; 1H NMR (500 MHz, CDCl3): d
¼ 1.72–1.77 (m, 4H, CH2CH2), 3.15–3.19 (m, 2H, CH2), 3.42–3.46
(m, 2H, CH2), 6.53 (br, 1H, NH), 7.12–7.28 (m, 10H, ArH), 12.17
(br, 1H, NH); 13C NMR (125 MHz, CDCl3): d ¼ 28.2, 28.2, 45.7,
46.4, 81.6, 125.9, 126.8, 127.5, 127.6, 128.5, 129.5, 135.7, 145.0,
170.7, 194.4; HRMS (TOF ES+): m/z calcd for C19H21N2OSe [(M +
H+)], 373.0814; found, 373.0816.
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none (5k). White solid, yield 93%, mp 125–127 ꢀC; IR (KBr):
3308, 1603, 1346, 1204, 818, 736 cmꢁ1 1H NMR (500 MHz,
;
CDCl3): d ¼ 1.72–1.77 (m, 4H, CH2CH2), 3.15–3.18 (m, 2H,
NCH2), 3.41–3.45 (m, 2H, NCH2), 6.50 (br, 1H, NH), 7.00 (d, J ¼
7.4 Hz, 2H, ArH), 7.13–7.26 (m, 7H, ArH), 12.19 (br, 1H, NH); 13
C
NMR (125 MHz, CDCl3): d ¼ 21.8, 28.1, 28.2, 45.7, 46.5, 81.5,
125.9, 127.0, 127.4, 128.3, 129.5, 135.8, 138.5, 142.1, 170.8,
194.5; HRMS (TOF ES+): m/z calcd for C20H23N2OSe [(M + H+)],
387.0970; found, 387.0970.
´
55, 11031–11041; (c) R. Puig-de-la-Bellacasa, L. Gimenez,
´
S. Pettersson, R. Pascual, E. Gonzalo, J. A. Este, B. Clotet,
´
2-(1,3-Diazepan-2-ylidene)-1-(4-uorophenyl)-2-(phenyl-
selanyl)ethanone (5l). White solid, yield 86%; mp 137–138 C;
J. I. Borrell, J. Teixido, Eur. J. Med. Chem., 2012, 54, 159–
ꢀ
174; (d) G. La Regina, R. Bai, W. Rensen, A. Coluccia,
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IR (KBr): 3319, 3053, 1598, 1349, 1207, 841, 737 cmꢁ1; 1H NMR
(500 MHz, CDCl3): d ¼ 1.73–1.80 (m, 4H, CH2CH2), 2.17 (s, 3H,
ArH), 3.18–3.22 (m, 2H, NCH2), 3.43–3.48 (m, 2H, NCH2), 6.54
(br, 1H, NH), 6.86 (t, J ¼ 8.5 Hz, 2H, ArH), 7.17–7.30 (m, 7H,
ArH), 12.14 (br, 1H, NH); 13C NMR (125 MHz, CDCl3): d ¼ 28.0,
28.2, 45.6, 46.5, 81.5, 114.4 (d, J ¼ 21.3 Hz), 126.0, 127.4, 129.0,
129.6, 135.5, 141.0, 163.0 (d, J ¼ 245.0 Hz), 170.7, 193.1; HRMS
(TOF ES+): m/z calcd for C19H20FN2Ose [(M + H+)], 391.0719;
found, 391.0718.
1-(4-Chlorophenyl)-2-(1,3-diazepan-2-ylidene)-2-(phenyl-
selanyl)ethanone (5m). White solid, yield 85%; mp 141–143 ꢀC;
IR (KBr): 3315, 3064, 1590, 1346, 1203, 739 cmꢁ1; 1H NMR (500
MHz, CDCl3): d ¼ 1.77–1.83 (m, 4H, CH2CH2), 3.22–3.25 (m, 2H,
NCH2), 3.46–3.50 (m, 2H, NCH2), 6.58 (br, 1H, NH), 7.14–7.33
(m, 9H, ArH), 12.15 (br, 1H, NH); 13C NMR (125 MHz, CDCl3): d
¼ 28.0, 28.0, 45.6, 46.4, 81.5, 126.1, 127.4, 127.8, 128.4, 129.6,
134.3, 135.4, 143.4, 170.6, 192.9; HRMS (TOF ES+): m/z calcd for
C
19H20ClN2OSe [(M + H+)], 407.0424; found, 407.0416.
5 R. W. Baker, H. Radzey, N. T. Lucas and P. Turner,
Organometallics, 2012, 31, 5622–5633.
Acknowledgements
¨
This work was supported by the Program for Changjiang
Scholars and Innovative Research Team in University
(IRT13095), the National Natural Science Foundation of China
(Nos. U1202221, 21262042, 21362042, 21162037, and 81160384)
and the Reserve Talent Foundation of Yunnan Province (no.
2012HB001).
6 M. J. E. Resendiz, A. Schon, E. Freire and M. M. Greenberg, J.
Am. Chem. Soc., 2012, 134, 12478–12481.
7 S. A. Herbert and G. E. Arnott, Org. Lett., 2010, 12, 4600–4603.
8 Selected examples for the transition-metal-catalyzed direct
coupling reaction of aromatic carbon with chalcogen, see
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2012, 134, 18237–18240; (b) M. Xu, X.-H. Zhang and
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