Regioselective C-3 arylation of coumarins with arylhydrazines via radical oxidation by potassium permanganate

Article abstract of DOI:10.1515/znb-2016-0109

An efficient protocol for oxidative C-3 arylation of coumarins with arylhydrazine has been developed using potassium permanganate as an oxidant. The arylated coumarins with different electronic properties were obtained in moderate to good yields. The deve

Full text of DOI:10.1515/znb-2016-0109

Z. Naturforsch. 2016; 71(11)b: 1115–1123
Jin-Wei Yuan*, Wei-Jie Li, Liang-Ru Yang, Pu Mao and Yong-Mei Xiao*
Regioselective C-3 arylation of coumarins
with arylhydrazines via radical oxidation
by potassium permanganate
DOI 10.1515/znb-2016-0109
coupling reactions through C–H bond activation [19–25].
Of these pathways, a direct arylation approach to form
-arylcoumarins has been realized via transition metal-
mediated cross-coupling reactions [26–29]. The common
limitations of most of these methods are inevitability
of transition metals which possess high cost and toxic-
ity, necessity of prefunctionalization of the C–H bond at
Received May 5, 2016; accepted June 8, 2016
3
Abstract: An efficient protocol for oxidative C-3 aryla-
tion of coumarins with arylhydrazine has been devel-
oped using potassium permanganate as an oxidant. The
arylated coumarins with different electronic properties
were obtained in moderate to good yields. The developed
protocol for direct C-3 arylation of coumarins could be
extended to quinolinones.
3
-position of the starting coumarins with a halogen or
carboxyl group, and use of expensive arylating counter-
parts such as boronic acid, elevated temperature, and
Keywords: arylation; arylhydrazine; coumarin; KMnO ; longer reaction time. Because a radical arylation reaction
radical reaction.
4
can basically offer a much more straightforward access to
reaction substrates, mainly due to the fact that such aryla-
tions are comparable to C–H activation reactions and less
functionalized starting materials are therefore required,
there has recently been increasing interest in improving
the reaction type [30–32]. Based on the traditional aryl
radical sources for arylation reactions, which are arenedi-
azonium salts, remarkable advances have recently been
achieved by employing photocatalysts and optimized
Gomberg–Bachmann conditions [33–35]. But arenediazo-
nium salts are difficult to synthesize, unstable, known as
explosive under certain circumstances, and give very poor
yield with formation of azoproducts. Therefore, with the
background of these inadequacies, developing an adapt-
able method for 3-arylation of coumarins, which has short
reaction time under mild reaction conditions, is still a sig-
nificant challenge.
Arylhydrazines are known to undergo oxidation
to form aryl radicals in the presence of oxygen [36, 37],
catalysts [38, 39], and stoichiometric amounts of high
valent metal oxidants such as lead(IV) acetate [40],
manganese(III) acetate [36, 41], ferrate salt [42, 43], or
hypervalent iodine(V) reagent [44, 45]. Another aspect
that will facilitate future applications is that arylhydra-
1
Introduction
Coumarins are significant natural products, which display
wide and interesting pharmacological properties such
as anti-breast cancer, anti-HIV, anti-Alzheimer, vasore-
laxant, and anti-aggregatory activities [1–4]. Coumarin
derivatives have proven to be useful skeletons in organic
synthesis as valuable building blocks and in pharma-
ceuticals. In particular, 3-arylcoumarins have important
applications in dyes [5, 6] and pharmaceutical industries
[
7, 8]. There are several drugs constituting functionalized
3
-arylcoumarin as the basic core in them, which possess
wide-ranging activities [9–15].
Despite pervasiveness of 3-arylcoumarins in several
fields of science, they can be obtained by a few general
methods such as using a cycloaddition ring construc-
tion approach [16–18], and by transition metal-catalyzed
*
Corresponding authors: Jin-Wei Yuan and Yong-Mei Xiao, School
of Chemistry and Chemical Engineering, Henan University of
Technology; Academician Workstation for Natural Medical Chemistry zines are simple and cheap starting materials. Recently,
of Henan Province, Zhengzhou 450001, P.R. China,
the oxidative radical 3-arylation of coumarins and quino-
lin-4-ones using arylhydrazines as aryl radical sources has
been reported in the presence of oxygen from air [46, 47].
But the oxidative radical coupling reaction has longer
time, and the scope of substrates is also narrow. Guided by
the recent studies on using arylhydrazines as aryl radical
e-mail: yuanjinweigs@126.com (J.-W. Yuan); mxyy9510@126.com
(
Y.-M. Xiao)
Wei-Jie Li, Liang-Ru Yang and Pu Mao: School of Chemistry and
Chemical Engineering, Henan University of Technology; Academician
Workstation for Natural Medical Chemistry of Henan Province,
Zhengzhou 450001, P.R. China
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1
116ꢀꢀꢀꢀꢁꢀJ.-W. Yuan et al.: Regioselective C-3 arylation of coumarins with arylhydrazines
sources, we decided to investigate the modular synthesis Table 1:ꢀOptimization of reaction conditionsa.
for 3-arylcoumarins by this method. Herein, we disclose
an oxidant radical regioselective arylation of coumarins
and quinolinones with arylhydrazines using KMnO as
4
oxidant to produce 3-arylcoumarin and 3-arylquinolinone
