6644 Chem. Mater., Vol. 22, No. 24, 2010
Reitzenstein et al.
Bis(2,3,4,5,6-pentachlorophenyl)-2,3,5,6-tetrachloro-4-{(1E),2-[4-
(bis(4-methoxyphenyl)amino)-phenyl]ethenyl}phenylmethyl
radical M.30 To a solution of the R-H compound30 of M (55.6 mg,
52.6 μmol) in dry THF (5 mL) was added n-Bu4NOH (70.1 μL,
105 μmol, ∼1.5 M in H2O) under the exclusion of air and light, and
the deep blue solution was stirred for 1 h during which it turned
deep purple. After the addition of p-chloranil (33.2 mg, 135 μmol),
the resulting brown solution was stirred for 16 h. The solvent was
removed and the mixture was diluted in dichloromethane and
washed twice with slightly acidic water (∼0.01 N), four times with
sodium hydroxide solution (5%), and twice with water. The
organic phase was dried over MgSO4, the solvent was removed,
and the raw product was purified by flash chromatography (petrol
ether/dichloromethane 1:1). Further purification by repeated
dropwise addition of a concentrated acetone solution into metha-
nol gave a brown solid. Yield: 31.8 mg (30.1 μmol, 57%).
[M-Hþ]- calcd for C21H6Cl13-, 712.64258; found, 712.64225
(Δ = 0.47 ppm).
[Bis(4-bromomethyl-2,3,5,6-tetrachlorophenyl)-(2,3,4,5,6-penta-
chlorophenyl)]methane 3. A mixture of 2 (5.00 g, 6.94 mmol),
N-bromosuccinimide (12.4 g, 69.4 mmol), azobis(isobutyronitrile)
(273 mg, 1.67 mmol), and CCl4 (150 mL) was refluxed for 60 h.
During the reaction, N-bromosuccinimide (4 ꢀ 2.48 g, 4 ꢀ 13.9 mmol)
and azobis(isobutyronitrile) (4 ꢀ 227 mg, 4 ꢀ 1.39 mmol) were
added every 10-14 h. The reaction mixture was cooled to r.t.,
filtered, washed with CCl4, and dried in a vacuum. The crude
product was refluxed in MeOH/CHCl3 (5:1 and 1:1), cooled to
r.t., filtered off, and dried in a vacuum. Yield: 4.98 g (5.67 mmol, 82%)
of a yellowish solid. Decomposition: 218 ꢀC (MeOH/CHCl3).
1H NMR (600 MHz, CDCl3): δ = 7.02 (s, 1H, CH), 4.816
(s, 2H, CH2), 4.814 (s, 2H, CH2). 13C NMR (151 MHz, CDCl3):
δ = 138.0 (2C, quart.), 136.25 (quart.), 136.21 (quart.), 136.20
(quart.), 135.09 (CCl), 135.07 (CCl), 135.0 (CCl), 134.59 (CCl),
134.58 (CCl), 134.03 (CCl), 134.01 (CCl), 133.96 (CCl), 133.7 (CCl),
133.53 (CCl), 133.47 (CCl), 133.46 (CCl), 132.5 (CCl), 56.7 (CH),
4,40-Dimethyltriphenylmethane 1.55 To a solution of 4-methyl-
phenylmagnesium bromide (40.6 g, 237 mmol) in 180 mL diethyl-
ether a solution of p-methylbenzophenone (28.1 g, 143 mmol)
in 150 mL diethylether was added dropwise over a period of
1 h. Subsequently, the red reaction mixture was refluxed for 1 h,
poured onto crushed ice and acidified with 6 N HCl (pH 3-4).
The phases were separated and the aqueous phase was extracted
with diethylether (3ꢀ100 mL). The combined organic extracts
were washed with water (3 ꢀ 100 mL) and dried over MgSO4.
After removal of the solvent formic acid (175 mL, 98-100%) was
added and the dark green mixture was refluxed for 3 h, where-
upon it turned brown. Then it was poured onto crushed ice and
after addition of diethylether the aqueous phase was separated
and extracted with diethylether (3ꢀ75 mL). The combined
organic phases were washed with saturated NaHCO3 until
neutral and dried over MgSO4. Evaporation of the solvent and
purification by flash chromatography (petrol ether/dichloro-
methane 10:1) gave an oily product, which could be crystallized
from n-hexane at -30 ꢀC. Yield: 22.8 g (83.7 mmol, 59%) of
colorless needles. 1H NMR (400 MHz, CDCl3): δ = 7.30-7.24
(m, 2H, phenyl), 7.22-7.17 (m, 1H, phenyl), 7.13-7.10 (m, 2H,
phenyl), 7.09 (AA0, 4H, phenyl), 7.00 (BB0, 4H, phenyl), 5.48
(s, 1H, CH), 2.32 (s, 6H, CH3).
28.9 (2C, CH2).ESIneg.(highresolution):calcdforXþ8of[M]•-
=
C21H5Cl13Br2•-, 876.45291; found, 876.45248 (Δ = 0.50 ppm).
[Bis(4-diethylphosphonomethyl-2,3,5,6-tetrachlorophenyl)-
(2,3,4,5,6-pentachlorophenyl)]methane 4. Under a nitrogen atmo-
sphere, a mixture of 3 (3.42 g, 3.90 mmol) in degassed triethyl
phosphite (15.6 mL) was heated to 180 ꢀC (2 h). Triethyl phosphite
was removed under reduced pressure (155 ꢀC/0.03 mbar at the end
of removal). The crude product was purified by flash chromatog-
raphy (ethyl acetate/acetone 5:1). