Catalytic olefination reaction. Synthesis of fluorinated ethers and thioethers

Article abstract of DOI:10.1007/s11172-012-0187-2

Novel synthetic approaches involving catalytic olefination to access fluorinated propyl, allyl, and propargyl ethers and thioethers were developed.

Full text of DOI:10.1007/s11172-012-0187-2

Russian Chemical Bulletin, International Edition, Vol. 61, No. 7, pp. 1445—1455, July, 2012
1445
Catalytic olefination reaction.
Synthesis of fluorinated ethers and thioethers*
V. M. Muzalevskiy,a E. S. Balenkova,a A. V. Shastin,b A. G. Goldberg,a and V. G. Nenajdenkoa
aDepartment of Chemistry, M. V. Lomonosov Moscow State University,
1, Build. 3 Leninskie Gory, 119992 Moscow, Russian Federation.
Fax: +7 (495) 932 8846. Eꢀmail: nen@acylium.chem.msu.ru
bInstitute of Problems of Chemical Physics, Russian Academy of Sciences,
1 prosp. Akad. Semenova, 142432 Chernogolovka, Moscow Region, Russian Federation
Novel synthetic approaches involving catalytic olefination to access fluorinated propyl,
allyl, and propargyl ethers and thioethers were developed.
Key words: catalytic olefination, polyhaloalkanes, copper salts, fluorinated compounds,
thioethers, catalysis, elimination, mechanism.
Developing of the novel methods for the C—C bond
formation is the most essential target of the modern orꢀ
ganic chemistry. A few years ago, in our group, a novel
reaction serving for the C=C bond formation was found,
namely, the catalytic olefination reaction.1 This versatile
and general reaction, which can be regarded as copper salt
catalyzed reaction of polyhaloalkanes with Nꢀunsubstiꢀ
tuted carbonyl compounds 1 (the latter used in the form of
the corresponding hydrazones 2), opens access to a wide
variety of alkenes 3 (Scheme 1). The byproducts of these
transformations of hydrazones 2 are azines 4; the reaction
is accompanied by nitrogen evolution.
involved in the radical reaction and reacts readily with
nucleophiles. High reactivity of 1,2ꢀdibromotetrafluoroꢀ
ethane is probably caused by two relatively mobile bromꢀ
ine atoms in the molecule. Reaction of 1,2ꢀdibromoꢀ
tetrafluoroethane with hydrazones proceeded unexpectꢀ
edly to give saturated compounds 5 instead of alkenes.2
Nevertheless, alkenes 6 and alkynes 7 were synthesized by
treatment of alkanes 5 with bases (Scheme 2).
Scheme 2
Scheme 1
Reagents and conditions: i. N2H4; ii. BrCF2CF2Br, CuCl (10 mol.%);
iii. NaOH, EtOH; iv. ButOK, THF.
R = Ar, Alk, R´ = Alk, H
Hal = Cl, Br; X = F, Cl, Br, H
Y = F, Cl, Br, CN, CO2Et, CF3, CF2Cl, CF2Br
Nowadays, compounds with fluorinated bridge are the
extensively used components for liquid crystal comꢀ
positions.3—6
The aim of the present work is the synthesis of fluoriꢀ
nated ethers and sulfides, which are of great interest for
the design of novel liquid crystal compounds. We describe
here reactions of hydrazones with two novel sulfurꢀ (8)
and oxygenꢀcontaining (9) olefinating agents bearing tetraꢀ
1,2ꢀDibromotetrafluoroethane is inexpensive and afꢀ
fordable fluorinated building block, which can easily be
* Based on the Materials of the International Congress on Orꢀ
ganic Chemistry dedicated to the 150th anniversary of the
Butlerov´s Theory of Chemical Structure of Organic Compounds
(September 19—23, 2011, Kazan, Russia).
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 7, pp. 1430—1440, July, 2012.
1066ꢀ5285/12/6107ꢀ1445 © 2012 Springer Science+Business Media, Inc.

1446
Russ.Chem.Bull., Int.Ed., Vol. 61, No. 7, July, 2012
Muzalevskiy et al.
fluoroethane bridge, which were derived from 1,2ꢀdiꢀ
bromotetrafluoroethane. Reagents 8 and 9 were syntheꢀ
sized in high yields from 1,2ꢀdibromotetrafluoroethane by
nucleophilic replacement of the bromine atoms upon treatꢀ
ment with cresol and thiocresol, respectively, in the presꢀ
ence of bases (Scheme 3).
quantitative. We also performed reactions of other aroꢀ
matic aldehydes under particular conditions. Similarly to
4ꢀchlorobenzaldehyde, the reactions resulted in the mixꢀ
tures of alkanes 10 and alkenes 11 in the ratios from 2 : 1
to 1 : 1 (see Table 1). This reaction is general and serves
for transformations of aldehydes bearing both electronꢀ
withdrawing and electronꢀdonating substituents. The high
stereoselectivity of the reaction is of note. In the obtained
mixtures, the major isomer of alkene 11 is Zꢀisomer; in
the case of 4ꢀnitrobenzaldehyde 1g, the content of Zꢀisoꢀ
mer is 100%. The reactions involving fluorinated ether 9
provided also the mixtures of alkane 10 and alkene 11 in
approximately equal amounts, although the total yields
were slightly lower. Similarly to sulfurꢀcontaining derivaꢀ
tives, the reactions favored the formation of Zꢀisomers of
alkenes 11 and, in some cases, Zꢀisomer of 11 was the
only isomer formed.
Scheme 3
Configurations of isomers of alkenes 11 were evaluated
from spinꢀspin coupling constants between the fluorine
1
atom and the vinyl proton in the H NMR (3JH,F).7
3
The corresponding coupling constants JH,F for Zꢀ and
Eꢀisomers are 34.3—36.6 and 20.2—23.3 Hz, respectively
(Fig. 1).
Reagents and conditions: i. 4ꢀMeC6H4SH, NaOH, DMF,
–50—+25 C; ii. 4ꢀMeC6H4OH, Cs2CO3, DMSO, 50 C.
Reactions of hydrazones of aromatic aldehydes with
compound 8were performed under conditions used earlier for
the reactions of 1,2ꢀdibromotetrafluoroethane. 4ꢀChloroꢀ
benzaldehyde was used as a model substrate. 4ꢀChloroꢀ
benzaldehyde hydrazone 2a generated in situ was heated
with thioether 8 at 45—50 C in ethanol in the presence of
ethylenediamine and catalyst CuCl (10 mol.%) (Scheme 4).
It was found that under the described conditions, the reꢀ
action was completed within 5 h giving a mixture of alꢀ
kane 10a and isomers of alkene 11a in 45% overall yield
(Table 1). Symmetric azine of 4ꢀchlorobenzaldehyde 4a
(53%) was the only isolated byproduct; besides, the total
yield of alkane 10a, alkene 11a, and azine 4a was nearly
The mixtures of alkanes 10 and alkenes 11 were sucꢀ
cessfully separated by column chromatography. Alkanes
10 can easily be transformed into alkenes 11 by treatment
with NaOH. Thus, pure alkenes 11 (without concomitant
alkane 10) were obtained by addition of 5 M NaOH
(2.5 equiv.) to the reaction mixtures followed by reflux. It
should be noted that this synthetic approach to alkenes 11
gave reduced amounts of Eꢀisomers. We have previously
found2 that elimination of hydrogen fluoride from closely
related alkanes 5 proceeded stereoselectively affording exꢀ
clusively Zꢀisomers of alkenes 6. Apparently, in the case of
alkanes 10, elimination of HF also afforded only Zꢀisoꢀ
mers; therefore, treatment of the alkane—alkene mixtures

Catalytic olefination reaction
Russ.Chem.Bull., Int.Ed., Vol. 61, No. 7, July, 2012
1447
Scheme 4
Starting compounds
Products
Products
1, 2
a
b
c
d
e
f
g
Ar
10, 11
Ar
X
S
S
S
S
S
S
S
10, 11
h
i
Ar
X
4ꢀClC6H4
4ꢀBrC6H4
4ꢀEtC6H4
4ꢀBuOC6H4
4ꢀMeOC6H4
3ꢀNO2C6H4
4ꢀNO2C6H4
a
b
c
d
e
f
4ꢀClC6H4
4ꢀBrC6H4
4ꢀEtC6H4
4ꢀBuOC6H4
4ꢀMeOC6H4
3ꢀNO2C6H4
4ꢀNO2C6H4
4ꢀClC6H4
4ꢀBrC6H4
3ꢀNO2C6H4
4ꢀNO2C6H4
3ꢀMeOC6H4
O
O
O
O
O
j
k
l
g
Reagents and conditions: i. N2H4•H2O, EtOH, 20 C, 3—5 h; ii. 8 or 9, NH2(CH2)2NH2 (2.2 equiv.), CuCl (10 mol.%), 45—50 C, 5 h
(method A); iii. 1) ii; 2) 5 M NaOH (2.5 equiv.), reflux, 4—5 h (11a—c,e,f,h—l) or 40 C, 1 h (11g) (method B).
with NaOH increased amounts and contents of Zꢀisomers
and decreased contents of minor Eꢀisomers.
In the case of alkenes 11g and 11k bearing 4ꢀnitroꢀ
phenyl groups, replacement of the fluorine atom gave rise
to a mixture of Zꢀ and Eꢀisomers of fluorinated ethoxyalkꢀ
enes 12 and 13. Lowering the temperature to 40 C and
shortening the reaction time to 1 h allowed synthesis of
alkene 11g, however, in the case of oxygenꢀcontaining
derivative 10k, ethoxystyrene 13 was formed even under
these refined conditions (see Schemes 4, 5 and Table 1).
Configuration of the major isomer of ethoxystyrenes 12
and 13 were established from coupling constants between
the carbon atom of the difluoromethyl group and the vinyl
Table 1. Yields (%) of compounds 10 and 11 formed in the
reactions of aromatic aldehyde hydrazones with comꢀ
pounds 8 and 9
Products
Method Aa
Total yield Method Ba
10, 11
of 10 and 11
(Z/E)
Alkane 10
(Z/E)
Scheme 5
a
b
c
d
e
f
g
h
i
29
29
22
15
17
22
37
12
16 (95 : 5)
23 (92 : 8)
14 (90 : 10)
10 (91 : 9)
16 (90 : 10)
12 (94 : 6)
15 (100 : 0)
9 (97 : 3)
—b95
45
52
36
25
33
34
52
21
31 (97 : 3)
39 (96 : 4)
36 (95 : 5)
—b95
—c95
35 (97 : 3)
33 (99 : 1)
29
b
b
—
—
—
—
21 (100 : 0)
20 (100 : 0)
—d95
b
b
j
k
l
—b95
10
18
8 (88 : 12)
15 (93 : 7)
18
33
—b95
a See Experimental and Scheme 4.
b No reaction was performed.
c Trace amounts.
d Under reaction conditions, complete conversion of alkene 11k
into ethoxystyrene 13 was observed (see below).
