Access to Amidines and Arylbenzimidazoles: Zinc-Promoted Rearrangement of Oxime Acetates

Article abstract of DOI:10.1002/adsc.201701490

An efficient and straightforward zinc-promoted rearrangement of oxime acetates with arylamines for the synthesis of amidines has been developed under mild conditions. This process involves N?O/C?C bond cleavages and C?C/C?N bond formations. Various oxime

Full text of DOI:10.1002/adsc.201701490

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DOI: 10.1002/adsc.201701490
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Access to Amidines and Arylbenzimidazoles: Zinc-Promoted
Rearrangement of Oxime Acetates
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Zhongzhi Zhu,a Jinghe Cen,a Xiaodong Tang,a Jianxiao Li,a Wanqing Wu,a and
Huanfeng Jianga,*
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a
Key Laboratory of Functional Molecular Engineering of Guangdong Province, School of Chemistry and Chemical
Engineering, South China University of Technology, Guangzhou 510640, People’s Republic of China
Fax: (+86) 20-87112906
E-mail: jianghf@scut.edu.cn
Received: November 22, 2017; Revised: March 9, 2018; Published online: &&&, &&&&
Supporting information for this article is available on the WWW under https://doi.org/10.1002/adsc.201701490
Abstract: An efficient and straightforward zinc-promoted rearrangement of oxime acetates with arylamines
for the synthesis of amidines has been developed under mild conditions. This process involves NÀO/CÀC
bond cleavages and CÀC/CÀN bond formations. Various oxime acetates and arylamines are suitable for this
transformation. Furthermore, diverse arylbenzimidazoles could also be prepared through simple one-pot
procedure.
Keywords: zinc-promoted; oxime acetates; amidines; one-pot; arylbenzimidazoles
29 1 Introduction
believed that high-valent metal intermediate or/and
iminyl radicals intermediate would be involved. The
30
31 Amidines are important compounds in biologically strategy through an oxidative NÀO cleavage of oxime
32 active molecules,[1] materials science,[2] and the design esters to formed high-valent metal intermediate have
33 of catalysts.[3] They are also found wide applications as become important solution in organic chemistry.[10]
34 superbases,[4] and used in the fixation of CO2.[5] More- Moreover, in many cases, the conversion of oxime
35 over, they were used as key precursors in the synthesis esters is more likely to undergo an iminyl radical
36 of various heterocycles such as pyrimidines, quinazo- intermediate which may be further converted to
37 lines, imidazoles, benzimidazoles and dihydrooxa- carbon radical species or metal-enamide intermedi-
38 zoles.[6] Classic synthetic strategies for these skeletons ate.[11–14] This radical strategy has represented as a
39 are nucleophilic addition of amines to nitriles, iso- tremendously powerful approach for the carbon-
40 cyanides, secondary amides or thioamides.[7] Several carbon and carbon-heteroatom bonds formation in the
41 other practical methods have also been developed for synthetic chemistry of heterocycles.
42 the synthesis of their derivatives over the past few
We have developed several annulations of oxime
43 decades.[8] For example, Ashfeld etc. reported an acetates with other synthons such as pyridines,
44 effective method for the synthesis of N-toluenesulfon- ketones, or potassium thiocyanate for the synthesis of
45 yl amidines via nitrilium ions intermediate.[8f] Zhang imidazo[1,2-a]yridines, thiazoles, 2-trifluoromethyl di-
46 and co-workers achieved the preparation of common hydropyrrol-2-ols via possible imino copper(III) inter-
47 amidines by carbodiimides intermediates.[8a] Despite mediate (Scheme 1a).[10a,c,e] Moreover, oxime acetates
48 these successful examples reported in this field, the could aslo serve as radical precursors through a-
49 development of alternative efficient and versatile carbon radical species to realize selective radical/
50 methods from easily available raw materials to con- radical cross-coupling with sulfonyl radicals and
51 struct this moiety under mild condition is still very benzoyl radicals for the preparation of sulfonylen-
52 meaningful.
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amine and enaminone derivatives, respectively (Sche-
Oxime esters as important parts of oxime deriva- me 1b).[12a,f] In addition, the possible copper-enamine
54 tives are fascinating synthetic building blocks which intermediate derived from iminyl radicals of oxime
55 are widely employed in transition-metal-catalyzed acetates have been shown to be highly active to
56 reactions, including Pd, Rh, Ir, and Cu catalysis.[9] undergo single-electron reduction of the NÀO bond.
57 Based on previous reports with oxime esters, it is With this strategy, many N-heterocycles such as
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Table 1. Optimization of the reaction conditions.[a]
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pyridines, pyrroles, pyrazoles, isoquinolines were de-
livered smoothly from oxime acetates with simple raw
materials such as alkynes, aldehydes, and ketones
(Scheme 1c).[15] Based on these inspiring works, we are
intrigued to develop more reaction styles for oxime
acetates, especially those catalyzed and promoted by
Lewis acids. Herein, we present a zinc-promoted
rearrangement of oxime acetates with arylamines for
the synthesis of general amidines. This protocol shows
Entry
Additive
Solvent
T (oC)
Yield (%)[b]
1
2
3
4
5
6
7
8
Zn(OTf)2
ZnCl2
ZnBr2
Zn(OAc)2
Ce(OTf)3
Bi(OTf)3
AlCl3
triflic acid
Et3N
Zn(OTf)2
Zn(OTf)2
Zn(OTf)2
Zn(OTf)2
Zn(OTf)2
Zn(OTf)2
Zn(OTf)2
Zn(OTf)2
Zn(OTf)2
–
CH3CN
CH3CN
CH3CN
CH3CN
CH3CN
CH3CN
CH3CN
CH3CN
CH3CN
DMSO
DMF
70
70
70
70
70
70
70
70
70
70
70
70
70
80
90
80
80
80
80
72
42
36
21
10 further application potential by the facile synthesis of
11 polysubstituted arylbenzimidazoles in one pot man-
12 ner.
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14
15
16
17
18
19
20
21
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23
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trace
trace
trace
n.d.
trace
n.d.
n.d.
trace
trace
78
72
90 (86)
88
62
n.d.
9
10
11
12
13
14
15
16[c]
17 [d]
18 [e]
19
toluene
DCE
CH3CN
CH3CN
CH3CN
CH3CN
CH3CN
CH3CN
[a] Reaction conditions: unless otherwise noted all reactions
were performed with 1a (0.1 mmol), 2a (0.11 mmol),
additive (0.1 mmol) in solvent (2 mL) for 8 h. n.d.=not
detected.
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Scheme 1. The NÀO bond cleavage of oxime acetates.
[b] Yields analyzed by GC/MS are based on 1a.
[c] Additive (0.15 mmol).
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[d] Additive (0.20 mmol).
2 Results and Discussion
[e] Additive (0.50 mmol).
33 We initiated our investigation by using acetophenone
34 oxime acetate (1a) and aniline (2a) as model sub-
35 strates to screen the reaction conditions and the
36 results are summarized in Table 1. The desired prod- stituted patterns on the benzene ring proceeded
37 uct 3aa could be obtained in 72% GC yield when 1 smoothly and the target products 3 could be obtained
38 equivalent of Zn(OTf)2 was used in CH3CN at 708C in moderate to good yields. Both electron-withdrawing
39 for 8 h (entry 1). While other zinc salts such as ZnCl2, and electron-donating groups were well compatible.
40 ZnBr2, Zn(OAc)2 exbitited less efficient results than Electron-donating functional group- (Me, Et, Bu, Ph,
41 Zn(OTf)2 (entries 2–4). Other additive such as OMe) substituted substrates underwent the reaction
42 Ce(OTf)3, Bi(OTf)3, AlCl3, triflic acid or base such as smoothly and afforded the desired arylamidine prod-
43 Et3N were explored, but none of them enable this ucts in good yields (3ab–3ae, 3aj, 3am). The trans-
44 reaction took place (entries 5–9). Further investiga- formation was also compatible with halide groups,
45 tions of solvent revealed that only acetonitrile is such as fluoride, chloride, bromide, and iodide (3af–
46 suitable for this transformation (entries 10–13). Sub- 3ai, 3ak, 3al), which provided new opportunities for
47 sequently, careful examination of temperature showed the functionalized products via cross-couplings. More-
48 that 808C proved to be the optimal, affording 3aa in over, oxime acetates derived from other aromatic
49 78% GC yield (entries 14–15). Additionally, increasing ketones could be accessed to the corresponding
50 the amount of Zn(OTf)2 to 1.5 equivalents, the products in modest to good yields (3an–3aq). In
51 product 3aa was detected with 90% GC yield (entries addition, heterocyclic and fused ring system oxime
52 16–18). Control experiment showed that the target acetates could be accessed through this route to
53 product could not be detected in the absence of zinc generate the corresponding products in moderate
54 salt (entry 19).
yields (3ar–3at). When 1-acetylnaphthalene oxime
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Based on the optimization study, the substrate was used as the substrate, 3au could be isolated in
56 scope of oxime acetates was investigated (Table 2). 65% yield. To our delight, the aliphatic oxime acetates
57 Generally, acetophenone oximes with different sub-
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also could be transformed into the desired products in
moderate yields (3av, 3aw).
Table 3. Substrate scope of various substituted arylamines.
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Table 2. Substrate scope of oxime acetates.[a]
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[a] Reactions were performed with 1 (0.3 mmol), 2a
(0.33 mmol), Zn(OTf)2 (0.45 mmol) in 2 mL CH3CN at
808C for 8 h. Isolated yields were given.
[a] Reactions were performed with 1a (0.3 mmol), 2
(0.33 mmol), Zn(OTf)2 (0.45 mmol) in 2 mL CH3CN at
808C for 8 h. Isolated yield was given.
These results drived us to further investigate the
32 scope of the arylamines and we found that this
33 reaction proceeded smoothly, which gave the desired
34 products 3 in moderate to good yields. As shown in
35 Table 3, the arylamines with different functional
36 groups, including methyl, n-butyl, tert-butyl, methoxy,
37 fluoro, chloro, bromo, iodo, and trifluoromethyl
38 reacted well under the optimal reaction conditions,
39 and good yields of the desired products were obtained
40 (3ax–3bk). Notably, those with two or three substitu-
41 ents in the aromatic rings also gave good yields of
42 products (3bl–3bn). The naphthylamine was also
Scheme 2. Large-scale synthesis of 3.
