Synthesis and epoxidation of 1,3-, 1,4-, and 1,5-alkadienes with pentafluoro-λ6-sulfanyl (SF5) groups

Article abstract of DOI:10.1055/s-2005-861859

This paper describes a convenient and efficient synthesis of new pentafluoro-λ⁶-sulfanyl-containing 1,3-, 1,4- and 1,5-alkadienes and their epoxidation. These compounds are useful as monomers or as intermediates in the preparation of polymers, polymer surface coating and SF₅-containing heterocyclic compounds. Georg Thieme Verlag Stuttgart.

Full text of DOI:10.1055/s-2005-861859

PAPER
1245
Synthesis and Epoxidation of 1,3-, 1,4-, and 1,5-Alkadienes with Pentafluoro-
l6-sulfanyl (SF5) Groups
1
, 3-, 1, 4-, and 1,5-
a
A
lkadienesl5
w
ith S
e
F
G
roups ry K. Brel*
Institute of Physiologically Active Compounds of Russian Academy of Science, Chernogolovka, Moscow region, 142432, Russia
Fax +7(095)7857024; E-mail: brel@ipac.ac.ru
Received 29 November 2004; revised 14 January 2005
troscopy data. All products are formed by attack of F5S
Abstract: This paper describes a convenient and efficient synthesis
radical on terminal carbon atom, i.e., the studied photo-
chemical reactions are completely regioselective.
of new pentafluoro-l6-sulfanyl-containing 1,3-, 1,4- and 1,5-alka-
dienes and their epoxidation. These compounds are useful as mono-
mers or as intermediates in the preparation of polymers, polymer
surface coating and SF5-containing heterocyclic compounds.
Cl
F5S
Key words: alkenes, epoxidations, fluorine, sulfur
hν,
+
1
2
Cl
Cl
F5S
SF5
Compounds in which a pentafluorothio group is present
are of special interest because they often possess the ad-
vantageous properties of the parent compound SF6,
among which are a high group electronegativity, large
steric bulk, a nonfunctional hexacoordinate stereochemis-
try, and high thermal and hydrolytic stability. These new
properties are manifested in a multitude of uses, or poten-
tial uses, such as fumigants, as perfluorinated blood sub-
stitutes, as thermally and chemically stable systems,1 as
energetic materials2 and rocket fuels.3 Besides, the high
radiative and chemical stability of the pentafluorothio
group make these compounds attractive as replacements
for compounds that contain a trifluoromethyl group.
F5SCl
Cl
F5S
Cl
hν,
3
4
+
F5S
SF5
Cl
Scheme 1
The second step of the preparation of alkadienes 5 and 6
is the dehydrochlorination of monoadducts 1 and 3 re-
spectively by heating with K2CO3 in sulfolane at 60 °C
during 3 hours (Scheme 2). Elimination of hydrogen chlo-
ride was monitored using thin layer chromatography. The
formation of 1-pentafluorosulfanylhexa-1,5-diene (6) is
straightforward. The formation of 1-pentafluorosulfanyl-
penta-1,4-diene (5) is accompanied by its partial isomer-
ization to 1-pentafluorosulfanylpenta-2,4-diene. The
extent of this isomerization increased with temperature.
Therefore, 1,4-pentadiene 5 was isolated by column chro-
matography on silica gel where as distillation at reduced
pressure was used for isolation of thermally stable product
6.
One of the most promising methods of preparation of pen-
tafluorosulfanyl-containing compounds is pentafluorosul-
fanylation of unsaturated substrates.4 Compounds with
the pentafluorosulfanyl group have been synthesized ear-
lier.5 At the same time, the preparation of SF5-alkadienes
with terminal CH2-group, to the best of our knowledge,
has not been described hitherto. Therefore, we have devel-
oped a convenient approach to the synthesis of pentafluo-
rosulfanyl-containing 1,3-, 1,4- and 1,5-alkadienes and
studied their reactivity.
1-Pentafluorosulfanylpenta-1,4-diene (5) and 1-penta-
fluorosulfanylhexa-1,5-diene (6) have been prepared by
similar two-step syntheses. In both cases, the first step is
the photo-induced radical addition of pentafluorosulfanyl
chloride to the corresponding 1,4- and 1,5-dienes with the
formation of adducts 1 and 3, respectively (Scheme 1).
These reactions were performed at room temperature in a
quartz ampule with Hg lamp as a source of irradiation. In
reactions with 1,4- and 1,5-dienes, bis-adducts 2 and 4, re-
spectively, are formed as by-products in the yields of 10–
15%. Products 1–4 were isolated by vacuum distillation
and their structures proved by 1H, 19F and 13C NMR spec-
SF5
Cl
K2CO3
F5S
( )n
5, 6
n
1, 3
n = 1 (1, 5 ), 2 (3, 6 )
Scheme 2
We have tried to synthesize 1-pentafluorosulfanylbuta-
1,3-diene by a similar two-step approach using photo-
chemical addition of F5SCl to unsaturated substrate fol-
lowed by HCl elimination. For that we have used 3-
SYNTHESIS 2005, No. 8, pp 1245–1250
Advanced online publication: 23.03.2005
DOI: 10.1055/s-2005-861859; Art ID: P14204SS
© Georg Thieme Verlag Stuttgart · New York
x
x
.
x
x
.2
0
0
5

1246
V. K. Brel
PAPER
1
chlorobut-1-ene as the substrate. Indeed, adduct 7 is in this elimination has been proved by H, 19F and 13C
formed in good yield. It has been isolated in pure form by NMR spectroscopy. The final step of our synthesis of 1-
vacuum distillation. Unfortunately, transformation of this pentafluorosulfanylbuta-1,3-diene (12) was dehydration
adduct into the 1,3-diene by elimination of two molecules of alcohol 11. We have found that removing the product
of hydrogen chloride with K2CO3 in DMF or sulfolane from the reaction mixture increases the yield of 12.
failed.
