1540, 1490, 1410, 1240, 1070, 750, 710, 690 cm−1. MS for
product was chromatographed (SiO , 50% CHCl –hexane) to
yield BIZ as needles, 0.37g (10%): mp 119 °C. 1H NMR
2
3
C H N O : calc. 238(M), found 238.
14 10
2 2
(90 MHz,CDCl ) d 6.55 (t,1H,J=8), 6.89 (d,1H,J=8), 7.01–7.50
(m,7H), 7.52–7.73 (m,3H), 7.75–7.91 (m,1H), 13.53 (br,1H).
3
2-(2-Methoxyphenyl)-5-phenyl-1,3,4-oxathiazole 3. A mix-
ture of 5.5 g (20 mmol) of 1, 5.5 g (12 mmol) of P S and
IR(KBr) 3050, 2600, 1580, 1480, 1380, 1280, 1255, 810, 740,
700 cm−1. MS for C H N O: calc. 286(M), found 286.
4 10
50 ml of xylene was stirred at 140 °C for 4 h. After cooling,
19 14
2
140 ml of water was added to the reaction mixture. This was
heated at 80 °C for 1 h. Sodium hydrogen carbonate was added
to the water layer until a pH of 6 was obtained. The xylene
layer was washed with water and dried over Na SO . The
Bis[2-(2-hydroxyphenyl)-5-phenyl-1,3,4-oxadiazolato]zinc
Zn(ODZ) . To a suspension of 500 mg (2.1 mmol) of ODZ
2
and 5 g of methanol was added chloroform until the suspension
2
4
solvent was removed by evaporation to yield a white solid.
The residue was dried in vacuo. The crude product was
chromatographed (SiO , CHCl ) to yield 3 as a pale yellow
was clear. To this solution was added a solution of 230 mg
(1.0 mmol) of zinc acetate in 1.55 g of methanol and the
mixture was heated at 70 °C for 1.5 h. The solvent was removed
by evaporation. The residue was washed with water and dried
in vacuo to give a pale yellow solid. The crude materials were
2
3
solid, 3.5 g (65%): mp 137 °C. 1H NMR (90 MHz,CDCl ) d
4.02 (s,3H), 6.98–7.22 (m,2H), 7.35–7.59 (m,4H), 7.92–8.20
3
(m,2H), 8.52 (d,1H,J=8Hz). IR(KBr)3050, 3000, 2940, 2830,
2700, 2530, 2560, 1595, 1450, 1410, 1300, 1260, 1015, 725,
680 cm−1. MS for C H N OS: calc. 268(M), found 268.
purified by the train sublimation method to give Zn(ODZ) .
Anal. Calc. for C H N O Zn: C,62.30; H,3.36; N,10.38.
Found: C,62.04; H,3.33; N,10.14%.
2
28 18
4 4
15 12
2
2-(2-Hydroxyphenyl)-5-phenyl-1,3,4-oxathiazole (TDZ). To
a solution of 3.5 g (13 mmol) of 3 in 40 ml of CH Cl at
Bis[2-(2-hydroxyphenyl)-5-phenyl-1,3,4-oxathiazolato]zinc
Zn(TDZ) . To a suspension of 597 mg (2.3 mmol) of TDZ,
2
2
2
204 mg (2.3 mmol) of morpholine and 5 g of methanol was
−78 °C was added dropwise 17.5 ml of a solution of 1.0
BBr in CH Cl . The reaction mixture was allowed to warm
added a solution of 258 mg (1.2 mmol) of zinc acetate and
1.7 g of methanol with stirring. The mixture was heated at
70 °C for 1 h and the solvent was removed. The residue was
washed with water and dried in vacuo. The crude materials
were purified by the train sublimation method to give
Zn(TDZ) . Anal. Calc. for C H N O S Zn: C,58.80; H,3.17;
3
2 2
slowly to room temperature overnight. Water (50 ml) was
added to the reaction mixture carefully, then the reaction
mixture was extracted twice with 30 ml of CH Cl . The organic
2
2
layer was dried over Na SO . The solvent was removed by
evaporation to yield TDZ as a white solid: 1.75 g (53%): mp
128 °C. 1H NMR (90 MHz,CDCl ) 6.85–7.43 (m,3H),
2
4
2
28 18 4 2 2
d
N,9.80. Found: C,58.63; H,3.13; N,9.56%.
