Reactions of 1,3,5-tris(fluorosulfonyl)benzene with some nucleophilic reagents

Article abstract of DOI:10.1016/j.jfluchem.2009.11.019

The reactions of 1,3,5-tris(fluorosulfonyl)benzene 1 with nucleophilic agents were investigated. It was found that morpholine, β,β,β-trifluoroethanol in the presence of triethylamine and sodium azide formed corresponding 1,3,5-trisulfonyl derivatives. In contrast, nucleophiles such as aniline, thiourea, and potassium thiocyanate do not react with compound 1 even in excess and under moderate heating. The conditions for the selective fluorine atom substitution in one SO₂F group with morpholine, DMAP and aniline in the presence of triethylamine as well as in two SO₂F groups with DMAP were found. Anionic σ-complex of compound 1 with nitromethane was isolated as individual compound.

Full text of DOI:10.1016/j.jfluchem.2009.11.019

Journal of Fluorine Chemistry 131 (2010) 248–253
Contents lists available at ScienceDirect
Journal of Fluorine Chemistry
journal homepage: www.elsevier.com/locate/fluor
Reactions of 1,3,5-tris(fluorosulfonyl)benzene with some nucleophilic reagents
*
Oksana M. Kamoshenkova, Vladimir N. Boiko
Institute of Organic Chemistry, National Academy of Sciences of Ukraine, Murmanskaya St. 5, 02094 Kyiv, Ukraine
A R T I C L E I N F O
A B S T R A C T
Article history:
The reactions of 1,3,5-tris(fluorosulfonyl)benzene 1 with nucleophilic agents were investigated. It was
Received 30 July 2009
found that morpholine,
b,b,b-trifluoroethanol in the presence of triethylamine and sodium azide
Received in revised form 19 November 2009
Accepted 24 November 2009
Available online 3 December 2009
Dedicated to the memory of
Prof. L.M. Yagupolskii.
formed corresponding 1,3,5-trisulfonyl derivatives. In contrast, nucleophiles such as aniline, thiourea,
and potassium thiocyanate do not react with compound 1 even in excess and under moderate heating.
The conditions for the selective fluorine atom substitution in one SO2F group with morpholine, DMAP
and aniline in the presence of triethylamine as well as in two SO2F groups with DMAP were found.
Anionic
s
-complex of compound 1 with nitromethane was isolated as individual compound.
ß 2009 Elsevier B.V. All rights reserved.
Keywords:
1,3,5-Tris(fluorosulfonyl)benzene
Anionic
s-complex
Aromatic sulfonic acid fluoride
Aromatic nucleophilic addition
1. Introduction
Moreover, the SO2F group is known to be a strong electron-
withdrawing substituent. Its sp values (0.91–1.54 defined by
The subject of our investigation is 1,3,5-tris(fluorosulfonyl)-
benzene 1. Recently [1] we have shown that compound 1 is able to
undergo nucleophilic addition at free position on the aromatic ring
various methods [6]) are almost identical to that of the SO2CF3
group (0.91–1.63 [6]). According to this fact, compound 1 can be
considered as an analog of 1,3,5-tris(trifluoromethylsulfonyl)ben-
zene (sulfone 2) [7].
with the formation of anionic
s-complexes. However, these
reactions often proceed ambiguously and products of fluorine
substitution in SO2F groups appear. Thus, taking into account that
compound 1 has at least two different reaction centers for a
nucleophilic attack—the fluorosulfonyl group and a free position of
the aromatic ring—we performed a detailed investigation of
compound’s 1 reactivity with various nucleophilic agents.
It should be noted that the reaction ability of aromatic sulfonic
acid fluorides towards nucleophilic agents is quite weak. These
compounds are essentially resistant to heating in weak alkaline
aqueous and organo-aqueous mediums [2] and can be distilled with
a steam. For example, during the fluorination of p-acetylaminoben-
zene sulfonyl chloride by aqueous KF (135–140 8C), apart from the
formation of the corresponding fluorosulfonyl derivative, hydrolysis
of the acetyl group was observed. The formed fluorosulfonyl group
was stableunder theseconditions [3]. Hydrolysis of benzene sulfonic
acid fluoride proceeded ꢀ5000 times slower than that of benzene
sulfonic acid chloride [4]. The reactions of p-substituted phenyl
sulfonyl fluorides with benzyl amines were significantly slower than
those of analogous aryl sulfonyl chlorides [5].
