Determination of pKa values of fluoroalkanesulfonamides and investigation of their nucleophilicity

Article abstract of DOI:10.1016/j.jfluchem.2010.03.013

The pK_a values of a series of fluoroalkanesulfonylamides were measured by potentiometric titration. Different kinds of alkyl halides and tosylates were employed to investigate the nucleophilicity of fluoroalkanesulfonylamides. Fluoroalkanesulfonylamides with longer fluoroalkyl chain have weaker nucleophilicity.

Full text of DOI:10.1016/j.jfluchem.2010.03.013

Journal of Fluorine Chemistry 131 (2010) 761–766
Contents lists available at ScienceDirect
Journal of Fluorine Chemistry
journal homepage: www.elsevier.com/locate/fluor
Determination of pKa values of fluoroalkanesulfonamides and investigation
of their nucleophilicity
Cheng-Pan Zhang a, Zong-Ling Wang a,b, Qing-Yun Chen a, Chun-Tao Zhang b,
Yu-Cheng Gu c, Ji-Chang Xiao a,
*
a Key Laboratory of Organofluorine Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, 345 Lingling Road, Shanghai 200032, China
b Hunan University of Chinese Medicine, Changsha, Hunan Province 410208, China
c Syngenta, Jealott’s Hill International Research Centre, Bracknell, Berkshire RG42 6EY, UK
A R T I C L E I N F O
A B S T R A C T
Article history:
The pKa values of a series of fluoroalkanesulfonylamides were measured by potentiometric titration.
Different kinds of alkyl halides and tosylates were employed to investigate the nucleophilicity of
fluoroalkanesulfonylamides. Fluoroalkanesulfonylamides with longer fluoroalkyl chain have weaker
nucleophilicity.
Received 11 February 2010
Received in revised form 21 March 2010
Accepted 24 March 2010
Available online 30 March 2010
ß 2010 Elsevier B.V. All rights reserved.
Keywords:
pKa values
Fluoroalkanesulfonamides
Nucleophilicity
Substitution
Alkylation
Nucleophiles
1. Introduction
mides and perfluoroalkanesulfonyl fluorides or perfluoroalkane-
sulfonyl chlorides, bis(perfluoroalkanesulfonyl)imides was
Since the discovery of Prontosil in 1932, a great deal of
benzenesulfonylamides have been synthesized and found effective
for the treatment of bacterial infections [1]. Common alkanesulfo-
nylamides, however, found little application in the pharmaceutical
or agrochemicalarea at thattime [1]. When fluorinewasintroduced
into these common alkanesulfonylamides, their biological activity
was satisfactorily improved [1–4]. For example, Trepka and Moore
found that fluorinated N-phenylalkanesulfonylamides showed
potent herbicidal and anti-inflammatory activities in 1970s [2–
4]. Lu recently reported that N-alkylfluoroalkanesulfonylamides
were environment-friendly insecticides [5]. The introduction of
fluorine atoms conferred them high acidity and lipophilicity,
resulting in their unique bioactivity. Fluoroalkanesulfonylamides
also have special physical and chemical properties. Addition of
fluorine atoms to aryl-substituted fluoroalkanesulfonylamides
gave a linear acidity increase of 1.47 pKa units per fluorine and
an excellent correlation of partition coefficient in a second-order
equation [6]. In the reaction between perfluoroalkanesulfonyla-
successfully synthesized [7]. Perfluoroalkanesulfonylamides react-
ing with sulfonyl chloride could generate N-sulfinylperfluoroalk-
anesulfonylamides which were very important intermediates [8,9].
N,N-Dichlorofluoroalkanesulfonylamides, another kind of reactive
species, could be conveniently synthesized by the reaction of
fluoroalkanesulfonylamides with aqueous KOH and chlorine gas
[10]. Transformation of perfluoroalkanesulfonylamides to the
corresponding RfSO2NHK by solid potassium hydroxide in 1,2-
dimethoxyethane, the nucleophilicity was increased strongly
enough to react with CS2 and RX forming (S,S)-dialkyl N-
(perfluoroalkylsulfonyl)carbodithioimidates [11]. N,N-Dialkyl-
fluoroalkanesulfonylamides were obtained as undesired products
with aqueous KOH using DMF as the solvent in the same reaction
[11]. However, nature of the reaction was still unknown. To the best
of our knowledge, efforts to investigate the details of the
nucleophilicity and acidity of fluoroalkanesulfonylamides as well
as the compatibility of fluoroalkanesulfonylamides with different
kinds of electrophiles have not already been made till now.
Therefore, it is important and meaningful to gain more insight into
the acidity and nucleophilicity of fluoroalkanesulfonamides, even
though some nucleophilic reactions of perfluoroalkanesulfonyla-
mides have been reported [12]. Herein, we report the results.
* Corresponding author. Fax: +86 21 64166128.
E-mail address: jchxiao@mail.sioc.ac.cn (J.-C. Xiao).
0022-1139/$ – see front matter ß 2010 Elsevier B.V. All rights reserved.
doi:10.1016/j.jfluchem.2010.03.013

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C.-P. Zhang et al. / Journal of Fluorine Chemistry 131 (2010) 761–766
Table 1
2. Results and discussion
Preparation of fluoroalkylsulfonamides and their pKa values.
ꢁ
< ꢀ60 Cacid
RfSO2 þ NH3 ðliquidÞ ꢀ! ꢀ! RfSO2 NH2
.
1aꢀi
Fluoroalkanesulfonylamides could be conveniently synthesized
by using fluoroalkanesulfonyl fluorides as starting materials [5,13].
1a–c and 1e–g were favorably obtained in high yield when
fluoroalkanesulfonyl fluorides reacted with liquid ammonia at a
temperature below ꢀ60 8C (entries 1–3 and 5–7, Table 1).
Treatment of 1c with NaOH in methanol, 1d was satisfactorily
formed according to our previous work [14]. FO2S(CF2)2O(CF2)2-
SO2F reacted with liquid ammonia, giving 1h in 97% yield (entry 8).