43 compatible with this transformation, affording the synthetic strategies of N-arylbenzimidazoles is the
44 desired product 3bo in 75% yield. Moreover, the intramolecular oxidative CÀH amination of N, N’-
45 secondary arylamines could be converted into the diarylamidines.[17] Therefore, one-pot synthesis of N-
46 desired products in good yields (3bp–3bs). In addi- arylbenzimidazoles derived from primary arylamines
47 tion, the substrate bearing an alkenyl group was and oxime acetates were next investigated. When 2.0
48 tolerated and 3bt was obtained in 78% yield.
equivalents of PhI(OAc)2 was directly added to the
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To demonstrate the synthetic practicality of this reaction system, the oxidative cyclization products
50 transformation, a gram-scale reaction of 1a was were obtained smoothly (Table 4). Firstly, different
51 carried out on a 10 mmol scale under the standard aryl oxime esters and anilines proved to be suitable
52 reaction conditions, and the desired product 3aa was substrates for the formation of the corresponding N-
53 obtained in 72% isolated yield (Scheme 2).
arylbenzimidazoles (4aa–4ae, 5aa–5ae) in good
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N-arylbenzimidazoles are important heterocycles, yields. According to the related literature, oxidative
55 which are known to exhibit various biological proper- cyclization reaction occurred preferentially on the
56 ties, and they have also been used as the backbone in electron-rich benzene ring over the electron-deficient
57 dyes, polymers, and ligands.[16] One of the common counterparts through an electrophilic pathway (5af,
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4ag, 4ah). Series of oxime esters with different func- indicated that amide 6 should not be the intermediates
tional groups were used to react with 3-(trifluorometh- for this transformation [eq. 2].
yl)-aniline, and the desired chemoselective products
(4ai–4aq) were obtained in moderate to high yields.
However, when 4-chloro and 4-bromo-substituted ani-
lines reacted with acetophenone oxime acetate (1a),
two regioisomers (4ar and 5ar, 4as and 5as) were
formed in a certain ratio with moderate yields. Similar
results were obtained when naphthylamine was used
10 as a substrate, and the oxidative cyclization reaction
11 took place preferentially on the benzene ring of oxime
12 acetate (4at and 5at).
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Scheme 3. Control experiments.
Table 4. One-pot synthesis of N-Arylbenzimidazoles.
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Based on previous reports[8f–i] and control experi-
ments, a tentative mechanism for the zinc-promoted
Beckmann-type rearrangement of oxime acetates with
arylamines was proposed (Scheme 4). First, with the
assistance of Zn(OTf)2, the aryl group migrates to the
nitrogen atom in a concerted pathway and the acetyl
group is expulsed. Subsequent the electrophilic carbon
atom in the nitrilium ion B is attacked by the aniline
to give the product 3.
Scheme 4. Possible mechanism.
3 Conclusion
In conclusion, we have successfully accomplished a
practical and general protocol for direct assembly of
amidines derivatives via zinc-promoted Beckmann-
type rearrangement of oxime acetates with arylamines.
This method starts from readily available materials
and affords amidines with a broad substrate scop
under mild reaction conditions. In addition, a series of
benzimidazoles were readily synthesized from primary
arylamines and oxime acetates through a simple one-
pot procedure.
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[a] Reactions were performed with 1 (0.3 mmol), 2
(0.33 mmol), Zn(OTf)2 (0.45 mmol) in 2 mL CH3CN at
808C for 8 h. Isolated yield was given.
50
To gain more insight into the reaction mechanism,
Experimental Section
51 two control experiments were performed (Scheme 3).
52 Firstly, when the reaction of oxime acetate 1b without General Methods
53 aniline was performed under the optimal conditions,
All purchased reagents and solvents were used without
54 amide 6 could be obtained in 31% yield [eq. 1].
55 Moreover, when treating aniline 2a, HOAc and 6
56 under the standard conditions in the absence of 1b,
57 the condensation product 3ab was not detected, which
further purification unless otherwise noted. Analytical thin
layer chromatography was performed by using commercially
prepared 100–400 mesh silica gel plates (GF254) and visual-
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ization was effected at 254 nm. The petroleum ether used for
1523, 1325, 1219, 902, 753; H NMR (400 MHz, CDCl3) d
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2
3
4
5
6
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chromatography is a 60–908C boiling ranges. All the oxime
7.41 (t, J=7.2 Hz, 2H), 7.26 (s, 6H), 7.17–7.14 (m, 1H), 6.55
(s, 1H), 2.79–7.74 (m, 2H), 2.01 (s, 3H), 1.42–1.35 (m, 3H).
13C NMR (100 MHz, CDCl3) d 154.0, 146.4, 142.5, 138.9,
129.1, 128.4, 122.8, 121.7, 121.6, 28.5, 18.6, 16.0; HRMS (ESI)
m/z: calcd for C16H19N2 [M+H]+ 239.1543; found 239.1547.
1
acetates were prepared according to known procedures. H
and 13C NMR spectra were recorded using a Bruker DRX-
400 spectrometer using CDCl3 and DMSO-d6 as solvent. The
chemical shifts are referenced to signals at 7.26 and
77.0 ppm, respectively. Mass spectra were recorded on a
Thermo Scientific ISQ gas chromatograph-mass spectrome-
ter. The data of HRMS was carried out on a high-resolution
mass spectrometer (LCMS-IT-TOF). IR spectra were ob-
tained either as potassium bromide pellets or as liquid films
between two potassium bromide pellets with a Bruker
TENSOR 27 spectrometer. Melting points were determined
N’-(4-Butylphenyl)-N-phenylacetimidamide (3ad): as a white
oil (64 mg, 73%); Rf =0.7 (petroleum ether: EtOAc=5:1)
IR (KBr): 3406, 3028, 2931, 2860, 1645, 1521, 1325, 1218, 753,
696 cmÀ1; H NMR (400 MHz, CDCl3) d 7.41–7.37 (m, 1H),
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7.31–7.18 (m, 2H), 7.15–7.11 (m, 1H), 2.74–2.67 (m, 2H), 2.00
(s, 3H), 1.76–1.69 (m, 2H), 1.55–1.45 (m, 2H), 1.08 (t, J=
7.3 Hz, 3H); 13C NMR (100 MHz, CDCl3) d 153.9, 146.2,
142.3, 137.5, 129.0, 129.0, 122.7, 121.6, 115.4, 35.2, 33.9, 22.5,
18.6, 14.2; HRMS (ESI) m/z: calcd for C18H23N2 [M+H]+
267.1856; found 267.1854.
¨
13 with a Buchi Melting Point B-545 instrument.
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General Procedure for the Synthesis of N,N’-
Diarylamidines 3
N’-(4-Methoxyphenyl)-N-phenylacetimidamide (3ae): as a
yellow oil (49.0 mg, 68%); Rf =0.35 (petroleum ether:
EtOAc=5:1); IR (KBr): 3401, 3048, 2941, 1643, 1508, 1229,
Oxime acetates
1 (0.3 mmol), anilines 2 (0.33 mmol),
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Zn(OTf)2 (163.5 mg, 0.45 mmol), and 2 mL of pre-dried
CH3CN were added to a 10 mL screw-capped tube. The
reaction mixture was stirred at 808C (oil bath) for 8 h. The
crude product was cooled to room temperature and concen-
trated in vacuum to give a residue, which was purified by
flash column chromatography to afford the N,N’-diarylami-
dines 3.
1032, 831, 699 cmÀ1; H NMR (400 MHz, CDCl3) d 7.22 (t,
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J=7.8 Hz, 2H), 7.08 (s, 4H), 6.96 (s, 1H), 6.78 (d, J=8.8 Hz,
2H), 3.69 (d, J=0.6 Hz, 3H), 1.82 (s, 3H); 13C NMR
(100 MHz, CDCl3) d 155.7, 154.3, 146.4, 137.7, 129.0, 123.2,
122.6, 121.6, 114.3, 55.5, 18.5; HRMS (ESI) m/z: calcd for
C15H17N2O [M+H]+ 241.1335; found 241.1338.
N’-(4-Fluorophenyl)-N-phenylacetimidamide (3af): as
a
white solid (44.5 mg, 65%); mp 112–1138C; Rf =0.5 (petro-
leum ether: EtOAc=5:1); IR (KBr): 3222, 3037, 2857, 1628,
1501, 1212, 834, 749 cmÀ1; 1H NMR (400 MHz, CDCl3) d
7.26–7.22 (m, 2H), 7.18–7.15 (m, 2H), 7.09–6.95 (m, 3H),
6.94–6.89 (m, 2H), 6.24 (s, 1H), 1.83 (s, 3H); 13C NMR
(100 MHz, CDCl3) d 158.9 (d, J=240.2 Hz), 154.0, 144.9,
141.9, 129.0, 123.0, 122.8 (d, J=7.2 Hz), 121.4, 115.62, 115.4,
18.5; HRMS (ESI) m/z: calcd for C14H14FN2 [M+H]+
229.1136; found 229.1140.
General Procedure for the Synthesis of N-
Arylbenzimidazole 4 or 5
Oxime acetates 1 (0.3 mmol), arylamines 2 (0.3 mmol),
Zn(OTf)2 (163.5 mg, 0.45 mmol), and 2 mL of dry CH3CN
were added to a 10 mL screw-capped tube. The reaction
mixture was stirred at 808C (oil bath) for 8 h. Then PhI
(OAc)2 (0.6 mmol, 2.0 equiv.) was added and the mixture was
stirred at the same temperature for 2 h, the reaction mixture
was concentrated in vacuo. The residue was purified by
column chromatography on silica gel to afford the corre-
sponding N-arylbenzimidazole products 4 or 5.
N’-(4-Chlorophenyl)-N-phenylacetimidamide (3ag): as
a
light yellow solid (45.4 mg, 62%); mp 86–878C; Rf =0.55
(petroleum ether: EtOAc=5:1); IR (KBr): 3419, 3043, 1649,
1500, 1325, 1222, 1089, 836, 747, 504 cmÀ1; 1H NMR
(400 MHz, CDCl3) d 7.36 (t, J=7.8 Hz, 3H), 7.32–7.27 (m,
3H), 7.14–7.09 (m, 3H), 6.34 (s, 1H), 1.94 (s, 3H); 13C NMR
(100 MHz, CDCl3) d 153.7, 145.2, 144.5, 129.0, 128.9, 127.6,
123.1, 122.6, 121.3, 18.5.; HRMS (ESI) m/z: calcd for
C14H14ClN2 [M+H]+ 245.0840; found 245.0843.
N,N’-Diphenylacetimidamide (3aa): as
a
white solid
(54.1 mg, 86%); mp 125–1268C; Rf =0.5 (petroleum ether:
EtOAc=5:1); IR (KBr): 3249, 3024, 1624, 1529, 1434, 1243,
749, 688 cmÀ1; 1H NMR (400 MHz, CDCl3) d 7.25 (t, J=
7.3 Hz, 4H), 7.14 (d, J=6.5 Hz, 3H), 6.99 (t, J=7.3 Hz, 2H),
6.11 (s, 1H), 1.88 (s, 3H); 13C NMR (100 MHz, CDCl3) d
153.4, 145.4, 129.0, 122.9, 121.3, 18.7; HRMS (ESI) m/z: calcd
for C14H15N2 [M+H]+ 211.1230; found 211.1234.
