L-Proline catalyzed condensation-cyclization tandem process: Facile and effective synthesis of 3-polyfluoroalkanesulfonyl coumarin

Article abstract of DOI:10.1016/j.jfluchem.2011.04.001

A l-proline catalyzed condensation-cyclization tandem process is reported, which affords the potentially pharmaceutic coumarin derivatives. The mild conditions, simplicity of the purification process and satisfactory yields makes the method a facile and e

Full text of DOI:10.1016/j.jfluchem.2011.04.001

Journal of Fluorine Chemistry 132 (2011) 409–413
Contents lists available at ScienceDirect
Journal of Fluorine Chemistry
journal homepage: www.elsevier.com/locate/fluor
L-Proline catalyzed condensation–cyclization tandem process:
Facile and effective synthesis of 3-polyfluoroalkanesulfonyl coumarin
*
Jianwei Han, Yong Xin, Jingwei Zhao, Shizheng Zhu
Key Laboratory of Organouorine Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, 345 Lingling Road, Shanghai 200032, PR China
A R T I C L E I N F O
A B S T R A C T
Article history:
A
L-proline catalyzed condensation–cyclization tandem process is reported, which affords the
Received 26 February 2011
Received in revised form 6 April 2011
Accepted 8 April 2011
potentially pharmaceutic coumarin derivatives. The mild conditions, simplicity of the purification
process and satisfactory yields makes the method
polyfluoroalkanesulfonyl coumarins.
a
facile and effective way toward the 3-
Available online 15 April 2011
ß 2011 Elsevier B.V. All rights reserved.
Keywords:
Salicylaldehyde
Condensation
Cyclization
Polyfluoroalkanesulfonyl
Coumarin
1. Introduction
in the presence of L-proline. So it would be meaningful if the
reaction could go further to afford the coumarin derivatives when
reacted with salicylaldehyde.
Coumarin and its derivatives represent one of the most active
classes of compound possessing a wide spectrum of biological
activity [1–3]. Novobiocin and chlorobiocin are established
antimicrobials containing a coumarin skeleton [4]. Many of these
compounds have proved to be active as, antibacterial [5–7],
antifungal [8], anti inflammatory [9], anticoagulant [10], anti-HIV
[11] and antitumor [12]. In addition, these compounds are used as
additives to food and cosmetics [13]. Coumarin derivatives are
commonly used as optical whiteners, luminescence dyes [14],
active media for lasers [15] and solar collector [16]. Various
analogues of 4-substituted coumarin such as 4-chlorocoumarins
exhibit antimicrobial activity. Thus, the synthesis of coumarin
derivatives is still a popular research topic in organic chemistry. To
the best of our knowledge, traditionally, these compounds are
achieved by Perkin reaction, Knoevenagel reaction, Pechmann
reaction, Michael reaction, Wittig reaction, Vilsmeier–Haack
reaction, and Pd-catalyzed reactions. Among them, the Knoeve-
nagel reaction represents one class of the mostly used methods,
which is usually catalyzed by base or acid, such as pyridine,
pyperidine, amine, acid and so on. During our research on the
chemical transformation of fluorine-containing active methylene
compounds, we found that they could react with aromatic
aldehydes readily to give the Knoevenagel condensation products
Herein, we reported the detailed results of the reaction.
2. Results and discussion
Initially, we found that the Knoevenagel condensation between
2-((perfluorobutyl)sulfonyl) acetonitrile 1c and benzaldehyde 2a
did not occur without any catalyst. After addition of 5 mol% of L-
proline, the reaction could give the condensation product 3a in a
yield of 78%. Increasing the loading of catalyst improved the yield
and shortened the reaction time (Table 1, entries 2–5). The yield
began to decrease when the amount of L-proline was more than
25 mol%. Thus, the amount of the catalyst was optimized as
20 mol% (Table 1).
With the optimized condition in hand, we examined the scope
of the fluorine-containing active methylene compounds. To our
delight, they worked very well and gave the desired products in
good yields (Table 2).
