A Route to Organyl(trialkoxysilyl)chalcogenides and Dichalcogenides, Bis(trialkoxysilylmethyl)chalcogenides and Dichalcogenides

Article abstract of DOI:10.1023/A:1014280007913

Reactions of organylchalcogenomagnesium halides RYMgX (in situ) (R = Me, Et, Ph; Y = S, Se, Te; X = Br, I) with (halomethyl)trialkoxysilanes X'CH2Si(OR')3 (X' = Cl, I; R' = Me, Et) at reflux in tetra-hydrofuran and the systems of tetrahydrofuran-acetonitrile 1 :2, and ether-acetonitrile 1:2 are studied. These reactions are shown to lead to formation of mixtures of corresponding organyl(trialkoxysilylmethyl)chalcogenide and -dichalcogenide, bis(trialkoxysilyl methyl)chalcogenide and -dichalcogenide, as well as the contaminants 2,2,6,6-tetraalkoxy-2,6-disila-4-chalcogen-1-oxane, diorganylchalcogenide and -dichalcogenide, and other organic and organosilicon compounds. Composition of the formed mixtures depends considerably on the structure of R, nature of the chalcogen Y (S, Se, Te), and halides X and X' in the initial reagents, and reaction conditions. The most of synthesized and isolated organosilicon chalcogenides are newly obtained compounds.

Full text of DOI:10.1023/A:1014280007913

Russian Journal of General Chemistry, Vol. 71, No. 12, 2001, pp. 1883 1890. Translated from Zhurnal Obshchei Khimii, Vol. 71, No. 12, 2001,
pp. 1988 1995.
Original Russian Text Copyright
2001 by Sorokin, Voronkov.
A Route to Organyl(trialkoxysilyl)chalcogenides
and Dichalcogenides, Bis(trialkoxysilylmethyl)chalcogenides
and Dichalcogenides
M. S. Sorokin and M. G. Voronkov
Favorskii Irkutsk Institute of Chemistry, Siberian Division, Russian Academy of Sciences, Irkutsk, Russia
Received December 29, 2000
Abstract Reactions of organylchalcogenomagnesium halides RYMgX (in situ) (R = Me, Et, Ph; Y = S,
Se, Te; X = Br, I) with (halomethyl)trialkoxysilanes X CH2Si(OR )3 (X = Cl, I; R = Me, Et) at reflux in tetra-
hydrofuran and the systems of tetrahydrofuran acetonitrile 1: 2, and ether acetonitrile 1: 2 are studied. These
reactions are shown to lead to formation of mixtures of corresponding organyl(trialkoxysilylmethyl)chalco-
genide and -dichalcogenide, bis(trialkoxysilyl methyl)chalcogenide and -dichalcogenide, as well as the
contaminants 2,2,6,6-tetraalkoxy-2,6-disila-4-chalcogen-1-oxane, diorganylchalcogenide and -dichalcogenide,
and other organic and organosilicon compounds. Composition of the formed mixtures debends considerably
on the structure of R, nature of the chalcogen Y (S, Se, Te), and halides X and X in the initial reagents, and
reaction conditions. The most of synthesized and isolated organosilicon chalcogenides are newly obtained
compounds.
Earlier [1 6] we developed simple methods for the
synthesis of organyl(trialkoxysilylalkyl)chalcogenides
with the general formula RY(CH2)nSi(OR )3 (n = 1 3).
One of the methods which produces the targed sul-
fides and selenides in a high yield is based on the
reaction of corresponding sodium organylchalcoge-
nates with (haloalkyl)trialkoxysilanes in boiling
(trialkoxysilylalkyl)tellurides
RTe(CH2)nSi(OR )3
might be performed by reaction of corresponding
RTeNa with (haloalkyl)trialkoxysilanes only. Ho-
wever, the sodium tellurolate RTeNa solutions in
liquid ammonia or alcohol generated for this purpose
from the corresponding diorganylditellurides are
hardly applicable owing to fast oxidation at the attem-
hexane (or heptane) [1 3, 5]. The initial sodium alkyl-, pted isolation of the target products for transfer them
benzyl-, phenylthiolates, alkyl- and phenylselenolates into hexane (or heptane) medium.
