(N-trifluoromethanesulfonyl)sulfimides of linear and cyclic organosilicon sulfides

Article abstract of DOI:10.1134/S1070363210030126

The reaction of sodium salt of N-(chloro)trifluoromethanesulfonamide with linear and cyclic fiveand six-membered organosilicon sulfides was studied and their first N-trifluoromethanesulfonyl-substituted imides were synthesized. The results are compared wi

Full text of DOI:10.1134/S1070363210030126

ISSN 1070-3632, Russian Journal of General Chemistry, 2010, Vol. 80, No. 3, pp. 442–450. © Pleiades Publishing, Ltd., 2010.
Original Russian Text © E.N. Suslova, А.I. Albanov, B.А. Shainyan, 2010, published in Zhurnal Obshchei Khimii, 2010, Vol. 80, No. 3, pp. 419–427.
(N-Trifluoromethanesulfonyl)sulfimides of Linear
and Cyclic Organosilicon Sulfides
E. N. Suslova, А. I. Albanov, and B. А. Shainyan
Favorskii Irkutsk Institute of Chemistry, Siberian Branch, Russian Academy of Sciences,
ul. Favorskogo 1, Irkutsk, 664033 Russia
e-mail: bagrat@irioch.irk.ru
Received October 29, 2009
Abstract―The reaction of sodium salt of N-(chloro)trifluoromethanesulfonamide with linear and cyclic five-
and six-membered organosilicon sulfides was studied and their first N-trifluoromethanesulfonyl-substituted
imides were synthesized. The results are compared with the data on the reaction of the same substrates with
chloramine B. The distinctly pronounced stabilizing effect of a highly electronegative trifluoromethanesulfonyl
group was observed, which decreased the reactivity of N-trifyl-substituted sulfimides with respect to
electrophilic reagents and increased their stability. Mass spectra of isomeric cyclic organosilicon N-
trifluoromethanesulfonyl-substituted sulfimides VII, X, their acyclic analog III, and the product of the
decomposition of the latter at the Si–C(S) bond IV were studied. The mechanism of formation of sulfimides in
nonaqueous media is discussed.
DOI: 10.1134/S1070363210030126
Sulfimide derivatives of organic sulfides, including
cyclic ones, are well studied. They are prepared both in
aprotic or in aqueous and other protic media,
depending on the reagents used [1–5]. N-Triflyl deriva-
tives of organic sulfimides are much less studied.
Taking into account a specific reactivity of trifluoro-
methanesulfonamide, they are prepared either by the
reaction of its N-sulfinyl derivative CF3SO2N=S=O
with dimethylsulfoxide [Eq. (1)] [6, 7], by
dehydrocondensation of aryltrifluoromethylsulfoxides
with trifluoromethanesulfonamide in the presence of
triflic anhydride [Eq. (2)] [8], or by oxidative imina-
tion of organic sulfides with N,N-dichlorotrifluoro-
methanesulfonamide [Eq. (3)] [9, 10]:
Me
Me
(1)
NSO2CF3
O + CF3SO2N
S
S
S
O
_SO2
Me
Ar
Me
O
(CF3SO2)2O
_H2O
ArSCF3 + CF3SO2NH2
RSR' + CF3SO2NCl2
NSO2CF3
(2)
(3)
S
CF3
S
Me
Me
NSO2CF3
_Cl2
R = Ar; R' = Ar, CF3.
We failed to find any data in the literature
concerning N-triflyl derivatives of cyclic sulfimides.
Also, until very recently, nothing was known about N-
triflyl derivatives of linear or cyclic organosilicon
sulfimides; their first representative, 4,4-dimethyl-4-
silathiane-1-(N-trifluoro-methanesulfonyl)sulfimide, was
synthesized by us a year ago [11]. Moreover, in a
recent review on diheteroatomic organosilicon hetero-
cycles [12] only our works on the synthesis of
organosilicon sulfimides [13–15] were cited.
At the same time, the introduction of the triflyl
group CF3SO2 to the nitrogen atom in sulfimides is of
considerable interest from the viewpoint of possible
442

(N-TRIFLUOROMETHANESULFONYL)SULFIMIDES
443
stabilization of these compounds, which is especially
important for organosilicon sulfimides that are
hydrolytically much less stable than their organic
analogs. It was reasonable to assume that the intro-
duction of the electron-withdrawing trifluoromethane-
sulfonyl group would decrease the reactivity of
sulfimides with respect to electrophiles and, hence,
increase their hydrolytic stability. It should be
mentioned that the hydrolytic stability of organosilicon
sulfimides depends mainly on the relative location of
heteroatoms, silicon and sulfur. We have prepared the
first six-membered cyclic organosilicon sulfimides
[13–15], but their five-membered analogs turned out to
be unstable and decomposed with the ring opening at
the Si–CН2S bond [15]. Linear and cyclic
organosilicon sulfimides are stable if the atoms of
silicon and sulfur are separated by two or three СН2
groups, and are unstable in the presence of the geminal
group Si–CН2–S [13–16]. For example, the aryl-
sulfimide derivatives of 1,3-thiasilacyclohexane are
very sensitive to the reaction conditions and can be
prepared only in aprotic medium (methylene chloride)
at cooling and in the presence of phase transfer
catalyst, triethylbenzylammonium chloride.
