Reaction of trifl uoromethanesulfonamide with heterodienes under oxidation conditions

Article abstract of DOI:10.1134/S107042801311002X

Reactions of trifl uoromethanesulfonamide with divinyl sulfone, divinyl sulfoxide, divinyl sulfide, diphenyl sulfide, vinyl allyl and diallyl ethers was investigated in the presence of oxidation system t-BuOCl + NaI. The reaction with divinyl sulfone afforded a product of 1,5-heterocyclization, 2,6-diiodo-4-[(trifl uoromethyl) sulfonyl]thiomorpholine 1,1-dioxide. The same product was obtained in the reaction with divinyl sulfoxide apparently due to its preliminary oxidation to sulfone. In reactions with divinyl sulfide and unsaturated ethers only the oxidation of substrates was observed accompanied with strong tarring; the products of a reaction with trifl uoromethanesulfonamide were absent. With diphenyl sulfide a product was formed resulting from the oxidation at the sulfur atom [S(II) → S(IV)], N-(diphenyl-λ4-sulfanylidene)trifl uoromethanesulfonamide. Pleiades Publishing, Ltd., 2013.

Full text of DOI:10.1134/S107042801311002X

ISSN 1070-4280, Russian Journal of Organic Chemistry, 2013, Vol. 49, No. 11, pp. 1567−1571. © Pleiades Publishing, Ltd., 2013.
Original English Text © M.Yu. Moskalik, V.V. Astakhova, B.A. Shainyan, 2013, published in Zhurnal Organicheskoi Khimii, 2013, Vol. 49, No. 11, pp. 1592−1596.
Reaction of Trifluoromethanesulfonamide
with Heterodienes under Oxidation Conditions
M. Yu. Moskalik, V. V. Astakhova, and B. A. Shainyan
Faworsky Irkutsk Institute of Chemistry, Siberian Branch, Russian Academy of Sciences, Irkutsk, 664033 Russia
е-mail: moskalik@irioch.irk.ru
Received April 20, 2013
Abstract—Reactions of trifluoromethanesulfonamide with divinyl sulfone, divinyl sulfoxide, divinyl sulfide,
diphenyl sulfide, vinyl allyl and diallyl ethers was investigated in the presence of oxidation system t-BuOCl +
NaI. The reaction with divinyl sulfone afforded a product of 1,5-heterocyclization, 2,6-diiodo-4-[(trifluoromethyl)
sulfonyl]thiomorpholine 1,1-dioxide. The same product was obtained in the reaction with divinyl sulfoxide
apparently due to its preliminary oxidation to sulfone. In reactions with divinyl sulfide and unsaturated ethers
only the oxidation of substrates was observed accompanied with strong tarring; the products of a reaction with
trifluoromethanesulfonamide were absent. With diphenyl sulfide a product was formed resulting from the oxidation
at the sulfur atom [S(II) → S(IV)], N-(diphenyl-λ4-sulfanylidene)trifluoromethanesulfonamide.
DOI: 10.1134/S107042801311002X
We formerly investigated the addition of trifluoro-
methanesulfonamide CF3SO2NH2 (TfNH2, triflamide)
to a series of alkenes and dienes in the presence of an
oxidation system t-BuOCl + NaI [1–6]. In contrast to
the reaction with unfluorinated sulfonamides [7] aziri-
dines were not found in the reaction with triflamide but
depending on the nature of the substarate and the process
conditions the formed products contained in various ratios
their dimers, isomeric piperazines [1–3], the conjugate
1,2-addition products CH(NHTf)–CHX (X = TfNH, OH,
Cl, I) [1–6], 9-heterobicyclo[4.2.1]nonanes [4]. The reac-
tion of triflamide with heteroatomic unsaturated substrates
was not investigated save our recent short communication
on the formation of the product of oxidation at the sulfur
atom in the reaction of triflamide with diallyl sulfide [8].
The unexpectedly easy oxidation of the sulfur atom
[S(II) → S(IV)] and the inertness of the double bond in the
diallyl sulfide were interpreted with the use of quantum-
chemical calculations revealing that the HOMO of the
diallyl sulfide molecule is localized on all olefin carbon
atoms to less than 2% and to over 55% on the sulfur atom
resulting in the ready oxidation of the latter [8].
