Poly(4-diphenylaminium-1,2-phenylenevinylene)
was then extracted with chloroform. The organic layer was
dried over anhydrous sodium sulfate and evaporated. The
crude product was purified using a silica gel column with a
hexane eluent to give 2-(2-bromo-4-iodo-phenyl)-1,3-dioxolane
6 as a white solid (6.96 g): yield 98%; mp 56 °C; 1H NMR (500
MHz, CDCl3; ppm) 7.92 (d, J ) 1.8 Hz, 1H), 7.66 (dd, J ) 8.1,
1.4 Hz, 1H), 7.31 (d, J ) 8.1 Hz, 1H), 6.02 (s, 1H), 4.09 (dd, J
) 3.5, 15.7 Hz, 4H); 13C NMR (500 MHz, CDCl3; ppm) δ 140.9,
136.6, 136.3, 129.2, 123.6, 102.2, 95.2, 65.5; IR (KBr pellet,
for C22H20NBrO2 410.3. Anal. Calcd for C22H20NBrO2: C, 64.4;
H, 4.9; N, 3.4; Br, 19.5. Found: C, 64.1; H, 5.0; N, 3.2; Br,
19.7.
4-[N ,N -Bis(4-t er t -b u t ylp h e n yl)a m in o]-2-b r om ot olu -
en e (8). To a 15 mL toluene solution of bis(4-tert-butylphenyl)-
amine (0.56 g, 2 mmol) were added 2-bromo-4-iodotoluene (0.59
g, 2.0 mmol), tris(dibenzylideneacetone)dipalladium (0.27 g,
0.30 mmol), tris(o-tolyl)phosphine (0.091 g, 0.30 mmol), and
sodium tert-butoxide (0.58 g, 6.0 mmol), and the mixture was
stirred for 15 h at 70 °C under nitrogen and then cooled to
room temperature. The crude product was extracted with
chloroform, washed with water, and dried over anhydrous
magnesium sulfate. The solvent was removed in vacuo, and
the residue was purified using a silica gel column with a
hexane eluent and recrystallized from hexane to afford 0.47 g
cm-1) 3080 (νC-H), 2952 (νC-H), 2886 (νC-H), 943 (νC-O-C) cm-1
;
MS (EI) m/e 354 ((M - 1)+), 356 ((M + 1)+), calcd for C9H8-
BrIO2 355.0.
Compound 6 (100 mg, 0.28 mmol) and bis(4-methoxyphen-
yl)amine (59 mg, 0.26 mmol) were dissolved in toluene (2.1
mL). Sodium tert-butoxide (37 mg, 0.38 mmol), tris(diben-
zylideneacetone)dipalladium (2.9 mg, 3.2 µmol), and (S)-(-)-
2,2′-bis(diphenylphosphino)-1,1′-binaphthyl (6.0 mg, 9.6 µmol)
were added, and then mixture was heated at 100 °C for 40 h
to yield a reddish brown precipitate. The reaction mixture was
neutralized with 1 N aqueous ammonia and extracted with
chloroform. The organic layer was washed with brine and
evaporated to give the crude product, which was purified using
a silica gel column with hexane/ethyl acetate (3/1) to afford
82.7 mg of (3-bromo-4-(1,3-dioxolan-2-yl)phenyl)bis(4-methoxy-
phenyl)amine as a yellow solid: yield 71%; mp 115 °C; 1H NMR
(500 MHz, CDCl3; ppm) δ 7.33 (d, J ) 8.6 Hz, 1H), 7.05-6.81
(m, 10H), 6.01 (s, 1H), 4.16-4.01 (m, 4H), 3.79 (s, 6H); 13C
NMR (500 MHz, CDCl3; ppm) δ 156.5, 150.6, 139.9, 128.1,
127.1, 127.1, 123.3, 122.9, 118.3, 114.9, 102.8, 65.3, 55.5; IR
(KBr pellet, cm-1) 2952 (νC-H), 2890 (νC-H), 2835 (νC-H), 1324
(νC-N), 946 (νC-O-C); MS (EI) m/e 455 ((M - 1)+), 457 ((M +
1
of 8 as white crystals: yield 52%; mp 133 °C; H NMR (500
MHz, CDCl3; ppm) δ 7.25-6.88 (m, 11H), 2.32 (s, 3H), 1.30 (s,
18H); 13C NMR (500 MHz, CDCl3; ppm) δ 147.2, 145.8, 144.8,
131.0, 130.9, 126.7, 126.1, 124.9, 123.7, 122.3, 34.3, 31.4, 22.1;
IR (KBr pellet, cm-1) 2956 (νC-H), 1267 (νBr-C), 1030 (νC-N);
MS (EI) m/e 449 ((M - 1)+), 451 ((M + 1)+), calcd for C27H32
-
NBr for 450.5. Anal. Calcd for C27H32NBr: C, 72.0; H, 7.2; N,
3.1; Br, 17.7. Found: C, 71.8; H, 7.0; N, 3.0; Br, 17.6.