RYNa (Y = S, Se) were prepared preliminary from the
In the synthesis of phenylethynyl- and trimethyl-
corresponding thiols and selenols and metallic sodium
silylethynyl(trimethoxysilylmethyl)chalcogenides with
in hexane or heptane, and sodium 4-methylphenyl-,
general formula RYCH2Si(OR )3 (R = PhC C,
naphthyl-, methoxycarbonylmethyl- and ethoxycar-
Me3SiC C; Y = S, Se, Te) [6] the initial sodium
bonylmethylthiolates at the action of sodium
organylchalcogenates RYNa were prepared from
methoxide in methanol on the corresponding thio
corresponding organylacetylenes, metallic sodium and
derivative. However, for the synthesis of organyl(tri-
elemental chalcogenes in ether or tetrahydrofuran.
alkoxysilylalkyl)sulfides RS(CH2)nSi(OR )3 (n = 2, 3)
In [8] we first described bis(trimethoxysilylmethyl)-
[1, 2, 4], alkyl- and phenyl(trimethoxysilylethyl)-
selenide and bis(triethoxysilylmethyl)telluride, syn-
selenides RSeCH2CH2Si(OMe)3 [5] the method based
thesized by reaction of corresponding sodium chalco-
on the reaction of photoinduced addition of thiols and
genide and (chloromethyl)trialkoxysilane in boiling
selenols to alkenyltrialkylsilanes was found more
methanol or acetonitrile. In this reaction besides the
effective. A problem of processing volatile and
linear chalcogenides were isolated and characterized
odorous and toxic methaneselenol restricted applica-
also the contaminating them sixmembered hetero-
tion of these methods for the synthesis of methyl(tri-
cycles, the corresponding 2,2,6,6-tetraalkoxy-2,6-di-
alkoxysilylalkyl)selenides with general formula
sila-4-chalcogen-1-oxanes.
MeSe(CH2)nSi(OR )3. Besides, alkanetellurides (un-
like alkanethiols and alkaneselenols) are practically
inaccessible (and aryltelluroles are unknown at all)
being extremely prone of oxidizing at the contact with
air [7], and therefore the synthesis of alkyl- and aryl-
Organyl(trialkoxysilylalkyl)sulfides and selenides
turned to be key compounds at the synthesis of
silatranyl derivatives of general formula RY(CH2)nSi
(OCH2CH2)m[OCH(CH3)CH2]3 m
N
(m
=
0 3)
1070-3632/01/7112-1883$25.00 2001 MAIK Nauka/Interperiodica

1884
SOROKIN, VORONKOV
[2, 5, 6]. At n = 1 the latter show enhanced reactivity
at the formation of corresponding oxides [3] and
onium salts [5], owing to super-electron-donor effect
of silatranyl group [9].
II, R = Me, Y = Se (a); R = Me, Y = Te (b); R = Et, Y =
S (c); R = Et, Y = Se (d); R = Et, Y = Te (e).
Actually, in the mixtures with a complex composi-
tion formed in reaction of RYMgX (in situ) with
(halomethyl)trialkoxysilanes in all the cases the
expected chalcogenides I (except Ia) and II are
formed.
In continuation of these investigations, we per-
formed a series of reactions of organylchalcogeno-
magnesium halides RYMgX (in situ) with (halo-
methyl)trialkoxysilanes in boiling tetrahydrofuran or
an 1:2 mixture of tetrahydrofuran or ether with aceto-
nitrile. The studied reagents, reaction conditions and
results obtained are listed in Table 1.
Besides, among the products of the studied reac-
tions were found sixmembered heterocycles, 2,2,6,6-
tetraalkoxy-2,6-disila-4-chalcogena-1-oxane (III) and
expected side compounds, dialkyl(diphenyl)chalco-
genides R2Y and -dichalcogenides R2Y2.
The initial RYMgX were prepared (in situ) from
the corresponding Grignard reagents and elemental
chalcogen in 1:1 ratio, in ether or tetrahydrofuran.
Y
R O
R O
OR
OR
RMgX + Y
RYMgX.
(1)
Si
Si
O
IIIa IIIe
Sulfur and selenium reacted intensively and com-
pletely with all the alkylmagnesium halides and
phenylmagnesium bromide in ether and THF at room
temperature, while tellurium (taken as fine crystalline
powder) reacted to 60% only even in boiling THF.
III, R = Me, Y = Se (a); R = Me, Y = Te (b); R = Et,
Y = S (c); R = Et, Y = Se (d); R = Et, Y = Te (e).
Formation of heterocycles III can be explained by
the hydrolysis of the corresponding open-chain chalco-
genides II with air moustre at the processing the reac-
tion mixture. {We obtained the similar heterocycles
in the synthesys of bis(trialkoxysilylmethyl)chalco-
genides [8].} However, the products of the studied
reactions besides above compounds contained un-
As is known, reaction of arylmagnesium bromides
with sulfur [10], selenium [11, 12] and tellurium
[13 15] even at mole ratio ArMgX:chalcogen
1:(0.8 0.9) is accompanied with side process (2, 3).
2RYMgX + Y
RYYR + (MgX)2Y,
RYR + RYMgX.
(2)
(3)
expectedly
organyl(trialkoxysilylmethyl)dichalco-
RMgX + RYYR
genides IV and bis(trialkoxysilylmethyl)dichalco-
genides (V).
