New pentafluoro-λ6-sulfanyl (SF5) perfluoroalkyl benzene derivatives

Article abstract of DOI:10.1016/S0022-1139(01)00499-7

Preparation of the following new SF₅-perfluoroalkyl benzene derivatives, m-SF₅CF₂CF₂C₆H₄X (X = NO₂, NH₂, OH, I, NHCOCH₃, SO₂Cl, SO₃H, SO₃K) has been achieved. The new compounds were characterized by their respective IR, NMR and HRMS or elemental analysis.

Full text of DOI:10.1016/S0022-1139(01)00499-7

Journal of Fluorine Chemistry 114 ꢀ2002) 3±8
New penta¯uoro-l6-sulfanyl ꢀSF5) per¯uoroalkyl benzene derivatives
A.M. Hodges, R.W. Winter, S.W. Winner, D.A. Preston, G.L. Gard*
Department of Chemistry, Portland State University, Portland, OR 97207-0751, USA
Received 13 June 2001; accepted 2 August 2001
Abstract
Preparation of the following new SF5-per¯uoroalkyl benzene derivatives, m-SF5CF2CF2C6H4X ꢀX ˆ NO2, NH2, OH, I, NHCOCH3,
SO2Cl, SO3H , SOK) has been achieved. The new compounds were characterized by their respective IR, NMR and HRMS or elemental
3
analysis. # 2002 Published by Elsevier Science B.V.
Keywords: Penta¯uorothio¯uoroalkyl benzene derivatives; IR and NMR spectroscopy; HRMS and MS
1. Introduction
3. During the reaction, a complex amine chlorostannate
precipitate was formed.
Recently, we reported the synthesis of a new class of
o-SF5-per¯uoroalkyl benzene compounds, SF5ꢀCF2)nC6H5
ꢀn ˆ 2, 4, 6, 8) [1]. As part of our ongoing research into SF5-
hydrocarbons, we have developed the chemistry of corre-
sponding SF5ꢀCF2)n-aromatic compounds; in particular,
we have used SF5CF2CF2C6H5 as the representative of this
new class of compounds. In view of the great importance
of ¯uorinated aromatic compounds and the properties asso-
ciated with the SF5 group, these new derivatives will serve as
a springboard for the development of new and improved
pharmaceuticals, agricultural chemicals and polymeric
materials. SF5-aromatic compounds ꢀSF5C6H4X) were ®rst
prepared by Sheppard in 1962 [2] and more recently by
Bowden et al. [3]; one of the major drawbacks associated
with the synthetic pathways used by these authors is the use
of extremely strong oxidizing agents such as AgF2 and F2.
In order to obtain m-SF5CF2CF2C6H4X ꢀI, OH) deriva-
tives, the diazonium salt intermediates were prepared:
m-SF5CF2CF2C6H4NH2 ‡ NaNO2 ‡ 2HCl
! ‰m-SF5CF2CF2C6H4N2 ClÀŠ ‡ NaCl ‡ 2H2O
‡
Its preparation was achieved at low temperatures ꢀ0±5 8C);
during the course of the reaction, precipitation of the corre-
sponding amine hydrochloride followed by dissolution and
the formation of a light yellow solution were observed. This
solution was then used to prepare the iodo derivative 4:
m-SF5CF2CF2C6H4N2 ClÀ ‡ KI
‡
! m-SF5CF2CF2C6H4I ‡ N2 ‡ KCl
In a like manner, using sulfuric acid the phenol derivative 5,
an orange oil, was prepared by heating:
‡
À
m-SF5CF2CF2C6H4N2 HSO4 ‡ H2O
! m-SF5CF2CF2C6H4OH ‡ N2 ‡ H2SO4
A major by-product thought to be 2-nitro-5-ꢀ1,1,2,2-tetra-
2. Results and discussion
fluoro-2-SF5-ethyl)-phenol was also isolated.
We have found that the SF5CF2CF2C6H5, 1, synthon is an
excellent reagent for preparing a number of derivatives. As
was expected, the SF5CF2CF2-grouping is meta directing in
electrophilic substitution reactions. This is borne out in the
nitration and chlorosulfonation described below. The nitra-
tion of 1 was accomplished by using 90% nitric acid and low
temperaturesꢀ0±5 8C).Theproduct,m-SF5CF2CF2C6H4NO2,
2, was reduced using SnCl2 giving m-SF5CF2CF2C6H4NH2,
The anilide, m-SF5CF2CF2C6H4NHCꢀO)CH3, 6, was
formed from 3 using acetic anhydride catalyzed with sul-
furic acid. The sulfonyl chloride derivative, m-SF5CF2CF2-
C6H4SO2Cl, 7, was prepared by treating 1 with a large
excess of chlorosulfonic acid:
m-SF5CF2CF2C6H5 ‡ xClSO3H
! m-SF5CF2CF2C6H4SO2Cl ‡ H2SO4 ‡ HCl
The base hydrolysis of 7 gave the corresponding pota-
ssium sulfonate salt 8 which when passed through an
* Corresponding author. Fax: ‡1-503-725-3888.
E-mail address: psu20653@pdx.edu ꢀG.L. Gard).
