Transsilylation of O-trimethylsilyl derivatives of α-dimethylaminoketones by chloro(chloromethyl)dimethylsilane

Article abstract of DOI:10.1016/j.jorganchem.2018.01.014

Reaction of O-trimethylsilyl (O-TMS) derivatives of α-dimethylamino ketones with chloro(chloromethyl)dimethylsilane led to the formation of six-membered heterocyclic compounds with tetracoordinated silicon atom - 3,4-dihydro-2H-1,4,2-oxazasilin-4-ium chlo

Full text of DOI:10.1016/j.jorganchem.2018.01.014

Journal of Organometallic Chemistry xxx (2017) 1e6
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Journal of Organometallic Chemistry
journal homepage: www.elsevier.com/locate/jorganchem
Transsilylation of O-trimethylsilyl derivatives of a-
dimethylaminoketones by chloro(chloromethyl)dimethylsilane
Boris A. Gostevskii, Alexander I. Albanov, Alexander V. Vashchenko, Nataliya F. Lazareva*
A.E. Favorsky Irkutsk Institute of Chemistry, Siberian Branch of the Russian Academy of Sciences, 1, Favorsky St., 664033, Irkutsk, Russian Federation
a r t i c l e i n f o
a b s t r a c t
Article history:
Reaction of O-trimethylsilyl (O-TMS) derivatives of a-dimethylamino ketones with chloro(chloromethyl)
Received 16 October 2017
Received in revised form
10 January 2018
Accepted 12 January 2018
Available online xxx
dimethylsilane led to the formation of six-membered heterocyclic compounds with tetracoordinated
silicon atom - 3,4-dihydro-2H-1,4,2-oxazasilin-4-ium chlorides. The exchange reactions of 2,2,4,4-
tetramethyl-6-phenyl-3,4-dihydro-2H-1,4,2-oxazasilin-4-ium chloride were examined with Me3SiI and
NaBPh4 and the corresponding iodide or tetraphenylborate of 2,2,4,4-tetramethyl-6-phenyl-3,4-dihydro-
2H-1,4,2-oxazasilin-4-ium were isolated. 2,2,4,4-Tetramethyl-6-phenyl-3,4-dihydro-2H-1,4,2-oxazasilin-
4-ium chloride easy reacts with MeOH to give N-((methoxydimethylsilyl)methyl)-N,N-dimethyl-2-oxo-2-
phenylethanaminium chloride. The structure of synthesized compounds 10e15 was proved by multi-
nuclear NMR spectroscopy, 11 was also characterised by X-ray crystallography.
Dedicated to Professor Irina P. Beletskaya on
the occasion of her birthday.
Keywords:
O-TMS derivatives of a-dimethylamino
© 2018 Elsevier B.V. All rights reserved.
ketones
Chloro(chloromethyl)dimethylsilane
Transsilylation
1. Introduction
both fundamental (theoretical, synthetic, physico-chemical) and
applied (material science, applications) aspects of modern orga-
Silanes are important starting compounds for the production of
zeolites, ceramics, silica based organiceinorganic hybrid materials
obtained by using the solegel method and they are widely used to
prepare protective silica films for electronic devices by using the
chemical vapor deposition (CVD) [1e10]. Organosilicon materials
have gained widespread use in the chemical and electrical engi-
neering, electronics, aerospace industry, medicine due to their
unique properties, such as high- and low-temperature resistances,
weather resistance, ozone resistance, ageing resistance, electrical
insulation and physiological inertia [11e14]. Silanes containing
geminal N-C-Si group are promising candidates for creation of new
materials as well as their application as cross-linking agents for
polysiloxanes and organic polymers [15e26]. N-Silylmethylamine,
-amides and related compounds are a matter for extensive syn-
thetic and structural investigations. The reactions of transsilylation
of N-TMS derivatives of lactams, ureas, and carboxamides by pol-
yfunctional silanes lead to formation of corresponding N-siyl-
methyl derivatives. The investigation of the structure of products
and mechanism of these reactions is of profound importance for
nosilicon chemistry [27e37].
