New aromatic pentafluoro-λ6-sulfanyl (SF5) derivatives, m-SF5(CF2)2C6H4X: (X = N3, Br, OC(O)CH=CH2, CH=CH2)

Article abstract of DOI:10.1016/S0022-1139(02)00059-3

Preparation of the following new m-SF₅CF₂CF₂C₆H₄X derivatives has been achieved: X=N₃(2), Br(3), OC(O)CH=CH₂(4), CH=CH₂(5). The compounds were characterized by their r

Full text of DOI:10.1016/S0022-1139(02)00059-3

Journal of Fluorine Chemistry 115 (2002) 101–105
Short communication
New aromatic pentafluoro-l6-sulfanyl (SF5) derivatives,
m-SF5(CF2)2C6H4X: (X ¼ N3, Br, OC(O)CH=CH2, CH=CH2)
R.W. Winter, S.W. Winner, D.A. Preston, J. Mohtasham, J.A. Smith, G.L. Gard*
Department of Chemistry, Portland State University, 1719 SW 10th Avenue, P.O. Box 751, Portland, OR 97207, USA
Received 8 January 2002; received in revised form 21 March 2002; accepted 25 March 2002
Abstract
Preparation of the following new m-SF5CF2CF2C6H4X derivatives has been achieved: X ¼ N3(2), Br(3), OC(O)CH=CH2(4), CH=CH2(5).
The compounds were characterized by their respective IR, NMR, mass spectra (MS) and high resolution mass spectrometry (HRMS). An
improved yield of SF5(CF2)2C6H5 (1) is also reported along with the synthesis of the polyacrylate (6) and polystyrene (7) from their respective
monomers. # 2002 Published by Elsevier Science B.V.
Keywords: Pentafluorothiofluoroalkyl benzene derivatives; SF5; Acrylate/stryrene monomers and polymers
1. Introduction
Several new and important derivatives of (1) have been
synthesized (Scheme 1). The first three steps have already
been reported [11]; the azide derivative (2) was formed from
the corresponding diazonium intermediate (4i); the acrylate
(4) from the phenol via steps 5i–7i and the styrene derivative
from the bromide (3), steps 9i–10i [12,13]. The polymeric
acrylate (6) and styrene (7) were prepared (steps 8i and 11i).
The polymers were soluble in the heated benzene solution;
the isolated (6) was a solid and (7) a viscous oil. The viscous
oil solidified upon exposure to air for several weeks. By
comparison, the polymerization of m-CF3C6H4CH=CH2
gave a polymer with a softening range of 130–155 8C
[14]; our polymer (7) has a softening range of 70–90 8C
and is stable to at least 300 8C.
The incorporation of the SF5-group into organic systems
imparts a number of useful properties that include low
wettability, low dielectric constant, high thermal stability,
high chemical resistance, low refractive index and low
surface energy [1–4]; these properties are also found in
polymeric films containing terminal SF5-groups [5–8]. It
should be noted that the interest in SF5-aromatic chemistry
has extended to the fine chemicals industry [9].
Recently, we reported the synthesis of a new class of
o-SF5-perfluoroalkylbenzene compounds, SF5(CF2)nC6H5
with n ¼ 2,4,6,8 [10] and also on a number of new
m-SF5(CF2)2C6H4X derivatives of synthetic value [11].
We have improved on the synthesis of SF5(CF2)2C6H5 (1)
and have extended its chemistry by preparing several impor-
tant derivatives, especially ones with polymerizable func-
tional groups.
The infrared (IR), mass spectral (MS) and HRMS data
for the new compounds (2–5) are listed in Table 1. Their IR
spectra showed the characteristic intense SF5 bands in
the 800–900 cmÀ1 and 605–613 cmÀ1 regions [15]. The
strong absorption peaks in the 1100–1300 cmÀ1 region
were attributed to the C–F stretching vibrations [16].
The absorption band for compound (2) at 2120 cmÀ1 is
assigned to the azido stretching mode [17]. For the acrylate
monomer (4), the vinyl stretching mode is located at
1632 cmÀ1; this band is absent in the polymeric solid
(6). The carbonyl absorption (6) is found at 1752 cmÀ1
and for the polymer (7) at 1761 cmÀ1. For the styrene
monomer (5) the vinyl stretching mode is at 1636 cmÀ1; it
is absent in the polymer (7).
2. Results and discussion
We have found that the yield of SF5(CF2)2C6H5 (1) can be
increased to 74% by using a Parr Bomb reactor (300 ml) that
is stirred under an argon atmosphere for 14 days at 145 8C;
previous work using a 350 ml Pyrex-glass Carius Tube gave
yields of only 30% [10].