R = 4ꢀMeC6H4
X = S (12), O (13)
Reagents and conditions: NaOH, EtOH, reflux.

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Muzalevskiy et al.
3
proton (3JH,C). The coupling constant JH,C values of
2.9 (12) and 4.4 Hz (13) unambiguously indicate Zꢀconfiꢀ
guration of 12 and 13 (see Scheme 5).8
In alternative olefination mechanism,10 the copper(I)
compounds serve for the generation of polyhaloalkyl radiꢀ
cals; addition of the latter to the multiple bond of hydrꢀ
azone 2 followed by several further transformations yields
diazene D (Scheme 7). Distraction of diazene D results in
the corresponding carbanions E, which eliminate the haꢀ
lide ion to give alkenes 3. Oxidation of hydrazones 2 and
subsequent dimerization of the formed diazoalkanes A proꢀ
vide azines 4 (see Scheme 7).
Despite the number of fundamental differences, these
two mechanisms are significantly similar involving the
C—Hal bond cleavage on the last stage of alkene 3 formaꢀ
tion. In the case of compounds 8 and 9, the cleavage of the
C—F bond is apparently more difficult and proceeds slower
in respect of "conventional olefination" because the C—F
bond is much stronger than other C—Hal bonds (the bindꢀ
ing energies are 115.7 (C—F), 77.2 (C—Cl), 64.3 (C—Br),
and 50.7 kcal mol–1 (C—I)).11 As a result, the competing
protonation of intermediates C or E to give alkanes 10 (the
reactions are performed in the protic media) becomes
noticeable (Scheme 8).
Despite the low yields, this approach is experimentally
simple, no inert atmosphere is required, there are no limiꢀ
tations on the functional groups, and the starting comꢀ
pounds are relatively cheap. It is of note that fluorinated
propyl (10h—l) and allyl (11h—l) ethers are poorly accesꢀ
sible class of compounds and fluorinated propyl (10a—g)
and allyl (11a—g) thioethers were not described to date.
The obtained data are very important from the fundaꢀ
mental viewpoint providing additional information about
reaction mechanism. Previously, we postulated possible
mechanisms of the catalytic olefination. The first mechaꢀ
nism9 involves initial oxidation of CuCl by polyhaloalkanes
to give CuII (Scheme 6). The formed CuII compounds
oxidize hydrazones 2 yielding diazoalkanes A. Subsequent
catalytic decomposition of diazoalkanes accompanied by
nitrogen evolution results in copperꢀcarbene complexes
B. Interaction of complex B with polyhaloalkanes lead to
saturated organocopper derivative C. Elimination of CuII
halide from derivative C furnishes alkene 3 and recovers
the CuII catalyst (see Scheme 6, inner cycle). Azines 4 are
the result of the catalytic dimerization of copperꢀcarbene
complex B with another molecule of diazoalkane A (see
Scheme 6, external cycle). The base is involved in comꢀ
plexation of copper compounds and binds the releasing
hydrogen halide.
We also studied synthetic potential of the novel comꢀ
pounds 10 and 11 for the synthesis of other fluorinated
compounds. Thus, oxidation of thioethers 10 and 11 to
sulfones were studied. The latter are interesting precursors
for polyfluorinated compounds due to the presence of
pꢀtolylsulfonyl group, which can be easily removed or reꢀ
placed by nucleophiles. Oxidation of compounds 10b,c,f
Scheme 6
L = NH3, Cl–

Catalytic olefination reaction
Russ.Chem.Bull., Int.Ed., Vol. 61, No. 7, July, 2012
1449
Scheme 7
Scheme 8
and 11b to sulfones by hydrogen peroxide in acetic acid
under reflux proceeded smoothly to give derivatives of tetꢀ
rafluoropropane 14 and trifluoropropene 15 in high yields
(Scheme 9).
Another important direction of our research is the study
of the fluorinated acetylenes bearing the CF2SR or CF2OR
groups. To date, these compounds are inaccessible and
poorly studied class of compounds. Several published
Scheme 9
R = 4ꢀMeC6H4
Ar = 4ꢀBrC6H4 (10b, 14a), 4ꢀEtC6H4 (10c, 14b), 3ꢀO2NC6H4 (10f, 14c)
Reagents and conditions: 30% H2O2, AcOH, reflux.

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Muzalevskiy et al.
plates; for visualization of the spots, acidified KMnO4 solution
and UV irradiation were used. Column chromatography was perꢀ
formed on a silica gel (63—200 mesh, Merck). Mass spectra
(ESI) were recorded on a Bruker microTOF II instrument. In
the NMR spectra of the minor Eꢀisomers, only characteristic
signals, nonꢀcoincided with the signals of major Zꢀisomer, are
methods for the synthesis of related acetylenes involved
either electrolytic fluorination,12,13 or twoꢀstep replaceꢀ
ment of the bromine atom of the bromodifluoromethyl
group upon treatment with thiolate or alkoxide via interꢀ
mediate bromodifluoroallene.14
Earlier, we successfully implemented the HF eliminaꢀ
tion from closely structurally related 3ꢀbromoꢀ2,2,3,3ꢀ
tetrafluoropropanes 5 by treatment with potassium tertꢀbuꢀ
tylate in THF (see Scheme 2). However, in the case of
alkanes 10, elimination of HF was more complicated reꢀ
sulting in hardly separable mixtures of alkene 11 and alkyne
16. Sodium hexamethyldisilazide was the reagent of choice
to solve this problem. Treatment of alkanes 10 with sodiꢀ
um hexamethyldisilazide (3 eqiuv.) at —80 C with subseꢀ
quent warming of the reaction mixture to room temperaꢀ
ture resulted in target alkynes 16 in high yields. It should
be noted that the reaction mixture contained no intermeꢀ
diate alkene, which significantly facilitated isolation and
purification of the product (Scheme 10).
1
given. The H NMR spectra of compounds 8 and 9 are in good
agreement with the published data.15
(2ꢀBromoꢀ1,1,2,2ꢀtetrafluoroethyl)(pꢀtolyl)sulfane (8). To
a cooled to 0 C suspension of NaH (28 g, 0.70 mol, 60% disperꢀ
sion in mineral oil) in anhydrous DMF (200 mL), a solution of
4ꢀmethylthiophenol (44.2 g, 0.36 mol) in DMF (100 mL) was
slowly added over a period of 45 min. The reaction mixture was
cooled to –50 C and 1,2ꢀdibromotetrafluoroethane (53 mL,
0.45 mol) was added over 1 h. The resulting mixture was stirred
mechanically at –50 C for 3 h and was warmed to room temꢀ
perature over 2 h. Excess NaH was quenched with water (400 mL)
at cooling (iceꢀwater). The organic phase was separated,
the aqueous layer was extracted with methylꢀtertꢀbutyl ether
(3×300 mL) and dried with CaCl2. The solvents were removed
in vacuo. Purification of the residue by column chromatography
(elution with hexane) afforded 83.4 g (76%) of sulfide 8, colorꢀ
less oil. Rf 0.6 (hexane). 1H NMR (CDCl3), : 2.42 (s, 3 H, CH3);
7.25 (d, 2 H, Ar, J = 8.1 Hz); 7.56 (d, 2 H, Ar, J = 8.1 Hz).
1ꢀ(2ꢀBromoꢀ1,1,2,2ꢀtetrafluoroethoxy)ꢀ4ꢀmethylbenzene
(9). A suspension of Cs2CO3 (32.6 g, 0.1 mol), 1,2ꢀdibromoꢀ
tetrafluoroethane (28.6 g, 0.11 mol) and pꢀcresol (10.8 g, 0.1 mol)
in DMSO (100 mL) was stirred at 50 C for 6 h, poured into
water (500 mL), the organic phase was separated, and the aqueꢀ
ous layer was extracted with methylꢀtertꢀbutyl ether (3×300 mL).
The combined organics were washed with water (300 mL) and
dried with CaCl2. The solvents were removed in vacuo. Purificaꢀ
tion of the residue by column chromatography afforded 18.9 g
Scheme 10
Compound
10a, 16a
10b, 16b
10c, 16c
10e, 16d
10g, 16e
Ar
4ꢀClC6H4
4ꢀBrC6H4
4ꢀEtC6H4
4ꢀMeOC6H4
4ꢀNO2C6H4
1
(60%) of compound 9, colorless oil. Rf 0.5 (hexane). H NMR
(CDCl3), : 2.43 (s, 3 H, CH3); 7.20 (d, 2 H, Ar, J = 7.9 Hz);
7.26 (d, 2 H, Ar, J = 7.9 Hz).
Olefination of aromatic aldehydes by sulfide 8 and ether 9
(general procedure). A. To hydrazine hydrate (1 M aqueous soluꢀ
tion, 1.05 mL, 1.05 mmol), a solution of the corresponding aroꢀ
matic aldehyde 1 (1 mmol) in EtOH (2 mL) was added with
stirring. After complete consumption of the starting aldehyde
(TLC monitoring), ethylenediamine (0.15 mL, 2.2 mmol) and
CuCl (10 mg, 0.2 mmol) were added in this order, the mixture
was stirred for 5 min, and then sulfide 8 or ether 9 (1.1 mmol)
was added at room temperature. The mixture was stirred at
45—50 C for 3—5 h until completion of the reaction (TLC monꢀ
itoring). The mixture was poured into 0.1 M HCl (50 mL) and
extracted with dichloromethane (3×30 mL). The combined orꢀ
ganics were washed with water (50 mL) and dried with Na2SO4.
The solvents were removed in vacuo, purification of the residue
by column chromatography (elution with hexane or apropriate
hexane—dichloromethane mixtures) afforded target product.
B. In the case of oneꢀpot synthesis of alkenes 11, after comꢀ
pletion of the reaction with sulfide 8 or ether 9, 5 M NaOH
(0.5 mL, 2.5 mmol) was added and the reaction mixture was
refluxed for 4—5 h (TLC monitoring).
–
Reagents and conditions: NaNTMS2, THF, 80—+20 C (16a—d)
or 80— 60 C (16e).
–
–
In summary, in the present work, we studied olefinaꢀ
tion of aromatic aldehyde hydrazones by derivatives of
1ꢀbromoꢀ1,1,2,2ꢀtetrafluoroethane, e.g., 4ꢀMeC6H4Sꢀ
CF2CF2Br and 4ꢀMeC6H4OCF2CF2Br, and developed
novel approaches towards fluorinated derivatives of proꢀ
pyl, allyl, and propargyl ethers and thioethers, which are
promising compounds for the design of the new materials
with liquid crystal properties.
Experimental
1
H and 13C were run on a Bruker AMX 400 spectrometer
(working frequencies of 400.1 and 100.6 MHz, respectively) in
CDCl3, acetoneꢀd6, and DMSOꢀd6 with Me4Si as internal stanꢀ
dard. 19F NMR spectra were recorded on Bruker AM 300 and
Bruker AM 200 spectrometers (working frequencies of 282.4 and
188 MHz, respectively). IR spectra were recorded on Carl Zeiss
URꢀ20 and IR 200 spectrophotometers in neat (for liquids) and
in Nujol (for solids). TLC was performed on SiluFol UVꢀ254
Yields and synthetic procedures used for the synthesis of
compounds 10 and 11 are given in Table 1.
