Metal-free catalyzed arylsulfonylation of chloroquinoline with sodium arylsulfinates under microwave irradiation

Article abstract of DOI:10.1515/znb-2018-0007

An efficient protocol for the synthesis of 2-arylsulfonyl quinolines has been developed via a metal-free catalyzed cross-coupling reaction of chloroquinoline with sodium arylsulfinates in moderate-to-good yields under microwave irradiation. The reactions proceed with a wide range of substrates with good functional group tolerance.

Full text of DOI:10.1515/znb-2018-0007

Z. Naturforsch. 2018; aop
XMi-YeontgaLil,-Yaf-rMeineSucnaantdaJilny-WzeieYduana* rylsulfonylation of
chloroquinoline with sodium arylsulfinates under
microwave irradiation
https://doi.org/10.1515/znb-2018-0007
reagents [10]. Chen’s group described a transition metal-
free one-pot approach to selective synthesis of 2-sulfonyl
quinolines via H-phosphite-mediated C–H activation [11].
He’s and Xiang’s groups independently developed the
synthesis of 2-sulfonyl quinolines by the iodine- or iodide-
induced 2-sulfonylation of quinoline N-oxides with sulfo-
nyl hydrazides in the presence of tert-butyl hydroperoxide
or hydrogen peroxide (H2O2) [12, 13]. Pan’s group synthe-
sized a variety of 2-sulfonyl quinoline derivatives via Cu-
Received January 6, 2018; accepted March 30, 2018
Abstract: An efficient protocol for the synthesis of 2-aryl-
sulfonyl quinolines has been developed via a metal-free
catalyzed cross-coupling reaction of chloroquinoline with
sodium arylsulfinates in moderate-to-good yields under
microwave irradiation. The reactions proceed with a wide
range of substrates with good functional group tolerance.
Keywords: 2-arylsulfonyl quinolone; chloroquinoline; catalyzed C2-sulfonylation of quinoline N-oxides with
metal-free catalysis; sodium arylsulfinates; sulfonylation. sodium sulfinates in the presence of potassium persulfate
(K2S2O8) [14]. Zhao’s and Yotphan’s groups achieved the
synthesis of 2-sulfonyl quinolines via iodine-mediated
sulfonylation of quinoline N-oxides with sodium sulfi-
nates [15, 16]. Although these reactions allowed the syn-
1 Introduction
thesis of the desired 2-sulfonylation of quinolines, these
Heterocyclic aromatic sulfone is recognized as a crucial
approaches suffered from a narrow range of substrates,
scaffold in natural products, pharmaceuticals, material
long reaction times, air-sensitive reaction conditions, and
sciences, and biologically active compounds [1–6]. In par-
required different oxidants and transition-metal catalysts.
ticular, quinoline sulfones exhibited antibacterial and
It is still highly desirable to develop new protocols that
antiproliferative activities [7, 8]. In the last decade, signifi-
can tolerate a wide range of functional groups, short reac-
cant effort has been devoted to the synthesis of sulfonyl
tion times, metal-free, air-insensitive reaction conditions.
quinoline derivatives. Traditionally, quinoline sulfones
Guided by the recent studies on using sodium arylsulfi-
can be synthesized by nucleophilic substitution of heter-
nate as a sulfonylation source, we decided to investigate
oaromatic halides with thiols to form thioethers, followed
the modular synthesis for arylsulfonylated quinolines
by oxidation to the corresponding sulfones [9]. However,
based on transition-metal-free catalyzed arylsulfonyla-
low efficiency and redundant steps of these methodolo-
tion of chloroquinoline. Herein, we disclose an efficient
gies are prohibitive for general applications. Thus, the
synthetic strategy for synthesizing a wide variety of sulfo-
search for novel methods for the synthesis of sulfonyl qui-
nylated quinoline derivatives by reacting chloroquinoline
nolines has attracted considerable attention in medicinal
with sodium arylsulfinates under microwave irradiation
and synthetic chemistry.
(Scheme 1). Interestingly, other N-heteroaryl chlorine com-
In the past few years, great efforts have been made
pounds also react smoothly with sodium arylsulfinates
to synthesize 2-sulfonyl quinoline scaffolds. Wu’s group
at these conditions. The advantages of our methodology
reported an efficient and concise protocol to synthesize
include short reaction times, a broad range of substrates,
sulfonylated quinoline N-oxides via C–H bond activa-
and good functional group tolerance.
tion with aryl sulfonyl chlorides as the sulfonylation
*Corresponding author: Jin-Wei Yuan, School of Chemistry and
2 Results and discussion
We initially chose 2-chloroquinoline (1a) as a model sub-
strate for the reaction with sodium phenylsulfinate (2a)
using dimethyl sulfoxide (DMSO) as solvent at 100°C for
Chemical Engineering, Henan University of Technology, Zhengzhou
450001, P.R. China, e-mail: yuanjinweigs@126.com
Xi-Yong Li and Ya-Min Sun: Department of Marine Biology and
Medicine, Weihai Ocean Vocational College, Weihai 264300,
P.R. China
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ꢀꢀꢀꢁ
2ꢀ
ꢀX.-Y. Li et al.: Synthesis of 2-arylsulfonyl quinoline derivatives
O
R2
O
was prolonged, the yields did not improve (Table 1, entries
1, 12–15). The effects of various ratios of substrates were
then probed and the ratio of 1a–2a of 1:1.5 was found to be
particularly effective for this sulfonylation (Table 1, entries
14, 16–17). The use of microwave irradiation is essential
for this reaction, as no products formed in the absence of
microwave irradiation even if the reaction time was pro-
longed to 5.0 h. After surveying a variety of solvents, tem-
perature, reaction times, and the ratio of substrates, we
found that the the ratio of substrates of 1:1.5 and DMSO as
solvent at 120°C for 30 min were the optimal conditions for
this transformation (Table 1, entry 14).
R2
R1
DMSO
MW
R1
S
Cl
+
NaO S
N
O
N
Scheme 1:ꢀSynthesis of arylsulfonylated quinoline derivatives.
20 min under microwave irradiation. Much to our delight,
the reaction proceeded to give access to the desired sul-
fonylation product 3aa, albeit with a low yield (30%,
Table 1, entry 1). The structure of 3aa was verified by IR,
NMR, and high-resolution mass spectra (HRMS) spectra.
Inspired by this result, various solvents, such as CH3CN,
1,4-dioxane, CH3OH, 1,2-dichloroethane (DCE), THF, and
H2O, were screened, but they gave lower yields than DMSO
(Table 1, entries 2–7). Thus DMSO proved to be definitely
superior to the others. Rising the reaction temperature
from 90 to 120°C showed a positive result, with the start-
ing material consumed completely in 20 min and the
yields improved up to 78%. However, a continued increase
in temperature to 130°C had a negative impact on the reac-
tion, and the yield decreased to 58%. Apparently, higher
temperatures led to an increase in side reactions (Table
1, entries 1, 8–11). Additionally, the reaction time was also
investigated, and 30 min proved to be ideal. If the time
With the optimal reaction conditions in hand, we
turned our attention to the substrates. Different sodium
arylsulfinates were evaluated in the reaction with 2-chlo-
roquinoline 1a (Table 2). In addition, a series of functional
groups on the phenyl ring of sodium arylsulfinates were
tested. Both electron-donating and -withdrawing groups
were well tolerated in this sulfonylation, affording the
desired products in moderate-to-good yields (60–92%)
(3aa–3aj). Generally, sodium arylsulfinates with electron-
donating substituents (3ab and 3ac) showed superior
reaction efficiency as compared to those with electron-
withdrawing ones (3ad–3ai). Fortunately, this protocol
was tolerant of synthetically valuable functional groups
on the phenyl moiety (in particular, chloro and bromo
substituents), which gave an opportunity for further
transformations (3ae, 3af). The sulfonylation process also
occurred well with strongly electron-withdrawing –CN and
Table 1:ꢀOptimization of reaction conditions.a
O
S
NaO2S
+
N
N
Cl
O
–CF
3 groups at the sodium phenylsulfinates, affording the
1a
2a
3a
target compounds 3ag and 3ah, respectively. Reactions of
sodium o- and p-chloro phenylsulfinate proceeded well,
and nearly equal yields were achieved (3ae and 3ai), sug-
gesting that the steric effect of substituents on aromatic
rings is negligible. Gratifyingly, when aliphatic sodium
sulfinates were employed, the sulfonylation reaction
also proceeded smoothly to provide the desired products
(3ak and 3al) with moderate yields (58% and 69%) under
current conditions. The scope of chloroquinoline was also
investigated. To our delight, the current catalytic system
was suitable for a wide range of substituted chloroqui-
nolines. No matter whether the quinoline ring is substi-
tuted with either electron-donating (–CH3 and –OCH3)
or electron-withdrawing substituents (–Cl), all of them
delivered the desired products in moderate-to-good yields
(75–86%). Regrettably, when 2-chloro-6-nitroquinoline
was employed, the desired product 3ba did not form.
