Effects of substitution on the reactivity of alkyl aryl tetrafluoro-λ6-sulfanes

Article abstract of DOI:10.1016/j.jfluchem.2014.07.017

The preparation of aliphatic aryl tetrafluoro-λ⁶-sulfanes was achieved by direct addition of readily available chlorotetrafluorosulfanyl arenes to alkenes and alkynes. Systematic substitution of the ligands bound to the tetrafluoro-λ⁶

Full text of DOI:10.1016/j.jfluchem.2014.07.017

Journal of Fluorine Chemistry 167 (2014) 192–197
Contents lists available at ScienceDirect
Journal of Fluorine Chemistry
journal homepage: www.elsevier.com/locate/fluor
Effects of substitution on the reactivity of alkyl aryl
tetrafluoro-l6-sulfanes
*
Linbin Zhong, Alexander S. Filatov, John T. Welch
Department of Chemistry, University at Albany, SUNY 1400 Washington Ave, Albany, NY 12222, United States
A R T I C L E I N F O
A B S T R A C T
The preparation of aliphatic aryl tetrafluoro-l6-sulfanes was achieved by direct addition of readily
available chlorotetrafluorosulfanyl arenes to alkenes and alkynes. Systematic substitution of the ligands
bound to the tetrafluoro-l6-sulfanyl group enabled investigations of the substituent effects on the
reactivity of aryl tetrafluoro-l6-sulfanyl-substituted products. The modulation of reactivity was effected
by variation of electron-withdrawing or electron-donating effects. All isolable products were fully
characterized. In addition structural characterization of these compounds suggested insights into the
influence of the substituents on the nature of bonding at the tetrafluoro-l6-sulfanyl group.
ß 2014 Published by Elsevier B.V.
Article history:
Received 2 May 2014
Received in revised form 22 July 2014
Accepted 23 July 2014
Available online 1 August 2014
Keywords:
Hypervalent sulfur fluorides
Aliphatic
Bonding
Substituent effects
1. Introduction
2. Results
The pentafluoro-l6-sulfanyl group (pentafluorosulfanyl, SF5
group) a highly stable functional group possesses unique and
unusual biological, chemical, medicinal, and physical properties
[1–4]. Renewed interest in the chemistry of SF5-containing
compounds accompanied the development of efficient and
convenient procedures for pentafluorosulfanylation [5–11]. Con-
current with these advances, recognition of the stability and
potential applications of tetrafluoro-l6-sulfanyl-containing mate-
rials suggests even more extensive applications of hypervalent
fluorinated sulfur compounds [12]. The preparation of diaryl
and dialkyl tetrafluoro-l6-sulfanes [13,14] and trifluoromethyl
tetrafluorosulfanes [2,15,16] are known.
Complimentary to the previous report [18] where the alkene
and alkyne addition partners were substituted by arenes, in this
work the limitations of the addition of arene tetrafluoro-l6
-
sulfanyl chlorides to aliphatic alkenes and alkynes are described.
The aliphatic substituted addition products were more sensitive
toward substituent effects than the aromatic-substituted com-
pounds previously communicated. The addition of ethereal
solutions of chlorotetrafluorosulfanyl arenes 1 to 1-hexyne 2
and 1-hexene 4 [18] was catalyzed by triethylborane [8,9]
(Scheme 1), forming 3 and 5, respectively, in as few as 15 min.
The addition reactions could also be initiated photochemically,
albeit longer reaction times were required. The enhanced stability
of 4-nitrophenyl tetrafluoro-l6-sulfanyl adducts was essential for
the isolation of the addition products. While 3 and 5 apparently
formed rapidly, 3a–3c decomposed during the characterization of
the products by 13C NMR. When the decomposition products were
examined by 19F NMR, it was clear that the tetrafluoro-l6-sulfanyl
group was no longer present as indicated by the absence of the
The reactivity of arene tetrafluoro-l6-sulfanyl chlorides can
be modulated by the selection of arene substituents [17]. The
preparation and characterization of alkenyl aryl tetrafluoro-l6
-
sulfanes have only been recently reported [18]. The aryl
substituents can profoundly influence both the reactivity of the
aryl tetrafluoro-l6-sulfanyl chloride as well as the stability of the
alkyl and alkenyl products formed on addition to alkenes or
alkynes, respectively.
characteristic doublet at
exhibited resonances consistent with other sulfur fluorides
(ꢀ F = 66–58 ppm) and also with resonances attributable to
ꢀdF = 69 ppm. The spectra instead
d
fluorocarbon products (ꢀ F = À99–-110, À147–-157 ppm).
d
However, 3d and 5d, where the aryl tetrafluoro-l6-sulfane was
substituted at the para-position by a nitro group, were sufficiently
stable to permit purification and characterization, to include
single crystal X-ray diffraction studies (Figs. 1 and 2 and Table 1).
*
Corresponding author. Tel.: +1 518 442 4455; fax: +1 518 442 3462.