N’-(4-Bromophenyl)-N-phenylacetimidamide (3ah): as a yel-
low solid (46.0 mg, 53%); mp 98–998C; Rf =0.55 (petroleum
ether: EtOAc=5:1); IR (KBr): 3222, 2857, 1628, 1501, 1212,
834, 749 cmÀ1 1H NMR (400 MHz, CDCl3) d 7.35 (d, J=
8.5 Hz, 2H), 7.29–7.25 (m, 2H), 7.21–7.16 (m, 2H), 7.04–6.98
(m, 3H), 5.95 (s, 1H), 1.89 (s, 3H); 13C NMR (100 MHz,
CDCl3) d 153.4, 145.6, 143.9, 131.9, 129.0, 122.9, 121.2, 116.8,
115.2, 18.6; HRMS (ESI) m/z: calcd for C14H14BrN2 [M+H]+
289.0335; found 289.0338.
N-Phenyl-N’-(p-tolyl)cetimidamide (3ab): as a white solid
(55.8 mg, 83%); mp 115–1168C; Rf =0.5 (petroleum ether:
EtOAc=5:1); IR (KBr): 2924, 1651, 1595, 1534, 1267,
1
754 cmÀ1; H NMR (400 MHz, CDCl3) d 7.45 (t, J=7.4 Hz,
2H), 7.34 (s, 2H), 7.27 (s, 3H), 7.19 (s, 1H), 6.78 (s, 1H), 2.49
(s, 3H), 2.02 (s, 3H); 13C NMR (100 MHz, CDCl3) d 154.1,
146.4, 142.4, 132.3, 129.7, 129.1, 122.8, 121.7, 121.5, 21.1, 18.6;
HRMS (ESI) m/z: calcd for C15H17N2 [M+H]+ 225.1386;
found 225.1392.
N’-(4-Iodophenyl)-N-phenylacetimidamide (3ai): as a light
yellow solid (51.4 mg, 51%); mp 101–1028C; Rf =0.6 (petro-
leum ether: EtOAc=5:1); IR (KBr): 3417, 3318, 1651, 1591,
N’-(4-Ethylphenyl)-N-phenylacetimidamide (3ac): as a white
solid (55.7 mg, 78%); mp 105–1068C; Rf =0.6 (petroleum
ether: EtOAc=5:1); IR (KBr): 3409, 3308, 2963, 1646, 1598,
1533, 1325, 1217, 1017, 825, 756 cmÀ1; H NMR (400 MHz,
1
CDCl3) d 7.53 (d, J=8.4 Hz, 2H), 7.28–7.19 (m, 2H), 7.21–
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7.16 (m, 2H), 7.02 (d, J=7.3 Hz, 1H), 6.87 (d, J=6.5 Hz,
2H), 5.83 (s, 1H), 1.88 (s, 3H); 13C NMR (100 MHz, CDCl3) d
153.4, 146.2, 137.9, 129.0, 123.4, 123.2, 121.2, 117.4, 85.7, 18.7;
HRMS (ESI) m/z: calcd for C14H14IN2 [M+H]+ 337.0196;
found 337.0200.
6.09 (s, 1H), 2.30–2.20 (m, 2H), 1.64–1.48 (m, 2H), 0.87 (t, J=
7.4 Hz, 3H); 13C NMR (100 MHz, CDCl3) d 156.0, 129.0,
122.7, 121.1, 121.0, 33.7, 20.9, 13.9; HRMS (ESI) m/z: calcd
for C16H19N2 [M+H]+ 239.1543; found 239.1544.
1
2
3
4
5
6
7
8
9
N,N’-Diphenylcyclopropanecarboximidamide (3ap): as
a
N-Phenyl-N’-(o-tolyl)cetimidamide (3aj): as a white solid
(54.4 mg, 81%); mp 148–1498C; Rf =0.45 (petroleum ether:
EtOAc=5:1); IR (KBr): 3218, 3026, 1638, 1593, 1491, 1221,
white oil (50.9 mg, 72%); Rf =0.55 (petroleum ether:
EtOAc=5:1); IR (KBr): 3211, 3023, 2963, 1629, 1538, 1441,
1
1209, 694 cmÀ1; H NMR (400 MHz, CDCl3) d 7.26 (t, J=
1
754 cmÀ1; H NMR (400 MHz, CDCl3) d 7.32 (d, J=7.7 Hz,
7.8 Hz, 4H), 7.12–7.08 (m, 3H), 7.01 (t, J=7.3 Hz, 2H), 5.96
(s, 1H), 1.69–1.62 (m, 1H), 1.05–1.01 (m, 2H), 0.84–0.72 (m,
2H); 13C NMR (100 MHz, CDCl3) d 156.7, 129.2, 128.9,
123.3, 123.2, 122.3, 12.9, 8.2; HRMS (ESI) m/z: calcd for
C16H17N2 [M+H]+ 237.1386; found 237.1389.
2H), 7.28–7.24 (m, 2H), 7.16–7.10 (m, 2H), 7.02–6.93 (m,
7.4 Hz, 3H), 5.76 (s, 1H), 2.17 (s, 3H), 1.87 (s, 3H); 13C NMR
(100 MHz, CDCl3) d 153.3, 145.8, 143.1, 130.5, 130.1, 129.0,
126.6, 123.4, 123.0, 122.4, 121.2, 18.8, 18.1; HRMS (ESI) m/z:
calcd for C15H17N2 [M+H]+ 225.1386; found 225.1391.
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
N,N’-(Z)-Diphenylbenzimidamide (3aq): as a white solid
(43.1 mg, 53%); mp 151–1528C; Rf =0.55 (petroleum ether:
EtOAc=5:1); IR (KBr): 3342, 3047, 1654, 1526, 1438, 753,
N’-(2-Fluorophenyl)-N-phenylacetimidamide (3ak): as
a
white solid (46.5 mg, 68%); mp 103–1048C; Rf =0.6 (petro-
leum ether: EtOAc=5:1); IR (KBr): 3238, 3037, 1633, 1541,
1
689 cmÀ1; H NMR (400 MHz, CDCl3) d 7.95 (s, 2H), 7.89–
1
1240, 747, 693 cmÀ1; H NMR (400 MHz, DMSO) d 9.11 (s,
7.82 (m, 3H), 7.65 (d, J=7.7 Hz, 3H), 7.53 (d, J=7.3 Hz,
2H), 7.46 (t, J=7.4 Hz, 3H), 7.36 (t, J=7.9 Hz, 3H), 7.16 (d,
J=7.4 Hz, 2H); 13C NMR (100 MHz, CDCl3) d 165.8, 138.0,
135.0, 131.8, 129.1, 128.8, 127.1, 124.6, 120.3; MS (EI) m/z 77,
152, 167, 180, 243, 272.
1H), 7.81 (s, 2H), 7.27 (t, J=7.9 Hz, 2H), 7.14 (d, J=10.7 Hz,
1H), 7.07 (d, J=7.5 Hz, 1H), 7.00–6.92 (m, 2H), 6.89 (s, 1H),
1.92 (s, 3H); 13C NMR (100 MHz, DMSO) d 155.3, 154.0 (d,
J=239.2 Hz), 141.4, 138.2, 128.9, 124.9, 124.6, 123.2 (d, J=
7.0 Hz), 122.2, 119.7, 115.9 (d, J=20.3 Hz), 18.6; HRMS
(ESI) m/z: calcd for C14H14FN2 [M+H]+ 229.1136; found
229.1135.
N-Phenyl-N’-(thiophen-2-yl)ropionimidamide (3ar): as
a
browm solid (46.2 mg, 67%); mp 105–1068C; Rf =0.5 (petro-
leum ether: EtOAc=5:1); IR (KBr) 3397, 3057, 1633, 1438,
1264, 1164, 753, 692 cmÀ1; 1H NMR (400 MHz, CDCl3) d
7.32–7.13 (m, 4H), 7.04–6.98 (m, 1H), 6.79–6.77 (m, 2H), 6.41
(s, 1H), 1.96 (s, 3H); 13C NMR (100 MHz, CDCl3) d 154.3,
129.1, 129.0, 125.6, 123.6, 123.3, 121.8, 117.7, 113.9, 18.4;
HRMS (ESI) m/z: calcd for C12H13N2S [M+H]+ 217.0794;
found 217.0797.
N’-(2-Chlorophenyl)-N-phenylacetimidamide (3al): as
a
white solid (48.3 mg, 66%); mp 136–1378C; Rf =0.6 (petro-
leum ether: EtOAc=5:1); IR (KBr): 3512, 3213, 3019, 1630,
1
1543, 1439, 1221, 742 cmÀ1; H NMR (400 MHz, DMSO) d
9.08 (s, 1H), 7.80 (d, J=7.5 Hz, 2H), 7.40 (d, J=7.9 Hz, 1H),
7.34–7.15 (m, 3H), 6.94 (d, J=6.9 Hz, 2H), 6.86 (d, J=
7.7 Hz, 1H), 1.87 (s, 3H); 13C NMR (100 MHz, DMSO) d
154.5, 148.5, 141.3, 129.7, 128.8, 128.0, 125.7, 123.5, 123.3,
122.2, 119.8, 18.7; HRMS (ESI) m/z: calcd for C14H14ClN2
[M+H]+ 245.0840; found 245.0840.
N’-(1-Methyl-1H-pyrrol-2-yl)-N-phenylacetimidamide (3as):
as a browm oil (40.9 mg, 64%); Rf =0.6 (petroleum ether:
EtOAc=5:1); IR (KBr) 3376, 2932, 1643, 1594, 1492, 1323,
1
695 cmÀ1; H NMR (400 MHz, CDCl3) d 7.48 (s, 2H), 7.34 (t,
N-Phenyl-N’-(m-tolyl)cetimidamide (3am): as a white solid
(55.1 mg, 82%); mp 96–978C; Rf =0.4 (petroleum ether:
EtOAc=5:1); IR (KBr): 2922, 1647, 1591, 1265, 754,
J=7.8 Hz, 2H), 7.10 (d, J=6.7 Hz, 1H), 6.63–6.45 (m, 1H),
6.14 (t, J=3.3 Hz, 1H), 5.72 (s, 1H), 3.57 (s, 3H), 2.16 (s, 3H);
13C NMR (100 MHz, CDCl3) d 153.6, 129.3, 129.0, 122.7,
120.5, 117.9, 117.8, 115.2, 106.4, 32.6, 19.6; HRMS (ESI) m/z:
calcd for C13H16N3 [M+H]+ 214.1339; found 214.1340.
1
694 cmÀ1; H NMR (400 MHz, CDCl3) d 7.31–7.25 (m, 2H),
7.17 (t, J=7.6 Hz, 3H), 7.06–6.93 (m, 3H), 6.85 (d, J=7.6 Hz,
1H), 5.35 (s, 1H), 2.31 (s, 3H), 1.96 (s, 3H); 13C NMR
(100 MHz, CDCl3) d 153.3, 147.5, 138.8, 129.0, 128.8, 123.8,
122.8, 122.1, 121.3, 118.4, 21.5, 18.8; HRMS (ESI) m/z: calcd
for C15H17N2 [M+H]+ 225.1386; found 225.1389.