4-[N ,N -Bis(4-t er t -b u t ylp h e n yl)a m in o]-2-b r om ost y-
r en e (5b). N-Bromosuccinimide (1.8 g, 10.0 mmol) and a trace
amount of azobisisobutyronitrile were added to a 50 mL
tetrachloromethane solution of 8 (9.0 g, 20 mmol). The mixture
was vigorously stirred at 60 °C for 3 h, filtered, and evaporated.
The residue was dissolved in a 5 mL benzene solution of
triphenylphosphine (2.6 g, 10 mmol) and stirred at 50 °C for
5 h. Evaporation gave a red oil, which was purified using a
silica gel column with a hexane/chloroform (1/1) eluent to give
a yellow oil as the corresponding phosphonium salt (5.4 g).
The phosphonium salt (5.4 g, 6.8 mmol) was dissolved in 1.0
N aqueous formaldehyde (19 mL). A 2 N aqueous sodium
hydroxide (3 mL) solution was added dropwise to the phos-
phonium salt solution, stirred for 3 h, and extracted with
diethyl ether. The organic layer was washed with brine, dried
over anhydrous sodium sulfate, and evaporated. The residue
was purified using a silica gel column with a hexane eluent to
1)+), calcd for C23H22NBrO4 456.3. Anal. Calcd for C23H22
-
NBrO4: C, 60.5; H, 4.9; N, 3.1; Br, 17.5. Found: C, 60.4; H,
4.8; N, 3.0; Br, 17.4.
(3-Bromo-4-(1,3-dioxolan-2-yl)phenyl)bis(4-methoxyphenyl)-
amine (728 mg, 1.59 mmol) was dissolved in a mixture of
acetone (16 mL) and water (0.50 mL) containing p-toluene-
sulfonic acid (214 mg, 1.13 mmol) and refluxed for 3 h. After
evaporation, the mixture was extracted with ether. The organic
layer was successively washed with aqueous sodium hydrogen
carbonate and aqueous saturated sodium chloride and then
evaporated. The crude product was purified using a silica gel
column with hexane/ethyl acetate (3/1) to give 7 as an orange
solid (656 mg): yield 93%; mp 146 °C; 1H NMR (500 MHz,
CDCl3; ppm) δ 10.08 (s, 1H), 7.68 (d, J ) 8.8 Hz, 1H), 7.13-
6.89 (m, 9H), 6.73 (dd, J ) 2.5, 8.9 Hz, 1H), 3.84 (s, 6H); 13C
NMR (500 MHz, CDCl3; ppm) δ 190.0, 157.7, 154.4, 138.0,
130.7, 129.0, 128.1, 124.4, 119.9, 115.6, 115.2, 55.4; IR (KBr
pellet, cm-1) 2955 (νC-H), 2929 (νC-H), 2908 (νC-H), 2836 (νC-H),
1677 (νCdO), 1341 (νC-N); MS (EI) m/e 411 ((M - 1)+), 413 ((M
1
give 5b as an amorphous white solid (0.91 g): yield 29%; H
NMR (500 MHz, CDCl3; ppm) δ 7.63-6.92 (m, 12H), 5.56 (d,
J ) 18.4 Hz, 1H), 5.21 (d, J ) 12.1 Hz, 1H), 1.30 (s, 18H); 13
C
NMR (500 MHz, CDCl3; ppm) δ 148.8, 146.6, 144.2, 135.2,
130.0, 126.7, 126.2, 125.1, 124.5, 124.0, 121.1, 114.1, 34.4, 31.4;
IR (KBr pellet, cm-1) 3033 (νC-H), 2954 (νC-H), 1622 (νCdC), 1267
(νC-N) cm-1; MS (EI) m/e 461 ((M - 1)+), 463 ((M + 1)+), calcd
for C28H32BrN 462.5. Anal. Calcd for C28H32NBr: C, 72.7; H,
7.0; N, 3.0; Br, 17.3. Found: C, 72.5; H, 6.8; N, 2.9; Br, 17.5.