0022-1139/02/$ ± see front matter # 2002 Published by Elsevier Science B.V.
PII: S 0 0 2 2 - 1 1 3 9 ꢀ 0 1 ) 0 0 4 9 9 - 7

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A.M. Hodges et al. / Journal of Fluorine Chemistry 114 22002) 3±8
‡
‡
ion-exchange column gave the corresponding sulfonic
acid 9.
2, peaks at m=e ˆ 30 ꢀNO ) and m=e ˆ 46 ꢀNO2 ) were
found; additional peaks at m=e ˆ 176, 126 and 76 were also
‡
‡
The infrared ꢀIR) spectral data for the new compounds
2±9 are listed in Section 3. Since all compounds contained
the SF5CF2CF2 group, bands characteristic for this group
were identi®ed in each of the spectra. The IR spectra of all
new compounds showed very intense bands in the 800±
900 cmÀ1 region and are attributed to the S±F stretching
modes; bands in the 605±613 cmÀ1 region are due to one of
the S±F deformation modes. Cross et al. have reported the
SF5 stretching frequency as a strong band in the 850±920
cmÀ1 region with a deformation mode near 600 cmÀ1 [4].
The strong absorption peaks in the 1100±1300 cmÀ1 region
were attributed to C±F stretching vibrations. The CF2 groups
have strong absorption bands in the 1100±1400 cmÀ1 region
[5].
observed due to the ꢀM±SF5±NO2) , ꢀM±SF5CF2±NO2)
‡
and ꢀM±SF5CF2CF2±NO2) fragments. The spectra of aro-
matic halogen compounds have characteristic peaks due to
the loss of a halogen radical; for compound 4, peaks at
‡
‡
m=e ˆ 303 and 126 due to ꢀM±I) and ꢀM±SF5CF2±I)
were found. The mass spectrum for ꢀ7) contained, in addi-
tion to a weak parent molecular ion, peaks at m=e ˆ 367,
‡
303, 176, 174 and 126 which were attributed to the ꢀM±Cl) ,
ꢀM±SO2Cl) , ꢀM±SF5±SO2Cl) , ꢀM±SF5CF2±O±Cl) and
‡
‡
‡
‡
ꢀM±SF5CF2±SO2Cl) fragments; the chlorine isotopic 3:1
doublet was observed for all fragments containing chlorine.
In lieu of elemental analyses, the HRMS of the parent ions
for 4±6 were obtained.
The 19F NMR results for compounds 2±9 are included in
Table 1. The eight new compounds contain the SF5CF2CF2
group and their 19F NMR spectra showed expected simila-
rities [6±8]. The axial ¯uorine ꢀA) of the SF5 group ꢀAB4
pattern) appears as a pentet or a nine-line pattern in which
either each line is further split into a triplet or appears as a
multiplet and is found in the range of 65.0±66.7 ppm. The
splitting of the A ¯uorine into a triplet was caused by long
range couplings with the ¯uorine atoms of the neighboring
3. Experimental details
The reactants, benzene, 99.9% HPLC grade, chlorosul-
fonic acid, 99%, HSO3Cl, 99%, and nitric acid ꢀ90% ACS
reagent) were used as obtained from Aldrich Chemical Co.
Anhydrous diethyl ether, methylene chloride ꢀhigh purity
solvent), sodium nitrite, SnCl2Á2H2O and hydrochloric acid
ꢀ36.5±38.0%) were obtained from J.T. Baker Co. and used
without further puri®cation. Potassium iodide was used as
obtained from Sigma Chemical Co. Sodium hydroxide
pellets were used as obtained from EM Science. In addition
to the purchased chemicals listed above, the compound
SF5CF2CF2C6H5 was prepared according to the literature
[1].
IR spectra were obtained using a Perkin-Elmer 2000 FTIR
system operating at 2.0 cmÀ1 resolution. For liquid and solid
samples, KBr plates were used. NMR spectra were obtained
using a Varian EM-390 spectrometer operating at 84.6 MHz
for 19F and/or a Bruker AMX-400 spectrometer operating at
376.5 MHz for 19F, 400.1 MHz for 1Hand/or a Bruker 500.
The standards, CFCl3 ꢀFreon-11) and ꢀCH3)4Si were used.
The solvents used were CDCl3 or D2O.
Mass spectra were obtained using a Hewlett-Packard
HP5890 series II gas chromatograph ꢀGC) equipped with
a HP5970 mass selective detector operated at 70 eV and a
30 m DB-5 column. For a standard run, the column was
maintained at 50 8C for 2 min, followed by an increase in
temperature of 11 8C minÀ1 until the temperature of the
column reached 280 8C. The precise molecular weights
determination ꢀHMRS) for compounds 4±6 were obtained
on a Kratos MS 50TC; chemical ionization with methane.
