Interaction of 2,4,6-tris(fluorosulfonyl)chlorobenzene with O-, N-, S-, C-nucleophiles and F-anion

Article abstract of DOI:10.1016/j.jfluchem.2012.05.015

Reactions of 2,4,6-tris(fluorosulfonyl)chlorobenzene 1 with O-, N-, S-, C-nucleophiles and F-anion showed high reactivity of 1 that was defined by three strong electron withdrawing SO₂F groups creating several electrophilic centers within the m

Full text of DOI:10.1016/j.jfluchem.2012.05.015

Journal of Fluorine Chemistry 143 (2012) 123–129
Contents lists available at SciVerse ScienceDirect
Journal of Fluorine Chemistry
journal homepage: www.elsevier.com/locate/fluor
Interaction of 2,4,6-tris(fluorosulfonyl)chlorobenzene with O-, N-, S-,
C-nucleophiles and F-anion
*
Andrey A. Filatov, Vladimir N. Boiko, Yurii L. Yagupolskii
Institute of Organic Chemistry, National Academy of Sciences of Ukraine, 5 Murmanskaya St., UA-02094 Kiev-94, Ukraine
A R T I C L E I N F O
A B S T R A C T
Article history:
Reactions of 2,4,6-tris(fluorosulfonyl)chlorobenzene 1 with O-, N-, S-, C-nucleophiles and F-anion
showed high reactivity of 1 that was defined by three strong electron withdrawing SO2F groups creating
several electrophilic centers within the molecule. Conditions for selective chlorine atom substitution
were defined that resulted in formation of corresponding ethers, amines and sulfides, while excess of
nucleophile commonly led to SO2F groups implication in the reaction. Two equivalents of fluoride-anion
Received 27 February 2012
Received in revised form 10 May 2012
Accepted 14 May 2012
Available online 20 May 2012
source gave rise not only to the chlorine-fluorine substitution but afforded in the anionic
s-complex
Keywords:
formation with two fluorine atoms in the hem-position. Reduction of chlorobenzene 1 with zinc/AcOH
was found to be a choice for 1,3,5-tris(fluorosulfonyl)benzene preparation.
ß 2012 Elsevier B.V. All rights reserved.
Arenes
Sulfonyl fluorides
Nucleophilic substitution
Synthetic methods
1. Introduction
which were previously studied by our group in detail [3–5], but
fluorosulfonyl derivatives are much more accessible. Noteworthy
In the frame of our continuous interest to aromatic systems
modified by fluorine containing electron withdrawing substituents
we would like to attract attention to the accessible, stable and
intriguing system of symmetric tris(fluorosulfonyl)benzenes [1,2]
as a flat platform for three general pathway designs of various
molecules (Picture 1):
to mention that electronic properties of the SO2F group (sp 1.01)
are similar to SO2CF3 sp 1.04–1.06 [6,7]). pKa values of above
mentioned 2,4,6-three substituted phenols in acetonitrile are close
to each other: phenol 2 – 5.53 and 2,4,6-(SO2CF3)3phenol – 4.79
that outdo the acidity of aromatic sulfonic acids [8,9]. DGacid values
of anilines in gaseous phase are: aniline 3 – 307.5 and 2,4,6-
(SO2CF3)3 aniline – 304.8 kcal/mol [10]. These facts predict high
mobility of chlorine atom in chlorobenzene 1.
(
(1) through nucleophilic attack of SO2F function (potentially
biologically active sulfamides, netlike polymers, etc.);
(2) by mild nucleophilic displacement of activated aromatic
halogen (based on easy obtainable 2,4,6-tris(fluorosulfonyl)-
benzene chloride 1) with fluorosulfonyl fragments preserva-
tion;
On the other hand, SO2F groups can also react with nucleophilic
agents. The last circumstance make it possible to realize a
consecutive introduction various fragments into the molecule of 1.
As to reactivity of SO2F group it is known that fluorosulfo-
nylbenzenes react with bases specifically. Appreciable hydrolysis
occurs when benzene ring is activated with nitro group or with
halogen atom [11]. Reaction rates of p-substituted fluorosulfo-
nylbenzenes with benzylamines were in 1000 times [12] and with
aniline in five degree less [13] than the rate of chlorosulfonyl-
benzenes reactions.
Some comparison of fluorosulfonyl aromatic moiety and
activated aromatic halogen atom reactivity towards various
nucleophilic agents [2,14–16] did not give exact predictions about
2,4,6-tris(fluorosulfonyl)chlorobenzene 1 regioselective behavior
in the basic conditions. The later has different electrophilic centers
and its reactions with nucleophiles may cause to unexpected but
important results. Previously investigated by us chemical reactivi-
ty of 1,3,5-tris(fluorosulfonyl)benzene gave no chance to general-
ize unambiguously outcome of nucleophilic attack towards this
molecule that was strongly dependent on the nucleophile type, its
(3) via combined processes including step by step procedures
(heterocyclizations as well as polymerization).
Simple and effective preparative synthetic procedures for the
syntheses of 2,4,6-tris(fluorosulfonyl)chlorobenzene (1), corre-
sponding phenol 2 and aniline 3 have been elaborated and
presented in our previous publications [1,2] that made these
compounds available for thorough investigations.
Above mentioned molecules correspond to the structural
analogs of 2,4,6-tris(trifluoromethylsulfonyl)benzene derivatives
* Corresponding author. Tel.: +380 44 5590349; fax: +380 44 5732643.
E-mail addresses: Yagupolskii@ioch.kiev.ua, gegols@yandex.ru
(Y.L. Yagupolskii).
0022-1139/$ – see front matter ß 2012 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.jfluchem.2012.05.015

124
A.A. Filatov et al. / Journal of Fluorine Chemistry 143 (2012) 123–129
Nu
products formation that showed the significant difference
(ꢀ7 ppm) in the position between ortho- and para-SO2F groups
in the coarse of various 1-position substitution, or exact change of
integral intensity and positioning of SO2F groups in case of the
attack towards fluorosulfonyl centers.
