MESOGENIC 4-(w-HYDROXYALKOXY)-4'-FORMYLAZOBENZENES
1115
+
2
2
1
2
+
+ 2
1
2
1
1
$
+
2
2
+
2
+
1
1
2
1
2
1
2
+
%
(13
respect to TMS and were measured from internal
C). Chemical shifts were presented in d-scale with
lized from 80% acetic acid. Yield of bright-orange
crystalline compound I 29.9 g (87%), mp 185°C.
1
13
references TMS ( H) and cyclohexane, 27.6 ppm ( C
4
-(2-Hydroxyethoxy)-4'-formylazobenzene (IIa). A
mixture of 2.3 g (10 mmol) of compound I, 0.81 g
10 mmol) of ethylene chlorohydrin, and 1.66 g
1
{
H}). The error in recalculation of the chemical shifts
1
3
in the C NMR spectra did not exceed ±0.01 ppm.
(
The phase transition temperature was measured and
textures of compounds obtained were investigated with
the use of polarization microscope Polam P-211 equipped
with a heating block. The phase transition temperatures
were measured with an accuracy ±0.2°C.
(12 mmol) of potassium carbonate in 150 ml of DMF
was heated at reflux at vigorous stirring for 4 h. The hot
reaction mixture was poured into 400 ml of ice water,
the precipitate was filtered off and dried in air. Then it
was passed through a column packed with Al O (eluent
2
3
chloroform) and recrystallized from ethanol. Yield of
orange crystalline compound IIa 2.5 g (92%), mp
4
-Hydroxy-4'-formylazobenzene (I). A suspension
of 18.3 g (150 mmol) of 4-aminobenzaldehyde was
prepared at 0°C in 100 ml of water. At the same
temperature was separately dissolved 9.9 g (160 mmol)
of sodium nitrite in 50 ml of water. To the suspension of
1
1
(
(
7
31.7°C. IR spectrum, n, cm : 3415 (OH), 2950, 2869
1
CH), 1698 (C=O). H NMR spectrum, d, ppm: 4.02 t
2H, HOCH ), 4.16 t (2H, CH O), 7.07 d (2H, ArH ),
.93 d (2H, ArH ), 8.00 s (4H, ArH ), 10.08 s (1H,
CH O). C NMR spectrum, d, ppm: 61.25 (HOCH ),
9.53 (CH OAr), 114.85 (C ), 123.04 (C ), 125.34 (C ),
30.67 (C ), 136.93 (C ), 147.17 (C ), 156.04 (C ),
61.85 (C ), 191.69 (C ). Found, %: C 67.31; H 5.84;
4
2
2
5
6,7
4
-aminobenzaldehyde was simultaneously added at
8
13
2
vigorous stirring the solution of sodium nitrite and 50
ml (330 mmol) of 24% hydrochloric acid solution
maintaining the pH of the reaction mixture at 7. The
completion of diazotization was checked by a starch-
iodide paper strip test. The solution of diazo compound
was adjusted to pH 7 by adding 4% NaOH solution. To
the neutral solution of diazo compound at cooling and
stirring was added a cooled to 0°C solution of 14.2 g
4
5
6
6
1
1
2
7
12
10
11
1
3
8
N 9.87. C H N O Calculated, %: C 66.67; H 5.19;
1
5
14
2
3.
N 10.37.
Likewise were prepared compounds IIbe.
The study was carried out under financial support of
the Russian Foundation of Basic Research (grant 02-03-
32463a) and of program of the Division of Chemistry,
Physics, and Mathematics of the Russian Academy of
Sciences ¹ 10002-251/OkhNM-02/129-134/280703-
1139.
(
150 mmol) of phenol in 50 ml (150 mmol) of 6% NaOH
solution. The end of the azo coupling was checked by a
drop test with sodium phenolate. The reaction product
was precipitated by adding to the reaction mixture 60 g
of NaCl, the precipitate was filtered off, and recrystal-
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 40 No. 8 2004
Kuvshinova