Meanwhile, 1i was generated from FO2S(CF2)2O(CF2)4O(CF2)2SO2F
in the same reaction condition (entry 9).
b
b
Entry
RfSO2NH2
Yielda (%)
pKa1
pKa2
1c
2
CF3SO2NH2
80 (1a)
88 (1b)
92 (1c)
87 (1d)
94 (1e)
93 (1f)
98 (1g)
97 (1h)
94 (1i)
6.28
6.17
6.22
5.83
5.70
4.22
5.74
5.67
5.90
9.37
7.82
7.80
7.75
7.66
7.57
7.56
7.92
7.80
Cl(CF2)2SO2NH2
3
I(CF2)2O(CF2)2SO2NH2
H(CF2)2O(CF2)2SO2NH2
I(CF2)4O(CF2)2SO2NH2
I(CF2)6O(CF2)2SO2NH2
Cl(CF2)6O(CF2)2SO2NH2
H2NO2S(CF2)2O(CF2)2SO2NH2
4d
5
6
7
8c
9
H2NO2S(CF2)2O(CF2)4O(CF2)2SO2NH2
a
There are several methods for the determination of pKa value
[15]. Among them, potentiometric titration has been the standard
method for pKa measurement due to its accuracy and reprodu-
cibility [16]. Furthermore, most fluorinated compounds are often
water-insoluble and have unfavorable molar absorption coeffi-
Isolated yield.
b
The pKa values were determined in MeOH using KOH as the base and METTLER
TOLEDO T70 3.0.0 as potentiometric titrator.
c
1a and 1h are water soluble.
d
1d was prepared from the hydrodehalogenation of 1c [14].
Table 2
Nucleophilicity of the fluoroalkanesulfonylamides.
K
CO
2
3
RfSO2 þ RX
ꢀ!
RfSO2NR2.
THF;Temperature
Entry
RfSO2NH2
RXa
RfSO2NR2
Conditions (temperature, time)
Yieldb (%)
1c
2
1a
1a
CH3I
CF3SO2N(CH3)2
CF3SO2N(C2H5)2
Reflux, 14 h
Reflux, 22 h
100 (2aa)
90 (2ab)
C2H5I
3c
4c
5c
1a
1a
1a
n-C3H7Br
CF3SO2NH(n-C3H7)
CF3SO2N(n-C3H7)2
90 8C, 2 d
90 8C, 2 d
90 8C, 2 d
33 (2ac)
57 (2ad)
n-C4H9I
CF3SO2NH(n-C4H9)
CF3SO2N(n-C4H9)2
15 (2ae)
85 (2af)
n-C4H9Br
CF3SO2NH(n-C4H9)
CF3SO2N(n-C4H9)2
28 (2ae)
66 (2af)
6c
7d
1a
1a
n-C4H9Cl
PhCH2Br
–
90 8C, 2 d
–
CF3SO2NHCH2C6H5
CF3SO2N(CH2C6H5)2
Reflux, 22 h
6 (2ag)
29 (2ah)
8
9
1a
1a
1a
1a
PhCH2Br
CF3SO2N(CH2C6H5)2
Reflux, 22 h
Reflux, 2 d
Reflux, 2 d
Reflux, 21 h
86 (2ah)
71 (2ai)
68 (2aj)
75 (2ak)
Ts(OCH2CH2)2OH
Ts(OCH2CH2)3OH
Ts(OCH2CH2)2OTs
CF3SO2N[(CH2CH2O)2H]2
CF3SO2N[(CH2CH2O)3H]2
10
11c
12
1a
Ts(OCH2CH2)3OTs
90 8C, 6d
9 (2al)
13
14
1d
1d
CH3I
H(CF2)2O(CF2)2SO2N(CH3)2
H(CF2)2O(CF2)2SO2N(C2H5)2
Reflux, 19 h
Reflux, 2 d
88 (2da)
89 (2db)
C2H5I
15
1d
n-C3H7Br
H(CF2)2O(CF2)2SO2NH(n-C3H7)
H(CF2)2O(CF2)2SO2N(n-C3H7)2
90 8C, 3 d
90 8C, 2 d
Reflux, 17 h
37 (2dc)
41 (2dd)
16
1d
n-C4H9I
H(CF2)2O(CF2)2SO2NH(n-C4H9)
H(CF2)2O(CF2)2SO2N(n-C4H9)2
43 (2de)
45 (2df)
17
18
19c
1d
1d
1d
PhCH2Br
H(CF2)2O(CF2)2SO2N(CH2C6H5)2
88 (2dg)
75 (2dh)
87 (2di)
CH25CHCH2Br
Ts(OCH2CH2)2OTs
H(CF2)2O(CF2)2SO2N(CH2CH5CH2)2
Reflux, 31 h
Reflux, 2 d
20
21
22
23
24
25
26
27
1h
1h
1h
1h
1i
CH3I
(CH3)2NO2S(CF2)2O(CF2)2SO2N(CH3)2
Reflux, 18 h
90 8C, 31 h
90 8C, 31 h
Reflux, 3 d
Reflux, 18 h
90 8C, 33 h
90 8C, 31 h
Reflux, 2 d
35 (2ha)
26 (2hb)
31 (2hc)
28 (2hd)
30 (2ia)
27 (2ib)
31 (2ic)
86 (2id)
C2H5I
(C2H5)2NO2S(CF2)2O(CF2)2SO2N(C2H5)2
CH25CHCH2Br
PhCH2Br
CH3I
(CH25CHCH2)2NO2S(CF2)2O(CF2)2SO2N(CH2CH5CH2)2
(C6H5CH2)2NO2S(CF2)2O(CF2)2SO2N(CH2C6H5)2
(CH3)2NO2S[(CF2)2O(CF2)2]2SO2N(CH3)2
1i
C2H5I
(C2H5)2NO2S[(CF2)2O(CF2)2]2SO2N(C2H5)2
(CH25CHCH2)2NO2S[(CF2)2O(CF2)2]2SO2N(CH2CH5CH2)2
(C6H5CH2)2NO2S[(CF2)2O(CF2)2]2SO2N(CH2C6H5)2
1i
CH25CHCH2Br
PhCH2Br
1i
a
The molar ratio of RfSO2NH2 to RX was about 1:2.2.
Isolated yield.
b
c
The yields of the products were determined by 19F NMR.
d
The molar ratio of 1a to PhCH2Br was 1:1.1.

C.-P. Zhang et al. / Journal of Fluorine Chemistry 131 (2010) 761–766
763
cients [17]. Therefore, potentiometric titration was employed for
the pKa determination of 1a–1i. The results are shown in Table 1. In
the cases of 1c, 1e and 1f, the titration must be conducted in
darkness to avoid the hydrodehalogenation [14]. Elongation of the
fluoroalkyl chain led to a gentle decrease of pKa1 and pKa2 (entries 1
and 2, entries 3, 5 and 6). The pKa1 difference (1.48) between 1e and
1f was larger than that (0.52) between 1c and 1e (entries 3, 5 and
6). It seems that the halogen bonding interaction between iodine
and negative ion of nitrogen in RfNHK (1f) played important role in
stabilizing the anion, which apparently decreased the pKa value
[18]. Replacement of iodine with hydrogen in 1c resulted in
increase of the acidity (1d), which was very close to 1e (entries 4
and 5). This was indicated that the hydrogen bonding interaction
between the hydrogen atom and the negative ion greatly stabilized
the anion, which further decreased the pKa value of product.