O
S
Cl
O
S
F
O
F
O
2.1. Reactions with O-nucleophiles
S
F
O
O
As we showed earlier [2], boiling of chlorobenzene 1 alcoholic
solution gave phenol 2 (Scheme 1). The reaction presumably
Picture 1. Various possible reaction centers of compound 1 towards nucleophile
proceeded via s-complex A formation followed by destruction that
attack.
may occur in two different ways (Scheme 1) both leading to the
formation of phenol 2.
quantity and reaction conditions [17–19]. Thus, in order to perform
consecutive introduction of various fragments into chlorobenzene
1 it is capitally crucial to ascertain the possibility of selective
nucleophilic substitution in this compound.
Formulated synthetic potential of above mentioned tris(fluor-
osulfonyl)benzenes family stimulated us to perform the thorough
investigation of 2,4,6-tris(fluorosulfonyl)chlorobenzene (1) chem-
ical behavior towards the set of O-, N-, S-, C-nucleophiles in order
to realize the scope and limitations of reaction pathways and
products formed.
GLC investigation of the reaction solution (Alk = C2H5) showed
that the second coproduct was diethylether that confirm the
reaction pathway 1 and gave rise to the idea to investigate
compounds 4 as alkylating agents due to the fact that they may be
considered as alkyl esters of the strong acid 2.
Alkyl ethers 4a and 4b were obtained in individual form by
phenol 2 silver salt alkylation with alkyl iodides in dichloro-
methane (Scheme 2) in high yields.
It was found that the only dissolving of compound 4b in ethanol
resulted in diethyl ether (GLC data) and phenol 2 quantitative
formation. Anisole 4a reacts analogously.
Compound 4a easily alkylates nitrogen containing heterocycles.
Thus, products of anisole 4a reactions with N-alkylimidazoles in
1 h were corresponding salts – N-methyl-N0-alkylimidazolium
2,4,6-tris(fluorosulfonyl)phenolates 5 and 6 (Scheme 3).
2. Results and discussion
General remark to investigation performed concerns the
importance of 19F NMR monitoring of reaction progress and
OAlk
SO2F
FSO2
way 1
-HCl
H
Cl O+
_
Cl
SO F
4a-c
2
Alk
SO2F
SO2F
FSO2
FSO2
AlkOH
boiling
AlkOH
-Alk2O
way 2
-AlkCl
SO2F
SO2F
OH
SO2F
FSO2
A
1
Alk = CH3 (a), C2H5 (b), i-C3H7 (c)
SO2F
OAlk
2 (97 %)
Scheme 1. Reactions of 1 with alcohols.
OH
OAg
SO2F
SO2F
SO2F
FSO2
FSO2
FSO2
Ag2CO3
H2O
AlkI
CH2Cl2
SO2F
SO2F
SO2F
2
Alk = CH3 (4a, 83 %), C2H5 (4b, 80 %)
Scheme 2. Syntheses of anisole 4a and phenetole 4b.
O
OCH3
CH3
N
R
N
N
FSO2
SO2F
SO2F
FSO2
M.p. 127.7 oC (5)
87 oC (6)
+
*
N
Benzene
r.t., 1 h
R
SO2F
SO2F
4a
R = C2H5 (5, 98 %), CF2-CF2H (6, 95 %)
Scheme 3. N-alkylation of imidazoles with anisole 4a.

A.A. Filatov et al. / Journal of Fluorine Chemistry 143 (2012) 123–129
125
OPh
Cl
SO2F
FSO2
SO2F
FSO2
PhOH / K2CO3
Dioxane
50 oC
SO2F 7 (84 %)
SO2F
1
Scheme 4. Reaction of 1 with potassium phenolate.
OCH2CF3
Cl
SO2F
CF3CH2OSO2
SO2OCH2CF3
FSO2
CF3CH2OH / K2CO3
Dioxane
r.t. 24 h
SO2F
SO2OCH2CF3 8 (89 %)
1
Scheme 5. Reaction of 1 with trifluoroethanol excess.
Salts 5 and 6 have rather low melting points and show high
stability on handling within half a year period in DMSO solution as
well as in crystalline state.
signal and no evidence of SO2F groups, that may be rationalized as
hydrolysis of SO2F groups in aqueous ammonia resulting in the
formation of fluorosulfonyl function ammonolysis products.
2,4,6-Tris(fluorosulfonyl)aniline 3 was obtained in high yield
using ammonia solution in dry acetonitrile. In these conditions
even an excess of ammonia gave no by-products (Scheme 6).
This conditions for aniline 3 synthesis are more convenient and
productive than the method described by us earlier [2] starting
with 2,4,6-tris(chlorosulfonyl)aniline.
Interaction of chlorobenzene 1 with aniline or secondary
amines passed with stoichiometrical ratio of reagents in acetoni-
trile at ambient temperature. The results were exclusively the
products of chlorine atom substitution (Scheme 7).
Noteworthy to outline that as it was described earlier [20], N-
(tetrafluoroethyl)imidasole was alkylated by methyl iodide within
long-term boiling in acetonitrile. Thus, one can suppose anisole 4a
to be stronger methylating agent in comparison with CH3I.
In contrast to reactions of chlorobenzene 1 with alcohols, its
interaction with alkoxides and phenolate using alcohols or phenol
in polar solvents (AlkOH, CH3CN) in the presence of equimolar
quantity of base even at negative temperature showed complete
lost of selectivity and mixture of products, mainly due to the attack
of SO2F groups, were observed. That may be considered as a critical
difference between chlorobenzene
1
and 2,4,6-tris(trifluoro-
Additional quantity of secondary amine leads to interaction
with SO2F group in step-by-step manner. Thus, using of 4 moles of
morpholine gave compound 12 as a result of 4-SO2F group attack
(Scheme 8).
methylsulfonyl)chlorobenzene – the later reacts mildly with
alkoholates forming products of chlorine atom substitution in
high yields [3,5].
Selective reaction of chlorobenzene 1 with phenol succeeded
when the less polar solvent (dioxane) was used and K2CO3 was
utilized as a base (Scheme 4).
Difference in reactivity for ortho- and para-groups may be due
to strong inductive deactivating influence of morpholyl moiety
towards ortho positioned SO2F reaction center accompanying with
steric factors.
Complete nucleophilic substitution on the all reactive centers
was achieved with excess of trifluoroethylate that resulted in the
product of chlorine and fluorine atoms substitution 8 (Scheme 5).