The 19F NMR results for compounds 2–5 are included in
Table 2. The values for the chemical shifts and coupling
* Corresponding author. Tel.: þ1-503-725-4274; fax: þ1-503-725-3888.
E-mail address: gardg@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 2 ) 0 0 0 5 9 - 3

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R.W. Winter et al. / Journal of Fluorine Chemistry 115 (2002) 101–105
Scheme 1. Synthesis of compounds 2–7: (i) HNO3, 0–5 8C, 2 h; (2i) HCl/SnCl2, 75–80 8C, 48 h, NaOH; (3i) HCl/NaNO2, 0 8C, 0.5 h; (4i) NaN3, 0–5 8C.
0.5 h, warmed to room temperature, 1 h; (5i) H2SO4/NaNO2, 0 8C, 0.67 h; (6i) H2SO4/H2O, 120–145 8C, 1 h; (7i) H2C=CHC(O)Cl/(CH3CH2)3N/CH2Cl2,
À78 8C to room temperature, 3 h; (8i) (CH3)3COOC(CH3)3/C6H6, 93–102 8C, 4 days; (9i) mod. Wohl-Ziegler bromination, room temperature, 8 h; (10i) (n-
C4H9)3SnCH=CH2, Pd[P(C6H5)3]4, CH3C6H5, reflux, 24 h; (11i) (CH3)3COOC(CH3)3/C6H6, 104–120 8C, 5 days.
constants agree with reported values for other SF5CF2CF2
derivatives [10,11]. The 1H NMR data are summarized
in Table 2; aromatic protons have chemical shifts ranging
between 7.22 and 7.76 ppm and appear as a singlet (H2),
triplet (H5) and two doublets (H4,H6). The coupling
constants between the ring protons range between 7.7
and 8.2 Hz; compounds (4) and (5) show in addition
the vinyl grouping with typical splitting, positioning and
coupling.
The major mass spectral peaks for each compound (2–5)
are listed in Table 1. In addition to the parent ion, additional
peaks are found that support the assigned structure. In lieu of
elemental analyses, the molecular weight of the compounds
(2–5) were determined to seven significant places by high
resolution mass spectrometry (HRMS). The IR, NMR, and
HRMS analyses were carried out on samples that were
shown to be pure via GC-MS.
3. Experimental details
The reactants N-bromosuccinimide, [(C6H5)3P]4Pd,
(n-C4H9)3SnCH=CH2, and acryloyl chloride were purcha-
sed from Aldrich. The compounds m-SF5(CF2)2C6H4X
(X ¼ NH2, OH) were prepared according to the literature
methods [11].
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
Table 1
IR, MS and HRMS data (compounds 2–5)
Compound
IR (cmÀ1
)
MS (m/z, %)
HRMS
Formula
Calculated
344.99822
Found
2
2120 (N3), 1291, 1255, 1201, 1161, 1132,
345 (Mþ, 6); 317 ((M–N2)þ, 51); 190
((M–N2–SF5)þ, 20); 140 ((CF2C6H2N)þ,
100); 127 (SF5þ, 6)
C8H4F9SN3
344.99788
1116 (C–F), 877, 845, 809, 605 (S–F)
3
4
5
1283, 1262, 1200, 1163, 1120 (C–F),
878, 817,607 (S–F)
384/382 (Mþ, 27/25); 207/205,
((M–SF5CF2)þ, 99/100); 127 (SF5þ, 6)
372 (Mþ, 5); 227 ((M–HSF6)þ, 8);