E-mail addresses: Lzhong@albany.edu (L. Zhong), afilatov@albany.edu
(A.S. Filatov), jwelch@albany.edu (J.T. Welch).
http://dx.doi.org/10.1016/j.jfluchem.2014.07.017
0022-1139/ß 2014 Published by Elsevier B.V.

L. Zhong et al. / Journal of Fluorine Chemistry 167 (2014) 192–197
193
l
C
F
l
F
4S
S
4C
or v s
e
Et3B
i ibl li ht
g
+
H9
C4
H9
C4
Et
2O
X
X
a
a-c
=
uan a ve
tit ti
1
3
X H
b
NMR
y
2
q
=
so a e
i
%
e
1b
3d
X
l
66
l t d i ld
y
C
c
1
1d
= r
X B
=
X N
O2
l
C
F
l
F
S
4C
4S
or v s
e
Et3B
i ibl li ht
g
+
+
H9
C4
H9
C4
Et
2O
X
X
X
a-c
5
uan a ve
tit ti
b
y
NMR
q
y
4
1
so a e
e
i l
d
5d
t
66
i
l
d
%
O
l
C
F
4C
l
F
4S
S
O
or v s
e
Et3B
i ibl li ht
g
2O
O
O
Et
X
6
1
1
so a e
e
i ld
y
7
d
31
i
l
t
d
%
l
C
F
l
F
4S
S
4C
or v s
e
Et3B
i ibl li ht
g
+
Et
2O
X
X
8
so a e
e
i ld
y
9d
t
d
68
i
l
%
Scheme 1. Triethylborane or visible light-catalyzed addition of chlorotetrafluorosulfanyl arenes to 1-hexyne and 1-hexene.
4-Nitrophenyl tetrafluoro-l6-sulfanyl chloride 1d also added to
prop-2-yn-1-yl benzoate 6 to form isolable 7d.
isolable and decomposed to unidentified fluorocarbons whether in
a solution of ether, pentane, dichloromethane or deuterochloro-
form or neat. Attempted addition of 1d to internal alkenes or
alkynes or to (trialkylsilyl)acetylenes led only to recovery of
unreacted 1d.
As with the reactions of the alkynes, the stability of the alkene
addition products was also dependent upon the use of 1d.
Although 5a–c decomposed, 5d and the adduct of 4-vinyl-1,
1-biphenyl 9d were isolable. The aryl substituent effects on the
reactivity of aryl tetrafluoro-l6-sulfanes could be assessed by
correlation of the 13C NMR chemical shifts with Hammett
substituent factors.
2.1. Dehydrohalogenation
The purified alkyl aryl tetrafluoro-l6-sulfanes 3d and 5d could
be subjected to dehydrohalogenation without decomposition of
the tetrafluorosulfanyl group. Dehydrochlorination with lithium
1d also adds to vinyl acetate, ethyl vinyl ether and [(ethyny-
loxy)methyl]benzene, however, the resulting products were not
Fig. 1. Molecular structure of 3d. Thermal ellipsoids are shown at 50% probability.
Fig. 2. Molecular structure of 5d. Thermal ellipsoids are shown at 50% probability.

194
L. Zhong et al. / Journal of Fluorine Chemistry 167 (2014) 192–197
Table 1
Selected 13C chemical shifts for 3a–d and 5a–d from 13C NMR studies.
3a
3b
3c
3d
13C NMRa
C4
C7
160.99
143.69
5a
158.49
143.07
5b
159.59
143.30
5c
164.41
142.55
5d
C4
C7
sb
161.13
83.42
0.0
158.62
83.00
0.23
159.80
83.39
0.23
164.60
83.16
0.78
Fig. 3. Molecular structure of 10d. Thermal ellipsoids are shown at 50% probability.
a
Chemical shifts in
dppm.
b
See Ref. [19].
with increasing electron density C7. The C4–S–C7 bond angle
compresses from 178.628(83)8 to 176.547(378)8 (Table 2). The
electron density at C7 increases with the change in hybridization
associated with the progressive unsaturation of 3d, 5d, and
10d. Concurrently, increase in electron density of C7 bond resulted
hydroxide formed the tetrafluoro-l6-sulfanes 10d and 11d
(Scheme 2) in good yields. Following purification by silica gel
column chromatography, a single crystal X-ray diffraction study of
10d (Fig. 3 and Table 2) confirmed the proposed structure and was
consistent with the observed spectroscopic details. In contrast to
the stability of 10d, 11d completely hydrolyzed to the sulfone on
exposure to silica gel. Fortunately 11d could be purified by
recrystallization from heptanes at À78 8C.
˚
in a systematic shortening of the S–C7 bond (1.8148(75) A to
˚
1.7402(17) A), in
a manner consistent with diminution of
ionic bond character [25] As shown previously a decrease in the
C4–S–C7 bond angle and an increase in the S–C7 bond
length accompanied the introduction of increasingly election
withdrawing substituents to the aryl group of the aryl tetrafluoro-
l6-sulfanyl construct [18,24]. The increased significance of an
ionic resonance form on the C4–S–C5 bonding and the consequent
distortion of geometry around sulfur would be predicted to
result in the S–F2 bond exo to the alkane being lengthened
relative to S–F4 bond. This phenomenon was previously observed
by Gerken [25] and in our previous work [18]. These findings are
consistent with the contribution of ionization to the C5–S bond
to the Rundle–Pimentel–Coulson [23,21,26]/charge-shift [24]
description of bonding at sulfur.
