Si-permethylcyclo(1-methoxyphosphoryloxy)siloxanes: New synthons in the processes of low-temperature production of dimethylsilanone

Full text of DOI:10.1134/S0012500813050030

ISSN 0012ꢀ5008, Doklady Chemistry, 2013, Vol. 450, Part 1, pp. 135–138. © Pleiades Publishing, Ltd., 2013.
Original Russian Text © S.V. Basenko, A.S. Soldatenko, M.G. Voronkov, 2013, published in Doklady Akademii Nauk, 2013, Vol. 450, No. 3, pp. 295–298.
CHEMISTRY
SiꢀPermethylcyclo(1ꢀmethoxyphosphoryloxy)siloxanes:
New Synthons in the Processes of LowꢀTemperature Production
of Dimethylsilanone
S. V. Basenko, A. S. Soldatenko, and Academician M. G. Voronkov
Received September 7, 2012
DOI: 10.1134/S0012500813050030
The chemistry of phosphorusꢀcontaining cyclohetꢀ ambient temperature without a solvent. As distinct from
erosiloxanes continues to attract attention of researchꢀ reaction (1), no expected cyclophosphasiloxanes form
according to 1Н, 13С, 29Si, and 31P NMR and gas chroꢀ
ers [1–6].
matography–mass spectrometry (reaction (2)).
It was found earlier that the condensation of diorgꢀ
anyldichlorosilanes with O,Oꢀdiorganyl methylphosꢀ
phonates RPO(OR')2 leads to 2,6ꢀdimethylꢀ4,4,8,8ꢀ
2MeOP(O)(OMe)2 + 2Cl2SiMe2
tetraorganylꢀ2,6ꢀdioxoꢀ
rasiloxanes [4, 7].
2
λ
5,6
λ
5ꢀdiphosphacyclotetꢀ
MeO(O)P
O
O
SiMe2
O
(2)
+ 4MeCl.
''
R(O)P
O
O
O
SiR2
Me2Si
O
P(O)OMe
''
+ 4R'Cl
(1)
2RPO(OR')2 + 2Cl2SiR2
O
The reaction proceeds by route (3) to give
3,3,5,5,7,7ꢀhexamethylcycloꢀ1ꢀmethoxyphosphoryꢀ
loxytrisiloxane (I) and 3,3,5,5,7,7,9,9ꢀoctamethylcyꢀ
''
R2Si
P(O)R
(R = H, Me, HO, PhO, Vin;
R' = H, Alk; R'' = Alk, Ar).
cloꢀ1ꢀmethoxyphosphoryloxytetrasiloxane (II) in 38
and 33% yields, respectively. The reaction also leads to
Developing new methods of lowꢀtemperature proꢀ
duction of diorganylsilanones, we have studied the reacꢀ
permethylcyclosiloxanes (Ме2SiO)m: III
= 4), and = 5) in 4, 15, and 10% yield,
at the 1 : 1 molar ratio. This reaction proceeds even at respectively, and methyl chloride.
(m = 3),
tion of dimethyldichlorosilane with trimethyl phosphate IV
(
m
V (m
Me
Si
O
P
O
O
MeO
Me
+
MeOP(O)(OMe)2 + Cl2SiMe2
–MeCl
(3)
O
Si Me
Me
O
Si Me
Me
n
m
[n = 3 (I), 4 (II); m = 3 (III), 4 (IV), 5 (V)].
According to NMR monitoring in DCCl3, the
reaction of dimethyldichlorosilane with trimethyl
phosphate (molar ratio 1 : 1) initially leads to linear
dimethyl(dimethoxyphosphoryloxy)chlorosilane (VI).
methoxyphosphoryoxy)siloxane (VII) to give dimethꢀ
ylsilanone (DMS) and methyl metaphosphate.
MeOP(O)(OMe)2 + Cl2SiMe2
MeOP(O)(OMe)2 + Cl2SiMe2
(MeO)2(O)POSiMe2Cl.
(4)
–MeCl
VI
O
MeO
O
The latter undergoes intramolecular cyclization via
intermediate formation of 3,3ꢀdimethylcyclo(1ꢀ
P
(5)
O
[MeOPO ].
2
[Me Si=O]
+
2
Si
DMS
Favorskii Irkutsk Institute of Chemistry, Siberian Branch,
Russian Academy of Sciences, ul. Favorskogo 1,
Irkutsk, 664033 Russia
Me
Me
VII
135

136
BASENKO et al.
