A convenient synthetic route to 2,4,6-tris(chlorosulfonyl)- and 2,4,6-tris(fluorosulfonyl)phenol, aniline and chlorobenzene

Article abstract of DOI:10.1016/j.jfluchem.2011.06.045

Convenient and preparative synthetic procedures of 2,4,6- tris(chlorosulfonyl)- and 2,4,6-tris(fluorosulfonyl)phenol, -chlorobenzene and -aniline have been elaborated. Chlorine exchange for fluorine by KF interaction on 2,4,6-tris(chlorosulfonyl)aniline and especially 2,4,6-tris(chlorosulfonyl) phenol proceeds easily and selectively under anhydrous conditions in dioxane. Unlike, 2,4,6-tris(chlorosulfonyl)chlorobenzene transformation requires the presence of water. On the basis of 2,4,6-tris(fluorosulfonyl)phenol and some of its salts, XRD measurements demonstrated the structural similarity to picric acid and its derivatives in the solid state.

Full text of DOI:10.1016/j.jfluchem.2011.06.045

Journal of Fluorine Chemistry 132 (2011) 1219–1226
Contents lists available at ScienceDirect
Journal of Fluorine Chemistry
journal homepage: www.elsevier.com/locate/fluor
A convenient synthetic route to 2,4,6-tris(chlorosulfonyl)- and
2,4,6-tris(fluorosulfonyl)phenol, aniline and chlorobenzene
b
b
Vladimir N. Boiko a, Andrey A. Filatov a, Yurii L. Yagupolskii a, , Wieland Tyrra , Dieter Naumann ,
*
Ingo Pantenburg b, Hendrik T.M. Fischer b, Frank Schulz b
a Institute of Organic Chemistry, National Academy of Sciences of Ukraine, 5 Murmanskaya St., UA-02094, Kiev 94, Ukraine
b
¨
¨
¨
Institut fu¨r Anorganische Chemie, Universitat zu Koln, Greinstrasse 6, D-50939 Koln, Germany
A R T I C L E I N F O
A B S T R A C T
Article history:
Convenient and preparative synthetic procedures of 2,4,6-tris(chlorosulfonyl)- and 2,4,6-tris(fluor-
osulfonyl)phenol, -chlorobenzene and -aniline have been elaborated. Chlorine exchange for fluorine by
KF interaction on 2,4,6-tris(chlorosulfonyl)aniline and especially 2,4,6-tris(chlorosulfonyl)phenol
proceeds easily and selectively under anhydrous conditions in dioxane. Unlike, 2,4,6-tris(chlorosulfo-
nyl)chlorobenzene transformation requires the presence of water. On the basis of 2,4,6-tris(fluor-
osulfonyl)phenol and some of its salts, XRD measurements demonstrated the structural similarity to
picric acid and its derivatives in the solid state.
Received 18 May 2011
Received in revised form 25 June 2011
Accepted 29 June 2011
Available online 6 July 2011
Keywords:
Arenes
ß 2011 Elsevier B.V. All rights reserved.
Sulfonylchlorides
Sulfonylfluorides
Nucleophilic substitution
Synthetic methods
Molecular structures
1. Introduction
methylation of the corresponding trimercapto compounds
obtained from 2,4,6-trisulfonylbenzene chlorides followed by
Phenols bearing three strong electron withdrawing groups in
2,4,6 ring positions – with picric acid being the most historically
famous representative – are involved in a variety of fundamental
processes of organic and applied chemistry. Unfailing interest in
the picric acid as well as polynitro benzene derivatives lie in their
unique chemical nature essence of its high reactivity towards
oxidation [9]. An alternative route to prepare 2,4,6-tris(trifluor-
omethylsulfonyl)phenol comprises a two step process reacting
phenol with CF3SCl followed by subsequent oxidation [8].
However, taking into account the high costs of CF3I and CF3SCl,
practical application of the above mentioned methods is difficult to
realize to prepare bigger quantities of the desired phenols.
In terms of electronic properties, the group SO2F (sp 1.01)
nucleophilic agents [1], formation of stable s- [2] and p-complexes
[3] and a number of other useful properties; utilization of these
compounds is limited due to their high explosive potential.
The replacement of nitro groups by more electronegative
SO2CF3 groups allows to minimize these negative properties and at
the same time to increase the activity of those compounds [4]. For
example, 2,4,6-tris(trifluoromethylsulfonyl)phenol (pKa ꢀ1 [5];
ꢀ2.5 [6]) is rather more acidic than 2,4,6-trinitrophenol (pKa 0.38
[7]), and in three exponent parts more effective as a metal
extractive reagent [6]. The conductivity of lithium 2,4,6-tris(tri-
fluoromethylsulfonyl)phenolate solutions essentially exceeds
these parameters for LiOSO2CF3, LiClO4 and LiN(SO2CF3)2 [8].
The synthesis of 2,4,6-tris(trifluoromethylsulfonyl) derivatives
of phenol, chlorobenzene and aniline is possible via trifluoro-
compares absolutely to the moiety SO2CF3 (sp 1.04–1.06) [10,11].
The electron withdrawing ability of the SO2F group is nearly the
same as that determined for the trifluoromethylsulfonyl one, but
substantially higher than that of the nitro group (sp 0.78 [7]).
Moreover, the aryl sulfonyl fluoride synthesis is convenient and
well developed. It is noteworthy to outline the high hydrolytic
stability of fluorosulfonyl arenes dramatically differing from other
haloanhydrides; i.e. a typical purification procedure for aryl
sulfonyl fluorides is steam distillation (!). Thus, it should be
admitted that, in our opinion, aromatic sulfonyl fluorides may
compete with expensive or rare aryl trifluoromethyl sulfones as
key compounds for various practical applications.
Up to present investigation, methods to obtain 2,4,6-tris(fluor-
osulfonyl)arenes were limited to the corresponding aniline, the
latter was prepared in low yield [12]. To the best of our knowledge,
the similar phenol and chlorobenzene derivatives were not
described apart from hypothetical record of the last in Beilstein
* Corresponding author. Tel.: +380 44 5590349; fax: +380 44 5732643.
E-mail address: Yagupolskii@ioch.kiev.ua (Y.L. Yagupolskii).
0022-1139/$ – see front matter ß 2011 Elsevier B.V. All rights reserved.
doi:10.1016/j.jfluchem.2011.06.045

1220
V.N. Boiko et al. / Journal of Fluorine Chemistry 132 (2011) 1219–1226
[13], while in the cited source [14a] the 2,3,6-isomer was
described.
OH
Cl
ClO2S
SO2Cl
ClO2S
SO2Cl
The intention of this work was to develop simple and effective
synthetic methods for 2,4,6-tris(fluorosulfonyl) derivatives of
phenol, chlorobenzene and aniline that would make these
compounds available for thorough investigations and potential
utilizations [15]. To reach this aim, it was necessary to revise
known methods to obtain the corresponding chlorosulfonyl
substituted benzenes as the most perspective precursors to be
finally converted into fluorosulfonyl derivatives by simple
chlorine-fluorine exchange.