C8H4F9SBr
C11H7O2F9S
C10H7F9S
381.90734
374.00231
330.01248
381.90735
374.00288
330.01265
1752 (CO), 1632 (CH=CH2), 1294, 1277,
1240, 1196, 1146, 1117 (C–F), 876, 609 (S–F) 89 (SF3þ, 3); 55 ((CH2CHCO)þ, 100)
1636 (CH=CH2), 1296,1272, 1198, 1157,
330 (Mþ, 5); 203 ((M–SF5)þ, 8;
153 ((M–SF5CF2)þ, 100, 127 (SF5þ, 4)
1116 (C–F), 877, 845, 809, 605 (S–F)

Table 2
Proton and fluorine NMR data
d2
d4
d5
d6
jA
jB
ja
jb
X ¼ Br (3)
7.76, s, 1.0H
7.55, d,
7.38, t,
7.72, d,
66.8, t of 9 lines,
JAB ¼ 149,
45.7, skewed
d-m, 4.0F
À96.4, p-d,
À115.2, p,
J45 ¼ 7.7 Hz, 1.0H
J ꢀ 8.1, 1.0H
J56 ¼ 8.05, 1.0H
JAa ¼ 4.9,
JbB ¼ 13.6, 2.0F
JAa ¼ 4.9, 1.0F
66.8, t of 9 lines,
JAB ¼ 150,
JaB ¼ 13.6, 2.1F
À97.3, p-d,
X ¼ N3 (2)
7.22, s, overlap
with H6
7,37, d, J45 ¼ 8.1,
H2 þ H4 ¼ 1.0H
7.49, t,
7.24, d, J56 ꢀ 8 Hz,
H2 þ H6 ¼ 2.0H
45.7, skewed
d-m, 4.1F
À113.7, p,
J ¼ 7.8, 1.0H
JAa ꢀ 5.1,
JbB ¼ 15.0, 2.0F
JAa ¼ 5.1, 1.0F
67.6, t of 9 lines,
JAB ¼ 151,
JaB ¼ 15.0, 2.0F
À95.3, p-d,
X ¼ CH=CH2 (5)
Vinyl: b0 trans to a
7.608, s, overlap
with H6
7.49, d, overlap
7.46, t, J ¼ 7.8 Hz,
H4 þ H5 ¼ 2.0H
7.615, d, J ꢀ 8 Hz,
H2 þ H6 ¼ 2.0H
45.8, skewed
d-m, 4.1F
À114.1, p,
with H5, J ꢀ 8Hz
JAa ꢀ 4.9,
JbB ¼ 14.5, 2.0F
JAa ꢀ 4.9, 1.0F
JaB ¼ 14.5, 2.0F
0
0
da ¼ 6.75, d-d, Jab ¼ 17:6 Hz, Jab ¼ 10.55 Hz, 1.0H; db ¼ 5.38, d, J ¼ 10.55 Hz, 1.0H; db ¼ 5:83, d, J ¼ 17.6 Hz, 1.0H
X ¼ CH2CHCOO (4) 7.41, s, overlap
7.50, d,
7.55, t,
7.40, dm, J ꢀ 8.2 Hz, 64.7, t of 9 lines,
45.5, skewed
d-m, 3.9F
À95.9, p-d,
À113.6, p,
with H6
J45 ¼ 7.8 Hz, 1.0H
J ¼ 8.0 Hz, 1.0H
H2 þ H6 ¼ 2.0H
JAB ¼ 150,
JAa ꢀ 4.9,
JBb ꢀ 14, 2.0F
JAa ¼ 4.9, 1.0F
JbB ꢀ 14.1, 2.0F
Vinyl: b0 trans to a
da ¼ 6.33, d-d, Jab ¼ 17. 7 Hz, Jab ¼ 10.55 Hz, 1.0H; db ¼ 6.07, d-d, J ¼ 10.55 Hz, Jbb ¼ 1:15 Hz, 1.0H; db ¼ 6:64, d-d, J ¼ 17.7 Hz, J ¼ 1.15 Hz, 1.0H
0
0
0
1H-NMR spectra at 500 MHz, solvent CDCl3, Si(CH3)4 ðinternalÞ ¼ 0, 19F-NMR spectra at 84.7 MHz, solvent CDCl3, CCl3F ðinternalÞ ¼ 0.

104
R.W. Winter et al. / Journal of Fluorine Chemistry 115 (2002) 101–105
for 19F and a GE 500 MHz spectrometer for 1H. The
standards CFCl3 (CFC-11) and (CH3)4Si were used in the
CDCl3 solvent.
of ice water; extracted with CH2Cl2 (6ꢁ, 50 ml); distillation
gave a product boiling at 93–95 8C/15 Torr; 2.31 g
(6.03 mmol) in 37% yield.
Mass spectra were obtained using a Hewlett-Packard
HP5890 series II gas chromatograph 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/min until the temperature of the col-
umn reached 280 8C. The precise molecular weight deter-
mination for compounds (2–5) were obtained on a Kratos
MS 50TC; chemical ionization with methane.