The published data on λ4-sulfanes containing S–N
bonds are very scarce [9–13], only S,S-dialkylsulfo-
diimines R2S(NH2)2 (R = Me, Et) are known formed in
reaction of chloramines with dialkyl sulfides followed by
the treatment with sodium ethylate [14].
O
S
O
R2NH
O
RNH2
O
O
O
R
R
R
R
S
S
N R
N
N
In extension of this research aiming at the investiga-
tion of the effect of the heteroatom nature and of the
position of double bonds we report here on the study of
triflamide (I) reactions with divinyl sulfone (II), divinyl
sulfoxide (III), divinyl sulfide (IV), diphenyl sulfide (V),
diallyl and vinyl allyl ethers (VI, VII).All reactions were
carried out in acetonitrile at cooling in the presence of
TfNH
t-BuOCl, NaI
+
2 TfNH2
S
S
CH3CN
TfNH
1567

MOSKALIK et al.
1568
the oxidation system t-BuOCl + NaI.
ppm was split into a doublet of doublets with a large gemi-
nal and a large vicinal constants (Jах–ах), and the downfield
signal of the equatorial hydrogen atom of the CH2 group
at 4.4 ppm possessed a large geminal and a small vicinal
constants (Jах–eq). The signal of the CHI group at 5.4 ppm
corresponds to the equatorial hydrogen atom since the
bulky iodine atoms are located in the equatorial position.
The 13С NMR spectrum without decoupling from protons
contains three signals: a doublet of the CHI group at 31.3
ppm and a triplet of the CH2 group at 54.6 ppm, and also
a quartet of the CF3 group at 121.7 ppm.
The reactions of divinyl sulfoxide and divinyl sulfone
with amines are described in the literature. For instance,
divinyl sulfone reacted with primary and secondary
N-nucleophiles by the type of 1,5-heterocyclization or
double 1,2-addition [15, 16].
Divinyl sulfoxide reacted similarly furnishing
1,4-perhydrothiazine 1-oxides [17–19]. As to the reac-
tions with sulfonamides, only the macrocycles formation
was described in the reaction of divinyl sulfone with
α,ω-bistosylamides in the presence of excess potassium
carbonate [16].
H
H
SO2CF3
SO2CF3
The reaction of divinyl sulfone with triflamide under
the oxidative conditions provided a single heterocycli-
zation product, 2,6-diiodo-4-(trifluoromethylsulfonyl)
thiomorpholine 1,1-dioxide (VIII).
H
I
N
N
I
I
O
O
S
S
H
I
O
O
VIII-(R,S)
IX-(R,R)
I
In the reaction of triflamide with divinyl sulfoxide also
O
oxide VIII was obtained, apparently due to the oxidation
of divinyl sulfoxide to divinyl sulfone by the system t-
BuOCl + NaI. We failed to detect the heterocyclization
product of the proper divinyl sulfoxide, 2,6-diiodo-4-
(trifluoromethylsulfonyl)thio-morpholine 1-oxide, but
the careful analysis by column chromatography made it
possible to isolate a fraction containing compound VIII
and close to it in the structure compound IX in the ratio
2 : 1. The 1Н NMR spectrum of this mixture is presented
in the figure.
O
O
t-BuOCl, NaI. 2H2O
TfNH2+
S
S
I
N Tf
MeCN
O
VIII
The composition and structure of compound VIII were
proved by elemental analysis and IR, 1H, 13C, 19F NMR
spectroscopy. In the 1H NMR spectrum three signals were
observed characteristic of an АВХ spin, where the upfield
signal of the axial hydrogen atom of the CH2 group at 3.9
1Н NMR spectrum of a mixture of S,R- and (R,R + S,S)-diastereomers of 2,6-diiodo-4-(trifluoromethylsulfonyl)thiomorpholine 1,1-di-
oxide (VIII, IХ), 2 : 1.
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REACTION OF TRIFLUOROMETHANESULFONAMIDE
1569
The presence of six separate signals in the spectrum of
of triflamide.
compound IX in contrast to three signals in the spectrum
of compound VIII suggests that the reaction results in
a mixture of S,R- and (R,R+S,S)-diastereomers of the
heterocyclization product with the former compound
prevailing. The main isomer apparently is conforma-
tionally rigid for both iodine atoms cannot be present in
the axial position, whereas the minor isomer should be
conformationally labile. Therewith the spin systems АВХ
and А'В'Х' in molecule IX remain nonequivalent although
in each system the coupling constants are averaged.
