Synthesis and relative stability of five- and six-membered S-functional derivatives of 1,3-thiasilacycloalkanes

Article abstract of DOI:10.1016/S0022-328X(03)00348-6

Oxidation, imidation, and S-methylation reactions of five- and six-membered 1,3-thiasilacycloalkanes have been examined under various conditions. The S-functional derivatives of 1,3-thiasilacycloalkanes undergo solvolytic Si - C(S) bond cleavage in protic

Full text of DOI:10.1016/S0022-328X(03)00348-6

Journal of Organometallic Chemistry 677 (2003) 73ꢀ79
/
www.elsevier.com/locate/jorganchem
Synthesis and relative stability of five- and six-membered S-functional
derivatives of 1,3-thiasilacycloalkanes
Elena N. Suslova, Aleksandr I. Albanov, Bagrat A. Shainyan *
A.E. Favorsky Irkutsk Institute of Chemistry, Siberian Branch of the Russian Academy of Sciences, 1 Favorsky Str., Irkutsk 664033, Russia
Received 20 February 2003; received in revised form 25 April 2003; accepted 25 April 2003
Abstract
Oxidation, imidation, and S-methylation reactions of five- and six-membered 1,3-thiasilacycloalkanes have been examined under
various conditions. The S-functional derivatives of 1,3-thiasilacycloalkanes undergo solvolytic SiÃ/C(S) bond cleavage in protic
media. The ease of the ring opening depends on the S-functionality and on the ring size.
# 2003 Elsevier Science B.V. All rights reserved.
Keywords: Thiasilacycloalkanes; S-Functionalization; Oxidation; Imidation; Methanolysis
1. Introduction
Therefore, the preparation of S-functional derivatives
of compounds of our continuing interest, 1,3-thiasilacy-
cloalkanes, is a challenging problem. Earlier we have
described the synthesis of some six-membered cyclic
compounds of this type [4,12,13]. Continuating our
studies on transformations of 1,3-thiasilacycloalkanes
we report here the synthesis of new five- and six-
membered S-functional derivatives of thiasilacycloalk-
anes. Subsequent transformations of these compounds
proceeding with the ring opening have been studied and
their relative solvolytic stability assessed.
S-Functionalization of thiacycloalkanes by oxidation
to sulfoxides or sulfones, or imidation to sulfimides, or
S-alkylation leading to sulfonium salts generally pre-
sents no problem and is not complicated by side
reactions of ring opening. Silicon-containing thiacy-
cloalkanes with two heteroatoms separated by one or
two methylene groups are also rather stable themselves
[1ꢀ4]. Only in the case of 2-phenyl-3,3-dimethyl-1,3-
/
silathiane the formation of the corresponding disiloxane
is observed due to alkaline hydrolytic opening of the
cycle (Scheme 1) [2].
Specific behavior of compound 1 is, apparently, due
to stabilization of the intermediate a-carbanion by the
phenyl group, which facilitates the SiÃCa bond rupture.
2. Results and discussion
/
We have previously shown that 3,3-dimethyl-3-si-
lathiane S-oxide (4) and 3,3-dimethyl-3-silathiane S,S-
dioxide (5) are formed in high yield by oxidation of
silathiane 3 with one or two equivalents of m-chloro-
perbenzoic acid (mCPBA) under aprotic conditions [4].
Both sulfoxide 4 and sulfone 5 are rather tolerant to
hydrolysis. They endure work up with sodium bicarbo-
nate and column chromatography on silica gel that
considerably facilitates their isolation. Moreover, both
are formed in high yield by oxidation with sodium
periodate in aqueous methanol (Scheme 2).
This effect of an intermediate a-carbanion stabilization
by S-functional group is responsible for the well-
documented SiÃCa bond cleavage by the action of
/
nucleophiles, in particular oxy-anions, on acyclic sili-
con-containing carbofunctional compounds having in
the a-position RSO, RSO2, RSÄ
/
NR?, or R2Sꢁ group
[5ꢀ11].
/
* Corresponding author. Tel.:
3952396046.
ꢁ
/
7-3952511425; fax:
ꢁ/7-
The corresponding five-membered analogs turned out
to be much less hydrolytically stable. Thus, oxidation of
E-mail address: bagrat@irioch.irk.ru (B.A. Shainyan).
0022-328X/03/$ - see front matter # 2003 Elsevier Science B.V. All rights reserved.
doi:10.1016/S0022-328X(03)00348-6

74
E.N. Suslova et al. / Journal of Organometallic Chemistry 677 (2003) 73ꢀ79
/
sulfide 6 and sulfoxide 7 even in nonpolar solvents, and
chromatographic lability of sulfoxide 7, we failed to
isolate it in pure form. The fact that five-membered
sulfoxide 7 is less stable than its six-membered analog 4
1
Scheme 1.
was proven directly by H-NMR monitoring of their
solutions in CDCl3. The former was more than half-
decomposed after 24 h, whereas the latter remained
intact after 2 weeks.
Oxidation of sulfide 6 with twofold excess of mCPBA
gives the corresponding sulfone 9 (Scheme 3). The latter
is much more stable as compared to sulfoxide 7 and was
obtained in high isolated yield. Yet, it is less stable than
its six-membered analog 5, since oxidation with two
equivalents of NaIO4 in methanol gives mainly disilox-
ane 8. Sulfone 9 also decomposes during aqueous work
up or column chromatography to afford disiloxane 10.
Only 10% of sulfone 9 remained in aqueous methanol
after 1 day, whereas its six-membered analog 5 remained
intact under these conditions after 4 days.