Although we did not studied such reactions for our
cases, we assumed [11] their contribution.
RYYCH2Si(OR )3
[(R O)3SiCH2]2Y2
One could expect for the generated organylchalco-
genomagnesium halides [reaction (1)] and appearing
in reaction (2) bis(magnesiumhalo)chalcogenides react
with with (halomethyl)trialkoxysilanes with formation
of corresponding organyl(trialkoxysilylmethyl)- (I)
and bis(trialkoxysilylmethyl)chalcogenides (II) accord-
ing to schemes (4) and (5).
IVa IVd
Va Vc
IV, R = Me, R = Et, Y = S (a); R = Me, R = Et, Y = Se
(b); R = Ph, R = Et, Y = Se (c); R = Ph, R = Me, Y =
Te (d). V, R = Me, Y = Se (a); R = Et, Y = Se (b); R =
Me, Y = Te (c).
Analysis of basic fractions of the reaction products
RYMgX + X CH2Si(OR )3
1
(Table 1) by chromatomass spectrometry, H, 13C,
29Si and 77Se NMR spectroscopy (Table 2) shows that
the relative amounts of the formed chalcogenides I
and II and dichalcogenides IV and V is defined by
the structure of R and nature of the atoms X, X and Y
in the initial reagents RYMgX and X CH2Si(OR )3.
However, regardless of complexity of the formed
mixtures they contain predominantly either the cor-
responding chalcogenide I, or chalcogenide II (or I
and II together), or dichalcogenides IV and V. This
allowed us to isolate some of them and obtain their
characteristics (Table 3).
RYCH2Si(OR )3 + MgXX ,
(4)
Ia Ii
I, R = Me, R = Et, Y = S (a); R = Me, R = Et, Y = Se (b);
R = Me, R = Et, Y = Te (c); R = Et, R = Me, Y = Se (d);
R = Et, R = Me, Y = Te (e); R = Ph, R = Me, Y = S (f);
R = Ph, R = Me, Y = Se (g); R = Ph, R = Et, Y = Se (h);
R = Ph, R = Me, Y = Te (i).
2(R O)3SiCH2X + (MgX)2Y
[(R O)3SiCH2]2Y + 2MgXX ,
(5)
IIa IIe
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 71 No. 12 2001

A ROUTE TO ORGANYL(TRIALKOXYSILYL)CHALCOGENIDES
1885
Table 1. Reaction of organylchalcogenomagnesium halides (in situ) with (halomethyl)trialkoxysilanes, the reaction
conditions and the most important isolated fractions and compounds
Main fractions
Degree of
conversion
of
XCH2Si(OR )3,
%
Reaction
duration,
h
Isolated
weight, compounds
g
No.
Initial reagents
Solvent
bp,
C
no.
n2D0
(p, mm)
1 MeSMgI + ICH2Si(OEt)3
2 MeSMgI +
Ether
CH3CN, 1:2
Ether MeCN,
2.0
2.0
I
II
I
74 76 (1.0) 1.4560 10.0
80 160 (1.0) 1.4480 10.0
to 60 (1.5) 1.4150 12.0
IIc
IIIc, IVa
ICH2Si
(OEt)3
IIc
60
90
90
ClCH2Si(OEt)3
1:2
II 72 75 (1.5) 1.4560
III 75 160 (1.5) 1.4460
I
II 81 82 (1.5) 1.4570
III 150 155 (2.0) 1.4490 12.0
6.5
7.0
1.5
4.0
IIIc, IVa
VI
3 MeSeMgI +
ICH2Si(OEt)3
Ether MeCN,
1:2
2.0
1.5
1.5
1.5
1.5
30 80 (1.0)
100
100
100
30
Ib
IId, IIId
VI
4 MeSeMgBr +
ClCH2Si(OEt)3
THF
THF
THF
THF
I
40 45 (1.5) 1.4200
8.0
9.5
2.0
2.0
7.0
1.5