In the reaction with diphenyl sulfide like in the re-
action with diallyl sulfide [8] triflamide provided the
product of the oxidation at the sulfur atom but in this
case it possessed the sulfimine structure: N-(diphenyl-λ4-
sulfanylidene)trifluoromethanesulfonamide (Х).
Ph
t-BuOCl, NaI
MeCN
+
TfN S
Ph2S
I
Ph
X
The composition and structure of amide X were proved
by IR, 1H, 13C, 19F NMR, and mass spectra, the latter also
of high resolution. The most characteristic change in the
1H NMR spectrum of compound X compared with the
spectrum of the initial diphenyl sulfide was the downfield
shift of all signals of aromatic protons by 0.3–0.4 ppm,
and in the 13C NMR spectrum, the downfield shift of Сp
signal by 7 ppm and the upfield shift of Сi signal by 5
ppm. The main directions of the molecular ion fragmen-
tation under the lectron impact were the rupture of the
CF3–SO2 bond with approximately equal probability of
the charge localization on both fragments, elimination of
CF3SO2 and CF3SO2N groups as netral radicalx, and the
formation of a phenyl cation.
The heterocyclization mechanism of sulfone II is
apparently analogous to that formerly assumed for the
reaction with cyclodienes [6] and involves the reaction
of CF3SO2NHI formed in situ at one double bond of the
divinyl sulfone giving the intermediate adduct A with the
subsequent attack of the second CF3SO2NHI molecule
resulting in adduct B, which undergoes cyclization into
compound VIII.
If the reaction of sulfoxide III with triflamide in the
presence of t-BuOCl + NaI would proceed as the oxida-
tion (III) → (II) and further along reaction (1), the spectra
of the reaction mixtures would be identical. However the
analysis of 1Н NMR spectra showed that even in the crude
reaction product obtained from triflamide with sulfone II
before chromatographic separation the signals of minor
isomer IX were totally absent in contrast to the product
of triflamide reaction with sulfoxide III. This shows
that the reaction of sulfoxide III with triflamide is more
complex and probably it involves the oxidation of sulfur
atom not only in initial substrate III but also in one of
the intermediate stages А or B.
Previously compound X was obtained by the oxida-
tive imination of diphenyl sulfide under the treatment
with precursors of trifluoromethylsulfonylnitrene like
N,N-dichlorotrifluoromethanesulfonamide [20] or triflu
oromethylsulfonylimino(aryl)-1-bromane [21]. Yet these
procedures require preliminary preparation of reagents
from triflamide whereas reaction (2) is a direct one-stage
synthesis.
We failed to carry out the triflamidation of diallyl
and allyl vinyl ethers under analogous conditions: In
both cases strong tarring was observed. The lack of the
triflamidation products in the reactions with divinyl
sulfide, diallyl and allyl vinyl ethers is apparently due to
the easier oxidation of these substrates compared with
triflamide. In the NMR spectra of the reaction mixture
obtained with diallyl ether the signals of the vinyl groups
disappeared, and only the signals of OСН, OСН2 groups
were observed in the region 3.4–4.3 (1Н) and 43–71 ppm
(13C). The attempt to isolate the individual substances by
column chromatography was unsuccessful.
I
O
t-BuOCl, NaI
+
S
I
II
NHTf
MeCN
O
A
I
O
TfNHI
_TfNH2
S
VIII
NTf
O
I
B
The reaction of triflamide with divinyl sulfide in the
presence of the system t-BuOCl + NaI proceeded with
a strong tarring, we succeeded only to isolate the initial
EXPERIMENTAL
1
triflamide. The Н NMR spectrum after the workup of
the reaction mixture also contained only the NH signal
IR spectra were recorded on a spectrophotometer
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 49 No. 11 2013

MOSKALIK et al.
1570
Bruker IFS-113 from pellets with KBr. NMR spectra were
registered on a spectrometer Bruker DPX-400 [operating
frequencies 400 (1Н), 100 (13С), 376 MHz (19F)], chemi-
cal shifts are reported with respect to TMS (1Н, 13С) and
CCl3F (19F). Mass spectra taken in the electron impact
mode (70 eV) were obtained on an instrument GC-MS
TRACE DSQ II (Thermo Fisher Scientific GmbH). The
precise masses were measured on an instrument Micro-
mass Q-TOFmicro (Waters) in the positive electrospray
mode. The reaction progress was monitored by TLC on
plates with silica gel 60 F-254, eluent–ether, 1 : 2.
ish powder of compound VIII identical to the above
described.