PCl
5
toluene
SO2Cl
SO2Cl
1
90-94 %
3
Scheme 3.
in SO2Cl groups for fluorine by KF action in water or water–organic
solvent mixture [14a–c]. As it was documented previously,
application of these conditions for 2,4,6-tris(chlorosulfonyl)phenol
(1) failed probably due to the hydrolysis of sulfonyl chloride groups
[14a]. For the similar halogen exchange in 1,3,5-tris(chlorosulfo-
nyl)benzene and 2,3,6-tris(chlorosulfonyl)chlorobenzene the same
authors recommended a water-xylene mixture to obtain the
tris(fluorosulfonyl) derivatives in moderate yields (46% and 40%,
2. Results and discussion
2.1. Preparation of 2,4,6-tris(chlorosulfonyl)phenol, -aniline and -
chlorobenzene
The at present known synthetic methods to obtain 2,4,6-
tris(chlorosulfonyl)phenol (1) [16a,b] and 2,4,6-tris(chlorosulfo-
nyl)aniline (2) [12a–d] did not exceed 9–10% yields (phenol 1), and
7–29% (aniline 2) that required considerable revision.
We found out that one pot two steps reaction of starting
compounds – phenol, acyl sulfanilic acid or acetanilide – with
chlorosulfonic acid (8–13 equiv.) followed by thionyl chloride
addition (4–5 equiv.) allowed to synthesize the corresponding
trisulfonyl chlorides 1 and 2 in 90 and 60% yields respectively. This
method does not only allow the use of HSO3Cl avoiding large
excess (10 equiv. for each group in typical procedure), but
substantially facilitates the isolation of the raw materials 1 and
2 as well (Schemes 1 and 2).
It was previously documented that conversion of 2,4,6-
tris(chlorosulfonyl)phenol (1) into 2,4,6-tris(chlorosulfonyl)chlor-
obenzene (3) by heating with a PCl5/POCl3 mixture [17] or with
PCl5 [16b] gave unpurified sulfonylchloride 3 in about 10% yield
[16b]. We revealed that desired sulfonyl chloride 3 can be obtained
in 90–94% yield by heating phenol 1 with PCl5 in toluene or with
POCl3/catalytic quantity of pyridine (Scheme 3).
respectively). Thus,
a principal improvement of the Halex
procedure with respect to substituents attached to the benzene
ring was necessary.
It has been found that short-term (30 min) boiling of 2,4,6-
tris(chlorosulfonyl)chlorobenzene (3) with KFꢁ2H2O in dioxane
caused chlorine substitution in SO2Cl groups with nearly exhaus-
tive conversion. But as it turned out, in these conditions not only
sulfonic acid halides are affected, but chlorine atom linked to
benzene ring was changed to a hydroxy function. The main
products of this reaction were 2,4,6-tris(fluorosulfonyl)phenole 5
and the corresponding potassium phenolate 4, while a minor
product was chlorobenzene 6, with a total conversion of 82%
(Scheme 4). Separation of the products was achieved by aqueous
work-up based on the experimental finding that the chloroben-
zene 6 was insoluble in hot water in contrast to compounds 4 and
5.
The disadvantage of this procedure is a reaction mixture
constituted of a dioxane solution and water–salt paste adhering to
walls making effective stirring difficult. In order to overcome this
complication, the quantity of water was decreased by using
anhydrous KF and addition of 1–1.5 equiv. of H2O giving a well-
stirred suspension.
2.2. Preparation of 2,4,6-tris(fluorosulfonyl)phenol, -aniline and -
chlorobenzene
The most common and inexpensive technique for aromatic
sulfonyl fluorides preparation is replacement of the chlorine atom
Attempts to carry out reactions in anhydrous dioxane with
dried KF with the expectation of 2,4,6-tris(fluorosulfonyl)fluor-
obenzene formation, did not give any evidence for an exchange at
all and the sulfonyl chloride 3 was recovered quantitatively. Under
anhydrous conditions, a reaction with KF was only observed in the
presence of a catalyst (such as crown-ethers [18a] or PEG-400
[18b]) or at elevated temperature [18c]. On the other hand, the
effectiveness of ZnF2 in pyridine [18c,19] in related transforma-
tions may be due to electrophilic catalysis by pyridine solvated
zinc cations.
OH
OH
1. HSO Cl
3
ClO2S
SO2Cl
2. SOCl
2
Anhydrous conditions were applied successfully for chlorine
substitution in 2,4,6-tris(chlorosulfonyl)phenol (1). Heating of the
phenol 1 in dioxane solution with calcinated KF caused the
formation of the desired phenolate 4 and phenol 5 within 30 min.
The water insoluble potassium salt 4 was isolated as the only
product in 85% yield by treatment of the reaction mixture with an
aqueous K2CO3 solution (Scheme 5). In case of KFꢁ2H2O, the key
compounds were obtained only in 20–30% yield. Thus, the
presence of a hydroxy group in this molecule, unlike 2,4,6-
tris(chlorosulfonyl)chlorobenzene (3), promotes the interaction in
the absence of water.
SO2Cl
1
90 %
Scheme 1.
NHCOOCH3
SO3Na
NH2
NHCOCH3
1. HSO Cl
3
1. HSO Cl
3
ClO2S
SO2Cl
2. SOCl
2
2. SOCl
2
SO2Cl
The phenol 5 is difficult to isolate from the reaction mixture due
to its high acidity and excellent solubility in water. Extraction with
CH2Cl2 after treatment of the potassium salt 4 with concentrated
2
58-61 %
Scheme 2.

V.N. Boiko et al. / Journal of Fluorine Chemistry 132 (2011) 1219–1226
1221
Scheme 4.
Scheme 5.
H2SO4 was less effective and required large quantities of
dichloromethane. Bubbling gaseous HCl into a methanolic solution
of potassium phenolate 4 afforded the conversion into the phenol 5
in quantitative yield. The phenol 5 was also obtained in high yield
upon refluxing 2,4,6-tris(fluorosulfonyl)chlorobenzene (6) in
methanol or propan-2-ol in the same manner as described for
the alcoholysis of 2,4,6-tris(trifluoromethylsulfonyl)chloroben-
zene [20]. In turn, 2,4,6-tris(fluorosulfonyl)chlorobenzene (6)
can be easily obtained from the phenolate 4 by reacting it with
PCl5 or POCl3/Py, respectively (Scheme 6).
Anhydrous conditions turned out to be suitable for the
fluorination of 2,4,6-tris(chlorosulfonyl)aniline (2). While in a
water–dioxane mixture 2,4,6-tris(fluorosulfonyl)aniline (7) for-
mation was achieved in only 26% [12c], heating to reflux for 5 h in
anhydrous dioxane with calcinated KF allowed halogen exchange
up to 60–70%. The reaction proceeded faster upon addition of
water (1–2 equiv.) (Scheme 7).
is able to form salts by interaction not only with bases (Li2CO3,
various pyridines, Bu4NOH) but also with metals (Mg, Zn), metal
salts of mineral acids (Cs2SO4, BaCl2) and tetraalkylammonium
halides ((CH3)4NI, (C2H5)4NI) (Scheme 8).