derivatives in moderate to good yields under mild condi-
tions (Scheme 1).
Entryꢁ Oxidant (eq)
ꢁ
Solvent ꢁ Temp. (°C)ꢁ Time (h)ꢁ Yieldb,c (%)
ꢂ
ꢈ
ꢃ
ꢃ
ꢃ
ꢃ
ꢃ
ꢃ
ꢃ
ꢃ
ꢃ
ꢃ
ꢃ
ꢃ
ꢃ
ꢃ
ꢃ
ꢃ
ꢃ
ꢃ
ꢃ
ꢃ
ꢃ
ꢃ
ꢃ
ꢃ
ꢃ
ꢃ
–
ꢃ
CH CN
ꢃ
ꢃ
ꢃ
ꢃ
ꢃ
ꢃ
ꢃ
ꢃ
ꢃ
ꢃ
ꢃ
ꢃ
ꢃ
ꢅꢆꢃ
ꢅꢆꢃ
ꢅꢆꢃ
ꢅꢆꢃ
ꢅꢆꢃ
ꢅꢆꢃ
ꢅꢆꢃ
ꢅꢆꢃ
ꢅꢆꢃ
ꢅꢆꢃ
ꢅꢆꢃ
ꢅꢆꢃ
ꢅꢆꢃ
ꢅꢆꢃ
ꢅꢆꢃ
ꢅꢆꢃ
ꢅꢆꢃ
ꢅꢆꢃ
ꢇꢆꢃ
ꢊꢆꢃ
ꢋꢆꢃ
ꢂꢆꢆꢃ
ꢅꢆꢃ
ꢅꢆꢃ
ꢅꢆꢃ
ꢅꢆꢃ
ꢇ.ꢆꢃ nr
ꢇ.ꢆꢃ
ꢄ
Fe(NO ) (ꢄ.ꢆ) ꢃ CH CN
ꢅ
ꢄ
ꢄ
ꢄ
2
Results and discussion
ꢄ
MnO (ꢄ.ꢆ)
ꢃ
CH CN
ꢇ.ꢆꢃ ꢃ<ꢃꢉ
ꢇ.ꢆꢃ nr
ꢇ.ꢆꢃ ꢇꢉ
ꢇ.ꢆꢃ ꢊꢉ
ꢇ.ꢆꢃ ꢂꢆ
ꢇ.ꢆꢃ nr
ꢇ.ꢆꢃ ꢂꢆ
ꢇ.ꢆꢃ ꢇꢉ
ꢇ.ꢆꢃ ꢊꢆ
ꢇ.ꢆꢃ ꢄꢆ
ꢇ.ꢆꢃ ꢄꢆ
ꢇ.ꢆꢃ ꢇꢆ
ꢇ.ꢆꢃ ꢉꢆ
ꢇ.ꢆꢃ ꢊꢄ
ꢇ.ꢆꢃ ꢊꢆ
ꢇ.ꢆꢃ ꢄꢈ
ꢇ.ꢆꢃ nr
ꢇ.ꢆꢃ ꢇꢆ
ꢇ.ꢆꢃ ꢅꢆ
ꢇ.ꢆꢃ 7ꢉ
ꢆ.ꢉꢃ ꢇꢆ
ꢂ.ꢆꢃ ꢊꢆ
ꢈ.ꢆꢃ ꢅꢆ
ꢄ.ꢆꢃ ꢅꢉ
ꢈ
ꢄ
ꢇ
Mn(OAc) (ꢄ.ꢆ)ꢃ CH CN
ꢈ
ꢄ
We began our study with the selection of coumarin (1a)
and phenylhydrazine (2a) as model substrates to optimize
the reaction condition (Table 1). Initially in the absence of
the oxidant, the desired product 3-arylcoumarin (3a) was
ꢉ
Mn(OAc) (ꢄ.ꢆ)ꢃ CH CN
ꢄ
ꢄ
ꢊ
KMnO (ꢄ.ꢆ)
ꢃ
ꢃ
ꢃ
ꢃ
ꢃ
ꢃ
ꢃ
ꢃ
ꢃ
ꢃ
ꢃ
ꢃ
ꢃ
ꢃ
ꢃ
ꢃ
ꢃ
ꢃ
ꢃ
ꢃ
ꢃ
CH CN
ꢇ
ꢄ
7
H O (ꢄ.ꢆ)
CH CN
ꢈ
ꢈ
ꢄ
ꢅ
TBHP (ꢄ.ꢆ)
CH CN
ꢄ
ꢋ
KMnO (ꢆ.ꢈ)
CH CN
ꢇ
ꢄ
not obtained when the reaction was carried out in CH CN
3
ꢂꢆ
KMnO (ꢂ.ꢆ)
CH CN
ꢇ
ꢄ
at 80°C for 4.0 h under air atmosphere (entry 1). Fe(NO ) , ꢂꢂ
KMnO (ꢈ.ꢆ)
CH CN
3
3
ꢇ
ꢄ
MnO , Mn(OAc) , Mn(OAc) , KMnO , H O , and t-butyl ꢂꢈ
KMnO (ꢇ.ꢆ)
CH CN
ꢇ
ꢄ
2
2
3
4
2
2
ꢂꢄ
ꢂꢇ
ꢂꢉ
ꢂꢊ
ꢂ7
KMnO (ꢄ.ꢆ)
H O
hydroperoxide (TBHP) were investigated as oxidants (Table
, entries 2–8), but only Mn(OAc) and KMnO gave the
ꢇ
ꢈ
KMnO (ꢄ.ꢆ)
Dioxaneꢃ
ꢇ
1
3
4
KMnO (ꢄ.ꢆ)
CH OH ꢃ
ꢇ
ꢄ
desired product in decent yields, and KMnO proved to be
4
KMnO (ꢄ.ꢆ)
DMSO
DCE
ꢃ
ꢃ
ꢃ
ꢃ
ꢃ
ꢃ
ꢃ
ꢃ
ꢃ
ꢃ
ꢃ
ꢇ
the most effective. The amount of KMnO was also examined
4
KMnO (ꢄ.ꢆ)
ꢇ
(
Table 1, entries 6 and 9–12). The best yield was 65% when ꢂꢅ
KMnO (ꢄ.ꢆ)
THF
ꢇ
ꢂꢋ
KMnO (ꢄ.ꢆ)
CH CN
3
.0 eq KMnO was used, which indicated that the oxidant
ꢇ
ꢄ
4
ꢈꢆ
ꢈꢂ
ꢈꢈ
ꢈꢄ
KMnO (ꢄ.ꢆ)
CH CN
KMnO and the quantity of oxidant played important roles
ꢇ
ꢄ
4
KMnO (ꢄ.ꢆ)
CH CN
ꢇ
ꢄ
in this reaction. Subsequently, different solvents such as
KMnO (ꢄ.ꢆ)
CH CN
ꢇ
ꢄ
CH CN, H O, dioxane, CH OH, dimethylsulfoxide (DMSO),
3
2
3
KMnO (ꢄ.ꢆ)
CH CN
ꢇ
ꢄ
1
,2-dichloroethane (DCE), and tetrahydrofuran (THF) were ꢈꢇ
KMnO (ꢄ.ꢆ)
CH CN
ꢇ
ꢄ
screened based on the solubility of the substrates (Table 1, ꢈꢉ
KMnO (ꢄ.ꢆ)
CH CN
ꢇ
ꢄ
ꢈꢊ
KMnO (ꢄ.ꢆ)
CH CN
entries 6 and 13–18) and CH CN was found to be the best
solvent for this transformation. The ratio of substrates
ꢇ
ꢄ
3
aReaction conditions: coumarin 1a (0.5 mmol, ꢌ3 mg), phenylhydrazine
coumarin and phenylhydrazine was investigated, and the 2a (1.0 mmol, 108 mg), oxidant in solvent (10 mL).
b
Isolated yields.
ratio 1:2 of coumarin and phenylhydrazine proved to be
c
nr ꢃ=ꢃ no reaction.
the best result, providing 80% yield of 3a (Table S1, Sup-
plementary Information available online). With increasing
amount of phenylhydrazine, the yield of 3a decreased as
yields dramatically dropped if the reaction temperature
the side reaction occurred to lead to byproducts. When the
reaction temperature was improved from 40°C to 100°C,
the yield of 3a was enhanced from 40% to 85% (Table S1,
entry 4, and Table 1, entries 19–22). However, the product
was higher than 80°C, and the optimal reaction tempera-
ture was 80°C. Finally, reaction times were also examined,
and 3.0 h gave good yield (Table 1, entries 23–26). After
screening the reaction conditions, the optimal result was
identified: the reaction of coumarin (1.0 equiv.) and phe-
nylhydrazine (2.0 equiv.) was carried out in the presence of
KMnO (3.0 equiv.) in CH CN at 80°C for 3.0 h (Table 1, entry
4
3
2
6), which afforded 3-arylcoumarin in 85% yield.
With optimal reaction conditions in hand, the scope
and generality of this methodology was further investi-
gated (Table 2). First, a variety of substituted arylhydra-
zines were allowed to react with coumarin (Table 2, 3a–3o).
Initially, the direct use of commercially available arylhy-
drazine hydrochlorides as the substrates did not lead to
Scheme 1:ꢀSynthesis of 3-arylcoumarins and 3-arylquinolinones.
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Table 2:ꢀSynthesis of 3-arylcoumarins from coumarins and
of arylhydrazines bearing electron-withdrawing groups
a
arylhydrazines .
such as –F, –Cl, –CN, and –OCF with coumarin proceeded
3
smoothly and afforded 3g–3j, 3m, and 3n in moderate
yields of 40%–70%. Especially, arylhydrazines bearing the
strong electron-withdrawing –CN and –OCF groups could
3
also provide corresponding 3-arylated products in moder-
ate yield (3i and 3j). It was noteworthy that arylhydrazine
halides were well tolerated, providing handles for further
functionalization (e.g. with a Suzuki reaction). However,
4
-bromine function in the phenylhydrazine afforded only
2
0% yield (3l); the reason remained unknown. On the
other hand, no expected product was observed in the case
of ortho-bromophenylhydrazine (3k). It is not suitable for
this transformation likely because of steric hindrance of
ortho-bromophenylhydrazine. It is worth mentioning that
an alkylhydrazine, tert-butylhydrazine, was also applied to
the reaction, and the expected product was obtained (3o)
in 35% yield. The fact demonstrated that alkylhydrazines
are suitable precursors for alkyl radicals in this process.
Further, the scope of this methodology was also
investigated with respect to coumarins (Table 2, 3p–3w).