N-(benzo[b]hiophen-2-yl)-N-phenylacetimidamide (3at): as
a browm solid (35.7 mg, 45%); mp 110–1118C; Rf =0.5
(petroleum ether: EtOAc=5:1); IR (KBr) 3397, 3055, 2924,
1
1635, 1590, 1528, 1324, 1153, 750 cmÀ1; H NMR (400 MHz,
N,N’-Diphenylpropionimidamide (3an): as a white solid
(55.1 mg, 82%); mp 101–1028C; Rf =0.6 (petroleum ether:
EtOAc=5:1); IR (KBr): 3266, 2992, 1620, 1524, 1214, 1067,
CDCl3) d 7.66 (d, J=7.9 Hz, 1H), 7.57 (d, J=7.9 Hz, 1H),
7.34–7.29 (m, 4H), 7.27–7.24 (m, 1H), 7.17 (t, J=7.6 Hz, 1H),
7.10 (t, J=7.1 Hz, 1H), 6.59 (s, 1H), 2.15 (s, 3H); 13C NMR
(100 MHz, CDCl3) d 139.71, 136.35, 129.07, 124.22, 124.07,
122.48, 121.93, 121.87, 109.49, 18.78; HRMS (ESI) m/z: calcd
for C16H15N2S [M+H]+ 267.0950; found 267.0953.
47 755, 695 cmÀ1; 1H NMR (400 MHz, CDCl3) d 7.25 (t, J=
7.8 Hz, 4H), 7.17 (s, 3H), 6.99 (t, J=7.3 Hz, 2H), 5.72 (s, 1H),
2.26 (q, J=7.7 Hz, 2H), 1.10 (t, J=7.6 Hz, 3H). 13C NMR
(100 MHz, CDCl3) d 157.4, 145.2, 129.0, 122.8, 121.3, 25.3,
12.2; HRMS (ESI) m/z: calcd for C15H17N2 [M+H]+
225.1386; found 225.1392.
48
49
50
51
52
53
N’-(Naphthalen-2-yl)-N-phenylacetimidamide (3au): as
a
blue solid (50.7 mg, 65%); mp 93–948C; Rf =0.4 (petroleum
ether: EtOAc=5:1); IR (KBr): 3409, 3050, 1645, 1538, 1320,
1
N,N’-Diphenylbutyrimidamide (3ao): as
a
white solid
1218, 935, 752 cmÀ1; H NMR (400 MHz, CDCl3) d 7.82–7.76
54 (50.6 mg,71%); mp 101–1028C; Rf =0.6 (petroleum ether:
(m, 4H), 7.47–7.45 (m, 1H), 7.39–7.28 (m, 2H), 7.09 (t, J=
5.7 Hz, 1H), 5.54 (s, 1H), 2.00 (s, 3H); 13C NMR (100 MHz,
CDCl3) d 153.7, 145.2, 143.0, 134.4, 130.1, 129.0, 128.6, 127.7,
127.3, 126.2, 124.2, 122.8, 122.4, 121.3, 117.0, 18.7; HRMS
EtOAc=5:1); IR (KBr): 3442, 3379, 3015, 1632, 1523, 1489,
55
56
1
1220, 757, 693 cmÀ1; H NMR (400 MHz, CDCl3) d 7.27 (t,
J=7.7 Hz, 4H), 7.20–7.16 (m, 3H), 7.00 (t, J=7.3 Hz, 2H),
57
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(ESI) m/z: calcd for C18H17N2 [M+H]+, 261.1386; found,
261.1388.
122.8, 121.6, 114.3, 55.5, 18.6; HRMS (ESI) m/z: calcd for
1
2
C15H17N2O [M+H]+ 241.1335; found 241.1340.
3
4
5
6
N-Phenyl-3,4,5,6,7,8-hexahydroazocin-2-amine (3av): as a
light yellow oil (35.2 mg, 58%); Rf =0.7 (petroleum ether:
EtOAc=5:1); IR (KBr): 3029, 3028, 1626, 1536, 1209,
N-(4-Fluorophenyl)-N’-phenylacetimidamide (3bb): as a
white solid (52.0 mg, 76%); mp 91–928C; Rf =0.4 (petroleum
ether: EtOAc=5:1); IR (KBr): 3414, 2926, 1648, 1501, 1393,
1
1
749 cmÀ1; H NMR (400 MHz, CDCl3) d 7.29 (d, J=7.6 Hz,
1210, 835, 753 cmÀ1; H NMR (400 MHz, DMSO) d 7.28 (t,
7
8
9
10
11
12
13
2H), 7.16 (d, J=7.5 Hz, 2H), 7.05 (s, 1H), 2.64–2.53 (m, 2H),
2.44–2.32 (m, 2H), 1.99 (s, 2H), 1.67–1.56 (m, 6H); 13C NMR
(100 MHz, CDCl3) d 164.4, 129.0, 123.2, 121.7, 33.8, 30.4,
30.4, 28.4, 27.6, 24.6; HRMS (ESI) m/z: calcd for C13H19N2
[M+H]+ 203.1543; found 203.1542.
J=7.8 Hz, 2H), 7.18 (d, J=7.0 Hz, 2H), 7.07–7.00 (m, 3H),
6.98–6.94 (m, 2H), 5.75 (s, 1H), 1.92 (s, 3H); 13C NMR
(100 MHz, CDCl3) d 158.9 (d, J=239.0 Hz), 153.6, 144.8,
129.0, 123.0, 122.6, 121.3, 115.5 (d, J=23.0 Hz), 18.6; HRMS
(ESI) m/z: calcd for C14H14FN2 [M+H]+ 229.1136; found
229.1139.
N-isopropyl-N-phenylisobutyrimidamide (3aw): as a light
yellow oil (48.2 mg, 79%); Rf =0.65 (petroleum ether:
N-(4-Chlorophenyl)-N’-phenylacetimidamide (3bc): as
a
14 EtOAc=5:1); IR (KBr): 3448, 2967, 1629, 1508, 1224, 1080,
white solid (54.9 mg, 75%); mp 99.0–1008C; Rf =0.5 (petro-
leum ether: EtOAc=5:1); IR (KBr): 3418, 3041, 1647, 1503,
1324, 1222, 836, 698 cmÀ1; 1H NMR (400 MHz, CDCl3) d
7.39–7.35 (m, 2H), 7.31–7.29 (m, 4H), 7.16–7.11 (m, 3H), 6.38
(s, 1H), 1.93 (s, 3H); 13C NMR (100 MHz, CDCl3) d 154.1,
144.5, 144.3, 129.1, 129.0, 127.6, 123.2, 122.8, 121.5, 18.5;
HRMS (ESI) m/z: calcd for C14H14ClN2 [M+H]+ 245.0840;
found 245.0842.
1
743 cmÀ1; H NMR (400 MHz, CDCl3) d 7.22 (t, J=7.6 Hz,
15
16
17
18
19
20
2H), 6.92 (s, 1H), 6.73 (d, J=7.6 Hz, 2H), 4.05 (d, J=
49.9 Hz, 1H), 2.90–2.68 (m, 1H), 1.19 (d, J=4.0 Hz, 6H), 1.03
(s, 6H); 13C NMR (100 MHz, CDCl3) d 161.4, 151.5, 128.7,
122.2, 121.3, 41.6, 28.4, 22.6, 20.9; HRMS (ESI) m/z: calcd for
C13H21N2 [M+H]+ 205.1699; found 205.1700.
N’-Phenyl-N-(p-tolyl)cetimidamide (3ax): as a yellow solid
(57.0 mg, 85%); mp 85.0–86.08C; Rf =0.45 (petroleum ether:
EtOAc=5:1); IR (KBr): 3405, 3030, 2923, 1646, 1598, 1218,
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
N-(4-Bromophenyl)-N’-phenylacetimidamide (3bd): as
a
light yellow solid (62.2 mg, 72%); mp 101.0–1028C; Rf =0.5
(petroleum ether: EtOAc=5:1); IR (KBr): 3414, 3040, 1648,
1
819 cmÀ1; H NMR (400 MHz, CDCl3) d 7.24 (t, J=7.2 Hz,
1
2H), 7.10 (d, J=7.2 Hz, 2H), 7.07–7.03 (m, 4H), 6.97 (d, J=
7.3 Hz, 1H), 6.83–6.12 (m, 1H), 2.27 (s, 3H), 1.88 (s, 3H); 13C
NMR (100 MHz, CDCl3) d 153.9, 146.0, 142.0, 132.5, 129.6,
129.0, 122.8, 121.6, 121.6, 20.9, 18.6; HRMS (ESI) m/z: calcd
for C15H17N2 [M+H]+ 225.1386; found 225.1390.
1498, 1324, 1222, 833, 699 cmÀ1; H NMR (400 MHz, CDCl3)
d 7.43 (d, J=8.3 Hz, 2H), 7.37–7.33 (m, 2H), 7.27–7.26 (m,
2H), 7.14–7.00 (m, 3H), 1.94 (s, 3H); 13C NMR (100 MHz,
CDCl3) d 153.6, 145.5, 144.1, 131.9, 129.0, 123.1, 123.0, 121.3,
115.2, 18.6; HRMS (ESI) m/z: calcd for C14H14BrN2 [M+H]+
289.0335; found 289.0340.
N-(4-Butylphenyl)-N’-phenylacetimidamide (3ay): as a yel-
low solid (62.0 mg, 78%); mp 132–1338C; Rf =0.5 (petroleum
ether: EtOAc=5:1); IR (KBr): 2958, 1645, 1590, 1525, 1326,
N-(4-Iodophenyl)-N’-phenylacetimidamide (3be): as a yel-
low solid (65.5 mg, 65%); mp 107–1088C; Rf =0.6 (petroleum
ether: EtOAc=5:1); IR (KBr): 3411, 3040, 1646, 1516, 1323,
1
1267, 1109, 754 cmÀ1; H NMR (400 MHz, CDCl3) d 8.85 (s,
1
1H), 8.01–7.50 (m, 2H), 7.25 (t, J=7.7 Hz, 2H), 7.07 (d, J=
8.1 Hz, 2H), 6.94 (t, J=7.3 Hz, 1H), 6.87–6.70 (d, J=8.0 Hz,
1H), 2.53 (t, J=7.6 Hz, 2H), 1.92 (d, J=14.3 Hz, 3H), 1.59–
1.50 (m, 2H), 1.35–1.30 (m, 2H), 0.92 (t, J=7.3 Hz, 3H); 13C
NMR (100 MHz, DMSO) d 153.4, 146.7, 135.6, 129.0, 128.90,
128.7, 121.7, 120.4, 114.6, 34.8, 33.9, 22.3, 18.2, 14.2; HRMS
(ESI) m/z: calcd for C18H23N2 [M+H]+ 267.1856; found
267.1859.