We have recently shown that acyclic organosilicon a-
sulfimides, which are N-analogs of a-sulfoxides, are
formed from the corresponding sulfides by the reaction
with chloramine B trihydrate under phase-transfer
conditions. For example, methyl-(trimethylsilyl)methyl
Scheme 2.
3,3-dimethyl-3-sila-1-thiacyclopentane (6) with one
equivalent of mCPBA in CH2Cl2 at ꢂ20 8C proceeds
with its complete conversion into sulfoxide 7, as proved
by H-, j-modulated 13C-, and 29Si-NMR spectra of the
/
1
crude product. Its structure was proven by the signals of
diastereotopic protons of all three methylene groups and
1
two signals of diastereotopic Me2Si groups in the H-
NMR spectrum. However, we failed to isolate pure
sulfoxide 7 due to its low stability. Work up similar to
that for sulfoxide 4 leads to decomposition and appear-
ance of new signals of Me2Si groups. An attempt to
isolate product 7 by three- to fourfold freezing out
mCPBA or column chromatography using protic or
aprotic eluents also led to complete decomposition of
sulfoxide 7. The only isolated product was disiloxane 8
formed by ring opening in 7 (Scheme 3).
sulfide
(Me3SiCH2S(Ä
as a solvent the latter suffers the SiÃ
Me3SiOMe and Me2SÄNSO2Ph [8].
(Me3SiCH2SMe)
NSO2Ph)Me). When methanol is used
Ca bond cleavage to
gives
a-silylsulfimide
/
/
/
Diastereotopic protons of the two methylene groups
in 8 have virtually equal vicinal coupling constants (13.6
and 5.2 Hz), which testifies to the s-trans arrangement
Based on these results we have examined in more
detail the reaction of imidation of cyclic sulfide 3
described in Ref. [13]. Cyclic sulfimide 11 is formed in
good yield (74%) when the reaction is performed under
aprotic conditions with the use of phase-transfer catalyst
(Scheme 4).
Pure sulfimide 11 is relatively stable and can be stored
without decomposition in the cold for several months.
However, in solution of 11 in aqueous methanol
of the two heteroatoms in the SÃ
/
CÃ
/
CÃ
/
Si fragment.
In order to avoid a necessary separation of the target
sulfoxide from the acid, we have studied oxidation of
sulfide 6 with mild neutral oxidizing agent NaIO4 under
various conditions. Under standard conditions of
Scheme 2, sulfide 6 is completely converted into
sulfoxide 7, but the latter suffers ring opening to afford
disiloxane 8, and only 10% of sulfoxide 7 was detected in
(MeOH:H2O, 6:1) the ring opening by the SiÃCa bond
/
1
takes place. H-NMR monitoring showed that half life
period at room temperature under these conditions is 24
h, and after 2 days the compound completely decom-
poses to afford the corresponding methoxysilane 12 and
disiloxane 14 in equimolar ratio. Though the signals of
diastereotopic methylene protons in the two compounds
the crude product by H- and 13C-NMR. Oxidation in
1
the two-phase system (CH2Cl2/H2O, 2:1) in the presence
of 10 mol% of benzyltriethylammonium chloride or 20
mol% of 15-crown-5 allowed us to avoid an undesirable
reaction of the ring opening, and disiloxane 8 was not
detected in the reaction mixture. However, because of
low conversion (not exceeding 50%), similar solubility of
1
overlap, the H-NMR spectrum of the crude product
shows the signals of MeOSi (d 3.34), SMe (d 2.60), and
Me2Si (d 0.024) groups in the ratio of 1:1:2, which
corresponds to methoxysilane 12.
Sulfimide 11 is much more sensitive to solvolysis than
its oxygen analog 4, which remains unchanged in
aqueous methanol during 4 days. After column chro-
matography it is completely converted into the mixture
of silanol 13 and disiloxane 14 of the 2:1 ratio.
Compounds 13 and 14 were identified by comparing
1
their H-NMR spectra to those of authentic samples.
Silanol 13 obtained by alkaline hydrolysis of sulfimide
Scheme 3.

E.N. Suslova et al. / Journal of Organometallic Chemistry 677 (2003) 73ꢀ
/79
75
Scheme 4.
11 affords disiloxane 14 on long storage. Note that no
hydrolysis of the SÄN moiety was detected under the
examined conditions.
it results in doubled splitting for each of diastereotopic
protons of the two methylene groups as compared to an
ordinary ABMN spin system (see Section 3). As in the
case of disiloxane 8, similar coupling of the diastereo-
topic protons of both methylene groups in 17 with
significantly different constants (14 and 4 Hz) is
/
Similar transformations take place when imidation of
sulfide 3 is carried out directly in methanol. Column
chromatography of the crude product affords the
mixture of silanol 13 and disiloxane 14 in the ratio
1.5:2 in 72% total yield. Silanol 13 is apparently formed
due to hydrolysis of methoxysilane 12 on silica gel. The
final product isolated after treatment with sodium
bicarbonate is pure disiloxane 14. Earlier we erroneously
assigned the structure of cyclic sulfimide 11 to this
indicative of stable s-trans arrangement of the SÃ
CÃ
Si fragment. The 29Si-NMR spectrum also shows two
close signals.
/
CÃ
/
/
Attempting to obtain five-membered cyclic sulfimide
15, we carried out the imidation in methylene chloride.
However, like in methanol and in contrast to Scheme 4,
silanol 16 and disiloxane 17 remain to be the major
products, and no traces of cyclic sulfimide were detected
in the reaction mixture. Imidation in aprotic medium
differs from the one in methanol only in that it affords
sulfoxide 7 as a by-product. Sulfoxide 7 (contaminated
with ring-opening products) was isolated by extraction
1
product [13]. The structure of 14 was proven by H-,
13C-, and 29Si-NMR spectroscopies. It should be noted
that 1H-NMR spectrum of disiloxane 14 shows two
multiplets of SiCH2C and two singlets of SMe groups.