Previously we found that the O-TMS- N0,N0-dimethylhydrazides
1 have been reacted with polyhalogenosilanes to give the corre-
sponding neutral, hexacoordinate chelates 2 (Scheme 1) [36,38,39].
The reaction of compounds 1 with chloro(chloromethyl)dime-
thylsilane 3 was finished by the formation of the cyclic ionic
compounds 4 (Scheme 2) [40,41].
The electronic distribution of molecules of compounds 4 could
formally be represented by a set of canonical structures A-D
(Scheme 3) [37] in which the negative charge can be located on the
second hydrazide nitrogen atom or on the oxygen atom or the
silicon atom or the chlorine atom.
The reaction of dimethylaminomethyl ketones Me2NCH2C(O)R
(R ¼ t-Bu, Ph) with trimethylsilyl trifluoromethanesulfonate (TfO-
SiMe3) in the presence of triethylamine smoothly afforded their
corresponding O-TMS derivatives 5 and 6. Similar to the com-
pounds 1, the O-TMS-derivatives of a-dimethylaminoketones 5, 6
interact with polyhalogenosilanes to form isomorphic ionic com-
pounds 7e9 containing two N/Si chelate cycles (Scheme 4) [42].
Herein, we report on the preparation, characterization and
reactivity of novel ionic heterocyclic organosilicon compounds
obtained by the interaction of chloro(chloromethyl)dimethylsilane
* Corresponding author.
E-mail address: nataly_lazareva@irioch.irk.ru (N.F. Lazareva).
https://doi.org/10.1016/j.jorganchem.2018.01.014
0022-328X/© 2018 Elsevier B.V. All rights reserved.
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B.A. Gostevskii et al. / Journal of Organometallic Chemistry xxx (2017) 1e6
Scheme 1. Reaction of O-TMS derivatives of N0,N0-dimethylhydrazides of carboxylic acids 1 with polyhalogenosilanes.
Scheme 2. The formation of the cyclic ionic compounds 4.
Scheme 3. The canonical structures of compounds 4.
Scheme 4. The reaction of O-TMS-derivatives of a-dimethylaminoketones 5, 6 with polyhalogenosilanes.
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B.A. Gostevskii et al. / Journal of Organometallic Chemistry xxx (2017) 1e6
3
3 with O-TMS-derivatives of a-dimethylaminoketones 5, 6.
2. Results and discussion
Compounds 5, 6 react with chloro(chloromethyl)dimethylsilane
3 in chloroform or acetonitrile solutions to form 6-tert-butyl-
2,2,4,4-tetramethyl-3,4-dihydro-2H-1,4,2-oxazasilin-4-ium chlo-
ride 10 and 2,2,4,4-tetramethyl-6-phenyl-3,4-dihydro-2H-1,4,2-
oxazasilin-4-ium chloride 11, respectively (Scheme 5). This reac-
tion proceeds only upon heating to 80e90 ꢀC in contrast to the
transsilylation reaction of O-TMS derivatives of N0,N0-dimethylhy-
drazides of carboxylic acids 1 by silane 3 taking place at room
temperature [40].
The structure of compounds 10 and 11 was confirmed by 1H, 13
C
and 29Si NMR spectroscopy. The 29Si NMR spectra of compounds 10
and 11 in CDCl3 showed the single resonance (18.33 ppm and
18.78 ppm, respectively). Their pronounced displacement in region
of down field shifts in comparison with 29Si chemical shift of
compound 4 (
d
29Si ¼ ꢁ17.4 ppm.) indicates that the silicon atom is
tetracoordinated.