2-Chloroquinoline could react smoothly with sodium
phenylsulfinate to obtain the desired product 3aa in 88%
yield. In order to investigate the effect of the position of the
chloro substituent, we explored the phenylsulfonylation
Entryꢁ
Solvent
ꢁ
Temp (°C)ꢁ
Time (min)ꢁ
Yieldb (%)
1
ꢂ
ꢂ
ꢂ
ꢂ
ꢂ
ꢂ
ꢂ
ꢂ
ꢂ
ꢂ
ꢂ
ꢂ
ꢂ
ꢂ
ꢂ
ꢂ
ꢂ
DMSO
CH3CN
1,4-Dioxaneꢂ
CH3OH
DCE
THF
H2O
DMSO
DMSO
DMSO
DMSO
DMSO
DMSO
DMSO
DMSO
DMSO
DMSO
ꢂ
ꢂ
100ꢂ
100ꢂ
100ꢂ
100ꢂ
100ꢂ
100ꢂ
100ꢂ
90ꢂ
110ꢂ
120ꢂ
130ꢂ
120ꢂ
120ꢂ
120ꢂ
120ꢂ
120ꢂ
120ꢂ
20ꢂ
20ꢂ
20ꢂ
20ꢂ
20ꢂ
20ꢂ
20ꢂ
20ꢂ
20ꢂ
20ꢂ
20ꢂ
5ꢂ
10ꢂ
30ꢂ
40ꢂ
30ꢂ
30ꢂ
30
2
21
3
18
4
ꢂ
ꢂ
ꢂ
ꢂ
ꢂ
ꢂ
ꢂ
ꢂ
ꢂ
ꢂ
ꢂ
ꢂ
ꢂ
ꢂ
Trace
15
5
6
12
7
Trace
10
8
9
40
10
11
12
13
14
15
16c
17d
78
58
10
52
88
85
50
70
aReaction conditions: 2-chloroquinoline 1a (0.2 mmol, 32.6 mg),
sodium phenylsulfinate 2a (0.3 mmol, 49.2 mg), solvent (2.0 mL)
under microwave irradiation. bIsolated yield. cThe molar ratio of
1a–2a is 1:1. dThe molar ratio of 1a–2a is 1:2.
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ꢁꢀꢀꢀ
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X.-Y. Li et al.: Synthesis of 2-arylsulfonyl quinoline derivativesꢃ
Table 2:ꢀSynthesis of 2-(arylsulfonyl)quinoline derivatives from substituted 2-chloroquinolines and sodium arylsulfinates.a,b
R2
R1
R1
DMSO
O
S
NaO2S
+
N
N
Cl
MW, 120 o
C
R2
O
1
2
3
O
O
S
O
S
N
S
N
N
O
O
O
O
3aa (88%)
3ab (89%)
3ac (92%)
O
O
O
N
S
N
S
N
S
O
O
O
F
Cl
Br
3ad (73%)
3ae (75%)
3af (78%)
Cl
O
O
O
N
S
N
S
N
S
O
O
O
CN
CF3
3ag (68%)
3ah (70%)
3ai (73%)
O
O
S
N
S
O
S
O
N
O
N
O
O
N
H
3aj (60%)
3ak (58%)
3al (69%)
Cl
O2N
O
S
O
O
S
N
N
S
N
O
O
O
3ba (0%)
3ca (75%)
3da (85%)
O
O
O
O
N
S
N
S
N
S
O
O
O
3ea (86%)
3fa (82%)
3ga (85%)
aReaction conditions: substituted 2-chloroquinoline 1 (0.2 mmol), sodium sulfinates 2 (0.3 mmol), in 2.0 mL DMSO solvent, 120°C for 30 min
under microwave irradiation. bIsolated yields.
of different chloroquinolines under the standard reaction organic synthesis [19, 20]. Recently, an efficient, concise,
conditions (Table 3). Unfortunately, when 3-chloroqui- and transition metal-free synthesis of functionalized sul-
noline and 6-chloroquinoline were employed, the sul- fonylated five-membered heterocyclic compounds via an
fonylation reactions did not occur and no products (3ha SNAr reaction has been developed using commercially
and 3ja) were formed. To our satisfaction, 4,7-dichloro- available sodium sulfinates as sulfonylation reagents [21].
quinoline and 2,6-dichloroquinoline did react smoothly However, synthesis of six-membered heterocyclic sulfones
with sodium phenylsulfinate to provide the products (3ia containing multiple heteroatoms has hardly been studied
and 3ca) in 68% and 75% yields, respectively. These facts [22–25]. Furthermore, the functionalized sulfonylated
showed that the reactivity of 2-chloro and 4-chloroqui- six-membered heterocyclic compounds containing one
nolines was higher than that of 3-chloro, 6-chloro, and and two nitrogen heteroatoms were synthesized in good
7-chloroquinolines.
yields (75–86%) using the standard reaction conditions
The heterocyclic sulfone moiety has been proven to (Table 4).
be useful building block in medicinal chemistry [17, 18]. In
addition, heterocyclic sulfones are useful intermediates in experiments were carried out (Scheme 2). When a radical
To clarify the reaction mechanism, some control
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4ꢀ ꢀX.-Y. Li et al.: Synthesis of 2-arylsulfonyl quinoline derivatives
Table 3:ꢀThe reaction of different chloroquinoline with sodium
O
S
DMSO
MW, 120oC
phenylsulfinate.a,b
NaO2S
+
N
N
Cl
O
O
1a
2a
3aa
DMSO
R
S
R
Cl
NaO2S
+
MW, 120 o
C
O
Yield: 83% (TEMPO, 2.0 eq)
N
N
1
2a
3
Yield: 80% (BHT, 2.0 eq)
Scheme 2:ꢀControl experiments.
O
O
S
O
S
N
O
S
O
O
O
S
O
N
N
Cl
3ia (68%)
2a
3ha (0%)
3ja (0%)
aReaction conditions: substituted chloroquinoline 1 (0.2 mmol),
sodium phenylsulfinates 2a (0.3 mmol, 49.2 mg), in 2.0 mL DMSO
solvent, 120°C for 30 min under microwave irradiation. bIsolated
yields.