Stability of compound 8 is due to low alkylating ability of
fluoroalkyl esters of arenesulfonic acids [21]. Furthermore, 2,4,6-
tris(trifluoroetoxysulfonyl)phenol [22] is somewhat weaker acid
than phenol 2 (pKa values 7.97 and 5.53, respectively [9]).
In general it must be noted that chlorine atom in 2,4,6-
tris(fluorosulfonyl)chlorobenzene (1) easily hydrolyses in moist
polar solvents with phenol 2 formation, while SO2F groups
remained unchanged.
2.3. Reactions with S-nucleophiles
Selective reactions of chlorobenzene 1 with sulfurous nucleo-
philes such as sodium p-nitrothiophenolate, potassium ethylxan-
togenate and benzylmercaptan/Et3N required milder conditions in
comparison with N-nucleophiles. Interaction of equimolar quanti-
ty of reagents at ꢁ30 8C in acetonitrile (or DME in case of
benzylmercaptane) and warming up to room temperature lead to
NRR'
SO2F
Cl
2.2. Reactions with N-nucleophiles
2 equiv
HNRR'
SO2F
FSO2
SO2F
FSO2
Chlorobenzene 1 reacted with nitrogen containing nucleophiles
smoothly but not as easy as in case of 2,4,6-tris(trifluoromethyl-
sulfonyl)chlorobenzene. The later with excess of aqueous ammo-
nia in acetonitrile gave 2,4,6-tris(trifluoromethylsulfonyl)aniline
in quantitative yield [3]. In the same conditions chlorobenzene 1
formed the set of water-soluble products. 19F NMR spectrum of
reaction solution showed only the presence of fluoride-anion
CH3CN
r.t.
SO2F
1
9-11
Boc
NRR' = NHPh (9, 92 %),
(10, 89 %), N
O
N
(11, 98 %)
N
Scheme 7. Reactions of 1 with amines.
Cl
NH2
Cl
SO2F
4 equiv
SO2F
FSO2
SO2F
SO2F
FSO2
FSO2
excess NH3
morpholine
O
N
SO2
N
O
CH3CN
r.t.
CH3CN
r.t
SO2F
SO2F
12 (75 %)
1
SO2F
SO2F 1
3 (85 %)
Scheme 6. Reaction of 1 with ammonia.
Scheme 8. Reaction of 1 with doubled quantity of morpholine.

126
A.A. Filatov et al. / Journal of Fluorine Chemistry 143 (2012) 123–129
SR
Cl
Cl
SO2F
FSO2
SO2F
FSO2
SO2F
SO2F
FSO2
FSO2
RS-Kat+
Zn / AcOH
CH3CN (or DME)
-30 oC -> r.t.
Dioxane, r.t.
SO2F 1
SO2F
SO2F
1
19 (75 %)
SO2F
13-15
RS-Kat+ = 4-NO2-C6H4-SNa (13, 77 %), C2H5OC(S)SK (14, 97 %),
PhCH2SH / NEt3 (15, 69 %)
Scheme 12. Reduction of 1 with zinc/acetic acid.
Scheme 9. Reactions of 1 with thiolates.
2.6. Reduction with zinc
Chlorine atom in compound 1 may be easily replaced with
hydrogen by zinc/acetic acid mixture in dioxane at 20–25 8C
(Scheme 12), that is the convenient method to obtain 1,3,5-
tris(fluorosulfonyl)benzene in substantial yield (75% isolated).
K+
N
N
C
Cl
SO2F
FSO2
SO2F
FSO2
CH2(CN)2 / K2CO3
3. Conclusions
Dioxane
50 oC
2,4,6-Tris(fluorosulfonyl)chlorobenzene (1) have confirmed its
ability to realize various nucleophilic substitution pathways in
dependence of reaction conditions that may led to regioselective
C–Ar center attack or further fluorosulfonyl groups involvement.
The 1-R-2,4,6-tris(fluorosulfonyl)benzenes family generated in-
cluded corresponding arene alkyl and aryl ethers, anilines, sulfides
and an example of arenemethide. In the course of investigations 1-
alkyloxy-2,4,6-tris(fluorosulfonyl)benzenes obtained were found
to be rather strong alkylating agents forming salts with 2,4,6-
tris(fluorosulfonyl)phenoxide, that applied to dialkyl imidazolium
system showed rather low melting point compounds. In case of
fluoride-anion the second equivalent of reactant adds to the 1-
SO2F
16 (99 %)
SO2F
1
Scheme 10. Reaction of 1 with malononitrile potassium salt.
the formation of corresponding sulfides 13–15 in good yields
without participation of SO2F groups (Scheme 9).
The excess of p-nitrothiophenolate used showed further attack
of reaction centers (para-SO2F, up to 19F NMR data). However
utilization of Na2S gave unfortunately complex mixture and
ambiguous results.
Saponification of compound 14 with K2CO3 in dioxane yielded
not to expected potassium 2,4,6-tris(fluorosulfonyl)thiophenoxide
but to potassium salt of phenol 2 that was isolated. The obtained
result may be rationalized as attack of base to aromatic carbon
atom bearing higher positive charge.
position of compound 17 to form the stable anionic
s-complex
with two fluorine atoms at sp3 C atom. Convenient method to
obtain 1,3,5-tris(fluorosulfonyl)benzene was elaborated upon
reduction of chlorine atom in 2,4,6-tris(fluorosulfonyl)chloroben-
zene (1) by Zn/AcOH.
2.4. Reactions with C-nucleophiles
4. Experimental
As an example for C-nucleophiles we choose malononitrile and
it was found that chlorobenzene 1 reacted with CH2(CN)2/K2CO3 in
dioxane at 50 8C to give the potassium salt 16 in quantitative yield
(Scheme 10).
4.1. General
All starting materials were obtained commercially. All solvents
were dried using literature procedures.
1H NMR spectra were recorded with a Varian-Gemini VXR 300
spectrometer at 299.9 MHz, 19F NMR spectra – with a Bruker 200
spectrometer at 188.1 MHz and 13C NMR spectra – with an Avance
DRX 500 spectrometer in the solvents indicated.