[3ꢀ(4ꢀChlorophenyl)ꢀ1,1,2,2ꢀtetrafluoropropyl](pꢀtolyl)sulfꢀ
ane (10a). White crystals, m.p. 84.5—85.4 C. 1H NMR (CDCl3),
: 2.41 (s, 3 H, CH3); 3.35 (t, 2 H, CH2CF2, J = 18.3 Hz); 7.23

Catalytic olefination reaction
Russ.Chem.Bull., Int.Ed., Vol. 61, No. 7, July, 2012
1451
(d, 2 H, 4ꢀMeC6H4, J = 8.1 Hz); 7.25 (d, 2 H, 4ꢀClC6H4,
J = 8.3 Hz); 7.34 (d, 2 H, 4ꢀClC6H4, J = 8.3 Hz); 7.55 (d, 2 H,
4ꢀMeC6H4, J = 8.1 Hz). 19F NMR (282 MHz, CDCl3), : –88.03
(t, CF2S, J = 3.3 Hz); –110.68 (tt, CF2CH2, JH,F = 18.3 Hz,
J = 3.3 Hz). 13C NMR (CDCl3), : 21.36, 36.78 (t, CH2CF2,
Found (%): C, 59.21; H, 4.65. C17H16F4OS. Calculated (%):
C, 59.29; H, 4.68.
[1,1,2,2ꢀTetrafluoropropylꢀ3ꢀ(3ꢀnitrophenyl)](pꢀtolyl)sulfane
(10f). White crystals, m.p. 72.2—73.8 C. Rf 0.6 (hexane—CH2Cl2,
2 : 1). IR, /cm–1: 1356, 1525 (NO2). 1H NMR (CDCl3),
: 2.42 (s, 3 H, CH3); 3.50 (t, 2 H, CH2CF2, J = 17.9 Hz); 7.25
(d, 2 H, 4ꢀCH3C6H4, J = 7.8 Hz); 7.52—7.59 (m, 3 H, Ar); 7.66
(d, 1 H, 3ꢀNO2C6H4, J = 7.6 Hz); 8.20—8.24 (m, 2 H,
3ꢀNO2C6H4). 19F NMR (188 MHz, CDCl3), : –88.35 (t, CF2S,
J = 3.4 Hz); –111.46 (tt, CF2CH2, JH,F = 18.1 Hz, J = 3.4 Hz).
13C NMR (CDCl3), : 21.36, 37.08 (t, CH2CF2, 2JC,F = 22.7 Hz);
1
2
2JC,F = 22.7 Hz); 117.50 (tt, CF2, JC,F = 253.2 Hz, JC,F
=
=
1
2
= 32.9 Hz); 120.30, 124.47 (tt, CF2, JC,F = 287.6 Hz, JC,F
= 35.9 Hz); 128.70, 128.86, 130.12, 132.17, 133.98, 137.19,
141.10. Found (%): C, 54.77; H, 3.96. C16H13ClF4S. Calculatꢀ
ed (%): C, 55.10; H, 3.76.
[3ꢀ(4ꢀBromophenyl)ꢀ1,1,2,2ꢀtetrafluoropropyl](pꢀtolyl)sulfꢀ
ane (10b). White crystals, m.p. 89.2—91.2 C. 1H NMR (CDCl3),
: 2.41 (s, 3 H, CH3); 3.34 (t, 2 H, CH2CF2, J = 18.3 Hz); 7.19
(d, 2 H, 4ꢀBrC6H4, J = 8.3 Hz); 7.24 (d, 2 H, 4ꢀMeC6H4,
J = 8.1 Hz); 7.50 (d, 2 H, 4ꢀBrC6H4, J = 8.3 Hz); 7.56 (d, 2 H,
4ꢀMeC6H4, J = 8.1 Hz). 19F NMR (282 MHz, CDCl3), : –88.03
(t, CF2S, J = 3.4 Hz); –110.65 (tt, CF2CH2, JH,F = 18.3 Hz,
J = 3.4 Hz). 13C NMR (CDCl3), : 21.28, 36.74 (t, CH2CF2,
1
2
117.32 (tt, CF2, JC,F = 254.7 Hz, JC,F = 32.9 Hz); 120.00,
1
2
123.05, 124.26 (tt, CF2, JC,F = 287.6 Hz, JC,F = 35.9 Hz);
125.75, 129.48, 130.16, 132.40, 136.93, 137.17, 141.24, 148.29.
Found (%): C, 53.50; H, 3.71. C16H13F4NO2S. Calculated (%):
C, 53.48; H, 3.65.
[1,1,2,2ꢀTetrafluoropropylꢀ3ꢀ(4ꢀnitrophenyl)](pꢀtolyl)sulfane
(10g). Yellow crystals, m.p. 78.5—79.7 C. Rf 0.4 (hexꢀ
ane—CH2Cl2, 2 : 1). IR /cm–1: 1390 (NO2), 1530 (NO2).
1H NMR (CDCl3), : 2.41 (s, 3 H, CH3); 3.49 (t, 2 H, CH2CF2,
J = 17.9 Hz); 7.07 (d, 2 H, 4ꢀCH3C6H4, J = 8.3 Hz); 7.17
(d, 2 H, 4ꢀCH3C6H4, J = 8.3 Hz); 7.53 (d, 2 H, 4ꢀNO2C6H4,
J = 8.6 Hz); 8.22 (d, 2 H, 4ꢀNO2C6H4, J = 8.6 Hz). 19F NMR
(282 MHz, CDCl3), : –88.42 (t, CF2S, J = 3.4 Hz); –111.52
(tt, CF2CH2, JH,F = 18.1 Hz, J = 3.4 Hz). 13C NMR (CDCl3), :
1
2
2JC,F = 22.7 Hz); 117.32 (tt, CF2, JC,F = 251.8 Hz, JC,F
=
1
= 32.9 Hz); 120.16, 122.03, 124.35 (tt, CF2, JC,F = 288.4,
2JC,F = 36.6); 129.27, 130.03, 131.56, 132.42, 137.09, 141.01.
Found (%): C, 48.81; H, 3.24. C16H13BrF4S. Calculated (%):
C, 48.87; H, 3.33.
[3ꢀ(4ꢀEthylphenyl)ꢀ1,1,2,2ꢀtetrafluoropropyl](pꢀtolyl)sulfane
(10c). White crystals, m.p. 69.3—70.5 C. 1H NMR (CDCl3),
: 1.28 (t, 3 H, CH3CH2, J = 7.6 Hz); 2.42 (s, 3 H, CH3); 2.69
(q, 2 H, CH2CH3, J = 7.6 Hz); 3.36 (t, 2 H, CH2CF2, J = 18.7 Hz);
7.21—7.27 (m, 6 H, Ar); 7.58 (d, 2 H, 4ꢀMeC6H4, J = 7.8 Hz).
19F NMR (188 MHz, CDCl3), : –88.67 (t, CF2S, J = 2.9 Hz);
2
21.31, 37.18 (t, CH2CF2, JC,F = 22.7 Hz); 117.35 (tt, CF2,
2
1
1JC,F = 252.1 Hz, JC,F = 34.3 Hz); 124.41 (tt, CF2, JC,F
=
2
= 276.4 Hz, JC,F = 32.9 Hz); 123.56, 123.88, 130.09, 131.72,
137.10, 137.77, 141.18, 147.73. MS (ESI), m/z: found 382.0479
[M + Na]+; calculated for C16H13F4NNaO2S+, [M + Na]+,
382.0495.
–111.37 (tt, CF2CH2, JH,F = 18.2 Hz, J = 2.9 Hz). 13C NMR
2
(CDCl3), : 15.41, 21.28, 28.47, 36.87 (t, CH2CF2, JC,F
=
= 22.7 Hz); 117.66 (tt, CF2, 1JC,F = 253.2 Hz, 2JC,F = 32.9 Hz);
[3ꢀ(4ꢀChlorophenyl)ꢀ1,1,2ꢀtrifluoroallyl](pꢀtolyl)sulfane (11a).
Mixture of Z/Eꢀisomers in a 97 : 3 ratio. White crystals, m.p.
72.8—73.6 C. Rf 0.7 (hexane). IR, /cm–1: 1593, 1691 (C=C).
Found (%): C, 58.54; H, 3.69. C16H12ClF3S. Calculated (%):
C, 58.45; H, 3.68.
1
2
120.46, 124.51 (tt, CF2, JC,F = 286.9 Hz, JC,F = 35.9 Hz);
127.43, 127.91, 129.48, 129.98, 131.11, 140.88, 143.76. Found (%):
C, 63.12; H, 5.28. C18H18F4S. Calculated (%): C, 63.14; H, 5.30.
[3ꢀ(4ꢀButoxyphenyl)ꢀ1,1,2,2ꢀtetrafluoropropyl](pꢀtolyl)sulfꢀ
ane (10d). White crystals, m.p. 59.6—60.7 C. Rf 0.8 (hexane—
CH2Cl2, 2 : 1). 1H NMR (CDCl3), : 1.00 (t, 3 H, CH3CH2,
J = 7.2 Hz); 1.52 (m, 2 H, CH2); 1.79 (m, 2 H, CH2); 2.41
(s, 3 H, CH3); 3.31 (t, 2 H, CH2CF2, J = 18.70 Hz); 3.98 (t, 2 H,
CH2O, J = 6.3 Hz); 6.89 (d, 2 H, 4ꢀ(BuO)C6H4, J = 8.1 Hz);
7.16—7.31 (m, 4 H, Ar); 7.56 (d, 2 H, 4ꢀMeC6H4, J = 7.6 Hz).
19F NMR (282 MHz, CDCl3), : –88.62 (t, CF2S, J = 3.3 Hz);
–111.75 (tt, CF2CH2, JH,F = 18.1 Hz, J = 3.5 Hz). 13C NMR
(CDCl3), : 13.89, 19.29, 21.35, 31.36, 36.52 (t, CH2CF2,
2JC,F = 22.7 Hz); 67.68 (s, CH2O); 114.46, 117.69 (tt, CF2,
ZꢀIsomer. 1H NMR (CDCl3), : 2.38 (s, 3 H, CH3); 5.98
(d, 1 H, CH=CF, J = 35.7 Hz); 7.19 (d, 2 H, 4ꢀClC6H4,
J = 8.0 Hz); 7.35 (d, 2 H, 4ꢀMeC6H4, J = 8.6 Hz); 7.41 (d, 2 H,
4ꢀMeC6H4, J = 8.6 Hz); 7.52 (d, 2 H, 4ꢀClC6H4, J = 8.0 Hz).
