A route to fluorocontaining N,S-heterocycles via octafluoro-2,3-epoxybutane

Article abstract of DOI:10.1016/j.jfluchem.2007.04.006

The reaction of octafluoro-2,3-epoxybutane 1 with 2-aminothiophenol gave three kinds of novel fluorocontaining N,S-heterocyclic compounds depending on the solvent nature: 2,3-bis(trifluoromethyl)-3,4-dihydro-2H-1,4-benzothiazin-2-ol 2, 2-trifluoromethyl-2-[1-(2-aminophenylthio)-2,2,2-trifluoroethyl]-1,3-ben zothiazolidine 6 and 5a,11a-bis(trifluoromethyl)-5a,6,11a,12-tetrahydro-5,11-dithia-6,12-diaz anaphthacene 5. Use of the toluene, dioxane, tetrahydrofuran, acetonitrile and dimethoxyethane gave the unexpected dihydrobenzothiazine 2 (RS,SR > RR,SS) in good to moderate yields. In dimethylsulfoxide and N,N-dimethylacetamide, unusual cyclization occurred resulting in benzothiazolidine 6 (RS,SR/RR,SS ～ 1:1) in moderate yields. Formation of minor 1,1,1,3,4,4,4-heptafluoro-3-(2-aminophenylthio)-2,2-dihydroxybutane 4 which was converted into bis(benzothiazine) 5 was observed in all solvents tested with the exception of toluene and dioxane. The molecular structure of the RS,SR-diastereomer of dihydrobenzothiazine 2, bis(benzothiazine) 5 and the RS,SR-diastereomer of benzothiazolidine 6 has been established by X-ray crystallography.

Full text of DOI:10.1016/j.jfluchem.2007.04.006

Journal of Fluorine Chemistry 128 (2007) 769–778
www.elsevier.com/locate/fluor
A route to fluorocontaining N,S-heterocycles via
octafluoro-2,3-epoxybutane
*
Lyudmila V. Saloutina , Aleksandr Ya. Zapevalov, Victor I. Saloutin, Pavel A. Slepukhin,
Mikhail I. Kodess, Valentina E. Kirichenko, Marina G. Pervova, Oleg N. Chupakhin
Institute of Organic Synthesis, Urals Branch of the Russian Academy of Sciences, 22/20 S. Kovalevskoy/Academicheskaya,
GSP-147, 620041 Ekaterinburg, Russia
Received 31 January 2007; received in revised form 4 April 2007; accepted 4 April 2007
Available online 8 April 2007
Abstract
The reaction of octafluoro-2,3-epoxybutane 1 with 2-aminothiophenol gave three kinds of novel fluorocontaining N,S-heterocyclic compounds
depending on the solvent nature: 2,3-bis(trifluoromethyl)-3,4-dihydro-2H-1,4-benzothiazin-2-ol 2, 2-trifluoromethyl-2-[1-(2-aminophenylthio)-
2,2,2-trifluoroethyl]-1,3-benzothiazolidine 6 and 5a,11a-bis(trifluoromethyl)-5a,6,11a,12-tetrahydro-5,11-dithia-6,12-diazanaphthacene 5. Use of
the toluene, dioxane, tetrahydrofuran, acetonitrile and dimethoxyethane gave the unexpected dihydrobenzothiazine 2 (RS,SR > RR,SS) in good to
moderate yields. In dimethylsulfoxide and N,N-dimethylacetamide, unusual cyclization occurred resulting in benzothiazolidine 6 (RS,SR/
RR,SS ꢀ 1:1) in moderate yields. Formation of minor 1,1,1,3,4,4,4-heptafluoro-3-(2-aminophenylthio)-2,2-dihydroxybutane 4 which was
converted into bis(benzothiazine) 5 was observed in all solvents tested with the exception of toluene and dioxane. The molecular structure
of the RS,SR-diastereomer of dihydrobenzothiazine 2, bis(benzothiazine) 5 and the RS,SR-diastereomer of benzothiazolidine 6 has been
established by X-ray crystallography.
# 2007 Elsevier B.V. All rights reserved.
Keywords: Octafluoro-2,3-epoxybutane; 2-Aminothiophenol; 2,3-Bis(trifluoromethyl)-3,4-dihydro-2H-1,4-benzothiazin-2-ol; 2-Trifluoromethyl-2-[1-(2-amino-
phenylthio)-2,2,2-trifluoroethyl]-1,3-benzothiazolidine; 1,1,1,3,4,4,4-Heptafluoro-2,2-dihydroxy-3-(2-aminophenylthio)butane; 5a,11a-Bis(trifluoromethyl)-
5a,6,11a,12-tetrahydro-5,11-dithia-6,12-diazanaphthacene
1. Introduction
Although the building block approach has been also applied
to the formation of perfluoroalkyl- and perfluoroarylcontaining
thiazines relatively few examples of such syntheses have been
published. Thus, the reaction of copper chelate of ethylpenta-
fluorobenzoylpyruvate with 2-aminothiophenol hydrochloride
The intensive development at last years of the chemistry of
N,S-heterocycles such as thiazines and thiazoles including
fluorocontaining ones is connected with their high physiolo-
gical activity [1–4]. Thiazine and thiazole skeleton belongs to
such biologically active compounds as pesticides, fungicides,
bactericides [5] and herbicides [6]. Some thiazine and thiazole
derivatives can be useful as organic electroluminescent material
[7].
gave 3,4-dihydro-3-pentafluorobenzoylmethyliden-2H-1,4-
benzothiazin-2-one [9]:
The principal methods for preparation of perfluoroalk-
ylcontaining thiazoles known from the literature are based on
interaction of fluorinated precursors such as perfluoroolefins,
their thiocyanate derivatives and fluorocontaining aldehydes
with mono- and dinucleophilic reagents [8].
The interaction of 4-ethoxy-1,1,1-trifluoro-3-buten-2-one
with 2-aminothiophenol led to 2-trifuoroacetyl-2H-1,4-ben-
zothiazine, and with thioethanolamine hydrochloride—to 5,6-
dihydro-2-trifluoroacetyl-4H-1,4-thiazine [10]:
* Corresponding author. Tel.: +7 343 374 59 54; fax: +7 343 374 59 54.
E-mail address: fc403@ios.uran.ru (L.V. Saloutina).