Similar destruction process was observed earlier in the pyrolysis (600°С) of methyl butenꢀ2ꢀylphosphonate [8].
O
P
t°
+ MeOPO2.
OMe
(6)
O
DMS formed in reaction (5) undergoes insertion into compounds VI and VII
.
(MeO)2(O)POSiMe2Cl + Me2Si=O
(MeO)2(O)P(OSiMe2)2Cl
(7)
(8)
VI
VIII
O
O
MeO
O
P
P
O
MeO
O
+ nMe2Si=O
O
Si Me
Me
Si
Me
Me
n + 1
VII
[n = 2 (I), 3 (II)].
Hexamethylcyclotrisiloxane formed as a rule upon 20°С) proceeds also unexpectedly. The expected
DMS trimerization was not identified in the initial
reaction stage. This fact indicates nearly complete
insertion of DMS into the molecule of linear phosꢀ
phoryloxychlorosilane VI, which was confirmed by
NMR data demonstrating the formation of only phosꢀ
sixꢀmembered 3,3,5,5ꢀtetramethylcylo(1ꢀmethoxyꢀ
phosphoryloxy)disiloxane (IX) was detected by
1Н, 13С, 29Si, and 31P NMR; however, eightꢀ, tenꢀ,
and twelveꢀmembered permethylcyclo(1ꢀmethoxyꢀ
phosphoryloxy)siloxanes
products formed in 65, 31, and 4% yields, respecꢀ
ane with trimethyl phosphate (molar ratio 1 : 1, tively.
I, II, and X are the major
phoryloxysiloxane VII
.
The reaction of 1,3ꢀdichlorotetramethyldisiloxꢀ
O
P
O
MeO
MeOP(O)(OMe)2 + (ClMe2Si)2O
–MeCl
O
Si Me
Me
(9)
n
[n = 3 (I), 4 (II), 5 (X)].
The reaction of 1,3ꢀdichlorotetramethyldisiloxane
with trimethyl phosphate (molar ratio 1 : 1) according to
NMR monitoring initially leads to 1,1,3,3ꢀtetramethylꢀ
(MeO)2(O)P(OSiMe2)2Cl + Me2Si=O
(MeO)2(O)P(OSiMe2)3(2)Cl.
(11)
XI
1ꢀdimethoxyphosphoryloxyꢀ3ꢀchlorodisiloxane (VIII
)
However, like in the reaction with dimethyldichloꢀ
rosilane, the major products according to 1Н, 13С, 29Si,
31P NMR and gas chromatography–mass spectromeꢀ
(MeO)3PO + ClMe2SiOSiMe2Cl
try data are cyclotrisiloxane
permethylcyclosiloxanes III
and MeCl.
The reaction of 1,5ꢀdichlorohexamethyltrisiloxane
with trimethyl phosphate (molar ratio 1 : 1, 20 ) proꢀ
I
–
, cyclotetrasiloxanes II
,
(10)
(MeO)2(O)P(OSiMe2)2Cl
–MeCl
V
(in trace amounts),
VIII
and 1,1,3,3,5,5ꢀhexamethylꢀ1ꢀdimethoxyphosphoryꢀ
loxyꢀ5ꢀchlorotrisiloxane (XI).
°
С
It is the product of DMS insertion into disiloxꢀ ceeds through the intermediate formation of linear
ane VIII trisiloxane XI
.
.
DOKLADY CHEMISTRY Vol. 450
Part 1
2013

SiꢀPERMETHYLCYCLO(1ꢀMETHOXYPHOSPHORYLOXY)SILOXANES
137
Table 1. NMR spectra of Siꢀpermethylcyclo(1ꢀmethoxyꢀ
phosphoryloxy)siloxanes (Me2SiO)nOP(O)(OMe), = 1
groups and absorption bands at 2963, 2908, 1413, and
808 cm–1 (Me), 1190 cm–1 (P–O–Me), 1263 cm–1
(Si–Me), and 1200–1235 cm–1 (P=O).