19F NMR (282 MHz, CDCl3), : –81.01 (d, CF2S, J = 18.8 Hz);
–123.29 (dt, CF=CH, JH,F = 35.7 Hz, J = 18.8 Hz). 13C NMR
(CDCl3), : 21.28, 109.26 (d, CH=CF, 2JC,F = 3.66 Hz); 122.29,
125.50 (td, CF2CF, 1JC,F = 278.1 Hz, 2JC,F = 38.1 Hz); 128.90,
4
129.99, 130.56 (d, JC,F = 7.3 Hz); 134.71 (d, JC,F = 2.9 Hz);
1
136.74, 136.97, 140.90, 149.29 (dt, CFCF2, JC,F = 267.9 Hz,
2
1JC,F = 252.5 Hz, JC,F = 32.9 Hz); 120.51, 121.99, 124.58 (tt,
2JC,F = 30.7 Hz).
CF2, 1JC,F = 286.9 Hz, 2JC,F = 35.9 Hz); 130.04, 131.85, 134.92,
137.17, 140.96, 158.88. Found (%): C, 62.20; H, 5.70. C20H22F4OS.
Calculated (%): C, 62.16; H, 5.74.
EꢀIsomer. 1H NMR (CDCl3), : 6.55 (d, 1 H, CH=CF,
J = 20.3 Hz); 6.98 (d, 2 H, Ar, J = 8.3 Hz); 7.24 (d, 2 H, Ar,
J = 8.3 Hz). 19F NMR (282 MHz, CDCl3), : –76.77 (d, CF2S,
J = 20.3 Hz).
[3ꢀ(4ꢀBromophenyl)ꢀ1,1,2ꢀtrifluoroallyl](pꢀtolyl)sulfane (11b).
Mixture of Z/Eꢀisomers in a 96 : 4 ratio. White crystals, m.p.
73.6—74.8 C. Rf 0.7 (hexane). IR, /cm–1: 1587, 1691 (C=C).
Found (%): C, 52.09; H, 3.54. C16H12BrF3S. Calculated (%):
C, 51.49; H, 3.24.
ZꢀIsomer. 1H NMR (CDCl3), : 2.37 (s, 3 H, CH3); 5.97
(d, 1 H, CH=CF, J = 35.4 Hz); 7.19 (d, 2 H, Ar, J = 8.4 Hz);
7.33 (d, 2 H, Ar, J = 8.3 Hz); 7.50 (d, 2 H, Ar, J = 8.4 Hz); 7.53
(d, 2 H, Ar, J = 8.3 Hz). 19F NMR (282 MHz, CDCl3), : –81.15
(d, CF2S, J = 19.4 Hz); –122.95 (dt, CF=CH, JH,F = 35.4 Hz,
[3ꢀ(4ꢀMethoxyphenyl)ꢀ1,1,2,2ꢀtetrafluoropropyl](pꢀtolyl)ꢀ
sulfane (10e). White crystals, m.p. 54.3—56.1 C. 1H NMR
(CDCl3), : 2.41 (s, 3 H, CH3); 3.32 (t, 2 H, CH2CF2, J = 18.4 Hz);
3.83 (s, 3 H, CH3O); 6.90 (d, 2 H, 4ꢀCH3OC6H4, J = 7.5 Hz);
7.21—7.24 (m, 4 H, Ar); 7.55 (d, 2 H, 4ꢀCH3C6H4, J = 7.1 Hz).
19F NMR (188 MHz, CDCl3), : –88.61 (t, CF2S, J = 3.5 Hz);
–111.50 (tt, CF2CH2, JH,F = 18.4 Hz, J = 3.5 Hz). 13C NMR
2
(CDCl3), : 21.14, 36.40 (t, CH2CF2, JC,F = 23.6 Hz); 54.99
1
2
(s, CH2O); 113.79, 117.64 (tt, CF2, JC,F = 252.0 Hz, JC,F
=
1
= 32.9 Hz); 120.34, 122.10, 124.53 (tt, CF2, JC,F = 288.3 Hz,
2JC,F = 36.3 Hz); 129.96, 131.79, 137.05, 140.89, 159.21.

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Muzalevskiy et al.
J = 19.4 Hz). 13C NMR (CDCl3), : 21.22, 109.30, 122.25,
122.76 (td, CF2CF, 1JC,F = 278.2 Hz, 2JC,F = 38.8 Hz); 123.07,
129.97, 130.75 (d, JC,F = 6.8 Hz); 131.82, 132.39, 136.70, 140.85,
149.36 (dt, CFCF2, 1JC,F = 267.3 Hz, 2JC,F = 30.4 Hz).
EꢀIsomer. 1H NMR (CDCl3), : 6.53 (d, 1 H, CH=CF,
J = 21.5 Hz). 19F NMR (282 MHz, CDCl3), : –76.87 (d, CF2S,
J = 19.1 Hz); –115.38 (dt, CF=CH, J = 21.2 Hz, J = 19.1 Hz).
[3ꢀ(4ꢀEthylphenyl)ꢀ1,1,2ꢀtrifluoroallyl](pꢀtolyl)sulfane (11c).
Mixture of Z/Eꢀisomers in a 95 : 5 ratio. White crystals, m.p.
43.3—44.5 C. Rf 0.7 (hexane). IR, /cm–1: 1597, 1691 (C=C).
Found (%): C, 66.82; H, 5.11. C18H17F3S. Calculated (%):
C, 67.06; H, 5.32.
ZꢀIsomer. 1H NMR (CDCl3), : 1.31 (t, 3 H, CH3, J = 7.6 Hz);
2.41 (s, 3 H, CH3); 2.72 (q, 2 H, CH2CH3, J = 7.6 Hz); 6.08
(d, 1 H, CH=CF, J = 36.3 Hz); 7.18 (d, 2 H, Ar, J = 8.2 Hz);
7.21 (d, 2 H, Ar, J = 8.2 Hz); 7.41 (d, 2 H, Ar, J = 8.2 Hz); 7.53
(d, 2 H, Ar, J = 8.2 Hz). 19F NMR (188 MHz, CDCl3), : –80.25
(d, CF2S, J = 19.0 Hz); –125.18 (dt, CFCH, JH,F = 36.2 Hz,
J = 18.9 Hz). 13C NMR (CDCl3), : 15.28, 21.19, 28.64, 110.34,
122.50, 122.94 (td, CF2CF, 1JC,F = 277.4 Hz, 2JC,F = 37.9 Hz);
128.14, 129.42 (d, JC,F = 7.6 Hz); 129.93, 136.68, 137.08, 140.70,
145.27, 148.46 (dt, CFCF2, 1JC,F = 265.6 Hz, 2JC,F = 31.2 Hz).
EꢀIsomer. 1H NMR (CDCl3), : 6.59 (d, 1 H, CHCF,
J = 22.6 Hz); 7.10 (d, 2 H, Ar, J = 8.08 Hz). 19F NMR (188
MHz, CDCl3), : –76.31 (d, CF2S, J = 19.1 Hz); –117.13 (dt,
CF=CH, J = 22.6 Hz, J = 19.1 Hz).
EꢀIsomer. 1H NMR (CDCl3), : 6.56 (d, 1 H, CH=CF,
J = 23.3 Hz); 6.81 (d, 2 H, 4ꢀCH3OC6H4, J = 8.6 Hz); 7.07
(d, 2 H, Ar, J = 8.6 Hz). 19F NMR (282 MHz, CDCl3), : –76.29
(d, CF2S, J = 17.0 Hz); –117.92 (dt, CF=CH, J = 23.3 Hz,
J = 17.0 Hz).
pꢀTolyl[1,1,2ꢀtrifluoroꢀ3ꢀ(3ꢀnitrophenyl)allyl]sulfane (11f).
Mixture of Z/Eꢀisomers in a 97 : 3 ratio. Colorless cyrstals, m.p.
64—65 C. Rf 0.4 (hexane—CH2Cl2, 3 : 1). IR, /cm–1: 1352
(NO2), 1533 (NO2), 1691 (C=C). Found (%): C, 56.78; H, 3.64;
N, 4.19. C16H12F3NO2S. Calculated (%): C, 56.63; H, 3.56; N, 4.13.
ZꢀIsomer. 1H NMR (CDCl3), : 2.36 (s, 3 H, CH3); 6.05
(d, 1 H, CH=CF, J = 35.2 Hz); 7.19 (d, 2 H, 4ꢀCH3C6H4,
J = 8.0 Hz); 7.51 (d, 2 H, 4ꢀCH3C6H4, J = 8.0 Hz); 7.57 (t, 1 H,
3ꢀNO2C6H4, J = 8.1 Hz); 7.78 (d, 1 H, 3ꢀNO2C6H4, J = 8.1 Hz);
8.18 (ddd, 1 H, 3ꢀNO2C6H4, J = 8.1 Hz, J = 1.9 Hz, J = 0.8 Hz);
8.27 (dd, 1 H, 3ꢀNO2C6H4, J = 1.9 Hz, J = 1.8 Hz). 19F NMR
(282 MHz, CDCl3), : –81.67 (d, CF2S, J = 19.1 Hz); –120.32
(dt, CF=CH, JH,F = 35.2 Hz, J = 19.1 Hz). 13C NMR (CDCl3),
: 20.91, 107.96 (m), 121.69 (d, JC,F = 2.2 Hz); 122.19
(td, CF2CF, 1JC,F = 277.9 Hz, 2JC,F = 37.6 Hz); 123.04, 123.54
(d, JC,F = 7.4 Hz); 129.32, 129.71, 131.83 (d, JC,F = 3.0 Hz);
134.44 (d, JC,F = 7.4 Hz); 136.39, 140.78, 148.01, 150.42
(dt, CFCF2, 1JC,F = 271.3 Hz, 2JC,F = 31.7 Hz).
EꢀIsomer. 1H NMR (CDCl3), : 6.59 (d, 1 H, CH=CF,
J = 20.9 Hz). 19F NMR (282 MHz, CDCl3), : –77.73 (d, CF2S,
J = 19.1 Hz); –113.36 (dt, CF=CH, JH,F = 20.9 Hz, J = 19.1 Hz).
pꢀTolyl[1,1,2ꢀtrifluoroꢀ3ꢀ(4ꢀnitrophenyl)allyl]sulfane (11g).
Mixture of Z/Eꢀisomers in a 99 : 1 ratio. Yellow crystals, m.p.
[3ꢀ(4ꢀButoxyphenyl)ꢀ1,1,2ꢀtrifluoroallyl](pꢀtolyl)sulfane (11d).
Mixture of Z/Eꢀisomers in a 91 : 9 ratio. White crystals, m.p.
110.4—111.3 C. Rf 0.4 (hexane—CH2Cl2, 2 : 1). MS (ESI),
m/z: found 389.1154 [M + Na]+; calculated for C20H21F3NaOS+,
[M + Na]+, 389.1157.
139.5—141.7 C. Rf 0.4 (hexane—CH2Cl2, 2 : 1). IR, /cm–1
:
1348 (NO2), 1520 (NO2), 1603, 1686 (C=C). MS (ESI), m/z:
found 362.0433 [M + Na]+; calculated for C16H12F3NNaO2S+,
[M + Na]+, 362.0433.