Substitution of the terminal iodine (1f) with chlorine (1g)
increased the pKa1 value by 1.52. But little difference was found
in their pKa2 values (entries 6 and 7). Comparing the pKa value of 1h
and 1i with 1d and 1e, no significant difference was observed in
either their pKa1 or pKa2 values (entries 8 and 9), indicating that the
introduction of another sulfonylamide group into fluoroalkane-
sulfonylamides had little influence on their acidity.
tosylate Ts(OCH2CH2)2OTs was used (entry 11). While in the case
of tri(ethylene glycol) di-p-tosylate, Ts(OCH2CH2)3OTs, only 9%
yield of intermolecular cyclization product 2al was formed (entry
12). It seems that the chelating interaction between potassium
cations and azacrown ether was inhibited by the strong electron
withdrawing effect of trifluoromethanesulfonyl group on N atoms,
thus leading to no template effects of potassium cation on the ring
closing procedure [19].
The length of fluoroalkyl chain not only affects the pKa value of
the fluoroalkanesulfonamides as aforementioned but also influ-
ences their nucleophilicity. As compared with trifluoromethane-
sulfonamide 1a, longer reaction time was required for 1,1,2,2-
tetrafluoro-2-(1,1,2,2-tetrafluoroethoxy)ethanesulfonamide 1d to
achieve the similar results (entries 13–16). Elongation of the
fluoroalkyl chain increased the electron withdrawing effect of the
fluoroalkylsulfonyl group, leading to the lower nucleophilicity of
1d.
In the case of di-sulfonamides 1h and 1i, tetraalkylated
products were readily obtained (entries 20–27). But the yields
were slightly low. Increasing the reaction temperature or
prolonging the reaction time had little improvement of the
transformation.
Generally, the pKa values of fluoroalkanesulfonamides are
lower than the non-fluorinated analogues, thus leading to their
weaker nucleophilicity. Although the N-substituted fluoroalkane-
sulfonylamides could be synthesized from the reaction of
fluoroalkanesulfonyl fluorides and the corresponding substituted
amines, most of the amines are not commercially available, thus
making the procedure not much versatile. Therefore, it is
interesting to investigate the nucleophilic substitution of fluor-
oalkanesulfonylamides.
3. Conclusion
In summary, the pKa1 and pKa2 values of
a series of
fluoroalkanesulfonylamides were measured by potentiometric
titration. The sulfonylamides with longer fluoroalkyl chain showed
stronger acidity. The terminal substituents also have influences on
their pKa values. Different alkyl halides and tosylates were
employed to investigate the nucleophilicity of fluoroalkanesulfo-
nylamides. It was demonstrated that elongation of the fluoroalkyl
chain reduced the nucleophilicity of the sulfonamides, which is, to
some extent, in accordance with the decrease of their pKa values.
Further investigation on the applications of these fluoroalkane-
sulfonylamides is going on.
As shown in Table 2, the nucleophilic reactions of fluoroalk-
anesulfonylamides were much influenced by the electrophilicity of
the electrophiles. Strong electrophilic alkyl halides favored the
alkylation reaction. For example, treatment of 1a with methyl
iodide and K2CO3 in refluxing THF for 14 h gave the dimethylated
product, 2aa, in 100% yield (entry 1). Replacing methyl iodide with
ethyl iodide under the same condition, however, longer reaction
time was necessary for complete conversion (entry 2). Taking n-
C3H7Br or n-C4H9I instead of ethyl iodide as the electrophile, the
reaction became more difficult and time consuming (entries 3 and
4). Higher temperature was needed for completion of the reaction.
Mono- and di-substitution occurred simultaneously while increas-
ing the temperature to 90 8C. Similar results were obtained in the
reaction between 1a and n-C4H9Br (entry 5). No reaction happened
in the case of n-C4H9Cl (entry 6). The electrophilicity of the alkyl
halides also has influence on the ratio of the products. Lower yield
of di-substituted product 2af was formed when n-C4H9Br was used
as compared with n-C4H9I (entries 4 and 5). Nevertheless, the
formation of the di-substituted fluoroalkanesulfonylamides was
still dominant. The di-substitution was accelerated by the first
alkylation. It was proposed that the electron donating effect of the
first alkyl group on the N atom improved its nucleophilicity, thus
resulting in the favorable formation of di-substituted ones. In
addition, the yield was obviously affected by the reactant ratio. The
dibenzylated product 2ah was obtained in 86% yield when 2.2
equivalent of PhCH2Br was used. However, only 6% yield of
monobenzylated product 2ag and 29% yield of 2ah were formed
when 1.1 equivalent of PhCH2Br was employed under the same
condition (entries 7 and 8). Di-substituted fluoroalkanesulfonyla-
mide was also the main product even in the presence of insufficient
of benzyl bromide (entry 8).
4. Experimental
4.1. General
Unless otherwise stated, NMR spectra were recorded in
deuterated chloroform at 300 MHz (1H NMR) and 282 MHz (19
F
NMR). 13C NMR spectra were recorded at 75 or 100 MHz in CDCl3.
All chemical shifts were reported in ppm relative to TMS and CFCl3
(positive for downfield shifts) as external standards. Melting points
were measured and uncorrected. MeOH was distilled from 4A
molecular sieves before use. Analytical pure THF was used without
further purification. All fluoroalkanesulfonyl fluorides except
Cl(CF2)2SO2F,
F2)4O(CF2)2SO2F were obtained from commercial source.
Cl(CF2)2SO2F, FO2S(CF2)2O(CF2)2SO2F and FO2S(CF2)2O(C-
FO2S(CF2)2O(CF2)2SO2F
and
FO2S(CF2)2O(C-
F2)4O(CF2)2SO2F were prepared according to the literature
[13c,20]. 1d was prepared according to our previous work [14].
