Synthesis of new pentafluorosulfanylacrylates (F5SCH{double bond, long}CHCHO, F5SCH{double bond, long}CHCN, F5SCH{double bond, long}CHCOOCH3) and use of them as dienophiles in Diels-Alder reaction

Article abstract of DOI:10.1016/j.jfluchem.2007.04.013

New pentafluoro-λ⁶-sulfanylacrylates (F₅SCH{double bond, long}CHCHO, F₅SCH{double bond, long}CHCN, F₅SCH{double bond, long}CHCOOCH₃) were synthesized by a convenient and efficient method. These compounds are useful as intermediates in the preparation of pentafluoro-λ⁶-sulfanyl-containing cyclic and heterocyclic Diels-Alder cycloadducts.

Full text of DOI:10.1016/j.jfluchem.2007.04.013

Journal of Fluorine Chemistry 128 (2007) 862–867
www.elsevier.com/locate/fluor
Synthesis of new pentafluorosulfanylacrylates
(F5SCH CHCHO, F5SCH CHCN, F5SCH CHCOOCH3)
and use of them as dienophiles in Diels-Alder reaction
*
Valery K. Brel
Institute of Physiologically Active Compounds of Russian Academy of Science, Chernogolovka 142432, Moscow Region, Russia
Received 9 March 2007; received in revised form 7 April 2007; accepted 9 April 2007
Available online 19 April 2007
Abstract
New pentafluoro-l6-sulfanylacrylates (F5SCH CHCHO, F5SCH CHCN, F5SCH CHCOOCH3) were synthesized by a convenient and
efficient method. These compounds are useful as intermediates in the preparation of pentafluoro-l6-sulfanyl-containing cyclic and heterocyclic
Diels-Alder cycloadducts.
# 2007 Elsevier B.V. All rights reserved.
Keywords: Alkenes; Diels-Alder; Fluorine; Sulfur
1. Introduction
as Diels-Alder synthons for preparing F5S-cyclic adducts are
presented.
Fluorinated acrylates have been widely used as building
blocks in organic synthesis for construction of organic
compounds and polymers. Though a great many number of
fluorinatedacrylatesareknownonly a limited numbercontaining
the SF5-group have been reported. The first SF5-containing
acrylates and its polymers in which the SF5 is present in the acid
moiety were synthesized at the end of 90 years [1–4]. At the same
time, the methods for the synthesis of acrylates with
pentafluorosulfanyl group in unsaturated moiety are still limited.
Only in 2004, did Gard and coworkers report the preparation of
esters of b-SF5-acrylic and methacrylic acids [5]. More recently,
in our laboratories, we have used new approach for synthesis of
SF5-containing unsaturated compounds and for the first time
were synthesized the F5SCH CHCOR (R OH, CH3) [6].
As a part of our interest in the development of synthetic
methods for organic compounds with the pentafluorosulfanyl
substituent, we synthesized of SF5-containing acrylates that had
not been described previously and used them for construction of
cyclic, bicyclic and heterocyclic compounds. In this paper, the
synthesis of F5SCH CHR (CHO, CN, COOCH3) and their use
2. Results and discussion
As the starting compounds in the synthesis of pentafluor-
osulfanyl-containing dienophiles we used 1-pentafluorosulfa-
nylprop-1-en-3-ol (3) [7,8]. Compound 3 were prepared in
two-steps, the first step was the photo-induced radical addition
of pentafluorosulfanyl chloride [9] to the allyl alcohol (1)
leading to the formation of adduct 2. Dehydrochlorination of 2
with potassium hydroxide gave 3 with good yield. The primary
alcohol 3 was oxidized by CAN (cerium (IV) ammonium
nitrate) [6,10] to afford trans-3-(pentafluoro-l6-sulfanyl)prop-
2-enal (4) obtained as a colourless liquid in 90% yield after
vacuum distillation by (Scheme 1).
When aldehyde 4 was reacted with a hydroxylamine [11] the
trans-3-(pentafluoro-l6-sulfanyl)prop-2-enal oxime (5) was
obtained as a mixture of syn- and anty-isomers (1:1 ratio),
which were separated by flash chromatography on silica gel.
The final step of synthesis of trans-1-cyan-2-(pentafluoro-l6-
sulfanyl)-ethen was dehydration of oxime 5 with used
phosphorus pentoxide. We have found that removing the
nitrile 6 from the reaction mixture increases the yield of target
product. Hence, the reaction was performed under reduced
pressure with simultaneous distillation of formed nitrile 6 into a
* Tel.: +7 496 5242539; fax: +7 496 5249508.
E-mail address: brel@ipac.ac.ru.
0022-1139/$ – see front matter # 2007 Elsevier B.V. All rights reserved.
doi:10.1016/j.jfluchem.2007.04.013

V.K. Brel / Journal of Fluorine Chemistry 128 (2007) 862–867
863
Scheme 2.
cyclopentadiene (10 equiv) under a nitrogen atmosphere in
closed glass ampoules at 50 8C for 4, 6 and at 110 8C for methyl
ester 7 (Scheme 2).