The elemental analysis determinations were performed
a
CF2 groups. The equatorial ¯uorines ꢀB4) appeared as a
doublet of a pentet or a doublet of a multiplet between 44.8
and 45.6 ppm. Long range coupling to the CF2 groups was
also observed for the equatorial ¯uorines. The experimental
b
a
coupling constants for the ¯uorinated group CF2 CF2 À
SF4BFA ꢀsee Table 1) are: JAB ranges between 145 and
147 Hz and for JAa between 3.8 and 4.8 Hz. Additional
coupling constants, JBa and JBb range between 12.7 and
15.2 Hz. The values for the chemical shifts and coupling
constants agree with reported values for other SF5CF2CF2
derivatives [1,7,8]. The chemical shifts for the CF2 ¯uorines
adjacent to the SF5 group ranged between À93.5 and
À98.7 ppm and were identi®ed as multiplets or doublets of
a pentet; the chemical shift values compared well with
published data [7,8]. The chemical shifts for the internal
CF2 groups that were resolved showed pentets ranging from
1
À113.7 to À111.3 ppm. The HNMR data for aromatic
compounds are summarized in Table 1. The protons have
chemical shifts ranging between 6.96 and 8.51 ppm and
appear as a singlet ꢀH2), triplet ꢀH5), and two doublets
ꢀH4, H6); the chemical shifts and splitting patterns are in
agreement with values expected for 1,3-disubstituted benzene
derivatives. The experimental coupling constants between the
ring protons ranged between 7.6 and 8.2 Hz. The protons of
the NH2 group resonate as a broad singlet at 3.6 ppm.
The major mass spectral peaks for each new compound
2±7 are listed in Section 3. In addition to the parent ion,
È
by Mikroanalytisches Laboratorium Beller in Gottingen,
Germany.
‡
‡
‡
‡
‡
‡
‡
3.1. Preparation of m-SF5CF2CF2C6H4NO2, 2
peaks such as ꢀM±SF5) , ꢀM±SF5CF2) , SF5 , C6H4CF2
‡
,
‡
C6H5CF or C6H4CF , C6H4 , C2F4C2H , CF2C2H ,
‡
‡
To 25 ml of 90% HNO3 in a 100 ml round-bottomed ¯ask
cooled to 0±5 8C was added dropwise, with stirring, 3.00 g
SF3 and CF2 were observed with varying intensities
for each compound. In the mass spectrum of compound

Table 1
Proton and fluorine NMR dataa
d2
d4
d5
d6
jA
jB
ja
jb
X ˆ NO2 ꢀb), ꢀd)
8.51, s, overlap 8.50, d, J45 ˆ 7.93, 7.80, t,
with H4 J ꢀ 7.8, 1.0H
H2 ‡ H4 ˆ 2.0H
6.87, s, overlap 6.85, d, J45 ꢀ 8.2, 6.96, t, J45
with H4 J56 ˆ 7.81, 1.0H
H2 ‡ H4 ˆ 2.0H
7.98, d,
65.5, p±t, JAB ˆ 147,
JAa ˆ 4.5, 1.0F
45.6, d±p, 4.0F
À94.1, d±p, JAa ꢀ 4,
JaB ꢀ 14, 2.0F
À111.3, p,
J56 ˆ 7.72, 1.0H
6.97, d,
JbB ꢀ 14, 2.0F
b
X ˆ NH2 ꢀa), ꢀd)
ˆ
66.7, p±t ꢀbr.), JAB
ˆ 146, JAa ꢀ 4, 1.0F
66.1, p±m, JAB
45.3, d±m, 4.0F
45.4, d±p, 4.0F
À93.5, d±p ꢀbr.), 2.0F À111.4, p ꢀbr.),
J56 ˆ 7.81, 1.0H
7.58, d,
2.0F
À111.6, p,
X ˆ I ꢀa), ꢀd)
7.93, s, overlap 7.92, d, J45 ꢁ 7.8, 7.25, t,
À93.8, d±p, JAa
ˆ
with H4
H2 ‡ H4 ˆ 2.0H
7.04, d ꢀbr.),
J ˆ 7.81, 1.0H
J ˆ 7.8, 1.0H
7.19, d,
ˆ 147, 1.0F
3.8, JaB ꢀ 14, 2.0F
JbB ꢀ 14, 2.0F
À112.3, p,
X ˆ OHꢀa), ꢀe)
7.07, s, 1.0H
7.38, t, J ˆ 8.01, 1.0H,
J ˆ average of J45 ‡ J56
7.45, t,
66.0, t, nine lines, JAB 45.7, skewed d±m, 4.0F À95.0, d±p, JAa ˆ