2.5. Reactions with Me4NF
Chlorine atom in compound 1 may be easily substituted with
fluorine by action with one equivalent of Me4NF in DME yielding
the fluorobenzene 17. Reaction with two equivalents of Me4NF
Residual signals of the solvent protons with the chemical shifts
gave the adduct of arene 17 with fluoride-anion –
s-complex 18
d
= 7.25 ppm (CDCl3), d = 2.07 ppm ([D6]acetone), d = 2.50 ppm
([D6]DMSO) were used as an internal reference. For 19F NMR
spectra CCl3F was used as an internal standard. Whenever possible
the reactions were monitored by thin-layer chromatography (TLC).
TLCs were run on Merck Kieselgel 60 F254 plates. Melting points
were measured with an electro thermal Stuart Scientific melting
point apparatus SMP3.
(Scheme 11). This adduct showed in NMR spectra the equivalence
of two fluorine atoms in cyclohexadiene ring as well as analogous
behavior of ‘‘aryl’’ protons and SO2F groups chemical shifts to that
of 1,3,5-tris(fluorosulfonyl)benzene anionic
s-complexes [18].
Analogous adduct of trinitrofluorobenzene with fluoride-anion
was described by Terrier [23] on the basis of NMR data.
F
Cl
F
F
SO2F
Me4N+
SO2F
FSO2
FSO2
SO2F
FSO2
Me4NF
2 eq. Me4NF
-
DME
DME
-30 oC -> 0 oC
-30 oC -> 0 oC
SO2F
18 (80 %)
SO2F
17 (81 %)
SO2F
1
Scheme 11. Reactions of 1 with fluoride.

A.A. Filatov et al. / Journal of Fluorine Chemistry 143 (2012) 123–129
127
4.2. 2,4,6-Tris(fluorosulfonyl)phenol (2)
5-C), 167.0 (s, 1C, 1-C) ppm. Anal. calcd for C12H13F3N2O7S3
(450.43): C 32.00, H 2.91, N 6.22, S 21.36. Found C 32.07, H 3.01, N
6.05, S 21.53.
A solution of chlorobenzene (1, 0.5 g, 1.39 mmol) in abs. MeOH
(25 ml) was boiled for 1 h. The solvent was removed under reduced
pressure to afford 2 (0.46 g, 97%).
4.7. 1-Methyl-3-(a,a,b,b-tetrafluoroethyl)imidazolium 2,4,6-
tris(fluorosulfonyl)phenolate (6)
4.3. 2,4,6-Tris(fluorosulfonyl)aniline (3)
Reaction was carried out similar to procedure for compound 5
An access of gaseous ammonia was bubbled through a solution
of chlorobenzene 1 (0.5 g, 1.39 mmol) in acetonitrile (15 mL) at
20 8C for about 1 min. Precipitate formed was filtered off. Filtrate
was concentrated under reduced pressure to afford 3 (0.4 g, 85%) as
starting from anisole 4 (0.25 g, 0.71 mmol) and N-(a,a,b,b-
tetrafluoroethyl)imidazole (0.12 g, 0.71 mmol). Reaction mixture
was additionally stirred overnight to afford 6 (0.35 g, 95%) as a
white solid; m.p. 85–87 8C (benzene). 1H NMR ([D6]DMSO):
1
a
white powder; m.p. 203.5–205.5 8C (benzene). 1H NMR
([D6]DMSO):
= 8.3 (s, 2 H, NH2), 8.6 (s, 2 H, ArH) ppm. 19F
NMR ([D6]DMSO): = 61.4 (s, 2 F, o-SO2F), 68.5 (s, 1 F, p-SO2F) ppm.
13C NMR ([D6]DMSO):
d
= 3.95 (s, 3 H, CH3N), 7.17 (t, JH,F 51.4 Hz, 1 H, CHF2), 8.06 (s,
d
1 H, C(5)H), 8.24 (s, 2 H, ArH), 8.29 (s, 1 H, C(4)H), 9.99 (s, 1 H,
C(2)H) ppm. 19F NMR ([D6]DMSO): = –137.4 (d, 2JF,H 51.4 Hz, 2 F,
CF2H), ꢁ99.1 (s, 2 F, CF2N), 55.5 (s, 2 F, o-SO2F), 69.2 (s, 1 F, p-
SO2F) ppm. 13C NMR ([D6]DMSO):
= 37.3 (s, 3C, CH3), 105.6 (d,
d
d
2
d
= 116.5 (d, JC,F = 27.3 Hz, 1C, 4-C), 116.9
(d, 2JC,F = 26.3 Hz, 2C, 2-C, 6-C), 140.6 (s, 2C, 3-C, 5-C), 149.3 (s, 1C,
d
1
2
1-C) ppm.
2JC,F = 26.8 Hz, 1C, 4-C), 108.0 (tt, JC,F = 252,3 Hz, JC,F = 38.8 Hz,
CF2H), 112.2 (tt, 1JC,F = 269.2 Hz, 2JC,F = 29.9 Hz, 1C, NCF2), 119.8 (s,
1C, 5-C (Im)), 124.3 (d, 2JC,F = 18.5 Hz, 2C, 2-C, 6-C), 126.3 (s, 1C, 2-C
(Im)), 137.9 (s, 1C, 4-C (Im)), 139.4 (s, 2C, 3-C, 5-C), 167.0 (s, 1C, 1-
C) ppm. Anal. calcd for C12H9F7N2O7S3 (522.40): C 27.59, H 1.74, N
5.36, S 18.41. Found C 27.51, H 1.80, N 5.21, S 18.65.
4.4. 2,4,6-Tris(fluorosulfonyl)anisole (4a)
A solution of phenol 2 (3.0 g, 8.82 mmol) and silver carbonate
(1.4 g, 5.08 mmol) in dist. H2O (10 mL) was stirred at 60 8C for 2 h.