ZꢀIsomer. 1H NMR (CDCl3), : 1.00 (t, 3 H, CH3CH2,
J = 7.6 Hz); 1.52 (m, 2 H, CH3CH2CH2); 1.79 (m, 2 H,
CH3CH2CH2); 2.38 (s, 3 H, CH3); 3.99 (t, 2 H, CH2O,
J = 6.4 Hz); 5.99 (d, 1 H, CH=CF, J = 36.8 Hz); 6.89 (d, 2 H,
Ar, J = 8.3 Hz); 7.19 (d, 2 H, Ar, J = 9.1 Hz); 7.43 (d, 2 H, Ar,
J = 9.1 Hz); 7.53 (d, 2 H, Ar, J = 8.3 Hz). 19F NMR (188 MHz,
CDCl3), : –80.16 (d, CF2S, J = 19.8 Hz); –127.35 (dt, CF=CH,
JH,F = 36.8 Hz, J = 19.8 Hz). 13C NMR (CDCl3), : 13.80,
19.21, 21.16, 31.22, 67.63, 110.17, 114.63, 121.98, 122.98, 123.34
(td, CF2CF, 1JC,F = 276.2 Hz, 2JC,F = 38.8 Hz); 129.94, 130.83,
136.64 (d, JC,F = 10.1 Hz); 140.68 (d, JC,F = 11.8 Hz); 147.64
(dt, CFCF2, 1JC,F = 264.7 Hz, 2JC,F = 31.2 Hz); 159.66.
EꢀIsomer. 1H NMR (CDCl3), : 6.57 (d, 1 H, CH=CF,
J = 22.7 Hz). 19F NMR (188 NHz, CDCl3), : –76.24 (d, CF2S,
J = 18.1 Hz); –118.12 (dt, CF=CH, J = 22.7 Hz, J = 18.1 Hz).
pꢀTolyl[1,1,2ꢀtrifluoroꢀ3ꢀ(4ꢀmethoxyphenyl)allyl]sulfane (11e).
Mixture of Z/Eꢀisomers in a 90 : 10 ratio. White crystals, m.p.
140.1—141.5 C. Rf 0.3 (hexane—CH2Cl2, 2 : 1). MS (ESI),
m/z: found 347.0689 [M + Na]+; calculated for C17H15F3NaOS+,
[M + Na]+, 347.0688.
ZꢀIsomer. 1H NMR (CDCl3), : 2.36 (s, 3 H, CH3); 6.07
(d, 1 H, CH=CF, J = 34.6 Hz); 7.18 (d, 2 H, 4ꢀCH3C6H4,
J = 8.0 Hz); 7.51 (d, 2 H, 4ꢀCH3C6H4, J = 8.0 Hz); 7.60 (d, 2 H,
4ꢀNO2C6H4, J = 8.9 Hz); 8.22 (d, 2 H, 4ꢀNO2C6H4, J = 8.9 Hz).
19F NMR (282 MHz, CDCl3), : –81.80 (d, CF2S, J = 17.0 Hz);
–118.79 (dt, CF=CH, JH,F = 34.5 Hz, J = 17.0 Hz). 13C NMR
(acetoneꢀd6), : 21.78, 110.44 (d, JC,F = 3.7 Hz); 123.12, 124.21
(td, CF2=CF, 1JC,F = 276.8 Hz, 2JC,F = 38.3 Hz); 131.55, 131.66,
131.74, 137.98, 138.19 (d, JC,F = 3.8 Hz); 142.76, 149.00 (d, JC,F
=
= 3.0 Hz); 151.88 (dt, CF=CF2, 1JC,F = 270.9 Hz, 2JC,F = 32.1 Hz).
EꢀIsomer. 1H NMR (CDCl3), : 2.40 (s, 3 H, CH3); 6.59
(d, 1 H, CH=CF, J = 21.6 Hz); 7.15 (d, 2 H, 4ꢀMeC6H4,
J = 8.6 Hz); 7.49 (d, 2 H, 4ꢀNO2C6H4, J = 8.6 Hz); 8.11 (d, 2 H,
4ꢀNO2C6H4, J = 8.6 Hz). 19F NMR (282 MHz, CDCl3),
: –77.33 (d, CF2S, J = 19.0 Hz).
Mixture of 1ꢀchloroꢀ4ꢀ[2,2,3,3ꢀtetrafluoroꢀ3ꢀ(pꢀtolyloxy)ꢀ
propyl]benzene (10h) and 1ꢀchloroꢀ4ꢀ[2,3,3ꢀtrifluoroꢀ3ꢀ(pꢀtolylꢀ
oxy)ꢀ1ꢀpropenyl]benzene (11h). Heavy oil.
Compound 10h. 1H NMR (CDCl3), : 2.38 (s, 3 H, CH3);
3.44 (t, 2 H, CH2CF2, J = 18.2 Hz); 7.12 (d, 2 H, Ar, J = 8.5 Hz);
7.25 (d, 2 H, Ar, J = 8.5 Hz); 7.31 (d, 2 H, Ar, J = 8.33 Hz); 7.37
(d, 2 H, Ar, J = 8.33 Hz). 19F NMR (282 MHz, CDCl3),
: –88.08 (s, CF2O); –117.28 (t, CF2, J = 18.0 Hz). 13C NMR
(CDCl3), : 20.71, 36.84 (t, CH2CF2, 2JC,F = 22.5 Hz); 115.49 (tt,
CF2, 1JC,F = 252.8 Hz, 2JC,F = 35.8 Hz); 117.67 (tt, CF2CF2O,
ZꢀIsomer. 1H NMR (CDCl3), : 2.39 (s, 3 H, CH3); 3.82
(s, 3 H, CH3O); 5.99 (d, 1 H, CH=CF, J = 36.6 Hz); 6.89 (d, 2 H,
4ꢀCH3OC6H4, J = 8.6 Hz); 7.22 (d, 2 H, Ar, J = 8.6 Hz); 7.43
(d, 2 H, Ar, J = 8.6 Hz); 7.54 (d, 2 H, Ar, J = 8.6 Hz). 19F NMR
(282 MHz, CDCl3), : –80.24 (d, CF2S, J = 19.1 Hz);
–127.13 (dt, CF=CH, JH,F = 36.6 Hz, J = 19.1 Hz). 13C NMR
(DMSOꢀd6), : 20.4, 55.03, 114.38, 129.71, 132.29, 132.36,
121.66 (td, CF2=CF, 1JC,F = 271.5 Hz, 2JC,F = 38.9 Hz); 134.34,
2
1JC,F = 274.6 Hz, JC,F = 33.0 Hz); 121.51, 128.64, 128.96,
130.09, 133.93, 134.14, 136.26, 146.74.
Compound 11h. MS (ESI), m/z: found 313.0543 [M + H]+;
calculated for C16H12ClF3OH+ [M + H]+, 313.0602.
1
2
136.35, 139.46, 166.48 (dt, CFCF2, JC,F = 266.4 Hz, JC,F
=
= 32.9 Hz), 160.77.

Catalytic olefination reaction
Russ.Chem.Bull., Int.Ed., Vol. 61, No. 7, July, 2012
1453
Zꢀisomer. 1H NMR (CDCl3), : 2.36 (s, 3 H, CH3); 6.37
(d, 1 H, CH=CF, J = 35.8 Hz); 7.14 (d, 2 H, 4ꢀClC6H4,
J = 8.7 Hz); 7.18 (d, 2 H, 4ꢀClC6H4, J = 8.7 Hz); 7.37 (d, 2 H,
4ꢀMeC6H4, J = 8.6 Hz); 7.52 (d, 2 H, 4ꢀMeC6H4, J = 8.6 Hz).
19F NMR (282 MHz, CDCl3), : –74.70 (d, CF2O, J = 12.7 Hz);
–128.64 (dt, CF=CH, JH,F = 36.0 Hz, J = 12.7 Hz). 13C NMR
MS (ESI), m/z: found 346.0666 [M + Na]+; calculated for
C16H12F3NNaO3+, [M + Na]+, 346.0661.
ZꢀIsomer. 1H NMR (CDCl3), : 2.38 (s, 3 H, CH3); 6.53
(d, 1 H, CH=CF, J = 34.3 Hz); 7.16 (d, 2 H, 4ꢀCH3C6H4,
J = 8.8 Hz); 7.21 (d, 2 H, 4ꢀCH3C6H4, J = 8.8 Hz); 7.76 (d, 2 H,
4ꢀNO2C6H4, J = 8.8 Hz); 8.27 (d, 2 H, 4ꢀNO2C6H4, J = 8.8 Hz).
19F NMR (282 MHz, CDCl3), : –74.90 (d, CF2O, J = 12.7 Hz);
–124.0 (dt, CF=CH, JH,F = 34.3 Hz, J = 12.7 Hz). 13C NMR
(CDCl3), : 20.77, 108.47 (d, JC,F = 2.9 Hz); 114.21 (td, CF2CF,
2
(CDCl3), : 20.74, 109.29 (d, CH=CF, JC,F = 3.3 Hz); 117.23
(td, CF2=CF, 1JC,F = 259.9 Hz, 2JC,F = 38.0 Hz); 121.78, 128.96,
130.03, 130.74 (d, J = 7.7 Hz); 132.07, 134.85 (d, JC,F = 4.1 Hz);
2
2
136.00, 147.31, 148.23 (dt, CF2=CF, 1JC,F = 269.4 Hz, JC,F
=
1JC,F = 260.5 Hz, JC,F = 37.6 Hz); 121.29, 121.72, 123.30,
= 38.1 Hz).
123.90, 130.09, 130.18 (d, JC,F = 8.1 Hz); 136.22, 136.87
(d, JC,F = 2.9 Hz); 150.17 (dt, CFCF2, JC,F = 275.2 Hz,
2JC,F = 38.1 Hz).
EꢀIsomer. 1H NMR (CDCl3), : 6.76 (d, 1 H, CH=CF,
J = 20.2 Hz); 6.97 (d, 2 H, Ar, J = 8.3 Hz); 7.10 (d, 2 H, Ar,
J = 8.1 Hz); 7.48 (d, 2 H, Ar, J = 8.1 Hz); 7.56 (d, 2 H, Ar,
J = 8.3 Hz).
Mixture of 3ꢀ[2,3,3ꢀtrifluoroꢀ3ꢀ(pꢀtolyloxy)ꢀ1ꢀpropenyl]ꢀ1ꢀ
methoxybenzene (11l) and 3ꢀ[2,2,3,3ꢀtetrafluoroꢀ3ꢀ(pꢀtolylꢀ
oxy)propyl]ꢀ1ꢀmethoxybenzene (10l). Heavy oil.