Various substituted coumarins were allowed to react with
phenylhydrazine. It could be seen that the substituted cou-
marins bearing electron-rich groups such as –OH, –CH3,
–
OCH , –OC H , and –N(C H ) were transformed into the
3 2 5 2 5 2
corresponding 3-arylcoumarins in good yields (3p–3v).
Notably, the standard reaction conditions could also be
applied to 4-substituted coumarins, affording the cor-
responding products (3s–3v) in 58%–70% yields, which
indicated that the steric hindrance of coumarins played a
weak role in this reaction. Pleasingly, even a sensitive func-
tionality such as the hydroxyl group was also tolerated
and the coupling reactions proceeded with no requisite
for protection of this group (3p, 3s, and 3v). This feature is
ubiquitous in hydroxycoumarin-based biologically active
products, which eliminates the requirement of protection
and deprotection of hydroxyl groups. Unfortunately, cou-
marin possessing an electron-withdrawing –NO group at
2
the C6 position did not furnish the desired product 3w.
To further illustrate the generality and efficacy of this
coupling reaction, a series of quinolinone substrates were
also briefly surveyed (Table 3). Pleasingly, the C3 posi-
tion of quinolinone derivatives was exclusively arylated,
affording 3-arylquinolinones in 30%–83% yields. It was
noteworthy that 2-quinolinone derivatives with a sensitive
amide group were also tolerated and the coupling reaction
a
Reaction conditions: coumarins 1 (0.5 mmol), arylhydrazines 2
(
1.0 mmol), KMnO (1.5 mmol), CH CN (10 mL) at 80°C for 3.0 h.
4
3
b
Isolated yields in parentheses.
the desired products. Pretreatment of these hydrochloride proceeded with no requisite for protection of this group
salts with NaOH is required. Reactions of arylhydrazines in good yield (5a and 5b). Notably, quinolinone deriva-
having electron-donating groups such as –CH , –C H , and tives bearing electron-rich (–OCH ) and electron-poor (–F,
3
2
5
3
–
OCH with coumarin afforded 3-arylcoumarins 3a–3f in –Br) groups could proceed smoothly under the current
3
good to excellent yields of 78%–89%. Also the reaction condition. Although quinolinones with an electron-poor
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118ꢀꢀꢀꢀꢁꢀJ.-W. Yuan et al.: Regioselective C-3 arylation of coumarins with arylhydrazines
Table 3:ꢀSynthesis of 3-arylquinolines from quinolinones and
3
Conclusions
a
arylhydrazines .
In summary, we have successfully developed an improved
and regioselective C-3 arylation on coumarins and quin-
olinones with arylhydrazines using KMnO as an oxidant.
4
This protocol provides a valuable approach to synthesize
biologically interesting 3-arylcoumarins and 3-arylqui-
nolinones. The advantages of this reaction are high effi-
ciency, moderate to good yield, a broad functional group
tolerance, and the use of cheap and readily available start-
ing materials.
4
Experimental section
a
Reaction conditions: quinolinones 1 (0.5 mmol), arylhydrazines 2
4
.1 General
(
1.0 mmol), KMnO (1.5 mmol), CH CN (10 mL) at 80°C for 3.0 h.
4
3
b
Isolated yields in parentheses.
All substrates were purchased from J & K Scientific Ltd.
without further purification. Nuclear magnetic resonance
spectra were recorded on a Bruker Avance 400 MHz
–
F or –Br substituent had lower reactivity than that with
1
spectrometer. Chemical shifts for H NMR spectra are
an electron-rich group, the corresponding 3-arylated quin-
olinones (5b and 5f) with intact halo groups could serve as
good precursors for further functionalization. The reaction
proved to be fairly general for other electron-poor and elec-
tron-rich heterocycles, such as quinolinone derivatives.
On the basis of the previous studies [36, 39], a plau-
sible reaction mechanism for all arylations described
above is proposed in Scheme 2. The phenylhydrazine A
recorded in parts per million from tetramethylsilane.
Data were reported as follows: chemical shift, multiplic-
ity (s ꢀ=ꢀ singlet, d ꢀ=ꢀ doublet, t ꢀ=ꢀ triplet, m ꢀ=ꢀ multiplet,
and br ꢀ=ꢀ broad), coupling constant in Hz, and integra-
1
3
tion. Chemical shifts for C NMR spectra were recorded in
parts per million from tetramethylsilane. High-resolution
mass spectra (HR MS) were obtained on a Q-TOF instru-
ment using the electrospray ionization (ESI) technique.
IR spectra were recorded on a Shimadazu IR-408 Fourier
transform infrared spectrophotometer using a thin film
supported on KBr pellets. Melting points were measured
on an XT4A microscopic apparatus and are uncorrected.
can be oxidized by KMnO to form a phenyldiazene B. The
4
diazene B is then rapidly converted to a phenyl radical C
by the release of N in the presence of KMnO . The phenyl
2
4
radical C can selectively add to the C3 position of coumarin
to form a radical intermediate D, allowing the carbocation
intermediate E to be formed by a single-electron transfer.
Finally, the intermediate E loses a proton to produce the
C3 arylated coumarin F.
4
.2 General experimental procedure for the
synthesis of 3-arylcoumarins (3) and
3
-arylquinolinone derivatives (5)
In a 50 mL Schlenk tube, a solution of coumarins 1 (or
quinolinone derivatives 4) (0.5 mmol), arylhydrazines 2
(
1.0 mmol), and KMnO (1.5 mmol, 237 mg) in CH CN (10
4
3
mL) was stirred at 80°C for 3.0 h. After the reaction was
finished, the mixture was diluted with saturated NaCl
solution (50 mL). Then the aqueous layer was extracted
with EtOAc (3 ꢀ×ꢀ 15 mL). The organic phase was dried over
anhydrous Na SO and concentrated under vacuum. The
2
4
crude product was purified by silica gel column chroma-
tography using ethyl acetate/petroleum ether (1:5 to 2:1) as
eluant to obtain the desired product 3 (or 5).
Scheme 2:ꢀPlausible reaction mechanism for the formation of
3-arylcoumarin.
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J.-W. Yuan et al.: Regioselective C-3 arylation of coumarins with arylhydrazinesꢍꢁꢀꢀꢀꢍ1119
4.2.1 3-Phenyl-2H-chromen-2-one (3a)
4.2.5 3-(3,5-Dimethylphenyl)-2H-chromen-2-one (3e)
1
Colorless solid; m.p. 138–139°C (from EtOAc; lit. [18]: Yellow solid; m.p. 126–127°C (from EtOAc). − H NMR (400
1
1
36–137°C). − H NMR (400 MHz, CDCl ): δ ꢀ=ꢀ 7.81 (s, 1H), MHz, CDCl ): δ ꢀ=ꢀ 7.78 (s, 1H), 7.52 (td, J ꢀ=ꢀ 7.9 Hz, JH-H ꢀ=ꢀ
3
3
H-H
7
.71–7.69 (m, 2H), 7.53 (t, JH-H ꢀ=ꢀ 8.0 Hz, 2H), 7.47–7.40 (m, 3H), 1.9 Hz, 2H), 7.36 (d, JH-H ꢀ=ꢀ 8.1 Hz, 1H), 7.30–7.26 (m, 3H),
1
3
7
.36 (d, J ꢀ=ꢀ 8.0 Hz, 1H), 7.29 (td, JH-H ꢀ=ꢀ 7.5 Hz, JH-H ꢀ=ꢀ 1.0 7.05 (s, 1H), 2.37 (s, 6H). − C NMR (100 MHz, CDCl ): δ ꢀ=ꢀ
H
-
H
3
13
Hz, 1H). − C NMR (100 MHz, CDCl ): δ ꢀ=ꢀ 160.6, 153.5, 139.9 160.6, 153.4, 139.6 (CH), 138.0, 134.6, 131.2 (CH), 130.6 (CH),
3
(
1
CH), 134.7, 131.4 (CH), 128.8 (CH), 128.6 (CH), 128.5 (CH), 128.7, 127.8 (CH), 126.3 (CH), 124.4 (CH), 119.7, 116.4 (CH),
28.3, 127.9 (CH), 124.5 (CH), 119.7, 116.4 (CH). − IR (KBr): 21.3 (CH ). − IR (KBr): ν ꢀ=ꢀ 2922, 2852, 1724 (Cꢀ=ꢀO), 1608,
3
−1
−1
ν ꢀ=ꢀ 1716 (Cꢀ=ꢀO), 1601, 1454, 1117 cm . − MS ((+)-ESI): m/z ꢀ=ꢀ 1456, 1117 cm . − HR MS ((+)-ESI): m/z ꢀ=ꢀ 251.1064 (calcd.