It was indicated in the results that the aromatic aldehyde
with an electron-withdrawing group gave a lower yield than
that with an electron-donating group. For instance, 3-nitro-
benzaldehyde led to a yield of 73% (Table 2, entry 6), but p-
anisaldehyde and 4-dimethylaminobenzaldehyde gave the
products in yields of 89% (Table 2, entry 3) and 85% (Table 2,
entry 10), respectively. Also, due to the electronic effect, 3-
indolealdehyde 2h afforded the product 3h in a yield of 88%
(Table 2, entry 8).
* Corresponding author. Tel.: +86 21 54925185; fax: +86 21 64166128.
E-mail addresses: zhusz@sioc.ac.cn, zhusz@mail.sioc.ac.cn (S. Zhu).
0022-1139/$ – see front matter ß 2011 Elsevier B.V. All rights reserved.
doi:10.1016/j.jfluchem.2011.04.001

410
J. Han et al. / Journal of Fluorine Chemistry 132 (2011) 409–413
Table 1
Encouraged by those results, we examined the reaction
Effect of the amount of
L
-proline.
between methyl 2-((perfluorobutyl)sulfonyl)acetate 1a and sali-
cylaldehyde 4a under the same condition (Table 3). After stirring
for 16 h, the reaction gave a product cleanly in a yield of 86%.
According to the data of 1H NMR spectrum, the disappearance of
the peaks of CHO at 10.3 ppm indicated the Knoevenagel
condensation proceeded successfully. Mass spectrum showed a
molecular ion peak at m/z = 430 that indicated the formation of
coumarin product. Other spectra data, such as elemental analysis
and FT-IR, further suggested the formation of coumarin. Then we
examine both the scopes of active methylene compounds and
salicylaldehydes. It could be inferred that the fluoroalkylsulfonyl
substituents of 1 had little influence on the yield. To our delight,
not only 1a and 1b, but also the CN substituted substrate 1c could
react smoothly. However, due to the weak electron-withdrawing
property, the reaction of 1c with salicylaldehydes consumed more
time and the yield was lower.
C4F9O2S
CN
CHO
L-proline (x mol%)
EtOH, R.T.
C4F9SO2CH2CN
1c
2a
3a
Entry
x
Time (h)
Yielda (%)
b
1
2
3
4
5
6
7
8
0
5
48
30
30
18
16
15
15
15
Trace
78
80
81
86
86
85
83
10
15
20
25
30
40
a
Isolated yield after recrystallization.
Determined by TLC analysis.
The proline catalyzed aldol reactions proceeded via an enamine
intermediate A. A reacted with salicylaldehyde via transition state
b
B
to give intermediate C. The following dehydration and
intramolecular transesterification gave the coumarin product
(Scheme 1).
Table 2
Results of the Knoevenagel condensation.
C4F9O2S
CN
Ar
3. Conclusion
L-proline (20mol%)
EtOH, R.T.
ArCHO
C4F9SO2CH2CN
In summary, L-proline has been employed as an efficient
2
catalyst for the preparation of 3-polyfluoroalkanesulfonyl couma-
rin. The reaction proceeded via a condensation–cyclization tandem
process under mild conditions and gave the coumarin products in
good yields. The reaction was proposed to proceed via an enamine
intermediate. The simple and convenient purification procedure
made the method a facile and effective way toward the 3-
polyfluoroalkanesulfonyl coumarins.
1c
3
Entry
ArCHO
Time (h)
Product
Yield (%)a
1
2
C6H5 (2a)
16
13
14
13
13
10
13
14
12
14
3a
3b
3c
3d
3e
3f
76
87
89
83
86
73
85
88
82
85
p-CH3C6H4 (2b)
p-CH3OC6H4 (2c)
o-BrC6H4 (2d)
C6H5CH5CH (2e)
p-NO2C6H4 (2f)
p-BrC6H4 (2g)
3
4
5
6
4. Experimental
7
3g
3h
3i
8
3-Indole (2h)
4.1. General information
9
o-FC6H4 (2i)
10
p-(CH3)2NC6H4 (2j)
3j
a
Melting points were measured on a Temp-Melt apparatus and
are uncorrected. 1H and 19F NMR spectra were recorded on Bruker
AM-300 instruments with Me4Si and CFCl3 as the internal
Isolated yield after recrystallization.