Compound 10l. 1H NMR (CDCl3), : 2.38 (s, 3 H, CH3);
3.45 (t, 2 H, CH2CF2, J = 18.4 Hz); 3.85 (s, 3 H, CH3O);
6.90—6.96 (m, 2 H, 3ꢀMeOC6H4); 6.98 (d, 1 H, 3ꢀMeOC6H4,
J = 7.6 Hz); 7.13 (d, 2 H, 4ꢀMeC6H4, J = 8.5 Hz); 7.20 (d, 2 H,
4ꢀMeC6H4, J = 8.5 Hz); 7.33 (d, 1 H, 3ꢀMeOC6H4, J = 8.0 Hz).
19F NMR (282 MHz, CDCl3), : 88.14 (s, CF2O); –116.76
(t, CF2CH2, JH,F = 18.0 Hz). 13C NMR (CDCl3), : 20.38 (CH3);
37.06 (t, JC,F = 22.3 Hz); 54.77 (CH3O); 112.88, 116.12, 115.32
1
Eꢀisomer. 1H NMR (CDCl3), : 6.67 (d, 1 H, CH=CF,
J = 21.3 Hz). 19F NMR (282 MHz, CDCl3), : –74.16 (d, CF2O,
J = 14.8 Hz).
1ꢀBromoꢀ4ꢀ[2,3,3ꢀtrifluoroꢀ3ꢀ(pꢀtolyloxy)ꢀ1ꢀpropenyl]benzꢀ
ene (11i) was obtained as pure Zꢀisomer. White crystals, m.p.
56.6—57.8 C. Rf 0.7 (hexane). 1H NMR (CDCl3), : 2.38 (s, 3 H,
CH3); 6.38 (d, 1 H, CH=CF, J = 35.6 Hz); 7.14—7.22 (m, 4 H,
4ꢀBrC6H4); 7.46 (d, 2 H, 4ꢀMeC6H4, J = 8.6 Hz); 7.55 (d, 2 H,
4ꢀMeC6H4, J = 8.6 Hz). 19F NMR (282 MHz, CDCl3), : –74.59
(d, CF2O, J = 12.7 Hz); –128.28 (dt, CF=CH, JH,F = 36.0 Hz,
J = 12.7 Hz). 13C NMR (CDCl3), : 20.73, 109.34 (d, JC,F
=
= 3.3 Hz); 117.23 (td, CF2=CF, 1JC,F = 260.0 Hz, 2JC,F = 37.6 Hz);
121.75, 123.14 (d, JC,F = 3.3 Hz); 129.43, 130.02, 130.95 (d, JC,F
= 7.6 Hz); 131.92, 135.96, 147.33, 148.27 (dt, CF2=CF, 1JC,F
= 269.8 Hz, JC,F = 38.0 Hz). Found (%): C, 54.20; H, 3.73.
C16H12BrF3O. Calculated (%): C, 53.80; H, 3.39.
1ꢀNitroꢀ3ꢀ[2,3,3ꢀtrifluoroꢀ3ꢀ(pꢀtolyloxy)ꢀ1ꢀpropenyl]benzꢀ
ene (11j) was obtained as pure Zꢀisomer. Yellow solid, m.p.
53—54 C. IR, /cm–1: 1354 (NO2), 1533 (NO2), 1703 (C=C).
1H NMR (CDCl3), : 2.36 (s, 3 H, CH3); 6.51 (d, 1 H, CH=CF,
J = 34.3 Hz); 7.15 (d, 2 H, 4ꢀCH3C6H4, J = 8.6 Hz); 7.19
(d, 2 H, 4ꢀCH3C6H4, J = 8.6 Hz); 7.60 (t, 1 H, 3ꢀNO2C6H4,
J = 8.0 Hz); 7.91 (d, 1 H, 3ꢀNO2C6H4, J = 8.0 Hz); 8.22 (ddd, 1 H,
3ꢀNO2C6H4, J = 8.0 Hz, J = 1.3 Hz, J = 0.9 Hz); 8.43 (br.s, 1 H,
3ꢀNO2C6H4, J = 2.98 Hz). 19F NMR (282 MHz, CDCl3),
=
=
2
1
2
(tt, CF2, JC,F = 252.5 Hz, JC,F = 35.4 Hz); 117.38
1
2
(tt, CF2CF2O, JC,F = 274.6 Hz, JC,F = 32.8 Hz); 121.21,
122.80, 129.00, 129.69, 131.43, 135.82, 146.42, 159.21. MS (ESI),
m/z: found 329.1169 [M + H]+; calculated for C17H16F4O2H+,
[M + H]+, 329.1159.
Compound 11l. Mixture of Z/Eꢀisomers in a 93 : 7 ratio. IR,
/cm–1: 1603, 1701 (C=C).
ZꢀIsomer. 1H NMR (CDCl3), : 2.37 (s, 3 H, CH3); 3.85
(s, 3 H, CH3O); 6.41 (d, 1 H, CH=CF, J = 36.1 Hz); 6.94 (ddd,
1 H, 3ꢀMeOC6H4, J = 8.2 Hz, J = 2.6 Hz, J = 0.8 Hz); 7.15—7.22
(m, 6 H, Ar); 7.33 (t, 1 H, 3ꢀMeOC6H4, J = 8.2 Hz). 19F NMR
(282 MHz, CDCl3), : –74.61 (d, CF2O, J = 12.7 Hz); –128.89
(dt, CF=CH, JH,F = 36.1 Hz, J = 12.7 Hz). 13C NMR (CDCl3),
: 20.40 (CH3); 54.83 (CH3O); 109.96 (d, JC,F = 3.3 Hz); 114.29
(d, JC,F = 8.1 Hz); 114.52 (d, JC,F = 1.8 Hz); 116.98
(td, CF=CF2, 1JC,F = 260.2 Hz, 2JC,F = 37.6 Hz); 121.42, 121.77
(d, JC,F = 7.0 Hz); 129.29, 129.63, 131.38 (d, JC,F = 3.7 Hz);
: –74.82 (d, CF2O, J = 12.7 Hz); –125.46 (dt, CF=CH, JH,F
=
= 34.3 Hz, J = 12.7 Hz). 13C NMR (CDCl3), : 20.40, 108.04
(d, JC,F = 3.0 Hz); 121.34, 123.19, 123.77 (d, JC,F = 7.4 Hz);
116.50 (td, CF2CF, 1JC,F = 260.6 Hz, 2JC,F = 37.6 Hz); 129.36,
129.69, 131.77 (d, JC,F = 3.3 Hz); 134.62 (d, JC,F = 3.3 Hz);
1
135.78, 146.76, 148.07, 149.19 (dt, CFCF2, JC,F = 271.3 Hz,
2JC,F = 38.3 Hz). Found (%): C, 59.50; H, 3.80; N, 4.15.
C16H12F3NO3. Calculated (%): C, 59.45; H, 3.74; N, 4.33.
1ꢀNitroꢀ4ꢀ[2,2,3,3ꢀtetrafluoroꢀ3ꢀ(pꢀtolyloxy)propyl]benzene
(10k). Yellow crystals, m.p. 88.2—88.9 C. Rf 0.3 (hexꢀ
ane—CH2Cl2, 2 : 1). 1H NMR (CDCl3), : 2.38 (s, 3 H,
CH3); 3.58 (t, 2 H, CH2CF2, J = 18.5 Hz); 7.10 (d, 2 H,
4ꢀCH3C6H4, J = 8.3 Hz); 7.21 (d, 2 H, 4ꢀCH3C6H4, J = 8.3 Hz);
7.56 (d, 2 H, 4ꢀNO2C6H4, J = 8.6 Hz); 8.26 (d, 2 H, 4ꢀNO2C6H4,
J = 8.6 Hz). 19F NMR (282 MHz, CDCl3), : –88.04 (s, CF2O);
–116.76 (t, CF2CH2, JH,F = 18.5 Hz). 13C NMR (CDCl3),
135.54, 147.01, 147.54 (dt, CF=CF2, 1JC,F = 269.1 Hz, 2JC,F
=
= 37.7 Hz); 159.29.
EꢀIsomer. 1H NMR (CDCl3), : 6.72 (d, 1 H, CH=CF,
J = 21.6 Hz). 19F NMR (282 MHz, CDCl3), : –74.07 (d, CF2O,
J = 14.8 Hz).
[2ꢀEthoxyꢀ1,1ꢀdifluoroꢀ3ꢀ(4ꢀnitrophenyl)allyl](pꢀtolyl)sulfꢀ
ane (12). Yellow crystals, m.p. 107—108 C. IR, /cm–1: 1338,
1514, 1594, 1651 (C=C). Found (%): C, 59.08; H, 4.68; N, 3.76.
C18H17F2NO3S. Calculated (%): C, 59.17; H, 4.69; N, 3.83.
ZꢀIsomer. 1H NMR (CDCl3), : 1.39 (t, 3 H, CH2CH3,
J = 7.0 Hz); 2.37 (s, 3 H, CH3); 4.11 (q, 2 H, CH2CH3, J = 7.0 Hz);
6.23 (s, 1 H, C=CH); 7.19 (d, 2 H, 4ꢀMeC6H4, J = 7.9 Hz); 7.53
(d, 2 H, 4ꢀMeC6H4, J = 7.9 Hz); 7.73 (d, 2 H, 4ꢀNO2C6H4,
J = 8.9 Hz); 8.19 (d, 2 H, 4ꢀNO2C6H4, J = 8.9 Hz). 19F NMR
(282 MHz, CDCl3), : –75.59 (s, CF2S). 13C NMR (CDCl3),
: 15.16, 20.92, 68.78, 113.2 (t, JC,F = 5.2 Hz); 122.28, 123.24,
2
: 20.73, 37.25 (t, CH2CF2, JC,F = 22.7 Hz); 115.24 (tt, CF2,
1JC,F = 254.0 Hz, JC,F = 35.9 Hz); 117.45 (tt, CF2,
2
1JC,F = 275.2 Hz, JC,F = 31.5 Hz); 121.42, 123.54, 130.12,
2
131.68, 136.41, 137.82, 146.55, 147.73. MS (ESI), m/z:
found 366.0715 [M + Na]+; calculated for C16H13F4NNaO3
[M + Na]+, 366.0724.
1ꢀNitroꢀ4ꢀ[2,3,3ꢀtrifluoroꢀ3ꢀ(pꢀtolyloxy)ꢀ1ꢀpropenyl]benzꢀ
ene (11k). Mixture of Z/Eꢀisomers in a 88 : 12 ratio. Yellow crysꢀ
tals, m.p. 119.5—120.7 C. Rf 0.4 (hexane—CH2Cl2, 2 : 1).
+
,

1454
Russ.Chem.Bull., Int.Ed., Vol. 61, No. 7, July, 2012
Muzalevskiy et al.
124.84 (t, JC,F = 282.1 Hz); 129.33, 129.50, 136.29, 139.75,
140.28, 146.34, 149.69 (t, JC,F = 24.9 Hz).