Such complexity of the spectrum (the main reason of
our erroneous assignment in Ref. [13]) is due to the fact
that compound 14 has two chiral centers in the molecule
and is a mixture of diastereomers.
1
and proven by coincidence of its H-, 13C-, and 29Si-
NMR spectra with those for the product of oxidation of
sulfide 6 (Scheme 3). From the two possible routes of
sulfoxide 7 formation, namely the hydrolysis of cyclic
sulfimide or oxidation of the starting sulfide 6 by
chloramine B, the latter path seems more plausible since
even in methanol the ring opening of cyclic sulfimide
proceeds with retention of the sulfimide moiety (Scheme
5).
Finally, we have studied hydrolytic ring opening in
sulfonium salts 18 and 21 (Scheme 6). Compounds 18
and 21 were prepared by treatment of sulfides 3 and 6,
respectively, with methyl iodide in dry ethanol or ether.1
The compounds were fairly stable under dry conditions.
Imidation of the five-membered sulfide 6 in methanol
proceeds similarly (Scheme 5). Sulfide 6 is completely
consumed after 1 h to afford two products, silanol 16
and disiloxane 17, in 80% total yield. Their structure was
confirmed by 1H-, 13C-, and 29Si-NMR spectra. The
formation of silanol 16 is unequivocally proved by 29Si
chemical shift (dSi 12.0) characteristic of this class of
organosilicon compounds. The ratio of 16:17 changes
from 1.5:1 to 1:2 after removal of the solvent, and the
subsequent column chromatography affords only dis-
iloxane 17. A more rapid conversion of silanol 16 to the
corresponding disiloxane 17 as compared to silanol 13
to disiloxane 14 conversion is indicative of its lower
stability. Treatment with sodium bicarbonate comple-
tely converts silanol 16 into disiloxane 17.
As follows from the 1H-NMR spectrum, disiloxane 17
is a mixture of two diastereomers. In 1H-NMR spectrum
Scheme 6.
1
Salt 21 was prepared by us earlier [3] but no spectroscopic
information was given.
Scheme 5.

76
E.N. Suslova et al. / Journal of Organometallic Chemistry 677 (2003) 73ꢀ79
/
When treated with aqueous methanol (MeOH:H2O,
6:1) salt 18 suffers ring opening via splitting of the SiÃCa
bond and gives silanol 19 and disiloxane 20 (75%
conversion after 1 h, 100% after 5 h) in ꢀ4:1 ratio.
vapors. All reactions were carried out under argon with
standard precautions taken to avoid moisture. Solvents
were dried and purified according to standard proce-
dures and stored over molecular sieves 4A. Merck
/
/
After 22 h exposure in aqueous methanol the ratio of
19:20 is inverted and consists 1:3, which indicates the
following sequence of transformations shown in Scheme
6.
Kieselgel 60 (35ꢀ70-mesh) was used for column chro-
/
matography and the eluents are given in parentheses.
Structural assignments for all new compounds were
supported by j-modulated 13C-NMR spectra.
Under the same conditions salt 21 is completely
ceased after only 1 h to afford disiloxane 23 as the
main product. It suggests that, as with the aforesaid S-
functional derivatives of thiasilacycloalkanes, the five-
membered salt 21 is less stable than the six-membered
salt 18. The same is true for the relative stability of the
silanols 19 and 22 derived from 18 and 21. No silanol 22
was detected 5 h after treatment of 21 with aqueous
methanol, whereas a similar treatment of 18 results in
silanol 19 predominating in the mixture with disiloxane
20. Pure silanol 22 was obtained by 17 h hydrolysis of 21
with D2O in an NMR tube and characterized by IR and
1H-, 13C-, and 29Si-NMR spectroscopies. On standing
during several days it is gradually converted into
Thiasilacycloalkanes 3 and 6, sulfoxide 4, and sulfone
5 were prepared according to Refs. [4,14]. 3,3-Dimethyl-
3-sila-1-thiacyclopentane (6). IR (neat): 2950ꢀ
1250 (MeSi), 830 (CÃ 0.19 (s, 6H,
S). 1H-NMR: dꢃ
Me2Si), 1.01 (t, 3Jꢃ
7.14 Hz, 2H, SiCH2C), 1.72 (s, 2H,
SiCH2S), 2.79 (t, 2H, CCH2S). 13C-NMR: dꢃ
2.79
(Me2Si), 13.35 (SiCC), 16.43 (SiCS), 30.92 (CCS). 29Si-
NMR: dꢃ24.71.
/2890,
/
/
/
/
ꢂ
/
/
3.1. Reaction of 3,3-dimethyl-3-sila-1-thiacyclohexane
(3) with NaIO4
To a solution of 3 (290 mg, 2.0 mmol) in MeOH (25
ml) was added NaIO4 (450 mg, 2.1 mmol) in H2O (6 ml)
1
disiloxane 23. Since the signals in H- and 13C-NMR
at ꢂ
room temperature (r.t.), filtered and concentrated under
vacuum. The residue was extracted with CH2Cl2 (4ꢄ
/
2 8C. The mixture was stirred for 1 h, warmed to
spectra of silanol 19 and disiloxane 20 (as well as of
silanol 22 and disiloxane 23) almost coincide, the ratios
of the products were determined from their 29Si-NMR,
which are clearly different. The structure of silanols 19
and 22 was also corroborated by the presence of OH
band in the IR spectra.