0022-1139/$ – see front matter # 2007 Elsevier B.V. All rights reserved.
doi:10.1016/j.jfluchem.2007.04.006

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Terminal perfluoroolefin oxides have been found to be
2. Results and discussion
convenient precursors for synthesis both of thiazols and
thiazines: the reaction of the former with thiourea yielded 2-
aminothiazolines containing perfluoroalkyl substituents [11],
and the reaction of hexafluoropropylene oxide with 2-
aminothiophenol yielded benzothiazine with trifluoromethyl
substituent [12] (Scheme 1).
As it has been shown earlier, 2-aminothiophenol readily
reacts with perfluoro-1,2-epoxypropane in N,N-dimethylace-
tamide to give 2-fluoro-2-trifluoromethyl-3,4-dihydro-2H-1,4-
benzothiazin-3-one as a result of the initial attack of SH group
of the dinucleophile at the central carbon atom [12] (Scheme 1).
We have found in contrast to that a similar reaction of
oxirane 1 with 2-aminothiophenol in toluene and dioxane
possessing low polarity, low ionizing and dissociating ability
[18] both at deficiency and excess of the dinucleophile leads to
an unexpected heterocyclic product, 2,3-bis(trifluoromethyl)-
At the same time, we have shown previously that oxides of
internal perfluoroolefins are excellent building blocks for
synthesis of a large variety of 5,6-membered heterocycles
such as diazines, quinaxolines, oxazines, benzoxazines and
thiazolines [13–16]. Continuing our efforts directed towards
synthesis of fluorocontaining heterocycles we report in the
present paper on conversion of internal octafluoro-2,3-epox-
ybutane 1 (cis:trans ꢀ 10:90) [17] into new N,S-heterocycles:
bis(trifluoromethyl)dihydrobenzothiazine 2, bis(trifluoro-
3,4-dihydro-2H-1,4-benzothiazin-2-ol
2 [2R3R,2S3S/2R3S,
2S3R ꢀ 2:98 (toluene); 2R3R,2S3S/2R3S,2S3R ꢀ 20:80 (diox-
ane)] (Scheme 2, path a; Table 1, runs 1 and 2).
Probably, in this case the other type of interacting takes
place: the first step of the reaction is the attack of amino group
of the dinucleophile at one of the epoxide carbon atoms giving
intermediate A and then 2,3-bis(trifluoromethyl)-2H-1,4-
benzothiazin-2-ol B. As in the case of diazenecarboxamides
containing N N bond [19] the intermediate B is reduced to
afford dihydrobenzothiazine 2 under the action of thiol
function of 2-aminothiophenol. At the same time, the
methyl)bis(benzothiazine)
5 and trifluoromethylcontaining
benzothiazolidine 6 using 2-aminothiophenol. To investigate
the effect of a solvent on a direction of the reaction aprotic
solvents possessing different polarity [18], such as toluene,
dioxane, tetrahydrofuran, dimethoxyethane, acetonitrile, N,N-
dimethylacetamide (DMAA) and dimethylsulfoxide (DMSO),
have been tested.
Scheme 1.
Table 1
Effect of a solvent type on a product distribution
Run no.
Solvent
Composition and ratio of the reaction products (mol.%, from 19F NMR)
1
2
3
4
5
6
7
Dioxane
2 (RR,SS/RS,SR ꢀ 20:80)
Toluene
2 (RR,SS/RS,SR ꢀ 2:98)
Tetrahydrofuran
Dimethoxyethane
Acetonitrile
2 (RR,SS/RS,SR ꢀ 37:63), 4 ꢀ 72:28
2 (RR,SS/RS,SR ꢀ 9:91), 4 ꢀ 57:43
2 (RR,SS/RS,SR ꢀ 16:84), 4 ꢀ 74:26
6 (RS,SR/RR,SS ꢀ 43:57), 4 ꢀ 75:25
6 (RS,SR/RR,SS ꢀ 46:54), 4, 2 (RR,SS/RS,SR ꢀ 29:71) ꢀ 74:22:4
Dimethylsulfoxide
N,N-Dimethylacetamide

L.V. Saloutina et al. / Journal of Fluorine Chemistry 128 (2007) 769–778
771
Scheme 2. (i) Dioxane, 100 8C, 20 h; (ii) toluene, 100 8C, 25 h; (iii) tetrahydrofuran, 100 8C, 5 h; (iiii) dimethoxyethane, 100 8C, 9.5 h; (iiiii) acetonitrile, 100 8C,
5.5 h.
1
nucleophile is oxidized to give 2,20-diaminodiphenyldisulfide
3.
The additional sets of signals in the 19F, H and 13C NMR
spectra of the crude 2 were assigned to (RR,SS)-diastereomer of
benzothiazine 2 with syn-arrangement of groups CF3.
Such direction of the reaction can be explained by higher
reactivity of NH2 group of the nucleophile probably due to the
absence of the charged S-nucleophile in toluene and dioxane.
The structure of (RS,SR)-diastereomer of benzothiazine 2
with anti-arrangement of groups CF3 isolated in an individual
The structure of the molecule (RS,SR)-2 determined by X-
ray study is shown in Fig. 1. Crystals are formed by two
independent molecules with H-bond between the hydroxy
˚
˚
groups (O(1)Hꢂ ꢂ ꢂO(1A) 2.082 A, O(1)ꢂ ꢂ ꢂO(1A) 2.816 A,
Fig. 2). It is noteworthy that H-bond is formed between
the centers with opposite configurations (RS and SR,
respectively) and crystal is heterochiral not only due to
centrosymmetric space group P-1. Other interesting inter-
1
form was determined by 19F, H, 13C NMR, IR spectroscopy,
GC–MS, elemental analysis and X-ray analysis.
In the 19F NMR spectrum of compound (RS,SR)-2 a doublet
of quartets at ꢁ70.3 ppm was found for the CF3CHNH group
5
(3JF–H 6.9, JF–F 4.3 Hz), and a quartet at ꢁ79.6 ppm was
molecular contacts are N(1)Hꢂ ꢂ ꢂF(3) 2.473 A (N(1)ꢂ ꢂ ꢂF(3)
˚
assigned to fluorine nuclei of the CF3(CS)OH group (5JF–F
4.3 Hz). The molecule of the compound was determined to
have anti-position of groups CF3 by a weak coupling between
the latter [14].
3.118 A) and F(3a)ꢂ ꢂ ꢂF(6a) 2.855 A. Measured C–CF3 bonds at
˚
˚
˚
C(9) 1.538 A and C(9A) 1.531 A are longer then C–CF3 at C(8)
˚
˚
˚
1.525 A and C(8a) 1.518 A, probably, due to presence C(9)–S
(C(9A)–S) and C(9)–O (C(9A)–O) bonds.