(s, 3 H, CH3); 3.68 (t, 2 H, CH2CF2, JH,F = 18.7 Hz); 7.45
(d, 2 H, 4ꢀCH3C6H4, J = 8.2 Hz); 7.55 (t, 1 H, 3ꢀNO2C6H4,
J = 7.7 Hz); 7.66 (d, 1 H, 3ꢀNO2C6H4, J = 7.7 Hz); 7.90 (d, 2 H,
4ꢀCH3C6H4, J = 8.2 Hz); 8.19—8.23 (m, 2 H, 3ꢀNO2C6H4).
EꢀIsomer. 1H NMR (CDCl3), : 1.45 (t, 3 H, CH2CH3,
J = 7.0 Hz); 2.37 (s, 3 H, CH3); 3.95 (q, 2 H, CH2CH3, J = 7.0 Hz);
5.86 (s, 1 H, C=CH); 7.34 (d, 2H, 4ꢀNO2C6H4, J = 8.7 Hz);
7.45 (d, 2 H, 4ꢀMeC6H4, J = 7.9 Hz); 8.10 (d, 2 H, 4ꢀNO2C6H4,
J = 8.7 Hz). 19F NMR (282 MHz, CDCl3), : –72.51 (s, CF2S).
1ꢀ[2ꢀEthoxyꢀ1,1ꢀdifluoroꢀ3ꢀ(4ꢀnitrophenyl)allyloxy]ꢀ4ꢀmeꢀ
thylbenzene (13). Yellow heavy oil. IR, /cm–1: 1342 (NO2),
1519 (NO2), 1658 (C=C). Found (%): C, 61.80; H, 4.95; N, 4.09.
C18H17F2NO4. Calculated (%): C, 61.89; H, 4.91; N, 4.01.
ZꢀIsomer. 1H NMR (CDCl3), : 1.42 (t, 3 H, CH2CH3,
J = 7.0 Hz); 2.36 (s, 3 H, CH3); 4.18 (q, 2 H, CH2CH3, J = 7.0 Hz);
6.52 (s, 1 H, C=CH); 7.14 (d, 2 H, 4ꢀMeC6H4, J = 8.6 Hz); 7.18
(d, 2 H, 4ꢀMeC6H4, J = 8.6 Hz); 7.85 (d, 2 H, 4ꢀNO2C6H4,
J = 8.9 Hz); 8.22 (d, 2 H, 4ꢀNO2C6H4, J = 8.9 Hz). 19F NMR
(188 MHz, CDCl3), : –70.71 (s, CF2O). 13C NMR (CDCl3),
19F NMR (188 MHz, CDCl3), : –109.79 (t, CF2CH2, JH,F
=
= 18.8 Hz); –114.15 (s, CF2SO2). 13C NMR (CDCl3), : 21.87,
1
36.82 (t, CH2CF2, JC,F = 21.9 Hz); 115.53 (tt, CF2, JC,F
=
2
= 253.8 Hz, JC,F = 35.9 Hz); 117.14, 120.97, 118.34 (tt, CF2,
1JC,F = 255.6 Hz, JC,F = 30.5 Hz), 123.18, 125.74, 129.48,
2
130.22, 130.94, 136.88, 137.44, 145.51. MS (ESI), m/z: found
414.0390 [M + Na]+; calculated for C16H13F4NNaO4S+,
[M + Na]+, 414.0394.
1ꢀBromoꢀ4ꢀ(3ꢀtozylꢀ2,3,3ꢀtrifluoropropꢀ1ꢀenyl)benzene (15)
was obtained as Zꢀisomer. Whity crystals, m.p. 146.2—147.9 C.
Rf 0.5 (hexane—CH2Cl2, 2 : 1). 1H NMR (CDCl3), : 2.53 (s, 3 H,
CH3); 6.37 (d, 1 H, CH=CF, JH,F = 35.8 Hz); 7.45—7.48 (m, 4 H,
Ar); 7.56 (d, 2 H, Ar, J = 8.6 Hz); 7.93 (d, 2 H, Ar, J = 8.1 Hz).
19F NMR (188 MHz, CDCl3), : –108.33 (t, CF2SO2, J = 15.5 Hz);
–124.27 (dt, CF=CH, JH,H = 35.8 Hz, J = 15.5 Hz). 13C NMR
(acetoneꢀd6), : 20.91, 114.84, 122.95 (td, CF2CF, 1JC,F = 278.1 Hz,
2JC,F = 38.8 Hz); 123.25, 129.19, 130.55, 130.79, 131.67 (d,
: 15.14, 20.37, 68.26, 112.53 (t, JC,F = 4.4 Hz); 118.59 (t, JC,F
=
= 265.4 Hz); 121.28, 123.24, 129.44, 129.59, 135.35, 139.83,
146.17, 147.17, 147.75 (t, JC,F = 31.7 Hz).
EꢀIsomer. 1H NMR (CDCl3), : 1.47 (t, 3 H, CH2CH3,
J = 7.0 Hz); 2.35 (s, 3 H, CH3); 3.96 (q, 2 H, CH2CH3, J = 7.0 Hz);
5.95 (s, 1 H, C=CH); 8.16 (d, 2 H, 4ꢀNO2C6H4, J = 8.9 Hz).
19F NMR (188 MHz, CDCl3), : –68.52 (s, CF2O).
Oxidation of sulfides 10 and 11 to sulfones 14 and 15 (general
procedure). To a solution of 1 mmol of the corresponding sulfide
in acetic acid (2 mL), 40% H2O2 (2 mL) was added dropwise.
The mixture was refluxed for 3 h and diluted with water (5 mL).
The crystals formed were filtered off, washed with water,
and dried.
JC,F = 7.3 Hz); 132.18, 133.04, 148.16, 149.55 (dt, CFCF2, 1JC,F
= 267.2 Hz, JC,F = 30.7 Hz). Found (%): C, 47.51; H, 3.24.
C16H12BrF3O2S. Calculated (%): C, 47.42; H, 2.98.
=
2
Synthesis of alkynes 18 (general procedure). Under argon,
50 mL threeꢀnecked flask was charged with a solution of 1 mmol
of the corresponding sulfide 10 in anhydrous THF (10 mL),
mixture was cooled to –80 C and a solution of sodium hexameꢀ
thyldisilazide (1.0 M, 3 mL, 3 mmol) in THF was slowly added.
After 1 h at –80 C, the reaction mixture was warmed to room
temperature over 1 h, and stirring was continued for additional
2 h. The reaction was quenched with 1 M HCl (10 mL), the
organic layer was separated, and the aqueous layer was extracted
with dichloromethane (3×30 mL). The combined organics were
washed with water (50 mL) and dried with Na2SO4. The solvents
were removed in vacuo, the residue was purified by column chroꢀ
matography (elution with hexane or hexane—dichloromethane).
In the case of 4ꢀnitro derivative 16e, the reaction mixture
was kept at –80 C for 2.5 h and quenched at –60 C; in the case
of 4ꢀmethoxy derivative 16d, the reaction mixture was kept at
room temperature for additional 4 h.
[3ꢀ(4ꢀChlorophenyl)ꢀ1,1ꢀdifluoropropꢀ2ꢀynyl](pꢀtolyl)sulfane
(16a). White crystals, m.p. 69.3—71.7 C. Rf 0.6 (hexane—CH2Cl2,
8 : 1). 1H NMR (CDCl3), : 2.42 (s, 3 H, CH3); 7.24 (d, 2 H,
4ꢀCH3C6H4, J = 8.0 Hz); 7.36 (br.s, 4 H, 4ꢀClC6H4); 7.59 (d, 2 H,
4ꢀCH3C6H4, J = 8.0 Hz). 19F NMR (188 MHz, CDCl3), :
–59.78 (s, CF2S). 13C NMR (CDCl3), : 21.40, 81.20 (t, CCCF2,
2JC,F = 39.5 Hz); 89.05 (t, CCCF2,3JC,F = 6.2 Hz); 117.89
(t, CF2, 1JC,F = 266.0 Hz); 118.5, 123.23, 128.97, 130.02, 133.36,
136.58, 136.77, 141.02. MS (ESI), m/z: found 331.0136 [M + Na]+;
calculated for C16H11ClF2NaS+, [M + Na]+, 331.0130.
1ꢀBromoꢀ4ꢀ(2,2,3,3ꢀtetrafluoroꢀ3ꢀtozylpropylsulfonyl)benzꢀ
ene (14a). White crystals, m.p. 99.9—101.3 C. Rf 0.5 (hexꢀ
1
ane—CH2Cl2, 2 : 1). H NMR (CDCl3), : 2.52 (s, 3 H, CH3);
3.51 (t, 2 H, CH2CF2, JH,F = 18.95 Hz); 7.20 (d, 2 H, Ar,
J = 8.34 Hz); 7.46 (d, 2 H, Ar, J = 8.34 Hz); 7.50 (d, 2 H, Ar,
J = 8.34 Hz); 7.92 (d, 2 H, Ar, J = 8.34 Hz). 19F NMR (188 MHz,
CDCl3), : –110.00 (t, CF2CH2, JH,F = 19.0 Hz); –113.96
(s, CF2SO2). 13C NMR (acetoneꢀd6), : 20.99, 36.89 (t, CH2CF2,
JC,F = 21.9 Hz); 115.71 (tt, CF2, 1JC,F = 254.0 Hz, 2JC,F = 35.8
Hz); 117.40 (tt, CF2, 1JC,F = 253.5 Hz, 2JC,F = 28.5 Hz); 121.82,
126.73, 130.12, 130.57, 130.90, 131.57, 133.03, 148.47. Found (%):
C, 45.42; H, 3.12. C16H13BrF4O2S. Calculated (%): C, 45.19;
H, 3.08.
1ꢀEthylꢀ4ꢀ(2,2,3,3ꢀtetrafluoropropylꢀ3ꢀtozylpropylsulfonyl)ꢀ
benzene (14b). White crystals, m.p. 68.9—70.5 C. Rf 0.5 (hexꢀ
ane—CH2Cl2, 10 : 7). 1H NMR (CDCl3), : 1.26 (t, 3 H,
CH3CH2, J = 7.58 Hz); 2.52 (s, 3 H, CH3); 2.67 (q, 2 H,
CH3CH2, J = 7.58 Hz); 3.50 (t, 2 H, CH2CF2, JH,F = 20.1 Hz);
7.20 (d, 2 H, Ar, J = 8.08 Hz); 7.24 (d, 2 H, Ar, J = 8.08 Hz);
7.45 (d, 2 H, Ar, J = 8.08 Hz); 7.93 (d, 2 H, Ar, J = 8.08 Hz).
19F NMR (188 MHz, CDCl3), : –110.18 (t, CF2CH2, JH,F
=
= 20.1 Hz); –113.90 (s, CF2SO2). 13C NMR (DMSOꢀd6), :
15.36, 21.83, 28.42, 37.58 (t, CH2CF2, JC,F = 22.0 Hz); 115.72
[3ꢀ(4ꢀBromophenyl)ꢀ1,1ꢀdifluoropropꢀ2ꢀynyl](pꢀtolyl)sulfane
(16b). White crystals, m.p. 73.8—74.7 C. Rf 0.6 (hexꢀ
ane—CH2Cl2, 8 : 1). IR, /cm–1: 2240 (CC). 1H NMR
(CDCl3), : 2.41 (s, 3 H, CH3); 7.24 (d, 2 H, 4ꢀCH3C6H4,
J = 8.1 Hz); 7.29 (d, 2 H, 4ꢀBrC6H4, J = 8.6 Hz); 7.52 (d, 2 H,
4ꢀBrC6H4, J = 8.6 Hz); 7.58 (d, 2 H, 4ꢀCH3C6H4, J = 8.1 Hz).