Hence, the reaction was performed under reduced pres-
sure with simultaneous distillation of formed 1,3-diene
into a cooled trap. This procedure provided 1-pentafluoro-
sulfanylbuta-1,3-diene (12) in 35–40% yield (Scheme 4).
We have now found that heating 7 with potassium carbon-
ate at 55–60 °C leads to elimination of one HCl molecule
only with formation of 3-chloro-1-pentafluorosulfanyl-
but-1-ene (8). Compound 8 is stable under these condi-
tions; elimination of a second HCl molecule is not
observed with the increase of reaction time. The dehydro-
chlorination of 7 at higher temperature (75–80 °C) pro-
ceeds with formation of the mixture of 8 and 2,3-
dichlorobut-1-ene (9) in a ratio of 2:1 (Scheme 3).
OH
OH
SF5Cl
F5S
hν
10
Cl
KOH
25–30 °C
OH
Cl
–H2O
F5S
F5S
F5S
12
8
11
K2CO3
55–60 °C
Scheme 4
Cl
Cl
SF5Cl
The structures of 1-pentafluorosulfanylhexa-1,5-diene
(6), 1-pentafluorosulfanylpenta-1,4-diene (5), and 1-pen-
tafluorosulfanylbuta-1,3-diene (12) have been unambigu-
F5S
hν
7
Cl
1
ously proved using H, 19F and 13C NMR spectroscopy.
K2CO3
75–80 °C
The most useful for this was the 13C NMR spectroscopy.
Coupling constants JC,F of carbon atom connected directly
to F5S group as well as JC,F of atom C-2 are characteristic
for the compounds containing pentafluorosulfanyl substit-
uent: dC-1 = 141.74 (doublet of a pentet, JC-1,F¢ = 1.6 Hz,
JC-1,F = 20.4 Hz); dC-2 = 136.62 (pentet, JC-2,F = 7.5 Hz).
C-3 and C-4 are singlets; their chemical shifts are the fol-
lowing: dC-3 = 131.35 (s) and dC-4 = 126.54 (s). The 19F
NMR spectra for compounds 5, 6 and 12 showed no sig-
nificant deviations from the chemical shifts or coupling
constants found for other unsaturated derivatives of sulfur
hexafluoride. The chemical shifts of the apical fluorine
atom in the SF5-group were in the range of d = 140–141,
while the basal fluorines were observed at d = 160–161,
with the typical appearance of the AB4-spin system,
JA,B = 144–151 Hz.
Cl
+
8
Cl
9
Scheme 3
The formation of dichloride 9 is the result of elimination
of HSF5 from adduct 7. So, under these conditions the F5S
group behaves as a pseudohalide and competes with the
chlorine atom in a base-induced elimination reaction. This
is unexpected while the interaction between bases and
alkyl halides containing a F5S group leads usually to elim-
ination of hydrogen halide but not HSF5. The formation of
9 can be explained by the increased acidity of H-2 atom in
2,3-dichloro-1-pentafluorosulfanylbutane (7) due to in-
ductive effects of electron-withdrawing substituents both
at C-1 and at C-3 atoms. Therefore, dehydrochlorination
of 7 at 55–60 °C leads to elimination of one HCl molecule
only. Increase of reaction temperature to 80 °C gives rise
to both the same dehydrochlorination and to elimination
of HSF5 but 1-pentafluorosulfanylbuta-1,3-diene is not
obtained.
We have studied the epoxidation of F5S-containing unsat-
urated compounds 5, 6 and 12 by m-chloroperoxybenzoic
acid.6 After 72 hours, these dienes were converted into
monoepoxides 13–15 in 80–90% yields (Scheme 5). Ep-
oxides 14 and 15 were also synthesized from adducts 1
and 3 by a two-step procedure. In the first step, these chlo-
roalkenes were epoxidized with m-chloroperoxybenzoic
acid; the second step is HCl elimination from the obtained
chloroalkyl epoxides 16 and 17.
Therefore, we have used another approach to the synthesis
of 1-pentafluorosulfanylbuta-1,3-diene. But-3-en-2-ol un-
derwent photochemical reaction with F5SCl to yield ad-
duct 10. Treatment of compound 10 with KOH in diethyl
ether affords allyl alcohol 11. The reaction is mild and rel-
atively fast: full conversion of 10 required 3 hours at 25–
30 °C. Unsaturated alcohol 11 has been isolated by vacu-
um distillation. Exclusive formation of the trans-isomer
In all cases, unsubstituted terminal double bond is exclu-
sively epoxidized. Double bond connected directly to F5S
group fails to react with the electrophilic oxidant. This can
be explained on account of the significant steric and elec-
tron-withdrawing effects of pentafluorosulfanyl groups.
Synthesis 2005, No. 8, 1245–1250 © Thieme Stuttgart · New York

PAPER
1,3-, 1,4-, and 1,5-Alkadienes with SF5 Groups
1247
13C NMR (50.3 MHz, CDCl3): d = 41.38 (s, CH2), 54.26 (pent,
JC,F = 4.2 Hz, CHCl), 75.74 (dpent, JC,F = 13.4 Hz, JC,F = 1.0 Hz,
F5SCH2), 120.04 (s, =CH2), 131.62 (s, CH=).