J45 ˆ 8.20, 1.0H
J56 ˆ 7.81, 1.0H
7.34, d,
ˆ 147, JAa ˆ 4.8, 1.0F
66.7, nine lines ꢀbr.),
1.0F, JAB ˆ 146
65.3, p, JAB ˆ 147,
1.0F
4.8, JaB ˆ 12.0, 2.0F
45.3, skewed d±m, 4.0F À93.5, m, poorly
resolved, 2.0F
JbB ˆ 12.7, 2.0F
À111.4, poorly
resolved, 2.0F
À111.6, p, JbB
ˆ 13.5, 2.0F
À113.0, not
X ˆ NHAcc ꢀa), ꢀe) 7.73, s, 1.0H7.81, d,
J45 ˆ 7.81, 1.0H
J ˆ 7.80, 1.0H
J56 ˆ 7.81, 1.0H
8.02, d,
X ˆ SO2Cl ꢀa), ꢀe) 8.30, s, overlap 8.31, d, J45 ˆ 7.82, 7.87, t, J ˆ 7.7, 1.0H,
45.5, d±p, 4.0F
À94.2, p, JaB ˆ
with H4
H2 ‡ H4 ˆ 2.0H
7.54, d,
J ˆ average of J45 ‡ J56
J56 ˆ 7.63, 1.0H
7.92, d,
13.5, 2.0F
X ˆ SO3Hꢀa), ꢀe)
X ˆ SO3K ꢀa), ꢀe)
7.97, s, 1.0H
7.45, t, J45
J56 ˆ 7.81
ˆ
65.8, nine lines,
JAB ˆ 146, 1.0F
66.6, nine lines, b,
JAB ˆ 145, 1.0F
44.8, skewed d±m, 4.0F À95.8, not
J45 ˆ 7.81 1.0H
J56 ˆ 7.81, 1.0H
7.89, d,
resolved, 2.0F
resolved, 2.0F
À113.7, p, JbB
ˆ 12.7, 2.0F
8.10, s, overlap 8.07, d, J45 ˆ 7.81, 7.74, t, J ˆ average of
45.3, skewed d±m, 4.0F À98.7, d±p, JaB
ˆ
with H4
H2 ‡ H4 2.0H
J45 ‡ J56 ˆ 7.9, 1.0H
J ꢀ 7.7, 1.0H
15.2, JAa ˆ 4.6, 2.0F
a
1H NMR spectrum at: ꢀa) 500 MHz; ꢀb) 400 MHz; ꢀc) 90 MHz. 19F NMR spectrum at: ꢀd) 376.5 MHz; ꢀe) 84.7 MHz.
b dNH ˆ 3:6, broad s, 2.1H.
2
c dNH ˆ 7:7, broad s, 0.8H.

6
A.M. Hodges et al. / Journal of Fluorine Chemistry 114 22002) 3±8
‡
‡
ꢀ9.87 mmol) of SF5CF2CF2C6H5, 1. After 2 h of stirring, the
mixture was poured into 50 ml of ice water and extracted
three times ꢀ75 ml) with methylene chloride. The extract
was dried ꢀMgSO4), the solvent distilled away at atmo-
spheric pressure and low-pressure distillation gave 2.82 g
ꢀ8.08 mmol) of a light yellow liquid m-SF5CF2CF2C6-
H4NO2, boiling point 134±136 8C at 18 Torr. The yield of
the reaction was 82%.
ꢀM±SF5CF2 , 100%); 140 ꢀM±SF5CF2±2H , 5%); 127
‡
‡
‡
‡
ꢀSF5 , 6%); 125 ꢀCF2CF2C2H , 6%); 114 ꢀCF2C5H4
‡
,
‡
9%); 95 ꢀCFC5H4 , 5%); 89 ꢀSF3 , 8%); 75 ꢀCF2C2H ,
‡
‡
‡
5%); 71 ꢀC4H4F < 6%); 65 ꢀC5H5 , 10%); 63 ꢀC5H3
‡
,
5%); 39 ꢀC3H3 , 6%).
Analysis: calculated for SF5CF2CF2C6H4NH2: C, 30.09;
H, 1.88; S, 10.03; F, 53.6%. Found: C, 30.33; H, 2.10; S,
9.69; F, 53.7%.
The IR spectrum for 2 shows the following peaks ꢀcmÀ1):
3099 ꢀmw), 2886 ꢀw), 1984 ꢀvw), 1932 ꢀvw), 1840 ꢀvw),
1814 ꢀvw), 1762 ꢀvw), 1623 ꢀm), 1593 ꢀw), 1539 ꢀs), 1485
ꢀmw), 1443 ꢀmw), 1353 ꢀs), 1298 ꢀms), 1267 ꢀs), 1245 ꢀm),
1201 ꢀs), 1164 ꢀms), 1124 ꢀs), 1111 ꢀms), 1087 ꢀmw), 1070
ꢀm), 1051 ꢀw), 1004 ꢀvw), 962 ꢀw), 932 ꢀmw), 880 ꢀvs), 818
ꢀs), 800 ꢀs), 749 ꢀms), 717 ꢀs), 687 ꢀs), 668 ꢀm), 650 ꢀmw),
608 ꢀs), 575 ꢀs), 534 ꢀvw), 498 ꢀvw), 454 ꢀvw), 418 ꢀmw).
The major mass spectral peaks include ꢀm/z, molecular
3.3. Preparation of m-SF5CF2CF2C6H4I, 4
m-ꢀSF5CF2CF2)C6H4NH2 ꢀ1.65 g, 5.2 mmol) was diazo-
tized at 0 8C in 30 ml of 6 N HCl by slowly adding a sodium
nitrite solution ꢀ0.6 g in 7.5 ml of water). After complete
addition, stirring was maintained for 30 min; a lightly
yellow solution was obtained. A solution of KI ꢀ1.43 g in
5 ml of water), pre-cooled to 0 8C, was then slowly added.