II 75 78 (1.5) 1.4350
III 85 130 (2.0) 1.4510
I
II 125 137 (1.5) 1.4650
III 137 142 (1.5) 1.4680
I
II 55 85 (1.5) 1.4780
III to 130 (1.5) 1.4800
I
II 50 70 (2.0) 1.4840
III 70 130 (2.0) 1.4910
IV 130 155 (2.0) 1.4790
V
I
II 32 85 (1.5) 1.4890
III 85 130 (1.5) 1.4950 10.0
I
II 118 122 (1.5) 1.5280
III 122 125 (1.5) 1.5380
IV 125 127 (1.5) 1.5410
Ib
IId, IIId
IIe, IIIe
5 MeTeMgI +
ICH2Si(OEt)3
to 125 (1.5) 1.4780
6 MeTeMgBr +
ClCH2Si(OEt)3
50 52 (1.5) 1.4150 10.0
2.0
1.5
7.0
1.5
2.0
1.5
9.5
0.8
7.0
7 EtSeMgBr +
ClCH2Si(OMe)3
30 50 (2.0) 1.4650
>90
160 165 (2.0) 1.4940
30 32 (1.5) 1.4200
Va
8 EtTeMgBr +
ClCH2Si(OMe)3
THF
THF
1.5
1.0
60
75
Ie
IIb, IIIb
9 PhSMgBr +
ClCH2Si(OMe)3
30 35 (1.5)
3.0
2.0
1.0
7.0
0.5
1.2
3.5
If
V
127 135 (1.5) 1.5530
VI 135 145 (1.5)
125 127 (1.5) 1.5450
Ph2S2
Ig
10 PhSeMgBr +
ClCH2Si(OMe)3
THF MeCN,
1:2
2.0
I
75
II 132 135 (1.5) 1.5400 10.0
III 137 150 (1.5) 1.5450
IV 150 180 (1.5) 1.5560
5.0
1.0
2.5
IIa, IIIa,
Ph2Se2
Ph Ph
IVc
Ph2Se2
VII
11 PhSeMgBr +
ClCH2Si(OEt)3
THF MeCN,
1:2
2.0
2.0
I
60 120 (2.0)
>95
100
II 120 175 (2.0) 1.5350 11.0
III 180 182 (2.0) 1.5650 10.5
12 PhTeMgBr +
ClCH2Si(OMe)3
THF
I
70 130 (1.5)
1.5
1.2
II 130 135 (2.0) 1.5650
III 135 137 (2.0) 1.5650 12.0
Ii
IV 137 140 (2.0) 1.5670
140 145 (2.0)
VI 145 160 (2.0)
1.5
2.0
1.0
V
Ph2Te2
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 71 No. 12 2001

1886
SOROKIN, VORONKOV
Table 2. 1H, 13C, 29Si and 77Se NMR spectra of the synthesized compounds ( , ppm)
Comp.
no.
C
Si
Se
H
Ib
1.73 s (2H, SiCH2), 1.24 t (3H, CH3), 2.06 s 2.49 (CSi), 7.21 (CSe), 18.26 (CH3), 58.94 (O C) 51.70 18.57
(3H, CH3Se), 3.88 q (2H, OCH2)
Ie
If
Ig
Ii
1.60 t (3H, CH3), 2.70 q (2H, CH2), 1.67 s (2H,
CH2Si), 3.57 s [9H, (OCH3)3]
2.29 s (2H, SiCH2), 3.62 s (9H, OCH3),
7.21 7.38 m (5H, C6H5)
45.45
.
(CSi), 51.04 (O C), 125.10, 126.56, 49.92
11 93
128.73, 139.18 (C6H5)
2.15 s (2H, SiCH2), 3.57 s (9H, OCH3), 7.21 3.20 (CSi), 50.72 (O C), 126.02, 128.73,
48.55 219.9
130.30, 7.41 m (5H, C6H5)
2.08 s (2H, SiCH2), 3.59 s (9H, OCH3), 7.23
7.77 m (5H, C6H5)
132.36 (C6H5)
20.93 (CSi), 51.09 (O C), 127.37, 129.12, 46.22
137.06, 137.97 (C6H5)
IIa
IIb
IIc
IId
1.98 s (4H, 2CH2Si), 3.63 s [18H, (OCH3)6] 15.07 (C Si), 50.55 (O C)
1.87 s (4H, 2CH2Si), 3.61 s [18H, (OCH3)6] 2.60 (C Si), 50.98 (O C)
1.83 s (4H, 2CH2Si), 3.62 s [18H, (OCH3)6] 24.84 (C Si), 50.92 (O C)
49.22
48.25 46.07
45.60
1.23 t (6H, 2CH3 C), 1.95 s (4H, 2CH2Si),
3.86 q (4H, 2OCH2)
.
(C Si), 18.21 (CH3), 58.84 (O C)
52.90
16 64
IIe
IIf
1.24 t (6H, 2CH3 C), 1.87 s (4H, 2CH2Si),
3.81 q (4H, 2OCH2)
1.22 t (6H, 2CH3 C), 1.84 s (4H, 2CH2Si),
3.85 q (4H, 2OCH2)
.
(C Si), 18.31 (CH3), 58.89 (O C)
51.70 42.57
49.03
3 95
.