F5S
O
13
19F NMR (188.3 MHz, CDCl3): d = 144.01 (dm, 4 F, JF,F = 146.0
Hz), 160.83 (9 lines, 1 F, JF,F = 146.0 Hz).
n = 0
MCPBA
O
MCPBA
Anal. Calcd for C5H8ClF5S (230.63): C, 26.04; H, 3.50; F, 41.19; S,
13.90. Found: C, 26.12; H, 3.49; F, 41.36; S, 14.02.
F5S
F5S
(
)
(
)
n
n
n = 1, 2
5, 6, 12
14, 15
Compound 2
K2CO3
1H NMR (200 MHz, CDCl3): d = 2.29 (d, 1 H, JH,F = 5.5 Hz, CHH),
2.33 (d, 1 H, JH,H = 5.7 Hz, CHH), 3.91 (ddpent, 2 H, JH,F = 8.0 Hz,
JH,H = 14.3 Hz, JH,H = 7.7 Hz, 2 F5SCHH), 4.10 (ddpent, 2 H,
JH,F = 8.5 Hz, JH,H = 14.3 Hz, JH,H = 5.1 Hz, 2 F5SCHH), 4.69 (m, 2
H, 2 CHCl).
13C NMR (50.3 MHz, CDCl3): d = 44.54 (pent, JC,F = 1.2 Hz, CH2),
52.44 (pent, JC,F = 4.8 Hz, 2 CHCl), 75.75 (dpent, JC,F = 14.0 Hz,
JC,F = 1.0 Hz, 2 F5SCH2).
Cl
Cl
O
MCPBA
F5S
F5S
(
)
n
(
)
n
n = 1, 2
1, 3
16, 17
n = 0 (12) , 1 (1, 5, 14, 16 ), 2 (3, 6, 15, 17 )
Scheme 5
19F NMR (188 MHz, CDCl3): d = 144.40 (dm, 4 F, JF,F = 146.0 Hz),
161.20 (9 lines, 1 F, JF,F = 146.0 Hz).
The epoxides 13–15 have been characterized by H, 19F
1
Anal. Calcd for C5H8Cl2F10S2 (393.14): C, 15.28; H, 2.05; F, 48.32;
S, 16.31. Found: C, 15.12; H, 1.97; F, 48.46; S, 16.44.
and 13C NMR spectroscopy.
In summary, we have described an easy and convenient
method for the preparation of new, synthetically valuable
1,3-, 1,4-, and 1,5-alkadienes with pentafluoro-l6-sulfa-
nyl (SF5) groups. The epoxidations of compounds 1, 3, 5,
6, 12 with meta-chloroperoxybenzoic acid occur in high
yield. In all cases, double bond connected directly to F5S
group fails to react with the electrophilic oxidant. Future
studies on this potentially important synthetic methodolo-
gy are currently in progress. Applications of 1,3-, 1,4-,
and 1,5-alkadienes containing pentafluoro-l6-sulfanyl
(SF5) groups to the synthesis of interesting heterocycles
will be reported in due course.
5-Chloro-6-(pentafluoro-l6-sulfanyl)hex-1-ene (3)
According to the procedure for the synthesis of 1, hexa-1,5-diene
(9.8 g, 0.12 mol) was allowed to react with F5SCl (16.2 g, 0.1 mol).
Distillation at reduced pressure gave 20.7 g (85%) of compound 3;
bp 61/7 mm Hg and 3.1 g (13%) of compound 4; bp 110 °C/2 mm
Hg.
Compound 3
1H NMR (200 MHz, CDCl3): d = 1.85 (m, 1 H, CHH), 2.03 (m, 1 H,
CHH), 2.31 (m, 2 H, CH2), 3.90 (ddpent, 1 H, JH,H = 6.2 Hz,
JH,H = 14.3 Hz, JH,F = 8.0 Hz, F5SCHH), 4.03 (ddpent, 1 H,
JH,H = 6.2 Hz, JH,H = 14.3 Hz, JH,F = 8.0 Hz, F5SCHH), 4.36 (tt, 1 H,
JH,H = 6.2 Hz, JH,H = 9.6 Hz, CHCl), 5.11 (ddd, 1 H, JH,H = 17.1 Hz,
JH,H = 1.5 Hz, JH,H = 1.5 Hz, =CCHH), 5.07 (dd, 1 H, JH,H = 10.1
Hz, JH,H = 1.5 Hz, JH,H = 1.0 Hz, =CCHH), 5.77 (ddt, 1 H,
JH,H = 17.1 Hz, JH,H = 10.1 Hz, JH,H = 6.3 Hz, CH=CH2).
NMR spectra were recorded on a Bruker CXP-200 spectrometer at
200 MHz (1H NMR), 188.3 MHz (19F NMR) and 50.3 MHz (13C
NMR). Chemical shifts for 1H NMR and 13C NMR are reported in
ppm relative to TMS as internal standard. 19F downfield shifts (d)
are expressed with a positive sign, relative to external CF3CO2H.
Starting materials penta-1,4-diene, hexa-1,5-diene, 3-chlorobut-1-
ene, but-3-en-2-ol, meta-chloroperoxybenzoic acid are commer-
cially available. SF5 was prepared from F4S according to the litera-
ture procedure.7
13C NMR (50.3 MHz, CDCl3): d = 30.05 (s, CH2), 36.45 (pent,
JC,F = 14.2 Hz, CH2), 54.92 (pent, JC,F = 4.4 Hz, CHCl), 76.72
(dpent, JC,F = 13.8 Hz, JC,F = 0.9 Hz, F5SCH2), 118.57 (s, =CH2),
135.82 (s, CH=).