In the present work we have studied the reaction of
linear and cyclic organosilicon sulfides with sodium
salt of N-chlorotrifluoromethanesulfonamide and per-
formed qualitative comparison of the stability of the
obtained N-triflyl-substituted sulfimides and their N-
arylsulfonyl-substituted analogs formed in the reaction
with chloramine B.
The stability of linear organosilicon N-arylsul-
fonylsulfimides with the β- and γ-location of the
silicon and sulfur atoms [13, 16] makes it possible to
synthesize them both in aprotic conditions (in
methylene chloride), and, for example, in methanol. As
distinct from that, their α-isomeric analog methyl
(trimethylsilylmethyl) sulfide reacts with chloroamine
B or T to form the corresponding S-(trimethylsilyl-
methyl)-S-methyl-N-(arylsulfonyl)sulfimides only under
dry aprotic conditions in the presence of a phase
transfer catalyst, and even then the yield is very low
[16] [Eq. (4)]. We have found that the linear
organosilicon sulfide, ethyl (trimethylsilylmethyl)
sulfide (I) under similar conditions reacts with the
sodium salt of N-chlorotrifluoromethanesulfonamide
(II) with a much higher yield [Eq. (5)]. The product of
reaction (5) is thermally stable (CCl4, 78°С, 7 h).
ArSO2NNaCl·3H2O
Me3SiCH2S NSO2Ar
Me
(6_10%)
(4)
_5oC, CH2Cl2
Me3SiCH2SR
CF3SO2NNaCl
Me3SiCH2S NSO2CF3 (~60%)
(5)
Et
III
R = Me ([16]), Et (present work); Ar = Ph, p-Tol.
of the yield of the target product, from 6–10% to 60%.
Moreover, N-triflyl-substituted sulfimide III withstands
short-term treatment with water and the conditions of
the column chromatography on silica. However, it is
still impossible to synthesize it in a protic medium:
when the reaction is carried out in methanol, S-methyl-
The structure of product III is confirmed by the
presence in the Н NMR spectrum of two doublets of
diastereotopic protons of the SiCH2S group at 2.3 and
2.5 ppm, and two doublets of quartets of diastereotopic
methylene protons of the SCH2Me group at 3 ppm.
1
S-ethyl-(N-trifluoromethanesulfonyl)sulfimide
(IV),
Therefore, for linear organosilicon N-sulfonyl-
substituted sulfimides the stabilizing effect of the triflyl
group CF3SO2 is manifested mainly in a sharp increase
that is, the product of decomposition of III at the Si–C
(S) bond, is formed in 80% yield as an oil, poorly
soluble in organic solvents:
MeOH
Me3SiCH2SEt + CF3SO2NNaCl
CH3S
Et
NSO2CF3
IV
(80%)
(6)
room
temperature
I
II
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444
SUSLOVA et al.
1
In the Н NMR spectrum of product IV a singlet of
the S-methyl protons is observed as well as the signals
of the SEt group with the coupling pattern fully identical
to that in the spectrum of compound III.
S,S-dimethyl- [16] or S-methyl-S-ethyl-N-(benzene-
sulfonyl)sulfimides [13].
The reaction of 4,4-dimethyl-4-silathiane (V) with
salt II [11] proceeds similar to its reaction with
chloramine B [14]. Products VI and VII are thermally
and hydrolytically stable.
In a similar way, compound I and its S-methyl
analog react in methanol with chloramine B, to form
PhSO2NNaCl·3H2O
Me2Si
Me2Si
S
NSO2Ph
70 (60)%
(7)
(8)
CH2Cl2 (MeOH)
_5oC
VI
Me2Si
S
or room
temperature
CF3SO2NNaCl
NSO2CF3 80 (40_50)%
V
S
CH2Cl2 (MeOH)
VII
The introduction of the =NSO2CF3 group to the
sulfur atom results in a downfield shift and splitting of
rine and HCl in the reaction mixture, water treatment)
~30% of the target product VII is formed. Compound
1
1
all signals in the Н NMR spectrum: the singlet of
VI, judged from the Н NMR data, also remains intact
SiMe2 in sulfide V is shifted by ~0.2 ppm and split in
two signals of the axial and equatorial methyl groups,
the signal of the SiCH2 protons at ~1 ppm is split in
two multiplets of the axial (~1 ppm) and equatorial
(1.5 ppm) protons, and the signal of the SCH2 protons
at 2.8 ppm is also split in two multiplets of the axial
(3.2 ppm) and equatorial (3.4 ppm) protons.
after staying for 16 h in the methanol solution of HCl
(pH = 3).