+
+
2
23.2 (calcd. 223.0 for C H O , [M+H] ).
251.1067 for C H O , [M+H] ).
15
11
2
17 15
2
4.2.2 3-(p-Tolyl)-2H-chromen-2-one (3b)
4.2.6 3-(4-Methoxyphenyl)-2H-chromen-2-one (3f)
Colorless solid; m.p. 160–161°C (from EtOAc; lit. [18]: 158– Colorless solid; m.p. 138–139°C (from EtOAc; lit. [18]: 140–
1
1
1
59°C). − H NMR (400 MHz, [D ]DMSO): δ ꢀ=ꢀ 8.19 (s, 1H), 141°C). − H NMR (400 MHz, CDCl ): δ ꢀ=ꢀ 7.74 (s, 1H), 7.66 (d,
6
3
7
.75 (d, JH-H ꢀ=ꢀ 7.6 Hz, 1H), 7.63–7.58 (m, 3H), 7.41 (d, JH-H ꢀ=ꢀ 8.2 JH-H ꢀ=ꢀ 8.9 Hz, 2H), 7.52–7.46 (m, 2H), 7.33 (d, JH-H ꢀ=ꢀ 8.2 Hz,
Hz, 1H), 7.36 (t, J ꢀ=ꢀ 7.5 Hz, 1H), 7.25 (d, JH-H ꢀ=ꢀ 8.0 Hz, 2H), 1H), 7.27 (td, JH-H ꢀ=ꢀ 7.5 Hz, J ꢀ=ꢀ 1.1 Hz, 1H), 6.96 (d, JH-H ꢀ=ꢀ
H-H
H-H
13
13
2
.34 (s, 3H). − C NMR (100 MHz, [D ]DMSO): δ ꢀ=ꢀ 160.2, 8.9 Hz, 2H), 2.83 (s, 3H). − C NMR (100 MHz, CDCl ): δ ꢀ=ꢀ
6
3
1
53.2, 140.3 (CH), 138.5, 132.1, 131.9 (CH), 129.2 (CH), 128.9 160.8, 160.1, 153.2, 138.5 (CH), 131.0 (CH), 129.8 (CH), 127.8,
(
CH), 128.7 (CH), 127.1, 125.0 (CH), 119.9, 116.2 (CH), 21.2 127.7 (CH), 127.1, 124.4 (CH), 119.8, 116.3 (CH), 113.9 (CH),
−1
(
CH ). − IR (KBr): ν ꢀ=ꢀ 1716 (Cꢀ=ꢀO), 1610, 1452, 1113 cm . − 55.3 (CH ). − IR (KBr): ν ꢀ=ꢀ 2918, 1716 (Cꢀ=ꢀO), 1608, 1514,
3 3
+
−1
MS ((+)-ESI): m/z ꢀ=ꢀ 237.3 (calcd. 237.0 for C H O , [M+H] ). 1452, 1252, 1128 cm . − MS ((+)-ESI): m/z ꢀ=ꢀ 253.4 (calcd.
16
13
2
+
2
53.0 for C H O , [M+H] ).
1
6
13
3
4
.2.3 3-(3,4-Dimethylphenyl)-2H-chromen-2-one (3c)
4
.2.7 3-(2-Fluorophenyl)-2H-chromen-2-one (3g)
Light yellow solid; m.p. 130–131°C (from EtOAc; lit. [47]:
1
1
1
10–112°C). − H NMR (400 MHz, CDCl ): δ ꢀ=ꢀ 7.75 (s, 1H), Yellow solid; m.p. 165–166°C (from EtOAc). − H NMR (400
3
7
.51–7.46 (m, 3H), 7.42 (dd, JH-H ꢀ=ꢀ 7.8 Hz, JH-H ꢀ=ꢀ 1.4 Hz, 1H), MHz, CDCl ): δ ꢀ=ꢀ 7.84 (s, 1H), 7.56–7.53 (m, 3H), 7.39–7.37
3
13
7
.33 (d, JH-H ꢀ=ꢀ 8.1 Hz, 1H), 7.26 (t, JH-H ꢀ=ꢀ 7.5 Hz, 1H), 7.18 (d, (m, 2H), 7.30 (t, JH-H ꢀ=ꢀ 7.3 Hz, 1H), 7.24–7.14 (m, 2H). − C
13
JH-H ꢀ=ꢀ 7.8 Hz, 1H), 2.30 (s, 3H), 2.28 (s, 3H). − C NMR (100 NMR (100 MHz, CDCl ): δ ꢀ=ꢀ 161.1 (d, J ꢀ=ꢀ 247.7 Hz), 159.9,
3
F-C
MHz, CDCl ): δ ꢀ=ꢀ 160.7, 153.4, 139.1 (CH), 137.6, 136.6, 132.2, 153.7, 142.6 (d, JF-C ꢀ=ꢀ 3.2 Hz) (CH), 131.6 (d, JF-C ꢀ=ꢀ 50.2 Hz)
3
1
31.1 (CH), 129.7 (CH), 129.6 (CH), 128.4, 127.8 (CH), 125.9 (CH), 131.3 (CH), 130.6 (d, JF-C ꢀ=ꢀ 8.2 Hz) (CH), 128.1 (CH),
(
CH), 124.4 (CH), 119.8, 116.4 (CH), 19.9 (CH ), 19.6 (CH ). − 124.5 (CH), 124.1 (d, JF-C ꢀ=ꢀ 3.5 Hz) (CH), 123.2, 122.4 (d, JF-C ꢀ=ꢀ
3
3
−1
IR (KBr): ν ꢀ=ꢀ 2922, 1718 (Cꢀ=ꢀO), 1605, 1454, 1101 cm . − MS 13.7 Hz), 119.2, 116.6 (CH), 116.0 (d, J ꢀ=ꢀ 21.9 Hz) (CH). −
F-C
+
19
(
(+)-ESI): m/z ꢀ=ꢀ 251.3 (calcd. 251.1 for C H O , [M+H] ).
F NMR (376 MHz, CDCl ): δ ꢀ=ꢀ –114.5. − IR (KBr): ν ꢀ=ꢀ 1728
17
15
2
3
−1
(Cꢀ=ꢀO), 1610, 1452, 1120 cm . − HR MS ((+)-ESI): m/z ꢀ=ꢀ
+
241.0663 (calcd. 241.0659 for C H FO , [M+H] ).