n
(VII), 2 (IX), 3 (
I
), 4 (II) (
δ
, ppm)
Comꢀ
pound
1Н, 13С, 29Si, and 31P NMR spectra were obtained
on a Bruker DPXꢀ400 spectrometer operating at
400.13, 100.61, 79.5, and 161.98 MHz, respectively, in
DCCl3 and CCl4, using SiMe4 as the internal reference
1H
13C
29Si
31P
VII
0.36
3.77 d
– 0.61
–1.34
53.71
–3.87 –6.04
–12.75 –8.74
for 29Si NMR and 85% H3PO4 as the external referꢀ
IX
0.34
3.77 d
2.50; 2.70
55.30; 55.70
ence for 31P NMR. Mass spectra were recorded on a
SHIMADZU GCMSꢀQP5050A mass spectrometer,
(
3JHP = 11.0 Hz)
injector temperature 200–250
°
С
, helium as a carrier
I
0.18; 0.30
3.74; 3.77
0.88; 3.93; 3.97 –19.35 –7.45
54.40; 54.45 –21.50
gas, detector temperature 200°С, quadrupole mass
analyzer, and electron ionization at an ionizing voltage
of 70 eV. IR spectra were recorded on a Specord IRꢀ75
spectrophotometer in the range 400–4000 cm–1 in
thin film.
II
0.13; 0.17
3.74; 3.76
1.50; 3.85; 4.05 –19.90 –18.36
54.96; 55.30 –21.93
(MeO)3PO + ClMe2Si(OSiMe2)2Cl
Dimethyldichlorosilane and trimethyl phosphate
are commercial products purified by distillation (bp. 70
and 193°С, respectively).
(MeO)2(O)P(OSiMe2)3(2)Cl.
(12)
–MeCl
XI
1,3ꢀDichlorotetramethyldisiloxane and 1,5ꢀdichloꢀ
rohexamethyltrisiloxane. Dimethyl sulfoxide (4.84 g)
was added dropwise to 32 g of cooled dimethyldichloꢀ
No linear siloxanes VI and VIII form in reaction
(12). Resulting 3,3,5,5,7,7ꢀhexamethylcycloꢀ1ꢀmethꢀ
oxyphosphoryloxytrisiloxane
I is more stable than
rosilane (5°С) over 60 min. The reaction mixture was
siloxanes VII and IX. This has been established by
multinuclear NMR and gas chromatography–mass
magnetically stirred at ambient temperature until disꢀ
solution of colorless precipitate (a complex of dimeꢀ
thyl sulfoxide with hydrogen chloride) for 4 h. Vacuum
distillation afforded 8.8 g (70%) of 1,3ꢀdichlorotetꢀ
spectrometry. However, compound
uum distillation (1 mmHg) or storage (5–12 days) to
give compounds II and
I degrades on vacꢀ
X.
ramethyldisiloxane, bp 35–37
2.5 g (15%) of 1,5ꢀdichlorohexamethyltrisiloxane,
bp 45–50 (20 mmHg).
°С (20 mmHg), and
All above data indicate that the stability of permeꢀ
thylcyclo(1ꢀmethoxyphosphoryloxy)siloxanes obtained
by us for the first time increases with the size of phosꢀ
°С
For C4Cl2H12OSi2 anal. calcd. (%): C, 32.76; Cl,
20.74; H, 6.05.
phoryloxysiloxane ring, i.e., in the series
IX VII
X > II > I >
>
.
Found (%): C, 33.15; Cl, 20.56; H, 6.30.
The structure and composition of all compounds
For C6Cl2H18O2Si3 anal. calcd. (%): C, 25.98; Cl,
25.56; H, 6.54.
were established by 1Н, 13С, 29Si, 31P NMR and gas
chromatography–mass spectrometry (Tables 1–3).
Absorption spectra of Siꢀpermethylcyclo(1ꢀmethoxyꢀ
phosphoryloxy)siloxanes MeO(O)PO(OSiMe2)n show
Found (%): C, 26.33; Cl, 25.84; H, 6.16.
Siꢀpermethylcyclo(1ꢀmethoxyphosphoryloxy)siloxanes
a strong absorption band at 1000–1100 cm–1 resulting
from overlapping of bands of Si–O–P and Si–O–Si
and permethylcyclosiloxanes [MeOP(O)O(Me2SiO)n,
n =
3 (I), 4 (II); (Me2SiO)m, = 3 (III), 4 (IV), 5 (V)].Triꢀ
m
Table 2. NMR spectra of Siꢀpermethylcyclo(dimethoxyphosphoryloxy)chlorosilanes Cl(Me2SiO)nP(O)(OMe)2,
n = 1
(VI), 2 (VIII), 3 (XI) ( , ppm)
δ
Compound
1H
13C
29Si
4.54
31P
–
VI
0.50
3.59; 4.10
54.23; 54.65
VIII
XI
0.45 (OSiMe2Cl);
0.14 (OSiMe2O);
0.88; 4.05
54.40; 54.45
3.93 (ClMe2SiO);
–18.56 (OSiMe2O)
–7.72
3.76 (d, 6Н, 3JHP = 11.3 Hz)
0.14; 0.18; 0.31
3.74; 3.77
1.08; 3.93; 4.03
3.65
–19.17
–21.24
–18.65
DOKLADY CHEMISTRY Vol. 450
Part 1
2013

138
BASENKO et al.