The pKa1 and pKa2 values of fluoroalkanesulfonylamides were
measured in MeOH. Samples in the range from 5 ꢂ 10ꢀ5 M to
1 ꢂ 10ꢀ2 M were dissolved in methanol and titrated with KOH
(0.02 M in the same solvent). Potentiometric titrator (METTLER
TOLEDO T70 3.0.0) was employed to monitor the whole titration
process.
4.2. Typical procedure for the preparation of 1a
Similar results were obtained when tosylates were used as
electrophiles (entries
intramolecular cyclization happened preferentially in the reaction
of 1a with di(ethylene glycol) di-p-tosylate, even 2.2 equivalent of
9
and 10). It is worth noting that
In a 500 mL three-neck flask equipped with katathermometer
and magnetic stirrer, CF3SO2F (170 g, 1.12 mol) was bubbled
into liquid NH3 (300 mL) within 1.5 h (during this procedure,

764
C.-P. Zhang et al. / Journal of Fluorine Chemistry 131 (2010) 761–766
temperature of the reaction system inevitably rose up to about
ꢀ60 8C. But it returned to ꢀ78 8C quickly when bubbling stopped. It
was the same case for 1b and c and 1e and i). The reaction was
stirred at ꢀ78 8C for 2 h under nitrogen atmosphere. Then the
excess of ammonia was removed by evaporation. The residue was
added in dioxane (500 mL), acidified with anhydrous HCl till the PH
value is below 2 and filtered. The filtrate was then distilled to give a
light yellow powder. Sublimation of the crude powder under
vacuum gave a white crystal 1a (134 g, 80%). 1H NMR (CD3COCD3):
8.03 (s, 4H). 19F NMR (CD3COCD3):
d
ꢀ117.2 (s, 4F), ꢀ81.2 (s, 4F).
MS (ESI, m/z, %): 375.0 [M]ꢀ (100). IR (KBr): 3406, 3307, 1532, 1376,
1347, 1305, 1232, 1183, 1156, 1114, 916, 771, 655, 637, 609, 565,
503, 481, 419 cmꢀ1. Anal. Calcd. for C4H4F8N2O5S2: C, 12.77; H,
1.07; N, 7.45. Found: C, 12.94; H, 0.79; N, 7.31.
4.5. Typical procedure for the preparation of 2aa–ah, 2ak, 2da–di,
2ha–hd and 2ia–id
d
7.60 (s, 2H). 19F NMR (CD3COCD3):
d
80.4 (s, 3F).
In a 15 mL round bottom sealed tube equipped with a magnetic
stirrer, 1d (0.220 g, 0.740 mmol) and 1-iodobutane (0.278 g,
1.51 mmol) were dissolved in THF (7 mL). K2CO3 (0.196 g,
1.42 mmol) was then added. After being heated at 90 8C for 2
days, the reaction mixture was cooled, concentrated and acidified
with diluted H2SO4 till pH < 2. The resulting emulsion was
extracted with ethyl ether (30 mL), washed by water
(3 ꢂ 15 mL) and dried over anhydrous Na2SO4. The crude product
was purified by column chromatography to give pure 2de (0.112 g,
0.317 mmol, 43%) and 2df (0.137 g, 0.335 mmol, 45%) using
petroleum ether/ethyl acetate (20:1) as the eluent.
4.3. Typical procedure for the preparation of 1b and c, 1e–g and 1i
1,1,2,2-Tetrafluoro-2-(1,1,2,2-tetrafluoro-2-iodoethoxy)etha-
nesulfonyl fluoride (9.80 g, 23.0 mmol) was added dropwise into
liquid NH3 (45 mL) which was cooled by acetone/dry ice bath. After
being stirred at ꢀ78 8C for 2 h, the excess of ammonia was removed
by evaporation. The resulting white slurry was acidified to a pH of 2
with diluted H2SO4 and extracted with diethyl ether (80 mL),
washed with water (3 ꢂ 20 mL), dried over anhydrous Na2SO4,
concentrated under reduced pressure and dried in vacuum to give
the crude product. 8.95 g of pure 1c (21.2 mmol, 92%) was obtained
as a white solid by column chromatography on silica gel using
2de: colorless liquid. Yield: 43%. 1H NMR:
J = 3.2 Hz, 1H), 4.82 (s, 1H), 3.33 (q, J = 6.8 Hz, 2H), 1.58 (m, 2H), 1.39
d 5.87 (tt, J = 52.6 Hz,
(m, 2H), 0.95 (t, J = 7.1 Hz, 3H). 19F NMR:
d
ꢀ137.2 (dt, J = 52.6 Hz,
dichloromethane as the eluent. 1H NMR:
d
5.36 (s, 2H). 19F NMR:
d
J = 5.2 Hz, 2F), ꢀ116.1 (s, 2F), ꢀ88.3 (m, 2F), ꢀ81.5 (m, 2F). 13C NMR:
ꢀ115.8 (s, 2F), ꢀ84.8 (m, 2F), ꢀ81.0 (t, J = 12.4 Hz, 2F), ꢀ64.3 (t,
d 44.6, 32.3, 19.4, 13.4. MS (EI, m/z, %): 310 (100), 136 (36.0), 128
J = 12.4 Hz, 2F).
(29.8), 119 (44.3), 101 (42.7), 78 (19.9), 57 (38.3), 56 (30.5). IR (KBr):
3313, 3133, 2968, 2881, 1430, 1398, 1330, 1285, 1200, 1143, 1078,
857, 749, 612, 583 cmꢀ1. Anal. Calcd. for C8H11F8NO3S: C, 27.20; H,
3.14; N, 3.97. Found: C, 27.46; H, 3.19; N, 3.88.
2df: colorless liquid. Yield: 45%. 1H NMR:
J = 3.2 Hz, 1H), 3.37 (d, J = 37.0 Hz, 4H), 1.61 (s, 4H), 1.34 (m, 4H),
1b: white solid; mp 76–77 8C. Yield: 88%. 1H NMR:
d 5.50 (s, 2H).