Phenolates 8 (Li) and 4 (K) may be obtained by metathesis one
from the other.
2.4. X-ray diffraction investigation
2.4.1. The molecular structure of 2,4,6-tris(fluorosulfonyl)phenol (5)
The molecular structure of the phenol 5 is monomeric with only
one intramolecular Hꢁ ꢁ ꢁO contact of the hydroxyl proton directed
onto an oxygen atom of one adjacent SO2F-group and resembles
the structure of picric acid [22] (Fig. 1). The contact falls into the
characteristic range of O–Hꢁ ꢁ ꢁO bridges with the hydrogen bonding
˚
˚
˚
mode D–H 0.74(5) A; Hꢁ ꢁ ꢁA 2.15(5) A; Dꢁ ꢁ ꢁA 2.80(5) A; D–Hꢁ ꢁ ꢁA
˚
146(5) A. This contact generates
a six-membered ring thus
characterized by the graph-set motif S(6) [23].
2.3. Preparation of metal, pyridinium and ammonium based 2,4,6-
tris(fluorosulfonyl)phenolates
2.4.2. The molecular structure of lithium 2,4,6-
tris(fluorosulfonyl)phenolate hydrate dimer (8), [Li(OC6H2(2,4,6-
SO2F)3ꢁH2O]2
Due to its high acidity, 2,4,6-tris(fluorosulfonyl)phenol (5) (pKa
5.66 in CH3CN [21]), which may be compared with the acidity of
2,4,6-tris(trifluoromethylsulfonyl)phenol (pKa 4.93 in CH3CN [21]),
The molecular structure of [Li(OC6H2(2,4,6-SO2F)3ꢁH2O]2 con-
stitutes a centrosymmetric dimer wherein a pair of anions are
bound together by a pair of cations in the manner as depicted in
Fig. 2. To a first approximation, the dimer appears to be planar in as
much as the lithium atoms are displaced out of the plane to the
centre of a square pyramid with a water molecule at its apex. This
motif resembles strongly that of the corresponding picrate [24].
Due to the increased sterical demand of the SO2F groups in
comparison with the NO2 groups of the picrate, Li–O contacts to the
oxygen atoms of the 2,6-substituents appear to be elongated by up
Cl
FO2S
SO2F
PCl5 or POCl3 / Py
SO2F
6
OK
toluene
90 %
FO2S
SO2F
CH3OHor (CH3)2CHOH / reflux
SO2F
gaseous HCl
OH
FO2S
SO2F
4
CH3OH
- KCl
SO2F
5
98 - 99 %
Scheme 6.
Scheme 7.

1222
V.N. Boiko et al. / Journal of Fluorine Chemistry 132 (2011) 1219–1226
Cat+
O-
OH
metal-X,
metal or
N-base
FO2S
SO2F
FO2S
SO2F
H2O, MeOH
or MeOH - H2O
SO2F
SO2F
5
8-19
Cat: Li (8), Cs (9), 1/2 Ba (10), 1/2 Mg (11), 1/2 Zn (12),
PyH (13), 2,4,6-(CH3)3PyH (14), 4-(N,N-(CH3)2)PyH (15),
N(CH3)4 (16), N(C2H5)4 (17), N(C4H9)4 (18)
Scheme 8.
Fig. 2. Molecular structure of lithium 2,4,6-tris(fluorosulfonyl)phenolate hydrate
(8).
˚
˚
to 0.14 A, while the Li–OH2 contact of approximately 1.92 A is
nearly identical in both cases.
2.4.3. The crystal structure of hexaaquazinc bis(2,4,6-
tris(fluorosulfonyl)phenolate) pentasesqui hydrate (12),
[Zn(H2O)6][OC6H2(2,4,6-SO2F)3]2ꢁ5.5H2O
Two formula units make up the asymmetric unit consisting of
two independent [Zn(H2O)6] dications without crystallographically
imposed symmetry, four independent phenolate anions and eleven
intercalated water molecules. Cations and anions form separate
stacks extending along the c axis without any ligation of the anions
to the metal cation (Fig. 3). To our knowledge, such a motif has been
reported only twice for the related picrates [Mg(H2O)6][OC6H2
(2,4,6-NO2)3]2ꢁ3H2O [25]and [Fe(H2O)6][OC6H2(2,4,6-NO2)3]2ꢁ2H2O
[26] and seems to be an exception in the solid state structures of
metal picrates in general [27].
2.4.4. The molecular structures of 2,4,6-trimethylpyridinium 2,4,6-
tris(fluorosulfonyl)phenolate (14), [2,4,6-Me3C5H2NH] [OC6H2(2,4,6-
SO2F)3] and 4-(N,N-dimethylamino)pyridinium 2,4,6-
tris(fluorosulfonyl)phenolate (15), [4-Me2NC5H4NH] [OC6H2(2,4,6-
SO2F)3]
Fig. 3. Viewontothe unitcellofhexaaquazinc bis(2,4,6-tris(fluorosulfonyl)phenolate)
pentasesqui hydrate (12) along the crystallographic a-axis.
such as pyridinium picrate [29] or 4-dimethylaminopyridinium
picrate [30] (Figs. 4 and 5).
In the molecular structures of [2,4,6-Me3C5H2NH]
[OC6H2(2,4,6-SO2F)3]
and
[4-Me2NC5H4NH]
[OC6H2(2,4,6-
The hydrogen bonding mode is for the 2,4,6-trimethylpyridi-
˚
˚
˚
SO2F)3], motifs which are well-documented for picrates of N-
containing heterocycles are retrieved [28]. Although cations and
anions are arranged in different manner, the graph-set motif R21ð6Þ
[23] found in both compounds is the same as in related picrates
num derivative D–H 0.89(4) A; Hꢁ ꢁ ꢁA 1.83(3) A; Dꢁ ꢁ ꢁA 2.72(2) A; D–
˚
˚
˚
Hꢁ ꢁ ꢁA 176(3) A for N–Hꢁ ꢁ ꢁO and D–H 0.89(4) A; Hꢁ ꢁ ꢁA 2.81(3) A;
˚
˚
Dꢁ ꢁ ꢁA 3.14(2) A; D–Hꢁ ꢁ ꢁA 103(3) A for N–Hꢁ ꢁ ꢁOSOF and for the 4-
˚
dimethylaminopyridinum derivative D–H 0.85(3) A; Hꢁ ꢁ ꢁA
Fig.
4.
Molecular
structure
4-(N,N-dimethylamino)pyridinium
2,4,6-
Fig. 1. Molecular structure of 2,4,6-tris(fluorosulfonyl)phenol (5).
tris(fluorosulfonyl)phenolate (15).

V.N. Boiko et al. / Journal of Fluorine Chemistry 132 (2011) 1219–1226
1223
Table 1
Crystallographic data for compounds 5, 8, 12, 14 and 15.