19F NMR (188.3 MHz, CDCl3): d = 144.03 (dm, 4 F, JF,F = 146.1
Hz), 160.96 (9 lines, 1 F, JF,F = 146.1 Hz).
Anal. Calcd for C6H10ClF5S (244.66): C, 29.46; H, 4.12; F, 38.83;
S, 13.11. Found: C, 29.30; H, 4.07; F, 38.97; S, 13.25.
4-Chloro-5-(pentafluoro-l6-sulfanyl)pent-1-ene (1); Typical
Procedure
Compound 4
A mixture of penta-1,4-diene (8.16 g, 0.12 mol), F5SCl (16.2 g, 0.1
mol) and Cl3CF (10 mL) contained in a Pyrex ampule was irradiated
for 2 h with UV light from a Hanovia S500 lamp placed at a distance
of 30 cm. The reaction mixture was freed from Cl3CF by distillation
leaving 24 g of a brownish oil. The oil was distilled in vacuo, giving
18.5 g (80%) of 1; bp 48 °C/8 mm Hg and 3.4 g (15%) of 2; bp
101 °C/2 mm Hg.
1H NMR (200 MHz, CDCl3): d = 2.11 (m, 4 H, 2 CH2), 3.90
(ddpent, 2 H, JH,F = 8.1 Hz, JH,H = 14.4 Hz, JH,H = 7.1 Hz, 2
F5SCHH), 4.08 (ddpent, 2 H, JH,F = 8.4 Hz, JH,H = 14.4 Hz,
JH,H = 5.0 Hz, 2 F5SCHH), 4.42 (m, 2 H, 2CHCl).
13C NMR (50.3 MHz, CDCl3): d = 33.23 (pent, JC,F = 1.5 Hz, CH2),
34.19 (pent, JC,F = 1.5 Hz, CH2), 54.35 (pent, JC,F = 5.5 Hz, CHCl),
54.98 (pent, JC,F = 5.4 Hz, CHCl), 76.21 (dpent, JC,F = 13.6 Hz,
JC,F = 1.0 Hz, F5SCH2), 76.27 (dpent, JC,F = 13.4 Hz, JC,F = 1.0 Hz,
F5SCH2).
19F NMR (188.3 MHz, CDCl3): d = 144.12, 144.19 (dm, 4 F,
JF,F = 146.1 Hz), 160.47, 160.48 (9 lines, 1 F, JF,F = 146.1 Hz).
Compound 1
1H NMR (200 MHz, CDCl3): d = 2.61 (m, 3 H, CH2), 3.93 (dpent,
2 H, JH,F = 8.0 Hz, JH,F = 6.0 Hz, F5SCH2), 4.42 (pent, 1 H,
JH,H = 6.0 Hz, CHCl), 5.21 (dd, 1 H, JH,H = 18.1 Hz, JH,H = 1.4
Hz, = CCHH), 5.23 (dd,
1 H, JH,H = 9.0 Hz, JH,H = 1.4
Anal. Calcd for C6H10Cl2F10S2 (407.16): C, 17.70; H, 2.48; F, 46.66;
S, 15.75. Found: C, 17.54; H, 2.39; F, 46.80; S, 15.85.
Hz, =CCHH), 5.85 (ddt, 1 H, JH,H = 18.1 Hz, JH,H = 9.0 Hz, JH,H
=
6.9 Hz, CH=).
Synthesis 2005, No. 8, 1245–1250 © Thieme Stuttgart · New York

1248
V. K. Brel
PAPER
1-(Pentafluoro-l6-sulfanyl)penta-1,4-diene (5); Typical Proce-
dure
duced pressure gave 2.17 g (50%) of compound 8; bp 58 °C/80 mm
Hg.
To K2CO3 (20 g) in sulfolane (50 mL) contained in a 100 mL round-
bottomed flask equipped with a magnetic stirring bar, a dropping
funnel, a thermometer and a reflux condenser was added adduct 1
(6.9 g, 0.03 mol) dissolved in sulfolane (10 mL). The mixture was
stirred at r.t. for 0.5 h and at 60 °C for 3 h. When the reaction was
complete, the crude product was distilled out under vacuum (35–40
°C/1–2 mm Hg), washed with H2O, and dried (MgSO4). The crude
product was purified by column chromatography on silica gel with
pentane–CHCl3 (10:2) as eluent; yield: 4.6 g (79.0%); Rf 0.53.
1H NMR (200 MHz, CDCl3): d = 2.98 (m, 2 H, CH2), 5.13 (ddt, 1
H, JH,H = 18.9 Hz, JH,H = 1.4 Hz, JH,H = 1.5 Hz, =CCHH), 5.15 (ddt,
1 H, JH,H = 10.4 Hz, JH,H = 1.4 Hz, JH,H = 2.1 Hz, =CCHH), 5.78
(ddt, 1 H, JH,H = 10.4 Hz, JH,H = 18.9 Hz, JH,H = 6.4 Hz, CH=), 6.47
(m, 2 H, F5SCH=CH).
Compound 8
1H NMR (200 MHz, CDCl3): d = 1.72 (d, 3 H, JH,H = 7.0 Hz, CH3),
4.59 (dq, 1 H, JH,H = 8.5 Hz, JH,H = 12.0 Hz, CHCl), 6.72 (m, 2 H,
F5SCH=CH).