19F NMR:
d
ꢀ110.7 (s, 2F), ꢀ65.6 (s, 2F). MS (ESI, m/z, %): 214.0 [M]ꢀ
(100). IR (KBr): 3377, 3284, 1539, 1361, 1198, 1180, 1162, 1131,
1085, 833, 698, 614, 588, 540, 493, 428 cmꢀ1. Anal. Calcd. for
C2H2ClF4NO2S: C, 11.14; H, 0.94; N, 6.50. Found: C, 11.15; H, 0.93;
N, 6.54.
d 5.86 (tt, J = 52.5 Hz,
0.95 (t, J = 6.8 Hz, 6H). 19F NMR:
d
ꢀ137.3 (dt, J = 52.5 Hz, J = 5.1 Hz,
1e: white solid. Yield: 94%. 1H NMR:
d
5.32 (s, 2H). 19F NMR:
d
2F), ꢀ115.9 (s, 2F), ꢀ88.5 (m, 2F), ꢀ81.7 (m, 2F). 13C NMR:
d 48.3,
ꢀ124.8 (m, 2F), ꢀ116.7 (d, J = 7.9 Hz, 2F), ꢀ113.8 (m, 2F), ꢀ83.5 (m,
30.5, 19.7, 13.6. MS (EI, m/z, %): 366 (17.8), 324 (100), 310 (26.8),
192 (16.1), 119 (20.1), 101 (17.5), 57 (38.6), 43 (14.6). IR (KBr):
2964, 2939, 2879, 1469, 1390, 1326, 1283, 1143, 1034, 925, 857,
748, 582 cmꢀ1. Anal. Calcd. for C12H19F8NO3S: C, 35.21; H, 4.68; N,
3.42. Found: C, 35.18; H, 4.80; N, 3.50.
2F), ꢀ81.5 (t, J = 12.9 Hz, 2F), ꢀ59.8 (t, J = 13.9 Hz, 2F).
1f: white solid; mp 90–92 8C. Yield: 93%. 1H NMR:
d 5.40 (s, 2H).
19F NMR:
d
ꢀ124.6 (s, 2F), ꢀ121.5 (s, 2F), ꢀ120.5 (s, 2F), ꢀ115.8 (s,
2F), ꢀ112.5 (s, 2F), ꢀ82.2 (m, 2F), ꢀ80.6 (t, J = 13.4 Hz, 2F), ꢀ58.6 (t,
J = 14.5 Hz, 2F). MS (ESI, m/z, %): 621.8 [M]ꢀ (100). IR (KBr): 3607,
3374, 3189, 1563, 1388, 1369, 1328, 1209, 1144, 1090, 1038, 999,
942, 842, 692, 647, 622, 543, 491 cmꢀ1
2aa: colorless liquid. Yield: 89%. 1H NMR:
NMR:
ꢀ75.1 (s, 3F).
2ab: colorless liquid. Yield: 90%. 1H NMR:
4H), 1.26 (t, J = 6.8 Hz, 6H). 19F NMR:
ꢀ77.0 (s, 3F).
2ac: white solid. Yield: 16%. 1H NMR:
4.79 (s, 1H), 3.28 (q,
d
3.07 (s, 6H). 19F
d
.
Anal. Calcd. for
d 3.46 (q, J = 6.8 Hz,
C8H2F16INO3S: C, 15.42; H, 0.32; N, 2.25. Found: C, 15.51; H,
<0.3; N, 2.43.
d
d
1g: white solid; mp 71–72 8C. Yield: 98%. 1H NMR:
d
5.36 (s, 2H).
J = 6.4 Hz, 2H), 1.65 (m, 2H), 0.99 (t, J = 6.4 Hz, 3H). 19F NMR:
ꢀ78.0 (s, 3F).
d
19F NMR:
d
ꢀ124.6 (m, 2F), ꢀ121.5 (s, 2F), ꢀ120.7 (s, 2F), ꢀ119.5 (s,
2F), ꢀ115.7 (s, 2F), ꢀ82.1 (m, 2F), ꢀ80.5 (t, J = 12.4 Hz, 2F), ꢀ67.4 (t,
J = 12.3 Hz, 2F). MS (ESI, m/z, %): 530.0 [M]ꢀ (100). IR (KBr): 3384,
3275, 1374, 1329, 1209, 1145, 1100, 1052, 998, 940, 882, 707, 698,
685, 656, 627, 547, 491 cmꢀ1. Anal. Calcd. for C8H2ClF16NO3S: C,
18.07; H, 0.38; N, 2.63. Found: C, 17.93; H, <0.3; N, 2.80.
1i: white solid. Yield: 94%. 1H NMR (CD3COCD3):
19F NMR (CD3COCD3):
2ad: colorless liquid. Yield: 46%. 1H NMR:
d
3.31 (t, J = 7.3 Hz,
ꢀ76.4 (s, 3F).
120.1 (q, J = 323.7 Hz, CF3), 50.0, 21.7, 10.9. MS (EI, m/z,
4H), 1.67 (m, 4H), 0.94 (t, J = 7.3 Hz, 6H). 19F NMR:
13C NMR:
d
d
%): 233 (12.3), 204 (100), 164 (12.8), 162 (38.2), 69 (8.4), 43 (66.8),
42 (11.4), 41 (13.4). IR (KBr): 2973, 2942, 2882, 1715, 1506, 1471,
1390, 1226, 1200, 1133, 1005, 874, 801, 741, 599, 511 cmꢀ1. Anal.
Calcd. for C7H14F3NO2S: C, 36.04; H, 6.05; N, 6.00. Found: C, 35.99;
H, 5.97; N, 5.75.
d
8.12 (s, 4H).
d
ꢀ125.9 (m, 4F), ꢀ117.9 (s, 4F), ꢀ83.5 (m,
4F), ꢀ81.8 (m, 4F).
2ae: colorless liquid. 1H NMR:
d 4.77 (s, 1H), 3.31 (q, J = 6.8 Hz,
4.4. Typical procedure for the preparation of 1h
2H), 1.60 (m, 2H), 1.39 (m, 2H), 0.95 (t, J = 7.3 Hz, 3H). 19F NMR:
ꢀ78.0 (s, 3F).
d
In a 100-mL three-neck flask equipped with katathermometer
and magnetic stirrer, FO2SCF2CF2OCF2CF2SO2F (5.02 g, 13.1 mmol)
was added dropwise into liquid NH3 (30 mL) within 40 min. The
reaction mixture was stirred at ꢀ78 8C for 2 h. After removing
excessive ammonia, the residue was acidified with diluted H2SO4
till pH value below 2. Then water was evaporated. The crude
product was extracted with acetone and purified by column
chromatography on silica gel using dichloromethane/acetonitrile
(4:1) as the eluent. 4.82 g of pure 1h (12.8 mmol, 97%) was
2af: colorless liquid. Yield: 77%. 1H NMR:
d 3.34 (t, J = 6.8 Hz,
4H), 1.61 (m, 4H), 1.34 (m, 4H), 0.95 (t, J = 7.3 Hz, 6H). 19F NMR:
d
ꢀ76.4 (s, 3F). 13C NMR:
d 120.1 (q, J = 323.7 Hz, CF3), 48.1, 30.4,
19.7, 13.6. MS (EI, m/z, %): 218 (13.6), 178 (5.3), 176 (100), 69 (2.9),
57 (21.8), 56 (6.3), 42 (4.6), 41 (9.1). IR (KBr): 2964, 2938, 2878,
1469, 1389, 1225, 1189, 1133, 1030, 926, 597, 510 cmꢀ1. Anal.