Such a comparison may be quite appropriate in the context of
the recognition of electron-withdrawing nature of sulfonyl groups.
This question is intensively discussed until present time [8]. For
example, delocalization of the negative charge in molecules
containing SO2CF3 groups is represented as follows:
In molecules containing SO2F groups, similar resonance
structures can be drawn:
* Corresponding author. Tel.: +380 44 5590349; fax: +380 44 5732643.
E-mail addresses: boikovolodymyr@yandex.ru, sandy34@yandex.ru
(V.N. Boiko).
Taking into account the resonance structures presented above,
it may be expected that the 19F NMR chemical shift of the fluorine
0022-1139/$ – see front matter ß 2009 Elsevier B.V. All rights reserved.
doi:10.1016/j.jfluchem.2009.11.019

O.M. Kamoshenkova, V.N. Boiko / Journal of Fluorine Chemistry 131 (2010) 248–253
249
atom, directly connected with a sulfonyl electrophilic center, must
be sensitive to the electronic environment and structure differ-
ences of the molecule’s core.
There were only two reports on the synthesis of 1,3,5-
tris(fluorosulfonyl)benzene 1 [2a,9]. Both of them were based on
with CF3CH2Oꢁ, despite changes in reaction conditions such as
variation of solvent (diethyl ether, benzene, acetonitrile, benzene/
acetonitrile), temperature (from ꢁ10 to 35 8C) and methods of
CF3CH2Oꢁ generation (CF3CH2OH/Et3N, CF3CH2ONa, CF3CH2O-
SiMe3/CsF or CF3CH2OSiMe3/Me4NF). It is found that the reaction
begins at 8–10 8C but even slow addition of any source of
CF3CH2Oꢁ at this temperature does not improve the selectivity.
The reaction of compound 1 with two equivalents of CF3CH2O
results in the formation of 1,3,5-tris(trifluoroethoxysulfonyl)ben-
zene 4 as the major product.
Nevertheless, we found reaction conditions for the selective
fluorine substitution for some nucleophiles. For example, the
reaction of compound 1 proceeds rather selectively with morpho-
line in THF or DME at 30–35 8C. The gradual addition of this
nucleophile (2 eq.) to the sulfonyl fluoride 1 leads to the formation
the substitution of the chlorine atom in
a deficient 1,3,5-
tris(chlorosulfonyl)benzene. Additionally, the yields of 1 were
rather low (46–50%). That is why chemical properties of sulfonyl
fluoride 1 were almost uninvestigated before our work. It was only
known that in the reaction with KF at 200–210 8C one or two SO2F
groups can be substituted by the fluorine atom [9].
Recently a new method of synthesis of compound 1 was
proposed based on the reduction of 2,4,6-tris(fluorosulfonyl)-
chlorobenzene with Zn [10].
of mono-sulfonyl morpholide
6 with a minor quantity of
2. Results and discussion
disubstituted product 7 (Scheme 2).
As mentioned above, aniline does not react with compound 1
even in excess and under moderate heating. But we found that this
reaction is possible when triethylamine is used as a base. Dropwise
addition of an equimolar mixture of aniline and triethylamine into
the diluted solution of sulfonyl fluoride 1 in acetonitrile provides
the sulfonic acid anilide 8 (Scheme 3).
A base was also required in the reaction of aniline with 1,3,5-
trinitrobenzene [11]. But as far as compound 1 is activated by
electron-withdrawing groups, which are stronger then NO2 and
possess several reaction centers, we expected reactions with
aniline even in the absence of a base as it occurs in the case of 4,6-
dinitrobenzofuroxan [12].
It was found that sulfonyl fluoride 1 exhibits a versatile
reactivity in reactions with nucleophilic agents. With morpholine,
triethylammonium-, and 4-dimethylaminopyridinium
b,b,b-tri-
fluoroethoxide, or even with such moderate nucleophile as sodium
azide, exclusive fluoride substitution in all SO2F groups occurs
yielding the corresponding trisulfonyl derivatives 3–5. Other
reagents such as aniline, thiourea, and potassium thiocyanate do
not react with compound 1 at all even in excess and under
moderate heating (Scheme 1).