1221, 829, 699 cmÀ1; H NMR (400 MHz, CDCl3) d 7.54–7.47
(m, 2H), 7.27–7.21 (m, 2H), 7.16 (s, 2H), 7.00 (d, J=7.1 Hz,
1H), 6.85 (d, J=5.7 Hz, 2H), 6.13 (s, 1H), 1.82 (s, 3H); 13C
NMR (100 MHz, CDCl3) d 153.6, 146.2, 144.0, 137.9, 129.1,
123.5, 123.2, 121.3, 85.8, 18.7; HRMS (ESI) m/z: calcd for
C14H14IN2 [M+H]+ 337.0196; found 337.0199.
N’-Phenyl-N-(o-tolyl)cetimidamide (3bf): as a white solid
(55.1 mg, 82%); mp 145–1468C; Rf =0.5 (petroleum ether:
EtOAc=5:1); IR (KBr): 2921, 2854, 1640, 1538, 1218, 934,
N-(4-(tert-Butyl)henyl)-N’-phenylacetimidamide (3az): as a
light yellow solid (60.6 mg, 76%); mp 138–1398C; Rf =0.5
(petroleum ether: EtOAc=5:1); IR (KBr): 3409, 3044, 1645,
1520, 1219, 837, 753 cmÀ1; 1H NMR (400 MHz, CDCl3) d
7.19–7.12 (m, 4H), 7.03–6.98 (m, 4H), 6.88 (t, J=7.2 Hz, 1H),
6.17 (s, 1H), 1.79 (s, 3H), 1.19 (s, 9H); 13C NMR (100 MHz,
1
749 cmÀ1; H NMR (400 MHz, CDCl3) d 8.85 (s, 1H), 8.06–
7.40 (m, 2H), 7.25 (t, J=7.8 Hz, 2H), 7.13 (t, J=7.7 Hz, 1H),
6.93 (s, 1H), 6.76 (d, J=7.4 Hz, 1H), 6.60 (s, 1H), 2.27 (s,
3H), 1.92 (s, 3H); 13C NMR (100 MHz, CDCl3) d 153.5, 145.5,
145.0, 138.8, 129.0, 128.8, 123.7, 122.8, 122.1, 121.4, 118.5,
21.6, 18.7; HRMS (ESI) m/z: calcd for C15H17N2 [M+H]+,
225.1386; found 225.1390.
47 CDCl3) d 153.6, 146.4, 145.8, 141.8, 129.0, 125.8, 122.7, 121.5,
121.2, 34.3, 31.6, 18.7; HRMS (ESI) m/z: calcd for C18H23N2
48
49
50
51
52
53
[M+H]+ 267.1856; found 267.1859.
N-([1,1’-Biphenyl]-2-yl)-N’-phenylacetimidamide (3bg): as a
white solid (70.4 mg, 82%); mp 101–1028C; Rf =0.6 (petro-
leum ether: EtOAc=5:1); IR (KBr): 3416, 3052, 1648, 1593,
1529, 1211, 749 cmÀ1;1H NMR (400 MHz, CDCl3) d 7.45 (d,
J=7.3 Hz, 3H), 7.41–7.37 (m, 3H), 7.32–7.29 (m, 3H), 7.26–
7.22 (m, 2H), 7.14–7.10 (m, 1H), 7.06 (s, 1H), 7.01 (t, J=
7.3 Hz, 1H), 5.70 (s, 1H), 1.75 (s, 3H); 13C NMR (100 MHz,
CDCl3) d 153.2, 139.8, 133.8, 130.3, 129.3, 128.9, 128.4, 128.3,
N-(4-Methoxyphenyl)-N’-phenylacetimidamide (3ba): as a
yellow oil (52.6 mg, 73%); Rf =0.35 (petroleum ether:
EtOAc=5:1); IR (KBr): 3397, 2927, 1643, 1505, 1227, 1031,
831, 754 cmÀ1; 1H NMR (400 MHz, CDCl3) d 7.27 (t, J=
54 7.8 Hz, 2H), 7.11–7.09 (m, 4H), 7.01 (d, J=7.4 Hz, 1H), 6.90–
6.76 (m, 2H), 5.58 (s, 1H), 3.76 (s, 3H), 1.92 (s, 3H); 13C NMR
55
(100 MHz, CDCl3) d 155.9, 154.2, 145.8, 137.2, 129.0, 123.3,
56
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1
127.0, 123.5, 122.7, 121.4, 18.9; HRMS (ESI) m/z: calcd for
1603, 1540, 1446, 1219, 825, 744 cmÀ1; H NMR (400 MHz,
1
2
3
4
5
6
7
8
9
10
11
12
13
C20H19N2 [M+H]+ 287.1543; found 287.1545.
DMSO) d 9.19 (s, 1H), 7.78 (d, J=7.7 Hz, 2H), 7.62 (d, J=
2.2 Hz, 1H), 7.39–7.36 (m, 1H), 7.27 (t, J=7.9 Hz, 2H), 6.96
(t, J=7.3 Hz, 1H), 6.83 (d, J=8.4 Hz, 1H), 1.88 (s, 3H); 13C
NMR (100 MHz, DMSO) d 154.9, 141.1, 131.7, 130.9, 128.9,
127.1, 125.2, 122.5, 119.9, 113.7, 18.8; HRMS (ESI) m/z: calcd
for C14H13BrClN2 [M+H]+ 322.9945; found 322.9949.
N-(2-Fluorophenyl)-N’-phenylacetimidamide (3bh) as
a
white solid (47.7 mg, 70%); mp 147–1488C; Rf =0.6 (petro-
leum ether: EtOAc=5:1); IR (KBr): 3423, 3051, 1648, 1629,
1
1233, 755, 696 cmÀ1; H NMR (400 MHz, DMSO) d 9.13 (s,
1H), 7.83 (s, 2H), 7.28 (t, J=7.8 Hz, 2H), 7.14 (d, J=10.4 Hz,
1H), 7.07 (d, J=7.5 Hz, 1H), 6.96 (t, J=7.3 Hz, 2H), 6.90 (s,
1H), 1.94 (s, 3H); 13C NMR (100 MHz, DMSO) d 155.3,
154.1 (d, J=239.0 Hz), 141.4, 139.1, 128.9, 124.9, 124.6, 123.2
(d, J=7.1 Hz), 122.2, 119.7, 116.1 (d, J=20.3 Hz), 18.6;
HRMS (ESI) m/z: calcd for C14H14FN2 [M+H]+, 229.1136;
found 229.1138.
N-Mesityl-N’-phenylacetimidamide (3bn): as a white solid
(59.6 mg, 79%); mp 128 À1298C; Rf =0.5 (petroleum ether:
ethyl acetate=5:1); IR (KBr): 2920, 1643, 1599, 1488, 1216,
752 cmÀ1; H NMR (400 MHz, DMSO) d 8.90 (s, 1H), 7.96–
1
7.94 (m, 2H), 7.30–7.27 (m, 2H), 6.97–6.92 (s, 1H), 6.84 (s,
2H), 2.25 (s, 3H), 2.06 (s, 6H), 1.78 (s, 3H); 13C NMR
(100 MHz, DMSO) d 153.1, 146.6, 142.3, 130.0, 128.7, 127.4,
121.5, 119.4, 20.9, 18.5, 18.4; HRMS (ESI) m/z: calcd for
C17H21N2 [M+H]+, 253.1699; found 253.1703.
14 N-(2-Chlorophenyl)-N’-phenylacetimidamide (3bi): as a light
yellow solid (52.7 mg, 72%); mp 132–1338C; Rf =0.6 (petro-
leum ether: EtOAc=5:1); IR (KBr):3249, 3022, 1621, 1535,
1433, 1217, 1033, 737, 510 cmÀ1; 1H NMR (400 MHz, DMSO)
d 9.11 (s, 1H), 7.83 (d, J=6.7 Hz, 2H), 7.41 (d, J=7.9 Hz,
1H), 7.27 (t, J=7.9 Hz, 2H), 7.22 (t, J=7.6 Hz, 1H), 6.96 (t,
J=7.5 Hz, 2H), 6.87 (d, J=6.9 Hz, 1H), 1.88 (s, 3H); 13C
NMR (100 MHz, DMSO) d 154.5, 148.5, 141.4, 129.7, 128.8,
128.0, 125.8, 123.5, 123.3, 122.3, 119.9, 18.7; HRMS (ESI)
m/z: calcd for C14H14ClN2 [M+H]+, 245.0840; found
245.0844.
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
N-(Naphthalen-1-yl)-N’-phenylacetimidamide (3bo): as
a
yellow solid (58.5 mg, 75%); mp 117–1188C; Rf =0.5 (petro-
leum ether: EtOAc=5:1); IR (KBr): 3408, 2050, 1647, 1531,
1435, 1323, 768 cmÀ1; H NMR (400 MHz, CDCl3) d 7.96 (d,
1
J=7.9 Hz, 1H), 7.77 (d, J=7.5 Hz, 1H), 7.47 (t, J=16.6 Hz,
3H), 7.42–7.33 (m, 3H), 7.24 (t, J=7.7 Hz, 2H), 6.99 (t, J=
7.3 Hz, 1H), 6.88 (d, J=6.8 Hz, 1H), 1.80 (s, 3H); 13C NMR
(100 MHz, CDCl3) d 154.0, 145.8, 141.4, 134.6, 129.1, 128.3,
128.1, 126.2, 126.1, 125.5, 123.9, 123.2, 122.9, 120.7, 117.0,
18.9; HRMS (ESI) m/z: calcd for C18H17N2 [M+H]+,
261.1386; found 261.1389.
N’-Phenyl-N-(m-tolyl)cetimidamide (3bj): as a white solid
(56.5 mg, 84%); mp 102–1038C; Rf =0.45 (petroleum ether:
EtOAc=5:1); IR (KBr): 3406, 3037, 1646, 1596, 1538, 1324,
1
1325, 757 cmÀ1; H NMR (400 MHz, CDCl3) d 7.25 (t, J=
N-Methyl-N,N’-diphenylacetimidamide (3bp): as a yellow oil
(55.8 mg, 83%); Rf =0.6 (petroleum ether: ethyl acetate=
5:1); IR (KBr): 3057, 2934, 1623, 1491, 1369, 1228, 772,
7.7 Hz, 2H), 7.14 (t, J=7.7 Hz, 3H), 6.97 (d, J=10.8 Hz, 3H),
6.81 (d, J=7.5 Hz, 1H), 5.95 (s, 1H), 2.28 (s, 3H), 1.89 (s,
3H); 13C NMR (100 MHz, CDCl3) d 153.5, 144.1, 138.8,
129.0, 128.8, 123.7, 122.8, 122.1, 121.4, 118.5, 21.6, 18.7;
HRMS (ESI) m/z: calcd for C15H17N2 [M+H]+, 225.1386;
found 225.1392.