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L.V. Saloutina et al. / Journal of Fluorine Chemistry 128 (2007) 769–778
Fig. 1. The molecular structure of (RS,SR)-isomer of compound (2).
A similar reaction of oxirane 1 with 2-aminothiophenol in
solvent [18] which promotes some activation of thiol
function.
tetrahydrofuran having polarity, ionizing and dissociating
ability, close to that of dioxane [18], also promoted the
preferable formation of benzothiazine 2 (72%, RR,SS/
RS,SR ꢀ 37:63). But in this case ꢀ28% of the starting
oxirane 1 reacted with 2-aminothiophenol affording the ring
opening product, 1,1,1,3,4,4,4-heptafluoro-2,2-dihydroxy-3-
(2-aminophenylthio)butane 4, which probably was formed
from 1,1,1,3,4,4,4-heptafluoro-3-(2-aminophenylthio)butane-
2-one C after adding of water into the reaction mixture
(Scheme 2, path b; Table 1, run 3). Formation of compound 4
can be explained by the initial attack of SH group of the
reagent. This is probably due to rather high basicity of the
The structure of compound 4 has been determined using
GC–MS, NMR 1H and 19F by comparing with model
compounds: 2,2-dihydroxyoctafluorobutane and 2,2-dihydrox-
ydodecafluorohexane [16]. Attempts to obtain diol 4 in
individual form were not successful: removal of the remaining
solvent and 2-aminothiophenol from the crude product led to
decomposition of compound 4 and formation of complex
product mixtures.
Use of acetonitrile, the aprotic solvent with rather a high
polarity but low ionizing and dissociating power [18] also gave
a mixture of products 2, 4 with predominant formation of
Fig. 2. The general view of the two independent isomers (RS and SR) of
compound (2) in unit cell.
Fig. 3. 5a,11a-Bis(trifluoromethyl)-5a,6,11a,12-tetrahydro-5,11-dithia-6,12-
diazanaphthacene (5) from X-ray data.

L.V. Saloutina et al. / Journal of Fluorine Chemistry 128 (2007) 769–778
773
compound 2 (74%, RR,SS/RS,SR ꢀ 16:84) (Scheme 2; Table 1,
run 5).
disappeared and the signal at ꢁ70.9 ppm of compound 5 was
appeared. The structure of compound 5 has been proved by IR,
1H, 19F, 13C NMR spectroscopy, elemental analysis and X-ray
analysis.
Dimethoxyethane having a low polarity, low ionizing and
dissociating power [18] led to formation of compounds 2, 4
approximately in equal percentage (2/4 ꢀ 57:43). Increase of
the compound 4 yield in this case is probably conditioned by
cation complexing properties of the solvent [18] promoting
thiolate anion formation (Scheme 2; Table 1, run 4).
Note, the intermediate C (Scheme 2) did not afford the
intramolecular cyclization product during the reactions,
possibly, due to solvation of NH2 and C O groups. But in
all cases crude products obtained containing compound 4 and
The structure of the molecule 5 determined by X-ray study is
shown in Fig. 3. Crystals of the compound are tetragonal, space
group I41. The structure has cis-orientation of CF3-groups.
Bond lengths and angles are typical for this class of compounds.
In polar dimethylsulfoxide and N,N-dimethylacetamide,
unusual cyclization occurred resulting in formation of 2-
trifluoromethyl-2-[1-(2-aminophenylthio)-2,2,2-trifluor-
oethyl]-1,3-benzothiazolidine 6. Thus, treating oxirane 1 with
2-aminothiophenol in dimethylsulfoxide yielded mainly com-
pound 6 as a mixture of diastereomers (RS,SR/RR,SS ꢀ 43:57,
ꢀ75%) and diol 4 (ꢀ25%) (Table 1, run 6). When the reaction
was carried out in N,N-dimethylacetamide benzothiazolidine 6
1
2-aminothiophenol (probably as adduct, from H NMR) gave
5a,11a-bis(trifluoromethyl)-5a,6,11a,12-tetrahydro-5,11-
dithia-6,12-diazanaphthacene 5 on standing for several weeks.
In 19F spectra of the crude products signals of compound 4 were
Scheme 3. (i) 2-Aminothiophenol, dimethylsulfoxide, 100 8C, 1 h; (ii) 2-aminothiophenol, N,N-dimethylacetamide, 100 8C, 3.5 h.

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L.V. Saloutina et al. / Journal of Fluorine Chemistry 128 (2007) 769–778
Fig. 4. The molecular structure of (RS,SR)-isomer of compound (6).
(RS,SR/RR,SS ꢀ 46:54, ꢀ74%), diol 4 (ꢀ22%) and benzothia-
zine 2 (RR,SS/RS,SR ꢀ 29:71, ꢀ4%) were obtained (Table 1,
run 7).
To obtain more precise information about the thiazolidine 6
structure the X-ray investigation of monocrystal 6 prepared by
fractional crystallization has been carried out. It has been found
RS,SR-configuration of the molecules. Due to centrosymmetric
space group P21/n crystals are formed by both (RS)- and (SR)-
enantiomers. Conformation of the molecules in crystals is
stabilized by strong intramolecular H-bond between benzothia-
zolidine NH and nitrogen of amino group (N(1)Hꢂ ꢂ ꢂN(2)
The scheme of the reactions can be rationalized as shown in
Scheme 3.
As in the case of the reaction between hexafluoro-1,2-
epoxypropane and 2-aminothiophenol [12] (Scheme 1), the
polar solvents apparently promote the formation of the
reactive thiolate anion which attacks the epoxide carbon atom
1 with subsequent ring opening and formation of intermediate
C (Scheme 3, path b). After that 2-aminothiophenol reduces
the carbonyl group of the latter resulting in 1,1,1,3,4,4,4-
heptafluoro-3-(2-aminophenylthio)buthan-2-ol D. The attack
of NH2 group at the C-3 atom of intermediate D with
elimination of HF gives benzothiazolidine E. The further
nucleophilic substitution of OH group in intermediate E by
SH function of 2-aminothiophenol with elimination of H2O
leads to product 6. At the same time, intermediate C can add
a molecule of H2O to yield hem-diol 4. Note, the reaction can
proceed via the initial attack of NH2 group of 2-
aminothiophenol and intermediates A and G (Scheme 3,
path a). But the preferable formation of compound 4 in a
similar reaction carried out in N,N-dimethylacetamide–water
(exp.) confirms the first path of the reaction (Scheme 3,
path b).