5
8
12
14
15
Empirical formula
Formula mass
Crystal system
Space group
C6H3F3O7S3
340.26
C12H8F6Li2O16S6
728.42
C24H54F12O51S12Zn2
1902.13
C14H14F3NO7S3
461.44
C13H13F3N2O7S3
462.43
Monoclinic
P21/c (no. 14)
12.681(2)
9.356(1)
Monoclinic
P21/c (no. 14)
12.419(1)
Orthorhombic
P212121 (no. 19)
9.621(1)
Triclinic
Monoclinic
C2/c (no. 15)
28.613(2)
8.104(1)
¯
P1 (no. 2)
˚
a [A]
9.095(1)
9.562(1)
10.806(2)
97.74(1)
94.74(1)
98.45(1)
916.0(2)
2
˚
b [A]
11.615(2)
24.955(2)
˚
c [A]
9.764(1)
9.553(1)
28.180(2)
17.284(1)
a
b
g
[8]
[8]
[8]
91.79(1)
111.98(1)
115.88(1)
3
˚
V [A ]
1157.9(2)
4
1277.8(3)
2
6765.7(9)
4
3605.9(6)
8
Z
Dcalcd. [g cmꢀ3
]
1.952
1.893
1.223
1.673
1.704
Independent reflections
R (Rw
CCDC
2785
2952
15064
5115
4023
)
0.0466 (0.1154)
675317
0.0340 (0.0888)
675318
0.0494 (0.1220)
675321
0.0379 (0.1002)
675320
0.0311 (0.0847)
675319
for the fluorination of 2,4,6-tris(chlorosulfonyl)chlorobenzene (3).
2,4,6-Tris(fluorosulfonyl)phenol (5) due to its high acidity is able to
produce corresponding salts by reactions not only with bases, but
as well with metals or metal salts. Crystallographic measurements
of 2,4,6-tris(fluorosulfonyl)phenol (5) and some of its salts have
been carried out elucidating impressively the similarity of their
structural motifs to picric acid and its derivatives.
4. Experimental
4.1. General
All starting materials were obtained commercially. All solvents
were dried using literature procedure.
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.
Fig. 5. Molecular structure of 2,4,6-trimethylpyridinium 2,4,6-tris(fluorosulfonyl)
phenolate (14).
˚
˚
˚
˚
Residual signals of the solvent protons with the chemical shifts
= 7.25 ppm (CDCl3), d = 2.07 ppm ([D6]acetone), d = 2.50 ppm
1.95(3) A; Dꢁ ꢁ ꢁA 2.73(2) A; D–Hꢁ ꢁ ꢁA 151(3) A for N–Hꢁ ꢁ ꢁO and D–H
˚
˚
˚
d
0.85(3) A; Hꢁ ꢁ ꢁA 2.45(3) A; Dꢁ ꢁ ꢁA 3.04(2) A; D–Hꢁ ꢁ ꢁA 126(3) A for
N–Hꢁ ꢁ ꢁOSOF. The contacts found in the 4-dimethylaminopyridi-
nium 2,4,6-tris(fluorosulfonyl)phenolate are marginally longer
than in the 4-dimethylaminopyridinium picrate [30]; a fact that
must be attributed to the bulkier SO2F substituents.
([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 are
uncorrected and were measured with an electro thermal appara-
tus.
In solid state structures, the picrate anions adopt a keto form in
most cases [26]. The same has to be applied for the 2,4,6-
tris(fluorosulfonyl)phenolate anion with C–O bond lengths of
˚
˚
4.2. X-ray crystallographic data
1.257(2) A (14) [1.252(2) A(15)] and C–C bond lengths (C1–C2; C1–
˚
˚
C6) of 1.442(2); 1.445(2) A (14) and 1.443(2); 1.447(2) A (15),
CCDC-675317–675321 contain supplementary crystallographic
data for this paper. These data can be obtained free of charge from
The Cambridge Crystallographic Data Centre via www.ccdc.ca-
m.ac.uk/data_request/cif.
respectively. These values differ considerably from those found in
˚
the ‘‘free’’ 2,4,6-tris(fluorosulfonyl)phenol (C–O: 1.335(4) A; C–C:
˚
1.401(4); 1.405(4) A) which crystallizes apparently in the enol
form.
These structural features demonstrate the similarity of both
picric acid and 2,4,6-tris(fluorosulfonyl)phenol and their deriva-
tives in the solid state (Table 1).
4.2.1. 2,4,6-Tris(chlorosulfonyl)phenol (1)
Chlorosulfonic acid (700 mL, 10.75 mol) was slowly added to
phenol (126 g, 1.34 mol) under stirring by a mechanical stirrer.
Temperature was kept at 60–70 8C and evolved HCl was absorbed
with H2O. The reaction mixture was heated to 140–145 8C for 3 h,
then cooled to 30–40 8C and SOCl2 (490 mL, 6.84 mol) was added
dropwise avoiding excessive foaming. The reaction mixture was
stirred at 70–90 8C until the gas evolution was finished (about 3 h),
cooled to room temperature, and the precipitate was filtered off,
mixed in portions with ice-water, filtered off, washed with cold
concentrated HCl and dried in a vacuum desiccator over NaOH and
H2SO4 to afford sulfonyl chloride 1 (473 g, 90.6%). M.p. 187–188 8C;
3. Conclusions
In this work, we demonstrated that 2,4,6-tris(chlorosulfonyl)-
phenol (1) and 2,4,6-tris(chlorosulfonyl)aniline (2) can be synthe-
sized on a preparative scale in high yields. The simple Halex-
process for the preparation of corresponding 2,4,6-tris(fluorosul-
fonyl) derivatives 5 and 6 is better to be realized with KF in dry or
almost dry dioxane, while anhydrous conditions are not suitable

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V.N. Boiko et al. / Journal of Fluorine Chemistry 132 (2011) 1219–1226
after crystallization from p-xylene: m.p. 189–190 8C (lit. m.p.
193 8C [16a]).
4.2.4.2. From
2,4,6-tris(chlorosulfonyl)chlorobenzene
(3)
by
KFꢁ2H2O. KFꢁ2H2O (68.7 g, 0.73 mol) was added by portions to
the boiling solution of 2,4,6-tris(chlorosulfonyl)chlorobenzene (3)
(49.5 g, 0.12 mol) in dioxane (130 mL). The mixture was stirred
under reflux for 1 h. The sticky precipitate that adhered to the walls
of the flask was scraped off periodically. Dioxane was removed
under reduced pressure and the crude product was extracted with
acetone. After solvent vacuum evaporation the residue was treated
with H2O and solution obtained was neutralized with K2CO3 up to
pH 7–8. The precipitated potassium salt was crystallized from H2O.
The residue insoluble in hot water was filtered off quickly and
extracted by CH2Cl2 to afford 2,4,6-tris(fluorosulfonyl)chloroben-
zene (6) (5.2 g, 12%). The hot water solution after cooling afforded 4
(31.2 g, 68.0%).
4.2.2. 2,4,6-Tris(chlorosulfonyl)aniline (2)
4.2.2.1. From sodium p-methoxycarbonylaminobenzene sulfonate.
Sodium p-methoxycarbonylaminobenzene sulfonate (40 g,
0.16 mol) was slowly added to chlorosulfonic acid (135 mL,
2.07 mol) under stirring and evolved HCl was absorbed with H2O.