To realize selective fluorine substitution in one or two
fluorosulfonyl groups seems to be rather difficult. The reaction
of compound 1 with morpholine and sodium azide in acetonitrile
even at low temperature (ꢁ60 8C) and equimolar amount of the
reagent affords a mixture of mono-, di-, and tri-substituted
sulfonyl derivatives. The same result is obtained in the reactions
Interestingly, the sulfonyl pyridinium derivative 9 is formed
when compound 1 is reacted with aniline in the presence of DMAP
instead of Et3N. Application of two or more equivalents of DMAP
Scheme 1.

250
O.M. Kamoshenkova, V.N. Boiko / Journal of Fluorine Chemistry 131 (2010) 248–253
Scheme 2.
(Scheme 5). The molar ratio of compounds 11, 8 and 1 in the
reaction mixture is 4.5:1:1.5. The adduct 11 is stable up to 60 8C.
As it was mentioned above, trisulfonic acid trifluoride 1 can add
nucleophilic reagents to an unsubstituted position in the aromatic
ring forming the anionic
These adducts exhibit different stabilities. The 19F NMR signals
of the anionic -complex 15 can be detected only within the first
s-complexes 12–17 (Scheme 6) [1].
s
15 min, besides of signals of the fluorine substitution products. In
contrast, the corresponding adducts with sodium sulfite 12,
malonic ester 14 and dimedone 17 are stable in DMSO solution
Scheme 3.
leads to the formation of the disulfonyl pyridinium derivative 10
(Scheme 4).
Thus, depending on the reaction conditions and type of
nucleophilic agent it is possible to prepare products of mono-,
di- or tri-substitution of fluorine in compound 1.
for 7–8 days. Despite the stability of these s-complexes in solution
we were not able to isolate them. Therefore, we tried to obtain
them in other polar solvents like DMF, acetonitrile, dioxane, and
acetone. It was possible to prepare these adducts in DMF but
isolation was also quite difficult. In other solvents the 19F NMR
signals of the variety of substitution products are seen immedi-
ately after mixing of the reagents. Later we found out that it is
An unexpected result is observed when an excess of PhNH2 and
Et3N (3–6 eq.) is used. Instead of the estimated tri-substituted
product an anionic
compound 8 either at 20–25 8C or under moderate heating
s
-complex 11 is formed in addition to
possible to obtain anionic
and THF (Scheme 7).
s-complex with nitromethane in DME
Scheme 4.
Scheme 5.
Scheme 6.

O.M. Kamoshenkova, V.N. Boiko / Journal of Fluorine Chemistry 131 (2010) 248–253
251
the molecular and electronic structure of the corresponding
anionic -complexes are of great interest and deserve to be
s
investigated in detail by computational methods.
3. Conclusions
Depending on the reaction conditions and the type of the
nucleophile the reactions of 1,3,5-tris(fluorosulfonyl)benzene 1
with various nucleophilic agents can proceed both at the sulfonyl
centre yielding products of complete or partial substitution of
Scheme 7.
fluorine atoms and/or anionic
s-complexes as a result of the
nucleophilic addition at a free position of the aromatic ring.
Triethylamine has been used as a base in the synthesis of all
adducts mentioned above except 12 and 13. However, using a
4. Experimental
sodium salt of nitromethane for the preparation of
s-complex 16
provides this adduct more selectively making its isolation possible
as an individual compound. Compound 16 is a yellow solid soluble
in polar organic solvents. Under anhydrous conditions it can be
stored for a long time. In the presence of mineral acids 16
transforms into the initial compound 1.
All reactions were carried out in a dry argon atmosphere by
using Schlenk techniques. 2,2,2-Trifluoroethoxytrimethylsilane
was synthesized according to literature procedure [14]. Sodium
salt of nitromethane was obtained by the reaction of nitromethane
with sodium hydride. All solvents were purified according to
literature procedures [15]. 1H, 19F, 13C NMR spectra were recorded
in DMSO-d6 as a solvent using Varian VXR-300 (299.95 MHz),
Varian Gemini-200 (188.14 MHz), and Bruker Avance DRX-500
(125.77 MHz) spectrometers, respectively. Chemical shifts are
During the investigation of anionic
s-complexes 12–17 we
observed an interesting phenomenon. As it was shown earlier [13],
the negative charge of the associated nucleophilic agent is
displaced into the aromatic rings of the initial compounds. That
is why in the NMR spectra both the signals of the aromatic protons
given in ppm. Tetramethylsilane (1H NMR:
d
= 0.00 ppm; 13C NMR:
in all anionic
s
-complexes and of the fluorine atoms of the adducts
d
= 0.00 ppm) and CCl3F (19F NMR:
d
= 0.00 ppm) were used as
of sulfones 2 [7a–c] are shifted to higher field as compared to their
positions in the NMR spectra of the initial compounds. Similar high
internal standards for 1H, 13C, and 19F NMR spectra. Melting points
were determined on the electro-thermal apparatus and are
uncorrected. Elemental analysis was carried out in the Analytical
Laboratory of the Institute of Organic Chemistry, NAS of Ukraine,
Kyiv.
field shifts are also observed for the proton resonances of the
s-
complexes 12–17 [1]. In contrast, their 19F NMR signals appear
downfield (Fig. 1). However, there is no clear regularity.