706 cmÀ1; H NMR (400 MHz, DMSO) d 7.43–7.37 (m, 2H),
1
7.30–7.22 (m, 5H), 6.94 (t, J=7.3 Hz, 1H), 6.86–6.70 (m, 2H),
3.31 (s, 3H), 1.64 (s, 3H); 13C NMR (100 MHz, DMSO) d
156.1, 152.2, 146.3, 129.7, 129.1, 127.7, 126.7, 122.2, 121.7,
39.2, 16.7; HRMS (ESI) m/z: calcd for C15H17N2 [M+H]+,
225.1386; found 225.1391.
N’-Phenyl-N-(3-(trifluoromethyl)henyl)cetimidamide (3bk):
as a yellow oil (67.6 mg, 81%); Rf =0.4 (petroleum ether:
EtOAc=5:1); IR (KBr): 3414, 3048,1650, 1601, 1529, 1323,
N-Methyl-N,N’-diphenylpropionimidamide (3bq): as a yel-
low oil (59.3 mg, 83%); Rf =0.65 (petroleum ether: ethyl
acetate=5:1); IR (KBr): 3056, 2975, 1613, 1491, 1298,
1
1116, 849, 754, 694 cmÀ1; H NMR (400 MHz, DMSO) d 9.23
(d, J=81.4 Hz, 1H), 7.94 (d, J=90.6 Hz, 2H), 7.57 (d, J=
5.9 Hz, 2H), 7.27 (t, J=7.7 Hz, 2H), 6.96 (t, J=7.2 Hz, 3H),
6.80 (s, 1H), 1.97 (s, 3H); 13C NMR (100 MHz, CDCl3) d13C
NMR (101 MHz, DMSO) d 155.4, 154.2, 151.1, 145.2, 141.4,
128.9, 126.1, 125.2 (q, J=270.1 Hz), 122.3, 122.0 (d, J=
70.1 Hz), 121.67, 119.3 (q, J=70.3 Hz), 118.98; HRMS (ESI)
m/z: calcd for C15H14F3N2 [M+H]+ 279.1104; found 279.1107.
727 cmÀ1; H NMR (400 MHz, CDCl3) d 7.36 (t, J=7.7 Hz,
1
2H), 7.24 (t, J=7.8 Hz, 3H), 7.17 (d, J=7.9 Hz, 2H), 6.94 (t,
J=7.3 Hz, 1H), 6.79 (d, J=8.0 Hz, 2H), 3.91 (q, J=7.0 Hz,
2H), 1.61 (s, 3H), 1.18 (t, J=7.1 Hz, 3H); 13C NMR
(100 MHz, CDCl3) d 155.6, 152.1, 144.7, 129.4, 128.8, 128.8,
126.8, 122.2, 121.7, 45.2, 17.0, 12.8; HRMS (ESI) m/z: calcd
for C16H19N2 [M+H]+, 239.1543; found 239.1547.
N-(3, 5-Dimethylphenyl)-N’-phenylacetimidamide (3bl): as a
white solid (60.7 mg, 85%); Rf =0.4 (petroleum ether:
N-Methyl-N,N’-Diphenylisobutyrimidamide (3br): as a yel-
low oil (52.2 mg, 69%); Rf =0.6 (petroleum ether: ethyl
acetate=5:1); IR (KBr): 2920, 1643, 1599, 1488, 1216,
47 EtOAc=5:1); mp 139–1408C; IR (KBr): 3403, 3024, 2921,
1645, 1595, 1542, 1263, 752 cmÀ1; 1H NMR (400 MHz,
48
49
1
DMSO) d 8.76 (d, J=34.5 Hz, 1H), 7.78 (s, 1H), 7.40 (s, 1H),
752 cmÀ1; H NMR (400 MHz, CDCl3) d 7.44–7.41 (m, 2H),
7.23 (t, J=7.8 Hz, 2H), 6.92 (t, J=7.1 Hz, 1H), 6.74 (s, 1H),
6.57 (s, 1H), 6.36 (s, 1H), 2.21 (s, 6H), 1.89 (s, 3H); 13C NMR
(100 MHz, DMSO) d 153.3, 151.5, 141.8, 138.0, 129.1, 123.5,
121.8, 119.5, 117.3, 21.6, 18.2; HRMS (ESI) m/z: calcd for
C16H19N2 [M+H]+, 239.1543; found 239.1547.
7.38–7.36 (m, 1H), 7.28 (t, J=7.8 Hz, 2H), 7.23–7.18 (m, 2H),
6.99 (d, J=7.4 Hz, 1H), 6.83 (d, J=7.3 Hz, 2H), 5.23 (dt, J=
13.5, 6.7 Hz, 1H), 1.56 (s, 3H), 1.15 (d, J=6.8 Hz, 6H); 13C
NMR (100 MHz, CDCl3) d 155.7, 152.1, 140.7, 131.3, 128.9,
128.8, 127.5, 122.2, 121.4, 46.2, 20.8, 17.5; HRMS (ESI) m/z:
calcd for C17H21N2 [M+H]+, 253.1699; found 253.1696.
50
51
52
53
54
55
56
57
N-(4-Bromo-2-chlorophenyl)-N’-phenylacetimidamide
(3bm): as a white solid (79.0 mg, 82%); mp 174–1758C; Rf =
0.55 (petroleum ether: EtOAc=5:1); IR (KBr): 3191, 2924,
1-(3,4-Dihydroquinolin-1(2H)-yl)-N-phenylethan-1-imine
(3bs): as a yellow oil (58.5 mg, 78%); Rf =0.55 (petroleum
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ether: ethyl acetate=5:1); IR (KBr): 3034, 2920, 2878, 1613,
1-Phenyl-2-propyl-1H-benzo[d]midazole (4ae): as a yellow
oil (51.7 mg, 73%); Rf =0.4 (petroleum ether: ethyl acetate=
4: 1); IR (KBr): 3054, 2963, 1683, 1599, 1503, 1451, 750 cmÀ1;
1H NMR (400 MHz, CDCl3) d 7.78 (d, J=8.0 Hz, 1H), 7.60–
7.50 (m, 3H), 7.34 (d, J=7.5 Hz, 2H), 7.29–7.25 (m, 1H), 7.17
(t, J=7.6 Hz, 1H), 7.08 (d, J=8.1 Hz, 1H), 2.81–2.68 (m,
2H), 1.83–1.73 (m, 2H), 0.93 (t, J=7.4 Hz, 3H); 13C NMR
(100 MHz, CDCl3) d 155.2, 142.6, 136.6, 136.0, 129.9, 128.9,
127.4, 122.6, 122.3, 119.0, 110.0, 29.6, 21.2, 13.9; HRMS (ESI)
m/z: calcd for C16H17N2 [M+H]+, 237.1386; found 237.1391.
1
2
3
4
5
6
7
8
9
1
1490, 1371, 1231, 755 cmÀ1; H NMR (400 MHz, CDCl3) d
7.26 (t, J=7.8 Hz, 2H), 7.10 (d, J=7.4 Hz, 2H), 6.99–6.96 (m,
3H), 6.80 (d, J=7.4 Hz, 2H), 3.89 (t, J=6.7 Hz, 2H), 2.67 (t,
J=6.4 Hz, 2H), 2.00–1.91 (m, 5H); 13C NMR (100 MHz,
CDCl3) d 156.6, 151.6, 140.7, 133.4, 129.0, 128.2, 126.0, 123.8,
123.4, 122.1, 121.7, 45.4, 27.6, 24.7, 17.9; HRMS (ESI) m/z:
calcd for C17H19N2 [M+H]+, 251.1543; found 251.1545.
N-Allyl-N,N’-diphenylacetimidamide (3bt): as a yellow oil
(58.5 mg, 78%); Rf =0.6 (petroleum ether: ethyl acetate=
5:1); IR (KBr): 3066, 2922, 1621, 1385, 1287, 1217, 914,
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
47
48
49
50
51
52
53
54
55
56
57
5-Isopropyl-2-methyl-1-phenyl-1H-benzo[d]midazole (4bg):
as a yellow solid (59.2 mg, 79%); mp 65–668C; Rf =0.25
(petroleum ether: ethyl acetate=3: 1); IR (KBr): 2960, 2872,
1
697 cmÀ1; H NMR (400 MHz, CDCl3) d 7.35 (d, J=7.7 Hz,
2H), 7.28–7.13 (m, 5H), 6.95 (d, J=7.1 Hz, 1H), 6.78 (d, J=
8.2 Hz, 2H), 6.02 (d, J=5.3 Hz, 1H), 5.09 (d, J=11.4 Hz,
2H), 4.47 (s, 2H), 1.65 (d, J=9.4 Hz, 3H); 13C NMR
(100 MHz, CDCl3) d 153.8, 151.4, 144.8, 134.3, 129.2, 128.8,
128.4, 126.7, 122.0, 121.7, 116.6, 53.3, 16.9; HRMS (ESI) m/z:
calcd for C17H19N2[M+H]+, 251.1543; found 251.1543.
1
1595, 1495, 1389, 819, 759 cmÀ1; H NMR (400 MHz, CDCl3)
d 7.57 (d, J=8.3 Hz, 1H), 7.49 (t, J=7.5 Hz, 2H), 7.42 (d, J=
7.4 Hz, 1H), 7.30–7.24 (m, 2H), 7.08–7.05 (m, 1H), 6.86 (s,
1H), 2.87 (dt, J=13.8, 6.9 Hz, 1H), 2.39 (s, 3H), 1.15 (d, J=
6.9 Hz, 6H); 13C NMR (100 MHz, CDCl3) d 151.1, 144.0,
140.9, 136.6, 136.2, 129.9, 128.7, 127.1, 121.3, 118.6, 107.2,
34.5, 24.5, 14.4; HRMS (ESI) m/z: calcd for C17H19N2 [M+
H]+, 251.1543, found 251.1545.
2-Methyl-1-phenyl-1H-benzo[d]midazole (4aa): as a yellow
oil (53 mg, 85%); Rf =0.25 (petroleum ether: ethyl acetate=
3: 1); IR (KBr): 3053, 2926, 1744, 1595, 1501, 1390, 748,
1
698 cmÀ1; H NMR (400 MHz, CDCl3) d 7.65 (d, J=8.0 Hz,
1-(4-Bromo-2-chlorophenyl)-2-methyl-1H-benzo[d]midazole
(4bh): as a blue oil (68.9 mg, 72%); Rf =0.35 (petroleum
ether: ethyl acetate=3: 1); IR (KBr): 3054, 2854, 1739, 1484,
1387, 1079, 744 cmÀ1; H NMR (400 MHz, CDCl3) d 7.83 (d,
J=1.8 Hz, 1H), 7.75 (d, J=7.9 Hz, 1H), 7.63–7.61 (m, 1H),
7.27 (d, J=8.2 Hz, 2H), 7.20 (t, J=7.6 Hz, 1H), 6.92 (d, J=
8.0 Hz, 1H), 2.42 (s, 3H); 13C NMR (100 MHz, CDCl3) d
151.5, 142.6, 136.0, 134.3, 133.7, 132.8, 131.6, 131.1, 124.0,
122.9, 122.7, 119.2, 109.6, 14.0; HRMS (ESI) m/z: calcd for
C14H11BrClN2 [M+H]+ 320.9789, found 320.9794.