After 10 h, 1H NMR analysis showed that the reaction
mixture contained the starting material cyclopentadiene, the
dimer of cyclopentadiene, and the new compounds 8–10 as a
mixture of endo- and exo-isomers (2.5:1 ratio) (Scheme 2). The
reaction products were then separated by preparative column
chromatography. Both endo-adducts 8a–10a and both exo-
adducts 8b–10b were isolated in pure form. Reaction of 2,3-
dimethylbutadiene with compounds 4, 7 (at 110 8C and 50 8C,
respectively) led to adducts 11 and 12 (Scheme 3). In contrast to
b-SF5-acrylates 6 and 7, trans-3-(pentafluoro-l6-sulfanyl)-
prop-2-enal 4 formed both Diels-Alder adduct 13 and hetero-
Diels-Alder adduct 14 [13], under similar reaction conditions.
Heterocyclic compounds containing the SF5 substituent are
a class of compounds that can be interesting with regard to
potential biological activity. At the same time, the methods for
Scheme 1.
cooled trap. This procedure provided trans-1-cyan-2-(penta-
fluoro-l6-sulfanyl)-ethen 6 with 56% yield.
The structures of trans-3-(pentafluoro-l6-sulfanyl)prop-2-
enal 4, syn- and anty-isomers of trans-3-(pentafluoro-l6-
sulfanyl)prop-2-enal oxime 5, and trans-1-cyan-2-(penta-
fluoro-l6-sulfanyl)-ethen 6 have been unambiguously proved
using 1=, 19F and 13E NMR spectroscopy. The most useful for
this was of the 13E NMR spectroscopy. Coupling constants JCF of
carbon atom connected directly to F5S group as well as JCF of
atom C(2) are characteristic to the compounds containing
pentafluorosulfanyl substituent: dC(1) = 141.74 ppm, doublet of a
0
pentet, JC(1)–F = 1.6 Hz, JC(1)–F = 20.4 Hz; dC(2) = 136.62 ppm,
pentet, JC(2)–F = 7.5 Hz. The 19F NMR spectra for compounds 4,
5 and 6 showed no significant 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 140–141 ppm, while
the basal fluorines were observed at 160–161 ppm, with the
typical appearance of the AB4-spin system, JAB = 144–151 Hz
[6,12].
Compounds 7 and 8 participated in Diels-Alder cycloaddi-
tion reactions to yield F5S-containing adducts. They react
readily with both aliphatic and cyclic electron-releasing dienes
with the formation of Diels-Alder cycloadducts 8–14 as
mixture of endo and exo-isomers. For example, the reaction was
performed by heating a mixture of dienophiles 4, 6, 7 with
Scheme 3.

864
V.K. Brel / Journal of Fluorine Chemistry 128 (2007) 862–867
9 lines). Anal. Calcd. for C3H3F5OS (182.112): C, 19.79; H,
1.66; F, 52.16. Found: C, 19.61; H, 1.74; F, 52.08.
3.3. trans-3-(Pentafluoro-l6-sulfanyl)prop-2-enal oxime
(syn-5, anty-5)
A mixture of 4.55 g (0.025 mol) of trans-3-(pentafluoro-l6-
sulfanyl)prop-2-enal, 5.52 g (0.8 mol) of hydroxylamine
hydrochloride, and 10.88 g (0.8 mol) of sodium acetate
trihydrate in 70 mL of absolute ethanol was refluxed for
45 min, and then ca. 60 mL of ethanol was removed in vacuum
at 258. The residue was added to 100 mL of ice water and the
product was extracted with 35 mL of methylene chloride. The
extract was dried and concentrated to leave 4.45 g of oil which
was purified by column chromatography on silica gel.
Scheme 4.
the synthesis of heterocyclic compounds with pentafluorosul-
fanyl group are still limited [14–16]. Well know, that furans
undergo Diels-Alder reactions with strong dienophiles and
generally afford exo-cycloadducts which are thermodynami-
cally more stable than the kinetically favored endo-adducts
[17]. We have shown that reaction of furan with methyl ester 7
led to hetero-adduct 15 as a mixture of endo- and exo-isomers
(3:1 ratio) (Scheme 4).
3.3.1. syn-Isomer
1H NMR spectral data (200 MHz, CDCl3): d 6.83 (1H, dquin,
J
HH = 15.0 Hz, JHF = 6.0 Hz, CHSF5), 7.02 (1H, ddquin,
HH = 15.0 Hz, JHH = 9.4 Hz, JHF = 1.4 Hz, CHCHNOH),
J
7.79 (1H, d, JHH = 9.4 Hz, CH NOH), 8.61 (1H, br.s, OH);
13C NMR (50.3 MHz, CDCl3): d 130.74 (quin, JCF = 7.5 Hz,
CH–), 146.64 (dquin, JCF = 1.0 Hz, JCF = 22.6 Hz, CHSF5),
147.15 (s, CH NOH); 19F NMR (188.3 MHz, CDCl3): d 140.82
(4F, dm, JFF = 150.4 Hz), 157.53–160.74 (1F, 9 lines). Anal.