Calcd. for C9H18F3NO2S: C, 41.37; H, 6.94; N, 5.36. Found: C, 41.45;
H, 6.87; N, 5.20.
2ag: white solid. Yield: 6%. 1H NMR:
1H), 4.45 (d, J = 5.9 Hz, 2H). 19F NMR:
d
7.42–7.32 (m, 5H), 5.03 (s,
obtained as a white solid. mp 125–126 8C. 1H NMR (CD3COCD3):
d
d
ꢀ77.8 (s, 3F).

C.-P. Zhang et al. / Journal of Fluorine Chemistry 131 (2010) 761–766
765
2ah: white solid. Yield: 29%. 1H NMR:
7.17 (m, 4H), 4.43 (s, 4H). 19F NMR:
ꢀ76.1 (s, 3F).
2ak: colorless liquid. Yield: 41%. 1H NMR:
3.77 (t, J = 3.2 Hz,
4H), 3.51 (s, 4H). 19F NMR:
ꢀ75.6 (s, 3F).
2da: colorless liquid. Yield: 88%. 1H NMR:
d
7.37–7.33 (m, 6H), 7.20–
1382, 1293, 1224, 1164, 1130, 1115, 1066, 975, 751, 705, 641, 599,
539, 482 cmꢀ1. Anal. Calcd. for C8H12F8N2O5S2: C, 22.23; H, 2.80; N,
6.48. Found: C, 22.68; H, 2.90; N, 6.38.
d
d
d
2hb: colorless liquid. Yield: 26%. 1H NMR:
8H), 1.26 (t, J = 7.3 Hz, 12H). 19F NMR:
ꢀ116.3 (s, 4F), ꢀ82.0 (s,
4F). 13C NMR:
42.9, 14.1. MS (EI, m/z, %): 473 (9.5), 136 (100), 120
d 3.49 (d, J = 30.1 Hz,
d
5.87 (tt, J = 52.5 Hz,
d
J = 3.2 Hz, 1H), 3.09 (s, 6H). 19F NMR:
d
ꢀ138.0 (dt, J = 52.6 Hz,
d
J = 5.2 Hz, 2F), ꢀ115.9 (s, 2F), ꢀ89.1 (m, 2F), ꢀ82.7 (m, 2F). 13C
(44.5), 72 (7.9), 71 (15.2), 56 (13.7), 44 (21.7), 42 (12.5). IR (KBr):
2988, 2947, 2887, 1509, 1459, 1389, 1334, 1299, 1214, 1138, 1023,
945, 792, 695, 585, 504 cmꢀ1. Anal. Calcd. for C12H20F8N2O5S2: C,
29.51; H, 4.13; N, 5.74. Found: C, 29.93; H, 4.20; N, 5.72.
NMR:
d 38.2. MS (EI, m/z, %): 119 (10.5), 110 (5.4), 108 (100), 101
(14.5), 92 (12.3), 51 (6.4), 44 (10.0), 42 (11.1). IR (KBr): 2962, 1424,
1386, 1329, 1286, 1200, 1135, 1001, 967, 857, 719, 581, 489 cmꢀ1
.
Anal. Calcd. for C6H7F8NO3S: C, 22.16; H, 2.17; N, 4.31. Found: C,
22.15; H, 2.22; N, 4.24.
2hc: light yellow liquid. Yield: 31%. 1H NMR:
d
5.83–5.69 (m,
ꢀ116.2
d 131.5, 120.7, 50.0. MS (EI, m/z, %):
4H), 5.34–5.24 (m, 8H), 3.98 (d, J = 5.0 Hz, 8H). 19F NMR:
d
2db: colorless liquid. Yield: 89%. 1H NMR:
d
5.86 (tt, J = 52.6 Hz,
J = 3.2 Hz, 1H), 3.48 (d, J = 27.0 Hz, 4H), 1.26 (t, J = 7.3 Hz, 6H). 19F
NMR:
(s, 4F), ꢀ81.8 (s, 4F). 13C NMR:
160 (28.3), 96 (83.4), 94 (23.1), 81 (15.3), 69 (36.7), 68 (15.8), 56
(15.1), 41 (100). IR (KBr): 3091, 2997, 2943, 2875, 1647, 1448,
1423, 1388, 1338, 1299, 1226, 1200, 1144, 992, 934, 910, 782, 737,
668, 603, 501 cmꢀ1. HRMS for C16H20F8N2O5S2: 536.0686. Found:
536.0682.
d
ꢀ138.0 (dt, J = 52.6 Hz, J = 5.2 Hz, 2F), ꢀ117.0 (s, 2F), ꢀ89.2
(m, 2F), ꢀ82.3 (m, 2F).
2dc: colorless liquid. Yield: 37%. 1H NMR:
d 5.87 (tt, J = 52.5 Hz,
J = 3.2 Hz, 1H), 3.41 (s, 1H), 3.30 (t, J = 6.8 Hz, 2H), 1.64 (m, 2H),
0.98 (t, J = 7.8 Hz, 3H). 19F NMR:
d
ꢀ137.9 (dt, J = 52.6 Hz, J = 5.2 Hz,
2hd: white solid; mp 112–113 8C. Yield: 28%. 1H NMR:
d
7.32–
ꢀ115.0 (s, 4F),
d 133.8, 128.8, 128.7, 128.4, 51.4. MS
2F), ꢀ116.8 (s, 2F), ꢀ89.0 (m, 2F), ꢀ82.2 (m, 2F). 13C NMR:
d
46.5,
7.29 (m, 12H), 7.17 (m, 8H), 4.46 (s, 8H). 19F NMR:
d
23.6, 10.7. MS (EI, m/z, %): 310 (100), 128 (27.4), 122 (76.4), 119
(47.0), 106 (18.5), 101 (47.5), 78 (21.6), 43 (43.9). IR (KBr): 3317,
2976, 2886, 1432, 1372, 1330, 1285, 1200, 1143, 1075, 986, 857,
750, 612, 584 cmꢀ1. HRMS for C7H9F8NO3S: 339.0175. Found:
339.0171.