Unreacted silver carbonate was filtered off, filtrate was concen-
trated under reduced pressure at 60 8C. Obtained silver phenoxide
was dissolved in dry CH2Cl2 (50 mL) and CH3I (10 mL, 160 mmol)
was added, reaction mixture was stirred for 16 h at room
temperature. Precipitate formed was filtered off. Filtrate was
concentrated under reduced pressure to afford 4a (2.6 g, 83%) as a
4.8. 2,4,6-Tris(fluorosulfonyl)diphenyl ether (7)
A mixture of chlorobenzene 1 (0.87 g, 2.43 mmol), phenol
(0.24 g, 2.55 mmol) and dry grinded potash (0.5 g, 3.62 mmol) in
dioxane (20 mL) was stirred at 50 8C for 8 h. Precipitate was filtered
off. Filtrate was concentrated under reduced pressure to afford 8
(0.85 g, 84.2%) as a white powder; m.p. 155–156.7 8C. 1H NMR
white powder; m.p. 164–166 8C. 1H NMR (CDCl3):
CH3), 8.94 (s, 2 H, ArH) ppm. 19F NMR (CDCl3):
= 63.7 (s, 2 F, o-
SO2F), 67.5 (s, 1 F, p-SO2F) ppm. 13C NMR (CDCl3):
= 67.8 (s, 3C,
d = 4.43 (s, 3 H,
d
2
2
d
([D6]DMSO):
7.5 Hz, 1 H, 4-C6H5), 7.39 (t, 2JH,H 7.9 Hz, 2 H, 3,5-C6H5), 9.16 (s, 2 H,
ArH) ppm. 19F NMR ([D6]DMSO):
= 64.6 (s, 2 F, o-SO2F), 66.4 (s, 1
F, p-SO2F) ppm. 13C NMR ([D6]DMSO): = 105.5 (d, 2JC,F = 26.4 Hz,
d = 7.08 (d, JH,H 8.3 Hz, 2 H, 2,6-C6H5), 7.20 (t, JH,H
CH3), 129.8 (d, 2JC,F = 30.9 Hz, 1C, 4-C), 132.5 (d, 2JC,F = 28.0 Hz, 2C,
2-C, 6-C), 138.1 (s, 2C, 3-C, 5-C), 163.4 (s, 1C, 1-C) ppm. Anal. calcd
for C7H5F3O7S3 (354.30): C 23.73, H 1.42, S 27.15. Found C 23.67, H
1.47, S 27.32.
d
d
1C, 4-C), 115.7 (s, 2C, 2,6-C6H5), 119.2 (s, 1C, 4-C6H5), 124.3 (d,
2JC,F = 19.1 Hz, 2C, 2-C, 6-C), 129.8 (s, 2C, 3,5-C6H5) 139.5 (s, 2C, 3-C,
5-C), 157.8 (s, 1C, 1-C6H5), 167.0 (s, 1C, 1-C) ppm. Anal. calcd for
4.5. 2,4,6-Tris(fluorosulfonyl)phenetole (4b)
C12H7F3O7S3 (416.37): C 34.62, H 1.69, S 23.10. Found C 34.55, H
Reaction was carried out similar to procedure for compound 4a.
C2H5I was used instead of CH3I to give 4b (2.46 g, 80%) as a white
1.74, S 22.89.
powder; m.p. 134–136 8C. 1H NMR (CDCl3):
d
= 1.62 (t,
4.9. 2,4,6-Tris(b,b,b-trifluoroethoxysulfonyl)-b,b,b-
trifluorophenetole (8)
2
2JH,F = 7.2 Hz, 3 H, CH3), 4.65 (q, JH,F = 7.2 Hz, 2 H, CH2), 8.90 (s,
2 H, ArH) ppm. 19F NMR (CDCl3):
d
= 63.1 (s, 2 F, o-SO2F), 67.4 (s, 1 F,
= 15.3 (s, 3C, CH3), 78.5 (s, 2C,
CH2) 129.4 (d, 2JC,F = 30.5 Hz, 1C, 4-C), 132.5 (d, 2JC,F = 27.8 Hz, 2C,
2-C, 6-C), 138.1 (s, 2C, 3-C, 5-C), 162.6 (s, 1C, 1-C) ppm. Anal. calcd
for C8H7F3O7S3 (368.33): C 26.09, H 1.97, S 26.12. Found C 26.19, H
2.01, S 26.33.
p-SO2F) ppm. 13C NMR (CDCl3):
d
A mixture of chlorobenzene 1 (0.5 g, 1.39 mmol), 2,2,2-trifluor-
oethanol(2 g, 20 mmol)and dry grinded potash (2 g, 14.47 mmol) in
dioxane (30 mL) was stirred at room temperature for 24 h. Reaction
mixture was diluted with water, formed precipitate was filtered off
to afford 7 (0.82 g, 89%) as a white powder; m.p. 133–134.5 8C. 1H
NMR ([D6]DMSO):
d
= 4.90 (q, 2JH,F 8.4 Hz, 2 H, Ar-OCH2CF3), 5.08 (q,
2
4.6. 1-Methyl-3-ethylimidazolium 2,4,6-
2JH,F 8.4 Hz, 4 H, o-SO2OCH2CF3), 5.13 (q, JH,F 8.4 Hz, 2 H, p-
tris(fluorosulfonyl)phenolate (5)
SO2OCH2CF3), 8.73 (s, 2 H, ArH) ppm. 19F NMR ([D6]DMSO):
d = -72.1
(br s, 9 F, SO2OCH2CF3), ꢁ72.0 (br s, 3 F, Ar-OCH2CF3) ppm. 13C NMR
2
To a stirred solution of anisole 4 (0.25 g, 0.71 mmol) in benzene
(2 mL) a solution of N-ethyl imidazole (0.07 g, 0.73 mmol) in
benzene (2 mL) was added. The reaction mixture was stirred at
room temperature for 1 h. The solvent was removed under reduced
pressure to afford 5 (0.31 g, 98%) as a white solid; m.p. 125.5–
([D6]DMSO):