Calcd. for C3H4F5NOS (197.127): C, 18.28; H, 2.05; F, 48.19.
Found: C, 28.39; H, 2.10; F, 48.02.
3. Experimental
3.1. General
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 H NMR and
1
3.3.2. anty-Isomer
1H NMR spectral data (200 MHz, CDCl3): d 6.91 (1H,
dquin, JHH = 15.0 Hz, JHF = 6.4 Hz, CHSF5), 7.20 (1H, d,
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 CF3COOH. Column
chromatography on silica gel was performed with Fluka
Silica gel 60 (0.035–0.070 mm). Preparative TLC was
performed on Fluka Silica gel/TLC-cards (20 cm ꢀ 20 cm ꢀ
ꢀ 0.2 cm). All reagents were of commercial quality or were
purified before use. Organic solvents were purified and dried
by standard procedures.
J
J
HH = 9.4 Hz, CH NOH), 7.56 (1H, ddquin, JHH = 15.0 Hz,
HH = 9.4 Hz, JHF = 1.5 Hz, CHCHNOH), 8.50 (1H, br.s,
OH); 13C NMR (50.3 MHz, CDCl3): d 122.92 (quin,
J
CF = 6.5 Hz, CHꢁ), 143.49 (s, CH NOH), 148.08 (dquin,
JCF = 1.5 Hz, JCF = 21.6 Hz, CHSF5); 19F NMR (188.3 MHz,
CDCl3): d 140.80 (4F, dm, JFF = 150.4 Hz), 156.90–160.12 (1F,
9 lines). Anal. Calcd. for C3H4F5NOS (197.127): C, 18.28; H,
2.05; F, 48.19. Found: C, 28.20; H, 2.02; F, 48.31.
3.2. trans-3-(Pentafluoro-l6-sulfanyl)prop-2-enal (4)
3.4. trans-1-Cyan-2-(pentafluoro-l6-sulfanyl)-ethen (6)
A mixture of 3-pentafluorosulfanylprop-2-en-1-ol 3 (1.68 g,
0.01 mol) and ammonium cerium (IV) nitrate (25.11 g,
0.045 mol) in 50% solution of acetic acid (50 mL) was stirred
at 85–90 8C 0.5 h. After the orange cerium (IV) solution had
turned to a pale yellow cerium (III) solution containing a small
amount of cerium (IV), the product mixture was extracted with
ether. The ether solution was washed with 5% potassium
hydroxide and dried. Removal of the ether and distillation at
74–75 8C/85 mm Hg, gave 1.5 g (90%) pure aldehyde 4.
1H NMR spectral data (200 MHz, CDCl3): d 6.75 (1H, dd,
The trans-3-(pentafluoro-l6-sulfanyl)prop-2-enal oxime
(3.34 g, 0.02 mol) were treated with P2O5 (8.5 g, 0.06 mol)
at ꢁ30 8C in a 20 mL flask equipped with a magnetic stirring
bar, thermometer and connected with the vacuum pump
(50 mm Hg) through trap cooled to ꢁ196 8C. The mixture was
stirred at 80–90 8C for 30 min. The liquid from trap was
distillation at 100 8C (50 mm Hg) gave 2.90 g of liquid.
Distillation at 68–69 8C/85 mm Hg, gave (56% yield) of
compound 6.
J
J
HH = 15.2 Hz, JHH = 6.8 Hz, CHCHO), 7.36 (1H, dquin,
HH = 15.2 Hz, JHF = 6.2 Hz, CHSF5), 9.71 (1H, d, JHH
1H NMR spectral data (200 MHz, CDCl3): d 6.30 (1H,
dquin, JHH = 15.4 Hz, JHF = 1.4 Hz, CHCN), 7.33 (1H, dquin,
=
6.8 Hz, CHO); 13C NMR (50.3 MHz, CDCl3): d 134.26 (quin,
J
HH = 15.4 Hz, JHF = 6.2 Hz, = CHSF5); 13C NMR (50.3 MHz,
J
CF = 6.0 Hz, CHCHO), 157.61 (dquin, JCF = 1.6 Hz, JCF
=
CDCl3): d 108.78 (quin, JCF = 8.6 Hz, CHCN), 112.78 (s,
CN), 157.39 (dquin, JCF = 2.0 Hz, JCF = 24.1 Hz, CHSF5);
19F NMR (188.3 MHz, CDCl3):
d 139.71 (4F, dm,
23.1 Hz, CHSF5), 189.72 (s, C O); 19F NMR (188.3 MHz,
CDCl3): d 140.39 (4F, dm, JFF = 146.6 Hz), 156.11–156.51 (1F,

V.K. Brel / Journal of Fluorine Chemistry 128 (2007) 862–867
865
JFF = 146.6 Hz), 152.90–158.14 (1F, 9 lines). Anal. Calcd. for
C3H2F5NS (179.112): C, 20.12; H, 1.13; F, 53.03. Found: C,
20.30; H, 1.28; F, 53.21.