2.2. 13C chemical shifts
The nature of the arene substituent correlates with the 13C NMR
chemical shifts of 3a–d and 5a–d (Table 1). In 3a–d and 5a–d the
13C chemical shift of the resonance attributed to C4 (see Fig. 1 for
numbering;
respectively) correlates weakly with
the Spiesecke–Schneider relationship [20], 13C chemical shifts may
be indicative of charge density. Therefore an increase in could be
d
= 158.49–164.41 ppm and
d = 158.62–164.60 ppm,
s
values [19]. Consistent with
s
predicted to result in the chemical shift of C4 moving to lower-
field. However, the 13C chemical shift of C7 of 3 decreases from
3. Discussion
d
= 143.69 to
with the trend observed with 3, the 13C chemical shift of C7 in 5
decreases from = 83.42 to 83.16 with increasing
(r2 = 0.923).
d 142.55 with increasing s
(r2 = 0.920). Consistent
3.1. Influence of vinylic chlorine on stability
d
d
s
The decrease in C7 chemical shift with strongly electron-
withdrawing para-substituents was previously observed in the
substitution products of aryl alkynes and alkenes [18] and was
postulated to be associated with an increase in charge density at
C7. This increase in density is consistent with the contribution of
ionization of the S–C7 bond predicted by the Rundle–Pimentel–
Coulson [21–23]/charge-shift bonding [24] description of bonding
at sulfur.
Vinylic substituent effects on the reactivity of the tetrafluoro-
l6-sulfanyl group were observed on comparison of 3d with 11d.
Table 2
Selected bond lengthsa of compounds 3d, 5d and 10d.
3d
5d
10d
C1–C6
C1–C2
C2–C3
C3–C4
C4–C5
C5–C6
C7–C8
C8–C9
C9–C10
1.3840(19)
1.3852(20)
1.3941(18)
1.3907(19)
1.3914(20)
1.3932(17)
1.3264(16)
1.5030(16)
1.5364(21)
C1–C2
C1–C6
C2–C3
C3–C4
C4–C5
C5–C6
C7–C8
C8–C9
C9–C10
1.3596(115)
1.3821(122)
1.3875(103)
1.3904(112)
1.3936(111)
1.3828(112)
1.5293(110)
1.5380(112)
1.5000(126)
C1–C2
C2–C3
C2–C3
C3–C4
C4–C5
C5–C6
C7–C8
C8–C9
C9–C10
C10–C11
C11–C12
C1–N1
C4–S1
1.3830(26)
1.3855(24)
1.3834(22)
1.3867(25)
1.3980(23)
1.3858(21)
1.1893(23)
1.4693(23)
1.5412(27)
1.5190(24)
1.5147(28)
1.4750(19)
1.8228(15)
1.7402(17)
1.2268(19)
1.2274(18)
1.6041(12)
1.6124(11)
1.6130(11)
1.620(1)
The presence of an electronegative aryl substituent, such as a
nitro group, in 3 and 5 stabilized the tetrafluoro-l6-sulfanyl-
containing molecules and decreased reactivity.
2.3. Single crystal X-ray diffraction studies
The C4–S–C7 bond angles of the aryl tetrafluoro-l6-sulfanyl-
substituted products show systematic distortions from linearity
C10–C11 1.5220(19)
C11–C12 1.5291(23)
C10–C11 1.5202(114)
C11–C12 1.5160(146)
C8–Cl1
C1–N1
C4–S1
C7–S1
N1–O1
N1–O2
S1–F3
S1–F1
S1–F4
S1–F2
Angleb
1.7592(13)
1.4759(16)
1.8261(11)
1.8024(12)
C8–Cl1
C1–N1
C4–S1
C7–S1
1.8026(86)
1.4753(99)
1.8121(75)
1.8148(75)
1.2122(104)
1.2294(97)
1.6237(50)
1.6266(50)
1.6273(55)
1.6511(55)
C7–S1
e
M
M
2SO
2SO
N1–O1
N1–O2
S1–F14
S1–F13
S1–F15
S1–F16
+
+
3d
5d
Li
H
O
O
N
F
H9
C4
O2
O2
S
4
1.2122(104) N1–O1
1.2294(97)
1.6231(7)
1.6231(7)
1.6255(8)
1.6286(10)
N1–O2
S1–F3
S1–F1
S1–F4
S1–F2
10d
7
8
%
e
N
F
S
Li
H
4
H9
C4
C4–S–C7 177.928(49)
176.547(378) 178.628(83)
11d
98
%
Carbon hydrogen bonds are omitted.
a
˚
Bond lengths in A.
b
In degrees.
Scheme 2. Dehydrochlorination of 3d and 5d to form acetylene 10d and alkene 11d.