The single crystal of compound 11 suitable for X-ray analysis
was obtained by its crystallization from MeCN. The summary of
crystallographic data is provided in experimental section. The bond
distances and bond angles are presented in Tables 1S and 2S
(Supporting information). A comparison of the molecular struc-
tures of compound 11 (Fig. 1 and Table 1) and the isostructural
Fig. 1. Molecular structure of 11 in the crystal. Anisotropic displacement parameters
are depicted at the 50% probability level, and hydrogen atoms are omitted for clarity.
Table 1
The selected geometrical parameters of compounds 4 and 11.
pentacoordinated silicon compound
4
(R ¼ 4-MeO-C6H4) [41]
O
Compound l, Å
Si-Cl
SC-Si-C,
Ref.
(Table 1) shows the substantial differences in their geometric pa-
rameters. The Si-Cl bond length in compound 11 is substantially
larger than in compound 4 (3.108 Å and 2.624 Å, respectively) and is
closely approximating the sum of the Van der Waals radii of the Si
and Cl atoms. The Si-O bond length in compound 11 is significantly
shorter than in compound 4 (1.713 Å and 1.788 Å, respectively) and
this value is only 0.03 Å longer than the value of Si-O covalent bond
length in compounds of tetrahedral silicon atom. The values of O-
Si-Cl angles in compounds 4 and 11 are closely (173.8ꢀ and 173.6ꢀ,
respectively). The sum of bond angles C-Si-C in 11 differ signifi-
cantly from the sum of the equatorial bond angles C-Si-C in 4
(348.44ꢀ and 357.29ꢀ, respectively). The displacement of the silicon
atom relative to the equatorial plane defined by three carbon atoms
towards the O atom substituent approximated 0.178 Å and 0.728 Å
for compounds 4 [41] and 11, respectively (see Figs. 1 and 2 in
Supporting information). The silicon atom in compound 11 has a
tetrahedral geometry common to tetracoordinated silicon com-
pounds in contrast to distorted trigonal-bipyramidal geometry of
silicon atom in compound 4. Based on these results, it may be
concluded that compound 11 exists as ionic compound with tet-
racoordinated silicon atom.
Si-O
Si-CH2
Si-Me
4
2.624(8) 1.788(1) 1.885(2) 1.849(2) 357.29
[41]
1.885(2)
3.108(2) 1.713(9) 1.900(1) 1.856(1) 348.44
1.865(1)
114
this work
The compounds 10, 11 contain simultaneously silyl enol ether
group and a fragment of a vinyl ammonium salt. Such unique
structure opens up new avenues for the future development of
syntetic organic chemistry. Considering the high reactivity of silyl
enol ethers and their wide application in chemistry [43e51] it was
interesting to study the reactivity of these new compounds. This
part of our investigation was performed using compound 11. Its
interaction with trimethyl iodosilane, much like the interaction of
Me3SiI with N-[chloro(dimethylsilyl)methyl]lactams [27], is
a
typical exchange reaction and leads to the quantitative formation of
the corresponding 2,2,4,4-tetramethyl-6-phenyl-3,4-dihydro-2H-
1,4,2-oxazasilin-4-yl iodide 12 (Scheme 6). It has been known that
Scheme 5. The transsilylation reaction of O-TMS-derivatives of
a
-dimethylaminoketones 5, 6 by with chloro(chloromethyl)dimethylsilane.
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B.A. Gostevskii et al. / Journal of Organometallic Chemistry xxx (2017) 1e6
Scheme 6. Synthesis of compounds 12 and 13.
trimethyliodisilane causes the cleavage of the Si-O-C bond to form
siloxanes [52e54]. However, under the conditions of our experi-
ment the products of the cleavage of Si-O-C bond not were
observed. Apparently this is due that the rate of the halogen ex-
change reaction is substantially higher than the rate of the bond
cleavage reaction. Compound 11 reacts with NaBPh4 with forming
the corresponding 2,2,4,4-tetramethyl-6-phenyl-3,4-dihydro-2H-
1,4,2-oxazasilin-4-yl tetraphenylborate 13 (Scheme 6).
group is currently in progress and we hope that results will be
useful for the development of synthetic organic chemistry and the
chemistry of materials.