Table 3
Results of the reactions between 1 and 4.
L-Proline
SO2Rf
CHO
OH
(20mmol%)
X
X
RfSO2CH2Y
+
EtOH, R.T.
O
O
Y=COOMe,Rf=C4F9(1a);
1b
Rf= ClC4F8( );
Y=CN, Rf=C4F9(1c).
5
1
4
Entry
1
X
Time (h)
Product
Yield (%)a
1
2
H (4a)
16
15
18
18
18
16
17
18
18
20
20
20
5a
5b
5c
5d
5e
5f
76
74
73
75
72
74
76
73
72
58
54
57
5-Br (4b)
5-Cl (4c)
4-OMe (4d)
3,5-2Cl (4e)
H (4a)
3
1a
4
5
6
7
1b
1c
5-Br (4b)
5-Cl (4c)
4-OMe (4d)
H (4a)
5g
5h
5i
8
9
10
11
12
5a
5b
5c
5-Br (4b)
5-Cl (4c)
a
Isolated yield after recrystallization.

J. Han et al. / Journal of Fluorine Chemistry 132 (2011) 409–413
411
CHO
HN
O
O
RfO2S
Ar
RfO2S
OH
N
HO -H2O
N
OMe
RfO2S
O
O
OMe
O
OMe
OH
O
H
B
A
OH
RfO2S
SO2Rf
OMe
SO2Rf
OMe
+H2O
N
-H2O
COO
OH OMe
O
H
O
OH
O
O
C
H
-MeOH
SO2Rf
O
O
Scheme 1. The proposed mechanism of the reaction of 2-((polyfluoroalkyl)sulfonyl)acetate and salicylaldehyde.
standards and external standards, respectively. FTIR spectra were
obtained with a Nicolet AV-360 spectrophotometer. Low resolu-
tion mass spectra (LRMS) were obtained on a Finnigan GC–MS
4021, using the electron impact ionization technique (70 eV). The
reaction mixture was directly recrystallized to afford the product
3a.
4.3.1. (E)-2-(perfluorobutylsulfonyl)-3-(p-methylphenyl)-
L-proline was commercially available and used without any
acrylonitrile (3b)
activation. The products 1a, 1c, 3a, 3c, 3d, 3f, 5a obtained were
characterized by comparison of their spectroscopic data with those
reported in the literature [16–18].
Light yellow solid, mp 102–103 8C. 1H NMR (300 MHz, CDCl3):
d
8.22 (s, 1H), 7.26–7.01 (m, 4H), 2.51 (s, 3H). 19F NMR (282 MHz,
CDCl3):
d
À80.6 (m, 3F, CF3), À109.6 (m, 2F, CF2–SO2), À120.7 (m,
2F, CF2CF2–SO2), À125.8 (m, 2F, CF2CF3). IR (KBr) cmÀ1: 3040, 2224,
1583, 1420, 1371, 1302, 1117, 1041, 980, 947, 816, 737, 648. MS
(70 eV, EI) m/z (%): 425 (M+, 18), 206 (89), 142 (100), 115 (62), 69
(21). Anal. Calcd. for C14H8F9NO2S: C 39.54, H 1.90, N 3.29; Found:
C 39.46, H 1.89, N 3.37.
4.2. General experimental procedures for the synthesis of 1a and 1b
A solution of 1,1,1,2,2,3,3,4,4-nonafluoro-4-(methylsulfonyl)-
butane (10 mmol, 2.98 g) in anhydrous THF (15 ml) was added
dropwise to the anhydrous THF (35 ml) containing NaH (60% in
mineral oil, 22 mmol, 0.8 g) at 0 8C under N2 atmosphere. After
30 min a solution of methyl chloroformate (10 mmol, 0.95 g) in
anhydrous THF (15 ml) was added dropwise at À15 8C the
resulting mixture was warmed to room temperature and after
2 h was hydrolyzed at 0 8C by addition of saturated NH4Cl. The
aqueous layer was extracted with ether. The combined organic
layers were washed with brine, dried with Na2SO4, and evaporated
under reduced pressure. The crude product was purified by flash
chromatography over silica gel.