13C NMR (50.3 MHz, CDCl3): d = 24.63 (s, CH3), 53.39 (s, CHCl),
139.19 (pent, JC,F = 7.1 Hz, F5SCH=CH), 141.74 (dpent, JC,F = 21.2
Hz, JC,F = 1.7 Hz, F5SCH=).
19F NMR (188.3 MHz, CDCl3): d = 141.15 (dm, 4 F, JF,F = 146.9
Hz), 159.87 (9 lines, 1 F, JF,F = 146.9 Hz). 159.87 (9 lines, 1 F,
JF,F = 146.9 Hz),
Anal. Calcd for C4H6ClF5S (216.60): C, 22.18; H, 2.79; F, 43.86; S,
14.80. Found: C, 22.30; H, 2.83; F, 43.92; S, 14.85.
13C NMR (50.3 MHz, CDCl3): d = 34.61 (s, CH2), 118.21
(s, =CH2), 132.60 (s, CH=), 136.93 (pent, JC,F = 7.0 Hz,
F5SCH=CH), 141.30 (dpent, JC,F = 19.6 Hz, JC,F = 1.5 Hz,
F5SCH=).
19F NMR (188.3 MHz, CDCl3): d = 140.65 (9 lines, 1 F, JF,F = 153.7
Hz), 161.48 (dm, 4 F, JF,F = 153.7 Hz).
2,3-Dichlorobut-1-ene (9)
1H NMR (200 MHz, CDCl3): d = 1.75 (d, 3 H, JH,H = 6.6 Hz, CH3),
4.67 (q, 1 H, JH,H = 6.6 Hz, CHCl), 5.38 (d, 1 H, JH,H = 1.8
Hz, =CHH), 5.59 (d, 1 H, JH,H = 1.8 Hz, =CHH).
13C NMR (50.3 MHz, CDCl3): d = 15.24 (s, CH3), 47.10 (s, CHCl),
125.06 (s, =CH2), 134.05 (s, =CCl).
Anal. Calcd for C5H7F5S (194.17): C, 30.93; H, 3.63; F, 48.92; S,
16.52. Found: C, 30.80; H, 3.58; F, 49.10; S, 16.61.
3-Chloro-4-(pentafluoro-l6-sulfanyl)butan-2-ol (10)
According to the procedure for the synthesis of 1, 3-buten-2-ol (7.2
g, 0.1 mol) was allowed to react with F5SCl (17.82 g, 0.11 mol).
Distillation at 93 °C/12 mm Hg gave 17.8 g (76%) of compound 10.
1H NMR (200 MHz, CDCl3): d (diastereomeric mixture) = 1.28 (d,
3 H, JH,H = 7.4 Hz, CH3), 1.86 (br s, 1 H, OH), 4.00 (m, 2 H,
F5SCH2), 4.18 (m, 1 H, CHOH), 4.31 (m, 1 H, CHCl).
13C NMR (50.3 MHz, CDCl3): d (diastereomeric mixture) = 18.80,
20.05 (s, CH3), 60.84, 60.83 (pent, JC,F = 4.0 Hz, CHCl), 68.73,
70.22 (s, CHOH), 73.68, 74.07 (dpent, JC,F = 14.2 Hz, JC,F = 1.0 Hz,
F5SCH2).
1-(Pentafluoro-l6-sulfanyl)hexa-1,5-diene (6)
According to the procedure for the synthesis of 5, adduct 3 (7.32 g,
0.03 mol) was allowed to react with K2CO3 (20 g). Distillation at re-
duced pressure gave 5.37 g (86% yield) of compound 6; bp 74–
75 °C/60 mm Hg.
1H NMR (200 MHz, CDCl3): d = 2.23 (m, 4 H, 2 CH2), 5.05 (dd, 1
H, JH,H = 10.4 Hz, JH,H = 1.4 Hz, =CHH), 5.07 (dd, 1 H JH,H = 17.4
Hz, JH,H = 1.4 Hz, =CHH), 5.77 (ddt, 1 H, JH,H = 10.4 Hz,
JH,H = 17.4 Hz, JH,H = 6.6 Hz, CH=), 6.44 (m, 2 H, F5SCH=CH).
13C NMR (50.3 MHz, CDCl3): d = 29.71 (s, CH2), 31.77 (s, CH2),
116.11 (s, =CH2), 136.18 (s, CH=), 138.24 (pent, JC,F = 7.1 Hz,
F5SCH=CH), 140.71 (dpent, JC,F = 19.5 Hz, JC,F = 1.6 Hz,
F5SCH=).
19F NMR (188.3 MHz, CDCl3): d = 140.62 (dm, 4 F, JF,F = 153.6
Hz), 160.91 (9 lines, 1 F, JF,F = 153.6 Hz).
19F NMR (188.3 MHz, CDCl3):
d
(diastereomeric
mixture) = 144.16 (dm, 4 F, JF,F = 146.1 Hz), 144.22 (dm, 4 F,
JF,F = 145.8 Hz), 160.82 (9 lines, 1 F, JF,F = 146.1 Hz), 161.00 (9
lines, 1 F, JF,F = 145.8 Hz).
Anal. Calcd for C4H8ClF5OS (234.62): C, 20.48; H, 3.44; F, 40.49;
S, 13.67. Found: C, 20.36; H, 3.37; F, 40.53; S, 13.75.