It was much more interesting to look for the
presence of such an effect by the example of cyclic
systems, containing, by analogy with the linear β-
silylated sulfides, the Si–CН2–S fragment with the
geminally arranged atoms of silicon and sulfur.
Therefore we studied the sulfimidation of 3,3-dimethyl-
3-silathiane VIII isomeric to compound V. When
carrying out the reaction in an aprotic medium,
products IX and Х were obtained in good comparable
yields. However, the relative stability of the N-triflyl-
substituted sulfimide Х as compared with the N-
arylsulfonyl-substituted analog IX is much higher, as
proved by its much larger resistance to hydrolysis (it
withstands water treatment and column chromato-
graphy on silica).
It is hard to talk about a stabilizing effect of the
triflyl group by the example of reactions (7) and (8),
for it is manifested here only in a slight increase of the
yield of the product of the sulfimidation. Apparently,
this is due to intrinsic stability of β-organosilicon
sulfimides, which is supported by rather high yields of
the products of the reaction performed in methanol.
This is also confirmed by the results of imidation of
sulfide
V
with N,N-dichlorotrifluoromethanesul-
fonamide CF3SO2NCl2. Even under these much more
severe conditions (40°С, presence of molecular chlo-
PhSO2NNaCl·3H2O
CH2Cl2
Me2Si
Me2Si
(74%)
(79%)
(9)
S
_5oC
NSO2Ph
Me2Si
IX
S
VIII
CF3SO2NNaCl
CH2Cl2
(10)
S
NSO2CF3
X
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(N-TRIFLUOROMETHANESULFONYL)SULFIMIDES
445
As in the case of sulfide V, the introduction of the
=NSO2CF3 group to the sulfur atom in sulfide VIII
results in a downfield shift and splitting of the signals
of the axial and equatorial SiMe groups and the
protons of the CH2 groups. With this, the singlet of
SiCH2S in sulfide VIII (1.7 ppm) is transformed in the
product Х into АВ quartet (2.6 ppm).
transformation of sulfimide derivatives of silanols of
the type XII into disiloxanes we demonstrated earlier
for phenylsulfonyl-substituted derivatives [15], and in
the present work it was confirmed spectroscopically
for sulfimidation of the five-membered cyclic
organosilicon sulfide (vide infra). The signals in the
13С NMR spectrum of disiloxane XIII were assigned
using the 2D{1H–13C} spectrum.
Earlier we showed that, when treated with methanol
or water, product IX decomposed with the rupture of
the Si–C(S) bond and the formation of a mixture of the
sulfimide derivatives of silanol, methoxysilane, and
At the same time, products IX and Х are thermally
stable and do not undergo any changes upon reflux in
CCl4 for 7 h.
1
disiloxane [15]. Similar to that, according to the Н,
29Si NMR spectroscopy data, when carrying out reac-
tion (10) in methanol or by the action of methanol or
water–alcohol alkali solution on the separately
prepared product Х, the latter is solvolytically split
with the formation of the corresponding silanol,
methoxysilane, and disiloxane:
Five-membered heterocycles, S-functional 1,3-thia-
silacyclopentanes, as we have shown earlier, are less
stable than their six-membered analogs, derivatives of
compounds V and VIII, and the sulfimide derivatives
are the least stable as compared to other S-functional
derivatives [15]. For example, 3,3-dimethyl-1-thia-3-
silacyclopentane-1-(N-phenylsulfonyl)sulfimide cannot
be detected in the reaction mixture by NMR
spectroscopy even when performing the reaction in an
aprotic medium. Only the corresponding sulfimide
derivatives of silanol and disiloxane, that is, the
products of the solvolytic splitting of the Si–C(S) bond,
have been obtained [15].