For example, the signals of all SO2F groups of adducts 12–15 are
shifted downfield. At that, in complexes 14 and 15 the signals of
these groups in the ortho- and para-positions coincide. In case of
compounds 16 and 17 the signals of p-SO2F groups are shifted
downfield while the signals of o-SO2F groups are shifted high field.
Furthermore, in the spectra of complex with dimedone 17 o-SO2F
groups exhibit two different resonances. Probably this can be
referred to the presence of the bulky dimedone moiety in the
4.1. General procedure for the preparation of tris-sulfonyl derivatives
(3–5)
To a stirred solution of 1,3,5-tris(fluorosulfonyl)benzene 1
(0.1 g, 0.31 mmol) in acetonitrile (5 ml) the excess of correspond-
ing nucleophile was added. The mixture was stirred at 20–25 8C for
6 h. The product formation was monitored by 19F NMR spectra. All
products were crystallized from benzene.
geminal position of
nonequivalent.
s-complex 17, which makes the o-SO2F groups
Thus, the position of the resonance signals in 19F NMR spectra
found for of 12–17 can not be simply correlated with changes of the
atomic charges and have a more complex nature. Consequently,
4.1.1. 1,3,5-Tris(azidosulfonyl)benzene (3)
The best results were obtained when sodium azide (0.06 g,
0.92 mmol) is used.
White solid: 79% yield; mp., 134–135 8C; 1H NMR spectral data
(299.9 MHz, DMSO-d6):
DMSO-d6): 131.69 (s, Ar), 140.97 (s, Ar). Anal. Calcd. for
C6H3N9O6S3: C 17.5; H 1.2; N 30.6. Found: C 17.22; H 1.5; N 31.3.
d
8.9 (H, s, Ar). 13C NMR (125.77 MHz,
d
4.1.2. 1,3,5-Tris(b,b,b-trifluoroethoxysulfonyl)benzene (4)
The best results are obtained when CF3CH2OH (1 mmol) and
DMAP (0.9 mmol) are used.
White solid: 78% yield; mp., 164–165 8C; 1H NMR spectral data
(299.9 MHz, DMSO-d6):
d 5.03 (6H, q, JH,F = 8.3 Hz, OCH2CF3), 8.87
(3H, s, Ar). 19F NMR (188.1 MHz, CCl3F):
CF3). 13C NMR (125.77 MHz, DMSO-d6):
d
ꢁ73.5 (t, 9F, JF,H = 8.2 Hz,
d
66.02 (q, JC,F = 34.47 Hz,
CH2), 122.26 (q, JC,F = 277.92 Hz, CF3), 133.0 (s, Ar), 137.88 (s, Ar).
Anal. Calcd. for C12H9F9O9S3: C 25.54; H 1.6; F 29.57; S 17.04.
Found: C 25.61; H 2.1; F 29.81; S 17.23.
4.1.3. 1,3,5-Tris(morpholinosulfonyl)benzene (5)
The best results are obtained when morpholine (0.16 g,
1.8 mmol) is used.
White solid: 68% yield; mp., >250 8C; 1H NMR spectral data
(299.9 MHz, DMSO-d6):
d 3.17 (12H, t, JH,H = 4.6 Hz, CH2), 3.75
Fig. 1. The position of the 19F NMR signals of adducts 12–17 relative to compound 1.
(12H, t, JH,H = 4.6 Hz, CH2), 8.3 (3H, s, Ar). 13C NMR (125.77 MHz,

252
O.M. Kamoshenkova, V.N. Boiko / Journal of Fluorine Chemistry 131 (2010) 248–253
DMSO-d6):
d
45.37 (s, CH2), 65.39 (s, CH2), 129.97 (s, Ar), 138.02 (s,
DMAP), 156.85 (s, DMAP). Anal. Calcd. for C13H13F3N2O6S3: C
34.98; H 2.94; F 12.77; N 6.27; S 21.55. Found: C 35.11; H 3.01; F
12.93; N 6.35; S 21.76.