˚
˚
2.236 A, N(1)ꢂ ꢂ ꢂN(2) 3.099 A). Also strong intermolecular
˚
˚
contacts N(2)Hꢂ ꢂ ꢂF(5a) 2.523 A (N(2)ꢂ ꢂ ꢂF(5a) 3.171 A) and
˚
˚
N(2)Hꢂ ꢂ ꢂC(9a) 2.677 A (N(2)ꢂ ꢂ ꢂC(9a) 3.486 A) are presented
to form ‘‘dimeric’’ packing of molecules in crystals. The
structure of the molecule RS,SR-6 determined by X-ray study is
shown in Fig. 4.
3. Conclusion
In conclusion, we have reported the approach towards
synthesis of novel 5-, 6-membered trifluoromethylcontaining
N,S-heterocyclic compounds – dihydrobenzothiazine 2, thia-
zolidine 6 and bis(benzothiazine) 5 – through the reaction of
octafluoro-2,3-epoxybutane 1 with 2-aminothiophenol.
Use of toluene, dioxane, tetrahydrofuran, acetonitrile and
dimethoxyethane gives the unexpected product, dihydroben-
zothiazine 2 (RS,SR > RR,SS), in good to moderate yields. This
is likely due to the initial attack of the amino group of the
dinucleophile and subsequent reduction of the intermediate
bezothiazine.
The structure of (RS,SR)-diastereomer 6 isolated in
individual form by recrystallization of stereoisomer mixture
1
was determined by IR, 19F, H, 13C NMR spectroscopy, GC–
MS and elemental analysis.
A similar reaction in dimethylsulfoxide and N,N-dimethy-
lacetamide affords benzothiazolidine 6 (RS,SR/RR,SS ꢀ 1:1)
probably as a result of the initial attack of thiol function of 2-
aminothiophenol, in moderate yields.
1
Additional sets of signals in H, 13C, 19F spectra of crude
product 6 were assigned to (RR,SS)-isomer 6. GC–MS specter
of the latter was practically identical to that of (RS,SR)-6.

L.V. Saloutina et al. / Journal of Fluorine Chemistry 128 (2007) 769–778
775
3
˚
Formation of minor 1,1,1,3,4,4,4-heptafluoro-3-(2-amino-
phenylthio)-2,2-dihydroxybutane 4 with subsequent its con-
version into bis(benzothiazine) 5 is observed in all solvents
studied excluding toluene and dioxane.
90.008, V = 1652.92(18) A , Z = 4, M = 303.23, dcalc =
1.641 g/cm3, m(Mo Ka) = 0.388 mmꢁ1, F(0 0 0) = 824. Inten-
sities of 2728 reflections were measured with ‘‘Xcalibur 3’’ CCD
˚
diffractometer, l(Mo Ka) = 0.71073 A, v-scans with 0.58 steps
Compounds prepared in this work are of interest as
biologically active substances and new convenient precursors
for synthesis of complex heterocyclic systems.
in v and 10 c per frame exposure, u range for data collection
3.50–26.368, and 1600 (R(int) = 0.0136) independent reflections
were used in further refinement. Absorption correction was not
performed. The structure was solved by direct methods and
refined by full-matrix least-squares technique against on F2 in
anisotropic approximation. Hydrogen atoms were located from
Fourier synthesis and refined in riding model. Final R indices
[I > 2s(I)] R1 = 0.0258, wR2 = 0.0656. R indices (all data)
R1 = 0.0305, wR2 = 0.0677. Goodness-of-fit onF2 1.001, largest
4. Experimental
1H, 13C (1H decoupled), 19F NMR spectra were recorded on
a Bruker DRX-400 spectrometer operating at 400, 100 and
376 MHz, respectively. Chemical shifts are reported in ppm (d)
from internal (CH3)4Si for hydrogen and carbon and internal
CCl3F for fluorine (CDCl3). Mass spectra were obtained on a
Fisions GC–MS instrument with detector MD 800, quartz
capillary column HP-5, 25 m ꢃ 0.25 mm, thickness of a
stationary phase film 0.25 mm, the carrier-gas—helium,
ionization energy 70 eV. Infrared spectra were obtained on a
Perkin Elmer Spectrum One FT-IR spectrometer in Nujol. The
diff. peak and hole 0.125 and ꢁ0.135 einstein Aꢁ3, complete-
˚
ness to u = 26.368 98.8%. All calculations were performed using
SHELXTL [20].
4.3. Crystallographic data for (RS,SR)-(2-trifluoromethyl-
2-[1-(2-aminophenylthio)-2,2,2-trifluoroethyl]-1,3-
benzothiazolidine) (6)
n
max. are reported in cmꢁ1. Elemental analyses were carried out
on a Perkin Elmer PE 2400 elemental analyzer. Thin-layer
chromatography (TLC) was performed on Silufol UV-254
plates, column chromatography—on silica gel 0.35–0.070 mm
(220–440 mesh). Melting points were measured in open
capillaries and are reported uncorrected. Oxirane (1) was
prepared according to a reported procedure [17].
C16H12F6N2S2 crystal at 295(2) K is monoclinic, space group
˚
˚
P21/n a = 9.1184(5) A, b = 17.9086(4) A, c = 10.6367(7) A,
˚
3
˚
a = 908, b = 94.332(5)8, g = 908, V = 1731.99(15) A , Z = 4,
M = 410.40, dcalc = 1.574 g/cm3, m(Mo Ka) = 0.370 mmꢁ1
F(0 0 0) = 832. Intensities of 20,479 reflections were measured
,
˚
with ‘‘Xcalibur 3’’ CCD diffractometer, l(Mo Ka) = 0.71073 A,
v-scans with 1.08 steps in v and 10 c per frame exposure, u range
for data collection 2.84–31.688, and 5329 (R(int) = 0.0411)
independent reflections were used in further refinement. The
structurewas solved by direct methods and refined by full-matrix
least-squares technique against on F2 in anisotropic–isotropic
approximation. Hydrogen atoms were located from Fourier
synthesis and refined in riding model. Final R indices [I > 2s(I)]
R1 = 0.0368, wR2 = 0.0676. R indices (all data) R1 = 0.1035,
wR2 = 0.0731, Goodness-of-fit on F2 1.001, largest diff. peak
4.1. Crystallographic data for structure for (RS,SR)-2,3-
bis(trifluoromethyl)-3,4-dihydro-2H-1,4-benzothiazine-2-ol
(2)
C10H7F6NOS crystal at 295(2) K is triclinic, space group P-1
˚
˚
˚
a = 7.675(3) A, b = 9.786(4) A, c = 16.036(9) A, a = 83.03(4)8,
3
˚
b = 84.93(4)8, g = 76.00(3)8, V = 1157.8(9) A , Z = 4, M =
303.23, dcalc = 1.740 g/cm3, m(Mo Ka) = 0.350 mmꢁ1
F(0 0 0) = 608. Intensities of 18,769 reflections were measured
,
and hole 0.213 and ꢁ0.163 einstein Aꢁ3, completeness to
˚
˚
with ‘‘Xcalibur 3’’ CCD diffractometer, l(Mo Ka) = 0.71073 A,
u = 26.008 99.2%. All calculations were performed using
SHELXTL on IBM PC AT [20].