O
S
Cl
O
O
S
I
O
N
N
S
N
4a
Cl
O
O
Cl
II
3a
scavenger 2,2,6,6-tetramethylpiperidyl-1-oxyl or butylated
hydroxytoluene was employed in the reaction of 2-chloro-
quinoline and sodium phenylsulfinate, the reaction still
Scheme 3:ꢀProposed reaction mechanism.
proceeded well under the optimal conditions. The product
Table 4:ꢀThe arylsulfonylation of six-membered N-heterocyclic com- 3aa was obtained in 83% and 80% yields, respectively,
pounds from heteroaryl halide with sodium phenylsulfinate.a,b
which suggests that the reaction possibly involves a non-
radical pathway.
O
X
DMSO
X
R
NaO2S
Cl
+
R
S
With the above results and evidence given in the lit-
erature [21–25], an addition-elimination mechanism was
proposed, as is shown in Scheme 3. Initially, sodium phe-
nylsulfinate 2a was transformed into phenysulfonyl anion
I by isomerization. Then the addition of the nucleophilic
anion I to the heteroaromatic electrophile 4a generated
the intermediate II, which was stabilized by resonance
and the electron was dispersed into the phenyl ring.
Finally, the intermediate II formed the desired product 3a
in a further elimination reaction.
MW, 120 o
C
N
N
O
4
2a
5
Cl
O
S
N
O
O
S
N
O
O
N
S
O
O
S
O
5aa (45%)
5'aa (30%)
5ba (78%)
N
O
S
O
O
S
O
S
3 Conclusion
S
O
N
Cl
N
N
O
O
O
In conclusion, an unexpected metal-free catalyzed aryl-
sulfonylation reaction of chloroquinolines has been
developed. This reaction is carried out under mild condi-
tions, which provides an easy pathway for the preparation
of bioactive 2-sulfonyl quinolines with sodium sulfinate as
a sulfonyl precursor. The features such as a wide range of
substrates, and functional group tolerance, short reaction
times, and air-insensitive reaction conditions make the
present method an attractive alternative for the prepara-
tion of 2-sulfonylquinolines. Furthermore, the arylsulfo-
nylation derivatives of six-membered N-heterocycles have
also been synthesized by the reaction of heteroaryl halide
with sodium arylsulfinates.
5ca (47%)
5'ca (28%)
5da (84%)
Cl
N
N
N
O
O
S
N
O
N
O
S
N
S
O
O
S
O
O
5ea (85%)
5fa (48%)
5'fa (28%)
aReaction conditions: six-membered N-heterocyclic compounds 4
(0.2 mmol), sodium phenylsulfinates 2a (0.3 mmol, 49.2 mg), in
2.0 mL DMSO solvent, 120°C for 30 min under microwave irradiation.
bIsolated yields.
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X.-Y. Li et al.: Synthesis of 2-arylsulfonyl quinoline derivativesꢃ
4 Experimental section
4.2.1 2-(Phenylsulfonyl)quinoline (3aa)
Light yellow solid; yield 47.3 mg (88%); m.p. 157–158°C
4.1 General information
1
(EtOAc) [lit. [14]: m.p. 164–165°C]. – H NMR (400 MHz,
CDCl3): δꢀ=ꢀ8.38 (d, JH−Hꢀ=ꢀ8.5 Hz, 1H), 8.22 (d, JH−Hꢀ=ꢀ8.5 Hz,
1H), 8.18 (d, JH−Hꢀ=ꢀ8.6 Hz, 1H), 8.15 (d, JH−Hꢀ=ꢀ8.6 Hz, 2H),
7.88 (d, JH−Hꢀ=ꢀ8.2 Hz, 1H), 7.79 (t, JH−Hꢀ=ꢀ7.2 Hz, 1H), 7.66
(t, JH−Hꢀ=ꢀ7.4 Hz, 1H), 7.61 (t, JH−Hꢀ=ꢀ7.2 Hz, 1H), 7.54 (t,
All substrates were purchased from J & K Scientific Ltd
(Beijing, China), and were used without further purifi-
cation. Column chromatography was performed using
300–400 mesh silica with the indicated solvent system
according to standard techniques. A CEM Discover micro-
wave reactor with an infrared pyrometer and pressure
control system was used. Nuclear magnetic resonance
spectra were recorded on a Bruker Avance 400 MHz
J
H−Hꢀ=ꢀ7.2 Hz, 2H). – 13C NMR (100 MHz, CDCl3): δꢀ=ꢀ158.1,
147.4, 139.1, 138.7 (CH), 133.7 (CH), 131.0 (CH), 130.4 (CH),
129.2 (CH), 129.1 (CH), 129.0 (CH), 128.8, 127.7 (CH), 117.7
(CH). – IR (KBr): νꢀ=ꢀ1587, 1493, 1462, 1317, 1161, 1130, 758,
721, 644 cm−1. – HRMS ((+)-ESI): m/zꢀ=ꢀ270.0583 (calcd.
1
spectrometer. Chemical shifts for H NMR spectra are
+
270.0583 for C15H12NO2S, [Mꢀ+ꢀH] ).
recorded in parts per million with tetramethylsilane as a
standard. Data were reported as follows: chemical shift,
multiplicity (sꢀ=ꢀsinglet, dꢀ=ꢀdoublet, tꢀ=ꢀtriplet, mꢀ=ꢀmulti-
plet, and brꢀ=ꢀbroad), coupling constant in Hz, and inte-
gration. Chemical shifts for 13C NMR spectra were recorded
in parts per million with tetramethylsilane as a standard.
Chemical shifts for 19F NMR spectra were recorded in parts
per million with CF3COOH as an external standard. HRMS
were obtained on a Thermo Scientific LTQ Orbitrap XL
instrument using the electrospray ionization (ESI) tech-
nique. 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 XT4A microscopic apparatus and were
uncorrected.
4.2.2 2-((4-(tert-Butyl)phenyl)sulfonyl)quinoline (3ab)
Light yellow solid; yield 57.8 mg (89%); m.p. 194–195°C
1
(EtOAc) [lit. [14]: m.p. 197–198°C]. – H NMR (400 MHz,
CDCl3): δꢀ=ꢀ8.37 (d, JH−Hꢀ=ꢀ8.5 Hz, 1H), 8.20 (d, JH−Hꢀ=ꢀ8.5 Hz,
2H), 8.06 (d, JH−Hꢀ=ꢀ8.6 Hz, 2H), 7.87 (d, JH−Hꢀ=ꢀ8.2 Hz, 1H),
7.79 (td, JH−Hꢀ=ꢀ7.7 Hz, JH−Hꢀ=ꢀ1.4 Hz, 1H), 7.65 (td, JH−Hꢀ=ꢀ7.5 Hz,
J
H−Hꢀ=ꢀ1.0 Hz, 1H), 7.54 (d, JH−Hꢀ=ꢀ8.6 Hz, 2H), 1.30 (s, 9H). –
13C NMR (100 MHz, CDCl3): δꢀ=ꢀ158.4, 157.7, 147.5, 138.6 (CH),
136.1, 130.9 (CH), 130.4 (CH), 129.1 (CH), 128.9, 128.8 (CH),
127.7 (CH), 126.1 (CH), 117.8 (CH), 35.2, 31.0 (CH3). – IR (KBr):
νꢀ=ꢀ2956, 2854, 1331, 1176, 1074, 764, 640 cm−1. – HRMS
((+)-ESI): m/zꢀ=ꢀ326.1209 (calcd. 326.1209 for C19H20NO2S,
+
[Mꢀ+ꢀH] ).
4.2 General experimental procedure for the
synthesis of 2-arylsulfonyl quinolines
(3) and six-membered N-heterocycles
arylsulfonylated derivatives (5)
4.2.3 2-((4-Methoxyphenyl)sulfonyl)quinoline (3ac)
Whitesolid;yield55.0mg(92%);m.p.133–134°C(EtOAc)[lit.