MeOH
X
Me2Si(CH2)3S(Me)
NSO2CF3
or OH−
OMe
XI
+ Me2Si(CH2)3S(Me)
NSO2CF3
OH
XII
Taking into account the stabilizing effect of the
triflyl group, which is indeed the case for the linear
and six-membered cyclic sulfimides with the geminal
fragment Si–CН2–S, we have examined how effective it
would be for synthesis of the least stable five-
membered cyclic sulfimides. It turned out that 3,3-
dimethyl-1,3-thiasilacyclopentane (XIV) reacts with
salt II by the following scheme:
[CF3SO2N S(Me)(CH2)3SiMe2]2O
(11)
XIII
The formation of compounds XI, XII is proved by
the presence in the 29Si NMR spectrum of the signals
at ~19 ppm and ~16 ppm, characteristic of methoxy-
silanes and silanols, respectively [17]. An easy
H2O
CH2Cl2
_7oC
Me2Si
S + CF3SO2NNaCl
Me2Si(CH2)2S
Me
Me2Si
S
NSO2CF3
NSO2CF3
OH
XIV
XIV
XVI
+ [Me2Si(CH2)2S(Me)
NSO2CF3]2O
(12)
XVII
Using the NMR spectroscopy, the target five-
membered cyclic organosilicon sulfimide XV was
identified in the reaction mixture, where its content
reached 75%. However, already 2 h later, after removal
of methylene chloride and addition of CCl4 for more
complete precipitation of admixtures, only trace
amounts of product XV remained in the reaction
mixture, the main components being silanol XVI and
disiloxane XVII, similar to the reaction with chlor-
amine B [15]. This is confirmed by the presence in the
29Si NMR spectrum of the signals at ~16 ppm and ~8 ppm
of similar intensity that are characteristic of silanols
and disiloxanes, respectively [17]. The presence in the
19F, 29Si NMR spectra of disiloxane XVII of two close
signals (–77.87 and –77.93; 8.14 and 8.35 ppm, respec-
tively) in the ratio of ~1:3 is due to the presence of two
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446
SUSLOVA et al.
chiral centers in the molecule and the existence of the
sulfonylsulfimides R2S=NSO2R. The second alter-
native is disproportionation of RSO2NNaCl, similar to
disproportionation of RSO2NНCl to RSO2NН2 and
RSO2NCl2:
RR(SS) and RS(SR) diastereomers.
The comparison of reactions (5) and (12) reveals a
substantial difference in behavior of the linear I and
five-membered cyclic XIV sulfides containing the
same geminal fragment Si–CH2–S with respect to the
sulfimidating reagent II. While the linear sulfimide III
is isolated in 60% yield, the cyclic sulfimide XV is
only registered in the reaction mixture. Apparently,
this is due to additional destabilization of product XV
by the ring strain.
RSO2NNaCl →← RSO2NNa2 + RSO2NCl2.
(13)
Even if Eq. (13) is strongly biased to the left, a high
activity of the dichloride, which is maximum in the
series of the sulfimidating reagents [18], can ensure the
proceeding of the sulfimidation to give good pre-
parative yields.
We have studied the electron impact induced
decomposition of N-(trifluoromethanesulfonyl)-sul-
fimides III, IV, VII, and X. In the mass spectrum of
compound III the peak of molecular ion (MI) is
lacking, as was also noted for other sulfimines [4]. The
first significant fragment peak corresponds to the
rearrangement radical-ion CF3SO2N(Me)SEt with m/z
223, which further eliminates radical SEt. to give the
cation CF3SO2NMe+ with m/z 162. The ions of maxi-
mum intensity in the spectrum are CF3 and SO2NH2
(Scheme 1).
The mechanism of imidation of sulfides by the salts
of N-chlorosulfonamides in protic media is studied in
detail; in the first stage it includes transformation of
salts RSO2NNaCl into more reactive intermediates
RSO2NHCl, which in the rate-determining step of the
process react with sulfides R2S by the mechanism of
electrophilic chlorination giving rise to RSO2NH– and
[R2SCl]+ that are rapidly converted into the final
product with evolution of HCl (see, e.g., [18]). Under
aprotic conditions this mechanism is impossible,
although it is known that the reaction of sulfimidation
under these condition proceeds in a higher yield, in
particular, due to the absence of a side reaction of
formation of sulfoxides [19]. The mechanism of
sulfimidation in the absence of proton-donors was not
discussed. It was not our task to study the mechanism
of the reaction, but a priori two alternatives might be
suggested. The first is based on the assumption that the
substantially lower activity of RSO2NNaCl relative to
RSO2NНCl [18] is characteristic of protic media,
which sharply decreases the activity of the ionic salt
form due to both nonspecific and specific solvation. In
an aprotic medium these effects are much weaker, and
salts RSO2NNaCl may react as independent
chlorinating agents to give with sulfides the
intermediates [R2SCl]+ and RSO2NNa–, which after
elimination of NaCl are converted into N-
The peak of MI is also lacking in the spectrum of
compound IV, the first fragment peak corresponds to
elimination of the molecule of ethylene from MI. The
main routes of further decomposition are shown in
Scheme 2.