JHH = 2.0 Hz, CH), 3.66 (1H, quin, JHF = 4.5 Hz,
CHCOOCH3), 3.71 (3H, s, CH3), 4.21 (1H, ddquin, JHH
2.2 Hz, JHH = 6.7 Hz, JHH = 5.1 Hz, CHSF5), 6.14 (1H, dd,
=
J
J
HH = 2.8 Hz, JHH = 5.6 Hz, CH ), 6.23 (1H, dd, JHH = 3.5 Hz,
HH = 5.6 Hz, CH ); 13C NMR (50.3 MHz, CDCl3): d 46.25 (s,
JCF = 1.5 Hz, CH2), 48.66 (quin,
CF = 4.0 Hz, CH), 48.83 (quin, JCF = 4.5 Hz, CH), 52.77 (s,
3.5. trans-Methyl 3-(pentafluoro-l6-sulfanyl)prop-2-enate
(7)
CH), 48.36 (quin,
J
Solution of F5SCH CHCOOH (1.98 g, 0.01 mol), MeOH
(10 mL), and H2SO4 (2–3 drops) was heated for 6 h. To reaction
mixture was added H2O (50 mL). The two layers were
separated and the aqueous phase was extracted with Et2O
(3 mL ꢀ 30 mL). The combined organic fractions were dried
(MgSO4) and the solvent was evaporated in vacuum and the
resulting crude was distilled to give 1.7 g (80% yield) of
compound 7; bp 75–78 8C/65 mm Hg.
CH3), 88.80 (dquin, JCF = 1.0 Hz, JCF = 8.0 Hz, CHSF5),
136.21 (s, CH ), 137.80 (s, CH ), 174.00 (s, C O); 19F
NMR (188.3 MHz, CDCl3): d 139.78 (4F, dm, JFF = 144.8 Hz),
162.7–166.3 (1F, 9 lines). Anal. Calcd. for C9H11F5O2S
(278.241): C, 38.85; H, 3.99; F, 34.14. Found: C, 38.90; H,
3.82; F, 34.30.
3.7. exo-3-Carboxaldehyde-endo-2-(pentafluoro-l6-
sulfanyl)-5-norbornene (endo-9) and endo-3-
carboxaldehyde-exo-2-(pentafluoro-l6-sulfanyl)-5-
norbornene (exo-9)
1H NMR spectral data (200 MHz, CDCl3): d 3.85 (3H, s,
CH3), 6.58 (1H, dquin, JHH = 14.8 Hz, JHF = 1.5 Hz, =
CHCOOMe), 7.44 (1H, dquin, JHH = 14.8 Hz, JHF = 6.8 Hz,
= CHSF5); 13C NMR (50.3 MHz, CDCl3): d 53.29 (s, CH2),
127.42 (quin, JCF = 7.5 Hz, CHCOOMe), 152.78 (dquin,
A mixture of 4 (1.82 g, 0.01 mol), cyclopentadiene (6.6 g,
0.1 mol) contained in a Pyrex seal tube was heated at 50–55 8C
for 6 h. The reaction mixture was freed from pentadiene by
evaporation under reduced pressure leaving 3.6 g of a brownish
oil. Isomers endo-9 and exo-9 were isolated by column
chromatography on silica gel.
J
CF = 2.0 Hz, JCF = 22.6 Hz, CHSF5), 164.00 (s, C O); 19F
NMR (188.3 MHz, CDCl3): d 140.55 (4F, dm, JFF = 146.0 Hz),
155.21–158.43 (1F, 9 lines). Anal. Calcd. for C4H5F5O2S
(212.138): C, 22.65; H, 2.38; F, 44.78. Found: C, 22.71; H, 2.40;
F, 44.63.
(endo-9) 1.31 g (52.8%) as a colorless oil. Rf = 0.8 (CHCl3).
1H NMR spectral data (200 MHz, CDCl3): d 1.32 (1H, d,
3.6. Methyl endo-2-(Pentafluoro-l6-sulfanyl)-5-
norbornene-exo-3-carboxylate (endo-8) and methyl exo-2-
(pentafluoro-l6-sulfanyl)-5-norbornene-endo-3-
carboxylate (exo-8)
J
J
HH = 9.2 Hz, CHH), 1.54 (1H, dddquin, JHH = 1.8 Hz,
HH = 2.0 Hz, JHH = 9.2 Hz, JHF = 2.2 Hz, CHH), 3.11 (1H,
dd, JHH = 2.0 Hz, JHH = 4.6 Hz, CHCHO), 3.20 (1H, m, CH),
3.50 (1H, m, CH), 4.99 (1H, ddquin, HH = 1.4 Hz,
HH = 4.6 Hz, JHF = 6.5 Hz, CHSF5), 6.26 (1H, m, = CH),
J
A mixture of 7 (2.12 g, 0.01 mol), cyclopentadiene (6.6 g,
0.1 mol) contained in a Pyrex seal tube was heated at 110 8C for
10 h. The reaction mixture was freed from pentadiene by
evaporation under reduced pressure leaving 3.2 g of a brownish
oil. Isomers endo-8 and exo-8 were isolated by column
chromatography on silica gel.