Ar). Anal. Calcd. for C18H27N3O9S3: C 40.67; H 2.94; N 8.18. Found:
C 40.56; H 3.11; N 8.33.
4.2. Preparation of 3,5-bis(fluorosulfonyl)benzene sulfonyl
4.4.2. Fluorosulfonylbenzene-3,5-bis(sylfonyl-40-
dimethylaminopyridinium) difluoride (10)
morpholide (6)
White solid: 92% yield; mp., 191–193 8C; 1H NMR spectral data
A solution of morpholine (0.14 g, 1.65 mmol) in THF (1 ml) was
added dropwise under stirring at 30–35 8C to the solution of
compound 1 (0.25 g, 0.77 mmol) in THF (2 ml). Then reaction
mixture was stirred at the same temperature for 4 h. The formed
precipitate (morpholine hydrochloride) was filtered and the
solvent was evaporated in vacuum. The crude product was washed
with cold aqueous HCl (5%, 3 ml), dried and crystallized from
methylene chloride to afford a desired product 6 (0.14 g), as a
white solid: 45% yield; mp. 207–209 8C; 1H NMR spectral data
(299.9 MHz, DMSO-d6): d 3.11 (12H, s, CH3), 6.86 (4H, d,
JH,H = 6.4 Hz, CH), 8.17 (4H, d, JH,H = 6.4 Hz, CH), 8.55 (2H, d,
JH,H = 1.5 Hz, Ar), 8.73 (1H, t, JH,H = 1.5 Hz, Ar). 19F NMR (188.1 MHz,
CCl3F):
125.77 MHz):
d
ꢁ155.63 (s, 2F, Fꢁ), 64.96 (s, 1F SO2F). 13C NMR (DMSO-d6,
d 39.09 (s, CH3), 106.82 (s, DMAP), 124.64 (s, Ar),
128.53 (s, Ar), 130.2 (s, Ar) 133.72 (d, JC,F = 28.92 Hz, Ar), 151.96 (s,
DMAP), 156.85 (s, DMAP). Anal. Calcd. for C20H23F3N4O6S3: C
42.24; H 4.08; N 9.85; S 16.92. Found: C 42.31; H 4.21; F 10.18; N
9.87; S 17.03.
(299.9 MHz, DMSO-d6):
JH,H = 4.6 Hz, CH2), 8.71 (2H, d, JH,H = 1.4 Hz, Ar), 9.12 (1H, t,
JH,H = 1.4 Hz, Ar). 19F NMR (188.1 MHz, CCl3F):
67.15 (s, F, SO2F).
13C NMR (125.77 MHz, DMSO-d6):
45.49 (s, CH2), 65.27 (s, CH2),
d 3.13 (4H, t, JH,H = 4.6 Hz, CH2), 3.65 (4H, t,
4.5. Preparation of sodium 1-nitromethyl-2,4,6-
d
tris(fluorosulfonyl)cyclohexadienate (16)
d
132.6 (s, Ar), 133.62 (s, Ar), 135.26 (d, JC,F = 28.92 Hz, Ar), 139.43 (s,
Ar). Anal. Calcd. for C10H11F2NO7S3: C 42.99; H 3.97; F 13.6; N 5.01;
S 34.43. Found: C 43.09; H 4.02; F 13.83; N 5.09; S 34.51.
To a cooled (ꢁ15 8C), stirred solution of compound 1 (0.1 g,
0.34 mmol) in THF (2 ml) a sodium salt of nitromethane (0.04 g,
0.3 mmol) was added. During the first 5 min the reaction mixture
was colored in bright yellow. Interaction was successfully
completed in 30 min. After the solvent evaporation a crude
product was washed with benzene (2 ml) and dried in vacuum to
afford compound 16 (0.55 g) as a yellow solid: 78% yield; mp.
4.3. Preparation of 3,5-bis(fluorosulfonyl)benzene sulfonyl anilide (8)
A solution of triethylamine (0.16 g, 1.63 mmol) in acetonitrile
(5 ml) was added dropwise under stirring at 40–45 8C to the
mixture of compound 1 (0.2 g, 0.62 mmol) and aniline (0.088 g,
0.95 mmol) in acetonitrile (5 ml). Then the reaction mixture was
stirred at the same temperature for 6 h, acidified with concentrat-
ed HCl to the pH 5–6 and the solvent was evaporated in vacuum.