Stirring was maintained at 0 8C for 3 h, and after warming to
ambient temperature, continued for another 18 h. Ether
extraction ꢀ1 Â 25 ml), and washing of the extract with
water left, after removal of the solvent, 1 g of crude product;
liquid ꢀfaint iodine discoloration) that was shown by GC±MS
to be very pure.
Infrared spectrum ꢀneat, KBr, cmÀ1): 3071 ꢀw), 1573
ꢀw±m), 1475 ꢀw±m), 1279 ꢀm), 1261 ꢀm), 1199 ꢀs), 1161
ꢀm), 1119 ꢀs), 1062 ꢀw±m), 1038 ꢀw), 996 ꢀw±m), 951 ꢀw),
928 ꢀw±m), 907 ꢀm, sh), 875 ꢀvs), 813 ꢀs), 786 ꢀm±s), 764
ꢀm), 724 ꢀs), 678 ꢀm), 672 ꢀw±m), 607 ꢀvs).
‡
‡
‡
ion, relative percentage): 349 ꢀM , 4%); 222 ꢀM±SF5
‡
,
,
15%); 176 ꢀM±SF5±NO2 , 13%); 172 ꢀM±SF5CF2
‡
‡
100%); 145 ꢀCF3C6H4 , 29%), 127 ꢀSF5 , 10%); 126
‡
‡
‡
ꢀCF2C6H4
,
45%); 125 ꢀCF2CF2C2H , 19%); 114
‡
‡
ꢀCF2C5H4 , 5%); 107 ꢀCFC6H4 , 8%); 89 ꢀSF3 , 9%); 76
‡
‡
‡
‡
ꢀC6H4 , 4%); 75 ꢀCF2C2H , 9%); 50 ꢀCF2 , 6%); 30 ꢀNO ).
Analysis: calculated for SF5CF2CF2C6H4NO2: C, 27.51;
H, 1.15%. Found: C, 27.81; H, 1.13%.
3.2. Preparation of m-SF5CF2CF2C6H4NH2, 3
Into a 100 ml round-bottomed ¯ask equipped with a
Te¯on-coated stirring bar, 25 ml of concentrated HCl and
7.11 g ꢀ31.5 mmol) of SnCl2Á2H2O were added. The
reagents were stirred and then 2.75 g ꢀ7.9 mmol) of m-
SF5CF2CF2C6H4NO2 was added dropwise. The reaction
mixture was stirred for 48 h at 75±80 8C ꢀan additional
5.00 g ꢀ22.2 mmol) of SnCl2Á2H2O was added after 24 h)
and then stirred for an additional 24 h at room temperature.
The reaction mixture was then added to about 50 ml of ice-
cold water and neutralized with a concentration NaOH
solution. The organic phase was extracted three times with
diethyl ether ꢀ75 ml), washed with water and dried over
magnesium sulfate. The ether was distilled away at atmo-
spheric pressure. A low-pressure distillation gave 2.04 g
ꢀ6.38 mmol) of a light yellow liquid m-SF5CF2CF2C6-
H4NH2, boiling point 116±118 8C/16 Torr. The yield of
reaction was 81%.
The IR spectrum contains the following bands ꢀcmÀ1):
3484 ꢀmw), 3399 ꢀm), 3227 ꢀw), 3071 ꢀvw), 3031 ꢀvw), 1627
ꢀs), 1601 ꢀm), 1499 ꢀms), 1465 ꢀms), 1388 ꢀvw), 1322 ꢀms),
1309 ꢀms), 1233 ꢀms), 1202 ꢀs), 1178 ꢀm), 1154 ꢀms), 1137
ꢀms), 1112 ꢀvs), 1072 ꢀm), 1044 ꢀw), 1028 ꢀvw), 998 ꢀmw),
968 ꢀvw), 943 ꢀmw), 875 ꢀvs), 816 ꢀms), 799 ꢀs), 767 ꢀs), 727
ꢀmw), 711 ꢀm), 678 ꢀms), 662 ꢀmw), 611 ꢀms), 580 ꢀms), 550
ꢀm), 503 ꢀw), 449 ꢀmw), 416 ꢀm).
Mass spectrum ꢀDB5, 30 m, 50 8C: 2 min, then 11 8C
‡
minÀ1 ! 280 8C; mass, percent, fragment): 430, 52%, M ;
‡
‡
303, 14, ꢀM±SF5, I) ; 253, 100, ꢀM±CF2SF5) ; 127, 10,
SF5 , I ; 126, 15, C6H4CF2 ; 107, 9, C6H4CF ; 89, 5,
‡
‡
‡
‡
‡
‡
SF3 ; 75, 8, C6H3
.
‡
High resolution mass spectrum: M ˆ 429:89320. Cal-
culated for 12C8 H419F9127I32S: M ˆ 429:89348.
1
3.4. Preparation of m-SF5CF2CF2C6H4OH, 5
m-ꢀSF5CF2CF2)-aniline ꢀ1.10 g, 3.4 mmol) was diazo-
tized at 0 8C in dilute H2SO4 ꢀ1.8 ml concentration
H2SO4 ‡ 8 ml H2O), by adding over a 20 min period a
solution of 0.54 g of NaNO2 ꢀ7.8 mmol) in 2 ml of H2O.
