SYNTHESIS OF NEW SYMMETRICAL
219
For C H O anal. calcd. (%): C, 86.14; H, 10.84. and a solution of 0.1 mL (0.142 g, 1.12 mmol) of oxalyl
76
114
2
chloride in 0.5 mL of anhydrous 1,2ꢀdichloroethane
was added; the mixture was stirred for 5 min, and a
solution of 1 g (2.23 mmol) of 9ꢀ(2'ꢀoctyldodecyl)ꢀ
Found (%): C, 86.02; H, 10.63.
ꢀBromoꢀ2ꢀoctyldodecane (5). A 500ꢀmL threeꢀ
necked flask equipped with magnetic stirrer, septum,
and thermometer was filled with argon. Tripheꢀ
nylphosphine (33.4 g, 0.127 mol, 1 equiv.) and 200 mL
of anhydrous dichloromethane were placed into the
flask. The solution was cooled to 0°C, and 6.52 mL
1
9
Hꢀcarbazole (7) in 0.18 mL (0.17 g, 2.2 mmol) of dry
pyridine and 0.5 mL of anhydrous 1,2ꢀdichloroethane
was added dropwise. The reaction mixture was stirred
for 20 min at –20°C, allowed to warm to 0°C, poured
into 100 g of crushed ice, and extracted with dichloꢀ
(
20.34 g, 0.127 mol, 1 equiv.) of bromine was added
romethane (3
×
50 mL). The organic extract was
dropwise so that the temperature of the reaction mixꢀ
ture was not higher 5°C. After bromine addition was
completed, the reaction mixture was stirred for 15 min
at 0°C, 45.36 mL (38.0 g, 0.127 mol, 1 equiv.) of
ꢀoctylꢀ1ꢀdodecanol was added. The reaction mixture
was stirred for 12 h at ambient temperature, concenꢀ
trated in a vacuum, the resultant suspension was
washed with water until neutral pH, dried with
MgSO , and concentrated in a vacuum. The residue
4
was purified by column chromatography with gradient
elution (PE, then PE : EtOAc = 3 : 1) to give 0.38 g of
viscous oil.
2
1H NMR (400 MHz, CDCl
= 8.5 Hz, 2H), 8.11 (d,
= 17.9, 8.1 Hz, 6H), 7.29 (t,
washed with petroleum ether, and concentrated in a 7.5 Hz, 2H), 4.19 (d, = 7.3 Hz, 4H), 2.12 (s, 2H),
vacuum to give 43.61 g (95%) of viscous oil.
1.43–1.16 (m, 64H), 0.91–0.83 (m, 12H).
1H NMR (400 MHz, CDCl3,
, ppm): 3.47 (d,
13C NMR (101 MHz, CDCl3,
, ppm): 195.2,
.7 Hz, 2H), 1.66–1.54 (m, 1H), 1.45–1.17 (m, 32H), 144.7, 141.8, 12.9, 126.8, 125.0, 124.2, 123.2, 123.2,
,
3
δ
, ppm): 8.81 (s,
= 7.7 Hz,
diluted with 100 mL of petroleum ether, and filtered. 2H), 8.22 (d,
The filtrate was passed through a thin layer of silica gel, 2H), 7.47 (dt,
J
J
J
J =
J
δ
J
=
δ
4
0
.91 (t,
J
= 6.7 Hz, 6H).
121.0, 120.5, 109.8, 109.3, 48.06, 37.96, 31.90, 31.83,
30.01, 30.0, 29.7, 29.7, 29.7, 29.6, 29.4, 29.3, 26.7,
13C NMR (101 MHz, CDCl3,
δ
, ppm): 39.7, 39.5,
22.8, 22.8, 14.3, 14.2.
3
2
2.5, 31.9, 29.8, 29.6, 29.6, 29.5, 29.3, 29.3, 26.5,
2.6, 14.1.
For C H N O anal. calcd. (%): C, 83.49; H, 10.19;
66
96
2
2
N, 2.95.
9
ꢀ(2'ꢀOctyldodecyl)ꢀ9Hꢀcarbazole (7). Carbazole
5 g, 30 mmol) was dissolved in 50 mL of DMF under
an argon atmosphere and then 1.67 g (1.4 equiv.) of
0% sodium hydride suspension in mineral oil was
(
Found (%): C, 83.23; H, 10.09; N, 2.81.
6
ACKNOWLEDGMENTS
added. After all sodium hydride was added, the reacꢀ
tion mixture was stirred for 20 min, and then, 11 g
30 mmol) of 1ꢀbromoꢀ2ꢀoctyldodecane (5) was added
in one portion in an argon counterflow. The reaction
mixture was stirred for 72 h, poured into water, and
extracted with petroleum ether. The organic extract
M.L. Keshtov, S.N. Osipov, M.A. Topchiy, and
S.A. Kuklin gratefully acknowledge the financial supꢀ
port of the Russian Science Foundation for conductꢀ
ing experimental studies and studying spectral characꢀ
teristics (project no. 14ꢀ13ꢀ01444).
(
was dried with MgSO , the solvent was removed in a
4
vacuum. The residue was chromatographed in petroꢀ
leum ether to give 10.3 g (76%) of viscous oil.
REFERENCES
1H NMR (400 MHz, CDCl3,
.7 Hz, 2H), 7.58–7.34 (m, 4H), 7.29–7.24 (m, 2H),
.19 (d, 2H), 2.20–2.15 (m, 1H), 1.40–1.24 (m, 32H),
.93–0.89 (m, 6H).
δ
, ppm): 8.13 (d,
J
=
1. Dailey, S., Faest, J.W., Peace, R.J., Sage, I.C., Till, S.,
and Wood, E.L., J. Mater. Chem., 2001, vol. 11,
pp. 2238–2243.
7
4
0
2
. Thomas, K.R.J., Valusamy, M., Lin, J.T., Chuen, Ch.H.,
and Tao, Y.T., Chem. Mater., 2005, vol. 17, pp. 1860–
1866.
13C NMR (101 MHz, CDCl3,
, ppm): 140.9,
δ
1
3
1
25.5, 122.8, 120.2, 118.6, 108.9, 47.7, 37.9, 31.9,
1.8, 29.9, 29.6, 29.5, 29.3, 29.2, 26.6, 22.7, 22.6,
4.1.
3. Dimitrakopolous, C.D. and Malenfant, P.R.L., Adv.
Mater., 2002, vol. 14, pp. 99–117.
4. Keshtov, M.L., Rusanov, A.L., Belomoina, N.M.,
Mikitaev, A.K., Sarkisyan, G.B., and Begretov, M.M.,
Izv. Akad. Nauk, Ser. Khim., 1996, no. 9, pp. 2359–
1
,2ꢀBis(9'ꢀ(2"ꢀoctyldodecyl)carbazolꢀ3'ꢀyl)ethaneꢀ
1
,2ꢀdione (8). Aluminum chloride (0.67 g, 5 mmol)
2365.
and 3 mL of anhydrous 1,2ꢀdichloroethane were
placed into a 100ꢀmL threeꢀnecked flask equipped
with magnetic stirrer, thermometer, and dropping funꢀ
nel. The resultant suspension was cooled to –20°C,
5
. Rusanov, A.L., Keshtov, M.L., Keshtova, S.V., Beloꢀ
moina, N.M., Shchegolikhin, A.N., Mikitaev, A.K.,
and Askadskii, A.A, Vysokomol. Soedin. Ser. A, 1997,
vol. 39, no. 9, pp. 1539–1547.
DOKLADY CHEMISTRY Vol. 463
Part 2
2015