1
5
10
2
4.2.4 3-(4-Ethylphenyl)-2H-chromen-2-one (3d)
1
Colorless solid [29]; m.p. 118–119°C (from EtOAc). − H NMR 4.2.8 3-(3-Fluorophenyl)-2H-chromen-2-one (3h)
400 MHz, CDCl ): δ ꢀ=ꢀ 7.79 (s, 1H), 7.63 (d, J ꢀ=ꢀ 8.2 Hz, 2H),
(
3
H-H
7
.54–7.49 (m, 2H), 7.36 (d, JH-H ꢀ=ꢀ 8.2 Hz, 1H), 7.31–7.27 (m, Colorless solid; m.p. 173–174°C (from EtOAc; lit. [47]: 152–
H), 2.69 (q, JH-H ꢀ=ꢀ 7.6Hz, 2H), 1.26 (t, JH-H ꢀ=ꢀ 7.6 Hz, 3H). − C 154°C). − H NMR (400 MHz, CDCl ): δ ꢀ=ꢀ 7.83 (s, 1H), 7.54 (t,
1
3
1
3
3
NMR (100 MHz, CDCl ): δ ꢀ=ꢀ 160.7, 153.4, 145.2, 139.2 (CH), JH-H ꢀ=ꢀ 7.4 Hz, 2H), 7.47 (t, JH-H ꢀ=ꢀ 7.5 Hz, 2H), 7.43–7.39 (m, 1H),
3
1
32.0, 131.2 (CH), 128.5 (CH), 128.3, 128.0, 127.8 (CH), 124.4 7.36 (d, JH-H ꢀ=ꢀ 8.6 Hz, 1H), 7.30 (d, J ꢀ=ꢀ 7.9 Hz, 1H), 7.09 (td,
H-H
13
(
CH), 119.8, 116.4 (CH), 28.7 (CH ), 15.5 (CH ). − IR (KBr): JH-H ꢀ=ꢀ 8.6 Hz, JH-H ꢀ=ꢀ 1.8 Hz, 1H). − C NMR (100 MHz, CDCl ):
2
3
3
−1
ν ꢀ=ꢀ 3012, 2948, 1716 (Cꢀ=ꢀO), 1558, 1452, 1115 cm . − MS ((+)- δ ꢀ=ꢀ 162.6 (d, JF-C ꢀ=ꢀ 244.4 Hz), 160.2, 153.5, 140.4 (CH), 136.6
+
ESI): m/z ꢀ=ꢀ 251.0 (calcd. 251.1 for C H O , [M+H] ).
(d, JF-C ꢀ=ꢀ 8.2 Hz), 131.8 (CH), 130.0 (d, JF-C ꢀ=ꢀ 8.2 Hz, CH), 128.1
17
15
2
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1
120ꢀꢀꢀꢀꢁꢀJ.-W. Yuan et al.: Regioselective C-3 arylation of coumarins with arylhydrazines
1
3
(
CH), 127.0 (d, JF-C ꢀ=ꢀ 2.2 Hz, CH), 124.6 (CH), 124.1 (d, JF-C ꢀ=ꢀ 7.00–6.91 (m, 2H). − C NMR (100 MHz, CDCl ): δ ꢀ=ꢀ 164.5,
3
2
.9 Hz, CH), 119.4, 116.5 (CH), 115.8 (d, J ꢀ=ꢀ 8.8 Hz, CH), 115.6 162.0, 160.0, 153.8, 142.7 (d, JF-C ꢀ=ꢀ 3.8 Hz) (CH), 132.3 (dd,
F-C
19
(
d, JF-C ꢀ=ꢀ 10.7 Hz, CH). − F NMR (376 MHz, CDCl ): δ ꢀ=ꢀ –112.6. JF-C ꢀ=ꢀ 9.6 Hz, JF-C ꢀ=ꢀ 9.4 Hz) (CH), 132.0 (CH), 128.1 (CH), 124.6
3
−1
−
IR (KBr): ν ꢀ=ꢀ 1709 (Cꢀ=ꢀO), 1610, 1588, 1456, 1180 cm . − MS (CH), 122.3, 119.1, 116.6 (CH), 111.6 (dd, JF-C ꢀ=ꢀ 3.5 Hz, JF-C ꢀ=ꢀ 3.6
+
19
(
(+)-ESI): m/z ꢀ=ꢀ 241.3 (calcd. 241.0 for C H FO , [M+H] ).
Hz) (CH), 104.4 (t, JF-C ꢀ=ꢀ 25.4 Hz) (CH). − F NMR (376 MHz,
15
10
2
CDCl ): δ ꢀ=ꢀ –108.3, –110.1. − IR (KBr): ν ꢀ=ꢀ 1710 (Cꢀ=ꢀO), 1611,
3
−
1
1
584, 1450, 1141 cm . − HR MS ((+)-ESI): m/z ꢀ=ꢀ 259.0568
+
4
.2.9 4-(2-Oxo-2H-chromen-3-yl)benzonitrile (3i)
(calcd. 259.0565 for C H F O , [M+H] ).
1
5
9
2
2
Light yellow solid; m.p. 239–240°C (from EtOAc; lit. [47]:
4
.2.13 3-(3-Chloro-4-methylphenyl)-2H-chromen-
-one (3n)
1
1
52–154°C). − H NMR (400 MHz, CDCl ): δ ꢀ=ꢀ 7.90 (s, 1H),
3
2
7
.85 (d, JH-H ꢀ=ꢀ 8.4 Hz, 2H), 7.74 (d, JH-H ꢀ=ꢀ 8.4 Hz, 2H), 7.59 (d,
JH-H ꢀ=ꢀ 7.5 Hz, 2H), 7.39 (d, J ꢀ=ꢀ 8.4 Hz, 1H), 7.34 (td, JH-H ꢀ=ꢀ 8.4
H-H
1
Yellow solid; m.p. 193–194°C (from EtOAc). − H NMR
400 MHz, CDCl ): δ ꢀ=ꢀ 7.79 (s, 1H), 7.70 (d, J ꢀ=ꢀ 1.6 Hz, 1H),
13
Hz, JH-H ꢀ=ꢀ 0.7 Hz, 1H). − C NMR (100 MHz, CDCl ): δ ꢀ=ꢀ 159.9,
3
(
3
H-H
1
53.7, 141.3 (CH), 139.1 (CH), 132.4 (CH), 132.2 (CH), 129.2
7
.55–7.51 (m, 3H), 7.35 (d, J ꢀ=ꢀ 8.6 Hz, 1H), 7.29 (t, JH-H ꢀ=ꢀ
H-H
(
CH), 128.3 (CH), 126.4, 124.8 (CH), 119.2, 118.5, 116.6 (CH),
1
3
7
.8 Hz, 2H), 2.40 (s, 3H). − C NMR (100 MHz, CDCl ): δ ꢀ=ꢀ
−1
3
1
12.4. − IR (KBr): ν ꢀ=ꢀ 1709 (Cꢀ=ꢀO), 1614, 1446, 1115 cm . − MS
1
60.3, 153.5, 139.8 (CH), 136.8, 134.4, 133.7, 131.6 (CH), 130.9
+
(
(+)-ESI): m/z ꢀ=ꢀ 248.2 (calcd. 248.0 for C H NO , [M+H] ).
16
10
2
(
CH), 128.8 (CH), 127.9 (CH), 126.9, 126.7 (CH), 124.6 (CH),
1
19.5, 116.5 (CH), 19.9 (CH ). − IR (KBr): ν ꢀ=ꢀ 1718 (Cꢀ=ꢀO),
454, 1356, 1113 cm . − HR MS ((+)-ESI): m/z ꢀ=ꢀ 271.7179
3
−1
1
4
.2.10 3-(4-(Trifluoromethoxy)phenyl)-2H-chromen-
-one (3j)
+
(
calcd. 271.7177 for C H ClO , [M+H] ).