2dd: colorless liquid. Yield: 41%. 1H NMR:
J = 3.2 Hz, 1H), 3.33 (d, J = 32.0 Hz, 4H), 1.66 (m, 4H), 0.94 (t,
ꢀ81.6 (s, 4F). 13C NMR:
(MALDI, m/z, %): 759.4 [M+Na], 775.3 [M+K]. IR (KBr): 3036, 1498,
1459, 1376, 1339, 1303, 1201, 1144, 1092, 1062, 938, 925, 906,
889, 796, 767, 742, 726, 693, 603, 509 cmꢀ1. Anal. Calcd. for
C32H28F8N2O5S2: C, 52.17; H, 3.83; N, 3.80. Found: C, 52.36; H, 4.03;
N, 3.57.
d 5.86 (tt, J = 52.5 Hz,
2ia: white solid; mp 81–83 8C. Yield: 30%. 1H NMR:
d 3.10 (s,
J = 7.3 Hz, 6H). 19F NMR:
d
ꢀ137.9 (dt, J = 52.5 Hz, J = 5.1 Hz, 2F),
12H). 19F NMR:
d
ꢀ126.2 (m, 4F), ꢀ115.8 (s, 4F), ꢀ83.6 (m, 4F),
ꢀ116.6 (s, 2F), ꢀ89.1 (m, 2F), ꢀ82.3 (m, 2F). 13C NMR:
d
50.2, 21.8,
ꢀ82.5 (s, 4F). 13C NMR:
d 38.2. MS (EI, m/z, %): 119 (3.7), 110 (4.9),
10.8. MS (EI, m/z, %): 352 (100), 310 (25.7), 164 (44.2), 119 (24.0),
101 (15.6), 70 (15.4), 43 (59.9), 42 (15.3). IR (KBr): 2974, 2943,
2884, 1472, 1390, 1327, 1284, 1203, 1139, 1015, 976, 873, 857,
744, 583, 524 cmꢀ1. Anal. Calcd. for C10H15F8NO3S: C, 31.50; H,
3.97; N, 3.67. Found: C, 31.80; H, 4.22; N, 3.62.
2dg: colorless liquid. Yield: 88%. 1H NMR:
(m, 4H), 5.87 (tt, J = 52.5 Hz, J = 3.2 Hz, 1H), 4.45 (s, 4H). 19F NMR:
109 (3.6), 108 (100), 100 (3.4), 92 (13.9), 44 (8.7), 42 (5.3). IR (KBr):
1379, 1336, 1287, 1213, 1150, 1129, 1001, 969, 881, 701, 658, 573,
485 cmꢀ1. Anal. Calcd. for C12H12F16N2O6S2: C, 22.23; H, 1.87; N,
4.32. Found: C, 22.34; H, 1.92; N, 4.33.
2ib: colorless liquid. Yield: 27%. 1H NMR:
d
3.48 (d, J = 25.1 Hz,
ꢀ126.2 (m, 4F), ꢀ116.7 (s,
42.8, 14.1. MS (EI, m/z,
d
7.32 (m, 6H), 7.18
8H), 1.26 (t, J = 7.3 Hz, 12H). 19F NMR:
d
d
4F), ꢀ83.6 (m, 4F), ꢀ82.2 (s, 4F). 13C NMR:
d
ꢀ137.9 (dt, J = 52.6 Hz, J = 5.1 Hz, 2F), ꢀ115.8 (s, 2F), ꢀ89.1 (m, 2F),
%): 689 (7.7), 137 (5.9), 136 (100), 120 (19.0), 119 (8.1), 71 (8.3), 56
(7.1), 44 (10.0). IR (KBr): 2987, 1471, 1390, 1314, 1288, 1214, 1148,
1024, 945, 791, 696, 590, 506 cmꢀ1. HRMS for C16H20F16N2O6S2:
704.0507. Found: 704.0503.
ꢀ82.0 (m, 2F). 13C NMR:
d 133.7, 128.8, 128.4, 51.4. MS (EI, m/z, %):
386 (5.0), 196 (6.0), 195 (7.6), 194 (11.7), 93 (5.0), 92 (67.9), 91
(100), 65 (8.4). IR (KBr): 3035, 2360, 1508, 1458, 1389, 1326, 1200,
1144, 1059, 932, 895, 748, 698, 610, 505 cmꢀ1. Anal. Calcd. for
2ic: colorless liquid. Yield: 31%. 1H NMR:
d 5.82–5.69 (m, 4H),
C
18H15F8NO3S: C, 45.29; H, 3.17; N, 2.93. Found: C, 45.07; H, 3.37;
N, 2.96.
2dh: colorless liquid. Yield: 75%. 1H NMR:
J = 3.2 Hz, 1H), 5.82–5.68 (m, 2H), 5.35–5.25 (m, 4H), 3.98 (d,
5.35–5.25 (m, 8H), 3.98 (d, J = 5.9 Hz, 8H). 19F NMR:
d
ꢀ126.1 (m,
4F), ꢀ116.6 (s, 4F), ꢀ83.5 (m, 4F), ꢀ82.0 (s, 4F). 13C NMR:
d
131.4,
d
5.87 (tt, J = 52.6 Hz,
120.8, 50.0. MS (EI, m/z, %): 160 (60.6), 144 (19.3), 96 (75.3), 94
(21.7), 81 (16.0), 69 (33.6), 68 (17.4), 41 (100). IR (KBr): 3091, 2992,
2937, 1645, 1446, 1423, 1395, 1333, 1288, 1217, 1148, 1058, 991,
J = 5.0 Hz, 4H). 19F NMR:
d
ꢀ138.0 (dt, J = 52.6 Hz, J = 5.2 Hz, 2F),
ꢀ116.9 (s, 2F), ꢀ89.1 (m, 2F), ꢀ82.1 (m, 2F). 13C NMR:
d
131.4,
935, 910, 892, 766, 720, 614, 573, 504 cmꢀ1
20H20F16N2O6S2: 752.0507. Found: 752.0511.