3
7.43–7.68 (m,4H), 7.91–8.08 (m,2H), 11.48 (s,1H). IR(KBr)
3060, 3030, 2920, 2730, 2630, 2570, 1600, 1455, 1430, 1310,
1260, 1100, 1000, 750, 680, 600 cm−1. MS for C H N OS:
Bis[2-(2-hydroxyphenyl)pyridinato]zinc Zn(PhPy) . To a
solution of 816 mg (4.8 mmol) of PhPy, 419 mg (4.9 mmol) of
2
14 10
2
calc. 254(M), found 254.
piperidine, 3 g of methanol and 10 g of chloroform was added
a solution of 523 mg (2.4 mmol) of zinc acetate in 3.5 g of
methanol. The solvent was evaporated slowly for 5 days. The
residue was washed with water and dried in vacuo to give a
pale yellow solid. The crude materials were purified by the
2-(2-Methoxyphenyl)pyridine 4. To a mixture of 1.28 g
(53 mmol) of Mg and 1 ml of THF was added a solution of
10 g (53 mmol) of o-methoxybromobenzene in 15 ml of dry
THF. The reaction mixture was refluxed for 30 min. This
Grignard solution was added dropwise to a mixture of 7.5 g
(47 mmol) of 2-bromopyridine, 0.25 g of 1,3-bis(diphenylphos-
phinopropane)nickel() chloride and 15 ml of dry THF over
10 min at 0 °C. The reaction mixture was allowed to warm to
room temperature and stirred overnight. To the reaction mixture
was added 30 ml of water and the solvent was then evaporated.
The residue was partitioned between 70 ml of water and 50 ml
of CHCl . The organic layer was dried over Na SO and
train sublimation method to give Zn(PhPy) . Anal. Calc. for
C H N O Zn: C,65.12; H,3.97; N,6.90. Found: C,64.70;
H,3.97; N,6.70%.
2
22 16
2 2
Bis[2-(2-hydroxyphenyl)-1-phenylbenzimidazolato]zinc
Zn(BIZ) . To a solution of 365 mg (1.3 mmol) of BIZ, 114 mg
2
(1.3 mmol) of piperidine and 2 g of methanol was added a
solution of 140 mg (0.64 mmol) of zinc acetate in 0.92 g of
methanol. The reaction mixture was stirred for 6 h. The
precipitates were filtered off and washed with water and dried
in vacuo. The crude materials were purified by the train
3
2
4
evaporated to yield 4 as a light brown oil: 8.84 g (quantative).
1H NMR (90 MHz,CDCl ) d 3.82 (s,3H), 6.91–7.50 (m,4H),
3
7.55–7.90 (m,3H), 8.7 (d,1H,J=6Hz). IR(KBr) 3060, 3000, 2950,
sublimation method to give Zn(BIZ) . Anal. Calc. for
C H N O Zn: C,71.76; H,4.12; N,8.81. Found: C,71.39;
H,4.13; N,8.66%.
2840, 1600, 1585, 1500, 1460, 1425, 1260, 1240, 1025, 755 cm−1.
2
MS for C H NO: calc. 185(M), found 185.
38 26
4 2
12 11
2-(2-Hydroxyphenyl)pyridine (PhPy). To a solution of 8.84 g
(48 mmol) of 4 in 50 ml of CH Cl at −78 °C was added
dropwise 49.5 ml of a solution of 1.0 BBr in CH Cl . The
Tris[2-(2-hydroxyphenyl)-5-phenyl-1,3,4-oxadiazolato]-
aluminium Al(ODZ) . To a solution of 1.00 g (4.2 mmol) of
2
2
3
ODZ and 0.75 g (8.6 mmol) of morpholine in 190 g of ethanol
3
2 2
reaction mixture was allowed to warm slowly to room tempera-
ture overnight. Water (60 ml) was added to the reaction
mixture carefully, then the reaction mixture was extracted
twice with 100 ml of CH Cl . The organic layer was dried over
was added a solution of 0.187 g (1.4 mmol) of aluminium
chloride in 3.15 g of ethanol. The reaction mixture was heated
at 80 °C for 4 h. The precipitates were filtered off and washed
with water and dried in vacuo. The crude materials were
2
2
Na SO . The solvent was removed by evaporation to yield
PhPy as a light brown oil: 3.35g (41%). 1H NMR
(90 MHz,CDCl ) d 6.79–7.35 (m,4H), 7.65–7.95 (m,3H), 8.52
2
4
purified by the train sublimation method to give Al(ODZ) .
Anal. Calc. for C H N O Al: C,68.29; H,3.68; N,11.38. Found:
C,68.32; H,4.08; N,10.96%.
3
42 27
6 6
3
(d,1H,J=6), 14.35 (br,1H). IR(KBr) 3400, 3060, 2950, 2840,
1600, 1505, 1495, 1260, 1025, 830, 760 cm−1. MS for C H NO:
11
9
calc. 171(M), found 171.
One of the authors would like to thank Mr. Masao Tsuji
(Toyota Central R&D Labs. Inc.) for the elemental analysis,
Mrs. Atsuko Takagi (Toyota Central R&D Labs. Inc.) for the
DSC measurements, Mr. Tadao Ogawa (Toyota Central R&D
Labs. Inc.) for the MS measurements and Mr. Koji Noda
(Toyota Central R&D Labs. Inc.) for the device fabrication.
2-(2-Hydroxyphenyl)-1-phenylbenzimidazole (BIZ). A mix-
ture of 2.0 g (13 mmol) of o-anisic acid, 2.42 g (13 mmol) of N-
phenyl-1,2-phenylenediamine and 5 ml of o-dichlorobenzene was
heated at 170 °C for 10 h, then at 220 °C for 30 h. The crude
2002
J. Mater. Chem., 1998, 8(9), 1999–2003