1H), 7.47 (t, J=7.4 Hz, 2H), 7.42 (d, J=7.2 Hz, 1H), 7.29–
7.23 (m, 2H), 7.19–7.13 (m, 1H), 7.08 (d, J=7.1 Hz, 1H), 7.02
(d, J=8.0 Hz, 1H), 2.41 (s, 3H); 13C NMR (100 MHz, CDCl3)
d 151.5, 142.6, 136.5, 136.1, 129.9, 128.8, 127.1, 122.6, 122.4,
119.0, 109.9, 14.4; HRMS (ESI) m/z: calcd for C14H13N2 [M+
H]+, 209.1073; found 209.1079.
2,7-Dimethyl-1-(o-tolyl)-1H-benzo[d]midazole (4ab): as a
yellow oil (57.3 mg, 81%); Rf =0.3 (petroleum ether: ethyl
acetate=3: 1); IR (KBr): 3049, 2924, 1603, 1503, 1497, 1447,
1
1382, 757 cmÀ1; H NMR (400 MHz, CDCl3) d 7.44–7.37 (m,
2-Methyl-1-(3-(trifluoromethyl)henyl)-1H-benzo[d]midazole
(4ai): as a white oil (67.8 mg, 82%); mp 135.5–136.58C; Rf =
0.25 (petroleum ether: ethyl acetate=3: 1); IR (KBr): 3067,
2H), 7.37–7.30 (m, 1H), 7.18 (d, J=7.7 Hz, 1H), 7.07–7.01
(m, 2H), 6.73–6.70 (m, 1H), 2.70 (s, 3H), 2.39 (s, 3H), 1.95 (s,
3H); 13C NMR (100 MHz, CDCl3) d 150.9, 136.4, 135.9,
135.0, 131.5, 129.5, 128.9, 128.4, 127.4, 122.7, 122.4, 107.5,
17.3, 16.8, 14.0; HRMS (ESI) m/z: calcd for C16H17N2 [M+
H]+, 237.1386; found 237.1390.
1
2925, 1603, 1448, 1452, 1321, 1109, 748, 703 cmÀ1; H NMR
(400 MHz, CDCl3) d 7.78 (d, J=7.9 Hz, 1H), 7.76–7.69 (m,
2H), 7.66 (s, 1H), 7.57 (d, J=7.8 Hz, 1H), 7.30–7.23 (m, 1H),
7.22–7.16 (m, 1H), 7.09 (d, J=7.9 Hz, 1H), 2.51 (s, 3H); 13C
NMR (100 MHz, CDCl3) d 151.1, 142.6, 136.8, 136.1, 132.6
(q, J=32.9 Hz), 130.7, 130.5, 125.6 (q, J=3.6 Hz), 124.0 (q,
J=3.6 Hz), 123.4 (q, J=271.0 Hz), 123.0, 122.8, 119.2, 109.5,
14.3; HRMS (ESI) m/z: calcd for C15H12F3N2 [M+H]+
277.0947, found 277.0949.
2,7-Dichloro-1-(o-tolyl)-1H-benzo[d]midazole (4ac): as
a
yellow solid (48.2 mg, 58%); mp 95–968C; Rf =0.35 (petro-
leum ether: ethyl acetate=3: 1); IR (KBr): 3064, 2925, 1584,
1
1496, 1386, 1178, 747; H NMR (400 MHz, CDCl3) d 7.61 (d,
J=7.7 Hz, 1H), 7.53–7.42 (m, 2H), 7.34 (d, J=7.6 Hz, 1H),
7.24 (d, J=7.8 Hz, 1H), 7.06 (s, 1H), 6.80 (d, J=8.0 Hz, 1H),
2.42 (s, 3H); 13C NMR (100 MHz, CDCl3) d 152.8, 139.9,
137.1, 133.1, 133.0, 131.2, 131.0, 129.9, 128.4, 123.8, 123.3,
122.5, 108.6, 14.0; HRMS (ESI) m/z: calcd for C14H11Cl2N2
[M+H]+, 277.0294; found 277.0290.
6-Ethyl-2-methyl-1-(3-(trifluoromethyl)henyl)-1H-benzo
[d]midazole (4aj): as a white solid (71.1 mg, 78%); mp 121–
1228C; Rf = 0.3 (petroleum ether: ethyl acetate=3:1); IR
1
(KBr): 3038, 2966, 1608, 1454, 1324, 1130, 1129, 813 cmÀ1; H
NMR (400 MHz, CDCl3) d 7.78 (d, J=7.9 Hz, 1H), 7.73 (t,
J=7.8 Hz, 1H), 7.68–7.61 (m, 2H), 7.58 (d, J=7.7 Hz, 1H),
7.13 (dd, J=8.2, 1.5 Hz, 1H), 6.90 (d, J=0.8 Hz, 1H), 2.70 (q,
J=7.6 Hz, 2H), 2.48 (s, 3H), 1.22 (t, J=7.6 Hz, 3H); 13C
NMR (100 MHz, CDCl3) d 150.6, 140.9, 139.7, 137.0, 136.4,
132.6 (q, J=33.0 Hz), 130.7, 130.5, 125.5 (q, J=3.2 Hz), 124.1
(q, J=3.0 Hz), 123.4 (q, J=271.0 Hz), 123.2, 118.9, 108.3,
29.2, 16.2, 14.4; HRMS (ESI) m/z: calcd for C17H16F3N2 [M+
H]+ 305.1260, found 305.1265.
2-Ethyl-1-phenyl-1H-benzo[d]midazole (4ad): as a yellow oil
(50.6 mg, 76%); Rf =0.4 (petroleum ether: ethyl acetate=3:
1); IR (KBr): 3053, 2976, 2928, 1597, 1504, 1454, 1268, 751,
1
691 cmÀ1; H NMR (400 MHz, CDCl3) d 7.77 (d, J=7.5 Hz,
1H), 7.55–7.50 (m, 3H), 7.34 (d, J=7.0 Hz, 2H), 7.23 (d, J=
5.8 Hz, 1H), 7.16 (s, 1H), 7.07 (d, J=7.7 Hz, 1H), 2.85–2.68
(m, 2H), 1.33 (t, J=7.0 Hz, 3H); 13C NMR (100 MHz,
CDCl3) d 142.3, 136.6, 136.0, 129.9, 128.9, 127.3, 122.6, 122.4,
119.1, 109.9, 100.0, 21.2, 12.1; HRMS (ESI) m/z: calcd for
C15H15N2 [M+H]+, 223.1230; found, 223.1234.
6-Methoxy-2-methyl-1-(3-(trifluoromethyl)henyl)-1H-benzo
[d]midazole (4ak): as a white solid (67.9 mg, 74%); mp 85–
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868C; Rf =0.2 (petroleum ether: ethyl acetate=3: 1); IR
2,4-Dimethyl-1-(3-(trifluoromethyl)henyl)-1H-benzo[d]mid-
azole (4ap): as a white solid (73 mg, 84%); mp 142–1438C;
Rf =0.3 (petroleum ether: ethyl acetate=3:1); IR (KBr):
1
2
3
4
5
6
7
8
9
(KBr): 3060, 2935, 2838, 1621, 1489, 1452, 1167, 813,
1
706 cmÀ1; H NMR (400 MHz, CDCl3) d 7.80–7.68 (m, 2H),
1
7.65 (s, 1H), 7.58 (t, J=9.0 Hz, 2H), 6.88 (dd, J=8.8, 2.4 Hz,
1H), 6.54 (d, J=2.3 Hz, 1H), 3.74 (s, 3H), 2.45 (s, 3H); 13C
NMR (100 MHz, CDCl3) d 156.9, 150.2, 137.0, 136.9, 136.7,
132.7 (q, J=32.7.0 Hz) 130.8, 130.5, 125.6 (q, J=3.7 Hz),
124.0 (q, J=3.7 Hz), 123.4 (q, J=271.0 Hz), 119.7, 111.4,
93.7, 55.8, 14.4; HRMS (ESI) m/z: calcd for C16H14F3N2O
[M+H]+ 307.1053, found 307.1056.
3054, 2924, 1603, 1507, 1451, 1321, 1170, 1122, 703 cmÀ1; H
NMR (400 MHz, CDCl3) d 7.76 (d, J=7.9 Hz, 1H), 7.70 (t,
J=7.8 Hz, 1H), 7.65 (s, 1H), 7.55 (d, J=7.8 Hz, 1H), 7.13–
7.02 (m, 2H), 6.96–6.85 (m, 1H), 2.69 (s, 3H), 2.53 (s, 3H); 13
C
NMR (100 MHz, CDCl3) d 150.3, 141.8, 137.0, 135.8, 132.6
(q, J=33.0 Hz), 130.7, 130.5, 129.3, 125.5 (q, J=3.7 Hz),
124.0 (q, J=3.7 Hz), 124.4 (q, J=271.1 Hz), 123.3, 122.9,
107.1, 16.7, 14.4; HRMS (ESI) m/z: calcd for C16H14F3N2
[M+H]+ 291.1104, found 291.1106.
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6-Fluoro-2-methyl-1-(3-(trifluoromethyl)henyl)-1H-benzo
[d]midazole (4al): as a white solid (63.5 mg, 72%); mp 118–
1198C; Rf =0.25 (petroleum ether: ethyl acetate=3:1); IR
4-Fluoro-2-methyl-1-(3-(trifluoromethyl)henyl)-1H-benzo
[d]midazole (4aq): as a white solid (57.3 mg, 65%); mp 133–
1348C; Rf =0.35 (petroleum ether: ethyl acetate=3:1); IR
(KBr): 3079, 1591, 1494, 1321, 1115, 1066, 702 cmÀ1; 1H NMR
(400 MHz, CDCl3) d 7.81–7.75 (m, 2H), 7.65 (s, 1H), 7.58 (d,
J=7.8 Hz, 1H), 7.11–7.08 (m, 1H), 6.98–6.90 (m, 1H), 6.87–
6.85 (m, 1H), 2.50 (s, 3H); 13C NMR (100 MHz, CDCl3) d
153.5 (q, J=251.5 Hz), 151.5, 138.9 (d, J=8.7 Hz), 136.5,
132.8 (q, J=33.1 Hz), 130.9, 130.5, 127.36, 126.0 (q, J=
3.7 Hz), 124.0 (q, J=3.8 Hz), 123.4, 123.3 (q, J=270.9 Hz),
108.4 (d, J=17.5 Hz), 105.7, 14.3; HRMS (ESI) m/z: calcd for
C15H11F4N2 [M+H]+ 295.0853, found, 295.0857.