[14]: m.p. 129–131°C]. – 1H NMR (400 MHz, CDCl3): δꢀ=ꢀ8.35
(d, JH−Hꢀ=ꢀ8.6 Hz, 1H), 8.17 (dd, JH−Hꢀ=ꢀ8.5 Hz, JH−Hꢀ=ꢀ5.9 Hz,
2-Chloroquinoline (substituted quinolines, and N-het- 2H), 8.07 (d, JH−Hꢀ=ꢀ8.9 Hz, 2H), 7.86 (d, JH−Hꢀ=ꢀ7.8 Hz, 1H),
eroaryl halide 4) 1 (0.3 mmol), and sodium sulfinates 7.77 (t, JH−Hꢀ=ꢀ7.6 Hz, 1H), 7.64 (t, JH−Hꢀ=ꢀ7.6 Hz, 1H), 6.99 (d,
2 (0.45 mmol) in 3.0 mL DMSO were added to a 5.0 mL
J
H−Hꢀ=ꢀ8.9 Hz, 2H), 3.84 (s, 3H). – 13C NMR (100 MHz, CDCl3):
microwave reaction tube. The reactant mixture was δꢀ=ꢀ163.9, 158.6, 147.4, 138.7 (CH), 131.2 (CH), 130.9 (CH),
heated at 120°C for 30 min under microwave irradia- 130.4, 130.3 (CH), 129.0 (CH), 128.7, 127.7 (CH), 117.5 (CH),
tion. After completion of the reaction, the solvent was 114.4 (CH), 55.6 (CH3). – IR (KBr): νꢀ=ꢀ3037, 2958, 1566, 1591,
distilled under vacuum. Then, 10 mL ethyl acetate was 1498, 1323, 1265, 1173, 1084, 795, 685 cm−1. – HRMS ((+)-ESI):
+
added to the residuum, and 30 mL saturated sodium m/zꢀ=ꢀ300.0684 (calcd. 300.0689 for C16H14NO3S, [Mꢀ+ꢀH] ).
chloride solution washed three times. The organic phase
was dried over anhydrous NaSO4 and concentrated
under vacuum. The crude product was purified by silica 4.2.4 2-((4-Fluorophenyl)sulfonyl)quinoline (3ad)
gel column chromatography to give the desired products
3 (or 5) using ethyl acetate-petroleum ether (1:10–1:5) as Light yellow solid; yield 41.9 mg (73%); m.p. 117–118°C
1
eluant.
(EtOAc) [lit. [14]: m.p. 120–122°C]. – H NMR (400 MHz,
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ꢀꢀꢀꢁ
6ꢀ ꢀX.-Y. Li et al.: Synthesis of 2-arylsulfonyl quinoline derivatives
CDCl3): δꢀ=ꢀ8.40 (d, JH−Hꢀ=ꢀ8.6 Hz, 1H), 8.22–8.14 (m, 4H), 139.0 (CH), 132.7 (CH), 131.3 (CH), 130.3, 129.8 (CH), 129.6
7.89 (d, JH−Hꢀ=ꢀ8.2 Hz, 2H), 7.80 (td, JH−Hꢀ=ꢀ7.0 Hz, JH−Hꢀ=ꢀ1.2 Hz, (CH), 129.0, 127.8 (CH), 117.5 (CH), 117.2. – IR (KBr): νꢀ=ꢀ2229,
1H), 7.67 (t, JH−Hꢀ=ꢀ7.2 Hz, 1H), 7.22 (t, JH−Hꢀ=ꢀ8.6 Hz, 2H). – 13C 1498, 1323, 1167, 1124, 1063, 829 cm−1. – HRMS ((+)-ESI):
+
NMR (100 MHz, CDCl3): δꢀ=ꢀ165.9 (d, JF−Cꢀ=ꢀ254.8 Hz), 157.9, m/zꢀ=ꢀ295.0538 (calcd. 295.0536 for C16H11N2O2S, [Mꢀ+ꢀH] ).
147.5, 138.8 (CH), 134.9, 132.0 (CH), 131.9 (CH), 131.1 (CH),
130.4 (CH), 129.3 (CH), 128.9, 127.7 (CH), 117.5 (CH), 116.4 (d,
J
F−Cꢀ=ꢀ22.5 Hz, CH). – 19F NMR (376 MHz, CDCl3): δꢀ=ꢀ–103.4. 4.2.8 2-((4-(Trifluoromethyl)phenyl)sulfonyl)quinoline
– IR (KBr): νꢀ=ꢀ1591, 1487, 1333, 1244, 1173, 1130, 1084, 850,
(3ah)
679, 550 cm−1. – HRMS ((+)-ESI): m/zꢀ=ꢀ288.0489 (calcd.
288.0489 for C15H11FNO2S, [Mꢀ+ꢀH] ).
+
White solid; yield 47.2 mg (70%); m.p. 122–123°C (EtOAc)
1
[lit. [14]: m.p. 128–129°C]. – H NMR (400 MHz, CDCl3):
δꢀ=ꢀ8.42 (d, JH−Hꢀ=ꢀ8.6 Hz, 1H), 8.29 (d, JH−Hꢀ=ꢀ8.3 Hz, 2H),
8.24 (d, JH−Hꢀ=ꢀ8.5 Hz, 1H), 8.16 (d, JH−Hꢀ=ꢀ8.6 Hz, 1H), 7.91 (d,
4.2.5 2-((4-Chlorophenyl)sulfonyl)quinoline (3ae)
J
H−Hꢀ=ꢀ8.2 Hz, 1H), 7.84–7.80 (m, 3H), 7.69 (td, JH−Hꢀ=ꢀ8.1 Hz,
Light yellow solid; yield 45.4 mg (75%); m.p. 131–132°C
J
H−Hꢀ=ꢀ1.0 Hz, 1H). – 13C NMR (100 MHz, CDCl3): δꢀ=ꢀ157.4,
1
(EtOAc) [lit. [14]: m.p. 136–137°C]. – H NMR (400 MHz, 147.5, 142.6, 139.0 (CH), 131.3 (CH), 130.3 (CH), 129.7 (CH),
CDCl3): δꢀ=ꢀ8.40 (d, JH−Hꢀ=ꢀ8.5 Hz, 1H), 8.21 (d, JH−Hꢀ=ꢀ8.5 Hz, 129.5 (CH), 128.9, 127.7 (CH), 126.1 (q, JF−Cꢀ=ꢀ3.6 Hz), 117.5
1H), 8.15 (d, JH−Hꢀ=ꢀ8.5 Hz, 1H), 8.08 (dd, JH−Hꢀ=ꢀ6.8 Hz, (CH). 19F NMR (376 MHz, CDCl3): δꢀ=ꢀ–63.2. – IR (KBr):
J
J
J
H−Hꢀ=ꢀ1.9 Hz, 2H), 7.89 (d, JH−Hꢀ=ꢀ8.2 Hz, 1H), 7.80 (td, νꢀ=ꢀ1410, 1323, 1173, 1053, 706, 644 cm−1. – HRMS ((+)-ESI):
+
H−Hꢀ=ꢀ8.4 Hz, JH−Hꢀ=ꢀ1.4 Hz, 1H), 7.67 (td, JH−Hꢀ=ꢀ8.0 Hz, m/zꢀ=ꢀ338.0456 (calcd. 338.0457 for C16H11F3NO2S, [Mꢀ+ꢀH] ).