Table 3. Mass spectra of Siꢀpermethylcyclo(1ꢀmethoxyphosphoryloxy)siloxanes (Me2SiO)nOP(O)(OMe),
n
= 3 (I), 4 (II),
5 (X
), 6 (XII
)
m/z (Irel, %)
Ion
I
II
X
XII
•
M+
316 (1)
301 (100)
287 (1)
285 (2)
271 (8)
227 (1)
213 (1)
–
390 (1)
375 (100)
361 (1)
359 (2)
345 (2)
301 (6)
285 (5)
227 (1)
193 (11)
73 (14)
464 (–)
449 (100)
435 (2)
433 (1)
419 (2)
375 (25)
361 (12)
301 (45)
193 (6)
73 (35)
538 (1)
[M – Me]+
523 (100)
–
[M – Me – CH2]+
[M – Me – CH4]+
[M – Me – MeO + H]+
[M – Me – C2H6SiO]+
[M – Me – Me4Si]+
[M – Me – 2C2H6SiO]+
C3H9Si3O4+
493 (1)
449 (2)
435 (11)
375 (8)
193 (5)
73 (63)
–
193 (22)
–
C3H9Si+
nosilicon Derivatives of Phosphorus and Sulfur), Lenꢀ
ingrad: Khimiya, 1968.
methyl phosphate (5.63 g) was added dropwise to 5.19 g
of dimethyldichlorosilane. The reaction mixture was
stirred at ambient temperature in argon atmosphere
2. Borisov, S.N., Voronkov, M.G., and Lukevits, E.J.,
Organosilicon Derivatives of Phosphorus and Sulfur,
New York: Plenum, 1971.
for 10 h. The yield of compounds
tion (3)).
I–V was 7.0 g (reacꢀ
3. Voronkov, M.G., Maletina, E.A., and Roman, V.K.,
Kremniikislorodnye soedineniya nemetallov. Proizvodnye
azota i fosfora (Nonmetal Silicon–Oxygen Comꢀ
pounds. nitrogen and Phosphorus Derivatives),
Novosibirsk: Nauka, 1988.
Siꢀpermethylcyclo(1ꢀmethoxyphosphoryloxy)siloxꢀ
anes MeOP(O)O(Me2SiO)n, = 3 (I), 4 (II), 5 (X).
Trimethyl phosphate (0.69 g) was added dropwise to 1 g
of 1,3ꢀdichlorotetramethyldisiloxane. The reaction
mixture was stirred at ambient temperature in argon
n
4. Voronkov, M.G., Maletina, E.A., and Roman, V.K.,
Heterosiloxanes. Derivatives of Nitrogen and Phosphoꢀ
rus., London: Hardwood Acad. Publ., 1991.
atmosphere for 5 h. The yield of compounds
I, II, and
X
was 1.5 g (reaction (9)). The yield of compounds
I
and II prepared through 1,5ꢀdichlorohexamethyltrisiꢀ
loxane was 3.3 g (reaction (12)).
5. HaoudiꢀMazzah, A., Dhamelincourt, P., Mazzah, A.,
and Lazraq, M., J. Raman Spectrosc., 1998, vol. 29,
no. 12, pp. 1047–1053.
6. Hampe, O., Weigend, F., and Stahl, S., Angew. Chem.,
Int. Ed. Engl., 2007, vol. 46, no. 25, pp. 4775–4779.
ACKNOWLEDGMENTS
We are grateful to A.I. Albanov for recording NMR
spectra and his help with the interpretation.
7. Goubeau, J., Wilborn, W., and Kerger, K., Mitteilungsbl.
Chem. Ges. DDR, 1963, vol. 10, no. 3, pp. 47–51.
8. Clapp, C.H., Satterthwait, A., and Westheimer, F.H.,
J. Am. Chem. Soc., 1975, vol. 97, no. 23, pp. 6873–
6874.
REFERENCES
1. Borisov, S.N., Voronkov, M.G., and Lukevits, E.Ya.,
Translated by I. Kudryavtsev
Kremneorganicheskie proizvodnye fosfora i sery (Orgaꢀ
DOKLADY CHEMISTRY Vol. 450
Part 1
2013