1
(KBr): 3052, 2926, 1612, 1467, 1327, 1174, 1135, 704 cmÀ1; H
NMR (400 MHz, CDCl3) d 7.80 (d, J=7.9 Hz, 1H), 7.74 (t,
J=7.8 Hz, 1H), 7.66–7.62 (m, 2H), 7.57 (d, J=7.8 Hz, 1H),
7.02–6.97 (m, 1H), 6.78–6.75 (m, 1H), 2.48 (s, 3H); 13C NMR
(100 MHz, CDCl3) d 159.9 (d, J=238.8 Hz), 151.8, 139.0,
136.5, 136.2(d, J=13 Hz) 132.9 (q, J=33.1 Hz), 130.9, 130.3,
125.9 (q, J=3.7 Hz), 123.9 (q, J=3.7 Hz), 123.3 (q, J=
271.1 Hz), 120.0 (d, J=9.9 Hz), 110.9 (d, J=24.9 Hz), 96.5
(q, J=27.9 Hz), 14.40; HRMS (ESI) m/z: calcd for
C15H11F4N2 [M+H]+ 295.0853, found 295.0856.
6-Chloro-2-methyl-1-(3-(trifluoromethyl)henyl)-1H-benzo
[d]midazole (4am): as a yellow solid (67.9 mg, 73%); mp
146–1478C; Rf =0.2 (petroleum ether: ethyl acetate=3:1); IR
6-Methoxy-2-methyl-1-phenyl-1H-benzo[d]midazole (5af):
as a yellow oil (53.6 mg, 75%); Rf =0.15 (petroleum ether:
ethyl acetate=3:1); IR (KBr): 3055, 2931, 1614, 1490, 1390,
1
(KBr): 3057, 2928, 1606, 1455, 1326, 1131, 810, 694 cmÀ1; H
1
NMR (400 MHz, CDCl3) d 7.79 (d, J=7.9 Hz, 1H), 7.73 (t,
J=7.8 Hz, 1H), 7.64–7.58 (m, 2H), 7.56 (d, J=7.9 Hz, 1H),
7.20 (dd, J=8.6, 2.0 Hz, 1H), 7.04 (d, J=1.7 Hz, 1H), 2.47 (s,
3H); 13C NMR (100 MHz, CDCl3) d 152.0, 141.3, 136.7,
136.3, 132.8 (q, J=23.1 Hz), 130.9, 130.4, 128.8, 126.0 (q, J=
3.7 Hz), 124.0 (q, J=3.8 Hz), 123.4, 123.3 (q, J=271.1 Hz),
120.1, 109.7, 14.4; HRMS (ESI) m/z: calcd for C15H11ClF3N2
[M+H]+ 311.0557, found, 311.0559.
1273, 1155, 815 cmÀ1; H NMR (400 MHz, CDCl3) d 7.61–
7.55 (m, 3H), 7.51 (d, J=7.1 Hz, 1H), 7.35 (d, J=7.3 Hz,
2H), 6.88 (dd, J=8.7, 2.4 Hz, 1H), 6.58 (d, J=2.4 Hz, 1H),
3.74 (s, 3H), 2.45 (s, 3H); 13C NMR (100 MHz, CDCl3) d
156.6, 150.6, 137.0, 136.9, 136.2, 130.0, 128.8, 127.1, 119.4,
111.2, 94.0, 55.9, 14.4; HRMS (ESI) m/z: calcd for C15H15N2O
[M+H]+, 239.1179; found 239.1183.
1-(4-Chlorophenyl)-2-methyl-1H-benzo[d]midazole (4ar) &
6-Bromo-2-methyl-1-(3-(trifluoromethyl)henyl)-1H-benzo
[d]midazole (4an): as a yellow solid ( 68.8 mg, 65%); mp
133–1348C; Rf =0.25 (petroleum ether: ethyl acetate=3:1);
IR (KBr):3057, 2926, 1627, 1495, 1459, 1328, 1131, 808, 702,
6-chloro-2-methyl-1-phenyl-1H-benzo[d]midazole
(4ar:5ar=1: 1, inseparable mixture): as
(5ar)
yellow oil
a
(51.3 mg, 71%); IR (KBr): 3055, 2926, 1602, 1496, 1450, 1388,
1
1317, 750 cmÀ1; H NMR (400 MHz, CDCl3) d 7.73 (d, J=
1
cmÀ1; H NMR (400 MHz, CDCl3) d 7.81 (d, J=7.9 Hz, 1H),
7.9 Hz, 1H), 7.62 (d, J=8.5 Hz, 1H), 7.60–7.58 (m, 1H), 7.56–
7.52 (m, 4H), 7.34–7.33 (m, 1H), 7.32–7.31 (m, 1H), 7.31 (s,
1H), 7.29 (s, 1H), 7.28–7.26 (m, 1H), 7.24–7.18 (m, 2H), 7.10–
7.06 (m, 1H), 2.49 (d, J=5.2 Hz, 3H), 2.47 (d, J=4.2 Hz,
3H); 13C NMR (100 MHz, CDCl3) d 152.5, 151.3, 142.5,
141.2, 137.0, 136.2, 135.5, 134.8, 134.5, 130.4, 130.2, 130.1,
129.2, 128.4, 127.0, 123.0, 122.8, 122.6, 119.8, 119.1, 110.1,
109.7, 14.34, 14.32; HRMS (ESI) m/z: calcd for C14H12ClN2
[M+H]+ 243.0684, found 243.0685.
7.74 (t, J=7.8 Hz, 1H), 7.63 (s, 1H), 7.57 (t, J=6.7 Hz, 2H),
7.36 (dd, J=8.5, 1.8 Hz, 1H), 7.21 (d, J=1.7 Hz, 1H), 2.47 (s,
3H); 13C NMR (100 MHz, CDCl3) d 152.0, 141.6, 137.2,
136.2, 132.9 (q, J=33.1 Hz), 130.9, 130.5, 126.1, 126.1 (q, J=
3.7 Hz), 124.0 (q, J=3.7 Hz), 123.2 (q, J=271.1 Hz), 120.5,
116.2, 112.7, 14.4; HRMS (ESI) m/z: calcd for C15H11BrF3N2
[M+H]+ 355.0052, found 355.0055.
6-Iodo-2-methyl-1-(3-(trifluoromethyl)henyl)-1H-benzo
[d]midazole (4ao): as a white solid (73.6 mg, 61%); mp 158–
1598C; Rf =0.25 (petroleum ether: ethyl acetate=3:1); IR
1-(4-Bromophenyl)-2-methyl-1H-benzo[d]midazole (4as) &
6-bromo-2-methyl-1-phenyl-1H-benzo[d]midazole
(5as)
1
(KBr): 3059, 2925, 1602, 1453, 1305, 1131, 808, 665 cmÀ1; H
(4as: 5as=1.3:1, inseparable mixture): as a yellow oil
NMR (400 MHz, CDCl3) d 7.79 (d, J=7.8 Hz, 1H), 7.73 (t,
J=7.8 Hz, 1H), 7.61 (s, 1H), 7.58–7.48 (m, 2H), 7.45 (d, J=
8.4 Hz, 1H), 7.38 (s, 1H), 2.46 (s, 3H); 13C NMR (100 MHz,
(51.3 mg, 71%); IR (KBr): 3053, 2925, 1602, 1494, 1389, 1316,
1
1008, 819, 748 cmÀ1; H NMR (400 MHz, CDCl3) d 7.75–6.69
(m, 3H), 7.60–7.57 (m, 2.33H), 7.56–7.51 (m, 0.8H), 7.36–7.33
(m, 2.39H), 7.28–7.23 (m, 3.91H), 7.21–7.17 (m, 1H), 7.09 ((d,
J=7.6 Hz, 0.83H)), 2.50 (s, 3H), 2.48 (s, 2.31H); 13C NMR
(100 MHz, CDCl3) d 152.4, 151.3, 142.5, 141.5, 137.5, 136.1,
135.5, 135.1, 133.2, 130.1, 129.2, 128.7, 127.0, 125.7, 122.9,
122.8, 122.7, 120.2, 119.1, 115.8, 113.0, 109.7, 14.4; HRMS
53 CDCl3) d 151.7, 142.2, 137.7, 136.2, 132.9 (q, J=33.2 Hz),
131.8, 131.0, 130.5, 126.1 (q, J=3.7 Hz), 124.1 (q, J=3.7 Hz),
54
123.3 (q, J=271.1 Hz), 121.0, 118.5, 86.3, 14.3; HRMS (ESI)
m/z: calcd for C15H11IF3N2 [M+H]+ 402.9914, found
402.9909.
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(ESI) m/z: calcd for C14H12BrN2 [M+H]+ 287.0178, found
287.0191.
[5] a) D. J. Heldebrant, P. K. Koech, M. T. C. Ang, C. Liang,
J. E. Rainbolt, C. R. Yonkera, P. G. Jessop, Green
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Sumathi, K. K. Balasubramanian, Eur. J. Org. Chem.
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2-Methyl-1-(naphthalen-1-yl)-1H-benzo[d]midazole (4at) &
2-methyl-3-phenyl-3H-naphtha [1,2-d]midazole (5at) (4at:
5at=1:3): 5at as a white solid (34.8 mg, 45%) mp 123–
1248C; IR (KBr): 3054, 2926, 1590, 1500, 1388, 1008, 803,
1
751 cmÀ1; H NMR (400 MHz, CDCl3) d 8.68 (d, J=8.2 Hz,
1H), 7.88 (d, J=8.2 Hz, 1H), 7.64–7.48 (m, 5H), 7.47–7.42
(m, 1H), 7.34 (d, J=7.5 Hz, 2H), 7.21 (d, J=8.8 Hz, 1H),
2.57 (s, 3H); 13C NMR (100 MHz, CDCl3) d 149.3, 137.7,
136.1, 132.4, 130.5, 130.0, 128.9, 128.4, 127.1, 126.6, 126.5,
124.4, 123.5, 121.8, 110.8, 14.4; HRMS (ESI) m/z: calcd for
C18H15N2 [M+H]+ 259.1230, found 259.1233.
Supporting Information
1
17 Copies of the H NMR and 13C NMR spectra for all
18 compounds are available in the supporting Informa-
19 tion.
20
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22
Acknowledgements
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We are grateful to the National Key Research and Develop-
ment Program of China (2016YFA0602900), the National
Natural Science Foundation of China (21420102003), and the
Fundamental Research Funds for the Central Universities
(2015ZY001) for financial support.
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Access to Amidines and Arylbenzimidazoles: Zinc-
Promoted Rearrangement of Oxime Acetates
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