EFFICIENT METHOD FOR THE SYNTHESIS
205
NMR parameters of α,ωꢀdichloroorganyldisiloxanes ClRR'Si–
O–SiRR'Cl (R = Me, R' = Me (I); R = H, R' = Et (II); R =
Me, R' = ClCH2 (III); R = Me, R' = Vin (IV); R = Me, R' =
Ph (V))
EXPERIMENTAL
Dimethyl sulfoxide was kept over KOH pellets,
decanted, frozen, and distilled in a vacuum. Initial
diorganyldichlorosilane and hexamethyldisiloxane
were purified by rectification on a column.
δ
, ppm
Comꢀ
pound
1H
13C
29Si
The mass spectra of previously described
(
(MePhSiO)n (
[13], ClMe2Si(OSiMe2)nCl
ClMeVinSi(OSiMeVin)nCl
Me3Si(OSiMeVin)nOSiMe3 (
given.
Me2SiO)n
(
n
n
= 3–6), (MeVinSiO)n
(
n
= 3, 4), [Me(ClCH2)SiO]n (
= 3–6),
n = 3–6)
I
0.49 (s, 12H, CH3)
3.83 (CH3)
7.25
II
0.90–0.99 (CH2)
1.04–1.11 (CH3)
5.16 (s, Si–H)
10.79 (CH2) –8.99
12.74 (CH3)
(
n
=
1–3) [14],
1–3), and
(
n
=
n
= 1–3) [15] are not
III 0.66 (s, 6H, CH3)
0.06 (CH3) –3.31
2.90–3.01 (q, 4H, ClCH2) 29.44 (ClCH2)
The 1H, 13C, and 29Si NMR data for the obtained
ꢀdichloroꢀ1,1,3,3ꢀtetraorganyldisiloxanes ClRR'Si–
O–SiRR'Cl (R = H, Me; R' = Me, Et, ClCH2, Vin, Ph)
IV 0.56; 0.57 (6H, CH3)
5.98–6.13 (m, 6H,
CH=CH2)
3.21 (CH3) –7.56
135.14–136.57
(CH=CH2)
α,ω
are presented in the table.
V
0.70; 0.74 (6H, CH3)
7.29–7.59 (m, 10H, C6H5) 127.80; 130.55;
2.74 (CH3) –5.95
1H, 13C, and 29Si NMR spectra were recorded on a
Bruker DRXꢀ400 spectrometer (operating at 400.13,
100.61, and 79.5 MHz, respectively) in CDCl3 using
TMS as an internal reference. Mass spectra were
recorded on a Shimadzu GCMSꢀQP5050A chroꢀ
matograph–mass spectrometer, injector temperature
132.85; 134.26
(C6H5)
MS (
[M – C2H5]+, 145(84) [M – 2C2H5 + H]+, 109(22)
Cl(C2H5)HSiO+
m/z (I
rel, %)): 201(8) [M – H]+, 173(100)
of 200–250
°
C, helium as a carrier gas, detector temꢀ
.
perature of 200
°
C
, quadrupole mass analyzer, and
electron ionization at an ionizing voltage of 70 eV. IR
spectra were recorded as thin films on a Specord IRꢀ75
spectrophotometer in the range 400–4000 cm–1.
1,3ꢀDichloroꢀ1,3ꢀbis(chloromethyl)ꢀ1,3ꢀdimethylꢀ
disiloxane (III) (72%) was obtained at –40 C, bp 98–
100 C (7 mmHg).
°
°
1,3ꢀDichloroꢀ1,1,3,3ꢀtetramethyldisiloxane (I).
Dimethyl sulfoxide (4.84 g, 0.06 mol) was added dropꢀ
wise to 32 g (0.25 mol) of cooled dichlorodimethylsiꢀ
For C4H10Cl4OSi2 anal. calcd. (%): C, 17.65; H,
3.70; Cl, 52.12; Si, 20.64.
lane (0 C) in 60 min. The reaction mixture was magꢀ
°
Found (%): C, 17.85; H, 3.95; Cl, 51.72; Si, 20.52.
netically stirred at ambient temperature until comꢀ
plete dissolution of a colorless precipitate for 2 h.
Vacuum distillation afforded 9.8 g (78%) of 1,3ꢀ
dichloroꢀ1,1,3,3ꢀtetramethyldisiloxane with bp 35–
1,3ꢀDichloroꢀ1,3ꢀdimethylꢀ1,3ꢀdivinyldisiloxane
(IV) (74%), bp 64–65°C (7 mmHg) (lit. [6]: bp 61–
63 C (0.9 mmHg)).
°
37
°
C (20 mmHg) (lit. [9]: bp 135.3
°
C (738 mmHg)).
For C6H12Cl2OSi2 anal. calcd. (%): C, 31.72; H,
5.32; Cl, 31.20; Si, 24.72.
For C4H12Cl2OSi2 anal. calcd. (%): C, 23.64; H,
5.95; Cl, 34.89; Si, 27.64.
Found (%): C, 31.92; H, 5.03; Cl, 31.60; Si, 24.55.
Found (%): C, 23.34; H, 5.70; Cl, 35.24; Si, 27.29.
1,3ꢀDichloroꢀ1,3ꢀdimethylꢀ1,3ꢀdiphenyldisiloxꢀ
1,5ꢀDichlorohexamethyltrisiloxane (2.5 g, 15%)
was also isolated, bp 60–63°C (20 mmHg) (lit. [9]:
bp 178°C (738 mmHg)).
ane (V) (91%) bp 201–205°C (20 mmHg) (literature
data [5]: bp 154 C (4 mmHg)).
°
For C14H16Cl2OSi2 anal. calcd. (%): C, 51.37;
H, 4.93; Cl, 21.66; Si, 17.16.
For C6H18Cl2O2Si3 anal. calcd. (%): C, 25.98; H,
6.54; Cl, 25.56.
Found (%): C, 26.33; H, 6.16; Cl, 25.84.
Found (%): C, 51.56; H, 5.05; Cl, 21.32; Si, 17.06.
1,3ꢀDichloroꢀ1,3ꢀdiethyldisiloxane (II) (76%) was
MS (m/z (I
rel, %)): 326(49) [M]+, 311(100) [M –
obtained in a similar manner, bp 38–39
(lit. [6]: bp 81–82 C (70 mmHg)).
°
C (5 mmHg)
Me]+, 291(4) [M – Cl]+, 275(57), 249(3) [M –
C6H5]+, 233(40), 215(13) [M – Ph – Cl + H]+,
195(17), 175(9), 155(9), PhMeSiCl+, 137(6), 130(11),
°
For C4H12Cl2OSi2 anal. calcd. (%): C, 23.64; H,
5.95; Cl, 34.89; Si, 27.64.
113(3), 91(16) C6H5CH+2 , 77(6) C6H5+
.
Found (%): C, 23.87; H, 6.18; Cl, 35.16; Si, 27.44.
DOKLADY CHEMISTRY Vol. 451
Part 2
2013