The pale yellow solution containing shiny crystalline plate-
lets was stirred at 0 8C for another 20 min; it was then added
at this temperature in small portions during a 30 min period
to a stirred mixture of 7 ml of concentration H2SO4 and
11 ml H2O heated at 120 8C in a 50 ml round-bottomed
¯ask. Gas was evolved upon addition after which a dark oil
separated. After addition was completed, a re¯ux condenser
was attached and the oil bath temperature raised to 140±
145 8C and held at this temperature for 1 h. The mixture was
cooled and ®nally chilled in an ice bath. Ether extraction
ꢀ4 Â 25 ml) produced, after evaporation, an orange oil.
Thin-layer chromatography ꢀKieselgel, methylene chloride)
showed several products to be present. Column chromato-
graphy ꢀ75 g silica gel, 7 cm i.d., CH2Cl2) gave, after a pale
The major mass spectral peaks include ꢀm/z, molecular
‡
‡
ion, relative percentage): 319 ꢀM , 65%); 192 ꢀM±SF5
‡
,
14%); 173 ꢀM±SF5±F , 9%); 172 ꢀM±SF5±HF , 8%); 142
‡

A.M. Hodges et al. / Journal of Fluorine Chemistry 114 22002) 3±8
7
yellow forerun, an orange fraction ꢀA, Rf ˆ 0:9) and a pale
yellow fraction ꢀB, Rf ˆ 0:6). The intermediate fractions
with additional components were discarded.
Infrared spectrum ꢀneat, KBr, cmÀ1): 3315 ꢀw), 3276 ꢀw),
3222 ꢀvw), 3106 ꢀvw), 1671 ꢀm±s), 1626 ꢀw±m), 1600 ꢀm),
1568 ꢀm), 1560 ꢀm), 1485 ꢀw), 1445 ꢀm), 1377 ꢀw), 1328
ꢀw), 1303 ꢀw), 1279 ꢀw±m), 1268 ꢀw±m), 1204 ꢀm±s), 1154
ꢀm±s), 1116 ꢀm±s), 1018 ꢀvw), 896 ꢀm±s), 866 ꢀvs), 799 ꢀs),
777 ꢀs±vs), 717 ꢀm), 677 ꢀm±s).
Fraction B was shown by GC±MS analysis to be the
‡
phenol ꢀM ˆ 320). Fraction B was again chromatographed
with 15 g of silica gel; 330 mg of an orange oil, pure by thin-
layer chromatography and GC±MS, was obtained
ꢀyield ˆ 30%). IR spectrum ꢀneat, KBr, cmÀ1): 3700 ꢀw),
3622 ꢀw), 3352 ꢀm±s, br.), 3073 ꢀvw), 3046 ꢀvw), 1612 ꢀm),
1597 ꢀm±s), 1490 ꢀw±m), 1458 ꢀs), 1343 ꢀw), 1299 ꢀs±vs),
1242 ꢀw±m), 1203 ꢀs±vs), 1160 ꢀs), 1116 ꢀs±vs), 1071 ꢀw),
1045 ꢀw), 1001 ꢀvw±w), 967 ꢀvw), 944 ꢀw±m), 875 ꢀvs), 816
ꢀm±s), 800 ꢀs±vs), 768 ꢀvs), 710 ꢀw±m), 702 ꢀw±m), 677 ꢀm),
659 ꢀvw), 611 ꢀm±s).
Mass spectrum ꢀDB5, 30 m, 50 8C: 2 min, then 11 8C
minÀ1 ! 280 8C; mass, percent, fragment): 361, 26%,
‡
‡
‡
M ; 319, 76, ꢀM±CH2=C=O) ; 214, 19, ꢀM±SF5±HF) ;
172, 12, ꢀM±SF5±HF±CH2=C=O) ; 142, 100, ꢀM±CF2SF5±
‡
‡
‡
‡
CH2=C=O) ; 127, 2, SF5 ; 114, 14, ꢀC2F3S ‡ H) ; 89, 2,
‡
‡
SF3 ; 43, 34, CH3CO .
High resolution mass spectrum: M ˆ 361:01856. Cal-
‡
12
culated for
C
10
1H819F914N16O32S: M ˆ 361:01829.
Mass spectrum ꢀDB5, 30 m, 50 8C: 2 min, then
11 8C minÀ1 ! 280ꢂC; mass, percent, fragment): 320,
3.6. Preparation of m-SF5CF2CF2C6H4SO2Cl, 7
‡
‡
‡
21%, M ; 193, 12, ꢀM±SF5) ; 174, 7, ꢀM±SF5±F) ; 143,
100, ꢀM±CF2SF5) ; 127, 3, SF5 ; 114, 10, ꢀC2F3S ‡ H) ;
‡
‡
‡
Into a 100 ml three-necked ¯ask equipped with trap-
bubbler, thermometer, dropping funnel and a Te¯on-coated
stirring bar, 14.9 ml ꢀ225.1 mmol) of HSO3Cl was added.