1
6
12
2
2
1
Colorless solid; m.p. 160–161°C (from EtOAc). − H NMR 4.2.14 3-(tert-Butyl)-2H-chromen-2-one (3o)
400 MHz, CDCl ): δ ꢀ=ꢀ 7.83 (s, 1H), 7.75 (dd, J ꢀ=ꢀ 6.8 Hz,
(
3
H-H
JH-H ꢀ=ꢀ 2.0 Hz, 2H), 7.57–7.54 (m, 2H), 7.38 (d, J ꢀ=ꢀ 8.6 Hz, Fait yellow solid; m.p. 81–82°C (from EtOAc; lit. [48]:82–
H-H
13
1
1
1
1
H), 7.34–7.28 (m, 3H). − C NMR (100 MHz, CDCl ): δ ꢀ=ꢀ 83°C). − H NMR (400 MHz, CDCl ): δ ꢀ=ꢀ 7.54 (s, 1H), 7.47–7.43
3
3
60.4, 153.6, 149.5, 140.2 (CH), 133.2, 131.7 (CH), 130.1 (CH), (m, 2H), 7.29 (d, J ꢀ=ꢀ 8.7 Hz, 1H), 7.23 (t, JH-H ꢀ=ꢀ 6.7 Hz, 1H),
H-H
13
28.0 (CH), 127.0, 124.6 (CH), 121.7, 120.8 (CH), 119.4, 116.5 1.40 (s, 9H). − C NMR (100 MHz, CDCl ): δꢀ=ꢀ 159.9, 153.2, 137.1,
3
19
(
CH). − F NMR (376 MHz, CDCl ): δ ꢀ=ꢀ –57.7. − IR (KBr): ν ꢀ=ꢀ 136.6 (CH), 130.5 (CH), 127.5 (CH), 123.9 (CH), 119.4, 116.0, 35.0,
3
−
1
−1
1
709 (Cꢀ=ꢀO), 1610, 1516, 1456, 1140 cm . − HR MS ((+)-ESI): 28.6 (CH ). − IR (KBr): ν ꢀ=ꢀ 2965, 1720 (Cꢀ=ꢀO), 1455, 1354 cm .
3
+
+
m/z ꢀ=ꢀ 301.0578 (calcd. 307.0577 for C H F O , [M+H] ).
− MS ((+)-ESI): m/z ꢀ=ꢀ 203.2 (calcd. 203.1 for C H O , [M+H] ).
16
10
3
3
13 15
2
4
.2.15 7-Hydroxy-3-phenyl-2H-chromen-2-one (3p)
4
.2.11 3-(4-Bromophenyl)-2H-chromen-2-one (3l)
White solid; m.p. 201–202°C (from EtOAc; lit. [28]:203–
Colorless solid; m.p. 189–190°C (from EtOAc; lit. [18]:188–
1
2
04°C. − H NMR (400 MHz, [D ]DMSO): δ ꢀ=ꢀ 10.66 (s, 1H),
1
6
1
89°C). − H NMR (400 MHz, CDCl ): δ ꢀ=ꢀ 7.81 (s, 1H), 7.60–
3
8
.15 (s, 1H), 7.69 (d, JH-H ꢀ=ꢀ 7.3 Hz, 2H), 7.60 (d, JH-H ꢀ=ꢀ 8.5 Hz,
7
.52 (m, 6H), 7.35 (d, J ꢀ=ꢀ 8.7 Hz, 1H), 7.30 (td, JH-H ꢀ=ꢀ 8.6 Hz,
H-H
1
H), 7.43 (d, JH-H ꢀ=ꢀ 7.6 Hz, 2H), 7.37 (t, JH-H ꢀ=ꢀ 7.3 Hz, 1H), 6.82
13
JH-H ꢀ=ꢀ 1.0 Hz, 1H). − C NMR (100 MHz, CDCl ): δ ꢀ=ꢀ 160.2,
3
(
dd, J ꢀ=ꢀ 8.5 Hz, JH-H ꢀ=ꢀ 2.2 Hz, 1H), 6.76 (d, JH-H ꢀ=ꢀ 2.0 Hz,
H-H
1
1
53.5, 139.9 (CH), 133.5, 131.7 (CH), 131.6 (CH), 130.1 (CH),
28.0 (CH), 127.1, 124.6 (CH), 123.1, 119.5, 116.5 (CH). − IR
1
3
1
H). − C NMR (100 MHz, [D ]DMSO): δ ꢀ=ꢀ 161.7, 160.6, 155.3,
6
1
41.6 (CH), 135.6, 130.4 (CH), 128.7 (CH), 128.6 (CH), 128.5
−1
(
KBr): ν ꢀ=ꢀ 1712 (Cꢀ=ꢀO), 1610, 1487, 1450, 1012 cm . − MS ((+)-
(
CH), 122.6, 113.8 (CH), 112.4 (CH), 102.2 (CH). − IR (KBr):
+
ESI): m/z ꢀ=ꢀ 301.1 (calcd. 301.0 for C H BrO , [M+H] ).
15
10
2
−1
ν ꢀ=ꢀ 3228, 1680 (Cꢀ=ꢀO), 1615, 1595, 1570, 1445, 1080 cm . −
+
MS ((+)-ESI): m/z ꢀ=ꢀ 239.1 (calcd. 239.0 for C H O , [M+H] ).
1
5
11
3
4
.2.12 3-(2,4-Difluorophenyl)-2H-chromen-2-one (3m)
4
.2.16 7-Methoxy-3-phenyl-2H-chromen-2-one (3q)
1
Light yellow solid; m.p. 172–173°C (from EtOAc). − H NMR
(
400 MHz, CDCl ): δ ꢀ=ꢀ 7.83 (s, 1H), 7.61–7.53 (m, 3H), 7.39 (d, Light yellow solid; m.p. 119–120°C (from EtOAc; lit. [18]:
3
1
JH-H ꢀ=ꢀ 8.2 Hz, 1H), 7.32 (td, JH-H ꢀ=ꢀ 7.8 Hz, JH-H ꢀ=ꢀ 0.8 Hz, 1H), 118–119°C). − H NMR (400 MHz, CDCl ): δ ꢀ=ꢀ 7.75 (s, 1H),
3
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J.-W. Yuan et al.: Regioselective C-3 arylation of coumarins with arylhydrazinesꢍꢁꢀꢀꢀꢍ1121
7
.68 (d, JH-H ꢀ=ꢀ 8.4 Hz, 2H), 7.45–7.41 (m, 3H), 7.39–7.35 (m, 4.2.20 7-Ethoxy-4-methyl-3-phenyl-2H-chromen-
13
1
H), 6.87–6.84 (m, 2H), 3.87 (s, 3H). − C NMR (100 MHz,
2-one (3u)
CDCl ): δ ꢀ=ꢀ 162.6, 160.8, 155.3, 139.9 (CH), 135.0, 128.8 (CH),
3
1
1
28.4 (CH), 124.8, 113.3, 112.7 (CH), 100.4 (CH), 55.7 (CH ). Yellow solid; m.p. 117–118°C (from EtOAc). − H NMR (400
3
−
IR (KBr): ν ꢀ=ꢀ 3053, 2970, 1716 (Cꢀ=ꢀO), 1614, 1506, 1464, MHz, CDCl ): δ ꢀ=ꢀ 7.52 (d, J ꢀ=ꢀ 8.8 Hz, 1H), 7.41 (d, JH-H ꢀ=ꢀ 7.0
3 H-H
−1
1439, 1120 cm . − MS ((+)-ESI): m/z ꢀ=ꢀ 253.3 (calcd. 253.1 for Hz, 2H), 7.35 (d, JH-H ꢀ=ꢀ 7.3 Hz, 1H), 7.29–7.25 (m, 2H), 6.85
+
C H O , [M+H] ).
(dd, JH-H ꢀ=ꢀ 8.8 Hz, JH-H ꢀ=ꢀ 2.5 Hz, 1H), 6.79 (d, JH-H ꢀ=ꢀ 2.2 Hz,
H), 4.06 (q, J ꢀ=ꢀ 7.0 Hz, 2H), 2.23 (s, 3H), 1.43 (t, JH-H ꢀ=ꢀ 7.0
16
13
3
1
H-H
1
3
Hz, 3H). − C NMR (100 MHz, CDCl ): δ ꢀ=ꢀ 161.7, 161.3, 154.3,
3
4
.2.17 6-Methyl-3-phenyl-2H-chromen-2-one (3r)
1
48.0, 134.7, 130.2 (CH), 128.3 (CH), 127.9 (CH), 126.1 (CH),
1
24.0, 113.9, 112.6 (CH), 101.0 (CH), 64.1 (CH ), 16.5 (CH ),
2
3
Colorless solid; m.p. 148–149°C (from EtOAc; lit. [27]:149–
1
4.6 (CH ). − IR (KBr): ν ꢀ=ꢀ 3062, 2979, 2947, 1712 (Cꢀ=ꢀO),
1
3
1
50°C). − H NMR (400 MHz, CDCl ): δ ꢀ=ꢀ 7.74 (s, 1H), 7.70–
3
−1
1
2
604, 1508, 1385, 1361, 1074 cm . − HR MS ((+)-ESI): m/z ꢀ=ꢀ
7
.67 (m, 2H), 7.46–7.37 (m, 3H), 7.33–7.31 (m, 2H), 7.24 (dd,
+
81.1175 (calcd. 281.1172 for C H O , [M+H] ).