J
6.43 (1H, dd, JHH = 5.8 Hz, JHH = 3.4 Hz, CH), 9.82 (1H, s,
CHO); 13C NMR (50.3 MHz, CDCl3): d 44.24 (s, CH), 45.52
(quin, JCF = 3.0 Hz, CH2), 47.79 (quin, JCF = 3.0 Hz, CH),
57.60 (quin, JCF = 3.0 Hz, CHCHO), 84.31 (dquin, JCF
=
1.0 Hz, JCF = 9.6 Hz, CHSF5), 136.61 (s, CH ), 136.99 (s,
CH ), 198.34 (s, CHO); 19F NMR (188.3 MHz, CDCl3): d
140.11 (4F, dm, JFF = 148.52 Hz), 162.92–166.02 (1F, 9 lines).
Anal. Calcd. for C8H9F5OS (248.215): C, 38.71; H, 3.66; F,
38.27. Found: C, 38.63; H, 3.58; F, 38.41.
(endo-8) 1.43 g (51.4%) as a colorless oil. Rf = 0.77
1
(CHCl3). H NMR spectral data (200 MHz, CDCl3): d 1.53
(1H, ddquin, JHH = 10.0 Hz, JHH = 2.0 Hz, JHF = 2.1 Hz,
CHH), 1.65 (1H, dquin, JHH = 10.0 Hz, JHF = 1.0 Hz, CHH),
2.92 (1H, dd, JHH = 2.0 Hz, JHF = 5.0 Hz, CHCOOCH3), 3.08
(1H, br.s, CH), 3.48 (1H, br.s, CH), 3.77 (3H, s, CH3), 4.98 (1H,
m, CHSF5), 6.21 (1H, m, CH ), 6.41 (1H, dd, JHH = 3.3 Hz,
(exo-9) 0.52 g (21.00%) as a colorless oil. Rf = 0.77
1
(CHCl3). H NMR spectral data (200 MHz, CDCl3): d 1.81
(1H, dddquin, JHH = 0.8 Hz, JHH = 1.0 Hz, JHH = 9.2 Hz,
J
HH = 5.5 Hz, CH ); 13C NMR (50.3 MHz, CDCl3): d 45.98
JHF = 0.7 Hz, CHH), 1.96 (1H, d, JHH = 9.2 Hz, CHH), 3.47
(1H, br.s, CH), 3.65 (1H, br.s, CH), 3.81 (1H, dd, JHH = 1.8 Hz,
(quin, JCF = 3.0 Hz, CH2), 47.82 (quin, JCF = 3.0 Hz, CH),
48.02 (s, CH), 49.4 (quin, JCF = 3.0 Hz, CH), 53.01 (s, CH3),
88.3 (dquin, JCF = 0.8 Hz, JCF = 9.6 Hz, CHSF5), 135.90 (s,
CH ), 137.60 (s, CH ), 173.66 (s, C O); 19F NMR
(188.3 MHz, CDCl3): d 140.08 (4F, dm, JFF = 146.9 Hz),
163.0–166.05 (1F, 9 lines). Anal. Calcd. for C9H11F5O2S
(278.241): C, 38.85; H, 3.99; F, 34.14. Found: C, 38.94; H,
3.92; F, 34.25.
J
J
HH = 4.4 Hz, CHCHO), 4.23 (1H, ddquin, JHH = 1.2 Hz,
HH = 4.4 Hz, JHF = 6.5 Hz, CHSF5), 6.21 (2H, m, CH
CH), 9.64 (1H, s, CHO); 13C NMR (50.3 MHz, CDCl3): d
44.12 (s, CH), 47.94 (quin, JCF = 1.5 Hz, CH2), 48.75 (quin,
CF = 3.5 Hz, CH), 57.2 (quin, JCF = 3.0 Hz, CHCHO), 85.56
(dquin, JCF = 1.3 Hz, JCF = 8.6 Hz, CHSF5), 136.03 (quin,
CF = 1.0 Hz, CH ), 137.43 (quin, JCF = 0.5 Hz, CH ), 198.36
(s, CHO); 19F NMR (188.3 MHz, CDCl3): d 39.13 (4F, dm,
FF = 142.9 Hz), 162.95–166.0 (1F, 9 lines). Anal. Calcd. for
J
J
(exo-8) 0.57 g (20.51%) as a colorless oil. Rf = 0.71
1
(CHCl3). H NMR spectral data (200 MHz, CDCl3): d 1.73
J
(1H, d, JHH = 9.0 Hz, CHH), 1.88 (1H, d, JHH = 9.0 Hz, CHH),
3.32 (1H, br.s, CH), 3.56 (1H, dquin,
C8H9F5OS (248.215): C, 38.71; H, 3.66; F, 38.27. Found: C,
38.60; H, 3.52; F, 38.45.
