˙
˙
1
284
I. Özaytekin and I. Karatas¸
Vol. 42
Methods of Investigation.
Values of III compound: LC/MS [m/z (rel. %)]: 341 (10),
40 (45), 325 (12), 309 (25), 300 (11), 293 (9), 281 (5), 266
3
(
(
Materials and Measurements.
26), 252 (44), 251 (11), 227 (5), 180 (9), 145 (16), 113
All chemicals (Merck and Fluka) were in analytical
grade and used without further purification. The H-NMR
spectra, mass spectra and elemental analysis for carbon,
hydrogen and nitrogen were carried out in the Laboratories
of the Scientific and Technical Research Council of Turkey
-1
98), 79 (20). IR (ν, cm ): 3022 ν (C-H arom.), 2921 ν (C-
1
H
Aliph.), 1635-1615 ν (C=N
), 1478 ν (C=C).
oxsazole ring
1
6
H-NMR (δ, ppm) (DMSO-d ): 8.30 (s, 4H, C-H
),
Arom
7.16-7.53 (m, 6 H, C-H Arom.), 2.48 (s, 6H, C-H aliph.).
Values of IV compound: LC/MS [m/z (rel. %)]: 346 (5),
45 (42), 344(10), 315 (20), 314 (89), 311 (29), 298 (5),
87 (18), 286 (96), 284 (25), 270 (6), 258 (10), 256 (25),
(
TUBITAK). Infrared spectra were recorded on a Perkin
3
2
2
3
Elmer Model 1605 FT-IR spectrophotometer as KBr pel-
lets in the region of 500-4000 cm .
-
1
-1
28 (8), 216 (5), 178 (5), 101 (57), 79 (8). IR (ν, cm ):
054 ν (C-H
), 1638-1618 ν (C=Nthiazole ring), 1481ν
Synthesis of Terephthalaldoxime and Terephthalohydrox-
imoyl Chloride.
arom.
1
6
(
C=C). H-NMR (δ, ppm) (DMSO-d ): 8.38 (s, 4H, C-H
Arom), 7.65 (q, 4H, C-H Arom, J=3.13 Hz), 7.28 (q, 4H, C-H
Arom, J=3.20 Hz).
In this study, terephthalaldoxime [C H N O ] and
terephthalohydroximoyl chloride [C H Cl N O ] have
been synthesized according to the methods in literature.
The starting material of terephthalaldoxime was synthe-
sized from terephthalaldehyde by the standard procedure.
After that terephthalohydroximoyl chloride was obtained
by passing chlorine gas (which was dried and passed under
safe conditions) through dioxane or CCl solutions of
terephthalaldoxime [6,7]. The structures of terephthalal-
doxime (I) and terephthalohydroximoyl chloride (II) are
8
8 2 2
8
6
2
2
2
Values of V compound: LC/MS [m/z (rel. %)]: 311 (7),
3
10 (25), 309 100), 281 (7), 255 (9), 236 (5), 218 (14). IR
-1
(
(
(
ν, cm ): 3413 ν (N-H), 3070 ν (C-H arom.), 1637-1618 ν
C=N
DMSO-d ): 8.32 (s, 4H, C-H
1
), 1437 ν (C=C). H-NMR (δ, ppm)
oxsazole ring
6
), 8.21 (d, 2H, C-H
Arom
Arom, J=7.82 Hz), 8.13 (d, 2H, C-H Arom, J=8.28 Hz), 7.60
4
(t, 2H, C-H Arom, J=8.16 Hz), 7.52 (t, 2H, C-H Arom
J=7.81 Hz), 7.37 ( s, 2H, N-H Arom ).
,
Results and Discussion.
-
1
shown in Figure 2. IR (ν, cm ) (I) : 3167 ν (O-H), 3072
ν (C-H arom.), 2988 (C-H aliph.), 1480 ν (C=C), 982 ν (N-
In general, the amidoximes and their derivatives were
synthesized from the condensation reaction of some pri-
mary and secondary amines of hydroxamoyl chlorides
-
1
O). IR(ν, cm ) (II): 3234 ν (O-H), 3037 ν (C-H arom.),
458 ν (C=C), 998 ν (N-O).
1
I: (C H N O )
I: (C H Cl N O )
8 6 2 2 2
8
8
2
2
Figure 2. Structures of terephthalaldoxime and terephthalohydroximoyl chloride
Synthesis of bis-Benzoxazole and its Derivatives.
[8]. Terephthalohydroximoyl chloride gave the het-
eroaromatic closing reaction with 2-amino-4-methyl phe-
nol, o-aminothiophenol, phenyelenediamine, although
N,N'-disubstituted amidoximes and their derivatives were
synthesized by the condensation reaction of the same
monomer with same primary amines at the same condi-
tions. The synthesis of several bis(benzthiazoles, benzox-
azoles and benzimidazoles) and related compounds were
prepared by the reactions of 2-amino-4-methylphenol, o-
aminothiophenol and phenyelene diamine with the dicar-
boxylic acid, anhydride or nitrile using polyphosphoric
acid (PPA) and the reaction was completed in two hours
with stirring as in literatures [4,9-18]. Benzoxazole and
benzimidazole were prepared by the condensation reac-
tion of o-aminothiophenol, phenyelenediamine of
O-alkylated oxime and by the transformations of
O-aminophenol in one of the literature [19].
Terephthalohydroximoyl chloride (0.30 g, 1.29 mmol)
was dissolved in 15 ml ethanol. Aqueous solution of
NaHCO and 2.84 mmol of amine (0.30 ml o-aminothio-
3
phenol, 0.31 g phenylenediamine or 0.35 g 2-amino-4-
methylphenol) were added to the solution. The mixture was
stirred for about one week at room temperature and then a
mixture of o-aminothiophenole was heated under reflux for
three hours. Bisbenzoxazole deposited as solid was col-
lected by filtration and recrystallized from dimethylfor-
mamide. Similar literature was used to synthesis the deriva-
tives of bisbenzoxazole [5]. Some physical properties of
synthesized compounds were tabulated in Table 1. Mass,
1
1
FT-IR, and H-NMR values of [5,5'-dimethyl-2,2' -(p-
1
phenylene)bis-(benzoxazole)](III); [2,2 (p-phenylene)bis-
1
(
benzthiazole)] (IV) and [2,2 (p-phenylene)bis-(benzimida-
zole)] (V) are given as following.