13
18 17
3
JH-H ꢀ=ꢀ 7.4 Hz, JH-H ꢀ=ꢀ 1.6 Hz, 1H), 2.41 (s, 3H). − C NMR (100
MHz, CDCl ): δ ꢀ=ꢀ 160.8, 151.6, 139.9 (CH), 134.8, 134.1, 132.4
3
(
CH), 128.7 (CH), 128.5 (CH), 128.4 (CH), 128.2, 127.7 (CH),
4
.2.21 3-(3,5-Dimethylphenyl)-7-hydroxy-4-methyl-
H-chromen-2-one (3v)
1
19.4, 116.1 (CH), 20.8 (CH ). − IR (KBr): ν ꢀ=ꢀ 2916, 2848, 1720
3
2
−1
(Cꢀ=ꢀO), 1616, 1577, 1448, 1111 cm . − MS ((+)-ESI): m/z ꢀ=ꢀ
+
2
37.2 (calcd. 237.1 for C H O , [M+H] ).
16
13
2
1
Yellow solid; m.p. 228–230°C (from EtOAc). − H NMR (400
MHz, CDCl ): δ ꢀ=ꢀ 8.01 (s, 1H), 7.51 (d, J ꢀ=ꢀ 8.7 Hz, 1H), 7.01–
3
H-H
7
.00 (m, 2H), 6.89 (bs, 2H), 6.85 (dd, J ꢀ=ꢀ 8.7 Hz, JH-H ꢀ=ꢀ
H-H
4
.2.18 7-Hydroxy-4-methyl-3-phenyl-2H-chromen-
1
3
2
.3 Hz, 1H), 2.33 (s, 6H), 2.26 (s, 3H). − C NMR (100 MHz,
2
-one (3s)
CDCl ): δ ꢀ=ꢀ 162.7, 159.9, 153.9, 149.2, 137.9, 134.3, 129.8 (CH),
3
1
27.7 (CH), 126.3 (CH), 123.8, 113.7, 113.6 (CH), 103.1 (CH),
White solid; m.p. 231–232°C (from EtOAc; lit. [49]:225–
2
1.3 (CH ), 16.6 (CH ). − IR (KBr): ν ꢀ=ꢀ 3062, 2979, 1712 (Cꢀ=ꢀO),
1
3 3
2
27°C). − H NMR (400 MHz, [D ]DMSO): δ ꢀ=ꢀ 10.5 (s, -OH),
6
−1
1
604, 1508, 1385, 1361, 1074 cm . − HR MS ((+)-ESI): m/z ꢀ=ꢀ
7
.61 (d, JH-H ꢀ=ꢀ 8.8 Hz, 1H), 7.43 (t, JH-H ꢀ=ꢀ 7.5 Hz, 2H), 7.36 (t,
JH-H ꢀ=ꢀ 7.2 Hz, 1H), 7.28 (d, JH-H ꢀ=ꢀ 6.9 Hz, 2H), 6.83 (dd, JH-H ꢀ=ꢀ
.8 Hz, J ꢀ=ꢀ 2.2 Hz, 1H), 6.74 (d, JH-H ꢀ=ꢀ 2.2 Hz, 1H), 2.17
+
2
81.1176 (calcd. 281.1172 for C H O , [M+H] ).
1
8
17
3
8
H-H
1
3
(
s, 3H). − C NMR (100 MHz, [D ]DMSO): δ ꢀ=ꢀ 161.3, 160.7,
6
4
.2.22 3-Phenylquinolin-2(1H)-one (5a)
1
54.3, 148.7, 135.3, 130.7 (CH), 128.4 (CH), 128.0 (CH), 127.5
(
CH), 122.7, 113.4 (CH), 112.8, 102.3 (CH), 16.7 (CH ). − IR
3
White solid; m.p. 226–227°C (from EtOAc; lit. [50]:228–
(
KBr): ν ꢀ=ꢀ 3228, 1682 (Cꢀ=ꢀO), 1614, 1593, 1577, 1446, 1078
1
2
30°C). − H NMR (400 MHz, [D ]DMSO): δ ꢀ=ꢀ 11.96 (s, 1H),
−1
6
cm . − MS ((+)-ESI): m/z ꢀ=ꢀ 253.2 (calcd. 253.1 for C H O ,
1
6
13
3
8
.10 (s, 1H), 7.77–7.72 (m, 3H), 7.50 (td, JH-H ꢀ=ꢀ 8.3 Hz, JH-H ꢀ=ꢀ
+
[
M+H] ).
1
.2 Hz, 1H), 7.45–7.41 (m, 2H), 7.40 (d, JH-H ꢀ=ꢀ 7.3 Hz, 1H),
7
.34 (d, J ꢀ=ꢀ 8.1 Hz, 1H), 7.20 (td, JH-H ꢀ=ꢀ 7.9 Hz, JH-H ꢀ=ꢀ 0.8
H-H
1
3
4
.2.19 7-Hydroxy-4-methyl-3-phenyl-2H-chromen-
Hz, 1H). − C NMR (100 MHz, [D ]DMSO): δ ꢀ=ꢀ 161.5, 138.8,
6
2
-one (3t)
138.0 (CH), 136.7, 131.9, 130.6 (CH), 129.1 (CH), 128.6 (CH),
128.4 (CH), 128.3 (CH), 122.3 (CH), 120.0, 115.1 (CH). − IR
1
Deep yellow solid; m.p. 102–103°C (from EtOAc). − H NMR (KBr): ν ꢀ=ꢀ 3428, 1635 (Cꢀ=ꢀO), 1610, 1464, 1454, 1120, 1028
−1
(
400 MHz, DMSO): δ ꢀ=ꢀ 7.46–7.40 (m, 3H), 7.34 (t, JH-H ꢀ=ꢀ 7.3 cm . − MS ((+)-ESI): m/z ꢀ=ꢀ 222.3 (calcd. 222.1 for C H NO,
15 12
+
Hz, 1H), 7.29 (d, JH-H ꢀ=ꢀ 7.0 Hz, 2H), 6.61(dd, JH-H ꢀ=ꢀ 9.0 Hz, [M+H] ).
JH-H ꢀ=ꢀ 2.5 Hz, 1H), 6.54 (d, JH-H ꢀ=ꢀ 2.5 Hz, 1H), 3.41 (q, J ꢀ=ꢀ
H-H
13
7
.1 Hz, 4H), 2.22 (s, 3H), 1.21 (t, JH-H ꢀ=ꢀ 7.1 Hz, 6H). − C NMR
(
100 MHz, DMSO): δ ꢀ=ꢀ 162.1, 155.1, 150.2, 148.3, 135.3, 130.5 4.2.23 3-(3,4-Dimethylphenyl)-8-fluoroquinolin-
CH), 128.2 (CH), 127.5 (CH), 126.1 (CH), 121.0, 109.5, 108.6 2(1H)-one (5b)
CH), 97.4 (CH), 44.7 (CH ), 16.3 (CH ), 12.4 (CH ). − IR (KBr):
(
(
2
3
3
−1
1
ν ꢀ=ꢀ 2987, 2856, 1707 (Cꢀ=ꢀO), 1618, 1587, 1522, 1074 cm . Light yellow solid; m.p. 238–239°C (from EtOAc). − H NMR
−
HR MS ((+)-ESI): m/z ꢀ=ꢀ 308.1648 (calcd. 308.1645 for (400 MHz, CDCl ): δ ꢀ=ꢀ 9.82 (s, 1H), 7.84 (s, 1H), 7.55 (s, 1H),
3
+
C H NO , [M+H] ).