d
= 66.4 (q, JC,F = 37.4 Hz, 1C, SOCH2), 66.7 (q,
2JC,F = 37.4 Hz, 2C, SOCH2), 72.2 (q, JC,F = 36.8 Hz, 1C, ArOCH2),
2
1
1
122.6 (q, JC,F = 277.3 Hz, 2C, SOCH2CF3), 122.8 (q, JC,F = 277.4 Hz,
1C, SOCH2CF3), 122.9(q, 1JC,F = 277.6 Hz,1C,ArOCH2CF3)132.7 (s, 1C,
4-C), 133.4 (s, 2C, 2-C, 6-C), 137.9 (s, 2C, 3-C, 5-C), 157.4 (s, 1C, 1-
C) ppm. Anal. calcd for C14H10F12O10S3 (662.40): C 25.39, H 1.52, S
14.52. Found C 25.30, H 1.58, S 14.33.
127.7 8C (benzene). 1H NMR ([D6]DMSO): = 1.41 (t, 2JH,H 7.3 Hz, 3
d
H, CH3CH2), 3.84 (s, 3 H, CH3N), 4.18 (q, 2JH,H 7.3 Hz, 2 H, CH2CH3),
7.68 (s, 1 H, C(5)H), 7.77 (s, 1 H, C(4)H), 8.24 (s, 2 H, ArH), 9.1 (s, 1 H,
C(2)H) ppm. 19F NMR ([D6]DMSO):
d
= 55.9 (s, 2 F, o-SO2F), 69.6 (s,
4.10. 2,4,6-Tris(fluorosulfonyl)diphenylamine (9)
1 F, p-SO2F) ppm. 13C NMR ([D6]DMSO):
d
= 15.5 (s, 1C, CH2CH3),
36.2 (s, 3C, NCH3), 44.6 (s, 1C, CH2CH3), 105.5 (d, 2JC,F = 26.8 Hz, 1C,
4-C), 122.4 (s, 1C, 5-C (Im)), 124.0 (s, 1C, 4-C (Im)), 124.3 (d,
2JC,F = 18.5 Hz, 2C, 2-C, 6-C), 136.7 (s, 1C, 2-C (Im)), 139.5 (s, 2C, 3-C,
To a solution of chlorobenzene 1 (0.5 g, 1.39 mmol) in CH3CN
(20 mL) a solution of aniline (0.27 g, 2.9 mmol) in CH3CN (2 mL)
was added at room temperature. Reaction mixture was stirred for

128
A.A. Filatov et al. / Journal of Fluorine Chemistry 143 (2012) 123–129
2
2
1 h and poured in water. Precipitate formed was filtered off to
afford (0.53 g, 91.5%) as yellow powder. 167–169 8C
(benzene + hexane). 1H NMR ([D6]DMSO):
= 7.35 (m, H,
= 63.2 (s,
(d, JH,F = 9.2 Hz, 2 H, p-NO2-C6H4-S), 8.12 (d, JH,F = 9.2 Hz, 2 H, p-
9
a
NO2-C6H4-S), 9.21 (s, 2H, ArH) ppm. 19FNMR ([D6]DMSO):
d = 62.2(s,
2 F, o-SO2F), 66.7 (s, 1 F, p-SO2F) ppm. Anal. calcd for C12H6F3NO8S4
(477.43): C 30.19, H 1.27, N 2.93, S 26.86. Found C 30.22, H 1.30, N
2.85, S 27.14.
d
5
C6H5), 8.96 (s, 2 H, ArH) ppm. 19F NMR ([D6]DMSO):
2 F, o-SO2F), 67.7 (s, 1 F, p-SO2F) ppm. 13C NMR ([D6]DMSO):
d
2
d
= 123.0 (s, 2C), 123.7 (d, JC,F = 43.6 Hz, 1C, 4-C), 125.7 (s, 1C),
127.9 (d, 2JC,F = 25.9 Hz, 2C, 2-C, 6-C), 129.4 (s, 2C), 140.7 (s, 2C, 3-C,
4.15. S-[2,4,6-Tris(fluorosulfonyl)phenyl] O-ethylxanthate (14)
5-C), 143.1 (s, 1C), 148.9 (s, 1C, 1-C) ppm. Anal. calcd for
C
12H8F3NO6S3 (415.39): C 34.70, H 1.94, N 3.37. Found C 34.46,
Reaction was carried out similar to procedure for compound 13,
starting from chlorobenzene 1 and potassium O-ethylxanthate to
afford 14 (1.2 g, 97%); m.p. 83–84 8C (benzene). 1H NMR ([D6]DMSO):
H 1.89, N 3.48.
4.11. N-[2,4,6-Tris(fluorosulfonyl)phenyl]morpholine (10)
d
= 1.14 (t, 2JH,H 7.0 Hz,3H,CH3),4.55 (q,2JH,H 7.0 Hz, 2H, CH2), 9.20(s,
2H,ArH) ppm. 19FNMR([D6]DMSO):
F, p-SO2F) ppm. 13C NMR (CDCl3):
d
= 62.4(s, 2F,o-SO2F), 66.7(s,1
Reaction was carried out similar to procedure for compound 9,
starting from chlorobenzene 1 and morpholine to afford 10 (0.51 g,
89.4%) as a yellow powder; m.p. (decomp.) 198 8C, (benzene). 1H
d = 13.3 (s, 3C, CH3), 72.3 (s, 2C,
2
CH2), 135.8 (s, 2C, 3-C, 5-C), 137.0 (d, JC,F = 31.3 Hz, 2C, 2-C, 6-C),
2
138.0 (s, 1C, 1-C), 143.5 (d, JC,F = 26.9 Hz, 1C, 4-C), 202.1 (s, 1C,
2
NMR ([D6]Aceton):
d
= 3.48 (t, JH,F = 4.8 Hz, 4 H, CH2N), 3.87 (t,
C55S) ppm. Anal. calcd for C9H7F3O7S5 (444.47): C 24.32, H 1.59, S
2JH,F = 4.8 Hz, 4 H, CH2O), 9.12 (s, 2 H, ArH) ppm. 19F NMR (Aceton):
= 61.5 (s, 2 F, o-SO2F), 66.5 (s, 1 F, p-SO2F) ppm. 13C NMR
([D6]DMSO): = 51.3 (s, 2C, CH2N), 66.2 (s, 2C, CH2O), 130.1 (d,
2JC,F = 29.2 Hz, 1C, 4-C), 137.8 (d, JC,F = 25 Hz, 2C, 2-C, 6-C), 139.1
(s, 2C, 3-C, 5-C), 155. (s, 1C, 1-C) ppm. Anal. calcd for
10H10F3NO7S3 (409.38): C 29.34, H 2.46, N 3.42. Found C 29.39,
H 2.50, N 3.53.