/
3
ml) and dried over MgSO4. The solvent was removed
and the crude product (270 mg, 84% yield) purified by
column chromatography to give 3,3-dimethyl-3-sila-1-
thiacyclohexane S-oxide (4) (140 mg, 44% yield) as fine
1
The conclusion can be drawn that S-functional
derivatives of 1,3-thiasilacycloalkanes suffer solvolytic
white crystals; m.p. 54ꢀ
/
55 8C. H- and 13C-NMR data
are consistent with those reported in Ref. [4]. With two
equivalents of NaIO4 3,3-dimethyl-3-sila-1-thiacyclo-
hexane S,S-dioxide (5) was obtained in 52% yield;
cleavage of the SiÃCa bond, with the ease of the ring
/
opening depending on the nature of the S-functionality
and the size of the ring. The five-membered compounds
are split more readily than their six-membered analogs
due to higher ring constraints. Six-membered S-func-
tional derivatives rank in the following order of their
solvolytic stability in aqueous methanol: sulfonium
m.p. 63ꢀ
that in Ref. [4]. 13C-NMR: dꢃ
(SiCC), 19.51 (CCC), 44.37 (SiCS), 54.50 (SCC). 29Si-
NMR: dꢃ1.17.
/
64 8C. Its 1H-NMR spectrum coincides to
3.03 (Me2Si), 11.42
/
ꢂ
/
/
saltB
is fulfilled for the five-membered analogs: sulfimideB
sulfoxideBsaltBsulfone.
/
sulfimideB
/
sulfoxide5
/
sulfone. Another sequence
3.2. Reaction of 3,3-dimethyl-3-sila-1-thiacyclopentane
(6) with mCPBA
/
/
/
To a solution of 6 (300 mg, 2.3 mmol) in CH2Cl2 (3.5
ml) was added a solution of mCPBA (85%, 460 mg, 2.3
3. Experimental
mmol) in CH2Cl2 (8 ml) at ꢂ
stirred for 40 min and allowed to warm to 10 8C. At this
stage the mixture consisted mainly (ꢁ90%) of sulfoxide
7 and only traces of sulfide 6. 3,3-Dimethyl-3-sila-1-
thiacyclopentane S-oxide (7), 1H-NMR: dꢃ
0.18 (s, 3H,
/
20 8C. The mixture was
Melting points were determined with a Boetius
apparatus (VEB Analytik) and are uncorrected. Infrared
spectra were obtained on a Specord 75 IR spectro-
photometer in thin layer or in pellets with KBr and
/
/
2
SiCH3), 0.36 (s, 3H, SiCH3), 1.04 (ddd, J4a4b
ꢃ
/
14.7,
given as nmax (cmꢂ1). H-, 13C-, and 29Si-NMR spectra
3J4a5a
3J4b5a
2J2a2b
4J2b5b
ꢃ
/
ꢃ
/
3.6 Hz, 1H, SiCH2C), 1.37 (ddd,
1
3
7.1, J4a5b
3
11.3, J4b5b
were recorded for CDCl3 solutions on a Bruker DPX-
400 spectrometer at 400, 100, and 80 MHz, respectively.
Chemical shifts were determined relative to residual
chloroform signal and are given in ppm with respect to
Me4Si. Thin layer chromatography was performed on
silica gel plates (60 F-254) and visualized by iodine
ꢃ
/
ꢃ
ꢃ
/7.6 Hz, 1H, SiCH2C), 1.78 (dd,
4
14.7, J2a5a
ꢃ
/
/
0.8 Hz, 1H, SiCH2S), 2.07 (dd,
2
ꢃ
/
2.6 Hz, 1H, SiCH2S), 2.45 (dddd, J5a5b
ꢃ13.7
/
Hz, 1H, CCH2S), 3.17 (dddd, 1H, CCH2S). 13C-NMR:
dꢃ 1.59 (MeSi), 0.01 (MeSi), 7.95 (SiCC), 38.96
(SiCS), 51.39 (CCS). 29Si-NMR: dꢃ
21.96. Removal
/
ꢂ
/
/

E.N. Suslova et al. / Journal of Organometallic Chemistry 677 (2003) 73ꢀ
/79
77
of mCPBA by threefold freezing-out the above mixture
in the presence of molecular sieves 4A gave crude
product (130 mg) containing 65% of 7. It was dissolved
in CH2Cl2 and washed with cold 5% solution of
NaHCO3. Organic layer was separated, aqueous phase
extracted twice with CH2Cl2, and combined organic
phases dried over MgSO4. The solvent was removed, the
residue chromatographed (ethyl acetate:MeOH, 7:3 to
3:7) to give 1,1,3,3-tetramethyl-1,3-[bis(methylsulfiny-
l)ethyl]disiloxane (8) (50 mg, 14% yield) as colorless
3.5. 1,1,3,3-Tetramethyl-1,3-bis[2-
(methylsulfonyl)ethyl]disiloxane (10)
3,3-Dimethyl-3-sila-1-thiacyclopentane S,S-dioxide
(9) was dissolved in MeOH:H2O (6:1). After 24 h the
solvent was removed and the product dried under
vacuum. IR (neat): 2950, 1280 and 1130 (SO2), 1250
(MeSi), 1060 (SiOSi). 1H-NMR: dꢃ
Me2Si), 0.92 (m, 2H, SiCH2), 2.81 (s, 3H, MeS), 2.89
(m, 2H, SCH2). 29Si-NMR: dꢃ
7.92.