Temperature of reaction mixture was slowly raised to 140–145 8C
and kept at this level for 4.5 h. After cooling to 35–40 8C SOCl2
(46 mL, 0.64 mol) was added dropwise and mixture was heated at
70–85 8C for 5 h. The reaction mass was mixed by portions with
crushed ice, the precipitate was filtered off, washed with cold water
up to pH 7 and dried under reduced pressure. The crude product
obtained (50.0 g) was dissolved in hot CHCl3 (ꢂ500 mL) and quickly
filtered through Al2O3 (15–20 mm layer). The solvent was removed
under reduced pressure to afford aniline 2 (37.5 g, 61%). M.p. 170–
172 8C (lit. m.p. 168–170 8C [12c]; 175–177 8C [12d]).
4.2.4.3. From 2,4,6-tris(chlorosulfonyl)chlorobenzene (3) by anhy-
drous KF with 1.5 equiv. H2O. A solution of H2O (0.7 mL, 0.04 mol) in
dioxane (10 mL) was added dropwise to a suspension of KFꢁ2H2O
(15.3 g, 0.16 mol), that was beforehand calcinated on the open
flame, in dioxane (15 mL). 2,4,6-Tris(chlorosulfonyl)chloroben-
zene (3) (11.0 g, 0.027 mol) was added and mixture was boiled
with stirring for 30 min. After cooling, acetone (50 mL) and K2CO3
(up to foam termination) were added, the solvents were
evaporated in vacuum and the residue was washed several times
with acetone. After removing acetone, the residue was crystallized
from H2O to afford the potassium salt 4 (7.3 g, 71%).
4.2.2.2. From acetanilide. The analogous to previous section
acetanilide (20.0 g, 0.15 mol) treated by chlorosulfonic acid
(100 mL, 1.54 mol) and then SOCl2 (43.0 mL, 0.60 mol) to afford
2, which was purified as mentioned above (34.0 g, 58.4%), m.p.
168–170 8C.
A mixing test of the samples obtained by different given
methods and with an authentic sample did not show a m.p.
depression.
4.2.4.4. From lithium 2,4,6-tris(fluorosulfonyl)phenolate (8). To a
stirred solution of lithium 2,4,6-tris(fluorosulfonyl)phenolate (8)
(18.8 g, 54.27 mmol) in H2O (40 mL) was added a solution of KBr
(6.64 g, 55.6 mmol) in H2O (10–15 mL). The precipitate was
filtered off, washed with H2O, dried at 100 8C to afford 4 (20.0 g,
97%).
4.2.3. 2,4,6-Tris(chlorosulfonyl)chlorobenzene (3)
4.2.3.1. Preparation by PCl5. A mixture of 2,4,6-tris(chlorosulfo-
nyl)phenol (1) (55.7 g, 0.14 mol) and PCl5 (60.0 g, 0.29 mol) in
toluene (450 mL) was refluxed for 4 h and evolved HCl was
absorbed with H2O. The solvent was evaporated in vacuum at 30–
45 8C and the residue like sour cream was cooled. The precipitate
was filtered off, washed with ice H2O up to pH 7 and dried in the
vacuum desiccator to afford 3 (55.7 g, 95.4%), m.p. 168–169 8C
(CHCl3) (lit. m.p. 170–171 8C [16b]).
The samples obtained by different given methods have identical
1H and 19F NMR spectra.
4.2.5. 2,4,6-Tris(fluorosulfonyl)phenol (5)
4.2.5.1. From potassium 2,4,6-tris(fluorosulfonyl)phenolate (4). A
solution of potassium 2,4,6-tris(fluorosulfonyl)phenolate (4)
(104.6 g, 0.27 mol) in MeOH (250 mL) was saturated with dry
HCl at 20 8C. The precipitated KCl was filtered off, the solvent was
removed under reduced pressure to afford 5 (92 g, 97.8%), m.p.
4.2.3.2. Preparation by POCl3 with Py. A mixture of 2,4,6-tris(-
chlorosulfonyl)phenol (1) (10 g, 26.0 mmol) and pyridine (0.6 mL,
7.45 mmol) in POCl3 (20 mL) was refluxed until the gas evolution
stopped (about 2 h). The cooled reaction mixture was poured into
H2O. The obtained oil was mashed to precipitate formation, that
was filtered off, washed with H2O up to pH 7 and dried in the
vacuum desiccator over NaOH and H2SO4 to afford 3 (9.54 g, 91%),
m.p. 165–169 8C (CHCl3).
143–144 8C (CHCl3). 1H NMR (CDCl3):
2H, ArH); ([D6]acetone):
= 8.44 (s, ArH) ppm. 19F NMR ([D6]ace-
tone):
= 55.6 (s, 2F, o-SO2F), 68.7 (s, 1F, p-SO2F) ppm. 13C NMR
([D6]acetone):
= 118.8 (m, 1C, 4-C), 124.6 (d, 2JC,F = 25.2 Hz, 2C, 2-
d = 6.0 (br. s, 1H, OH), 8.86 (s,
d
d
d
C, 6-C), 139.1 (s, 2C, 3-C, 5-C), 163.1 (s, 1C, 1-C) ppm. C6H3F3O7S3
(340.27); calcd. C 21.18, H 0.89, S 28.27; found C 21.09, H 0.90, S
28.38.
A mixing test of the samples obtained by different given
methods did not show a m.p. depression.
4.2.5.2. From 2,4,6-tris(fluorosulfonyl)chlorobenzene (6). A solution
of 2,4,6-tris(fluorosulfonyl)chlorobenzene (6, 0.05 g, 0.14 mmol) in
MeOH (2 mL) was heated under reflux (about 3.5 h). The solvent
was removed under reduced pressure to afford phenol 5 (0.047 g,
99.0%), m.p. 141–143 8C (CHCl3).
4.2.4. Potassium 2,4,6-tris(fluorosulfonyl)phenolate (4)
4.2.4.1. From 2,4,6-tris(chlorosulfonyl)phenol (1). KFꢁ2H2O (61.0 g,
0.65 mol) was calcinated on the open flame and poured without
cooling quickly by portions into a warm solution of 2,4,6-
tris(chlorosulfonyl)phenol (1) (41.8 g, 0.10 mol) in dioxane
(170 mL). The mixture was heated under reflux and stirring for
0.5 h, diluted with H2O (about 100 mL), K2CO3 was added till the
foaming terminated (pH 7–8) and dioxane was evaporated in
vacuum. The residue was crystallized from H2O (the hot solution
was treated with charcoal) to afford 4 (30.6 g, 80.8%) in the form of
a snow-white crystals. M.p. > 250 8C. 1H NMR ([D6]acetone):
A mixing test of the samples obtained by different given
methods did not show a m.p. depression.