N-(Diphenyl-λ4-sulfanylidene)trifluoromethane-
sulfonamide (Х). To a solution of 2 g (13 mmol) of tri-
flamide, 5.85 g (39 mmol) of NaI, and 2.3 mL (13 mmol)
of diphenyl sulfide in 80 mL of CH3CN was added drop-
wise 4.5 mL(39 mmol) t-BuOCl under argon, in the dark,
at cooling to 6°С. The reaction mixture was maintained
for 24 h, the solvent was distilled off at a reduced pres-
sure, the residue was dissolved in ethyl ether, and washed
with Na2S2O3 solution. The extract was dried with CaCl2
and evaporated in a vacuum, the residue (2.58 g, 59%)
was twice subjected to column chromatography on silica
gel in order to remove tarry impurities, eluents hexane
and ether–hexane, 1:1. We obtained 200 mg of triflamide
and 500 mg of light yellow analyticqally pure compound
X. Yellow crystals, mp 98°С (2-PrOH). IR spectrum, ν,
cm–1: 3099, 3067, 1585, 1478, 1450, 1338, 1220, 1175,
1143, 1009, 995. 1Н NMR spectrum (acetone-d6), δ, ppm:
7.63 m (3Н, Hm+p), 7.95 m (2Н, Ho). 13С NMR spectrum
(acetone-d6), δ, ppm: 121.3 q (CF3, J 322.6 Hz), 128.0
(Сo), 131.4 (Сm), 134.2 (Сp), 136.7 (С1). 19F NMR spec-
trum (CD3CN): δ –77.82 ppm. Mass spectrum, m/z (Irel,
%): 333 (100) [M]+, 264 (85) [M – CF3]+, 200 (95) [M
– Tf]+, 186 (90) [Ph2S]+, 77 (70) [Ph]+, 69 (65) [CF3]+.
Found [M]+ 333.0104. C13H10F3NO2S2. Calculated M
333.0105.
2,6-Diiodo-4-(trifluoromethylsulfonyl)thiomorpho-
line 1,1-dioxide (VIII). To a solution of 2 g (13 mmol)
of triflamide, 5.85 g (39 mmol) of NaI, and 1.35 mL
(13 mmol) of divinyl sulfone in 80 mL of CH3CN was
added dropwise 4.5 mL (39 mmol) of t-BuOCl under ar-
gon, in the dark, at cooling to 4°С. The reaction mixture
was maintained for 24 h, the solvent was distilled off at
a reduced pressure, the residue was dissolved in ethyl
ether, and washed with Na2S2O3 solution. The extract
was dried with CaCl2 and evaporated in a vacuum, the
residue (2.59 g, 38%) was purified by column chromatog-
raphy on silica gel (0.063–0.200 mm), eluents hexane and
ether–hexane, 1 : 1. The reaction product was recrystal-
lized from chloroform. Yellowish crystals, mp 275°С. IR
spectrum, ν, cm–1: 3009, 2963, 2955, 1629, 1450, 1386,
1201, 1132, 1075, 934, 597. 1Н NMR spectrum (CD3CN),
δ, ppm: 3.86 d.d (1H, CHА, 2J 14.1, 3J 12.2 Hz), 4.44 d.d
(1H, CHB, 2J 14.1, 3J 3.4 Hz), 5.43 d.d (1H, CHI, 3J 12.2,
3.4 Hz). 13С NMR spectrum (CD3CN), δ, ppm: 31.28 d
(CHI, J 165.3 Hz), 54.64 t (CH2, J 152.6 Hz), 121.69
(CF3, J 319.9 Hz). 19F NMR spectrum (CD3CN), δ, ppm:
–76.33. Found, %: С 12.31; Н 1.45; I 49.54; N 2.83;
S 12.11. C5H6F6I2NO4S2. Calculated, %: С 11.57; Н 1.17;
I 48.90; N 2.70; S 12.36.
ACKNOWLEDGMENTS
The study was carried out under the financial support
of the Russian Foundation for Basic Research (grants
nos. 12-03-31295 and 13-03-00055).
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