Anal. Calcd for C6H9F5S (208.19): C, 34.62; H, 4.36; F, 45.63; S,
15.40. Found: C, 34.60; H, 4.35; F, 45.76; S, 15.50.
4-(Pentafluoro-l6-sulfanyl)but-3-en-2-ol (11)
To a mixture of KOH (11.2 g, 0.2 mol) in anhyd Et2O (100 mL) in
a 200 mL flask equipped with a magnetic stirring bar, thermometer
and dropping funnel, was added a solution consisting of 10 (11.7 g,
0.05 mol) in anhyd Et2O (20 mL) dropwise at 20–25 °C. The mix-
ture was stirred at 25–30 °C for 1.5 h, and then was added to H2O
(100 mL). The two layers were separated and the aqueous phase was
extracted with Et2O (3 × 30 mL). The combined organic fractions
were dried (MgSO4) and the solvent was evaporated in vacuum and
the resulting crude was distilled to give 7.52 g (76%) of compound
11; bp 71 °C/12 mm Hg.
1H NMR (200 MHz, CDCl3): d = 1.39 (d, 3 H, JH,H = 6.6 Hz, CH3),
1.79 (br s, 1 H, OH), 4.53 (m, 1 H, CHOH), 6.53 (ddpent, 1 H,
JH,H = 4.4 Hz, JH,H = 14.5 Hz, JH,F = 1.1 Hz, =CH), 6.68 (dpent, 1 H,
JH,H = 14.5 Hz, JH,F = 6.5 Hz, F5SCH=).
2,3-Dichloro-1-(pentafluoro-l6-sulfanyl)butane (7)
According to the procedure for the synthesis of 1, 3-chlorobut-1-ene
(9 g, 0.1 mol) was allowed to react with F5SCl (17.8 g, 0.11 mol).
Distillation at 57 °C/10 mm Hg gave 22.9 g (91%) of compound 7.
1H NMR (200 MHz, CDCl3): d (diastereomeric mixture) = 1.62,
1.70 (d, 3 H, JH,H = 7.1 Hz, CH3), 4.20 (m, 2 H, F5SCH2), 4.63 (m,
2 H, 2 CHCl).
13C NMR (50.3 MHz, CDCl3): d (diastereomeric mixture) = 21.38,
22.19 (s, CH3), 58.81, 59.06 (pent, JC,F = 1.4 Hz, CHClCH3), 59.20,
59.59 (pent, JC,F = 4.2 Hz, F5SCH2CHCl), 74.39, 75.01 (dpent,
JC,F = 14.9 Hz, JC,F = 1.2 Hz, F5SCH2).
19F NMR (188.3 MHz, CDCl3):
mixture) = 144.21 (dm, 4 F, JF,F = 146.0 Hz), 160.50 (9 lines, 1 F,
JF,F = 146.0 Hz).
d
(diastereomeric
13C NMR (50.3 MHz, CDCl3): d = 22.61 (s, CH3), 65.86 (s,
CHOH), 139.86 (dpent, JC,F = 20.5 Hz, JC,F = 1.6 Hz, F5SCH=),
141.39 (pent, JC,F = 6.5 Hz, =CH).
19F NMR (188.3 MHz, CDCl3): d = 141.16 (dm, 4 F, JF,F = 150.6
Hz), 161.28 (9 lines, 1 F, JF,F = 150.6 Hz).
Anal. Calcd for C4H7Cl2F5S (253.06): C, 18.99; H, 2.79; F, 37.54;
S, 12.67. Found: C, 18.84; H, 2.75; F, 37.68; S, 12.75.
3-Chloro-1-(pentafluoro-l6-sulfanyl)but-1-ene (8)
According to the procedure for the synthesis of 5, adduct 7 (5.06 g,
0.02 mol) was allowed to react with K2CO3 (11 g). Distillation at re-
Anal. Calcd for C4H7F5OS (198.16): C, 24.25; H, 3.56; F, 47.94; S,
16.18. Found: C, 24.33; H, 3.59; F, 47.86; S, 16.10.
Synthesis 2005, No. 8, 1245–1250 © Thieme Stuttgart · New York

PAPER
1,3-, 1,4-, and 1,5-Alkadienes with SF5 Groups
1249
1-(Pentafluoro-l6-sulfanyl)but-1,3-diene (12)
Anal. Calcd for C5H7F5OS (210.17): C, 28.58; H, 3.36; F, 45.20; S,
15.26. Found: C, 28.62; H, 3.38; F, 45.17; S, 15.24.
The 4-(pentafluoro-l6-sulfanyl)but-3-en-2-ol (11; 4.0 g, 0.02 mol)
was treated with conc. H2SO4 (1 mL) at –20 °C in a 10 mL flask
equipped with a magnetic stirring bar, thermometer and connected
with the vacuum pump (50 mm Hg) through trap cooled to –196 °C.
The mixture was stirred at 40–50 °C for 20 min and at 60–70 °C for
1 h. The liquid from the trap was washed with 10% aq NaHCO3 and
H2O. The organic layer was dried (Na2SO4). Distillation at 52 °C/
100 mm Hg gave 1.44 g (40%) of compound 12.
5,6-Epoxy-1-(pentafluoro-l6-sulfanyl)hex-1-ene (15)
According to the procedure for the synthesis of 13, compound 6
(2.08 g, 0.01 mol) was allowed to react with m-chloroperoxybenzo-
ic acid (3.44 g, 0.02 mol). Distillation at 87–88 °C/8 mm Hg gave
2.06 g (92%) of compound 15.