4.2.6. 2,4,6-Tris(fluorosulfonyl)chlorobenzene (6)
4.2.6.1. Preparation with PCl5. A mixture of potassium 2,4,6-
tris(fluorosulfonyl)phenolate (4, 10.0 g, 26.43 mmol) and PCl5
(11.0 g, 52.8 mmol) in toluene (90 mL) was refluxed for 3.5 h. The
solvent was condensed in vacuo, the residue was pressed out,
washed with ice-water till pH 7 and finally the precipitate was
d
= 8.6 (s, ArH) ppm. 19F NMR ([D6]acetone):
d = 55.6 (s, 2F, o-SO2F),
68.9 (s, 1F, p-SO2F) ppm. C6H2F3O7S3K (378.37): calcd. C 19.05, H
0.53, S 25.42; found C 19.18, H 0.68, S 25.15.

V.N. Boiko et al. / Journal of Fluorine Chemistry 132 (2011) 1219–1226
1225
dried in a vacuum desiccator over P4O10 to afford 6 (8.5 g, 89.6%),
m.p. 186.8–189.3 8C (CHCl3, twice), Rf = 0.8 (benzene). 1H NMR
([D6]acetone):
4.2.9. Cesium 2,4,6-tris(fluorosulfonyl)phenolate (9)
To a stirred solution of 2,4,6-tris(fluorosulfonyl)phenol (5, 2.0 g,
5.88 mmol) in H2O (25 mL) a solution of Cs2SO4 (1.12 g, 3.1 mmol)
in H2O (10 mL) was added. The precipitate was filtered off, washed
d
= 9.20 (s, ArH) ppm. 19F NMR ([D6]acetone):
d
= 59.6 (s, 2F, o-SO2F), 66.6 (s, 1F, p-SO2F) ppm. 13C NMR
2
([D8]THF):
d
= 132.9 (d, JC,F = 31.2 Hz, 1C, 4-C), 136.7 (d,
with H2O to afford 9 (2.13 g, 76.7%). 1H NMR ([D6]acetone):
(s, ArH) ppm. 19F NMR ([D6]DMSO):
d
= 8.24
2JC,F = 28.6 Hz, 2C, 2-C, 6-C), 137.6 (s, 2C, 3-C, 5-C), 140.8 (s, 1C,
1-C) ppm. C6H2ClF3O6S3 (358.73): calcd. C 20.09, H 0.56, Cl 9.88, S
26.82; found C 20.23, H 0.41, Cl 10.08, S 26.64.
d = 57.1 (s, 2F, o-SO2F), 70.8 (s,
1F, p-SO2F) ppm. C6H2CsF3O7S3 (472.17); calcd. C 15.26, H 0.43, F
12.06, S 20.37; found C 15.17, H 0.63, F 12.10, S 20.14.
4.2.6.2. Preparation with POCl3 and pyridine. A mixture of potassi-
um 2,4,6-tris(fluorosulfonyl)phenolate (4, 3.0 g, 7.93 mmol) and
pyridine (0.2 mL, 2.48 mmol) in POCl3 (3 mL) was refluxed for 2 h
and poured out onto ice. The obtained oil was rubbed with a glass
stick until solidification. The latter was filtered off, washed with
ice-water till pH 7 and dried under reduced pressure over P4O10 to
4.2.10. Barium 2,4,6-tris(fluorosulfonyl)phenolate (10)
To a stirring solution of 2,4,6-tris(fluorosulfonyl)phenol (5,
0.6 g, 1.76 mmol) in H2O (1.0 mL) a solution of BaCl2ꢁ2H2O (0.52 g,
2.13 mmol) in H2O (0.3 mL) was added. The precipitate was filtered
off, washed with water and dried under reduced pressure (0.1 Torr)
to afford 10 (0.59 g, 70.3%). 1H NMR ([D6]acetone):
ppm. 19F NMR ([D6]acetone):
= 55.6 (s, 2F, o-SO2F), 67.7 (s, 1F, p-
d = 8.24 (s, ArH)
afford
6
(2.56 g, 90%), Rf = 0.8 (benzene). M.p. 177–180 8C
d
(toluene).
SO2F) ppm. C12H4BaF6O14S6 (815.86); calcd. C 17.67, H 0.49, S
27.45; found C 17.52, H 0.60, S 27.21.
A mixing test of the samples obtained by different given
methods did not show a m.p. depression.
4.2.11. Hexaaquamagnesium bis(2,4,6-
4.2.7. 2,4,6-Tris(fluorosulfonyl)aniline (7)
tris(fluorosulfonyl)phenolate)) trihydrate (11)
KFꢁ2H2O (1.5 g, 15.94 mmol) was calcinated on an open flame
and poured without cooling in portions into a warm solution of
2,4,6-tris(chlorosulfonyl)aniline (2 1.0 g, 2.57 mmol) in dioxane
(4 mL) with H2O (0.08 mL, 4.44 mmol). The mixture was refluxed for
about 1.5–2 h. After addition of H2O the precipitate formed was
filtered off and dried to afford aniline 7 (0.68 g, 77.9%). M.p. 203.5–
205.5 8C (benzene) (lit. m.p. 196–198 8C [12c]). 1H NMR
A mixture of 2,4,6-tris(fluorosulfonyl)phenol (5, 1.54 g,
4.52 mmol) with magnesium shavings (0.10 g, 4.12 mmol) in
H2O (5 mL) was stirred until gas evolution was no more observed.
After filtration, the solution was concentrated under reduced
pressure (0.1 Torr), formed precipitate was filtered off to afford 11
(1.25 g, 64%). 1H NMR ([D6]acetone):
(s, 2H, ArH) ppm. 19F NMR ([D6]acetone):
d
= 4.55 (br. s, 9H, H2O), 8.38
= 55.0 (s, 2F, o-SO2F),
d
([D6]DMSO):
([D6]DMSO):
NMR ([D6]DMSO):
d
d
= 8.3 (s, 2H, NH2), 8.6 (s, 2H, ArH) ppm. 19F NMR
68.0 (s, 1F, p-SO2F) ppm. C12H22F6MgO23S6 (864.98); calcd. C 16.66,
H 2.56, S 22.24; found C 16.68, H 2.49, S 21.96.
= 61.4 (s, 2F, o-SO2F), 68.5 (s, 1F, p-SO2F) ppm. 13C
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, 1-C)
4.2.12. Hexaaquazinc bis(2,4,6-tris(fluorosulfonyl)phenolate))
ppm.
pentasesqui hydrate (12)
A mixing test with an authentic sample [12c] does not show an
m.p. depression.
A mixture of 2,4,6-tris(fluorosulfonyl)phenol (5, 1.15 g,
3.38 mmol) with zinc powder (0.20 g, 3.06 mmol) in H2O
(1.5 mL) was stirred until gas evolution was no more observed.