4.3.2. (2E,4E)-2-(perfluorobutylsulfonyl)-3-(1,3-butadienyl-phenyl)-
acrylonitrile (3e)
Yellow solid, mp 93–94 8C. 1H NMR (300 MHz, CDCl3):
d
7.99–
8.03 (d, 1H), 7.40–7.62 (m, 6H), 7.18–7.24 (m, 1H). 19F NMR
(282 MHz, CDCl3):
d
À80.6 (m, 3F, CF3), À110.2 (2F, m, CF2–SO2),
À120.7 (m, 2F, CF2CF2–SO2), À125.8 (m, 2F, CF2CF3). IR (KBr) cmÀ1
:
3027, 2223, 1607, 1578, 1554, 1376, 1354, 1234, 1140, 999, 752,
683, 619. MS (70 eV, EI) m/z (%): 437 (M+, 22.6), 218 (28.8), 154
(62.9), 137 (100.0). Anal. Calcd. for C15H8F9NO2S: C 41.20, H 1.84, N
3.20; Found: C 41.15, H 1.93, N 3.29.
2-((perfluorobutyl)sulfonyl)acetonitrile 1c was prepared fol-
lowing the Subramanian’s procedure [18].
4.3.3. (E)-2-(perfluorobutylsulfonyl)-3-(p-bromophenyl)-
4.2.1. Methyl (4-chloro-1,1,2,2,3,3,4,4-octafluorobutyl-1-sulfonyl)-
acrylonitrile (3g)
acetate (1b)
Light yellow solid, mp 102–103 8C. 1H NMR (300 MHz, CDCl3):
d
Colorless oil. Yield: 79%. 1H NMR (300 MHz, CDCl3):
d
4.31 (s,
8.23 (s, 1H), 7.77–7.98 (m, 4H). 19F NMR (282 MHz, CDCl3):
d
À80.5
2H, CH2), 3.92 (s, 3H, CH3). 19F NMR (282 MHz, CDCl3):
d
À67.8 (m,
(m, 3F, CF3), À109.6 (m, 2F, CF2–SO2), À120.6 (m, 2F, CF2CF2–SO2),
À125.7 (m, 2F, CF2CF3). IR (KBr) cmÀ1: 2223, 1609, 1582, 1578,
1488, 1456, 1369, 1360, 1209, 1140, 1056, 956. MS (70 eV, EI) m/z
(%): 489 (M+), 272 (41), 270 (40), 208 (40), 206 (42), 127 (100), 69
(22). Anal. Calcd. for C13H5BrF9NO2S: C 31.86, H 1.03, N 2.86;
Found: C 31.87, H 1.07, N 2.90.
2F, CF2Cl), À109.1 (m, 2F, CF2–SO2), À119.2 to À120.5 (m, 4F,
CF2CF2). IR (film) cmÀ1: 3013, 2963, 1757, 1440, 1383, 1288, 1204,
1144, 1082, 961, 696. MS (70 eV, EI) m/z (%): 341 (M+ÀOMe, 18),
235 (6), 137 (33). Anal. Calcd. for C7H5F8ClO3S (%): C 22.55, H 1.34;
Found: C 22.66, H 1.70.
4.3. General experimental procedures for the synthesis of 2-aryl-
(perfluorobutylsulfonyl l)-acrylonitriles
4.3.4. (E)-2-(perfluorobutylsulfonyl)-3-indole-acrylonitrile (3h)
Yellow solid, mp 196–197 8C. 1H NMR (300 MHz, CDCl3):
d
9.66
(br. s, 1H), 8.81 (s, 1H), 8.53 (s, 1H), 7.41–7.81 (m, 4H). 19F NMR
To a solution of (nonafluorobutanesulfonyl) acetonitrile 1c
(2 mol, 646 mg) and benzaldehyde 2a (2 mol, 212 mg) in EtOH
(282 MHz, CDCl3):
d
À80.6 (m, 3F, CF3), À110.6 (m, 2F, CF2–SO2),
À120.7 (m, 2F, CF2CF2–SO2), À125.8 (m, 2F, CF2CF3). IR (KBr) cmÀ1
:
(8 ml) was added
L-proline (0.4 mmol, 46 mg) and the solution was
3387, 2220, 1589, 1560, 1504, 1422, 1379, 1351, 1203, 1135, 1056.