/
0.055 (s, 6H,
/
oil. IR (KBr): 2950, 1250 (MeSi), 1025 (SO), 1045
1
(SiOSi). H-NMR: dꢃ/0.14 (s, 12H, Me2Si), 0.86 (ddd,
3.6. 3-(Benzenesulfonylimino)-1,1-dimethyl-1,3-
silathiane (11)
2Jꢃ
/
15.2, 3Jꢃ
/
13.6, 5.2 Hz, 2H, HA in SiCH2), 0.99
3
2
(ddd, Jꢃ
/
15.2, Jꢃ
/
13.6, 5.2 Hz, 2H, HB in SiCH2),
2.55 (s, 6H, CH3SO), 2.62 (ddd, 2Jꢃ
/13.6 Hz, 2H, HA in
To a mixture of sulfide 3 (350 mg, 2.4 mol%),
tetraethylbenzylammonium chloride (28 mg, 5 mol%)
and molecular sieves 4A (770 mg) in CH2Cl2 (6 ml),
chloramine B trihydrate (700 mg, 2.6 mmol) was added
CH2SO), 2.67 (ddd, 2H, HB in CH2SO). Small splittings
were observed for the upfield HA signal of the SCH2
group (1.3 Hz) and for the CH3SO group (1.0 Hz) due to
nonequivalence of some chemical shifts in the two
diastereomers of 8 possessing two chiral sulfur atoms.
by portions for 30 min at ꢂ5 8C. The mixture was
/
stirred for 40 min, then warmed to 15 8C. Liquid part
was decanted and solvent removed under vacuum. The
residue (550 mg) was thrice washed with ether and dried
under vacuum to give 11 (530 mg, 74% yield) as white
13C-NMR: dꢃ
/
0.36 (MeSi); 10.18 (SiCH2); 37.70 (SMe);
8.22. Anal. Calc. for
49.18 (SCH2). 29Si-NMR: dꢃ
/
C10H26S2Si2O3: C, 38.22; H, 8.28; S, 20.38; Si, 17.83.
Found: C, 37.90; H, 8.24; S, 20.20; Si, 17.87%.
crystals; m.p. 105ꢀ
/
107 8C. IR (KBr): 2850ꢀ
/
3070 (CH),
1630 (Ph), 1250 (MeSi), 1290, 1130, 1150 (SO2), 970, 760
1
(SN), 845, 695 (CS-cycle). H-NMR: dꢃ0.17 (s, 3H,
MeSi), 0.22 (s, 3H, MeSi), 0.62 (ddd, Jꢃ
12.7, 4.6 Hz, 1H, SiCH2C), 0.78 (ddd, Jꢃ
/
2
3
/
15.0, Jꢃ
5.9, 3.3 Hz,
15.0, 1H, H5, CCH2C),
/
3.3. Reaction of 3,3-dimethyl-3-sila-1-thiacyclopentane
(6) with NaIO4
3
/
2
1H, SiCH2C), 1.81 (ddddd, Jꢃ
2.36 (m, 1H, CCH2C), 2.40 (dd, Jꢃ
Hz, 1H, SiCH2S), 2.45 (d, 1H, SiCH2S), 2.85 (ddd, 2Jꢃ
13.0, 3Jꢃ12.4, 2.2 Hz, 1H, CCH2S), 3.04 (m, 3J6,5
6.3
Hz, 1H, CCH2S), 7.41 (3H, m, Hm,p), 7.86 (2H, m, Ho).
13C-NMR: dꢃ
3.62 (MeSi), ꢂ1.91 (MeSi), 11.36
/
2
4
/
13.1, J2,6
ꢃ1.5
/
The reaction of 6 (340 mg, 2.6 mmol) with NaIO4 (580
mg, 2.7 mmol) was carried out and treated similar to
that in Section 3.1. The crude product (260 mg, 70%)
was purified by column chromatography to give 8 (150
mg, 37% isolated yield).
/
/
ꢃ
/
/
ꢂ
/
/
(SiCC), 18.63 (CCC), 36.17 (SiCS), 50.52 (CCS),
126.07 (Co), 128.56 (Cm), 131.04 (Cp), 144.74 (Ci).
29Si-NMR: dꢃ
C, 47.84; H, 6.31; N, 4.65; S, 21.26; Si, 9.30. Found: C,
47.78; H, 6.52; N, 4.78; S, 21.04; Si, 9.41%.
/
ꢂ0.14. Anal. Calc. for C12H19NS2SiO2:
/
3.4. 3,3-Dimethyl-3-sila-1-thiacyclopentane S,S-dioxide
(9)
A solution of mCPBA (80%, 1.0 g, 5.8 mmol) in
CH2Cl2 (10 ml) was added to a solution of 6 (380 mg,
3.7. Alkaline hydrolysis of sulfimide 11 to silanol 13
2.9 mmol) in CH2Cl2 (10 ml) at ꢂ
/
20 8C and stirred for 2
To a solution of sulfimide 11 (130 mg, 0.4 mmol) in
acetone (2 ml), KOH (70 mg, 1.3 mmol) in H2O (2 ml)
was added and stirred for 15 min at r.t. Then saturated
aqueous solution of NH4Cl was added, organic layer
separated, water layer extracted with CH2Cl2, combined
organic phase dried over MgSO4 and evaporated in
vacuum. The residue was washed with ether and dried
under vacuum to give 13 (110 mg, 80%) as white
h at ꢂ15 8C. mCPBA was separated by twofold
/
freezing-out in the presence of powdered molecular
sieves 4A. The solvent was removed, the crude solid
product (340 mg) washed with hexane (12 ml), and dried
under vacuum. Sulfone 9 (300 mg, 86% yield) was
obtained as white crystals; m.p. 95ꢀ
2955, 1290 and 1140 (SO2), 1255 (MeSi), 860, 820. H-
NMR: dꢃ 10.0 Hz, 2H,
0.37 (s, 6H, Me2Si), 1.23 (t, 3Jꢃ
SiCH2C), 2.44 (s, 2H, SiCH2S), 3.10 (t, 2H, CCH2S).