The electron impact induced decomposition of
isomeric sulfimides VII and X occurs in different
ways. As we have already mentioned [11], the peak of
MI is lacking for compound VII in the regime of direct
injection, but it was detected in the regime of
chromatomass spectrometry. The first fragment peak is
the peak of ion with m/z 265, corresponding to
expulsion of ethylene from MI, which is in agreement
with the direction of decomposition of the precursor of
compound VII, 4,4-dimethyl-4-silathiane (V) [20].
Further decomposition is shown in Scheme 3.
Scheme 1.
+
+
+
MeNSO2CF3
CF3SO2N+
·
·
EtSN(Me)SO2CF3
[M]
−EtS·
−Me·
−Me2Si=CH2
m/z 162, 10%
m/z 147, 4%
m/z 295
m/z 223, 4%
·
−N
·
−CHF3
+
SO2+
m/z 64, 25%
CF3+
CF3SHO2
+
Me3SiCH2S(Et)=NSHO2
SO2NH+2
−CH2=C=S
−Me4Si
m/z 133, 3%
m/z 69, 100%
m/z 226, 1%
m/z 80, 92%
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 80 No. 3 2010

(N-TRIFLUOROMETHANESULFONYL)SULFIMIDES
447
Scheme 2.
+
·
·
CF3SO2 + MeSNH
MeSNH + CF3SO+2
m/z 62, 41%
m/z 133, 2%
Me
Et
+
+
·
·
MeS+ +CF3SO2NH
S=NSO2 + CF3+
MeSNHSO2CF3
m/z 195, 3.5%
·
·
[M]
−C2H4
m/z 47,
m/z 69,
m/z 223
27%
100%
·
−CF3
+
SO+2
m/z 64, 27%
MeSNHSO2
SHO2N+H2
−NH2
−CH2=S
m/z 126, 2%
m/z 80, 92%
Scheme 3.
Me2Si
S
Me2Si
S
N
or
N
+
CF3SO2SiMe2+
m/z 191, 13%
SO2
O
S
O
m/z 77, 66%
SO2
F
CF3
CF2
+
·
−SO2, −Me2SiH2
·
Me2SiC2H4SNSO2 + CF3+
CF3NSHCH=+CH2
Me2Si−S=NSO2CF3
m/z 69,
m/z 141, 23%
m/z 265, 6%
31%
−C2H4
−NSO2CF3
−H2
−NSO2CF3
+
Me2SiCH=CHS+
m/z 116, 10%
MeSiS+
Me2Si=S
·
−Me·
m/z 90, 23%
m/z 75,
−SO2CF3
32%
MeSi+
m/z 43,
+
65%
Me2SiSN+
m/z 104, 100%
Me2SiH+
MeSi S=N
−C2H4
−C2H3NS
m/z 59,
Me2Si+
m/z 132, 54%
37%
·
m/z 58,
38%
The peak of MI for sulfimide X also has very low
intensity (1%). The first significant fragment peak with
m/z 224 corresponds to expulsion of the
trifluoromethyl radical, although the main direction of
decomposition is splitting of the CF3–S bond with
localization of the charge on the CF3 group. Further
transformations are connected with fragmentation of
the silathiane ring, as can be seen in Scheme 4.
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 80 No. 3 2010

448
SUSLOVA et al.
Scheme 4.
+
·
Me2Si
Me2Si
CF3+ + Me2Si
m/z 69,100%
·
−CF3
S
S
S
+
·
NSO2
NSO2CF3
NSO2
m/z 224, 11%
m/z 293, 1%
·
−CH3SO2NH
+
+
·
·
Me2Si
S
Me2Si
Me2SiSH+
Me2Si
S
−CH·
·
−C2H3
−CH2
S +
m/z 145, 16%
m/z 91, 16%
m/z 132, 12%
m/z 118, 12%
EXPERIMENTAL
ether was removed to obtain 0.419 g (60%) of the
crude product III as a white powder. The compound
was purified by column chromatography on silica gel
(Merck) in the system hexane, hexane–ether from 8:1 to
1:7, mp 84°С. IR spectrum, ν, cm–1: 2960 (CH2), 1310
(SO2), 1230 (SiMe), 1200, 1165 (CF3), 1120 (SO2),
Melting points were determined on a Micro-Hot-
Stage Polytherm A device. IR spectra were taken on a
Specord IR 75 in thin layer or in KBr. 1Н, 13С, 19F, and
29Si NMR spectra were recorded for solutions in
CDCl3 (if not differently specified) on a Bruker DPX
400 spectrometer (400, 100, 376, and 79.5 MHz,
1
990 (S=N), 970 (NSO2), 820 (CS), 595 (SO2). H
NMR spectrum, δ, ppm: 0.29 s (9H, SiMe3), 1.45 t
(3H, СMe, J 7.4 Hz), 2.31 d (1Н, SCHАSi, J 13.7 Hz),
2.52 d (1Н, SCHВSi, J 13.7 Hz), 3.00 d.q (1Н, SCHАС,
J 13.0, 7.1Hz), 3.05 d.q (1Н, SCHВС, J 13.0, 7.2 Hz).