(C Si), 18.21 (CH3), 58.96 (O C)
22 98
IIIa
IIIb
IIIc
1.60 s (4H, 2CH2Si), 3.64 s (12H, 4OCH3) 1.57 (C Si), 50.98 (O C)
1.62 s (4H, 2CH2Si), 3.62 s (12H, 4OCH3) 27.64 (C Si), 50.92 (O C)
1.24 t (12H, 4CH3), 1.67 s (4H, 2CH2Si), 3.90 q 11.34 (C Si), 18.21 (CH3), 59.11 (O C)
(8H, 4OCH2)
53.01 45.57
49.90
56.64
IIId
IIIe
IVa
IVc
1.24 t (12H, 4CH3), 1.61 s (4H, 2CH2Si), 3.86 q 0.43 (C Si), 18.21 (CH3), 59.05 (O C)
(8H, 4OCH2)
1.22 t (12H, 4CH3), 1.61 s (4H, 2CH2Si), 3.85 q 26.56 (C Si), 25.83 (CH3), 58.96 (O C)
(8H, 4OCH2)
1.23 t (3H, CH3 C), 2.31 s (2H, SiCH2), 2.42 s 18.21 (CH3), 20.38 (C Si), 22.00 (CH3S), 59.06 54.72
(3H, CH3S), 3.88 q (2H, OCH2 C) (O C)
1.22 t (3H, CH3 C), 2.47 s (2H, CH2Si), 3.80 q 10.20 (C Si), 18.21 (CH3), 59.01 (O CH2),
(2H, OCH2 C), 7.20 7.58 m (5H, C6H5) 126.00, 127.70, 129.11, 131.49 (C6H5)
55.34 46.98
52.23
468.84
(Se1)a,
332.86
(Se2)a
Va
VI
2.45 s (2H, CH2Si), 3.59 s [9H, (OCH3)3] 7.27 (C Si), 50.93 (O C)
1.26 t (9H, 3CH3 C), 2.95 s (2H, CH2Si),
49.37 336.29
.
(CH3 C), 18.91 (C Si), 24.60 (C Se+), 58.08
18 26
3.22 s [6H, (CH3)2Se+], 3.95 q (6H, 3OCH2) 59.75 (O C)
2.56 s (2H, CH2Si), 3.60 s (9H, OCH3), 7.27 9.98 (C Si), 51.10 (O C), 129.65, 131.27, 50.51
VII
3
7.96 m (5H, C6H5)
133.93, 134.20 (C6H5)
a 77
1
2
Se chemical shifts in C H Se Se CH Si(OC H ) (IVc).
6
5
2
2 5 3
Thus, from the mixture of products formed in the
reaction of MeSMgI with iodomethyltriethoxysilane
(No. 1, Table 1) we isolated by GLC bis(triethoxy-
silylmethyl)sulfide (IIc), 2,2,6,6-tetraethoxy-2,6-di-
sila-4-thia-1-oxane (IIIc) and methyl(triethoxysilyl
methyl)disulfide (IVa). According to GLC, the ratio
IIc:IIIc:IVa = 6:2:1. Mass spectra contain mole-
cular ion peaks correspondfing to these compouns,
M + 386, 312 and 284, respectively. However ex-
pected
methyl(triethoxysilylmethyl)sulfide
(Ia)
[scheme (4)] was not found among the reaction pro-
ducts and 40% of initial compound ICH2Si(OEt)3
returned unchanged.
The same compounds IIc, IIIc, and IVa were
isolated from the mixture obtained in a reaction of
MeSMgI with (chloromethyl)triethoxysilane under
the same onditions (No. 2, Table 1). Besides, in this
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 71 No. 12 2001

A ROUTE TO ORGANYL(TRIALKOXYSILYL)CHALCOGENIDES
1887
Table 3. Physicochemical characteristics and elemental analysis data of the synthesized compounds
Found, %
Si
Calculated, %
Si
Comp. Yield,
bp,
(p, mm)
C
n2D0
Formula
no.