3.4. Preparation of m-SF5(CF2)2C6H4OC(O)CH=CH2 (4)
To a 50 ml round bottomed flask containing a Teflon
stirring bar, 1.20 g (3.75 mmol) of m-SF5(CF2)2C6H4OH
and 25 ml of CH2Cl2 were added. The mixture was cooled
to À78 8C and acryloyl chloride (0.390 g, 4.31 mmol) in
5 ml of CH2Cl2 was added followed by the dropwise addi-
tion of a solution of triethylamine (0.400 g, 3.95 mmol in
5 ml CH2Cl2). The reaction mixture was warmed to room
temperature over a 3 h period. Since the analysis via GC-MS
showed that the reaction was not complete, an additional
0.5 ml of acryloyl chloride followed by 1 ml of triethyla-
mine were added (3 h). After removing the solvent, the
mixture was washed with water and extracted with CH2Cl2
(2ꢁ 25 ml); CH2Cl2 was removed giving a clear brown
liquid. A pure orange oily product, (4), (1.33 g) was obtained
by column chromatography (20 g silica gel and 1:1 hexane/
CH2Cl2). The yield of the reaction was 95%.
3.1. Preparation of SF5(CF2)2C6H5 (1)
Into a Parr Bomb (300 ml, series 4560 bench-top mini-
reactor with series 4840 temperature controller) was added
SF5CF2CF2I (30.0 g, 0.085 mol) and benzene (175.7 g,
2.2 mol, 26:1 molar ratio). The Parr Bomb was sealed,
cooled to À196 8C, evacuated and then charged at room
temperature to 3 atm pressure with argon. The reaction
mixture was gradually heated (22 8C to 145 8C, 4 h) and
stirred (100 rpm); it was then heated at 145 8C for 14 days.
The bomb was cooled to room temperature and vented. The
dark blue/black liquid was twice distilled with a spinning
band distillation system (B/R Instrument Corp., 800 Micro-
system). The pot fractions were combined and washed with a
10% aqueous solution of sodium sulfite, a saturated sodium
bicarbonate solution, water and then dried over MgSO4. The
dried fractions were filtered; the solid residues were washed
with 2 ml of CH2Cl2. Distillation under reduced pressure
gave 19.74 g (0.064 mol) of the product; (1) bp 85–87 8C/
44 Torr, 74.4% yield. The IR, 19F NMR, and GC-MS data
agreed with published values [9].
3.5. Preparation of m-SF5(CF2)2C6H4CH=CH2 (5)
Into a cylindrical Pyrex-glass reaction vessel (30 ml) and
equipped with a Teflon stirring bar, m-SF5(CF2)2C6H4Br
(0.320 g, 0.836 mmol), Pd (Pf3)4 (19 mg, 0.016 mmol), (n-
C4H9)3SnCH=CH2 (0.29 g, 0.90 mmol), and 3 ml toluene
were added [12]. The mixture was heated to reflux and stirred
for 21 h; since the reaction was not complete, additional
Pd(Pf3)4 (50 mg) and (n-C4H9)3SnCH=CH2 (11 drops) were
added. The mixture was heated to reflux with stirring for 3 h.
The solvent was removed under vacuum and the residue was
passed through a column chromatography unit containing
20 g silica gel; hexane was used as the solvent. The combined
middle fractions were passed through a fresh column; the
middle fractions contained the pure styrene product; 0.126 g
(0.382 mmol), with a yield of 45.7%.
3.2. Preparation of m-SF5CF2CF2C6H4N3 (2)
m-SF5CF2CF2C6H4NH2 (1.0 g, 3.13 mmol) was diazo-
tized [11]; 0.22 g of NaN3 in 0.35 ml of water was added
dropwise (below 5 8C). The reaction mixture was stirred for
30 min at 0 8C, 1 h at 20 8C and then added to 300 ml of ice-
water; the product was extracted 6ꢁ, with 75 ml aliquots
of ether. Distillation of the evaporated residue obtained
from the combined ether fractions gave a clear liquid
of m-SF5CF2CF2C6H4N3 (0.50 g, 1.45 mmol) boiling at
70 8C/0.5 Torr in 46% yield.
3.6. Preparation of polyacrylate (6)
To a 50 ml Quartz reaction vessel equipped with a Teflon
stirring bar and a Kontes Teflon stopcock, 0.480 g
(1.28 mmol) of (4), (0.02 g) of tert-butyl peroxide, and
0.82 g of benzene were added. After degassing, the mixture
was heated for 4 days at 93–102 8C. The benzene solvent
was removed leaving behind a light yellow solid polymer
(0.40 g, 1.07 mmol); yield of 83.6%. The polymer appeared
to melt in the 60–70 8C range and decomposed when heated
to 255 8C.
3.3. Preparation of m-SF5CF2CF2C6H4Br (3)
Into a 50 ml round-bottomed flask with a Teflon coated
stirring bar and containing 4.96 g (16.3 mmol) of (1), 8.2 ml
of CF3C(O)OH and 2.5 ml of conc. H2SO4 were added [13].