The crude product was washed quickly with cold water (10 ml),
dried and crystallized from dioxane to afford a desired product 8
(0.16 g) as a white solid: 65% yield; mp. >200 8C; 1H NMR spectral
>250 8C; 1H NMR spectral data (299.9 MHz, DMSO-d6):
d, JH,H = 5 Hz, CH2), 4.71 (1H, t, JH,H = 5 Hz, CHgem), 7.53 (2H, s, CH).
19F NMR (188.1 MHz, CCl3F):
63.67 (s, 2F, o-SO2F), 67.89 (s, 1F, n-
SO2F). 13C NMR (125.77 MHz, DMSO-d6):
25.09 (s, CH2NO2),
d 4.5 (2H,
d
d
66.98 (s, CHgem), 93.7 (d, JC,F = 28.92 Hz, C-SO2F), 98.9 (d,
JC,F = 25.15 Hz, C-SO2F), 139.63 (s, 3,5-CH). Anal. Calcd. for
C7H5F3NNaO8S3: C 20.64; H 1.24; F 13.99; S 23.62. Found: C
20.77; H 1.37; F 14.07; S 23.98.
data (299.9 MHz, DMSO-d6):
JH,H = 1.4 Hz, Ar), 9.13 (1H, t, JH,H = 1.4 Hz, Ar), 10.02 (1H, s, NH). 19
NMR (188.1 MHz, CCl3F):
67.15 (s, F, SO2F). 13C NMR
(125.77 MHz, DMSO-d6): 127.91 (s, C6H5NH), 128.64 (s Ar),
129.79 (s, C6H5NH), 131.61 (s, Ar), 132.05 (s, Ar), 133.82 (d,
JC,F = 26.4 Hz, Ar), 152.02 (s, C6H5NH). Anal. Calcd. for C12H9F2O6S3:
C 36.27; H 2.28; F 9.56; N 3.5. Found: C 36.33; H 2.4; F 9.67; N 3.45.
d 7.81 (5H, m, C6H5), 8.96 (2H, d,
F
References
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d
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4.4. General procedure for the preparation of 3,5-
bis(fluorosulfonyl)benzenesulfonyl-40-dimethylaminopyridinium
fluoride (9) and fluorosulfonylbenzene-3,5-bis(sylfonyl-40-
dimethylaminopyridinium) difluoride (10)
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A solution of compound 1 (0.1 g, 0.31 mmol) and 4-dimethy-
laminopyridine (0.037 g, 0.303 mmol for 9 and 0.075 g, 0.61 mmol
for 10) in acetonitrile (2 ml) was well stirred at 50–55 8C for 7 h
and then at r.t. overnight. The product formation was monitored by
19F NMR spectra. The solvent was evaporated in vacuum. The crude
product was washed with benzene (2 ꢂ 2 ml) to remove the excess
of the initial compound 1 and crystallized from dioxane to afford a
desired products 9 (0.1 g) or 10 (0.163 g).
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(1979) 806–816; J. Org. Chem. [USSR] 15 (1979) 720–729;
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4.4.1. 3,5-Bis(fluorosulfonyl)benzenesulfonyl-40-
dimethylaminopyridinium fluoride (9)
White solid: 75% yield; mp, 186–187 8C; 1H NMR spectral data
[8] (a) F. Terrier, E. Kizilian, R. Goumont, N. Faucher, C. Wakselman, J. Am. Chem. Soc.
120 (1998) 9496–9503;
(299.9 MHz, DMSO-d6):
d 3.11 (6H, s, CH3), 6.98 (2H, d,
JH,H = 6.4 Hz, CH), 8.22 (2H, d, JH,H = 6.4 Hz, CH), 8.55 (2H, d,
JH,H = 1.5 Hz, Ar), 8.73 (1H, t, JH,H = 1.5 Hz, Ar). 19F NMR (188.1 MHz,
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CCl3F):
d
ꢁ155.63 (s, 1F, Fꢁ), 66.82 (s, 1F SO2F). 13C NMR (DMSO-d6,
125.77 MHz):
d 39.09 (s, CH3), 106.88 (s, DMAP), 124.65 (s, Ar),
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128.58 (s, Ar), 130.0 (s, Ar), 133.71 (d, JC,F = 28.92 Hz, Ar), 152.05 (s,

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