v-scans with 1.08 steps in v and 10 c per frame exposure, u range
for data collection 2.26–31.698, and 7103 (R(int) = 0.0411)
independent reflections were used in further refinement. The
structurewas solved by direct methods and refined by full-matrix
least-squares technique against on F2 in anisotropic–isotropic
approximation. Hydrogen atoms were located from Fourier
synthesis and refined in riding model. Final R indices [I > 2s(I)]
R1 = 0.0392, wR2 = 0.0381. R indices (all data) R1 = 0.1413,
wR2 = 0.0413, Goodness-of-fit on F2 1.000, largest diff. peak
Crystallographic data for the structure reported in this paper
have been deposited with the Cambridge Crystallographic Data
Center as supplementary no. CCDC 642383–642385. Copies of
the data can be obtained free of charge on application to CCDC,
12 Union Road, Cambridge CB2 1EZ, UK (fax: +44-1223/336-
033; e-mail: deposit@ccdc.cam.ac.uk).
4.4. The reaction of oxirane (1) with 2-aminothiophenol
and hole 0.242 and ꢁ0.343 einstein Aꢁ3, completeness to
˚
u = 26.008 99.7%. All calculations were performed using
SHELXTL [20].
4.4.1. Procedure 1
A mixture of oxirane 1 (4.8 g, 22.4 mmol), 2-aminothio-
phenol (2.8 g, 22.4 mmol) and dioxane (10 ml) was heated in a
sealed tube in a boiling water bath, with intermittent shaking.
After cooling (ꢁ70 8C), the tube was opened and the residual
oxirane condensed into a cooled trap (ꢁ70 8C). Then a solid of
2-aminothiophenol hydrofluoride was filtered off. The filtrate
was poured into ice water (200 ml), and the resultant precipitate
was collected by filtration and dried at room temperature. The
4.2. Crystallographic data for structure 5a,11a-
bis(trifluoromethyl)-5a,6,11a,12-tetrahydro-5,11-dithia-
6,12-diaza-naphthacene (5).
C16H10F6N2S2 crystal at 295(2) K is tetragonal, space group
˚
I41 a = b = 11.6434(5) A, c = 12.1925(11) A, a = b = g =
˚

776
L.V. Saloutina et al. / Journal of Fluorine Chemistry 128 (2007) 769–778
solid obtained (3.4 g) containing benzothiazine 2 (RR,SS/
1
4.4.2. Procedure 2
RS,SR ꢀ 20:80) and disulfide 3 [from 19F, H NMR and TLC
In a similar manner, oxirane 1 (2.9 g, 13.4 mmol) was
treated with 2-aminothiophenol (1.7 g, 13.6 mmol) in toluene
(20 ml). After cooling (ꢁ70 8C), the tube was opened and the
residual oxirane condensed into a cooled trap (ꢁ70 8C). The
precipitate of 2-aminothiophenol hydrofluoride was filtered off,
and the filtrate was evaporated to give yellow solid (1.6 g)
containing benzothiazine 2 (RR,SS/RS,SR ꢀ 2:98) and disulfide
3 (from 19F, 1H NMR, Table 1, run 2). The solid was extracted
with hot hexane, and the extract was evaporated. The obtained
crystals (compound 2 with residual disulfide 3) was purified by
a column chromatography (SiO2, eluent: CHCl3–MeOH,
10:0.5) to yield 0.6 g (43.8%) of RS,SR-isomer of benzothia-
zine 2.
(eluent: CHCl3–MeOH, 10:0.5; RF 2 = 0.36; RF 3 = 0.74)]
(Table 1, run 1) was extracted with hot hexane. The hexane
extract was dried under MgSO4 and evaporated. The solid
residue (mainly the compound 2 with remaining disulfide 3)
was separated by a column chromatography (SiO2, eluent:
CHCl3–MeOH, 10:0.5) to give 1.0 g (44.2%) of the benzothia-
zine 2 (RR,SS/RS,SR ꢀ 5:1). After that compound 2 was
recrystallized from hexane, then—from a mixture hexane–
benzene (10:0.5) to give colorless crystals of compound RS,SR-
(2), 0.75 g (33%). Recrystallization of crude compound 3 from
a mixture hexane–CHCl3 (10:1) afforded yellow crystals of
disulfide 3.
4.4.1.1. (RS,SR)-2,3-Bis(trifluoromethyl)-3,4-dihydro-2H-1,4-
benzothiazine-2-ol (2). mp 71–73 8C. IR: n 1570 (C C), 2640,
2710, 3320, 3360, 3410 (NH, OH). H NMR: d 3.56 (1H, s,
4.4.3. Procedure 3
The reaction of oxirane 1 (4.8 g, 22.4 mmol) with 2-
aminothiophenol (2.8 g, 22.4 mmol) in 14 ml of THF gave
yellow solid product (2.5 g) containing benzothiazine 2, hem-
diol 4, disulfide 3 and residual 2-aminothiophenol [from 19F, 1H
NMR and TLC (eluent: CHCl3–MeOH, 10:0.5; RF 2 = 0.36; RF
3 = 0.74)] (Table 1, run 3). The crude product was allowed to
stand at room temperature over 3 weeks. The product obtained
consisted of compounds 2, 3 and 5 [from 19F, 1H NMR and TLC
(eluent: CHCl3–hexane, 1:2; RF 2 = 0.28; RF 3 = 0.18; RF
5 = 0.95)] was worked up as in Procedure 1. Column
chromatography (SiO2, eluent: CHCl3–hexane, 1:2) gave
0.7 g (31%) of compound (2, RR,SS/RS,SR ꢀ 7:11) and 0.1 g
(2.2%) of compound 5 as colorless crystals.