36.07. Found C 24.32, H 1.59, S 36.23.
d
d
4.16. 2,4,6-Tris(fluorosulfonyl)phenylbenzylsulfide (15)
2
8
Reaction was carried out similar to procedure for compound 13,
starting from chlorobenzene 1 (1 g, 2.8 mmol) and benzylmer-
captane (0.35 g, 2.8 mmol) and triethylamine (0.31 g, 3.07 mmol)
in DME (30 mL) to afford 15 (0.86 g, 69%); m.p. 191–192 8C
C
4.12. N-(2,4,6-Tris(fluorosulfonyl)phenyl)piperazine-N0-Boc (11)
(benzene + hexane). 1H NMR (CDCl3):
5 H, C6H5), 9.10 (s, 2 H, ArH) ppm. 19F NMR (CDCl3):
d
= 4.50 (s, 2 H, CH2), 7.46 (m,
= 58.2 (s, 2 F,
d
To a stirred solution of chlorobenzene 1 (0.91 g, 2.54 mmol) in
CH3CN (20 mL) at ꢁ30 8C a solution of N-Boc-piperazine (0.50 g,
2.68 mmol) and N-ethyldiisipropylamine (0.36 g, 2.78 mmol) in
CH3CN (5 mL) was slowly added. Reaction mixture was stirred for
1 h at ambient temperature and then poured in water. Formed
precipitate was filtered off to afford 11 (1.26 g, 97.7%) as a yellow
o-SO2F), 66.1 (s, 1 F, p-SO2F) ppm. Anal. calcd for C13H9F3O6S4
(446.46): C 34.97, H 2.03, S 28.73. Found C 35.15, H 2.10, S 28.28.
4.17. Potassium 2,4,6-tris(fluorosulfonyl)phenyldicyanomethide (16)
A mixture of chlorobenzene 1 (3 g, 8.36 mmol), malononitrile
(0.6 g, 9.08 mmol) and dry grinded potash (2.5 g, 18.1 mmol) in
dioxane (80 mL) was stirred at 60 8C for 10 h. Orange precipitate
formed was filtered off and washed with acetone. Filtrate was
concentrated under reduced pressure to afford 16 (3.54 g, 99%). 1H
powder; m.p. (decomp.) 173 8C. 1H NMR (CDCl3):
CH3), 3.36 (m, 4 H, CH2N), 3.64 (m, 4 H, CH2N), 8.92 (s, 2 H,
ArH) ppm. 19F NMR (CDCl3):
= 61.1 (s, 2 F, o-SO2F), 67.4 (s, 1 F, p-
SO2F) ppm. 13C NMR ([D6]DMSO):
= 28.5 (s, 9C, CH3), 43.0–44.3
d = 1.48 (s, 9 H,
d
d
(m, 2C, NCH2), 50.8 (s, 2C, NCH2), 79.8 (s, 1C, C(CH3)3), 130.3 (d,
2JC,F = 28.7 Hz, 1C, 4-C), 137.7 (d, 2JC,F = 24.5 Hz, 2C, 2-C, 6-C), 139.1
(s, 2C, 3-C, 5-C), 154.4 (s, 1C, C(O)O), 156.1 (s, 1C, 1-C) ppm. Anal.
calcd for C15H19F3N2O8S3 (508.51): C 35.43, H 3.77, N 5.51, S 18.92.
Found C 35.45, H 3.70, N 5.59, S 19.02.
NMR ([D6]DMSO):
d
= 8.44 (s, 2 H, ArH) ppm. 19F NMR ([D6]DMSO):
= 71.4 (s, 2 F, o-SO2F), 68.5 (s, 1 F, p-SO2F) ppm. 13C NMR
d
2
([D6]DMSO):
d
= 53.0 (s, 2C, Cꢁ), 114.7 (d, JC,F = 28.3 Hz, 1C, 4-C),
117.9 (s, 2C, CN), 120.7 (d, 2JC,F = 27.1 Hz, 2C, 2-C, 6-C), 140.2 (s, 2C, 3-
C, 5-C), 143.7 (s, 1C, 4-C) ppm. Anal. calcd for C9H2F3N2O6S3 (426.42):
C 25.35, H 0.47, N 6.57, S 22.56. Found C 24.97, H 0.66, N 6.49, S 22.85.
4.13. 1-Morpholino-4-morpholinosulfonyl-2,6-
bis(fuorosulfonyl)benzene (12)
4.18. 2,4,6-Tris(fluorosulfonyl)fluorobenzene (17)
Reaction was carried out similar to procedure for compound 10,
starting from chlorobenzene 1 and doubled quantity of morpholine
to afford 12 (0.5 g, 75%); m.p. (decomp.) ꢀ215 8C (toluene + ethy-
To a stirred solution of chlorobenzene 1 (1.2 g, 3.34 mmol) in
dry DME (25 mL) at ꢁ30 8C in dry argon atmosphere Me4NF [24]
(0.44 g, 4.72 mmol) was added in one portion. Reaction mixture
was slowly heated to 0 8C. Precipitate was filtered off. Filtrate was
concentrated under reduced pressure. Extraction with dry benzene
afforded 17 (0.93 g, 81%) as a white powder (insoluble in benzene
lacetate). 1H NMR ([D6]DMSO):
d = 3.09 (s, 4 H, CH2N), 3.28 (s, 4 H,
CH2N), 3.68 (s, 4 H, CH2O), 3.75 (s, 4 H, CH2O), 8.54 (s, 2 H,
ArH) ppm. 19F NMR ([D6]DMSO): = 61.0 (s, 2 F, SO2F) ppm. 13C
NMR ([D6]DMSO): = 45.9 (s, 2C, CH2NSO2), 50.8 (s, 2C, CH2N),
d
d
residue was identified as s H
-complex 18); m.p. 132.5–134.0 8C. 1
4
65.8 (s, 2C, CH2O), 66.4 (s, 2C, CH2O), 134.9 (s, 1C, 4-C), 137.2 (s, 2C,
NMR (CDCl3):
(CDCl3):
= –89.0 (tt, 4JF,F = 11.9 Hz, 4JF,H = 5.3 Hz, 1 F, ArF), 65.5 (d,
4JF,F = 11.9 Hz, 2 F, o-SO2F), 67.3 (s, 1 F, p-SO2F). 13C NMR (CDCl3):
d
= 8.94 (d, JH,F = 5.3 Hz, 2 H, ArH) ppm. 19F NMR
2
3-C, 5-C),138.1 (d, JC,F = 23 Hz, 2C, 2-C, 6-C), 153. 4 (s, 1C, 1-
d
C) ppm. Anal. calcd for C14H18F2N2O8S3 (476.50): C 35.29, H 3.81, N
5.88, S 20.19. Found C 35.35, H 3.79, N 5.66, S 19.53.
d
= 124.7 (dd, 2JC,F = 31.6 Hz, 2JC,F = 15.1 Hz, 2C, 2-C, 6-C), 129.7 (dd,
2JC,F = 31.5 Hz, 4JC,F = 4.6 Hz, 1C, 4-C), 137.4 (s, 2C, 3-C, 5-C), 159.4
1
4.14. 2,4,6-Tris(fluorosulfonyl)-40-nitrodiphenylsulfide (13)
(d, JC,F = 283.6 Hz, 1C, 1-C) ppm. Anal. calcd for C6H2F4O6S3
(342.26): C 21.06, H 0.59, S 28.10. Found C 21.11, H 0.62, S 27.81.