13C-NMR: dꢃ
1.82 (MeSi), 8.57 (SiCC), 39.42 (SiCS),
52.03 (CCS). 29Si-NMR: dꢃ
12.73. Anal. Calc. for
/
96 8C. IR (KBr):
1
/
/
crystals; m.p. 80ꢀ
/
82 8C. IR (KBr): 3320 (OH), 3060
(Ph), 1250 (MeSi), 1290 and 1140 (SO2), 920 and 740
1
/
(SN). H-NMR (acetone-d6): dꢃ
/0.03 (s, 6H, Me2Si),
/
0.57 (m, 2H, SiCH2), 1.68 (m, 2H, CCH2C), 2.66 (s, 3H,
C5H12SiSO2: C, 36.56; H, 7.34; S, 19.52; Si, 17.08.
Found: C, 36.81; H, 7.22; S, 19.19; Si, 17.02%.
SMe), 3.00 (m, 2H, CH2S), 4.36 (s, 1H, OH), 7.49ꢂ
/
7.83
(m, 5H, Ph). 13C-NMR: dꢃ
/
ꢂ
/
0.35 (MeSi), ꢂ
/
0.21

78
E.N. Suslova et al. / Journal of Organometallic Chemistry 677 (2003) 73ꢀ79
/
(MeSi), 16.39 (SiCH2), 17.28 (CCC), 34.06 (SMe), 53.50
(CH2S), 126.29 (Co), 128.83 (Cm), 131.47 (Cp), 144.16
21.62; Si, 9.46. Found: C, 44.49; H, 5.91; N, 4.58; S,
21.99; Si, 9.39%.
(C1). 29Si-NMR: dꢃ
15.45. Anal. Calc. for
/
C12H21NS2SiO3: C, 45.14; H, 6.58; N, 4.38; S, 20.06;
Si, 8.78. Found: C, 45.45; H, 6.70; N, 4.39; S, 20.27; Si,
9.16%.
3.10. Imidation of 6 in CH2Cl2
Under the conditions of synthesis of sulfimide 11 the
reaction of sulfide 6 (400 mg, 3.0 mmol) with chloramine
B trihydrate (810 mg, 3.0 mmol) after 1 h gave a mixture
of silanol 16 (48%), disiloxane 17 (24%), and sulfoxide 7
(28%). The latter was separated by extraction with ether
as an oil. Its 13C-NMR spectrum completely coincided
with that from oxidation of sulfide 6 with mCPBA. At
the same time, the SiCS and SCC signals in the six-
3.8. Imidation of 3 in methanol
Imidation of 3 (350 mg, 2.4 mmol) with chloramine B
trihydrate (680 mg, 2.6 mmol) was performed as
described in Ref. [8]. After 1 h the mixture consisted
of only decomposition products of sulfimide 11. The
crude product (800 mg) was chromatographed (hexa-
ne:ethyl acetate, 9:1 to 1:1, methanol) to give a 1.5:1
mixture (520 mg, 72% total yield) of silanol 13 and
disiloxane 14. Treatment of this mixture with 5%
aqueous sodium bicarbonate completely converted sila-
nol 13 to disiloxane 14 obtained as white crystals; m.p.
membered compounds 4 and 11 differ by 4ꢀ6 ppm.
/
Therefore, we can rule out the formation of cyclic
sulfimide 15 in the reaction of 6 with chloramine B.
The residue after extraction consisted of silanol 16 and
disiloxane 17 in the ratio 1:2 contaminated with
benzenesulfonamide. Column chromatography (hexa-
ne:ether, 7:1; ether:methanol, from 20:1 to 1:1) afforded
pure disiloxane 17 (110 mg, 24%).
66ꢀ
(SO2), 1240 (Me2Si), 1060 (SiOSi), 930 and 740 (SÄ
1H-NMR: dꢃ
0.05 (s, 12H, Me2Si), 0.42 (m, 2H, HA
/
68 8C. IR (KBr): 3050, 1560 (Ph), 1280 and 1135
/N).
/
ꢂ
/
in SiCH2), 0.52 (m, 2H, HB in SiCH2), 1.56 (m, 4H,
CCH2C), 2.54 (s, 3H, SMe), 2.55 (s, 3H, SMe), 2.89 (m,
4H, CH2S), 7.37 (m, 6H, Hm,p), 7.80 (m, 4H, Ho). 13C-
3.11. 1,3,3-Trimethyl-1,3-thiasilinan-1-ium iodide (18)
A mixture of sulfide 3 (610 mg, 4.2 mmol) and CH3I
(1.78 g, 12.5 mmol) in EtOH (3 ml) was kept for 5 days
at r.t., the solvent removed, and the residue (1.17 g)
crystallized from CH2Cl2/ether (1:3) to give 17 (1.14 g,
NMR: dꢃ
34.32 (SMe), 53.37 (CH2S), 126.35 (Co), 128.96 (Cm),
131.53 (Cp), 144.57 (C1). 29Si-NMR: dꢃ
7.30. Anal.
/0.38 (MeSi), 17.22 (SiCH2), 17.49 (CCC),
/
Calc. for C22H40N2O5S4Si2: C, 46.01; H, 6.41; N, 4.58;
S, 20.94; Si, 8.79. Found: C, 46.42; H, 6.49; N, 4.51; S,
20.65; Si, 9.05%.