The acid was cooled to 0 8C and then 2.5 g ꢀ8.2 mmol) of
SF5CF2CF2C6H5 ꢀ1) was added dropwise and at such a rate
that the temperature of the stirred mixture did not rise above
5 8C. After complete addition of 1, the chilled reaction
mixture was stirred for 1 h, then warmed to room tempera-
ture and stirred for another 34 h; a GC±MS spectrum was
taken in order to assure completion of the reaction. The
liquid mixture was added dropwise to ice-cold water and
the white oily liquid that formed was extracted with methy-
lene chloride and dried over magnesium sulfate. The solvent
was distilled away at atmospheric pressure; a low-pressure
distillation of the residue gave 1.96 g ꢀ4.87 mmol) of a
colorless liquid, boiling point 83±85 8C/1 Torr. The yield
of the product was 59%.
The IR spectrum contains the following peaks ꢀcmÀ1):
3083 ꢀw), 1985 ꢀvw), 1935 ꢀvw), 1725 ꢀvw), 1606 ꢀw), 1584
ꢀw), 1480 ꢀw), 1437 ꢀm), 1387 ꢀs), 1314 ꢀw), 1295 ꢀm), 1269
ꢀms), 1247 ꢀm), 1201 ꢀs), 1183 ꢀs), 1123 ꢀs), 1098 ꢀm), 1076
ꢀm), 1047 ꢀmw), 1018 ꢀvw), 998 ꢀw), 960 ꢀw), 939 ꢀvw), 924
ꢀmw), 878 ꢀvs), 824 ꢀvs), 806 ꢀms), 765 ꢀmw), 748 ꢀs), 699
ꢀm), 685 ꢀm), 675 ꢀms), 654 ꢀm), 613 ꢀms), 591 ꢀs), 572 ꢀs),
552 ꢀs), 510 ꢀm), 466 ꢀvw), 416 ꢀmw).
‡
89, 14, SF3
.
‡
High resolution mass spectrum: M ˆ 319:99145. Cal-
culated for 12C8 H519F916O32S: M ˆ 319:99174.
1
3.4.1. Fraction A
After evaporation, 230 mg of a dark-orange oil was
obtained. The highest mass in the mass spectrum was
‡
‡
‡
M ˆ 365, 48%; ꢀM±SF5† ˆ 238, 23%; ꢀM±SF5CF2†
ˆ 188, 100%. The GC spectrum contained a single band
with Rf ˆ 6:7 min. The oil was dissolved in aqueous NaOH
ꢀorange color solution); from this solution, acidi®cation
with HCl produced a pale yellow emulsion. The acetylation
ꢀAc2O ‡ H2SO4) of the oil gave a pale yellow solid, Rf ˆ
0:9 ꢀKieselgel, CH2Cl2). The GC spectrum contained a
‡
‡
single band, Rf ˆ 13:5 min, M ˆ 407, 3%; ꢀMH±SF5†
‡
ˆ 281, 10%; CH3CO ˆ 43, 100%.
1HNMR spectrum ꢀCDCl , 500 MHz): d ˆ 7:24 ppm, d
3
ꢀbr.), J ꢀ 8:8 Hz, 1.0H; d ˆ 7:47, s ꢀbr.), 1.0H; d ˆ 8:26, d,
J ꢀ 8:8, 1.0H; d ˆ 10:58, s ꢀsharp), 0.94Hꢀchelated H).
This information suggests that the substance of fraction
A
is 2-nitro-5-ꢀ1,1,2,2-tetra¯uoro-2-SF5-ethyl)-phenol.
Yield ˆ 18%.
3.5. Preparation of m-2SF5CF2CF2)-acetanilide, 6
The major mass spectra peaks include ꢀm/z, molecular ion,
‡
m-SF5CF2CF2C6H4NH2 ꢀꢀ100 mg), 3, was stirred with a
solution of 2 ml of acetic anhydride containing one drop of
concentration H2SO4 at room temperature overnight. The
mixture was poured into water ꢀ20 ml), stirred ꢀ30 min) and
extracted ꢀ2 Â 20 ml of ether). After washing with water
ꢀ3 Â 10 ml) and drying, the product was chromatographed
on 15 g of silica gel ꢀcolumn i:d: ˆ 3 cm). The column was
®rst eluted with 150 ml of methylene chloride in order to
wash out two fast-running weak bands, then with 140 ml of a
mixture of methylene chloride ꢀ140 ml) and acetone ꢀ3 ml).
Evaporation of the latter solution furnished 80 mg ꢀꢀ70%)
of a white, crystalline solid; re-crystallization ꢀÀ12 8C) from
aqueous alcohol gave 60.3 mg ꢀm:p: ˆ 119±120 8C).
relative percentage): 404, 402 ꢀ37;35Cl, M , 1.4, 3.5%); 367
‡
‡
‡
ꢀM±Cl , 71%); 303 ꢀM±SO2Cl , 62%); 275 ꢀM±SF5 , 25%);
‡
‡
225 ꢀM±SF5CF2 , 70%); 176 ꢀM±SF5±SO2Cl , 56%); 174
‡
‡
‡
ꢀCF2C6H4SO , 13%); 127 ꢀSF5 , 31%); 126 ꢀCF2C6H4 ,
‡
‡
‡
19%); 89 ꢀSF3 , 25%); 75 ꢀCF2C2H , 23%); 50 ꢀCF2 , 17%).