L. Zhong et al. / Journal of Fluorine Chemistry 167 (2014) 192–197
195
Fig. 4. The effects of vinyl chlorine on the stability of tetrafluoro-l6-sulfanyl group by resonance.
Absent chlorination, 11d was unstable toward silica gel chroma-
tography although it survives aqueous workup. In contrast, the
chlorinated compound 3d could be isolated by silica gel column
chromatography in good yield. Vinylic chlorination reduced the
reactivity of the tetrafluoro-l6-sulfanyl group. The reactivity of
compound 11d could be rationalized by consideration of the
relative contributions of the trifluorosulfonium cation III [12]
(Fig. 4) and the stable carbocation IV resonance forms to a
description of the reactivity. An increased contribution of
resonance form IV leads to a greater distribution of positive
charge away from the sulfur of the tetrafluoro-l6-sulfanyl group
and is associated with increased reactivity. In contrast to
compound 11d, the unfavorable carbocation II does not contribute
significantly to an ionic description of bonding in 3d, therefore in a
counterintuitive manner, the more localized charge deficiency on
on sulfur. In contrast 3a and 3b which cannot form a related
resonance contributor decompose in deuteriochloroform to
unidentified fluorocarbons.
3.3. Influence of para-substituents on reactivity
The aryl para-substituent effects on the stability of the
tetrafluoro-l6-sulfanyl group of 3d and 5d were pronounced.
The para-nitro substituted aryl tetrafluoro-l6-sulfane adducts 3d
and 5d were sufficiently stable that purification and characteriza-
tion was possible, while 3a–3c and 5a–5c, substituted with a
weakly electron donating or neutral substituents, decomposed to
form unidentified fluorocarbons during acquisition of the 13C NMR
spectra. A strongly electron withdrawing para-substituent leads to
an increase in covalent-ionic mixing in charge shift bonding. The
observed increase in stability [24] is consistent with the similar
influence of chlorination described in Section 3.1.
sulfur leads to the diminished reactivity of the tetrafluoro-l6
-
sulfanyl group.
3.2. Influence of alkyl substituents and the substituted aryl
tetrafluoro-l6-sulfanyl group on stability
4. Conclusion
The preparation of tetrafluoro-l6-sulfanyl-containing mole-
cules has been extended to aliphatic systems. The influence of the
para-substituent on reactivity is consistent with the previously
described aromatic compounds [18]. In addition, the vinylic
substituent effects modulate the reactivity of the aliphatic-
tetrafluoro-l6-sulfanes. By understanding the substituent effects
on the reactivity of tetrafluoro-l6-sulfanyl-containing molecules,
it will be possible to predict the ease of isolation and reactivity of
these molecules in further transformations.
The alkyl substituent on the vinylic group also influenced the
reactivity of the tetrafluoro-l6-sulfanyl group. The reactivity of 3a
and 3b can be compared with that of the previously reported [(E)-
2-(phenyltetrafluoro-l6-sulfanyl)-1-chloroethenyl]benzene 12a
and [(E)-2-(4-chlorophenyltetrafluoro-l6-sulfanyl)-1-chloroethe-
nyl]benzene 12b [18] (Fig. 5). The latter two compounds contain a
phenyl substituent, were easily purified by recrystallization, and
did not show evidence of decomposition. The stability of 12a and
12b could be attributed to the dominant contribution of a benzylic
cation resonance form that leads to a decrease in electron density
5. Experimental
Unless otherwise noted, commercial reagents were purchased
from Sigma Aldrich, and Alpha Aesar, and other commercial
suppliers and used as received. Chloroform-d (D, 99.8%) + (0.05%
v/v TMS) was purchased from Cambridge Isotope Laboratories, Inc.
The known compounds 3a, b and d were synthesized according to
published methods [17]. Compound 1c was generously provided
by UBE America, Inc. All reactions were carried out under an inert
atmosphere. Reagents were purchased from commercial sources
and used without further purification. All solvents were purified by
standard methods and freshly distilled under argon. Proton NMR
spectra were recorded at (400 MHz), 13C at (100 MHz), and 19F at
(376 MHz). The chemical shifts of 1H are reported relative to the
residual signal of CDCl3 or. The chemical shifts of 13C NMR spectra
Fig. 5. The comparison of the vinylic substituent effects on the reactivity of the
tetrafluoro-l6-sulfanes.
See Ref. [18].
are reported relative to the carbon resonances in CDCl3 or. All 13
C
[a]

196
L. Zhong et al. / Journal of Fluorine Chemistry 167 (2014) 192–197
NMR spectra were acquired in the proton-decoupled mode. 19F
NMR spectra are reported relative to the resonance assigned to
124.60 (s), 35.93 (s), 29.42 (s), 22.38 (d, J = 13.1 Hz), 13.94 (s). 19F
NMR (376 MHz, CDCl3)
F (ppm) = 69.09 (d, 3JF,H = 8.9 Hz).
d
CFCl3 (d = 0). Thin layer chromatography was performed with silica
gel F254 as the adsorbent on 0.2 mm thick, plastic-backed plates.