MS (70 eV, EI) m/z (%): 450 (M+), 367 (3), 231 (15), 167 (50), 140
stirred at r.t. until completion of reaction as indicated by TLC. The

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J. Han et al. / Journal of Fluorine Chemistry 132 (2011) 409–413
(100), 69 (15). Anal. Calcd. for C15H5F9N2O2S: C 41.01, H 1.57, N
6.22. Found: C 39.93, H 1.48, N 6.13.
4.4.4. 6,8-Dichloro-3-(perfluorobutylsulfonyl)-2H-chromen-2-one (5e)
Light yellow crystals, mp 163–164 8C. 1H NMR (300 MHz,
CDCl3):
NMR (282 MHz, CDCl3):
d
8.73 (s, 1H), 7.67–7.69 (m, 1H), 7.31–7.39 (m, 1H). 19F
4.3.5. (E)-2-(perfluorobutylsulfonyl)-3-(o-fluorophenyl)-acrylonitrile
d
À80.0 (m, 3F, CF3), À108.3 (m, 2F, CF2–
(3i)
SO2), À120.3 (m, 2F, CF2CF2–SO2), À125.1 (m, 2F, CF2CF3). IR (KBr)
cmÀ1: 1758, 1607, 1555, 1442, 1368, 1355, 1230, 1202, 1175, 1148,
994, 866, 838, 762, 699, 641. MS (70 eV, EI) m/z (%): 458 (M+, 33),
239 (35), 175 (100), 119 (32), 69 (23). Anal. Calcd. for C14H7F9O5S
(%): C 31.11, H 0.61; Found: C 31.38, H 0.53.
Yellow solid, mp 78–79 8C. 1H NMR (300 MHz, CDCl3):
d
8.54 (s,
1H), 7.19–7.73 (m, 4H). 19F NMR (282 MHz, CDCl3):
d
À80.5 (m, 3F,
CF3), À108.4 (m, 1F), À109.6 (m, 2F, CF2–SO2), À120.6 (m, 2F,
CF2CF2–SO2), À125.7 (m, 2F, CF2CF3). IR (KBr) cmÀ1: 3057, 2224,
1608, 1593, 1568, 1480, 1462, 1388, 1375, 1353, 1292, 1170, 1135,
1033, 853, 783, 770, 740. MS (70 eV, EI) m/z (%): 429 (M+, 8), 210
(50), 146 (100), 126 (54). Anal. Calcd. for C13H5F10NO2S: C 36.38, H
1.17, N 3.26; Found: C 36.23, H 1.07, N 2.90.
4.4.5. 3-(4-chloro-1,1,2,2,3,3,4,4-octafluorobutyl-1-sulfonyl)-2H-
chromen-2-one (5f)
Light yellow crystals, mp 172–173 8C. 1H NMR (300 MHz,
CDCl3):
NMR (282 MHz, CDCl3):
SO2), À119.7 to 120.0 (m, 4F, CF2CF2). IR (KBr) cmÀ1: 1757, 1601,
1565, 1464, 1444, 1370, 1279, 1205, 1138, 1158, 1138, 1095, 1078,
932, 789, 760, 762, 616. MS (70 eV, EI) m/z (%): 476 (M++2, 4), 474
(9), 239 (36), 175 (100), 119 (28), 85 (6). Anal. Calcd. for
d
8.82 (s, 1 H), 7.77–7.87 (m, 2H), 7.46–7.52 (m, 2H), 19F
4.3.6. (E)-2-(perfluorobutylsulfonyl)-3-(p-(dimethylamino)phenyl)-
d
À68.1 (m, 2F, CF2Cl), À113.8 (m, 2F, CF2–
acrylonitrile (3j)
Yellow solid, mp 146–147 8C. 1H NMR (300 MHz, CDCl3):
d
7.86–7.89 (d, J = 9.3, 2H), 7.79 (s, 1H), 7.66–7.69 (d, J = 9.3, 2H), 3.15
(s, 6H). 19F NMR (282 MHz, CDCl3):
d
À80.5 (m, 3F, CF3), À109.6 (m,
2F, CF2–SO2), À120.6 (m, 2F, CF2CF2–SO2), À125.7 (m, 2F, CF2CF3).