1
3
3
OH), 4.28 (1H, qd, JHF 6.9, JHH 3.0 Hz, CF3CHNH,), 4.45
(1H, br.s, NH), 6.76 (1H, dd, J 7.4, 1.1 Hz, H-5), 6.86 (1H, ddd,
J 8.1, 7.1, 1.1 Hz, H-7), 7.04–7.08 (2H, m, H-6, H-8). 13C NMR
2
2
(DMSO-d6): d 52.9 (q, JCF 27.9 Hz, C-3), 76.2 (q, JCF
30.0 Hz, C-2), 114.4 (s, C-8a), 115.6 (s, C-5), 118.4 (s, C-7),
1
1
123.9 (q, JCF 287.4 Hz, CF3), 124.4 (q, JCF 287.0 Hz, CF3),
125.4 (s), 125.8 (s) (C-6, C-8), 137.5 (s, C-4a). 19F NMR: d
5
3
ꢁ79.6 (3F, q, JFF 4.3 Hz, CF3-C2), ꢁ70.3 (3F, dq, JHF 6.9,
5JFF 4.3 Hz, CF3-C3). GC–MS, m/z (rel. int.): 304 [M + 1]+
(7.7), 303 [M]+ (88.1), 234 [M ꢁ CF3]+ (18.4), 216
[M ꢁ CF3 ꢁ H2O]+ (10.4), 207 [M + 1 ꢁ CF3 ꢁ CO]+ (8.5),
206 [M ꢁ CF3 ꢁ CO]+ (100), 204 [M ꢁ CF3H ꢁ COH]+ (8.4),
184 [M ꢁ C2F5]+ (11.0), 174 [M ꢁ CF3CSO]+ (10.4), 166
(13.2), 165 [M ꢁ 2CF3]+ (14.3), 150 (14.2), 146
[M ꢁ 2CF3 ꢁ H2O ꢁ H]+ (15.1), 142 [M ꢁ C6H4NH2 ꢁ CF3]+
]+ (8.9), 137 (9.6), 136 [M ꢁ 2CF3 ꢁ CO ꢁ H]+ (84.3), 109
(27.0), 108 [C6H4S]+ (7.9), 104 [C6H4NHCH]+ (16.4), 96
[CF3CNH]+ (10.5), 93 [C6H5NH2]+ (8.8), 77 [C6H5]+ (10.1), 69
[CF3]+ (29.7). Anal. Calcd for C10H7F6NSO: C, 39.6; H, 2.3; F,
37.6; N, 4.6; S, 10.6. Found: C, 39.6; H, 2.3; F, 37.7; N, 4.3; S,
10.2.
4.4.3.1. 5a,11a-Bis(trifluoromethyl)-5a,6,11a,12-tetrahydro-
5,11-dithia-6,12-diaza-naphthacene (5). mp 180 8C. IR: n
1494, 1592 (NH, C C), 2750, 3377, 3400 (NH). 1H NMR: d 4.38
(2H, s, 2NH), 6.44 (2H, d, 2CH), 6.81–6.85 (2H, m, 2CH), 6.95–
6.99 (2H, m, 2CH), 7.04 (2H, d, 2CH). 13C NMR: d 67.4 (q, 2JCF
27.0 Hz, C-5a, C-11a), 122.5 (q, 1JCF 287.7 Hz, 2 CF3), 113.2 (s,
C-4a, C-10a), 116.0 (s, C-1, C-7), 121.1 (s, C-3, C-9), 127.2 (s),
127.6(s)(C-2, C-4, C-8, C-10), 137.0(s, C-6a, C-12a). 19FNMR:
d ꢁ70.9 (2CF3). GC–MS, m/z (rel. int.): 408 [M]+ (10.5), 285
[M ꢁ C6H4(S)NH]+ (6.5), 204 [M ꢁ CF3CSC6H4NH]+ (100),
184 [M ꢁ CF3CSC6H4NH ꢁ HF]+ (48), 136 (23), 102 (14), 69
[CF3]+ (12.5). Anal. Calcd for C16H10F6N2S2: C, 47.1; H, 2.5; F,
27.9; N, 6.9; S, 15.7. Found: C, 46.9; H, 2.5; F, 27.9; N, 6.9; S,
15.7.
4.4.1.2. (RR,SS)-2,3-Bis(trifluoromethyl)-3,4-dihydro-2H-ben-
zothiazin-2-ol (2). 1H NMR: d 3.44 (1H, s, OH), 4.17 (1H, dq,
3JHF JHH 6.8 Hz, CF3CHNH), 4.65 (1H, br.s, NH), 6.78 (1H,
3
m, H-5), 6.88 (1H, m, H-7), 7.04–7.08 (2H, m, H-6, H-8). 13
C
NMR (DMSO-d6): d 56.8 (q, 2JCF 30.3 Hz, C-3), 76.4 (q, 2JCF
31.5 Hz, C-2), 114.9 (s, C-8a), 115.7 (s, C-5), 118.2 (s, C-7),
1
1
123.0 (q, JCF 283.1 Hz, CF3), 123.7 (q, JCF 279.5 Hz, CF3),
126.4 (s), 127.6 (s) (C-6, C-8), 138.3 (s, C-4a). 19F NMR: d:
4.4.4. Procedure 4
The reaction of oxirane 1 (5.0 g, 23.1 mmol) with 2-
aminothiophenol (2.9 g, 23.2 mmol) in 10 ml of dimethox-
yethane gave yellow solid product (2.7 g) containing
benzothiazine 2, hem-diol 4, disulfide 3 and remaining 2-
aminothiophenol (Table 1, run 4). The crude product
was allowed to stand at room temperature over 3 weeks
and then worked up as in Procedure 3. Column chromato-
graphy (SiO2, eluent: CHCl3–hexane, 1:2) gave 0.35 g (15%)
of compound 2 (RR,SS/RS,SR ꢀ 1:9) and 0.2 g (4.2%) of
compound 5.
5
5
ꢁ76.5 (3F, q, JFF 9.6 Hz, CF3-C2), ꢁ72.2 (3F, qd, JFF 9.6,
3JFH 6.9 Hz, CF3-C3).