The chromatograms were visualized under UV (254 nm) or by
staining with a KMnO4 aqueous solution followed by heating.
Column chromatography was performed using silica gel 60
(70–230 mesh). The C, H, an N elemental analysis was preform
on a Carlo Erba CHN Analyzer (Complete Analysis Laboratories,
Inc., Parsippany, NJ, USA).
5.1.4. [(E)-2-chlorohex-1-ene-1-(4-nitrophenyltetrafluoro-l6
sulfanyl)] (3d)
-
Yield: 66%, colorless crystals: mp: 44.9–45.4 8C. 1H NMR
(400 MHz, CDCl3) dH (ppm) = 8.26 (d, J = 9.0 Hz, 2H), 7.95 (d,
3
J = 9.2 Hz 2H), 6.85 (quintet, JH,F = 9.0 Hz, 1H), 2.76 (t, J = 2.8 Hz,
2H), 1.65 (quintet, J = 7.6 Hz, 2H), 1.39 (sex, J = 7.8, 2H), 0.94 (t,
J = 7.3 Hz, 3H). 13C NMR (101 MHz, CDCl3) dC (ppm) = 164.26
(quintet, 2JC,F = 26.8 Hz), 148.18 (s), 144.53 (quintet, 3JC,F = 7.2 Hz),
5.1. General procedure for the addition phenyltetrafluoro-l6-sulfanyl
chlorides to alkenes or alkynes promoted by triethylboron or light (3
and 5)
142.40 (quintet, JC,F = 28.1 Hz), 127.43 (quintet, JC,F = 5.3 Hz),
2
3
123.56 (s), 35.83 (s), 29.26 (s), 22.17 (s), 13.80 (s). 19F NMR
(376 MHz, CDCl3) dF (ppm) = 68.93 (d, JF,H = 9.0 Hz). Anal. Calcd.
3
For C12H14ClF4NO2S: C, 41.39; H, 4.11; N, 3.96. Found: C, 41.45; H,
4.06; N, 4.03.
To diethyl ether (3.0 mL) at room temperature in a round-
bottom flask under argon was added a para-substituted phenylte-
trafluoro-l6-sulfanyl chloride
1
(1.13 mmol, 1.0 eq) and the
5.1.5. [2-Chlorohexane-1-(phenyltetrafluoro-l6-sulfanyl)] (5a)
appropriate alkene or alkyne (1.7 mmol, 1.5 eq). Triethylboron
(0.1 mL of 1.0 M hexane solution, 0.1 mmol, 0.09 eq) was then
added dropwise. The reaction was monitored by 19FNMR. Five
minutes after the addition of triethylboron, there was complete
conversion to product. The reaction mixture was filtered through a
0.5 g plug of silica gel. The solvent was removed by rotatory
evaporation and the residual sample was placed under high
vacuum. Alternatively, without the use of triethylboron, the
addition reaction under fluorescent illumination (60 W
(800 lumens) compact fluorescent bulb 10 cm from a pyrex
reaction flask) was complete after 18 h of stirring at room
temperature. Compounds 3d, 5d were purified by column
chromatography eluting with hexane/dichloromethane (9:1)
mixture.
Yield: 100% conversion, colorless oil: not isolable. 1H NMR
(400 MHz, CDCl3) dH (ppm) = 7.74(m, 2H), 7.38 (m, 3H), 4.57 (dddd,
J = 9.0, 7.1, 5.4, 3.6 Hz, 1H), 4.25 (m, 2H), 210 (m, 1H), 1.79 (dtd,
J = 14.2, 9.4, 4.7 Hz, 1H), 1.47(m, 4H), 0.94 (t, J = 7.3 Hz, 3H). 13C
NMR (101 MHz, CDCl3)
d
C (ppm) = 164.59 (quintet, 2JC,F = 27.1 Hz),
3
148.26 (s), 127.55 (quintet, JC,F = 5.5 Hz), 123.65 (s), 83.16
2
3
(quintet, JC,F = 18.8 Hz), 57.27 (quintet, JC,F = 5.2 Hz), 37.49 (s),
28.35 (s), 22.13 (s), 14.04 (s). 19F NMR (376 MHz, CDCl3) dF
3
(ppm) = 67.45 (t, JF,H = 8.6 Hz).