H−Hꢀ=ꢀ1.1 Hz, 1H), 7.51 (d, JH−Hꢀ=ꢀ6.8 Hz, 2H). – 13C NMR
(100 MHz, CDCl3): δꢀ=ꢀ157.8, 147.5, 140.6, 138.9 (CH), 137.5,
131.2 (CH), 130.6 (CH), 130.3 (CH), 129.4 (CH), 129.3 (CH), 4.2.9 2-((2-Chlorophenyl)sulfonyl)quinoline (3ai)
128.9, 127.7 (CH), 117.5 (CH). – IR (KBr): ν =1581, 1319, 1161,
1134, 1084, 764, 652 cm−1. – HRMS ((+)-ESI): m/zꢀ=ꢀ304.0190 Light yellow solid; yield 44.2 mg (73%); m.p. 165–166°C
+
1
(calcd. 304.0193 for C15H11ClNO2S, [Mꢀ+ꢀH] ).
(EtOAc) [lit. [14]: m.p. 166–167°C]. – H NMR (400 MHz,
CDCl3): δꢀ=ꢀ8.52–8.50 (m, 1H), 8.45 (d, JH−Hꢀ=ꢀ8.6 Hz, 1H),
8.34 (d, JH−Hꢀ=ꢀ8.6 Hz, 1H), 8.05 (d, JH−Hꢀ=ꢀ8.6 Hz, 1H), 7.92
(d, JH−Hꢀ=ꢀ8.5 Hz, 1H), 7.79–7.74 (m, 1H), 7.70–7.66 (m, 1H),
4.2.6 2-((4-Bromophenyl)sulfonyl)quinoline (3af)
13
7.59–7.56 (m, 2H), 7.43–7.40 (m, 1H). – C NMR (100 MHz,
Light yellow solid; yield 53.9 mg (78%); m.p. 141–142°C CDCl3): δꢀ=ꢀ157.4, 147.2, 138.3 (CH), 136.7, 134.9 (CH), 133.1,
1
(EtOAc) [lit. [14]: m.p. 143–145°C]. – H NMR (400 MHz, 132.2 (CH), 131.5 (CH), 130.9 (CH), 130.3 (CH), 129.2 (CH),
CDCl3): δꢀ=ꢀ8.39 (d, JH−Hꢀ=ꢀ8.6 Hz, 1H), 8.20 (d, JH−Hꢀ=ꢀ8.6 Hz, 129.0, 127.8 (CH), 127.2 (CH), 118.4 (CH). – IR (KBr): νꢀ=ꢀ1572,
1H), 8.15 (d, JH−Hꢀ=ꢀ8.6 Hz, 1H), 8.00 (d, JH−Hꢀ=ꢀ8.6 Hz, 2H), 1448, 1309, 1157, 1039, 748, 559 cm−1. – HRMS ((+)-ESI):
+
7.89 (d, JH−Hꢀ=ꢀ8.2 Hz, 1H), 7.80 (td, JH−Hꢀ=ꢀ7.0 Hz, JH−Hꢀ=ꢀ1.4 Hz, m/zꢀ=ꢀ304.0197 (calcd. 304.0193 for C15H11ClNO2S, [Mꢀ+ꢀH] ).
1H), 7.69–7.67 (m, 3H). – 13C NMR (100 MHz, CDCl3): δꢀ=ꢀ157.7,
147.5, 138.9 (CH), 138.0, 132.4 (CH), 131.2 (CH), 130.6 (CH),
130.3 (CH), 129.4, 129.3 (CH), 128.9, 127.7 (CH), 117.5 (CH). 4.2.10 N-(4-(Quinolin-2-ylsulfonyl)phenyl)acetamide
– IR (KBr): νꢀ=ꢀ1566, 1331, 1132, 1003, 742, 646 cm−1. – HRMS
((+)-ESI): m/zꢀ=ꢀ347.9686 (calcd. 347.9688 for C15H11BrNO2S,
(3aj)
+
[Mꢀ+ꢀH] ).
Colorless solid; yield 39.1 mg (60%); m.p. 220–221°C
1
(EtOAc). – H NMR (400 MHz, CDCl3): δꢀ=ꢀ10.45 (s, 1H),
8.72 (d, JH−Hꢀ=ꢀ8.6 Hz, 1H), 8.22 (d, JH−Hꢀ=ꢀ8.6 Hz, 1H), 8.11
(d, JH−Hꢀ=ꢀ8.2 Hz, 1H), 8.06 (d, JH−Hꢀ=ꢀ8.5 Hz, 1H), 7.99 (d,
4.2.7 4-(Quinolin-2-ylsulfonyl)benzonitrile (3ag)
J
H−Hꢀ=ꢀ8.7 Hz, 2H), 7.89–7.82 (m, 3H), 7.75 (t, JH−Hꢀ=ꢀ7.5 Hz, 1H),
13
Light yellow solid; yield 39.9 mg (68%); m.p. 190– 2.07 (s, 3H). – C NMR (100 MHz, CDCl3): δꢀ=ꢀ169.7, 158.5,
1
191°C (EtOAc). – H NMR (400 MHz, CDCl3): δꢀ=ꢀ8.43 146.9, 144.9, 140.3 (CH), 132.1 (CH), 132.0, 130.4 (CH), 129.8
(d, JH−Hꢀ=ꢀ8.5 Hz, 1H), 8.27 (d, JH−Hꢀ=ꢀ8.5 Hz, 2H), 8.23 (CH), 129.7 (CH), 128.9, 128.7 (CH), 119.2 (CH), 117.9 (CH),
(d, JH−Hꢀ=ꢀ8.5 Hz, 1H), 8.13 (d, JH−Hꢀ=ꢀ8.6 Hz, 1H), 7.91 (d, 24.6 (CH3). – IR (KBr): νꢀ=ꢀ3338, 3286, 1699, 1591, 1520,
J
H−Hꢀ=ꢀ8.3 Hz, 1H), 7.84 (d, JH−Hꢀ=ꢀ8.5 Hz, 2H), 7.72–7.68 (m, 1498, 1313, 1171, 1130, 1072, 719 cm−1. – HRMS ((+)-ESI):
+
1H). – 13C NMR (100 MHz, CDCl3): δꢀ=ꢀ157.0, 147.5, 143.2, m/zꢀ=ꢀ327.0795 (calcd. 327.0798 for C17H15N2O3S, [Mꢀ+ꢀH] ).
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ꢁꢀꢀꢀ
X.-Y. Li et al.: Synthesis of 2-arylsulfonyl quinoline derivativesꢃ ꢃ7
4.2.11 2-(Methylsulfonyl)quinoline (3ak)
NMR (100 MHz, CDCl3): δꢀ=ꢀ157.1, 146.3, 138.9, 138.7 (CH),
138.4, 133.6 (CH), 130.9 (CH), 129.4 (CH), 129.0 (CH), 128.9,
Light yellow solid; yield 24.0 mg (58%); m.p. 98–99°C 128.8 (CH), 125.5 (CH), 116.7 (CH), 17.4 (CH3). – IR (KBr):
1
(EtOAc) [lit. [14]: m.p. 100–101°C]. – H NMR (400 MHz, νꢀ=ꢀ3068, 2922, 1493, 1452, 1323, 1167, 1074, 731, 580 cm−1.
CDCl3): δꢀ=ꢀ8.38 (d, JH−Hꢀ=ꢀ8.5 Hz, 1H), 8.14 (d, JH−Hꢀ=ꢀ8.5 Hz, – HRMS ((+)-ESI): m/zꢀ=ꢀ284.0739 (calcd. 284.0740 for
+
1H), 8.06 (d, JH−Hꢀ=ꢀ8.5 Hz, 1H), 7.88 (d, JH−Hꢀ=ꢀ8.2 Hz, 1H), 7.79 C16H14NO2S, [Mꢀ+ꢀH] ).
(t, JH−Hꢀ=ꢀ8.0 Hz, 1H), 7.65 (t, JH−Hꢀ=ꢀ7.7 Hz, 1H), 3.34 (s, 3H).