JHH = 1.4 Hz,

866
V.K. Brel / Journal of Fluorine Chemistry 128 (2007) 862–867
3.8. exo-3-Cyan-endo-2-(pentafluoro-l6-sulfanyl)-5-
norbornene (endo-10) and endo-3-cyan-exo-2-
(pentafluoro-l6-sulfanyl)-5-norbornene (exo-10)
(188.3 MHz, CDCl3): d 134.16 (4F, dm, JFF = 141.0 Hz),
161.98–164.99 (1F, 9 lines). Anal. Calcd. for C10H15F5O2S
(294.284): C, 40.81; H, 5.14; F, 32.28. Found: C, 40.94; H,
5.29; F, 32.50.
According to the procedure 3.7 for the synthesis of endo-9,
and exo-9, trans-1-cyan-2-(pentafluoro-l6-sulfanyl)-ethen 6
(1.79 g, 0.01 mol) was allowed to react with pentadiene (6.6 g,
0.1 mol).
3.10. 5-Cyano-1, 2-dimethyl-4-(pentafluoro-l6-sulfanyl)-
cyclohex-1-en (12)
(endo-10) 1.07 g (44.00%) as a colorless oil. Rf =
0.62 (CHCl3/C6H14 = 10:2). 1H NMR spectral data
According to the procedure 3.7 for the synthesis of endo-9,
and exo-8, trans-1-cyan-2-(pentafluoro-l6-sulfanyl)-ethen 6
(1.79 g, 0.01 mol) was allowed to react with 2,3-dimethylbu-
tadiene (8.2 g, 0.1 mol). Yield 12 1.41 g (54%) as a colorless
oil. Rf = 0.81 (CHCl3). 1H NMR spectral data (200 MHz,
CDCl3): d 1.61 (3H, s, CH3), 1.65 (3H, s, CH3), 2.32 (2H, dm,
(200 MHz, CDCl3): d 1.74 (1H, dquin, JHH = 9.6 Hz, JHF
2.0 Hz, CHH), 1.85 (1H, ddquin, JHH = 1.6 Hz, JHH = 9.6 Hz,
HF = 2.2 Hz, CHH), 2.92 (1H, dd, JHH = 1.6 Hz, JHH = 5.2 Hz,
=
J
CHCN), 3.36 (1H, br.s, CH), 3.62 (1H, br.s, CH), 4.67 (1H,
ddquin, JHH = 2.6 Hz, JHH = 5.6 Hz, JHF = 5.8 Hz, CHSF5),
6.25 (1H, m, CH), 6.40 (1H, dd, JHH = 5.8 Hz, JHH = 3.2 Hz,
J
J
J
HH = 6.4 Hz, CH2), 2.64 (2H, m, CH2), 3.22 (1H, dt,
HH = 7.4 Hz, JHH = 7.0 Hz, CHCN), 4.49 (1H, dquin,
HH = 7.0 Hz, JHF = 6.0 Hz, CHSF5); 13C NMR (50.3 MHz,
CH); 13C NMR (50.3 MHz, CDCl3): d 34.37 (quin, JHF
=
3.5 Hz, CHCN), 46.86 (quin, JCF = 2.5 Hz, CH2), 47.60 (quin,
CDCl3): d 18.76 (s, CH3), 19.07 (s, CH3), 31.70 (quin,
CF = 1.5 Hz, CH2), 36.03 (quin, JCF = 6.0 Hz, CH2), 46.62
(quin, JCF = 2.5 Hz, CHCN), 86.67 (dquin, JCF = 0.6 Hz,
JCF = 10.6 Hz, CHSF5), 120.51 (s, CN), 123.09 (s, CH ),
J
J
CF = 2.5 Hz, CH), 47.74 (s, CH), 88.52 (dquin, Jcf = 0.5 Hz,
CF = 10.5 Hz, CHSF5), 120.4 (s, CN), 135.22 (s, CH ), 135.97
J
(s, CH ); 19F NMR (188.3 MHz, CDCl3): d 140.16 (4F, dm,
J
FF = 146.6 Hz), 160.72–163.72 (1F, 9 lines). Anal. Calcd. for
123.59 (s, CH ); 19F NMR (188.3 MHz, CDCl3): d 133.33 (4F,
dm, JFF = 143.0 Hz), 161.03–164.05 (1F, 9 lines). Anal. Calcd.
for C9H12F5NS (261.258): C, 41.38; H, 4.63; F, 36.36. Found:
C, 41.50; H, 4.64; F, 36.42.
C8H8F5NS (245.215): C, 39.19; H, 3.29; F, 38.74. Found: C,
39.32; H, 3.32; F, 38.57.
(exo-10) 0.43 g (17.6%) as a colorless oil. Rf = 0.59 (CHCl3/
1
C6H14 = 10:2). H NMR spectral data (200 MHz, CDCl3): d
1.88 (1H, dquin, JHH = 9.4 Hz, JHF = 2.0 Hz, CHH), 1.98 (1H,
dquin, JHH = 9.4 Hz, JHF = 2.0 Hz, CHH), 2.53 (1H, m,
CHCN), 3.43 (1H, br.s, CH), 3.71 (1H, br.s, CH), 3.89 (1H,
ddquin, JHH = 5.0 Hz, JHF = 6.0 Hz, CHSF5), 6.42 (1H, m,
CH), 6.51 (1H, dd, JHH = 5.6 Hz, JHH = 3.3 Hz, CH); 13C
NMR (50.3 MHz, CDCl3): d 35.07 (quin, JHF = 3.0 Hz,
3.11. 5-Carboxaldehyd-1,2-dimethyl-4-(pentafluoro-l6-
sulfanyl)-cyclohex-1-en (13) and 4,5-dimethyl-2-(2-
(pentafluoro-l6-sulfanyl)ethen-1-yl)-3,6-dihydro-2H-pyran
(14)
According to the procedure 3.7 for the synthesis of endo-9,
and exo-8, trans-3-(pentafluoro-l6-sulfanyl)prop-2-enal
4
(1.82 g, 0.01 mol) was allowed to react with 2,3-dimethylbu-
tadiene (8.2 g, 0.1 mol).