5.1.6. [2-Chlorohexane-1-(4-chlorophenyltetrafluoro-l6-sulfanyl)]
(5b)
Yield: 100% conversion, colorless oil: not isolable. 1H NMR
(400 MHz, CDCl3) dH (ppm) = 7.67 (d, J = 9.0 Hz, 2H), 7.34 (d,
J = 8.7 Hz, 2H), 4.59–4.49 (m, 1H), 4.22 (m, 2H), 2.07 (ddt, J = 9.7,
5.5, 4.8 Hz, 1H), 1.77 (dtd, J = 14.2, 9.5, 4.6 Hz, 1H), 1.44 (m, 4H),
0.94 (t, J = 7.3 Hz, 3H). 13C NMR (101 MHz, CDCl3) dC
5.1.1. [(E)-2-chlorohex-1-ene-1-(phenyltetrafluoro-l6-sulfanyl)]
(3a)
2
Yield: 100% conversion, colorless oil: not isolable. 1H NMR
(400 MHz, CDCl3) dH (ppm) = 7.77 (m, 2H), 7.40 (m, 3H), 6.87
(ppm) = 158.50 (quintet, JC,F = 26.1 Hz), 135.83 (s), 128.14 (s),
3
2
127.26 (quintet, JC,F = 4.5 Hz), 83.00 (quintet, JC,F = 20.1 Hz),
3
3
(quintet, JH,F = 8.9 Hz, 1H), 2.78 (t, J = 7.6 Hz, 2H), 1.66 (quintet,
57.72 (quintet, JC,F = 5.0 Hz), 37.18 (s), 28.32 (s), 22.09 (s),
J = 15.3, 7.6 Hz, 2H), 1.40 (m, J = 14.7, 7.4 Hz, 2H), 0.94 (t, J = 7.1 Hz,
3H). 13C NMR (101 MHz, CDCl3) dC (ppm) = 161.00 (quintet,
14.27 (s). 19F NMR (376 MHz, CDCl3) dF (ppm) = 67.52 (t,
3JF,H = 8.5 Hz).
2
2JC,F = 24.3 Hz), 143.69 (quintet, JC,F = 29.7 Hz), 143.46 (quintet,
3JC,F = 7.7 Hz), 130.44 (s), 128.36 (s), 126.02 (quintet, 3JC,F = 5.3 Hz),
5.1.7. [2-Chlorohexane-1-(4-bromophenyltetrafluoro-l6-sulfanyl)]
(5c)
35.97 (s), 29.46 (s), 22.36 (s), 13.97 (s). 19F NMR (376 MHz, CDCl3)
3
dF (ppm) = 68.31 (d, JF,H = 8.9 Hz).
Yield: 100% conversion, colorless oil: not isolable. 1H NMR
(400 MHz, CDCl3) dH (ppm) = 7.59 (d, J = 9.1 Hz, 2H), 7.49 (d,
J = 8.8 Hz, 2H), 4.53 (m, 1H), 4.21 (m, 2H), 2.06(m, 1H), 1.77 (dtd,
J = 14.1, 9.4, 4.6 Hz, 1H), 1.47 (m, 4H) 0.95 (t, J = 7.3 Hz, 3H). 13C
NMR (101 MHz, CDCl3) dC (ppm) = 159.79 (t, J = 25.9 Hz), 132.92
(s), 131.28 (s), 127.65 (quintet, J = 5.4 Hz), 83.38 (quintet,
J = 20.1 Hz), 57.55 (quintet, J = 5.0 Hz), 37.46 (s), 28.33 (s), 22.09
(s), 13.99 (s). 19F NMR (376 MHz, CDCl3) dF (ppm) = 67.51 (d,
3JF,H = 8.6 Hz).
5.1.2. [(E)-2-chlorohex-1-ene-1-(4-chlorophenyltetrafluoro-l6
sulfanyl)] (3b)
-
Yield: 100% conversion, colorless oil: not isolable. 1H NMR
(400 MHz, CDCl3) dH (ppm) = 7.70 (d, J = 9.0 Hz, 2H), 7.36 (d,
J = 8.7 Hz, 2H), 6.83 (quintet, 3JH,F = 8.9 Hz, 1H), 2.76 (m, 2H), 1.64
(dt, J = 12.4, 7.6 Hz, 2H), 1.39 (dq, J = 14.7, 7.3 Hz, 2H), 0.94 (t,
J = 7.3 Hz, 3H). 13C NMR (101 MHz, CDCl3) dC (ppm) = 158.49
2
3
(quintet, JC,F = 25.7 Hz), 143.74 (quintet, JC,F = 7.3 Hz), 142.92
2
(quintet, JC,F = 29.3 Hz), 136.04 (s), 128.24 (s), 127.35 (quintet,
5.1.8. [2-Chlorohexane-1-(4-nitrophenyltetrafluoro-l6-sulfanyl)]
(5d)
3JC,F = 4.7 Hz), 35.90 (s), 29.21 (s), 22.32 (s), 14.16 (s). 19F NMR
3
(376 MHz, CDCl3) dF (ppm) = 69.16 (d, JF,H = 9.0 Hz).