–
13C NMR (100 MHz, CDCl3): δꢀ=ꢀ157.4, 146.9, 139.0 (CH),
131.3 (CH), 130.0 (CH), 129.3 (CH), 129.1, 127.9 (CH), 116.2
(CH), 39.9 (CH3). – IR (KBr): νꢀ=ꢀ3014, 2931, 1581, 1498, 1304,
1171, 1130, 831, 769 cm−1. – HRMS ((+)-ESI): m/zꢀ=ꢀ208.0431
4.2.15 6-Methoxy-2-(phenylsulfonyl)quinoline (3ea)
White solid; yield 51.4 mg (86%); m.p. 145–146°C (EtOAc)
+
(calcd. 208.0427 for C10H10NO2S, [Mꢀ+ꢀH] ).
1
[lit. [13]: m.p. 147–149°C]. – H NMR (400 MHz, CDCl3):
δꢀ=ꢀ8.22 (d, JH−Hꢀ=ꢀ8.5 Hz, 1H), 8.17–8.11 (m, 3H), 8.06 (d,
J
H−Hꢀ=ꢀ9.3 Hz, 1H), 7.61–7.57 (m, 1H), 7.54–7.51 (m, 2H), 7.42
4.2.12 2-(Ethylsulfonyl)quinoline (3al)
(dd, JH−Hꢀ=ꢀ9.3 Hz, JH−Hꢀ=ꢀ2.8 Hz, 1H), 7.09 (d, JH−Hꢀ=ꢀ2.8 Hz,
13
1H), 3.94 (s, 3H). – C NMR (100 MHz, CDCl3): δꢀ=ꢀ159.8,
Light yellow solid; yield 30.5 mg (69%); m.p. 104–105°C 155.4, 143.7, 139.5, 136.8 (CH), 133.5 (CH), 131.8 (CH), 130.4,
1
(EtOAc) [lit. [14]: m.p. 106–107°C]. – H NMR (400 MHz, 129.0 (CH), 128.9 (CH), 124.3 (CH), 118.3 (CH), 104.6 (CH),
CDCl3): δꢀ=ꢀ8.44 (d, JH−Hꢀ=ꢀ8.5 Hz, 1H), 8.22 (d, JH−Hꢀ=ꢀ8.5 Hz, 55.7 (CH3). – IR (KBr): νꢀ=ꢀ2925, 2844, 1618, 1500, 1321, 1173,
1H), 8.13 (d, JH−Hꢀ=ꢀ8.5 Hz, 1H), 7.94 (d, JH−Hꢀ=ꢀ8.2 Hz, 1H), 7.85 850, 604 cm−1. – HRMS ((+)-ESI): m/zꢀ=ꢀ300.0685 (calcd.
+
(td, JH−Hꢀ=ꢀ6.9 Hz, JH−Hꢀ=ꢀ1.2 Hz, 1H), 7.71 (t, JH−Hꢀ=ꢀ7.1 Hz, 1H), 300.0689 for C16H14NO3S, [Mꢀ+ꢀH] ).
3.59 (q, JH−Hꢀ=ꢀ7.5 Hz, 2H), 1.37 (t, JH−Hꢀ=ꢀ7.5 Hz, 3H). – 13C NMR
(100 MHz, CDCl3): δꢀ=ꢀ156.4, 147.2, 138.8 (CH), 131.2 (CH),
130.1 (CH), 129.2 (CH), 129.1, 127.9 (CH), 117.4, 46.4 (CH2), 6.9
4.2.16 6-Methyl-2-(phenylsulfonyl)quinoline (3fa)
(CH3). – IR (KBr): νꢀ=ꢀ2927, 1581, 1498, 1313, 1149, 1130, 1099,
847, 764, 719 cm−1. – HRMS ((+)-ESI): m/zꢀ=ꢀ222.0585 (calcd.
Yellow solid; yield 46.4 mg (82%); m.p. 149–150°C (EtOAc)
+
222.0583 for C11H12NO2S, [Mꢀ+ꢀH] ).
1
[lit. [13]: m.p. 150–152°C]. – H NMR (400 MHz, CDCl3):
δꢀ=ꢀ8.26 (d, JH−Hꢀ=ꢀ8.5 Hz, 1H), 8.17–8.11 (m, 3H), 8.05 (d,
J
H−Hꢀ=ꢀ8.5 Hz, 1H), 7.61–7.56 (m, 3H), 7.54–7.50 (m, 2H),
13
4.2.13 6-Chloro-2-(phenylsulfonyl)quinoline (3ca)
2.54 (s, 3H). – C NMR (100 MHz, CDCl3): δꢀ=ꢀ157.1, 146.1,
139.7, 139.3, 137.8 (CH), 133.6 (CH), 133.4 (CH), 130.0 (CH),
Light yellow solid; yield 45.4 mg (75%); m.p. 161–162°C 129.0 (CH), 128.9 (CH), 126.4 (CH), 117.8 (CH), 21.8 (CH3).
1
(EtOAc) [lit. [14]: m.p. 165–166°C]. – H NMR (400 MHz, – IR (KBr): νꢀ=ꢀ2916, 2844, 1454, 1321, 1167, 1070, 600 cm−1.
CDCl3): δꢀ=ꢀ8.30 (d, JH−Hꢀ=ꢀ8.6 Hz, 1H), 8.23 (d, JH−Hꢀ=ꢀ8.6 Hz, – HRMS ((+)-ESI): m/zꢀ=ꢀ284.0733 (calcd. 284.0740 for
+
1H), 8.14–8.08 (m, 3H), 7.86 (d, JH−Hꢀ=ꢀ2.2 Hz, 1H), 7.71 (dd, C16H14NO2S, [Mꢀ+ꢀH] ).
J
H−Hꢀ=ꢀ8.9 Hz, JH−Hꢀ=ꢀ2.2 Hz, 1H), 7.62 (t, JH−Hꢀ=ꢀ7.3 Hz, 1H), 7.55
(t, JH−Hꢀ=ꢀ7.8 Hz, 2H). – 13C NMR (100 MHz, CDCl3): δꢀ=ꢀ158.4,
145.8, 138.8, 137.8 (CH), 136.2, 135.3, 133.8 (CH), 132.1 (CH), 4.2.17 4-Methyl-2-(phenylsulfonyl)quinoline (3ga)
131.9 (CH), 129.2 (CH), 129.1 (CH), 126.4, 118.7 (CH). – IR
(KBr): νꢀ=ꢀ1493, 1437, 1327, 1161, 1136, 727, 679, 586 cm−1. – Light yellow solid; yield 48.1 mg (85%); m.p. 146–147°C
1
HRMS ((+)-ESI): m/zꢀ=ꢀ304.0195 (calcd. 304.0194 for (EtOAc) [lit. [13]: m.p. 145–146°C]. – H NMR (400 MHz,
+
C15H11ClNO2S, [Mꢀ+ꢀH] ).