19F NMR (188 MHz, CDCl3), : –59.88 (s, CF2S). 13C NMR
1
2
(tt, CF2, JC,F = 253.5 Hz, JC,F = 35.9 Hz); 117.14 (tt, CF2,
2
1JC,F = 253.0 Hz, JC,F = 35.8 Hz); 126.40, 127.96, 129.76,
130.12, 130.89, 130.99, 143.99, 147.63. MS (ESI), m/z:
found 397.0871 [M + Na]+; calculated for C18H18F4NaO2S,
[M + Na]+, 397.0856.
1ꢀMethylꢀ4ꢀ[1,1,2,2ꢀtetrafluoroꢀ3ꢀ(4ꢀnitrophenyl)propylꢀ
sulfonyl]benzene (14c). White crystals, m.p. 136.5—139.1 C.
Rf 0.4 (hexane : CH2Cl2 = 2 : 1). 1H NMR (CDCl3), : 2.51
2
(CDCl3), : 21.32, 81.27 (t, CCCF2, JC,F = 40.4 Hz); 89.03
(t, CCCF2, 3JC,F = 6.0 Hz); 117.83 (t, CF2, 1JC,F = 266.0 Hz);
118.54, 123.16, 124.85, 129.94, 131.82, 133.40, 136.68, 140.93.

Catalytic olefination reaction
Russ.Chem.Bull., Int.Ed., Vol. 61, No. 7, July, 2012
1455
MS (ESI), m/z: found 374.9625 [M + Na]+; calculated for
C16H11F2BrNaS+, [M + Na]+, 374.9625.
E. S. Balenkova, Synthesis, 2001, 2081; (g) V. N. Korotchenko,
A. V. Shastin, V. G. Nenajdenko, E. S. Balenkova, Org. Bioꢀ
mol. Chem., 2003, 1, 1906; (h) A. V. Shastin, V. N. Korotꢀ
chenko, G. N. Varseev, V. G. Nenajdenko, E. S. Balenkova,
Zh. Org. Khim., 2003, 39, 433 [Russ. J. Org. Chem.
(Engl. Transl.), 2003, 39, 427]; (i) V. N. Korotchenko, A. V.
Shastin, V. G. Nenajdenko, E. S. Balenkova, Tetrahedron,
2001, 57, 7519; (j) V. G. Nenajdenko, A. V. Shastin, V. N.
Korotchenko, G. N. Varseev, E. S. Balenkova, Eur. J. Org.
Chem., 2003, 302; (k) V. G. Nenajdenko, G. N. Varseev,
V. N. Korotchenko, A. V. Shastin, E. S. Balenkova, J. Fluoꢀ
rine Chem., 2003, 124, 115; (l) V. G. Nenajdenko, O. N.
Lenkova, A. V. Shastin, E. S. Balenkova, Synthesis, 2004,
573; (m) V. G. Nenajdenko, A. V. Shastin, I. V. Golubinskii,
O. N. Lenkova, E. S. Balenkova, Russ. Chem. Bull. (Int. Ed.),
2004, 53, 228 [Izv. Akad. Nauk, Ser. Khim., 2004, 218];
(n) V. G. Nenajdenko, V. N. Korotchenko, A. V. Shastin,
D. A. Tyurin, E. S. Balenkova, Russ. Chem. Bull. (Int. Ed.),
2003, 52, 1835 [Izv. Akad. Nauk, Ser. Khim., 2003, 1740];
(o) V. G. Nenajdenko, V. N. Korotchenko, A. V. Shastin,
E. S. Balenkova, Russ. Chem. Bull. (Int. Ed.), 2004, 53, 1034
[Izv. Akad. Nauk, Ser. Khim., 2004, 991]; (p) V. G. Nenaꢀ
jdenko, A. L. Reznichenko, O. N. Lenkova, A. V. Shastin,
E. S. Balenkova, Synthesis, 2005, 605; (q) A. V. Shastin,
V. M. Muzalevsky, E. S. Balenkova, V. G. Nenajdenko, Menꢀ
deleev Comm., 2006, 16, 179.
[3ꢀ(4ꢀEthylphenyl)ꢀ1,1ꢀdifluoropropꢀ2ꢀynyl](pꢀtolyl)sulfane
(16c). White crystals, m.p. 45.6—47.0 C. Rf 0.7 (hexane—CH2Cl2,
4 : 1). 1H NMR (CDCl3), : 1.27 (t, 3 H, CH3CH2, J = 7.6 Hz);
2.42 (s, 3 H, CH3); 2.70 (q, 2 H, CH3CH2, J = 7.6 Hz); 7.21
(d, 2 H, 4ꢀCH3C6H4, J = 8.1 Hz); 7.25 (d, 2 H, 4ꢀClC6H4,
J = 7.8 Hz); 7.38 (d, 2 H, 4ꢀClC6H4, J = 7.8 Hz); 7.62 (d, 2 H,
4ꢀCH3C6H4, J = 8.1 Hz). 19F NMR (188 MHz, CDCl3), : –59.06
(s, CF2S). 13C NMR (CDCl3), : 15.19, 21.40, 29.74, 79.84
(t, CCCF2, 2JC,F = 39.6 Hz); 90.73 (t, CCCF2,3JC,F = 6.3 Hz);
116.84, 118.01 (t, CF2, 1JC,F = 264.7 Hz); 123.51, 128.08, 129.96,
132.17, 136.73, 140.82, 146.92. MS (ESI), m/z: found 303.0976
[M + H]+; calculated for C18H17F2S+, [M + H]+, 303.1014.
[1,1ꢀDifluoroꢀ3ꢀ(4ꢀmethoxyphenyl)propꢀ2ꢀynyl](pꢀtolyl)ꢀ
sulfane (16d). White crystals, m.p. 51.3—53.8 C. 1H NMR
(CDCl3), : 2.42 (s, 3 H, CH3); 3.85 (s, 3 H, OMe); 6.89 (d, 2 H,
4ꢀCH3OC6H4, J = 8.8 Hz); 7.25 (d, 2 H, 4ꢀCH3C6H4, J = 7.8 Hz);
7.40 (d, 2 H, 4ꢀCH3OC6H4, J = 8.8 Hz); 7.61 (d, 2 H,
4ꢀCH3C6H4, J = 7.8 Hz). 19F NMR (188 MHz, CDCl3), : –58.76
(s, CF2S). 13C NMR (CDCl3), : 21.38, 55.36 (s, OMe); 79.35
(t, CCCF2, 2JC,F = 40.1 Hz); 90.82 (t, CCCF2, 3JC,F = 6.3 Hz);
114.17, 118.06 (t, CF2, 1JC,F = 265.9 Hz); 123.49, 129.96, 130.96
(d, J = 7.6 Hz); 133.82, 136.73, 140.84, 161.08. MS (ESI), m/z:
found 327.0627 [M + Na]+; calculated for C17H14F2NaOS+,
[M + Na]+, 327.0626.
[1,1ꢀDifluoroꢀ3ꢀ(4ꢀnitrophenyl)propꢀ2ꢀynyl](pꢀtolyl)sulfane
(16e). White crystals, m.p. 92.0—93.8 C. Rf 0.4 (hexane—CH2Cl2,
2 : 1). H NMR (CDCl3), : 2.42 (s, 3 H, CH3); 7.26 (d, 2 H,
2. V. G. Nenajdenko, G. N. Varseev, V. N. Korotchenko, A. V.
Shastin, E. S. Balenkova, J. Fluorine Chem., 2004, 125, 1339.
3. P. Kirsch, M. Bremer, F. Huber, H. Lannert, A. Ruhl,
M. Lieb, T. Wallmichrath, J. Am. Chem. Soc., 2001, 123, 5414.
4. E. Bartmann, Adv. Mater., 1996, 8, 570.
1
4ꢀCH3C6H4, J = 7.8 Hz); 7.59 (m, 4 H, Ar); 8.25 (d, 2 H,
4ꢀNO2C6H4, J = 8.1 Hz). 19F NMR (188 MHz, CDCl3), :
–60.87 (s, CF2S). 13C NMR (CDCl3), : 21.25, 84.19 (t, CCCF2,
5. P. Kirsch, M. Bremer, A. Taugerbeck, T. Wallmichrath, Anꢀ
gew. Chem., Int. Ed., 2001, 40, 1480.
3
2JC,F = 41.3 Hz); 87.38 (t, CCCF2, JC,F = 6.1 Hz); 117.66
(t, CF2, 1JC,F = 267.2 Hz); 123.58, 125.04, 126.08, 129.99, 132.91,
136.66, 141.17, 148.24. MS (ESI), m/z: found 342.0374 [M + Na]+;
calculated for C16H11F2NNaO2S+, [M + Na]+, 342.0371.
6. (a) Pat. US 6319570; http://www.google.com/patents/
US6319570; (b) Pat. US 6001275; http://www.google.com/
patents/US6001275; (c) Pat. WO 2007/147516; http://
patentscope.wipo.int/search/en/WO2007147516; (d) WO
Pat. 2007/147516, 2007; (d) P. Kirsch, M. Lenges, A. Ruhl,
D. V. Sevenard, G.ꢀV. Roeschenthaler, J. Fluorine Chem.,
2004, 125, 1025.
7. E. Pretsch, P. Buhlmann, M. Badertscher, Structure Deꢀ
termination of Organic Compounds, SpringerꢀVerlag, Berꢀ
lin—Heidelberg, 2009, 433 pp.
8. P. E. Hansen, Prog. Nucl. Magn. Reson. Spectrosc., 1981, 14, 175.
9. A. V. Shastin, V. M. Muzalevskiy, V. N. Korotchenko, E. S.
Balenkova, V. G. Nenajdenko, Zh. Org. Khim., 2006, 42, 200
[Russ. J. Org. Chem. (Engl. Transl.), 2006, 42, 183].
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Moscow State Univ., Moscow, 2008, 382 pp. (in Russian).
11. K. D. Sen, C. K. Jorgensen, Electronegativity, Springer, New
York, 1987, 198 pp.
This work was financially supported by the Russian
Foundation for Basic Research (Project No. 10ꢀ03ꢀ00897ꢀa),
The Ministry of Science and Education of the Russian
Federation (State Contract P962), and the Council for
Grants at the President of the Russian Federation (the
Program for the State Support of Young Russian Scienꢀ
tistsꢀPhDs, Grant MKꢀ7121.2012.3).
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Received December 21, 2011;
in revised form April 5, 2012