4.4.1.3. 2,20-Diaminodiphenyldisulfide (3). mp 90–91 8C (lit.
mp 91.5–92.5 8C [21]). IR: n 1555, 1570, 1600, 1610 (C C,
NH), 3165, 3190, 3285, 3365 (NH). 1H NMR: d 4.28 (4H, br.s,
2NH2), 6.58 (2H, m, 2CH), 6.71 (2H, m, 2CH), 7.15 (4H, m,
4CH). Anal. Calcd for C12H12N2S2: C, 58.1; H, 4.8; N, 11.3; S,
25.8. Found: C, 58.2; H, 4.8; N, 11.2; S, 26.0.

L.V. Saloutina et al. / Journal of Fluorine Chemistry 128 (2007) 769–778
777
4.4.5. Procedure 5
CF3CH-S), 5.10 (1H, br.s, NH), 6.65 (1H, dd, J 7.9, 0.6 Hz, CH
ar), 6.75 (2H, m, 2CH ar), 6.82 (1H, td, J 7.6, 1.0 Hz, CH ar), 7.00
(1H, td, J 7.7, 1.1 Hz, CH ar), 7.09 (1H, dd, J 7.6, 1.1 Hz, CH ar),
7.20 (1H, ddd, J 8.0, 7.3, 1.4 Hz, CH ar), 7.56 (1H, dd, J 7.7,
1.2 Hz). 13C NMR: d 60.8 (q, 2JCF 27.7 Hz, C-2), 80.6 (q, 2JCF
31.7 Hz, C-3), 124.2 (q, JCF 285.7 Hz, CF3), 124.8 (q, JCF
281.0 Hz, CF3), 109.6 (s), 115.3 (s), 115.9 (s), 119.3 (s), 121.1
(s), 123.4 (s), 126.3 (s), 131.7 (s), 137.2 (s), 145.1 (s), 148.6 (s)
(carbonatoms of aromatic cycles). 19F NMR: d ꢁ78.6 (3F, q, 5JFF
9.8 Hz, CF3-C2), ꢁ64.9 (3F, dq, 3JHF 8.7, 5JFF 9.8 Hz, CF3-C3).
GC–MS, m/z (rel. int.): 217 [M ꢁ C6H4S(NH)2 ꢁ CF3]+ (7.1),
207 (14.2), 206 [C6H4(NH2)(S)CHCF3]+ (6.7), 204
[CF3C(S)(NH)C6H4]+ (100), 184 (27.9), 136 [C6H4(NH2)SC]+
(5.8), 109 (6.5), 108 [C6H4S]+ (8.4), 102 (7.2), 97 (9.0), 93 (7.1),
80 (45.4), 69 [CF3]+ (11.4). Anal. Calcd for C16H12F6N2S2: C,
46.8; H, 2.9; F, 27.8; N, 6.8; S, 15.6. Found: C, 46.7; H, 2.8; F,
27.5; N, 6.9; S, 15.8.
The reaction of oxirane 1 (6.0 g, 27.7 mmol) with 2-
aminothiophenol (3.5 g, 28 mmol) in 10 ml of acetonitrile gave
yellow solid product (3.3 g) containing benzothiazine 2, hem-
diol 4, disulfide 3 and remaining 2-aminothiophenol (Table 1,
run 5). The crude product was allowed to stand at room
temperature over 3 weeks and then worked up as in Procedure
3. Column chromatography (SiO2, eluent: CHCl3–hexane, 1:2)
gave 0.7 g (24.7%) of compound 2 (RR,SS/RS,SR ꢀ 3:17) and
0.1 g (2.2%) of compound 5.
1
1
4.4.6. Procedure 6
Inasimilarmanner, oxirane1(3.3 g, 15.28 mmol)wastreated
with 2-aminothiophenol (1.9 g, 15.20 mmol) in 5 ml of DMAA
for 3.5 h. After cooling (ꢁ70 8C), the tube was opened and the
residual oxirane condensed into a cooled trap (ꢁ70 8C). Then the
reaction mixture was poured into ice water (200 ml), and the
lower organic layer was separated, twice washed with water and
dried (ꢀ40 8C). The resinous residue obtained (2.7 g) consisted
of benzothiazolidine 6 (RS,SR/RR,SS ꢀ 46:54), diol 4, ben-
zothiazine 2 (RR,SS/RS,SR ꢀ 29:71) and disulfide 3 (from IR,
4.4.6.3. 1,1,1,3,4,4,4-Heptafluoro-2,2-dihydroxy-3-(2-amino-
phenylthio)butane (4). IR: n 1586 (C C), 1610 (NH), 3070,
3180, 3390 br., 3480 (NH, OH). 1H NMR: d 3.8 (4H, br.s, NH2,
2OH), 6.6 (1H, m, CH), 6.7 (1H, m, CH), 7.2 (2H, m, 2CH)
1
19F, H NMR and GC–MS) (Table 1, run 7). The residue was
3
4
(aromatic protons). 19F NMR: d ꢁ140.4 (1F, qq, JFF JFF
reprecipitated from chloroform by hexane to give yellow crystals
of disulfide 3 which were filtered off. The filtrate obtained was
evaporated, and the residue containing thiazolidine 6 as a major
product was purified by column chromatography (eluent:
hexane–CHCl3, 1:1; RF 6RS,SR = 0.90, RF 6RR,SS = 0.85) to give
0.8 g (51%) of the compound 6 (RS,SR/RR,SS ꢀ 7:3). Fractional
recrystallization from hexane–benzene yielded 0.2 g (13%) of
compound 6 (RS,SR/RR,SS = 2:3, mp 80–125 8C), 0.15 g (10%)
of compound 6 (RS,SR/RR,SS = 4:1, mp 77–82 8C) and 0.15 g
(10%) of compound RS,SR-6 as colorless crystals.
4
5
11.2 Hz, CF3CF), ꢁ78.4 (3F, dq, JFF 11.2, JFF 9.5 Hz,
CF3C(OH)2), ꢁ72.8 (3F, dq, 3JFF 11.2, 5JFF 9.5 Hz, CF3CFS).