Yield: 66%, colorless crystals. 1H NMR (400 MHz, CDCl3) dH
(ppm) = 8.24 (d, J = 9.0 Hz, 2H), 7.92 (d, J = 9.1 Hz, 2H), 4.53 (m, 1H),
4.26 (dddd, J = 15.7, 13.9, 8.1, 2.4 Hz, 2H), 2.04 (ddd, J = 9.8, 7.3,
4.2 Hz, 1H), 1.80 (dt, J = 14.2, 4.8 Hz, 1H), 1.47 (m, 4H), 0.94 (t,
J = 7.3 Hz, 3H). 13C NMR (101 MHz, CDCl3) dC (ppm) = 164.59
(quintet, 2JC,F = 27.0 Hz), 148.26 (s), 127.55 (quintet, 3JC,F = 5.4 Hz),
5.1.3. [(E)-2-chlorohex-1-ene-1-(4-bromorophenyltetrafluoro-l6
sulfanyl)] (3c)
-
Yield: 100% conversion, colorless oil: not isolable. 1H NMR
(400 MHz, CDCl3) dH (ppm) = 7.64 (d, J = 8.8 Hz, 2H), 7.52 (d,
3
2
J = 8.5 Hz, 2H), 6.85 (quintet, JH,F = 8.8 Hz, 1H), 2.77 (t, J = 7.5 Hz,
123.65 (s), 83.16 (quintet, JC,F = 18.8 Hz), 57.27 (quintet,
2H), 1.66 (quintet, J = 15.1, 7.6 Hz, 2H), 1.40 (sex, J = 7.3 Hz, 2H), 0.95
(t, J = 7.3 Hz, 3H). 13C NMR (101 MHz, CDCl3) dC (ppm) = 159.58
3JC,F = 5.2 Hz), 37.49 (s), 28.35 (s), 22.13 (s), 14.04 (s). 19F NMR
3
(376 MHz, CDCl3) dF (ppm) = 67.45 (t, JF,H = 8.6 Hz). Anal. Calcd.
2
3
(quintet, JC,F = 25.8 Hz), 143.85 (quintet, JC,F = 7.5 Hz), 143.15
For C11H14ClF4NO2S: C, 41.21; H, 4.61; N, 4.00. Found: C, 41.32; H,
4.61; N, 4.20.
2
3
(quintet, JC,F = 29.2 Hz), 131.38 (s), 127.69 (quintet, JC,F = 5.2 Hz),

L. Zhong et al. / Journal of Fluorine Chemistry 167 (2014) 192–197
197
5.1.9. [(E)-2-chloroprop-1-ene benzoate-1-(4-
nitrophenyltetrafluoro-l6-sulfanyl)] (7d)
5.3. Single Crystal X-ray Diffraction Studies
Yield: 31%, colorless oil. 1H NMR (400 MHz, CDCl3)
d
8.27
Slow cooling to À20 8C of a saturated heptane solution of 3d, 5d,
or 10d overnight yielded crystals suitable single crystal
X-ray diffraction studies. The X-ray intensity data were collected
for 3d, 5d, and 10d on a Bruker APEX CCD X-ray diffractometer
(d, J = 8.9 Hz, 2H), 8.10 (d, J = 7.4 Hz, 2H), 7.97 (d, J = 9.2 Hz, 2H),
7.61 (t, J = 7.4 Hz, 1H), 7.47 (t, J = 7.7 Hz, 2H), 7.08 (quintet,
3JH,F = 8.9 Hz, 1H), 5.38 (s, 2H). 13C NMR (101 MHz, CDCl3)
d
2
165.81 (s), 163.59 (quintet, JC,F = 26.5 Hz), 148.52 (s), 144.95
(quintet, 2JC,F = 30.3 Hz), 138.18 (s), 137.35 (quintet,
3JC,F = 6.9 Hz), 133.68 (s), 130.04 (s), 128.67 (s), 127.54 (quintet,
equipped with a graphite monochromated Mo K
a
radiation source
˚
(g
= 0.71073 A). Data reduction and integration were performed
with the software package SAINT [27], and absorption corrections
were applied using the program SADABS [28]. All structures were
solved and refined using the SHELXTL program package [29]. All
non-hydrogen atoms were refined anisotropically. Hydrogen
atoms were included at idealized positions as a riding model.
Further details of the crystallographic investigations can be
obtained from the Cambridge Crystallographic Data Centre
and were allocated the deposition numbers CCDC 996936 (3d),
996937 (5d), and 9969938(10d). Copies of the data can be obtained
free of charge, on application to CCDC 12 Union Road, Cambridge
CB2 1EZ, UK (fax: +44 1223 336033 or deposit@ccdc.com.ac.uk or
http://www.ccdc.cam.ac.uk/Community/Requestastructure/Pages/
DataRequest aspx
3JC,F = 5.3 Hz), 123.83 (s), 62.92–62.75 (quintet, 4JC,F = 3.1 Hz). 19
F
NMR (376 MHz, CDCl3)
d
69.82 (d, 3JF,H = 9.0 Hz). Anal. Calcd. For
C16H12ClF4NO4S: C, 45.13; H, 2.84; N, 3.29. Found: C, 45.03; H,
2.67; N, 3.33.