(13) Yield 1.53 g (58%). Rf = 0.79 (CHCl3). 1H NMR
spectral data (200 MHz, CDCl3): d 1.62 (3H, s, CH3), 1.66 (3H,
s, CH3), 2.35 (2H, d, JHH = 5.0 Hz, CH2), 2.45 (1H, dd,
CHCN), 48.74 (quin, JCF = 1.0 Hz, CH2), 49.0 (quin, JCF
2.4 Hz, CH), 49.14 (s, CH), 88.95 (dquin, JCF = 1.0 Hz,
CF = 9.8 Hz, CHSF5), 122.4 (s, CN), 135.67 (s, CH ), 136.05
(s, CH ); 19F NMR (188.3 MHz, CDCl3): d 138.51 (4F, dm,
FF = 148.0 Hz), 159.54–163.92 (1F, 9 lines). Anal. Calcd. for
=
J
J
C8H8F5NS (245.215): C, 39.19; H, 3.29; F, 38.74. Found: C,
39.36; H, 3.30; F, 38.51.
JHH = 17.5 Hz, JHH = 1.2 Hz, CHH), 2.63 (1H, dd, JHH
17.5 Hz, JHH = 2.0 Hz, CHH), 3.13 (1H, ddt, JHH = 1.8 Hz,
=
3.9. Methyl 1,2-dimethyl-4-(pentafluoro-l6-sulfanyl)-
cyclohex-1-en-5-carboxylate (11)
J
J
HH = 6.4 Hz, JHH = 6.6 Hz, CHCHO), 4.53 (1H, dquin,
HH = 6.4 Hz, JHF = 6.6 Hz, CHSF5), 9.54 (1H, m, CHO);
13C NMR (50.3 MHz, CDCl3): d 18.84 (s, CH3), 19.16 (s, CH3),
30.70 (quin, JCF = 1.5 Hz, CH2), 33.03 (quin, JCF = 6.0 Hz,
CH2), 49.62 (quin, JCF = 2.5 Hz, CHCHO), 81.87 (dquin,
According to the procedure for the synthesis of endo-8, and
exo-8, methyl 3-(pentafluoro-l6-sulfanyl)prop-2-enate (2.12 g,
0.01 mol) was allowed to react with 2,3-dimethylbutadiene
(8.2 g, 0.1 mol). Yield 11 1.91 g (65%) as a colorless oil.
Rf = 0.76 (CHCl3).
1H NMR spectral data (200 MHz, CDCl3): d 1.66 (6H, m,
2CH3), 2.36 (2H, dm, JHH = 6.4 Hz, CH2), 2.65 (2H, m, CH2),
3.26 (2H, dt, JHH = 7.4 Hz, JHH = 7.0 Hz, CHCOOCH3), 3.77
(3H, s, OCH3), 4.60 (1H, dquin, JHH = 6.8 Hz, JHF = 6.2 Hz,
CHSF5); 13C NMR (50.3 MHz, CDCl3): d 18.55 (s, CH3), 19.10
(s, CH3), 33.68 (quin, JCF = 4.5 Hz, CH2), 34.57 (quin,
J
CF = 0.6 Hz, JCF = 10.6 Hz, CHSF5), 123.11 (s, CH ), 123.60
(s, CH ), 199.77 (quin, JCF = 1.5 Hz, CHO); 19F NMR
(188.3 MHz, CDCl3): d 134.45 (4F, dm, JFF = 141.0 Hz),
162.03–165.05 (1F, 9 lines). Anal. Calcd. for C9H13F5OS
(264.258): C, 40.91; H, 4.96; F, 35.95. Found: C, 40.80; H,
4.88; F, 36.13.