IR (KBr) cmÀ1: 3087, 2210, 1612, 1539, 1514, 1442, 1391, 1331,
1239, 1199, 1152, 1040, 996, 942, 816, 738. MS (70 eV, EI) m/z (%):
454 (M+, 13), 171 (100), 69 (8). Anal. Calcd. for C13H5BrF9NO2S: C
39.66, H 2.44, N 6.17; Found: C 39.63, H 2.64, N 6.15.
C13H5ClF8O4S (%): C 35.11, H 1.13; Found: C 35.16, H 1.42.
4.4.6. 6-Bromo-3-(4-chloro-1,1,2,2,3,3,4,4-octafluorobutyl-1-
sulfonyl)-2H-chromen-2-one (5g)
Light yellow crystals, mp 155–157 8C. 1H NMR (300 MHz,
CDCl3):
NMR (282 MHz, CDCl3):
d
8.73 (s, 1H), 7.91–7.94 (m, 2H), 7.35–7.38 (m, 1H). 19F
4.4. General experimental procedures for the synthesis of 3-perfluoro -
butanesulfonyl coumarins
d
À67.9 (m, 2F, CF2Cl), À108.9 (m, 2F, CF2–
SO2), À119.2 to 119.8 (m, 4F, CF2CF2). IR (KBr) cmÀ1: 1758, 1610,
1554, 1453, 1374, 1283, 1236, 1210, 1170, 1136, 1109, 1031,
769,757, 732, 623. MS (70 eV, EI) m/z (%): 524 (M++2, 16), 522 (13),
289 (100), 287 (94), 225 (59), 223 (64), 169 (55), 167 (58), 85 (19).
Anal. Calcd. for C13H4BrClF8O4S (%): C 29.82, H 0.77; Found: C
29.80, H 0.76.
To a solution of methyl (perfluorobutanesulfonyl)-acetate 1a
(1 mmol, 356 mg) and 2-hydroxybenzaldehyde 4a (1 mmol,
122 mg) in EtOH (7 ml) was added L-proline (0.2 mmol, 23 mg)
and the solution was stirred at r.t. until completion of reaction as
indicated by TLC. The reaction mixture was directly recrystallized
to afford the product 5a as a colorless crystal.
4.4.7. 6-Chloro-3-(4-chloro-1,1,2,2,3,3,4,4-octafluorobutyl-1-
sulfonyl)-2H-chromen-2-one (5h)
4.4.1. 6-Bromo-3-(perfluorobutylsulfonyl)-2H-chromen-2-one (5b)
Light yellow crystals, mp 148–149 8C. 1H NMR (300 MHz,
Light yellow crystals; mp 147–148 8C. 1H NMR (300 MHz,
CDCl3):
NMR (282 MHz, CDCl3):
d
8.73 (s, 1H), 7.75–7.80 (m, 2H), 7.41–7.44 (m, 1H). 19F
CDCl3):
d
8.73 (s, 1H), 7.91–7.94 (m, 2H), 7.35–7.38 (m, 1H). 19F
d
À67.4 (m, 2F, CF2Cl), À108.3 (m, 2F, CF2–
NMR (282 MHz, CDCl3):
d
À80.6 (m, 3F, CF3), À109.1 (m, 2F, CF2–
SO2), À118.7 to 119.1 (m, 4F, CF2CF2). IR (KBr) cmÀ1: 1758, 1611,
1554, 1475, 1369, 1348, 1249, 1203, 1147, 1113, 970, 956, 834,
761, 735. MS (70 eV, EI) m/z (%): 478 (M+, 4), 243 (100), 181 (25),
179 (75), 125 (26), 123 (85), 69 (18). Anal. Calcd. for C13H4Cl2F8O4S
(%): C 32.59, H 0.84; Found: C 32.10, H 0.64.