95%) as white crystals; m.p. 84ꢀ85 8C. IR (KBr): 2920,
/
1
1250 (MeSi), 1090 (SMe). H-NMR: dꢃ
/
0.34 (s, 6H,
15.2 Hz, 1H, HA in SiCH2C), 1.12
2
Me2Si), 0.95 (d, Jꢃ
/
3
(ddd, Jꢃ
2Jꢃ
14.3 Hz, 1H, HA in CCH2C), 2.55 (m, Jꢃ
1H, HB in CCH2C), 3.02 (d, Jꢃ
/
14.3, 4.8 Hz, 1H, HB in SiCH2C), 2.03 (ddd,
3
3.9. Imidation of 6 in methanol
/
/
4.8 Hz,
2
/
12.5 Hz, 1H, HA in
In a similar way, 6 (190 mg, 1.4 mmol) reacted with
chloramine B trihydrate (410 mg, 1.5 mmol) with 100%
conversion after 1 h into the mixture of silanol 16 and
disiloxane 17 in the ratio 1.5:1. After filtering on Celite
521 the ratio changed to 1:2 (total yield: 400 mg, 80%).
Column chromatography or washing with 10% sodium
bicarbonate gave pure disiloxane 17 as white glassy
solid. IR (KBr): 3060 and 1580 (Ph), 1290 and 1130
(SO2), 1250 (MeSi), 1060 (SiOSi), 940 and 750 (SN). 1H-
SiCH2S), 3.44 (s, 3H, SMe), 3.50 (d, 1H, HB in SiCH2S),
2
3
3.82 (d, Jꢃ
14 Hz, 1H, HB in CCH2S). 13C-NMR: dꢃ
10.92 (SiCC), 20.68 (CCC), 24.55 (SiCS), 29.92 (SMe),
41.70 (CCS). 29Si-NMR: dꢃ
2.21. Anal. Calc. for
/
13.1 Hz, 1H, HA in CCH2S), 3.97 (t, Jꢃ
/
/
ꢂ
/
2.5 (MeSi),
/
ꢂ
/
C7H17ISSi: I, 44.09; S, 11.11. Found: I, 44.36; S, 11.47%.
3.12. 1,3,3-Trimethyl-1,3-thiasilolan-1-ium iodide (21)
NMR: dꢃ
/
ꢂ
/
0.06 (s, 12H, Me2Si), 0.718 (ddd, 2Jꢃ
13.8, 4.3 Hz, 1H, HA in SiCH2), 0.723 (ddd,
/
13.8
In a similar way from 6 (230 mg, 1.7 mmol) and CH3I
(710 mg, 5.0 mmol), 21 (470 mg, 96%) was obtained as
3
Hz, Jꢃ
/
3Jꢃ13.8, 4.2 Hz, 1H, HB in SiCH2), 0.86 (ddd, 2Jꢃ
/
/
13.8
white crystals; m.p. 160ꢀ
(KBr): 2940, 1240 (MeSi), 1080 (SMe). H-NMR: dꢃ
/
161 8C (lit.: 159ꢀ160 8C [3]). IR
/
3
1
Hz, Jꢃ
/
13.8, 4.3 Hz, 1H, HA in SiCH?); 0.88 (ddd,
/
2
3Jꢃ
/
13.7, 4.3 Hz, 1H, HB in SiCH?2); 2.61 (s, 3H, MeS),
0.52 (s, 3H, MeSi), 0.45 (s, 3H, MeSi), 1.38 (ddd, Jꢃ
/
2
2.63 (s, 3H, MeS), 2.85 (ddd, 2Jꢃ
/
13.2 Hz, 3Jꢃ
/
10.2, 3.9
10.1, 4.1 Hz, 1H,
15.2 Hz, Jꢃ
(ddd, 3Jꢃ7.2 Hz, 3Jꢃ
(dd, 2Jꢃ14.8 Hz, 4Jꢃ
/
10.1, 8.3 Hz, 1H, HA in SiCH2C), 1.49
3
3
Hz, 1H, HA in SCH2), 2.88 (ddd, Jꢃ
HB in SCH2), 3.02 (ddd, 2Jꢃ
2H, HAꢁ
Ho). 13C-NMR: dꢃ
(SMe), 45.44 (CCS), 125.53 (Co), 128.23 (Cm), 130.86
(Cp), 143.66 (C1). 29Si-NMR: dꢃ
8.23, 8.29. Anal. Calc.
for C20H36N2O5S4Si2: C, 44.59; H, 6.08; N, 4.73; S,
/
/
/4.8 Hz, 1H, HB in SiCH2C), 2.74
/
13.3 Hz, 3Jꢃ
/
13.3, 4.4 Hz,
/
/1.2 Hz, 1H, HA in SiCH2S), 3.05
/
HB in SCH?); 7.44 (m, 6H, Hm,p), 7.82 (m, 4H,
(d, 1H, HB in SiCH2S), 3.16 (s, 3H, SMe), 4.07 (ddd,
2Jꢃ
13.9 Hz, 1H, HA in CCH2S), 4.14 (m, 1H, HB in
CCH2S). 13C-NMR: dꢃ
1.60 (MeSi), ꢂ0.47 (MeSi),
10.67 (SiCC), 24.80 (SiCS), 25.51 (SMe), 43.98 (CCS).
29Si-NMR: dꢃ
30.27.
2
/
ꢂ
/
0.33 (MeSi), 10.20 (SiCC), 32.22
/
/
ꢂ
/
/
/
/

E.N. Suslova et al. / Journal of Organometallic Chemistry 677 (2003) 73ꢀ
/79
79
3.13. Methanolysis of salt 18
3.15. Methanolysis of salt 21
120 mg (0.42 mmol) of salt 18 was dissolved in 2.4 ml
of aqueous methanol (MeOH:H2O, 6:1). The reaction
leading to silanol 19 and disiloxane 20 was monitored at
intervals by removing the solvent, drying the residue,
and taking its NMR spectra. Pure disiloxane 20 was
obtained by reprecipitation from acetone into ether (110
mg, 89%).