1H NMR (200 MHz, CDCl3): d = 1.77 (m, 2 H, CH2), 2.39 (m, 2 H,
CH2), 2.54 (dd, 1 H, JH,H = 2.6 Hz, JH,H = 4.8 Hz, CHH), 2.83 (dd, 1
H, JH,H = 4.0 Hz, JH,H = 4.8 Hz, CHH), 2.98 (m, 1 H, CH), 6.54 (m,
2 H, F5SCH=CH).
13C NMR (50.3 MHz, MHz, CDCl3): d = 27.54 (s, CH2), 31.19
(pent, JC,F = 1.0 Hz, CH2), 47.40 (s, CH2), 51.50 (s, CH), 138.25
(pent, JC,F = 7.0 Hz, F5SCH=CH), 141.49 (dpent, JC,F = 20.0 Hz,
JC,F = 1.5 Hz, F5SCH=).
19F NMR (188.3 MHz, CDCl3): d = 140.44 (dm, 4 F, JF,F = 150.6
Hz), 161.65 (9 lines, 1 F, JF,F = 150.6 Hz).
1H NMR (200 MHz, CDCl3): d = 5.55 (dd, 1 H, JH,H = 10.0 Hz,
JH,H = 0.9 Hz, =CHH), 5.63 (ddpent, 1 H, JH,H = 16.9 Hz, JH,H = 0.9
Hz, JH,F = 0.9 Hz, =CHH), 6.29 (ddd, 1 H, JH,H = 16.9 Hz,
JH,H = 10.0 Hz, JH,H = 11.5 Hz, CH=CH2), 6.58 (dpent, 1 H,
JH,H = 14.5 Hz, JH,F = 6.7 Hz, F5SCH=CH), 6.88 (ddpent, 1 H,
JH,H = 14.5 Hz, JH,H = 11.5 Hz, JH,F = 0.8 Hz, F5SCH=CH).
13C NMR (50.3 MHz, CDCl3): d = 126.54 (s, =CH2), 131.35 (s,
CH=CH2), 136.62 (pent, JC,F = 7.5 Hz, F5SCH=CH), 141.74 (dpent,
JC,F = 20.4 Hz, JC,F = 1.6 Hz, F5SCH=).
19F NMR (188.3 MHz, CDCl3): d = 141.41 (dm, 4 F, JF,F = 149.3
Hz), 161.53 (9 lines, 1 F, JF,F = 149.3 Hz).
Anal. Calcd for C6H9F5OS (224.19): C, 32.15; H, 4.05; F, 42.37; S,
14.30. Found: C, 32.31; H, 4.09; F, 42.30; S, 14.24.
Anal. Calcd for C4H5F5S (180.14): C, 26.67; H, 2.80; F, 52.73; S,
17.80. Found: C, 26.65; H, 2.81; F, 52.76; S, 17.82.
2-Chloro-4,5-epoxy-1-(pentafluoro-l6-sulfanyl)pentane (16)
According to the procedure for the synthesis of 13, adduct 1 (2.3 g,
0.01 mol) was allowed to react with m-chloroperoxybenzoic acid
(3.44 g, 0.02 mol). Distillation at 78 °C/5 mm Hg gave 2.21 g (80%)
of compound 16.
1H NMR (200 MHz, CDCl3): d (diastereomeric mixture) = 1.86–
2.96 (m, 2 H, CH2), 2.91 (dd, 1 H, JH,H = 2.4 Hz, JH,H = 4.4 Hz,
CHH), 2.90 (dd, 1 H, JH,H = 4.4 Hz, JH,H = 4.8 Hz, CHH), 3.24 (m,
1 H, CH), 4.08 (dpent, 2 H, JH,H = 6.4 Hz, JH,F = 8.0 Hz, F5SCH2),
4.62 (m, 1 H, CHCl).
13C NMR (50.3 MHz, CDCl3): d (diastereomeric mixture) = 40.52,
41.35 (pent, JC,F = 0.8 Hz, CH2), 46.38, 47.80 (s, CH2), 48.81, 49.57
(s, CH), 53.46, 53.51 (pent, JC,F = 4.6 Hz, CHCl), 76.90 (pent, 13.8
Hz, F5SCH2).
19F NMR (188.3 MHz, CDCl3): d (diastereomeric mixture) =
143.89 (dm, 4 F, JF,F = 143.1 Hz), 144.27 (dm, 4 F, JF,F = 146.9 Hz),
160.54 (9 lines, 1 F, JF,F = 143.1 Hz), 160.74 (9 lines, 1 F,
JF,F = 146.9 Hz).
3,4-Epoxy-1-(pentafluoro-l6-sulfanyl)but-1-ene (13); Typical
Procedure
A solution of m-chloroperoxybenzoic acid (3.44 g, 0.02 mol) in
CH2Cl2 (20 mL) was added to a well-stirred solution of the com-
pound 12 (1.8 g, 0.01 mol) in CH2Cl2 (20 mL) at r.t. The reaction
mixture was stirred for 2 h at 40 °C and 3 d at r.t. Progress of the
reaction was monitored by TLC analysis. The mixture was filtered,
and washed with 20% aq Na2SO3, and again with 10% aq NaHCO3
and H2O. The organic layer was dried (Na2SO4). Evaporation of the
solvent and distillation at 80 °C/60 mm Hg gave 1.76 g (90%) of
compound 13.
1H NMR (200 MHz, CDCl3): d = 2.74 (dd, 1 H, JH,H = 2.4 Hz,
JH,H = 5.4 Hz, CHH), 3.12 (dd, 1 H, JH,H = 5.4 Hz, JH,H = 4.4 Hz,
CHH), 3.47 (m, 1 H, CH), 6.33 (ddpent, 1 H, JH,H = 6.2 Hz,
JH,H = 14.6 Hz, JH,H = 1.2 Hz, F5SCH=CH), 6.79 (dpent, 1 H,
JH,H = 14.6 Hz, JH,F = 6.4 Hz, F5SCH=).