Analysis: calculated for SF5CF2CF2C6H4SO2Cl: C,
23.85; H, 0.99; S, 15.90; F, 42.5%. Found: C, 24.01; H,
1.04; S, 15.80; F, 42.6%.
3.7. Preparation of SF5CF2CF2C6H4SO3ÀK , 8
‡
Into a 50 ml round-bottomed ¯ask equipped with a
Te¯on-coated stirring bar and a condenser, were added

8
A.M. Hodges et al. / Journal of Fluorine Chemistry 114 22002) 3±8
SF5CF2CF2C6H4SO2Cl ꢀ5.60 g, 17.9 mmol), KOHpowder
ꢀ0.59 g, 1.9 eq.) and 10 ml of water. The reaction mixture
was heated under re¯ux overnight. The solution was acid-
i®ed with a 10% HCl solution and passed through an ion-
exchange column containing Amberlite ꢀIR-120, 40 ml).
The acid, after removal of water under vacuum, was then
titrated with a standardized KOHsolution. The water was
then removed under vacuum; a dry white solid powder,
1239 ꢀvs), 1180 ꢀm), 1045 ꢀvs), 861 ꢀvs, b), 777 ꢀw), 605 ꢀw),
575 ꢀw).
The composition of the acid was established by conver-
sion to the corresponding potassium salt. The spectral data
agreed with those described above.
Acknowledgements
SF5CF2CF2C6H4SO3ÀK ꢀ4.19 g, 9.9 mmol, decomposition
‡
at 250 8C) was formed in 55% yield.
We are grateful to the National Science Foundation
ꢀCHE-9904316) and the Petroleum Research Foundation
ꢀACS-PRF No. 34624-AC7) for support of this work.
We would like to acknowledge also the work of Henry Li
who made preliminary contributions to the preparation
of SF5CF2CF2C6H4SO3M ꢀM ˆ K, H).
The IR spectrum contains the following bands ꢀcmÀ1):
3079 ꢀw), 2931 ꢀvw), 2848 ꢀvw), 1605 ꢀvw), 1482 ꢀvw),
1438 ꢀw), 1293 ꢀvw), 1277 ꢀw), 1242 ꢀw), 1216 ꢀvs), 1197
ꢀvs), 1162 ꢀm), 1128 ꢀm), 1115 ꢀs), 1096 ꢀw±m), 1078 ꢀw),
1051 ꢀm), 1043 ꢀw±m), 1001 ꢀvw), 925 ꢀw), 902 ꢀw), 885 ꢀs),
874 ꢀvs), 832 ꢀs), 826 ꢀs), 809 ꢀm), 757 ꢀm), 751 ꢀs), 704 ꢀw±
m), 686 ꢀw±m), 681 ꢀw±m), 661 ꢀw±m), 632 ꢀw±m), 613 ꢀw±
m), 588 ꢀm), 575 ꢀw±m), 568 ꢀw±m), 515 ꢀw).
References
Analysis: calculated for SF5CF2CF2C6H4SO3K: C, 22.75;
H, 0.95; S, 15.18; F, 40.5%. Found: C, 22.58; H, 1.05; S,
14.95; F, 40.1%.
[1] A.M. Hodges, R. Winter, J. Mohtasham, P. Bailey, G.L. Gard,
J. Fluorine Chem., 2001, in press.
[2] W.A. Sheppard, J. Am. Chem. Soc. 84 ꢀ1962) 3064.
[3] R.D. Bowden, P.J. Comina, M.P. Greenhall, B. M Kariuki, A.
Loveday, D. Philp, Tetrahedron 56 ꢀ2000) 3399.
[4] H.L. Cross, G. Cushing, H.L. Roberts, Spectrochim. Acta 17 ꢀ1961)
344.
3.8. Preparation of m-SF5CF2CF2C6H4SO3HÁxH2O, 9
A portion of the potassium salt ꢀ0.66 g in 10 ml of water)
was passed through an Amberlite column. The water was
removed from the eluent via vacuum drying; 0.68 g of the
acid 9 was recovered as a soap-like white semi-solid.
The IR spectrum contained the following bands ꢀcmÀ1):
3499 ꢀvs, b), 3000 ꢀvw, b), 1740 ꢀw), 1658 ꢀm), 1432 ꢀw),
[5] J.K. Brown, K.J. Morgan, Adv. Fluorine Chem. 4 ꢀ1965) 258.
[6] J. Hutchinson, J. Fluorine Chem. 3 ꢀ1973/1974) 429.
[7] R.J. Terjeson, J. Renn, R. Winter, G.l. Gard, J. Fluorine Chem. 82
ꢀ1997) 73.
[8] P.G. Nixon, J. Renn, R.J. Terjeson, Y.S. Choi, R. Winter, G.L. Gard,
J. Fluorine Chem. 91 ꢀ1998) 13.