3. Experimental section
3.1. General procedures
The addition of methanol to compound 11 runs at 80 ꢀC without
use of any catalyst and finish by the formation of N-((methox-
ydimethylsilyl)methyl)-N,N-dimethyl-2-oxo-2-
All experiments were carried out under a dry argon atmosphere
using standard Schlenk techniques. Solvents were dried and freshly
distilled under argon prior to use [57].
The NMR spectra 1Н, 13С and 29Si were recorded on a Bruker
phenylethanaminium chloride 14 (Scheme 7). Notice that signal in
29Si NMR spectrum of 14 is shifted highfield compared to the
compound 11 (12.53 ppm and 18.78 ppm, respectively). Similar
changes in 29Si NMR chemical shifts are observed in acyclic silyl
enol ethers at the replacement of a alkenyloxy substituent by an
alkoxy group. For example the highfield chemical shifts in 29Si NMR
spectra of Me2CCH2CH2OSiMe3 and PhCH2OSiMe3 (15.6 ppm and
17.4 ppm, respectively) [55] are observed compared to
Me2C ¼ CHOSiMe3 and Me2C ¼ CPhOSiMe3 (18.7 ppm and
22.4 ppm, respectively) [56].
DPX-400
tively). Chemical shifts (
thylsilane (
following abbreviations were used: s ¼ singlet, d ¼ doublet,
m ¼ multiplet. Carbon, hydrogen and nitrogen elemental analysis
was performed on a Thermo Scientific Flash 2000 CHNS analyzer.
The content of silicon, bor and halogene was determined ther-
mogravimetrically. Crystal data were collected on a Bruker D8
и
Bruker AV-400 (400.13, 100.61
и 161.98 MHz, respec-
d
, ppm) are referenced to TMS ¼ tetrame-
d
¼ 0.0). For the assignment of the multiplicities the
Venture diffractometer with a Photon 100 detector using
u-2q
Interaction of compound 14 with boron trifluoride etherate in
THF gave rise to N-((fluorodimethylsilyl)methyl)-N,N-dimethyl-2-
oxo-2-phenylethanaminium chloride 15 with quantitative yield
(Scheme 7).
scanning (Table 2). The intensity of the reflections was integrated
using the Bruker SAINT software. The absorption of X-ray by a
crystal is taken into account from the analysis of the intensities of
equivalent reflections. Only independent reflections were used af-
ter averaging the intensities of equivalent reflections. The struc-
tures were solved and refined by direct methods using the SHELX
programs set [58]. Nonhydrogen atoms were refined anisotropi-
cally using SHELX [58]. CCDC 1549966 contain the supplementary
crystallographic data for this paper. These data can be obtained free
of charge from the Cambridge Crystallographic Data Centre via
www.ccdc.cam.ac.uk/data_request/cif.
In conclusion, we have demonstrated that the transsilylation
reaction of O-TMS
a-dimethyamino ketones by ClCH2SiMe2Cl is
efficient approach for the synthesis of novel Si-containing hetero-
cyclic compounds. Structure of these silanes is unique: simulta-
neously they are N-silylmethylamines, silyl enol ethers and vinyl
ammonium salts. Further application of this strategy for the syn-
thesis of novel Si-containing compounds with geminal N-C-Si
Scheme 7. Synthesis of compounds 14 and 15.
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B.A. Gostevskii et al. / Journal of Organometallic Chemistry xxx (2017) 1e6
5
5.65 mmol) and 10 mL CHCl3 was stirred at 20 ꢀC for 5 h. The solid
residue obtained after removal of the highly volatile substances
was washed with Et2O (3 ꢂ 20 mL). The slightly cream-colored
powder was dried in vacuo. Yield 1.58 g (96%, 4.37 mmol). M. p.