P olym er iza tion . The polymerization was carried out by
modifying the procedure described in the previous papers.7,25
Palladium acetate, tris(o-tolylphosphine), triethylamine, and
lithium chloride were added to the monomer 5 solution of
DMF, and the mixture was heated (examples of the polymer-
ization conditions are given in Table 3). The polymerization
mixture was poured into methanol, and the precipitated
polymer powder was purified by reprecipitation from chloro-
form into the mixture of methanol/benzene (3/7) to afford the
polymer 1.
+ 1)+), calcd for C21H18NBrO3 412.3. Anal. Calcd for C21H18
-
NBrO3: C, 61.2; H, 4.4; N, 3.4; Br, 19.4. Found: C, 60.3; H,
4.2; N, 3.3; Br, 19.3.
4-[N,N-Bis(4-m eth oxyp h en yl)a m in o]-2-br om ostyr en e
(5a ). To 0.344 mL of a dry THF solution of triphenylmeth-
ylphosphonium bromide (117 mg, 0.327 mmol) were dropwise
added a 0.136 mL hexane solution of n-butyllithium (0.218
mmol) and a dry 0.30 mL THF solution of 7 (45.6 mg, 0.111
mmol), and the mixture was stirred at room temperature for
1 h. After evaporation, the crude product was extracted with
diethyl ether, washed with brine, dried over anhydrous sodium
sulfate, evaporated, and purified with a silica gel column with
a hexane/ethyl acetate (20/1) to give 44.7 mg of 5a as a pale-
Ma gn etic Mea su r em en ts. The PF6- salt of 1+ was isolated
by pouring the methylene chloride solution of 1+ oxidized with
a small excess of NOPF6/18-crown-6-ether into dimethyl ether
(Anal. Calcd for C22H19NF6O2P: C, 55.7; H, 4.0; N, 3.0.
Found: C, 55.3; H, 4.2; N, 2.9). Besides the neat sample, 1+
was also isolated in the presence of polystyrene or poly-
(styrenesulfonate tetrabutylammonium) 4. The neat sample
was dissolved again in the methylene chloride solution of
polystyrene or 4 ([polystyrene or 4]/[1+] ) 100 w/w), and the
1
yellow viscous liquid: yield 98%; H NMR (500 MHz, CDCl3;
ppm) δ 7.34 (d, J ) 8.9 Hz, 1H), 7.06-6.21 (m, 11H), 5.54 (dd,
J ) 1.2, 17.4 Hz, 1H), 5.19 (dd, J ) 1.3, 11.1 Hz, 1H), 3.82 (s,
6H); 13C NMR (500 MHz, CDCl3; ppm) δ 156.4, 149.3, 140.0,
135.2, 128.8, 127.0, 126.6, 124.1, 122.9, 118.9, 114.9, 113.7,
55.5; IR (KBr pellet, cm-1) 2952 (νC-H), 2930 (νC-H), 2834 (νC-H),
1325 (νC-N); MS (EI) m/e 409 ((M - 1)+), 411 ((M + 1)+), calcd
(25) (a) Heitz, W.; Bru¨gging, W.; Freund, L.; Gailberger, M. Mak-
romol. Chem. 1988, 189, 119. (b) Brenda, M.; Greiner, A.; Heitz, W.
Makromol. Chem. 1990, 191, 1083. (c) Bao, Z.; Chen, Y.; Cai, R.; Yu,
L. Macromolecules 1993, 26, 5281.
J . Org. Chem, Vol. 69, No. 3, 2004 637