7.49 (d, JH-H ꢀ=ꢀ 7.2 Hz, 1H), 7.37 (d, JH-H ꢀ=ꢀ 7.8 Hz, 1H), 7.21 (d,
2
0
22
2
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122ꢀꢀꢀꢀꢁꢀJ.-W. Yuan et al.: Regioselective C-3 arylation of coumarins with arylhydrazines
J
ꢀ=ꢀ 7.9 Hz, 2H), 7.15–7.10 (m, 1H), 2.33 (s, 3H), 2.30 (s, 3H). (CH), 98.4 (CH), 55.6 (CH ), 29.9 (CH ). − IR (KBr): ν ꢀ=ꢀ 2979,
H-H
3
3
− 1
3
C NMR (100 MHz, CDCl ): δ ꢀ=ꢀ 150.1, 147.6, 137.2, 136.7 2927, 1645 (Cꢀ=ꢀO), 1616, 1595, 1508, 1454, 1248, 1211, 1036
3
−1
(
CH), 136.4, 133.1, 129.9 (CH), 129.6 (CH), 126.6, 126.5, 126.2 cm . − HR MS ((+)-ESI): m/z ꢀ=ꢀ 266.1179 (calcd. 266.1176 for
+
(
CH), 123.2 (d, JF-C ꢀ=ꢀ 7.9 Hz) (CH), 122.1 (d, J ꢀ=ꢀ 7.9 Hz) (CH), C H NO , [M+H] ).
F-C 17 16 2
19
1
14.8 (d, JF-C ꢀ=ꢀ 7.9 Hz) (CH), 19.9, 19.6. − F NMR (376 MHz,
CDCl ): δ ꢀ=ꢀ –135.3. − IR (KBr): ν ꢀ=ꢀ 2944, 2848, 1645 (Cꢀ=ꢀO),
3
4
.2.27 6-Bromo-1-methyl-3-phenylquinolin-
(1H)-one (5f)
−
1
1
614, 1454, 1259 cm . − HR MS ((+)-ESI): m/z ꢀ=ꢀ 268.1130
2
+
(calcd. 268.1132 for C H FNO, [M+H] ).
1
7
15
Pale yellow solid, m.p. 175–176°C (from EtOAc; lit. [50]:176–
1
1
78°C). − H NMR (400 MHz, CDCl ): δ ꢀ=ꢀ 7.73 (d, J ꢀ=ꢀ 2.2
3
H-H
4
.2.24 3-(4-Methoxyphenyl)-1-methylquinolin-
(1H)-one (5c)
Hz, 1H), 7.70–7.67 (m, 3H), 7.63 (dd, JH-H ꢀ=ꢀ 8.9 Hz, JH-H ꢀ=ꢀ 2.2
Hz, 1H), 7.44 (t, JH-H ꢀ=ꢀ 7.6 Hz, 2H), 7.40–7.37 (m, 1H), 7.25 (d,
2
1
3
JH-H ꢀ=ꢀ 6.7 Hz, 1H), 3.77 (s, 3H). − C NMR (100 MHz, CDCl ):
3
Pale yellow solid; m.p. 113–114°C (from EtOAc; lit. [50]:114–
δ ꢀ=ꢀ 161.1, 138.5, 136.3, 135.3 (CH), 133.7, 132.9 (CH), 130.8
1
1
16°C). − H NMR (400 MHz, CDCl ): δ ꢀ=ꢀ 7.73 (s, 1H), 7.67
3
(
CH), 128.9 (CH), 128.4 (CH), 128.2 (CH), 122.2, 115.7 (CH),
(
dd, JH-H ꢀ=ꢀ 7.0 Hz, JH-H ꢀ=ꢀ 1.9 Hz, 2H), 7.56 (dd, JH-H ꢀ=ꢀ 7.8 Hz,
1
14.9, 30.1 (CH ). − IR (KBr): ν ꢀ=ꢀ 2954, 2924, 1647 (Cꢀ=ꢀO),
3
JH-H ꢀ=ꢀ 1.0 Hz, 1H), 7.51 (td, JH-H ꢀ=ꢀ 7.2 Hz, JH-H ꢀ=ꢀ 1.4 Hz, 1H),
.32 (d, JH-H ꢀ=ꢀ 8.5 Hz, 1H), 7.21 (td, JH-H ꢀ=ꢀ 7.2 Hz, JH-H ꢀ=ꢀ 0.6 Hz,
−1
1
579, 1487, 1444, 1415, 1228, 1209, 1118 cm . − MS ((+)-ESI):
7
+
m/z ꢀ=ꢀ 314.1 (calcd. 314.0 for C H BrNO, [M+H] ).
1
3
16 13
1
H), 6.95 (d, JH-H ꢀ=ꢀ 8.8 Hz, 2H), 3.83 (s, 3H), 3.76 (s, 3H). − C
NMR (100 MHz, CDCl ): δ ꢀ=ꢀ 161.6, 159.5, 139.3, 135.7 (CH),
3
1
1
31.9, 130.2 (CH), 129.9 (CH), 129.2, 128.6 (CH), 122.1 (CH),
20.8, 113.9 (CH), 113.6 (CH), 55.3 (CH ), 29.9 (CH ). − IR
5
Supplementary information
3
3
(
KBr): ν ꢀ=ꢀ 3032, 2952 (–CH ), 1637 (Cꢀ=ꢀO), 1604, 1598, 1510,
3
Further experimental details and NMR spectra of com-
pounds 3a–3v and 5a–5f are given as Supplementary
Information available online (http://dx.doi.org/10.1515/
znb-2016-0109).
−1
1458 (Ar–), 1246, 1178, 1030 cm . − MS ((+)-ESI): m/z ꢀ=ꢀ
+
2
66.2 (calcd. 266.1 for C H NO , [M+H] ).
17
16
2
4
.2.25 1-Methyl-3-phenylquinolin-2(1H)-one (5d)
Acknowledgments: The work was supported by the
National Natural Science Foundation of China (Nos.
White solid; m.p. 134–135°C (from EtOAc; lit. [50]:135–
2
1172055 and 21302042), Natural Science Foundation of
1
1
37°C). − H NMR (400 MHz, CDCl ): δ ꢀ=ꢀ 7.77 (s, 1H), 7.70
3
Henan scientific committee (No. 142102210410), Natural
Science Foundation of Henan Educational Committee
(
dd, JH-H ꢀ=ꢀ 7.0 Hz, JH-H ꢀ=ꢀ 1.4 Hz, 2H), 7.59–7.25 (m, 2H), 7.42 (t,
JH-H ꢀ=ꢀ 7.5 Hz, 2H), 7.35 (t, J ꢀ=ꢀ 8.4 Hz, 2H), 7.22 (t, JH-H ꢀ=ꢀ 7.3
Hz, 1H), 3.77 (s, 3H). − C NMR (100 MHz, CDCl ): δ ꢀ=ꢀ 161.5,
H-H
(
No. 14B150053), and the Program for Innovative Research
13
3
Team from Zhengzhou (No. 131PCXTD605), and Scien-
tific Fund Project of Zhengzhou Science and Technology
Bureau (No. 20130883).
1
1
39.6, 136.8 (CH), 132.4, 130.3 (CH), 128.9 (CH), 128.8 (CH),
28.1 (CH), 128.0 (CH), 122.2 (CH), 120.7, 114.0 (CH), 29.9
(
CH ). − IR (KBr): ν ꢀ=ꢀ 3049, 3032, 1645 (Cꢀ=ꢀO), 1591, 1454
3
−
1
cm . − MS ((+)-ESI): m/z ꢀ=ꢀ 236.2 (calcd. 236.1 for C H NO,
1
6
14
+
[M+H] ).
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