13С NMR spectrum, δ, ppm: –1.13 (SiMe), 7.03
(СCН3), 35.90 (SСSi), 46.36 (SCC), 120.29 q (CF3,
1
respectively) with the residual protons (for Н) or the
carbon atom (for 13С) of the solvent as an internal
standard, chemical shifts are given relative to TMS
(1Н, 13С, 29Si) or CCl3F (19F). Electron impact mass
spectra were obtained at 70 eV on a GCMS-QP5050A
Shimadzu instrument with the quadrupole mass
analyzer.
J
CF 323.3 Hz). 19F NMR spectrum, δ, ppm: –77.71. 29Si
NMR spectrum, δ, ppm: 2.29. Found, %: С 28.25, Н
5.30; F 18.83, N 5.07; S 21.54. C7H16F3NO2S2Si.
Calculated, %: С 28.47, Н 5.46, F 19.29, N 4.74; S 21.71.
Solvents were dried and purified by standard pro-
cedures and stored over molecular sieves 4A. N,N-
Dichlorotrifluoromethanesulfonamide and its sodium
salt were prepared as described in [21]. Ethyl-
(trimethylsilylmethyl)sulfide (I), 4,4-dimethyl-4-sila-
thiane (V), 3,3-dimethyl-3-silathiane (VIII), 3,3-
dimethyl-1,3-thiasilacyclopentane (XIV) were pre-
pared by procedures described in [14, 22–24],
respectively.
S-(Trimethylsilyl)-S-ethyl-(N-trifluoromethane-
sulfonyl)sulfimide (III). To a mixture of 0.35 g of
sulfide I, 0.027 g of triethylbenzylammonium chloride
and freshly calcined zeolites in 5 ml of anhydrous
CH2Cl2 at temperature from 0 to –4°С in an argon
atmosphere 0.486 g of salt II was added by portions
during 40 min, the reaction mixture was stirred for 1 h
at 0°С and 3 h at room temperature. The solvent was
removed, the residue was extracted with ether, the
extract was washed with water, dried over MgSO4,
Methylethyl-(N-trifluoromethanesulfonyl)sulf-
imide (IV). To a solution of 0.154 g of sulfide I in
3 ml of methanol a solution of 0.376 g of salt II in
4 ml of methanol was added dropwise during 15 min at
room temperature, the mixture was stirred for 20 h, the
solvent was removed, the residue thoroughly washed
with ether, and dried over MgSO4 to obtain 0.19 g
(82%) of crude product IV, which was purified by
column chromatography on silica gel (Merck) in the
system hexane–ether from 20:1 to 1:1, ether–methanol
from 20:1 to 1:4. IR spectrum, ν, cm–1: 2886 (CH2),
1335 (SO2), 1218, 1182 (CF3), 1141 (SO2), 1010, 736
1
(S=N), 961 (NSO2), 610. H NMR spectrum, δ, ppm:
1.35 t (3H, СMe, J 7.4 Hz), 2.73 s (3Н, SМе), 2.99 d.q
(1Н, SCHА, J 13.2, 7.2 Hz), 3.05 d.q (1Н, SCHВ, J
1
13.2, 7.2 Hz). H NMR spectrum, DMSO-d6, δ, ppm:
1.31 t (3H, СMe, J 7.3 Hz), 2.83 s (3Н, SМе), 3.07 d.q
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(N-TRIFLUOROMETHANESULFONYL)SULFIMIDES
449
(1Н, SCHА, J 13.2, 7.2 Hz), 3.23 d.q (1Н, SCHВ, J
13.2, 7.3 Hz). 13С NMR spectrum, δ, ppm: 6.88
(СCН3), 33.15 (SMe), 44.24 (SCC), 120.05 q (CF3, JCF
322.8 Hz). 19F NMR spectrum, δ, ppm: –77.53. Found,
%: С 21.25, Н 3.50, N 6.63, F 25.53, S 29.12.
C4H8F3NO2S2. Calculated, %: С 21.52, Н 3.59, N 6.28,
F 25.56, S 28.70.