%
C
H
Y
C
H
Y
Iba
45
38
40
65
56
35
1.4530 75 78 (1.5)
1.4980 78 80 (1.5)
1.5410 125 127 (1.5)
1.5415 132 134 (1.5)
1.5650 135 137 (1.5)
1.4910 127 130 (1.5)
1.4470 144 146 (1.5)
1.4490 152 154 (2.0)
1.4650 155 157 (1.5)
1.4675
35.17 7.26 10.02 28.75 C8H20O3SeSi
24.52 5.48 9.32 42.34 C6H16O3SiTe
48.78 6.31 11.02 13.56 C10H16O3SSi
35.41 7.43 10.35 29.11
24.69 5.53 9.02 43.71
49.15 6.60 11.49 13.12
Iea
If
Ig
41.24 5.56
35.39 4.83
8.44 27.98 C10H16O3SeSi
8.53 37.81 C10H16O3SiTe
41.23 5.54
35.39 4.75
9.64 27.12
8.27 37.60
Iia
IIba
IIca
IIda
IIe
24.37 5.85 14.26 32.32 C8H22O6Si2Te
43.07 8.58 14.12 7.91 C14H34O6SSi2
37.94 7.51 13.20 18.97 C14H34O6SeSi2
34.42 7.15 11.43 26.17 C14H34O6Si2Te
37.10 7.17 10.36 24.71 C8H20O3S2Si
24.14 5.57 14.14 32.05
43.49 8.86 14.53 8.29
38.78 7.90 12.95 18.22
34.87 7.10 11.65 26.46
37.47 7.86 10.95 25.00
25
42
IVaa
IVca
Vaa
VIa
VIIa
25
35
1.5600 184 186 (1.5)
1.5020 165 167 (2.0)
69 70b
38.05 5.30
5.63 37.68 C13H22O3Se2Si
37.87 5.38
6.81 38.30
21.84 5.41 12.81 36.08 C8H22O6Se2Si2
22.43 5.18 13.11 36.84
26.19 5.48
29.85 4.09
6.77 19.17 C9H23IO3SeSic
26.17 5.61
6.79 19.12
114 115b
C10H16Cl2O3SiTed 29.30 3.93
a
b
c
d
Newly synthesized compound. mp, C. Found I, %: 30.83. Calculated I, %: 30.67. Found Cl, %: 16.56. Calculated Cl, %: 17.29.
case was also isolated iodomethyltriethoxysilane.
Formation of the latter can be explained by the ex-
change reaction of the magnesium iodides with chloro-
methyltriethoxysilane (Scheme 6).
CH3SeCH2Si(OC2H5)3 + CH3I
Ib
+
I (CH3)2SeCH2Si(OC2H5)3.
(7)
VI
RYMgI + ClCH2Si(OEt)3
RYMgCl + ICH2Si(OEt)3. (6)
iodide could be contained in the fraction bp 30 80 C
(1 mm). Moreover, completing of reaction (7) requires
5 10 min only, whereas the crystals of selenonium
iodide VI in the first fraction occurs for 1.5 2 h after
distillation.
The main components in the mixture of the pro-
ducts formed in reactions of MeSeMgI with iodo-
methyltriethoxysilane (no. 3, Table 1) and MeTeMgI
with iodomethyltriethoxysilane (no. 5, Table 1) were
corresponding bis(triethoxysilylmethyl)chalcogenides
IId and IIe, and 2,2,6,6-tetraethoxy-2,6-disila-4-
chalcogena-1-oxanes IIId and IIIe. Theywere isolated
as two fractions distilling in narrow temperature
ranges with component ratio IId:IIId and IIe:IIIe
Reaction of chloromethyltriethoxysilane with
MeSeMgBr being conducted in THF (no. 4, Table 1),
leads to methyl(triethoxysilylmethyl)selenide Ib
in 45% yield on the parent ClCH2Si(OEt)3 and can be
used as a preparative synthesis. Other products in this
reaction, as shown by chromato-mass spectrometry
10:1, according to the data of H and 13C NMR
1
1
spectra. The total yield of the compounds IId + IIId
and IIe + IIIe on the initial iodomethyltriethoxysilane
was 65 and 45%, respectively. Besides, in the reaction
of MeSeMgI with ICH2Si(OEt)3 from the first fraction
(no. 3, Table 1) was isolated methyl(triethoxysilyl-
methyl)selenide Ib, but in yield 10% or less on the
parent ICH2Si(OEt)3. From the same fraction we iso-
lated a colorless flake crystalline compound with mp
and H, 13C, 29Si and 77Se NMR spectra include bis-
(triethoxysilylmethyl)selenide IId and methyl(tri-
ethoxysilylmethyl)diselenide IVb. Selenide IId was
isolated in 25% yield [contaminated with 2,2,6,6-
tetraethoxy-2,6-disila-4-selena-1-oxane IIId.
The products of reaction of MeTeMgBr with chlo-
romethyltriethoxysilane (no. 6, Table 1) include
methyl(triethoxysilylmethyl)telluride Ic, however,
we failed to isolate it from the complex mixture of
the easily oxidized tellurides. Conversion of the initial
ClCH2Si(OEt)3 in this process for 1.5 h was 30%
or less.
1
70 C. According to H and 13C NMR spectra and
elemental analysis it was dimethyl(triethoxysilyl-
methyl)selenonium (VI). Its structure was confirmed
by synthesis from methyl(triethoxysilylmethyl)se-
lenide Ib by the scheme (7).