After filtration, the solution was concentrated under reduced
pressure (0.1 Torr), formed precipitate was filtered off to afford 12
4.2.8. Lithium 2,4,6-tris(fluorosulfonyl)phenolate (8)
(0.77 g, 48%). 1H NMR ([D6]acetone):
8.30 (s, 2H, ArH) ppm. 19F NMR ([D6]acetone):
d
= 4.10 (br. s, 11.5H, H2O),
= 55.2 (s, 2F, o-
4.2.8.1. From potassium 2,4,6-tris(fluorosulfonyl)phenolate (4). A
solution of LiCl (3.98 g, 93.9 mmol) in propanol-2 (86 mL) was
added to a boiling solution of potassium 2,4,6-tris(fluorosulfo-
nyl)phenolate (4, 32.13 g, 84.9 mmol) in propanol-2 (250 mL).
After cooling the precipitated KCl was filtered off, the solvent was
removed under reduced pressure. The colourless powder obtained
was washed with anhydrous CHCl3 and dried in vacuo (0.1 Torr) at
110–120 8C to afford 8 (28.5 g, 96.9%), m.p. > 250 8C. 1H NMR
d
SO2F), 68.1 (s, 1F, p-SO2F) ppm. C12H27F6O25.5S6Zn (951.08); calcd.
C 15.15, H 2.86, S 20.23; found C 14.87, H 2.95, S 19.92.
4.2.13. Various pyridinium 2,4,6-tris(fluorosulfonyl)phenolate
derivatives (13–15). General procedure
To a stirred solution of 2,4,6-tris(fluorosulfonyl)phenol (5, 2.0 g,
5.88 mmol) in MeCN (30 mL) a solution of a corresponding
pyridine (5.88 mmol) in MeCN (10 mL) was added. The solution
was stirred for 5 min, MeCN was removed under reduced pressure
(0.1 Torr) to afford 13–15 in quantitative yields.
(CDCl3): d d = 54.3 (s, 2F, o-
= 8.39 (s, ArH) ppm. 19F NMR (CD3CN):
SO2F), 66.7 (s, 1F, p-SO2F) ppm. C6H2F3O7S3Li (346.22); calcd. C
20.82, H 0.58, S 27.78; found C 20.93, H 0.80, S 27.68.
4.2.8.2. From 2,4,6-tris(fluorosulfonyl)phenol (5). A mixture of
2,4,6-tris(fluorosulfonyl)phenol (5, 5 g, 14.7 mmol) and, Li2CO3
(1.4 g, 18.95 mmol) in MeOH (20 mL) was kept for 18–24 h at 20–
25 8C. The excess of Li2CO3 was filtered off, MeOH was removed
under reduced pressure. The residue was washed with anhydrous
CHCl3, toluene, dried by azeotropic distillation with toluene,
filtered off and dried in vacuo (0.1 Torr) at 70 8C to afford 8 (5.08 g,
4.2.13.1. Pyridinium 2,4,6-tris(fluorosulfonyl)phenolate (13). Pyri-
dine was used. M.p. 175.8–177.2 8C (propanol-2). 1H NMR
([D6]DMSO):
8.52 (m, 1H, 4-ArH (Py)), 8.89 (m, 2H, 2,6-ArH (Py)) ppm. 19F NMR
([D6]DMSO): = 57.2 (s, 2F, o-SO2F), 70.9 (s, 1F, p-SO2F) ppm.
11H8F3NO7S3 (419.38); calcd. C 31.50, H 1.92, N 3.34, S 22.94;
d = 8.00 (m, 2H, 3,5-ArH (Py)), 8.24 (s, 2H, ArH),
d
C
99.8%). 1H NMR ([D6]acetone):
d
= 8.36 (s, ArH) ppm. 19F NMR
found C 31.72, H 1.98, N 3.34, S 22.95.
([D6]acetone): = 55.5 (s, 2F, o-SO2F), 68.9 (s, 1F, p-SO2F) ppm.
d
4.2.13.2. 2,4,6-Trimethylpyridinium 2,4,6-tris(fluorosulfonyl)pheno-
4.2.8.2.1. Crystallization of lithium 2,4,6-tris(fluorosulfonyl)phenolate
(8) hydrate dimer for X-ray investigation. Anhydrous lithium 2,4,6-
tris(fluorosulfonyl)phenolate (8) was dissolved in mixture of
diethyl ether and hexane. The mother liquor was stored at room
temperature under a ventilated hood for several days to precipitate
colourless crystals of [Li(OC6H2(2,4,6-SO2F)3ꢁH2O]2.
late (14). 2,4,6-Trimethylpyridine (collidine) was used. M.p.
201.8–204.7 8C (propan-2-ol). 1H NMR ([D6]acetone):
d
= 2.48 (s,
3H, 4-CH3-Py), 2.62 (s, 6H, 2,4-CH3-Py), 7.57 (s, 2H, 3,5-ArH (Py)),
8.23 (s, 2H, ArH) ppm. 19F NMR ([D6]DMSO):
= 55.2 (s, 2F, o-SO2F),
d
68.9 (s, 1F, p-SO2F) ppm. C14H14F3NO7S3 (461.46); calcd. C 36.44, H
3.06, N 3.04, S 20.85; found C 36.45, H 2.85, N 2.98, S 20.78.

1226
V.N. Boiko et al. / Journal of Fluorine Chemistry 132 (2011) 1219–1226
(e) S.S. Gitis, A.Ya. Kaminskii, Usp. Khim. (Russ. Chem. Rev.), 47 (1978) 1970–
2013 (in Russian);
Chem. Abstr. 90 (1979) 71249g;
4.2.13.3. 4-(N,N-Dimethylamino)pyridinium 2,4,6-tris(fluorosulfo-
nyl)phenolate (15). 4-(N,N-Dimethylamino)pyridine (DMAP) was
used. M.p. 179.8–181.5 8C. 1H NMR ([D6]acetone):
d = 3.36 (s, 6H,
(f) T.N. Hall, Ch.F. Poranski, in: H. Feuer (Ed.), The Chemistry of Nitro and Nitroso
Groups, Pt. 2, Interscience, New York, 1970, pp. 329–384.
[3] (a) V.P. Parini, Usp. Khim. (Russ. Chem. Rev.), 31 (1962) 822–837 (in Russian);
Chem. Abstr. 58 (1963) 2330e;
2
NMe2), 7.14 (d, JH,H = 7.4 Hz, 2H, 3,5-ArH (Py)), 8.30 (d,
2JH,H = 7.4 Hz, 2H, 2,6-ArH (Py)), 8.39 (s, 2H, ArH) ppm. 19F NMR
([D6]acetone):
d
= 54.8 (s, 2F, o-SO2F), 67.7 (s, 1F, p-SO2F) ppm. 13
C
(b) D.V. Bunthorpe, Chem. Rev. 70 (1970) 295–322.
2
[4] (a) V.N. Boiko, L.M. Yagupolskii, Izv. Sibir. Otdel. Akad. Nauk USSR, Ser. Khim.