GC–MS, m/z (rel. int.): 322 [M ꢁ OH]+ (8.2), 321 [M ꢁ H2O]+
(89.8), 252 [M ꢁ H2O ꢁ CF3]+ (38.7), 235 [M ꢁ OH ꢁ H2O
ꢁ CF3]+ (10.5), 234 (11.0), 233 (7.2), 232 [M ꢁ H2O ꢁ
HF ꢁ CF3]+ (54.7), 205 (9.4), 204 [M ꢁ H2O ꢁ HF ꢁ CF3CO]+
CF3CO]+ (100), 189 (6.1), 188 (40.2), 185 (9.0), 184 (61.7), 172
(14.5), 168 (5.5), 162 (8.6), 154 [C6H4(NH)SCF]+ (14.7), 151
(5.5), 150 (12.9), 135 [C6H4(NH)SC]+ (6.7), 124 [C6H4(S)NH2]+
(8.9), 123 (6.8), 122 (7.7), 120 [C6H4SC]+ (27.3), 109 (12.4), 108
[C6H4S]+ (8.3), 102 (7.2), 96 (19.0), 95 (9.6), 93 (6.3), 92
[C6H4NH2]+ (22.7), 91 (7.7), 80 (6.7), 77 [C6H5]+ (14.7), 70
(7.6), 69 [CF3]+ (40.4).
4.4.6.1. (RS,SR)-(2-Trifluoromethyl-2-[1-(2-aminophe-
nylthio)-2,2,2-trifluoroethyl]-1,3-benzothiazolidine) (6). mp
82–83 8C. IR: n 1582, 1614 (C C, NH2), 3226 (br), 3344,
1
3
3389, 3438 (NH, NH2). H NMR: d 4.09 (1H, q, JHF 8.8 Hz,
CF3CH-S), 4.32 (2H, br.s, NH2), 5.78(1H, br.s, NH), 6.62 (1H, d,
J 7.7 Hz, CH ar), 6.74 (2H, m, 2CH ar), 6.95 (1H, td, J 7.7,
1.2 Hz, CH ar), 6.98 (1H, dd, J 7.6, 1.0 Hz, CH ar). 7.17 (1H, ddd,
4.4.7. Procedure 7
The reaction of oxirane 1 (6.4 g, 29.6 mmol) with 2-
aminothiophenol (3.7 g, 29.6 mmol) in 10 ml of DMSO gave
yellow solid product (3.7 g) containing thiazolidine 6 (RS,SR/
RR,SS ꢀ 43:57), hem-diol 4, disulfide 3 and remaining 2-
aminothiophenol (Table 1, run 6). The crude product was
allowed to stand at room temperature over 3 weeks and then
worked up as in Procedure 6. Column chromatography (SiO2,
eluent: CHCl3–hexane, 1:2) gave 1.2 g (40%) of compound 6
(RR,SS/RS,SR ꢀ 7:11) and 0.1 g (1.7%) of compound 5.
J 8.2, 7.3, 1.7 Hz, CH ar), 7.46 (1H, dd, J 7.9, 1.4 Hz, CH ar). 13
NMR: d 62.2 (q, 2JCF 27.4 Hz, C-2), 78.2 (q, 2JCF 31.4 Hz, C-3),
C
1
1
124.2 (q, JCF 285.6 Hz, CF3), 124.6 (q, JCF 280.7 Hz, CF3),
109.1(s), 116.1(s), 116.2 (s), 120.1 (s), 120.7(s), 121.0(s), 123.0
(s), 126.2 (s), 131.5 (s), 136.6 (s), 143.5 (s), 148.1 (s) (carbon
atoms of aromatic cycles). 19F NMR: d ꢁ77.8 (3F, q, 5JFF 8.1 Hz,
CF3-C2), ꢁ65.2 (3F, dq, 3JHF JFF 8.2 Hz, CF3-C3). GC–MS, m/z
5
(rel. int.): 217 [M ꢁ C6H4S(NH)2 ꢁ CF3]+ (7.1), 207 (14.2), 206
[C6H4(NH2)(S)CHCF3]+ (6.7), 204 [CF3C(S)(NH)C6H4]+ (100),
184 (27.9), 136 [C6H4(NH2)SC]+ (5.8), 109 (6.5), 108 [C6H4S]+
(8.4), 102 (7.2), 97 (9.0), 93 (7.1), 80 (45.4), 69 [CF3]+ (11.4).
Anal. Calcd for C16H12F6N2S2: C, 46.8; H, 2.9; F, 27.8; N, 6.8; S,
15.6. Found: C, 46.7; H, 2.8; F, 27.5; N, 6.9; S, 15.8.
4.4.8. Procedure 8
In a similar manner, oxirane 1 (5.2 g, 24.07 mmol) was
treated with 2-aminothiophenol (3.0 g, 24 mmol) in 5 ml of
DMAA + H2O (ꢀ98:2) at 70–75 8C for 1.5 h. Then the reaction
mixture was poured into ice water (200 ml), and the lower
organic layer was separated, washed with water once more and
dried (ꢀ40 8C). The resinous residue obtained (7.0 g) consisted
of diol 4, benzothiazine 2 (RR,SS/RS,SR ꢀ 1:2) at a ratio ꢀ4:1,
4.4.6.2. (RR,SS)-(2-Trifluoromethyl-2-[1-(2-aminophe-
nylthio)-2,2,2-trifluoroethyl]-1,3-benzothiazolidine) (6). 1H
3
NMR: 3.80 (2H, br.s, NH2): d 4.00 (1H, q, JHF 8.2 Hz,

778
L.V. Saloutina et al. / Journal of Fluorine Chemistry 128 (2007) 769–778
[9] V.I. Saloutin, S.G. Perevalov, O.N. Chupakhin, Zh. Org. Khim. 36
(2000) 727–732 [Russ. J. Org. Chem. (Engl. Transl.) 36 (2000) 700–
705]..
2-aminothiophenol and small amounts of unidentified products
1
(from IR, 19F, H NMR and GC–MS).
[10] Q. Chu, L. Song, G. Jin, S. Zhu, J. Fluorine Chem. 108 (2001) 51–
56.
Acknowledgement
[11] I.L. Knunyants, V.V. Shokina, I.V. Galakhov, Khim. Geterotsikl. Soedin.
(1966) 873–878 [Chem. Heterocycl. Compd. (Engl. Transl.) 2 (1966) 666–
670]..
The research has been financially supported by the State
Programme for supporting leading scientific schools of Russian
Federation (grant No. 9178.2006.3).
[12] N. Ishikawa, S. Sasaki, Bull. Chem. Soc. Jpn. 50 (1977) 2164–2167.
[13] L.V. Saloutina, A.Ya. Zapevalov, M.I. Kodess, V.I. Saloutin, J. Fluorine
Chem. 87 (1998) 49–55.
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