4,4-Dimethyl-4-silathiane-1-(N-trifluoromethane-
sulfonyl)sulfimide (VII). To 0.1 g of compound V in
1.5 ml of МеОН a solution of 0.224 g of salt II in
3.5 ml of methanol was added dropwise during 30 min
at room temperature, the mixture was stirred for 5 h,
methanol was removed, the extract after water–ether
treatment was dried over MgSO4. After removal of
solvent and drying in a vacuum 0.105 g (52%) of the
crude product VII was obtained. The yield of pure
product VII after washing with ether for removal of
siloxanes was 40%. NMR spectra coincide with those
of the authentic sample prepared under aprotic
conditions [11].
12.5, 3J4ax5eq 4.6 Hz), 0.86 d.d.d.t (1Н, H4eq 3J4eq5ax 6.2,
4
4
3J4eq5eq 3.4, J4eq6eq = J4eq2eq 1.0 Hz), 1.94 d.d.d.d.d
3
3
(1H, H5 2J5ax5eq 16.0, J5ax6ax 12.0, J5ax6eq 6.6 Hz),
ax,
2.48 d.d.d.d.d (1H, H5eq), 2.58 d (1H, H2ax, 2J2ax2eq 13.1
Hz), 2.63 d.d.d (1H, H2 , J2eq6eq 2.5, J2eq4eq 1.0 Hz),
4
4
eq
2
3
3
3.02 d.d.d (1H, H6ax, J6ax6eq 13.1, J6ax5ах 12.0, J6ax5eq
2.3 Hz), 3.24 d.d.d.d.d (1H, H6 , J6ax6eq 13.1, J6eq5ax
2
3
eq
6.6, 3J6eq5eq 2.4 Hz). 13С NMR spectrum, δ, ppm: –3.45,
–1.93 (SiMe), 11.15 (SiCC), 18.58 (CCC), 36.21
1
(SiCS), 50.71 (CCS), 120.16 q (CF3, JCF 322.8 Hz).
19F NMR spectrum, δ, ppm: –78.22. 29Si NMR
spectrum, δ, ppm: 0.24. Found, %: С 28.86; Н 4.48; F
18.96; N 4.62; S 21.78. C7H14F3NO2S2Si. Calculated,
%: С 28.67; Н 4.78; F 19.45; N 4.78; S 21.84.
Reaction of 3,3-dimethyl-3-silathiane (VIII) with
salt II in methanol. To a solution of 0.105 g of
compound VIII in 2 ml of anhydrous methanol the
solution of 0.229 g of salt II in 3 ml of methanol was
added dropwise during 25 min at –5°С, and the
reaction mixture was stirred for 1 h at –5°С. Analysis
1
by the Н and 29Si NMR spectroscopy showed the
Reaction of 4,4-dimethyl-4-silathiane (V) with
N,N-dichlorotrifluoromethanesulfonamide. To
a
absence in the reaction mixture of cyclic compounds
VIII or X. After column chromatography on silica gel
(eluents hexane, hexane–ether 8:1–1:5, ether–methanol
20:1–1:1) the fraction was obtained, which contained,
according to NMR, methoxysilane XI and silanol XII
in comparable amounts.
Me2Si(OMe)(CH2)3S(CH3)=NSO2CF3 (XI). 1H
NMR spectrum, δ, ppm: 0.10 s (6H, SiMe2), 0.70 m
(2Н, SiCH2), 1.65 m (2Н, CCH2C), 2.80 s (3Н, SMe),
2.98 m (2Н, SCH2), 3.34 s (3H, MeO). 13С NMR
spectrum, δ, ppm: –2.80 (SiMe), 14.61 (SiCC), 17.13
(CCC), 34.08 (SMe), 50.54 (OMe), 53.67 (CCS). 19F
NMR spectrum, δ, ppm: –77.89. 29Si NMR spectrum,
δ, ppm: 19.99.
solution of 0.251 g of compound V in 5 ml of ССl4
0.432 g of N,N-dichlorotrifluoro-methanesulfonamide
in 5 ml of СС14 was added dropwise during 30 min at
room temperature, the reaction mixture was stirred for
15 min at 40°С and 1 h at room temperature, washed
with water, dried over MgSO4. After removal of
solvent, 0.203 g of oil was obtained that contained, by
1
the data of Н NMR spectroscopy, ~30% of the target
product VII, as well as the products of its decom-
position with the ring opening.