Table 2
Experimental data for compound 11.
ꢀ
CCDC N 1549966
Formula
Mr, g/mol
Temperature, К
Crystal system
Space group
a, Å
C13H20NOSi, Cl
269.84
100(2)
triclinic
P-1
6.6889(5)
8.8221(7)
12.9551(11)
77.662(3)
76.194(3)
88.492(3)
725.00(10)
2
148 ꢀC (in a capillary under vacuum). 1Н (CDCl3):
d
0.65 (s, 6 Н,
SiMe2), 3.83 (s, 8 H, NMe2, NCH2), 6.79 (s, 1 H, ¼CH), 7.37e7.41 (m, 3
Н, 2 Но, Нp), 7.69e7.71 (m, 2 Н, Нm). 13С (CDCl3):
d
ꢁ0.11 (SiCH3),
56.53 (СН2), 59.37 (NCH3), 115.00 (¼CH), 125.64, 128.66 (Co, Cm),
130.69 (Cp), 132.02 (Сi), 149.69 (¼СО). 29Si (CDCl3):
d 19.09. Anal.
b, Å
c, Å
Calc. for C13H20NOSiI: C 43.22; H 5.58; N 3.88; Si 7.77%. Found C
43.31; H 5.46; N 3.67; Si 7.85%.
a
, deg
, deg
b
g
, deg
V, Å3
3.2.4. Synthesis of 2,2,4,4-tetramethyl-6-phenyl-3,4-dihydro-2H-
1,4,2-oxazasilin-4-ium tetraphenylborate (13)
Z
P
calc, Mg/m3
1.236
A mixture of compound 11 (0.91 g, 4.63 mmol), NaBPh4 (1.44 g,
5.43 mmol) and 20 mL СН3СN was stirred at 90 ꢀC for 2 h. The so-
lution was decanted carefully and residue was washed by СН3СN
(20 mL). The combined solution was evaporated under reduced
pressure, the solid residue was washed with Et2O (2 ꢂ 30 mL). The
white powder was dried in vacuo. Yield 1.793 g (96%, 3.24 mmol).
F(000)
qrange, deg
Ref. collected
Independ. ref
288.0
4.728 to 60.554
44171
4326
0.0305
4326
159
1.047
Rint
Max. And min. broadcast
Num. of refinement parameters
Goodness-of-fit on F2
M. p. 175e176 ꢀC with decomposition. 1Н (CD3CN):
d 0.48 (s, 6 H,
R1 wR2 [I > 2
R1 wR2 [all data]
Dr)max and (Dr)min, e/Å3
sI]
R1 ¼ 0.0278, wR2 ¼ 0.0738
R1 ¼ 0.0332, wR2 ¼ 0.0766
0.41/-0.32
SiMe2), 3.02 (s, 2 H, CH2), 3.05 (s, 6 H, NMe2), 6.17 (s, 1 H, ¼CH),
6.82e6.86 (m, 4 Н, BPh4, Hp), 6.98e7.01 (m, 8 Н, BPh4, Нm), 7.30 (br,
9 Н, 1 Нp; BPh4, 8 Но), 7.39e7.43 (m, 2 Н, Нm), 7.56e7.58 (m, 1 Н, Но).
(
13С (CD3CN):
d
ꢁ0.61 (SiC), 56.65 (CH2), 59.43 (NCH3),115.38 (¼CH),
122.75 (BPh4, CP), 126.56 (Сm), 126.58 (BPh4, Cm) 129.68 (Со), 131.55
3.2. Experimental procedure
(Сp), 133.59 (Сi), 136.70 (BPh4, Co), 150.58 (PhCO), 164.76 (q,
JCB ¼ 49.3 Hz, BPh4, Ci). 29Si (CD3CN):
d 19.46. Anal. Calc. for
3.2.1. Synthesis of 6-tert-butyl-2,2,4,4-tetramethyl-3,4-dihydro-
2H-1,4,2-oxazasilin-4-ium chloride (10)
The chloro(chloromethyl)dimethylsilane 3 (0.93 g, 6.40 mmol),
10 mL CHCl3 were condensed into a Schlenk flask using a glass
C37H40NOSiB: C 80.27; H 7.28; N 2.53; Si 5.07; B 1.95%. Found C
80.31; H 7.16; N 2.41; Si 5.26; B 1.65%.