Reaction of EtSeMgBr with (chloromethyl)tri-
methoxysilane in boiling THF (no. 7, Table 1) pro-
However, seems little probable that volatile methyl
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 71 No. 12 2001

1888
SOROKIN, VORONKOV
NMR spectra and elemental analysis, it was phenyl-
ceeded with conversion of ClCH2Si(OMe)3 higher
than 90%. The mixture of the reaction products ac- (trimethoxysilylmethyl)telluride dichloride VII.
cording to the data of chromato-mass spectrometry,
Cl
1H, 13C, 29Si and 77Se NMR spectra includes small
PhTeCH2Si(OMe)3
amount of ethyl(trimethoxysilylmethyl)selenide Id
and bis(trimethoxysilylmethyl)selenide IIa, (tri-
methoxysilylmethyl)diselenide (Va) and diethyldi-
selenide Et2Se2. In the mass spectra these products
were registered as the molecular ion peaks M + 243,
322, 350 and 216, respectively. Among them predo-
minated the earlier unknown bis(trimethoxysilyl-
methyl)diselenide Va, and we succeeded to isolate it
from the mixture (yield 35%).
Cl
VII
By chromato-mass spectrometry and H, 13C and
29Si NMR spectroscopy we also identified in the
mixture a few other compounds: bis(trimethoxysilyl-
methyl)telluride IIb, phenyl(trimethoxysilylmethyl)-
ditelluride IVd, and bis(trimethoxysilylmethyl)di-
telluride Vc.
1
In the mixture of the products in the reaction of
EtTeMgBr with (chloromethyl)trimethoxysilane (no. 8,
Table 1) the main products were the earlier unknown
Formation of organyl(trialkoxysilylmethyl)dichal-
cogenides and bis(trialkoxysilylmethyl)dichalco-
genide, IVa, IVc, and Va which dominates in some
cases can be explained by side reactions (8), (9).
ethyl(trimethoxysilylmethyl)telluride
Ie,
bis(tri-
methoxysilylmethyl)telluride IIb and sixmembered
heterocycle 2,2,6,6-tetramethoxy-2,6-disila-4-tellura-
1-oxane IIIb.
RYYMgX + X CH2Si(OR )3
Y2(MgX)2 + 2X CH2Si(OR )3
IVa IVd,
Va Vc.
(8)
(9)
By refluxing PhSMgBr with (chloromethyl)tri-
methoxysilane in THF (no. 9, Table 1) we obtained a
mixture of products contained predominantly phenyl-
(trimethoxysilylmethyl)sulfide If and diphenyldisul-
fide, in total yield more than 50% on PhSMgBr.
Organyldichalcogenomagnesium halides RYYMgX
and bis(halomagnesium)dichalcogenides Y2(MgX)2
could be formed in turn as side products at generation
of RYMgX, according to the schemes (10) and (11):
Reaction of PhSeMgBr with (chloromethyl)tri-
methoxysilane at reflux in a THF and MeCN 1:2
mixture for 1.5 h (no. 10, Table 1) leads to a mixture
of products contained predominantly phenyl(tri-
methoxysilylmethyl)selenide Ig. We also identified
bis(trimethoxysilylmethyl)selenide IIa, 2,2,6,6-tetra-
methoxy-2,6-disila-4-selena-1-oxane IIIa and di-
phenyldiselenide Ph2Se2. Conversion of ClCH2Si
(OMe)3 was higher than 75%.
RYMgX + Y
2RYYMgX
RYYMgX,
(10)
(11)
RYYR + Y2(MgX)2.
Together with the reactions proceeding by schemes
(4), (5) and (8), (9) leading to asymmetric and sym-
metric organosilicon chalcogenides I and II and
dichalcogenides IV and V, the presence of admixture
of a Grignard reagent defines proceeding of some side
reactions according to typical schemes (12) and (13)
[16, 17].
Even more complex mixture was obtained in the
reaction of PhSeMgBr with chloromethyltriethoxy-
silane at reflux in THF-MeCN 1:2 mxture. It con-
sisted of phenyl(triethoxysilylmethyl)selenide Ih, bis-
(triethoxysilyl methyl)selenide IId, 2,6-disila-2,2,6,6-
tetraethoxy-4-selena-1-oxane IIId, phenyl(triethoxy-
silylmethyl)diselenide IVc, and bis(triethoxysilyl-
methyl)diselenide Vb. Chromato-mass spectra con-
tained the peaks of corresponding molecular ions M +
334, 433, 360, 413 and 512. We also identified bi-
phenyl, diphenylselenide and diphenyldiselenide.
RMgX + RX
R R + MgX2,
(12)
RMgX + X CH2Si(OR )3
RCH2Si(OR )3 + MgXX ,
(13)
X CH2Si(OR )2R + MgX(OR ).
This was confirmed experimentally: the products
of reaction of PhSeMgBr with (chloromethyl)tri-
ethoxysilane (no. 11, Table 1) contain biphenyl,
benzyltriethoxysilane (M + 254) and (chloromethyl)-
phenyldiethoxysilane (M + 218). Biphenyl was isolated
and characterized as an individual compound.