3,3-Dimethyl-3-silathiane-1-(N-trifluoromethane-
sulfonyl)sulfimide (Х). To a mixture of 0.158 g of
compound VIII, 0.0126 g of triethylbenzylammonium
chloride, and freshly calcined zeolites in 2.5 ml of
anhydrous CH2Cl2 at –5°С 0.266 g of salt II was added
by portions during 30 min, the reaction mixture was
stirred for 45 min, allowed to warm to room tempera-
ture, kept for another 3 h, washed with cold water (2×
5 ml), dried over MgSO4. After removal of solvent,
0.251 g (79%) of the product was obtained that was
purified by column chromatography on silica gel
(Merck) in the system hexane–ether from 8:1 to 1:7,
ether. White crystalline compound was obtained with
mp 149–151°С. IR spectrum, ν, cm–1: 2900 (CH2),
1420 (SiCH2), 1290 (SO2), 1230 (SiMe), 1190, 1140,
(CF3), 1100 (SO2), 960, 780 (S=N), 920 (NSO2), 800,
Me2Si(OH)(CH2)3S(CH3)=NSO2CF3 (XII). 1H
NMR spectrum, δ, ppm: 0.14 s (6H, SiMe2), 0.78 m
(2Н, SiCH2), 1.89 m (2Н, CCH2C), 2.79 s (3Н, SMe),
3.15 m (2Н, SCH2), 4.62 s (1H, OH). 19F NMR
spectrum, δ, ppm: –77.79. 29Si NMR spectrum, δ, ppm:
16.22. 29Si NMR spectrum of the product of alkaline
hydrolysis of sulfimide Х in water–organic media
contains the only signal at 8 ppm, which is indicative
of formation of disiloxane CF3SO2N=S(Me)·
1
(CH2)3SiMe2]2O (XIII). H NMR spectrum, DMSO-
d6, δ, ppm: 0.06 s (6H, SiMe2), 0.60 m (1Н, SiCHА),
0.69 m (1Н, SiCHВ), 1.65 m (1Н, CCHАC), 1.73 m
(1Н, CCHВC), 2.85 s (3Н, SМе), 3.17 t (2Н, SCH2, J
1
580. H NMR spectrum, δ, ppm: 0.27 s (3H, SiMe),
0.31 s (3H, SiMe), 0.73 d.d.d (1Н, Н4ах 2J 15.2, 3J4ax5ax
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 80 No. 3 2010

450
SUSLOVA et al.
7.2 Hz). 13С NMR spectrum, DMSO-d6, δ, ppm: 0.25
(SiMe2), 16.40 (SiCC), 16.79 (CCC), 33.79 (SiMe),
52.10 (CCS). 19F NMR spectrum, CDCl3, δ, ppm:
–77.82. 29Si NMR spectrum, DMSO-d6, δ, ppm: 8.03.
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benzylammonium chloride, and freshly calcined
zeolites in 4 ml of anhydrous CH2Cl2 at –7°С in an
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1
1
to the data of Н NMR, was 75%. H NMR spectrum,
δ, ppm: 0.26 s (3H, SiMe), 0.43 s (3H, SiMe), 1.22
d.d.d (1Н, H4А, 2J 14.79, 3J4А5А 7.3, 3J4А5В 3.8 Hz), 1.53
d.d.d (1Н, H4В, 3J4В5А 10.7, 3J4В5В 7.87 Hz), 2.09 d (1Н,
2
4
H2А, J 15.0 Hz), 2.27 d.d (1Н, H2В, J2В5В 2.4 Hz),
2.92 d.d.d (1Н, H5А, 2J 13.8 Hz), 3.44 d.d.d.d (1Н, H5В,
4J5В2В 2.4 Hz). 13С NMR spectrum, δ, ppm: –2.43, –0.99
(SiMe), 8.31 (SiCC), 33.13 (SiCS), 49.70 (CCS). 19F
NMR spectrum, δ, ppm: –78.56. 29Si NMR spectrum,
δ, ppm: 25.34.
After treatment of the reaction mixture with water,
separation of organic layer, drying and removal of
solvent, 0.218 g of the residue was obtained (yield of
the crude product 95%), which was purified by column
chromatography on silica gel, eluents hexane, hexane–
ether (8:1–1:5), ether–methanol (20:1–1:1) to give
disiloxane [CF3SO2N=S(Me)(CH2)2SiMe2]2O (XVII).
1H NMR spectrum, δ, ppm: 0.18 s (6H, SiMe2), 1.01
2
3
d.d.d (1Н, SiCHА, J 14.8, J 13.4 and 4.6 Hz), 1.14
d.d.d (1Н, SiCHВ), 2.79 s (3Н, SCH3), 3.07 d.d.d (1Н,
SCHА, J 14.0 Hz). 13С NMR spectrum, δ, ppm: 0.50
2
(SiMe2), 11.20 (SiCН2), 33.01 (SCН3), 47.01 (CН2S),
120.30 q (CF3, JCF 320.0 Hz). 19F NMR spectrum, δ,
1
ppm: –77.87, –77.93. 29Si NMR spectrum, δ, ppm:
8.14, 8.35.
AKNOWLEDGMENTS
This work was financially supported by the Russian
Foundation for Basic Research (grants nos. 07-03-
00425 and RFBR-DFG 08-03-91954).
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 80 No. 3 2010