adapter and then the O-TMS a-aminoketone 5 (1.04 g, 4.80 mmol)
3.2.5. Synthesis of N-((Methoxydimethylsilyl)methyl)-N,N-
dimethyl-2-oxo-2-phenylethanaminium chloride (14)
was added in one portion. The mixture was stirred at 90 ꢀC for 40 h.
The solid residue obtained after removal of the volatile substances
was washed with hexane (2 ꢂ 20 mL). The white powder was dried
in vacuo. Yield 0.57 g (47%, 2.29 mmol). M. p. 173 ꢀC (In a capillary
A mixture of compound 11 (0.42 g, 1.56 mmol) and 5 mL MeOH
(excess) was stirred at 80 ꢀC for 1 h. The volatile matter was
removed under reduced pressure. The obtained residue was
washed with THF (20 mL), than Et2O (20 mL) and colorless resin
under vacuum). 1Н (CDCl3):
d 0.54 (s, 6 Н, SiMe2), 1.11 (s, 9 H, CMe3),
3.73 (s, 6 H, NMe2), 3.75 (s, 2 H, NCH2), 5.90 (s, 1 H, ¼CH). 13C
was dried in vacuo. Yield 0.46 g (98%, 1.52 mmol). 1Н (CDCl3):
d 0.32
(CDCl3):
d
ꢁ0.23 (SiCH3), 26.99 [C(CH3)3], 36.16 (CMe3), 56.00
(s, 6 Н, SiMe2), 3.43 (s, 3 H, OCH3), 3.73 (s, 2 H, SiCH2), 3.75 (s, 6 H,
NCH3), 5.96 (s, 2 H, CH2CO), 7.46e7.50 (m, 2 H, Hm), 7.58e7.61 (m, 1
(SiCH2), 58.92 (NCH3), 113.68 (¼CH). Anal. Calc. for C11H24NOSiCl: C
52.89; H 9.68; N 5.61; Si 11.24; Cl 14.19%. Found C 52.93; H 9.73; N
5.48; Si 11.32; Cl 13.97%.
Н, Нp), 8.01e8.09 (m, 2 Н, Но). 13С (CDCl3):
d
ꢁ1.25 (SiCH3), 50.84
(OCH3), 55.49 (NCH3), 56.76 (SiCH2), 69.58 (CH2CO), 126.66
(Ci),128.40 (Со),129.11 (Сm),134.67 (Сp),192.19 (С ¼ О). 29Si (CDCl3):
d
12.53. Anal. Calc. for C14H24NO2SiCl: C 55.70; H 8.01; N 4.64; Si
3.2.2. Synthesis of 2,2,4,4-tetramethyl-6-phenyl-3,4-dihydro-2H-
1,4,2-oxazasilin-4-ium chloride (11)
9.30; Cl 11.74%. Found C 55.38; H 8.27; N 4.38; Si 8.97; Cl 11.43%.
The chloro(chloromethyl)dimethylsilane 3 (0.60 g, 4.16 mmol),
5 mL СН3CN were condensed into a Schlenk flask using a glass
3.2.6. Synthesis of N-((fluorodimethylsilyl)methyl)-N,N-dimethyl-
2-oxo-2-phenylethanaminium chloride (15)
adapter and then the O-TMS a-aminoketone 6 (0.87 g, 3.70 mmol)
was added in one portion. The mixture was stirred at 80 ꢀC for 3 h.