SO2), À120.9 (m, 2F, CF2CF2–SO2), À125.8 (m, 2F, CF2CF3). IR (KBr)
cmÀ1: 1758, 1610, 1554, 1490, 1374, 1353, 1170, 1136, 1109, 922,
757, 732. MS (70 eV, EI) m/z (%): 508 (M++2, 22), 506 (27), 289
(100), 287 (92), 225 (67), 223 (61), 169 (78), 167 (63), 69 (72); Anal.
Calcd. for C13H11F3O4 (%): C 54.18, H 3.85; Found: C 54.32, H, 4.05.
4.4.8. 7-Methoxy-3-(4-chloro-1,1,2,2,3,3,4,4-octafluorobutyl-1-
sulfonyl)-2H-chromen-2-one (5i)
4.4.2. 6-Chloro-3-(perfluorobutylsulfonyl)-2H-chromen-2-one (5c)
Light yellow crystals, mp 158–159 8C. 1H NMR (300 MHz,
Light yellow crystals, mp 147–148 8C. 1H NMR (300 MHz,
CDCl3):
d
8.76 (s, 1H), 7.77–7.82 (m, 2H), 7.42–7.45 (m, 1H). 19F
CDCl3):
(282 MHz, CDCl3):
d
8.78 (s, 1H), 7.36–7.38 (m, 3H), 4.01 (s, 3H). 19F NMR
NMR (282 MHz, CDCl3):
d
À80.6 (m, 3F, CF3), À109.1 (m, 2F, CF2–
d
À67.9 (m, 2F, CF2Cl), À108.9 (m, 2F, CF2–SO2),
SO2), À120.9 (m, 2F, CF2CF2–SO2), À125.8 (m, 2F, CF2CF3). IR (KBr)
cmÀ1: 1758, 1610, 1554, 1453, 1374, 1283, 1170, 1136, 1109,
1031, 757, 769, 732. MS (70 eV, EI) m/z (%): 464 (M++2, 7), 462 (18),
245 (38), 243 (100), 181 (24), 179 (73), 125 (24), 123 (79), 69 (35).
Anal. Calcd. for C13H11F3O4 (%): C 33.75, H 0.87; Found: C 33.34, H
0.86.
À119.2 to 119.8 (m, 4F, CF2CF2). IR (KBr) cmÀ1: 1741, 1604, 1563,
1465, 1372, 1354, 1280, 1195, 1146, 1117, 982, 756, 738. MS
(70 eV, EI) m/z (%): 474 (M+, 18), 239 (37), 175 (100), 119 (30), 69
(19). Anal. Calcd. for C14H7ClF8O5S (%): C 35.42, H 1.49; Found: C
35.38, H 1.48.
Acknowledgement
4.4.3. 7-Methoxy-3-(perfluorobutylsulfonyl)-2H-chromen-2-one
(5d)
We are grateful to the National Natural Science Foundation of
China (NNSFC No. 21032006) for the financial support on this
research.
Light yellow crystals, mp 163–164 8C. 1H NMR (300 MHz,
CDCl3):
d 8.76 (s, 1H), 7.42–7.45 (m, 1H), 7.31–7.39 (m, 3H), 3.93 (s,
3H). 19F NMR (282 MHz, CDCl3):
d
À80.6 (m, 3F, CF3), À109.3 (m,
References
2F, CF2–SO2), À120.9 (m, 2F, CF2CF2–SO2), À125.7 (m, 2F, CF2CF3).
IR (KBr) cmÀ1: 1741, 1604, 1563, 1465, 1372, 1354, 1280, 1195,
1146, 1117, 982, 756, 738. MS (70 eV, EI) m/z (%): 458 (M+, 33), 239
(35), 175 (100), 119 (32), 69 (23). Anal. Calcd. for C14H7F9O5S (%): C
36.69, H 1.54; Found: C 36.54, H 1.67.
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