CDCl3): δꢀ=ꢀ8.16–8.12 (m, 3H), 8.04 (s, 1H), 7.99 (d,
H−Hꢀ=ꢀ8.4 Hz, 1H), 7.74 (td, JH−Hꢀ=ꢀ6.9 Hz, JH−Hꢀ=ꢀ1.2 Hz, 1H),
J
7.64 (td, JH−Hꢀ=ꢀ8.2 Hz, JH−Hꢀ=ꢀ1.2 Hz, 1H), 7.60–7.56 (m, 1H),
7.51 (t, JH−Hꢀ=ꢀ7.0 Hz, 2H), 2.77 (s, 3H). – 13C NMR (100 MHz,
CDCl3): δꢀ=ꢀ157.7, 148.0, 147.2, 139.2, 133.6 (CH), 131.0 (CH),
4.2.14 8-Methyl-2-(phenylsulfonyl)quinoline (3da)
Light yellow solid; yield 48.1 mg (85%); m.p. 105–106°C 130.5 (CH), 129.0 (CH), 128.9 (CH), 128.7, 123.8 (CH), 118.1
1
(EtOAc) [lit. [13]: m.p. 106–107°C]. – H NMR (400 MHz, (CH), 19.1 (CH3). – IR (KBr): νꢀ=ꢀ3072, 2922, 1570, 1437, 1321,
CDCl3): δꢀ=ꢀ8.33 (d, JH−Hꢀ=ꢀ8.5 Hz, 1H), 8.22–8.17 (m, 3H), 7.69 1161, 729, 621 cm−1. – HRMS ((+)-ESI): m/zꢀ=ꢀ284.0739
13
+
(d, JH−Hꢀ=ꢀ8.1 Hz, 1H), 7.63–7.50 (m, 5H), 2.65 (s, 3H). – C (calcd. 284.0740 for C16H14NO2S, [Mꢀ+ꢀH] ).
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ꢀꢀꢀꢁ
8ꢀ ꢀX.-Y. Li et al.: Synthesis of 2-arylsulfonyl quinoline derivatives
4.2.18 7-Chloro-4-(phenylsulfonyl)quinoline (3ia)
4.2.22 2-Chloro-6-(phenylsulfonyl)pyridine (5ca) [9]
Colorlesssolid;yield41.2mg(68%);m.p.170–171°C(EtOAc). Colorlesssolid;yield23.7mg(47%);m.p.131–132°C(EtOAc).
1
– 1H NMR (400 MHz, DMSO): δꢀ=ꢀ9.24 (d, JH−Hꢀ=ꢀ4.4 Hz, 1H), – H NMR (400 MHz, CDCl3): δꢀ=ꢀ8.11 (d, JH−Hꢀ=ꢀ7.6 Hz,
8.57 (d, JH−Hꢀ=ꢀ9.2 Hz, 1H), 8.26 (d, JH−Hꢀ=ꢀ4.5 Hz, 1H), 8.23 1H), 8.07 (d, JH−Hꢀ=ꢀ8.0 Hz, 2H), 7.88 (t, JH−Hꢀ=ꢀ7.8 Hz, 1H),
(d, JH−Hꢀ=ꢀ2.2 Hz, 1H), 8.06 (d, JH−Hꢀ=ꢀ8.8 Hz, 2H), 7.80 (dd, 7.64 (t, JH−Hꢀ=ꢀ7.1 Hz, 1H), 7.55 (t, JH−Hꢀ=ꢀ7.7 Hz, 2H), 7.47 (d,
13
J
H−Hꢀ=ꢀ9.2 Hz, JH−Hꢀ=ꢀ2.2 Hz, 1H), 7.73 (t, JH−Hꢀ=ꢀ7.4 Hz, 1H), 7.64
J
H−Hꢀ=ꢀ8.0 Hz, 2H). – C NMR (100 MHz, CDCl3): δꢀ=ꢀ158.7,
(t, JH−Hꢀ=ꢀ7.3 Hz, 2H). – 13C NMR (100 MHz, DMSO): δꢀ=ꢀ157.3 152.3, 140.4 (CH), 138.2, 134.1 (CH), 129.2 (CH), 129.1 (CH),
(CH), 154.2, 149.2, 144.4, 140.5, 139.8 (CH), 135.2 (CH), 134.9 128.1 (CH), 120.6 (CH). – IR (KBr): νꢀ=ꢀ1582, 1447, 1395, 1307,
(CH), 134.1 (CH), 132.9 (CH), 130.8 (CH), 127.3 (CH), 124.8. 1151, 1126, 1082 cm−1. – HRMS ((+)-ESI): m/zꢀ=ꢀ254.0039
– IR (KBr): νꢀ=ꢀ1485, 1433, 1315, 1151, 870 cm−1. – HRMS ((+)- (calcd. 254.0037 for C11H9ClNO2S, [Mꢀ+ꢀH] ).
+
ESI): m/zꢀ=ꢀ304.0189 (calcd. 304.0194 for C15H11ClNO2S,
[Mꢀ+ꢀH] ).
+
4.2.23 2,6-Bis(phenylsulfonyl)pyridine (5′ca)
4.2.19 4-Chloro-2-(phenylsulfonyl)pyridine (5aa)
Colorless solid; yield 20.1 mg (28%); m.p. 178–179°C
(EtOAc) [lit. [26] m.p. 178.1–180.4°C]. – 1H NMR (400 MHz,
Colorless solid; yield 22.7 mg (45%); m.p. 102–103°C
CDCl3): δꢀ=ꢀ8.29 (d, JH−Hꢀ=ꢀ7.9 Hz, 2H), 8.16 (d, JH−Hꢀ=ꢀ7.6 Hz,
(EtOAc). – 1H NMR (400 MHz, CDCl3): δꢀ=ꢀ8.60 (d,
1H), 7.91 (d, JH−Hꢀ=ꢀ8.1 Hz, 4H), 7.64 (t, JH−Hꢀ=ꢀ7.2 Hz, 2H), 7.49
J
H−Hꢀ=ꢀ5.1 Hz, 1H), 7.98 (d, JH−Hꢀ=ꢀ7.9 Hz, 2H), 7.82 (s, 1H),
(t, JH−Hꢀ=ꢀ7.7 Hz, 4H). – 13C NMR (100 MHz, CDCl3): δꢀ=ꢀ159.5,
140.5 (CH), 137.4, 134.2 (CH), 129.4 (CH), 129.0 (CH), 124.1
(CH). – IR (KBr): νꢀ=ꢀ1534, 1452, 1427, 1325, 1137, 1075 cm−1.
– HRMS ((+)-ESI): m/zꢀ=ꢀ360.0357 (calcd. 360.0359 for
7.70 (t, JH−Hꢀ=ꢀ5.1 Hz, 1H), 7.66 (d, JH−Hꢀ=ꢀ7.6 Hz, 1H), 7.58 (t,
J
H−Hꢀ=ꢀ7.6 Hz, 2H). – 13C NMR (100 MHz, CDCl3): δꢀ=ꢀ152.8,
152.4, 151.2 (CH), 138.9, 134.5 (CH), 129.8 (CH), 128.2 (CH),
121.7 (CH), 119.5 (CH). – IR (KBr): νꢀ=ꢀ1534, 1458, 1423, 1305,
1152, 879 cm−1. – HRMS ((+)-ESI): m/zꢀ=ꢀ254.0038 (calcd.
+
C17H14NO4S2, [Mꢀ+ꢀH] ).
+
254.0037 for C11H9ClNO2S, [Mꢀ+ꢀH] ).
4.2.24 5-Ethyl-2-(phenylsulfonyl)pyrimidine (5da)
4.2.20 2,4-Bis(phenylsulfonyl)pyridine (5′aa)
Colorless liquid; yield 41.6 mg (84%); – 1H NMR (400 MHz,
Colorless solid; yield 21.5 mg (30%); m.p. 107–108°C CDCl3): δꢀ=ꢀ8.66 (s, 2H), 8.23 (d, JH−Hꢀ=ꢀ4.9 Hz, 1H), 8.06–
(EtOAc). – 1H NMR (400 MHz, CDCl3): δꢀ=ꢀ8.85 (d, 8.04 (m, 2H), 7.62–7.58 (m, 1H), 7.52–7.48 (m, 2H), 2.67
13
J
H−Hꢀ=ꢀ4.9 Hz, 1H), 8.61 (s, 1H), 8.05 (d, JH−Hꢀ=ꢀ8.0 Hz, 2H), (q, JH−Hꢀ=ꢀ7.6 Hz, 2H), 1.22 (t, JH−Hꢀ=ꢀ7.6 Hz, 3H). – C NMR
7.99 (d, JH−Hꢀ=ꢀ8.0 Hz, 2H), 7.94 (d, JH−Hꢀ=ꢀ4.9 Hz, 1H), 7.68–7.55 (100 MHz, CDCl3): δꢀ=ꢀ164.4, 157.9 (CH), 139.5, 137.8, 134.2
(m, 6H). – 13C NMR (100 MHz, CDCl3): δꢀ=ꢀ160.7, 152.5, 152.0 (CH), 129.3 (CH), 129.1 (CH), 23.5 (CH2), 14.5 (CH3). – IR
(CH), 138.6, 137.7, 134.8 (CH), 134.4 (CH), 130.0 (CH), 129.3 (KBr): νꢀ=ꢀ2974, 1937, 1556, 1396, 1325, 1134, 1078, 729 cm−1.