An air condenser was attached and over an 8 h period, 3.05 g
of N-bromosuccinimide (1.05 equivalent) was added in
small portions; the solution turned a deep orange-red color
during the addition. The reaction mixture was added to 200 g
The IR spectrum contains the following peaks (cmÀ1):
3084 (w), 2936 (w), 1761 (w-m), 1596 (w-m), 1491 (w-m),
1448 (m), 1296 (m), 1275 (m-s), 1244 (m), 1202 (s), 1159
(m-s), 1143 (m-s), 1117 (s), 876 (vs), 803 (s), 766 (s), 711
(w-m), 676 (m-s), 608 (s-vs), 574 (s).

R.W. Winter et al. / Journal of Fluorine Chemistry 115 (2002) 101–105
105
3.7. Preparation of polystyrene (7)
References
[1] H.L. Roberts, Quart. Rev. Chem. Soc. 15 (1961) 30.
To a 15 ml Pyrex-glass vessel equipped with a Young
Teflon stopcock, 0.09 g (0.273 mmol) of (5), 0.02 g of tert-
butyl peroxide, and 0.68 g of benzene were added. After
degassing, the reaction mixture was heated at 104–120 8C
for 5 days. The benzene was removed leaving behind a clear
polymeric material, 0.07 g (0.212 mmol); the yield of poly-
mer was 77.7%. The polymer appears to begin melting in
the 70–90 8C range; no decomposition was evident up to
300 8C.
[2] R. Winter, G.L. Gard, in: J.S. Thrasher, S.H. Strauss (Eds.),
Proceedings of the ACS Symposium Series, Vol. 555, 1994, p. 128.
[3] R.D. Verma, R.L. Kirchmeier, J.M. Shreeve, Adv. Inorg. Chem. 41
(1994) 125.
[4] K. Seppelt, D. Lentz, SF5 Compounds of Carbon, Vol. 295, Wiley,
New York, 1997.
[5] R. Winter, P.G. Nixon, G.L. Gard, D.G. Castner, N.R. Holcomb,
Y.-H. Hu, D.W. Grainger, Chem. Mater. 11 (1999) 3044.
[6] P.G. Nixon, R. Winter, D.G. Castner, N.R. Holcomb, D.W. Grainger,
G.L. Gard, Chem. Mater. 12 (2000) 3108.
The IR spectrum contained the following peaks (cmÀ1):
3077 (vw), 3043 (vw), 2929 (w-m), 2853 (w), 1490 (w),
1447 (w-m), 1284 (m-s), 1265 (m), 1243 (w-m) 1196 (vs),
1157 (s), 1116 (vs), 1077 (w-m), 1045 (w), 1003 (vw), 959
(vw), 933 (vw), 875 (vs), 828 (vs), 808 (s), 786 (m), 756
(vs), 707 (m), 697 (w-m), 680 (s), 661 (m), 604 (s), 574
(vs).
[7] R.W. Winter, P.G. Nixon, R.J. Terjeson, J. Mohtasham, N.R.
Holcomb, D.W. Grainger, D. Graham, D.G. Castner, G.L. Gard, J.
Fluorine Chem., in press.
[8] T.L. St. Clair, A.K. St. Clair, J.S. Thrasher, US Patent 5,220,070 (1993).
[9] S.C. Stinson, Chem. Eng. News 78-28 (2000) 63.
[10] A.M. Hodges, R. Winter, J. Mohtasham, P. Bailey, G.L. Gard, J.
Fluorine Chem. 110 (2001) 1.
[11] A.M. Hodges, R.W. Winter, S.W. Winner, D.A. Preston, G.L. Gard,
J. Fluorine Chem. 114 (2002) 3.
[12] D.R. McKean, G. Parrinello, A.F. Reanaldo, J.K. Stille, J. Org.
Chem. 52 (1987) 422.
[13] J. Duan, L.H. Zhang, W.R. Dolbier, Synletter, 1999, 1245.
[14] C.S. Marvel, C.G. Overberger, R.E. Allen, J.H. Saunders, J. Am.
Chem. Soc. 68 (1946) 736.
Acknowledgements
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.
[15] H.L. Cross, G. Cushing, H.L. Roberts, Spectrochim. Acta 17 (1961) 344.
[16] J.K. Brown, K.J. Morgan, Adv. Fluorine Chem. 4 (1965) 258.
[17] A.L. Logothetis, J. Org. Chem. 29 (1964) 3049.