Nauk (Siberian J. Chem. USSR), 4 (1983) 50–58 (in Russian);
V.N. Boiko, Chem. Abstr. 99 (1983) 174914k;
NMR ([D6]acetone):
d
= 39.5 (s, 2C, NMe2), 106.9 (d, JC,F = 27 Hz,
1C, 4-C), 107.2 (s, 2C, 3-C, 5-C (Py)), 124.6 (d, 2JC,F = 21 Hz, 2C, 2-C,
6-C), 138.9 (s, 2C, 3-C, 5-C), 139.1 (s, 2C, 2-C, 6-C (Py)), 167.4 (s, 1C,
1-C) ppm. C13H13F3N2O7S3 (462.44); calcd. C 33.77, H 2.83, N 6.06,
S 20.80; found C 33.66, H 2.79, N 6.15, S 20.75.
(b) V.N. Boiko, Izv. Sibir. Otdel. Akad. Nauk USSR, Ser. Khim. Nauk (Siberian J.
Chem. USSR), 4 (1990) 126–136 (in Russian);
V.N. Boiko, Chem. Abstr. 114 (1991) 184522y.
[5] J.M. Carpentier, F. Terrier, R. Schall, N.V. Ignatev, V.N. Boiko, L.M. Yagupolskii, Bull.
Soc. Chim. Fr. (1985) 150–154.
[6] A.Yu. Nazarenko, V.N. Boiko, I.V. Gogoman, G.M. Shchupak, Zh. Obshch. Khim. (J.
Gen. Chem. USSR), 58 (1988) 1389–1394 (in Russian);
Chem. Abstr. 110 (1989) 192152k.
[7] A.J. Gordon, R.A. Ford, The Chemist’s Companion, John Wiley & Sons, New York,
1972.
[8] H.-S. Lee, L. Geng, T. Scotheim, WO 96/29753 (1996).
[9] V.N. Boiko, G.M. Shchupak, N.V. Ignatev, L.M. Yagupolskii, Zh. Organ. Khim. (J. Org.
Chem. USSR), 15 (1979) 1245–1253 (in Russian);
4.2.14. Tetraalkylammonium 2,4,6-tris(fluorosulfonyl)phenolates
(16–18). General procedure
To a stirred solution of 2,4,6-tris(fluorosulfonyl)phenol (5, 2.0 g,
5.88 mmol) in H2O (120 mL) a solution of a corresponding
tetraalkylammonium iodide or hydroxide (6.17 mmol) in H2O or
MeOH (60 mL) was added. The formed precipitate was filtered off,
washed with water to afford the tetraalkylammonium 2,4,6-
tris(fluorosulfonyl)phenolate (16–18).
Chem. Abstr. 91 (1979) 157378f.
[10] W.A. Sheppard, C.M. Sharts, Organic Fluorine Chemistry, W.A. Benjamin INC, New
York, 1969, p. 355.
[11] L.M. Yagupolskii, in: L.N. Markovskii (Ed.), Aromatic and Heterocyclic Compounds
with Fluorine-containing Substituents (Aromaticheskie i Geterotsiklicheskie Soe-
dineniya s Ftorosoderzhazchimi Zamestitelyami), ‘‘Naukova Dumka’’ Publishing,
Kiev, USSR, 1988, 320 pp. (in Russian);
Chem. Abstr. 111 (1989) 232772s.
[12] (a) O. Lustig, E. Katscher, Monatsh. Chem. 48 (1927) 87–97;
(b) G. Booth, Synth. Commun. 13 (1983) 659–661;
4.2.14.1. Tetramethylammonium 2,4,6-tris(fluorosulfonyl)phenolate
(16). Tetramethylammonium iodide was used. Yield 81%. m.p.
240–242.7 8C. 1H NMR ([D6]DMSO):
d
d
= 3.09 (s, 12H, CH3), 8.24 (s,
= 57.2 (s, 2F, o-SO2F), 70.9 (s,
2H, ArH) ppm. 19F NMR ([D6]DMSO):
1F, p-SO2F) ppm. C10H14F3NO7S3 (413.41); calcd. C 29.05, H 3.41, N
3.39, S 23.27; found C 29.17, H 3.34, N 3.48, S 23.35.
(c) L.Z. Gandelsman, L.I. Trushanina, Ukr. Khim. Zh. (Ukrainian Chem. J. USSR), 56
(1990) 1118–1119 (in Russian);
Chem. Abstr. 114 (1991) 184907c;
(d) V. Percec, T.K. Bera, B.B. De, Y. Sanai, J. Smith, M.N. Holerea, B. Barboiu, J. Org.
Chem. 66 (2001) 2104–2117.
4.2.14.2. Tetraethylammonium
2,4,6-tris(fluorosulfonyl)phenolate
(17). Tetraethylammonium iodide was used. Yield 93%. m.p.
[13] Beilsteins Handbuch der Organischen Chemie, 11, III, p. 483.
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Tret’yakov, Patent of Ukraine 72649 (2005).
168–170 8C (propanol-2). 1H NMR ([D6]DMSO):
d = 1.16 (t,
2JH,H = 7.3 Hz, 12H, CH3), 3.20 (q, JH,H = 7.3 Hz, 8H, CH2) 8.24 (s,
2
2H, ArH) ppm. 19F NMR ([D6]DMSO):
d = 55.2 (s, 2F, o-SO2F), 68.8 (s,
1F, p-SO2F) ppm. C14H22F3NO7S3 (469.52); calcd. C 35.81, H 4.72, N
2.98, S 20.49; found C 35.79, H 4.79, N 3.07, S 20.35.
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(b) W. Davies, E.S. Wood, J. Chem. Soc. (1928) 1122–1131.
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[19] A. Sekiya, N. Ishikawa, Bull. Chem. Soc. Jpn. 51 (1978) 1267–1268.
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[22] E.N. Duesler, J.H. Engelmann, D.Y. Curtin, I.C. Paul, Cryst. Struct. Commun. 7
(1978) 449–753, CAN 89: 98183; PICRAC.
4.2.14.3. Tetrabuthylammonium 2,4,6-tris(fluorosulfonyl)phenolate
(18). Tetrabuthylammonium hydroxide 0.1 M solution in MeOH
was used. Yield 95%. m.p. 91.6–93.6 8C. 1H NMR ([D6]DMSO):
2
2
d
= 0.93 (t, JH,H = 7.2 Hz, 12H, CH3), 1.30 (m, JH,H = 7.5 Hz, 8H,
CH2), 1.56 (m, 8H, CH2), 3.15 (m, 8H, CH2) 8.24 (s, 2H, ArH) ppm. 19
NMR ([D6]DMSO): = 57.1 (s, 2F, o-SO2F), 70.8 (s, 1F, p-SO2F) ppm.
22H38F3NO7S3 (581.74); calcd. C 45.42, H 6.58, N 2.41, S 16.54;
F
d
C
found C 45.55, H 6.68, N 2.49, S 16.31.
[23] J. Bernstein, R.E. Davis, L. Shimoni, N.-L. Chang, Angew. Chem. 107 (1995) 1689–
1708;
Acknowledgment
J. Bernstein, R.E. Davis, L. Shimoni, N.-L. Chang, Angew. Chem., Int. Ed. Engl. 34
(1995) 1555–1573.
The generous financial support of this work by the DFG (Grant
436 UKR 113) is gratefully acknowledged.
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Yoshida, S. Fujiwara, Acta Cryst. C59 (2003) m319–m321.
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