(CH), 129.2 (CH), 128.4 (CH), 123.9 (CH), 119.2 (CH). – IR – HRMS ((+)-ESI): m/zꢀ=ꢀ249.0690 (calcd. 249.0692 for
+
(KBr): νꢀ=ꢀ1526, 1450, 1417, 1321, 1143 cm−1. – HRMS ((+)-ESI): C12H13N2O2S, [Mꢀ+ꢀH] ).
+
m/zꢀ=ꢀ360.0362 (calcd. 360.0359 for C17H14NO4S2, [Mꢀ+ꢀH] ).
4.2.25 2-(Phenylsulfonyl)pyrimidine (5ea)
4.2.21 4-(Phenylsulfonyl)pyridine (5ba)
Light yellow solid; yield 37.4 mg (85%); m.p. 117–118°C
1
Colorlesssolid;yield34.1mg(78%);m.p.128–129°C(EtOAc). (EtOAc) [lit. [27]: m.p. 118–119°C]. – H NMR (400 MHz,
1
– H NMR (400 MHz, CDCl): δꢀ=ꢀ8.84 (d, JH−Hꢀ=ꢀ5.7 Hz, 2H), CDCl3): δꢀ=ꢀ8.82 (d, JH−Hꢀ=ꢀ4.9 Hz, 2H), 8.02 (dd, JH−Hꢀ=ꢀ7.8 Hz,
8.01 (d, JH−Hꢀ=ꢀ7.5 Hz, 2H), 7.82 (d, JH−Hꢀ=ꢀ5.8 Hz, 2H), 7.63
J
H−Hꢀ=ꢀ1.4 Hz, 2H), 7.59 (t, JH−Hꢀ=ꢀ7.4 Hz, 1H), 7.50–7.45 (m, 3H).
13
(t, JH−Hꢀ=ꢀ7.4 Hz, 1H), 7.55 (t, JH−Hꢀ=ꢀ7.7 Hz, 3H). – 13C NMR – C NMR (100 MHz, CDCl3): δꢀ=ꢀ166.5, 158.8 (CH), 137.4,
(100 MHz, CDCl3): δꢀ=ꢀ151.2 (CH), 149.6, 139.5, 134.2 (CH), 134.4 (CH), 129.4 (CH), 129.2 (CH), 123.5 (CH). – IR (KBr):
129.6 (CH), 128.0 (CH), 120.5 (CH). – IR (KBr): νꢀ=ꢀ1553, 1437, νꢀ=ꢀ1576, 1446, 1385, 1317, 1203, 1146, 1084, 715, 602 cm−1.
1420, 1322, 1134 cm−1. – HRMS ((+)-ESI): m/zꢀ=ꢀ220.0430 – HRMS ((+)-ESI): m/zꢀ=ꢀ221.0381 (calcd. 221.0379 for
+
+
(calcd. 220.0427 for C11H10NO2S, [Mꢀ+ꢀH] ).
C10H9N2O2S, [Mꢀ+ꢀH] ).
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ꢁꢀꢀꢀ
X.-Y. Li et al.: Synthesis of 2-arylsulfonyl quinoline derivativesꢃ ꢃ9
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4.2.26 4-Chloro-2-(phenylsulfonyl)pyrimidine (5fa)
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White solid; yield 24.3 mg (48%); m.p. 115–116°C (EtOAc). –
1H NMR (400 MHz, CDCl3): δꢀ=ꢀ8.95 (d, JH−Hꢀ=ꢀ4.9 Hz, 1H), 8.08–
13
8.05 (m, 3H), 7.74–7.70 (m, 1H), 7.63–7.59 (m, 2H). – C NMR
(100 MHz, CDCl3): δꢀ=ꢀ168.8, 162.7 (CH), 162.1, 136.4, 135.0
(CH), 129.6 (CH), 129.5 (CH), 116.1 (CH). – IR (KBr): νꢀ=ꢀ1545,
1452, 1333, 1182, 1084, 727, 679 cm−1. – HRMS ((+)-ESI):
+
m/zꢀ=ꢀ254.9992 (calcd. 254.9990 for C10H8ClN2O2S, [Mꢀ+ꢀH] ).
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4.2.27 2,4-Bis(phenylsulfonyl)pyrimidine (5′fa)
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51, 12111.
Light yellow solid; yield 20.1 mg (28%); m.p. 107–108°C
(EtOAc). – 1H NMR (400 MHz, CDCl3): δꢀ=ꢀ9.24 (d,
J
J
J
H−Hꢀ=ꢀ4.9 Hz, 1H), 8.23 (d, JH−Hꢀ=ꢀ4.9 Hz, 1H), 7.96 (dd,
H−Hꢀ=ꢀ8.2 Hz, JH−Hꢀ=ꢀ0.9 Hz, 2H), 7.89 (dd, JH−Hꢀ=ꢀ8.2 Hz,
H−Hꢀ=ꢀ0.9 Hz, 2H), 7.73–7.66 (m, 2H), 7.56–7.53 (m, 4H). – 13C
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NMR (100 MHz, CDCl3): δꢀ=ꢀ167.9, 167.0, 162.4 (CH), 136.2,
135.7, 135.1 (CH), 134.7 (CH), 129.8 (CH), 129.7 (CH), 129.4
(CH), 129.2 (CH), 119.3 (CH). – IR (KBr): νꢀ=ꢀ1554, 1535, 1323,
1157, 1090, 727, 685 cm−1. – HRMS ((+)-ESI): m/zꢀ=ꢀ361.0315
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+
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Org. Chem. 2017, 2017, 1025.
(calcd. 361.0311 for C16H13N2O4S2, [Mꢀ+ꢀH] ).
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5 Supplementary information
The NMR spectra of 3aa–3ia, 5aa–5′fa are given as Sup-
plementary Information available online (https://doi.
org/10.1515/znb-2018-0007).
Acknowledgments: We gratefully acknowledge the Depart-
ment of Henan Province Natural Science and Technology
Foundation (No. 172102210225), Natural Science Founda-
tion in Henan Province Department of Education (No.
17A150005), the Program for Innovative Research Team
from Zhengzhou (No. 131PCXTD605), and the Project of
Youth Backbone Teachers of Henan University of Techno-
logy (2016).
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Supplemental Material: The online version of this article offers
supplementary ma(https://doi.org/10.1515/znb-2018-0007).
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Z. Naturforsch.ꢃ
ꢃ2018 | Volume x | Issue x(b)
Graphical synopsis
Xi-Yong Li, Ya-Min Sun and Jin-Wei Yuan
Metal-free catalyzed arylsulfonylation
of chloroquinoline with sodium
arylsulfinates under microwave irradiation
https://doi.org/10.1515/znb-2018-0007
Z. Naturforsch. 2018; x(x)b: xxx–xxx
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