The solid residue obtained after removal of the volatile substances
was washed with Et2O (2 ꢂ 10 mL). The white powder was dried in
vacuo. Yield 0.82 g (82%, 3.03 mmol). M. p. 160e162 ꢀC (in a capil-
A mixture of compound 14 (1.29 g, 4.26 mmol), BF3$Et2O (0.94 g,
6.62 mmol) and 20 mL THF was stirred at 80 ꢀC four 2 h. The volatile
matter was removed under reduced pressure and obtained residue
was washed with mixture of Et2O and THF (~2: 1, 2 ꢂ 20 mL). The
lary under vacuum). 1Н (CDCl3):
d 0.62 (s, 6 Н, SiMe2), 3.85 (s, 8 H,
colorless resin was dried in vacuo. Yield 1.18 g (95%, 4.07 mmol). 1Н
NMe2, NCH2), 6.86 (s, 1 H, ¼CH), 7.38 (m, 3Н, 2Нm, 1Нp), 7.67 (m 2 Н,
3
(CDCl3):
d
0.41 (d, JHF ¼ 7.15 Hz, 6 Н, SiMe2), 3.43 (s, 6 Н, NMe2),
Но). 13С (CDCl3):
d - 0.10 (SiCH3), 56.04 (SiCH2), 59.17 (NCH3), 115.05
3.60 (br s, 2 Н, СН2Si), 5.08 (s, 2 Н, СН2С ¼ О), 7.42e7.45 (m, 2 Н,
(¼CH), 125.65, 128.42 (Co, Cm), 130.64 (Cp), 132.40 (Сi), 149.58
Нm), 7.58e7.62 (m, 1 Н, Нp), 7.91e7.93 (m, 2 Н, Но). 13С (CDCl3):
(PhCO). 29Si (CDCl3):
d 18.78. Anal. Calc. for C13H20NOSiCl: C 57.86;
2
d
ꢁ0.75 (d, JCF ¼ 13.38 Hz, SiCH3), 55.33 (NCH3), 56.98 (d,
H 7.47; N 5.19; Si 10.41; Cl 13.14%. Found C 57.91; H 7.43; N 5.21; Si
10.53; Cl 13.21%.
2JCF ¼ 14.15 Hz, CH2Si), 69.12 (СН2С ¼ О), 128.13 (Со), 129.13 (Сm),
133.94 (Сi), 135.04 (Сp), 190.86 (С ¼ О). 29Si (CDCl3):
d 26.27 (d, JSi-F
285.79 Hz). Anal. Calc. for C13H21NOSiFCl: C 53.87; H 7.30; N 4.83; Si
9.69%. Found C 53.80; H 7.46; N 4.56; Si 9.34%.
3.2.3. Synthesis of 2,2,4,4-tetramethyl-6-phenyl-3,4-dihydro-2H-
1,4,2-oxazasilin-4-ium iodide (12)
These results were obtained using analytical equipment of the
Baikal Analytical Center for collective use of the SB RAS.
A mixture of compound 11 (1.22 g, 4.52 mmol), Me3SiI (1.13 g,
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B.A. Gostevskii et al. / Journal of Organometallic Chemistry xxx (2017) 1e6
A.I. Albanov, M.G. Voronkov, V.A. Pestunovich, Zh. Obshch. Khim. 59 (1989)
Appendix A. Supplementary data
127e145.
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1210e1227.
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[30] A.R. Bassindale, Prog. Org. Chem. (1995) 191.
Supplementary data related to this article can be found at
https://doi.org/10.1016/j.jorganchem.2018.01.014.
[31] V.V. Negrebetsky, Yu.I. Baukov, Russ. Chem. Bull. 46 (1997) 1807e1831.
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Organic Silicon Compounds, Wiley, Chichester, U. K., 1998, p. 1340.
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Please cite this article in press as: B.A. Gostevskii, et al., Journal of Organometallic Chemistry (2017), https://doi.org/10.1016/
j.jorganchem.2018.01.014