Fially, reaction of PhTeMgBr with chloromethyl-
trimethoxysilane at reflux in THF (no. 12, Table 1)
gave a mixture, contained mainly the earlier unknown
phenyl(trimethoxysilylmethyl)telluride Ii, which was
isolated in 30% yield on ClCH2Si(OMe)3. In addition,
from the first fraction we isolated a compound with
Thus, reaction of organylchalcogenomagnesium
halides RYMgX (in situ) with (halomethyl)trialkoxy-
1
mp 114 115 C. According to the data of H and 13C
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 71 No. 12 2001

A ROUTE TO ORGANYL(TRIALKOXYSILYL)CHALCOGENIDES
1889
silane at reflux in organic solvents (ether, tetrahydro-
furan, or their mixture with acetonitrile) is not uni-
formly proceeding. It leads to a mixturture, consisting
mainly of organyl(trialkoxysilylmethyl)chalcogenide
and -dichalcogenide, and bis(trialkoxysilylmethyl)-
chalcogenide and -dichalcogenide. The most of these
compounds were not known earlier. The studied
reactions can be taken as a basis for the preparative
synthesis of some of them, namely, methyl(triethoxy-
silylmethyl)selenide Ib, ethyl- Ie and phenyl(tri-
methoxysilylmethyl)telluride Ii.
action mixture then was refluxed for 1 2 h and again
cooled to 20 C. The upper liquid layer was quickly
decanted from the precipitate of magnesium salts. The
precipitate with liquid residue was quickly transferred
on a Schott filter, separated using a vacuum and twice
washed with ether. The decanted solution and filtrates
were collected together, solvents and volatile reaction
products were distilled off under atmospheric pressure
and the residue was distilled in a vacuum.
Dimethyl(triethoxysilylmethyl)selenonium iodide
(VI). To a solution of 2.35 g of methyl(triethoxy-
silylmethyl)selenide Ib in 5 ml of ether was added
1.0 g of methyl iodide. After 5 10 min a light yellow
precipitate of the salt was formed. It was separated by
vacuum filtration and washed on the Schott filter with
ether. Yield 2.9 g (95%). After recrystallization color-
less flackes formed with mp 69 70 C (from C2H5OH).
EXPERIMENTAL
1H, 13C, 29Si and 77Se NMR spectra of individual
compounds and mixtures (narrow fractions) were
registered on a multinuclear NMR spectrometer Jeol
FX90Q (solvent CDCl3, internal reference HMDS).
The instrument operating frequencies (MHz) are:
89.55 (1H), 22.45 (13C), 17.75 (29Si) and 17.03 (77Se).
77Se chemical shifts were measured relatively to
Me2Se.
REFERENCES
1. Voronkov, M.G., Sorokin, M.S., D’yakov, V.M., and
Sigalov, M.V., Zh. Obshch. Khim., 1975, vol. 45,
no. 8, pp. 1807 1812.
Chromato-mass spectrometric investigations were
conducted on a MAT-212 instrument with a 20 m
capillary column, phase is SE-54, programmed
growing of temperature 15 deg/min to 270 C,
Vaccelerator 3 kV, Vion 70 eV.
2. Voronkov, M.G., Sorokin, M.S., and D’yakov, V.M.,
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IVa from the fraction boiling at 80 160 C (2.0 mm)
by GLC was conducted on a PAXB-07 instrument
with 1000 10 mm column filled with Chezasorb
(0.25 0.36 mm) with 15% of polymethylphenylsil-
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Solvents (ether, THF and MeCN) priorly to use
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All reaction were performed under argon atmosphere.
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Rostov. Gos. Univ., 1983.
Reaction of organylchalcogenomagnesium
halides (in situ) with (halomethyl)trialkoxysilanes
(no. 1 12, Table 1, general procedure). To a
Grignard reagent prepared from 2.4 g of Mg and
0.1 mol of corresponding RX (alkyl halide or bromo-
benzene) in ether or THF at stirring and cooling
(20 C) 0.1 g-at of a chalcogen (finely powdered sulfur
or tellurum, or amorphous selenium) was added
portionwise. The reaction mixture was stirred at 20 C
for 1 h. When the formed RYMgX salt was poorly
soluble in ether or THF (splitting to layers) a part of
the solvent (0.5 of the total volume) was distilled off
and 1 volume of MeCN was added. After 0.5 h stir-
ring at 20 C to the obtained solution of RYMgX was
added dropwise 0.1 mol of a halomethyltrialkoxysi-
lane, with maintaining temperature at 20 C. Then re-
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1890
SOROKIN, VORONKOV
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New York: Wiley, 1972.
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