To a stirred solution of chlorobenzene 1 (0.5 g, 1.39 mmol) in
dioxane (20 mL) sodium p-nitrothiophenolate (0.05 g, 0.28 mmol)
was added. Reaction mixture was stirred for 8 h at ambient
temperature. Formed precipitate was filtered off. Filtrate was
concentrated under reduced pressure to afford 13 (0.51 g, 77%);
4.19. Tetramethylammonium 1,1-difluoro-2,4,6-
tris(fluorosulfonyl)cyclohexadienate (18)
Reaction was carried out similar to procedure for compound 17
but with a halved quantity of chlorobenzene 1 to afford 18 as a
m.p. 177–178.5 8C (benzene). 1H NMR ([D6]DMSO):
d = 7.41

A.A. Filatov et al. / Journal of Fluorine Chemistry 143 (2012) 123–129
129
greenish powder (0.58 g, 80%). 1H NMR ([D6]DMSO):
d = 3.10 (s, 14
[5] V.N. Boiko, N.V. Ignatev, L.M. Yagupolskii, Zhurnal Organicheskoi Khimii (Journal
of Organic Chemistry of USSR), 17 (1981) 1952–1958 (in Russian);
Chemical Abstracts 96 (1982) 6298g.
[6] L.M. Yagupolskii, A.Y. Ilchenko, N.V. Kondratenk, Uspekhi Khimii 43 (1974) 64–94
(in Russian);
H, CH3), 7.91 (t, 4JH,F = 3.8 Hz, 2 H, ArH) ppm. 19F NMR ([D6]DMSO,
282.2 MHz):
d
= ꢁ36.6 to ꢁ36.8 (m, 2 F, CF2), 69.2 (t, 6JF,F = 10 Hz, 1
4
F, p-SO2F), 71.4 (t, JF,F = 13.5 Hz, 2 F, o-SO2F) ppm. 13C NMR
Chemical Abstracts 80 (1974) 94766f.
1
([D6]DMSO):
d
= 54 9 (s, 12C, CH3), 56.2 (br t, JC,F = 154.7 Hz, 1C,
[7] C. Hansch, A. Leo, D. Hoekman, Exploring QSAR Hydrophobic, Electronic and Steric
Constants, ACS Professional Reference Book, Washington, DC, 1995.
[8] A. Ku¨tt, I. Leito, I. Kaljurand, L. Soovali, V.M. Vlasov, L.M. Yagupolskii, I.A. Koppel,
Journal of Organic Chemistry 71 (2006) 2829–2838.
2
2
CF2), 96.5 (d, JC,F 25.3 Hz, 1C, 4-C), 105.6 (dt, JC,F = 22.4 Hz,
4JC,F = 33.4 Hz, 2C, 2-C, 6-C), 138.5 (s, 2C, 3-C, 5-C) ppm.
[9] I. Leito, E. Raamat, A. Ku¨ tt, J. Saame, K. Kipper, I.A. Koppel, I. Koppel, M. Zhan, M.
Mishima, L.M.R. Yagupolskii, Yu. Garlyauskayte, A.A. Filatov, Journal of Physical
Chemistry A 113 (2009) 8421–8424.
4.20. 1,3,5-Tris(fluorosulfonyl)benzene (19)
[10] I.A. Koppel, R.W. Taft, F. Anvia, S.-Z. Zhu, L.-Q. Hu, K.-S. Sung, D.D. DesMarteau,
L.M. Yagupolskii, Yu.L. Yagupolskii, Journal of American Chemical Society 116
(1994) 3047–3057.
[11] P.Y. Rodriguez, E.A. Meyers, C. Kinney, Hancock, Journal of Organic Chemistry 35
(1970) 1819–1825.
[12] I. Lee, C.S. Shim, S.Y. Chung, H.Y. Kim, H.W. Lee, Journal of Chemical Society,
Perkins Transactions 2 (11) (1988) 1919–1923.
[13] E. Ciuffarin, L. Senatore, M. Isola, Journal of Chemical Society, Perkins Transactions
2 (4) (1972) 468.
[14] H. Suzuki, H. Kageyama, Y. Yoshida, Y. Kimura, Journal of Fluorine Chemistry 55
(1991) 335–337.
[15] Neth. Appl. 6511883, ICI C 07C. Arenesulfonyl fluorides, Publ. 17.03.1966.
Chemical Abstracts 65 (1966) 5447c.
[16] H.C. Fielding, J.M. Shirley, Journal of Fluorine Chemistry 59 (1992) 15–31.
[17] O.M. Kamoshenkova, V.N. Boiko, Journal of Fluorine Chemistry 131 (2010) 248–
253.
[18] V.N. Boiko, O.M. Kamoshenkova, A.A. Filatov, Tetrahedron Letters 49 (2008)
2719–2721.
A mixture of chlorobenzene 1 (10 g, 27.88 mmol), zinc dust
(3.7 g, 56.59 mmol), glacial acetic acid (30 mL) and dioxan (30 mL)
was stirred at room temperature for 16 h. Precipitate was filtered
off and washed with dioxane. Filtrate was concentrated under
reduced pressure and then poured in water. The formed precipitate
was filtered off to afford 19 (6.78 g, 75%) as a white powder; m.p.
166–167 8C. 1H NMR ([D6]DMSO):
NMR ([D6]DMSO): = 67.6 (s,
d
= 9.26 (s, 3 H, ArH) ppm. 19F
3
F, SO2F) ppm. 13C NMR
d
2
([D6]DMSO):
CH) ppm.
d = 135.7 (d, JC,F = 28.9 Hz, 3C, CS), 136.1 (s, 3C,
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