2206
GLUKHOV et al.
lane, respectively [20, 21], followed by vacuum was collected and transferred to a flask; 10 g of urea
distillation.
A glass ampoule was charged with 0.1 mol of the
and 0.5 mL of water was added and stirred until the
reaction was complete (with neutral pH of the
organic phase). Urea was filtered off, and the filtrate
was evaporated in vacuum. The residue was subjected
to fractional distillation in vacuum (with an 80-cm
Vigreux column). The first fraction (34–36°C/2
mmHg) consisted of 1,3-di(chloromethyl)-1,1,3,3-
tetramethyldisiloxane. The target product was distilled
at 108–110°C/1 mmHg. The yield of the purest frac-
tion was 19 g (36%).
corresponding disiloxane, 25 mL of acetonitrile, and
21.15 g (0.22 mol) of 1,2-dimethylimidazole. The
ampoule was sealed under vacuum after degassing
and was held for 72 h at 100°C. After cooling, the
precipitated crystals were washed with small
amounts of acetonitrile, and then three times with
1,2-dichloroethane and dried in vacuum. The yields
were about 80%.
1,5-Bis((3-methylimidazolium-1-yl)methyl)-
1,1,3,5,5-pentamethyl-3-phenyltrisiloxane dichloride.
A glass ampoule was charged with a mixture of 7.0 g
(0.019 mol) of the abovementioned trisiloxane, 3.75 g
(0.046 mol, 20%-excess) of 1-methylimidazole, and
20 mL of acetonitrile. The ampoule was sealed after
degassing under vacuum and held at 80°C for 48 h.
The acetonitrile was then distilled off in vacuum and
the residue was washed five times with THF (under
stirring and gentle heating). The completeness of the
removal of the impurities soluble in THF was con-
trolled by TLC. The residue was dried in vacuum. The
obtained product did not crystallize, so it could not be
purified to the same extent as the other compounds
obtained in this work. The impurities, which were
present in small quantity, were likely to have been of a
salty nature. The yield was 9.5 g (94%).
A solution of 0.01 mol of the salt obtained from the
previous stage in 5 mL of water was added to a solution
of 6.31 g (0.022 mol) of lithium bis(trifluoromethyl-
sulfonyl)imide in 20 mL of water. The mixture was
stirred with a magnetic stirrer at room temperature for
~30 min and then transferred to a separatory funnel
with 30 mL of dichloromethane. The organic layer was
separated and washed several times with ~5 mL-por-
tions of water until the washings produced a negative
test for Cl− with silver nitrate. Dichloromethane was
distilled off using a rotary evaporator at room tem-
perature. The residue was dried in vacuum
(0.01 mmHg), first at room temperature; the tempera-
ture was then gradually raised to 80°C and kept for 6 h.
The yields were about 90%.
1,1,3,3-Tetramethyl-1,3-bis((2,3-dimethylimidaz-
olium-1-yl)methyl)disiloxane bis(trifluoromethylsulfo-
nyl)imide (IL-1): 1H NMR (300 MHz, DMSO-d6), δ,
ppm: 0.14 (12H, s, OSi(CH3)2CH2), 2.51 (6H, s,
CCH3), 3.74 (6H, s, NCH3), 3.81 (4H, s, NCH2Si),
7.39 (2H, d, C(5)H), 7.60 (2H, d, C(4)H).
Ion exchange was conducted in a manner similar to
the procedure for IL-1. A solution of IL in dichloro-
methane was additionally treated with activated char-
1
coal. H NMR (300 MHz, DMSO-d6), δ, ppm: 0.13
(12H, d, OSi(CH3)2), 0.29 (3H, s, C6H5SiCH3), 3.77
(6H, s, NCH3), 3.88 (4H,s, NCH2Si), 7.25-7.55 (5H,
m, C6H5), 7.65 (4H, s, C(4)HC(5)H), 8.83 (2H, s,
C(2)H).
1,1,3,3-Tetraethyl-1,3-bis((2,3-dimethylimidaz-
olium-1-yl)methyl)disiloxane bis(trifluoromethylsulfo-
nyl)imide (IL-2): 1H NMR (300 MHz, DMSO-d6), δ,
ppm: 0.63 (8H, q, SiCH2CH3), 0.86 (12H, t,
SiCH2CH3) 2.53 (6H, s, CCH3), 3.74 (6H, s, NCH3),
3.87 (4H, s, NCH2Si), 7.38 (2H, s, C(5)H), 7.62 (2H,
s, C(4)H).
Synthesis of IL-5
1,3-Di(imidazolyl-1)propane: Imidazole (13.6 g,
0.2 mol) was dissolved in 50 mL of acetonitrile, and
22.4 g (0.2 mol) of potassium tert-butoxide was added
portionwise (the reaction is exothermic) with stirring
on a magnetic stirrer. The resulting mixture was stirred
1,3-Bis(3-(2,3-dimethylimidazolium-1-yl)propyl)-
1,1,3,3-tetramethyldisiloxane bis(trifluoromethylsul-
1
fonyl)imide (IL-3): H NMR (300 MHz, DMSO-d6),
δ, ppm: 0.04 (12H, s, OSi(CH3)2CH2), 0.49 (4H, m,
OSi(CH3)2CH2), 1.67 (4H, m, SiCH2CH2CH2), 2.55 for 1 h, and the solvent was then distilled off in vacuum
(to remove tert-butanol). Acetonitrile (70 mL) was
added to the dry residue, and 20.4 g (0.1 mol) of
1,3-dibromopropane dissolved in 20 mL of acetoni-
trile was added dropwise over 1 h under stirring. The
precipitate of KBr was filtered off the next day, the fil-
trate was evaporated in vacuum, and the residue was
distilled in vacuum. The product was distilled at 198–
200°C/<1 mmHg as a pale-yellow viscous liquid that
crystallizes later, m.p. 45°C. The yield was 9.1 g (52%).
(6H, s, CCH3), 3.73 (6H, s, NCH3), 4.06 (4H, t,
NCH2CH2), 7.60 (4H, s, C(4)HC(5)H).
Synthesis of IL-4
1,1,3,5,5-Pentamethyl-3-phenyl-1,5-di(chloro-
methyl)trisiloxane. A solution of 5.3 mL of water in
50 mL of THF was added dropwise over 2 h under vig-
orous stirring with an overhead stirrer to a mixture of
41 g of (chloromethyl)dimethylchlorosilane, 27.3 g of
1,3-Bis(3-(1,1,3,3-tetramethyl-3-phenyldisilox-
phenyldimethylchlorosilane, 150 mL of THF and 50 g anylmethyl)imidazolium-1-yl)propane dichloride.
A
of urea. The mixture was then stirred for a further 3 h glass ampoule was charged with a mixture of 4.1 g
and transferred to a separatory funnel. The upper layer (0.023 mol) of 1,3-di(imidazolyl-1)propane, 14 g
RUSSIAN JOURNAL OF PHYSICAL CHEMISTRY A
Vol. 89
No. 12
2015