Methanolysis of 180 mg (0.66 mmol) of salt 21 was
performed and monitored similar to that in Section 3.13.
Pure disiloxane 23 was obtained by reprecipitation from
acetone into ether (140 mg, 74%) as yellowish crystals;
m.p. 131ꢀ
1020 (SiOSi). H-NMR (D2O): dꢃ
1.06 (m, 2H, SiCH2C), 2.77 (s, 6H, Me2S), 3.29 (m, 2H,
CCH2S). 13C-NMR (D2O): dꢃ
0.30 (MeSi), 11.81
(SiCH2), 23.79 (Me2S), 40.23 (SCC). 29Si-NMR (D2O):
dꢃ9.22. Anal. Calc. for C12H32I2OS2Si2: I, 44.88; S,
/
134 8C. IR (KBr): 1260 (MeSi), 1050 (MeS),
1
/
0.16 (s, 6H, Me2Si),
/
ꢂ
/
3.13.1. Silanol 19
IR (KBr, vaseline oil): 3400 (OH), 1250 (MeSi), 1080
/
1
11.31. Found: I, 44.84; S, 11.70%.
(Me2S). H-NMR (acetone-d6): dꢃ
/0.12 (s, 6H, Me2Si),
0.80 (m, 2H, SiCH2), 2.01 (m, 2H, CCH2C), 3.31 (s, 6H,
Me2S), 3.79 (m, 2H, SCH2). 13C-NMR (acetone-d6): dꢃ
0.06 (MeSi), 17.22 (SiCC), 19.14 (CCC), 25.21
/
References
ꢂ
/
(Me2S), 46.06 (CCS). 29Si-NMR (acetone-d6): dꢃ
/12.49.
[1] R.J. Fessenden, M.D. Coon, J. Org. Chem. 29 (1964) 1607.
[2] R. Dedeyne, M.J.O. Anteunis, Bull. Soc. Chim. Belg. 85 (1976)
319.
3.13.2. Disiloxane 20
Light-yellow crystals; m.p. 141ꢀ
/
143 8C. IR (KBr):
[3] M.G. Voronkov, S.V. Kirpichenko, E.N. Suslova, V.V. Keiko,
A.I. Albanov, J. Organomet. Chem. 243 (1983) 271.
[4] (a) S.V. Kirpichenko, E.N. Suslova, L.L. Tolstikova, A.I.
Albanov, B.A. Shainyan, Zh. Obshch. Khim. 67 (1997) 1542;
(b) S.V. Kirpichenko, E.N. Suslova, L.L. Tolstikova, A.I.
Albanov, B.A. Shainyan, Russ. J. Gen. Chem. (Engl. Transl.)
67 (1997) 1449.
1250 (MeSi), 1090 (MeS), 1020 (SiOSi). 1H-NMR
(D2O): dꢃ
1.79 (m, 2H, CCH2C), 2.85 (s, 3H, MeS), 3.28 (m, 2H,
SCH2). 13C-NMR (acetone-d6): dꢃ
0.04 (MeSi), 17.23
(SiCC), 19.28 (CCC), 25.42 (Me2S), 46.08 (CCS). 29Si-
NMR (acetone-d6): dꢃ7.69. Anal. Calc. for
/
0.076 (s, 6H, Me2Si), 0.69 (m, 2H, SiCH2),
/
ꢂ
/
/
[5] A.G. Brook, D.G. Anderson, Can. J. Chem. 46 (1968) 2115.
[6] E. Block, M. Aslam, Tetrahedron 44 (1988) 281.
[7] G.D. Cooper, J. Am. Chem. Soc. 76 (1954) 3713.
[8] E.N. Suslova, S.V. Kirpichenko, A.I. Albanov, B.A. Shainyan, J.
Chem. Soc. Perkin Trans. 1 (2000) 3140.
C14H36I2OS2Si2: I, 42.76; S, 10.77. Found: I, 42.05; S,
10.69%.
3.14. Hydrolysis of salt 21
[9] J.C. McMullen, N.E. Miller, Inorg. Chem. 9 (1970) 2291.
[10] E. Vedejs, F.G. West, Chem. Rev. 86 (1986) 941.
[11] S.N. Borisov, M.G. Voronkov, E.J. Lukevits, Organosilicon
Derivatives of Phosphorus and Sulfur (Chapter 7), Plenum Press,
London/New York, 1971, p. 343.
3.14.1. Silanol 22
Hydrolysis of salt 21 in D2O for 17 h at r.t. gave
silanol 22. IR (after careful drying in KBr and in
1
vaseline oil): 3410 (OH), 1250 (MeSi), 1050 (MeS). H-
[12] (a) L.L. Tolstikova, B.A. Shainyan, Zh. Obshch. Khim. 67 (1997)
1836;
(b) L.L. Tolstikova, B.A. Shainyan, Russ. J. Gen. Chem. (Engl.
Transl.) 67 (1997) 1728.
NMR (D2O): dꢃ
SiCH2), 2.76 (s, 6H, Me2S), 3.30 (m, 2H, SCH2). 13C-
NMR (D2O): dꢃ 1.91 (MeSi), 11.08 (SiCC), 23.41
(Me2S), 39.70 (CCS). 29Si-NMR: dꢃ
16.00 (in D2O);
12.49 (in acetone-d6).
/
0.14 (s, 6H, Me2Si), 1.06 (m, 2H,
[13] S.V. Kirpichenko, E.N. Suslova, A.I. Albanov, B.A. Shainyan,
Sulfur Lett. 22 (2000) 245.
/
ꢂ
/
/
[14] K. Borisenko, S. Samdal, E.N. Suslova, V.A. Sipachev, I.F.
Shishkov, L.V. Vilkov, Acta Chem. Scand. 52 (1998) 975.