5.1.10. [2-Chlor(4-ethyl-1,1-biphenyl)-1-(4-nitrophenyltetrafluoro-
l6-sulfanyl)] (9d)
Yield: 68%, white solid. 1H NMR (400 MHz, CDCl3)
d 8.21
(d, J = 8.9 Hz, 2H), 7.88 (d, J = 9.2 Hz, 2H), 7.63 (dd, J = 15.3, 7.8 Hz,
4H), 7.54 (d, J = 8.3 Hz, 2H), 7.46 (t, J = 7.5 Hz, 2H), 7.38
(t, J = 7.3 Hz, 1H), 5.62 (t, J = 6.8 Hz, 1H), 4.66 (m, 2H). 13C NMR
2
(101 MHz, CDCl3)
d
164.25 (quintet, JC,F = 26.5 Hz), 148.24 (s),
142.10 (s), 140.27 (s), 138.25 (s), 129.00 (s), 127.86 (s), 127.77 (s),
3
127.71 (s), 127.51 (quintet, JC,F = 5.5 Hz), 127.24 (s), 123.60 (s),
Acknowledgements
82.56 (quintet, JC,F = 18.9 Hz), 57.36 (quintet, JC,F = 5.5 Hz). 19F
67.96 (t, JF,H = 8.2 Hz). Anal. Calcd. For
20H16ClF4NO2S: C, 53.88; H, 3.62; N, 3.14. Found: C, 54.02; H,
2
4
3
NMR (376 MHz, CDCl3)
d
We gratefully acknowledge the National Science Foundation
(CHE0957544) for financial support of this work and UBE, America
Inc for generous provision of intermediates.
C
3.56; N, 3.27.
5.2. Dehydrohalogenation reactions (10d and 11d)
Appendix A. Supplementary data
To dimethylsulfoxide (9.0 mL) at room temperature in a round-
bottom flask under argon was added 1 (0.3 mmol, 1 eq) and 0.126 g
(3.0 mmol, 10 eq lithium hydroxide monohydrate. The reaction
progress was followed by 19F NMR, and after 5 h the 19F NMR
indicated a complete conversion to product. The reaction mixture
was poured onto ice and extracted with diethyl ether twice. The
ethereal phase was dried with magnesium sulfate and concentrat-
ed to obtain the crude product. 10d was purified by silica gel
column chromatography and crystallized from pentane for
overnight at À20 8C. 11d was purified by recrystallization from
heptanes at À78 8C.
Supplementary data associated with this article can be found, in
the online version, at http://dx.doi.org/10.1016/j.jfluchem.2014.
07.017.
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5.2.1. [Hex-1-yne-1-(4-nitrophenyltetrafluoro-l6-sulfanyl)] (10d)
Yield: 78%, colorless crystals. 1H NMR (400 MHz, CDCl3) dH
(ppm) = 8.23 (d, J = 9.0 Hz, 2H), 7.89 (d, J = 9.2 Hz, 2H), 2.33
5
(tquintet, JHÀF = 7.5, 3.8 Hz, 2H), 1.58 (m, 2H), 1.45 (m, 2H),
0.93 (t, J = 7.3 Hz, 3H). 13C NMR (101 MHz, CDCl3) dC
2
(ppm) = 163.39 (quintet, JC,F = 25.8 Hz), 148.42 (s), 127.45
3
2
(quintet, JC,F = 5.1 Hz), 123.72 (s), 86.38 (quintet, JC,F = 51.6 Hz),
3
76.25 (quintet, JC,F = 9.7 Hz), 29.45 (s), 21.98 (s), 17.32 (s), 13.53
(s). 19F NMR (376 MHz, CDCl3) dF (ppm) = 87.50 (t, JF,H = 3.8 Hz).
5
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46.35; H, 4.28; N, 4.46.
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5.2.2. [Hex-1-ene-1-(4-nitrophenyltetrafluoro-l6-sulfanyl)] (11d)
Isolated as a mixture; Yield: 98%, white solid. 1H NMR
(400 MHz, CDCl3) dH (ppm) = 8.23 (d, J = 8.9 Hz, 2H), 7.94
(d, J = 9.2 Hz, 2H), 6.65 (dt, J = 14.0, 6.9 Hz, 1H), 6.48 (dt, J = 14.2,
7.1 Hz, 1H), 2.18 (m, 2H), 1.47 (quintet, J = 7.6, 2H), 1.38 (septet,
J = 7.4, 2H),0.93 (t, J = 7.3 Hz, 3H). 13C NMR (101 MHz, CDCl3) dC
2
(ppm) = 165.04 (quintet, JC,F = 28.0 Hz), 148.10 (s), 146.42
2
3
(quintet, JC,F = 25.3 Hz), 135.83 (quintet, JC,F = 7.9 Hz), 127.63
3
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[27] Bruker AXS, Inc., SAINT, Version 6.02, Bruker AXS, Inc., Madison, WI, 2001.
[28] Bruker AXS, Inc., SADABS, Bruker AXS, Inc., Madison, WI, 2001.
[29] G.M. Sheldrick, SHELXTL, Version 6.14, Bruker AXS, Inc, Madison, WI, 2001.
(quintet, JC,F = 5.2 Hz), 123.55 (s), 30.31 (s), 30.08 (s), 22.26 (s),
13.92 (s). 19F NMR (376 MHz, CDCl3) dF (ppm) = 64.66
3
(d, JF,H = 6.8 Hz). Anal. Calcd. For C12H15F4NO2S: C, 46.00; H,
4.83; N, 4.47. Found: C, 46.02; H, 4.85; N, 4.43.