(14) Yield 0.55 g (21%). Rf = 0.89 (CHCl3). 1H NMR
spectral data (200 MHz, CDCl3): d 1.56 (3H, s, CH3), 1.66 (3H,
s, CH3), 1.98 (1H, d, JHH = 16.0 Hz, CHH), 2.15 (1H, dd,
J
(s, OCH3), 84.07 (dquin, JCF = 0.8 Hz, JCF = 10.0 Hz, CHSF5),
CF = 1.5 Hz, CH2), 43.76 (quin, JCF = 3.0 Hz, CH2), 52.86
J
HH = 16.0 Hz, JHH = 10.8 Hz, CHH), 4.05 (2H, m, OCH2),
4.19 (1H, dddquin, JHH = 10.8 Hz, JHH = 3.8 Hz, JHH = 1.8 Hz,
JHF = 2.0 Hz, OCH), 6.56 (1H, m, ddquin, JHH = 14.6 Hz,
122.76 (s, CH ), 123.44 (s, CH ), 173.86 (s, C O); 19F NMR

V.K. Brel / Journal of Fluorine Chemistry 128 (2007) 862–867
867
JHH = 3.8 Hz, JHF = 1.0 Hz, CH), 6.75 (1H, m, ddquin, JHH
=
C7H9F5O3S (268.202): C, 31.35; H, 3.58; F, 35.42. Found: C,
31.48; H, 3.60; F, 35.50.
14.6 Hz, JHH = 1.8 Hz, Jm = 6.2 Hz, CHSF5); 13C NMR
(50.3 MHz, CDCl3): d 14.23 (s, CH3), 18.67 (s, CH3), 36.04
(s, CH2), 69.91 (s, OCH2), 71.67 (s, OCH), 123.04 (s, C),
124.96 (s, C), 138.47 (quin, JCF = 2.6 Hz, CH), 140.75
(dquin, JCF = 1.5 Hz, JCF = 20.0 Hz, CHSF5); 19F NMR
(188.3 MHz, CDCl3): d 141.03 (4F, dm, JFF = 148.5 Hz),
159.91–169.91 (1F, 9 lines). Anal. Calcd. for C9H13F5OS
(264.258): C, 40.91; H, 4.96; F, 35.95. Found: C, 40.74; H,
4.78; F, 36.10.
4. Conclusions
In conclusion, our results demonstrate a simple and efficient
synthesis of novel pentafluorosulfanyl-containing dienophiles
and their reaction with cyclic and aliphatic electron-releasing
dienes and with furane. Further application of this methodology
to the synthesis of potentially interesting pentafluorosulfany
derivatives as well as the exploration of their properties will be
reported.
3.12. 5-Methoxycarbonyl-6-(pentafluoro-l6-sulfanyl)-7-
oxabicyclo[2.2.1]hept-2-en (endo-15) and (exo-15)
Acknowledgements
According to the procedure for the synthesis of endo-8, and
exo-8, methyl 3-(pentafluoro-l6-sulfanyl)prop-2-enate (2.12 g,
0.01 mol) was allowed to react with furane (6.8 g, 0.1 mol).
(endo-15) 1.00 g (35.7%) as a colorless oil. Rf = 0.49
(CHCl3). H NMR spectral data (200 MHz, CDCl3): d 3.07–4
(1H, d, JHH = 4.6 Hz, CH), 3.86 (3H, s, CH3), 5.00 (1H, ddquin,
This work was supported by the European Office of
Aerospace Research and Development (EOARD #037004) and
the International Science and Technology Center (ISTC
2791p).
1
JHH = 4.4 Hz, JHH = 4.4 Hz, JHF = 7.0 Hz, CHSF5), 5.20 (1H,
dquin, JHH = 0.6 Hz, JHF = 1.0 Hz, CH), 5.37 (1H, JHH =
References
5.6 Hz, CH), 6.54 (1H, dd, JHH = 1.8 Hz, JHH = 5.8 Hz, CH ),
6.71 (1H, dd, JHH = 1.6 Hz, JHH = 5.8 Hz, CH ); 13C NMR
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CHCOOCH3), 53.30 (s, CH3), 83.34 (quin, JCF = 5.0 Hz,
OCH), 83.39 (s, OCH), 86.58 (dquin, JCF = 0.5 Hz, JCF
d
49.46 (quin, JCF = 3.0 Hz,
=
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FF = 144.8 Hz), 161.40–164.52 (1F, 9 lines). Anal. Calcd. for
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31.50; H, 3.62; F, 35.60.
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3.87 (1H, d, JHH = 4.5 Hz, CH), 4.26 (1H, dquin, JHH = 4.0 Hz,
JHF = 6.3 Hz, CHSF5), 5.30 (1H, d, JHH = 5.3 Hz, CH), 5.54
(1H, br.s, CH), 6.43 (1H, dd, JHH = 5.7 Hz, JHH = 0.7 Hz,
CH ), 6.51 (1H, dd, JHH = 5.7 Hz, JHH = 1.0 Hz, CH ); 13C
NMR (50.3 MHz, CDCl3): d 48.88 (quin, JCF = 3.5 Hz,
CHCOOCH3), 53.00 (s, CH3), 79.58 (quin, JCF = 4.0 Hz,
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OCH), 79.58 (s, OCH), 82.67 (dquin, JCF = 1.0 Hz, JCF
10.6 Hz, CHSF5), 135.58 (s, CH ), 135.68 (s, CH ), 171.28 (s,
C O); 19F NMR (188.3 MHz, CDCl3): d 142.42 (4F, dm,
=
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Practical Methods, John Wiley & Sons, Ltd, 2002, pp. 40–42.
J
FF = 146.6 Hz), 161.44–164.52 (1F, 9 lines). Anal. Calcd. for