13C NMR (50.3 MHz, CDCl3): d = 49.18 (s, CH2), 49.64 (pent,
JC,F = 1.0 Hz, CH), 136.59 (pent, JC,F = 7.0 Hz, F5SCH=CH),
143.13 (dpent, JC,F = 21.6 Hz, JC,F = 1.5 Hz, F5SCH=).
Anal. Calcd for C5H8ClF5OS (246.63): C, 24.35; H, 3.27; F, 38.52;
S, 13.00. Found: C, 24.42; H, 3.29; F, 38.43; S, 13.08.
19F NMR (188.3 MHz, CDCl3): d = 140.73 (dm, 4 F, JF,F = 150.0
Hz), 160.03 (9 lines, 1 F, JF,F = 150.0 Hz).
2-Chloro-5,6-epoxy-1-(pentafluoro-l6-sulfanyl)hexane (17)
According to the procedure for the synthesis of 13, adduct 3 (2.44
g, 0.01 mol) was allowed to react with m-chloroperoxybenzoic acid
(3.44 g, 0.02 mol). Distillation at 80 °C/2 mm Hg gave 2.08 g (80%)
of compound 17.
1H NMR (200 MHz, CDCl3): d (diastereomeric mixture) = 1.52–
2.29 (m, 4 H, 2 CH2), 2.54 (dd, 1 H, JH,H = 2.5 Hz, JH,H = 4.6 Hz,
CHH), 2.83 (dd, 1 H, JH,H = 4.2 Hz, JH,H = 4.6 Hz, CHH), 2.96 (m,
1 H, CH), 4.00 (dpent, 2 H, JH,H = 6.2 Hz, JH,F = 8.0 Hz, F5SCH2),
4.50 (m, 1 H, CHCl).
13C NMR (50.3 MHz, CDCl3): d (diastereomeric mixture) = 29.16,
29.70 (s, CH2), 34.06, 34.69 (pent, JC,F = 1.4 Hz, CH2), 47.18, 47.33
(s, CH2), 51.29, 51.80 (s, CH), 55.58, 55.86 (pent, JC,F = 4.5 Hz,
CHCl), 73.10 (dpent, JC,F = 0.8 Hz, JC,F = 13.4 Hz, F5SCH2).
19F NMR (188.3 MHz, CDCl3): d (diastereomeric mixture) = 144.1
(dm, 4 F, JF,F = 145.0 Hz), 160.8 (9 lines, 1 F, JF,F = 145.0 Hz).
Anal. Calcd for C4H5F5OS (196.14): C, 24.50; H, 2.57; F, 48.43; S,
16.35. Found: C, 24.53; H, 2.56; F, 48.40; S, 16.33.
4,5-Epoxy-1-(pentafluoro-l6-sulfanyl)pent-1-ene (14)
According to the procedure for the synthesis of 13, compound 5
(1.94 g, 0.01 mol) was allowed to react with m-chloroperoxybenzo-
ic acid (3.44 g, 0.02 mol). Distillation at 73 °C/25 mm Hg gave 1.85
g (88%) of compound 14.
1H NMR (200 MHz, CDCl3): d = 2.37 (m, 1 H, CHH), 2.52 (m, 1 H,
CHH), 2.56 (dd, 1 H, JH,H = 2.6 Hz, JH,H = 4.6 Hz, CHH), 2.85 (dd,
1 H, JH,H = 4.6 Hz, JH,H = 4.6 Hz, CHH), 3.07 (m, 1 H, CH), 6.56
(m, 2 H, F5SCH=CH).
13C NMR (50.3 MHz, CDCl3): d = 32.58 (s, CH2), 45.84 (s, CH2),
49.15 (pent, JC,F = 1.0 Hz, CH), 133.36 (pent, JC,F = 7.0 Hz,
F5SCH=CH), 141.92 (dpent, JC,F = 20.1 Hz, JC,F = 1.5 Hz,
F5SCH=).
19F NMR (188,3 MHz, CDCl3): d = 140.21 (dm, 4 F, JF,F = 150.6
Hz), 161.08 (9 lines, 1 F, JF,F = 150.6 Hz).
Anal. Calcd for C6H9ClF5OS (259.65): C, 27.76; H, 3.49; F, 36.58;
S, 12.35. Found: 27.84; H, 3.53; F, 36.50; S, 12.31.
Synthesis 2005, No. 8, 1245–1250 © Thieme Stuttgart · New York

1250
V. K. Brel
PAPER
(2) (a) Witucki, E. F.; Frankel, M. B. J. Chem. Eng. Data 1979,
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L.; Thrasher, J. S. J. Energ. Mater. 1990, 8, 352.
(c) Sitzmann, M. E. J. Fluorine Chem. 1991, 52, 195.
(d) Sitzmann, M. E.; Gilardi, R. D. J. Fluorine Chem. 1993,
63, 203.
Acknowledgment
This work was supported by the European Office of Aerospace Re-
search and Development (EOARD # 037004) and International Sci-
ence and Technology Center (ISTC 2791p). The author thanks Dr.
M.D. Vorob’ev for the preparation of the starting compounds.
(3) Bovin, J. L. Can. Patent 1085875, 1980; Chem. Abstr. 1981,
94, 156285.
(4) Case, J. R.; Ray, N. H.; Roberts, H. L. J. Chem. Soc. 1961,
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Synthesis 2005, No. 8, 1245–1250 © Thieme Stuttgart · New York