2id: white solid; mp 135–136 8C. Yield: 86%. 1H NMR:
. HRMS for
120.8, 50.0. MS (EI, m/z, %): 348 (14.5), 160 (25.6), 119 (15.4), 101
(15.6), 96 (17.7), 69 (20.4), 68 (14.4), 41 (100). IR (KBr): 3091, 2993,
2939, 1646, 1447, 1423, 1390, 1328, 1284, 1200, 1144, 1059, 992,
936, 910, 857, 778, 749, 615, 578, 504 cmꢀ1. Anal. Calcd. for
C
d
7.32–
ꢀ126.1 (m, 4F),
133.7, 128.8,
7.30 (m, 12H), 7.17 (m, 8H), 4.45 (s, 8H). 19F NMR:
d
ꢀ115.7 (s, 4F), ꢀ83.6 (m, 4F), ꢀ81.9 (s, 4F). 13C NMR:
d
C
10H11F8NO3S: C, 31.84; H, 2.94; N, 3.71. Found: C, 32.04; H, 3.09;
N, 3.67.
2di: colorless liquid. Yield: 71%. 1H NMR:
J = 3.2 Hz, 1H), 3.77 (s, 4H), 3.56 (s, 4H). 19F NMR:
J = 52.6 Hz, J = 5.2 Hz, 2F), ꢀ116.2 (s, 2F), ꢀ88.8 (m, 2F), ꢀ82.2 (m,
2F). 13C NMR:
66.5, 46.9. MS (EI, m/z, %): 119 (100), 107 (38.8),
128.7, 128.4, 51.4. MS (EI, m/z, %): 260 (5.0), 196 (24.0), 195 (19.9),
194 (14.7), 93 (4.8), 92 (63.4), 91 (100), 65 (4.5). IR (KBr): 3034,
1497, 1458, 1379, 1363, 1327, 1289, 1217, 1172, 1141, 1062, 1007,
936, 923, 906, 889, 744, 708, 693, 606, 690, 533, 499 cmꢀ1. Anal.
Calcd. for C36H28F16N2O6S2: C, 45.38; H, 2.96; N, 2.94. Found: C,
45.39; H, 3.28; N, 2.74.
d
5.87 (tt, J = 52.6 Hz,
ꢀ137.8 (dt,
d
d
106 (59.4), 66 (65.7), 54 (74.6), 52 (26.4), 43 (49.7), 41 (37.3). IR
(KBr): 2980, 2936, 2871, 1456, 1394, 1330, 1286, 1266, 1200, 1118,
1078, 991, 958, 857, 751, 711, 699, 610, 578, 495 cmꢀ1. Anal. Calcd.
for C8H9F8NO4S: C, 26.17; H, 2.47; N, 3.81. Found: C, 26.32; H, 2.46;
N, 3.77.
4.6. Typical procedure for the preparation of 2ai, 2aj and 2al
1a (0.152 g, 1.02 mmol) and 2-(2-hydroxyethoxy)ethyl 4-
methylbenzenesulfonate (0.580 g, 2.23 mmol) were dissolved in
THF (10 mL) and placed in a 25 mL round bottom flask which was
equipped with a magnetic stirrer. K2CO3 (0.286 g, 2.10 mmol) was
then added. After being refluxed for 2 days, the reaction mixture
was diluted by Et2O (30 mL) and filtered. The solvent was
2ha: white solid; mp 72–73 8C. Yield: 35%. 1H NMR:
d
3.09 (s,
12H). 19F NMR:
d
ꢀ115.3 (s, 4F), ꢀ82.3 (s, 4F). 13C NMR:
d 38.2. MS
(EI, m/z, %): 110 (4.9), 109 (3.5), 108 (100), 100 (5.1), 92 (18.6), 44
(18.9), 43 (5.8), 42 (12.2). IR (KBr): 2920, 2851, 1491, 1459, 1394,

766
C.-P. Zhang et al. / Journal of Fluorine Chemistry 131 (2010) 761–766
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evaporated and the crude product was purified by column
chromatography to give 0.232 g of pure 2ai (colorless liquid,
0.714 mmol, 71%) using dichloromethane/methanol (20:1) as the
eluent. 1H NMR:
d d
3.75–3.59 (m, 16H), 2.89 (s, 2H). 19F NMR:
ꢀ75.7 (s, 3F). 13C NMR:
d 120.0 (q, J = 323.8 Hz, CF3), 72.6, 69.7,
61.6, 49.6. MS (EI, m/z, %): 190 (15.8), 176 (16.2), 118 (31.4), 88
(28.5), 75 (17.9), 56 (25.5), 45 (100), 44 (17.7). IR (KBr): 3400, 2938,
2877, 1385, 1226, 1191, 1127, 1066, 1004, 701, 594 cmꢀ1. Anal.
Calcd. for C9H18F3NO6S: C, 33.23; H, 5.58; N, 4.31. Found: C, 32.95;
H, 5.46; N, 4.00.
2aj: colorless liquid. Yield: 68%. 1H NMR:
3.58 (m, 4H), 3.16 (s, 2H). 19F NMR:
d 3.72–3.65 (m, 20H),
d
ꢀ75.9 (s, 3F). 13C NMR:
d 119.9
(q, J = 323.1 Hz, CF3), 72.7, 70.3, 70.1, 69.9, 61.5, 49.1. MS (EI, m/z, %):
220 (15.1), 176 (17.4), 174 (28.2), 162 (17.7), 89 (58.4), 87 (25.6), 56
(20.1), 45 (100). IR (KBr): 3414, 2877, 1456, 1386, 1355, 1225, 1193,
1126, 1070, 1004, 701, 595 cmꢀ1. Anal. Calcd. for C13H26F3NO8S: C,
37.77; H, 6.34; N, 3.39. Found: C, 37.41; H, 6.60; N, 3.24.
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8684.
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673.
2al: light yellow liquid. Yield: 9%. 1H NMR:
d
3.70 (m, 16H), 3.62
(s, 8H). 19F NMR:
d
ꢀ76.0 (s, 6F). 13C NMR:
d 119.9 (q, J = 323.9 Hz,
´
ˇ ´
´
ˇ
[15] S. Babic, A.J.M. Horvat, D. Mutavdzic Pavlovic, M. Kastelan-Macan, Trends Anal.
CF3), 70.5, 70.1, 49.3. MS (EI, m/z, %): 393 (82.3), 220 (17.6), 100
(39.1), 70 (20.3), 69 (28.1), 56 (100), 45 (18.6), 42 (24.2). IR (KBr):
2876, 1456, 1386, 1359, 1226, 1190, 1125, 1002, 769, 730, 701,
595 cmꢀ1. HRMS for C14H24F6N2O8S2: 526.0878. Found: 526.0871.
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Acknowledgements
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We thank the Chinese Academy of Sciences (Hundreds of
Talents Program), the National Natural Science Foundation
(20772147, 20972179) and the Syngenta PhD Studentship Award
for financial support.
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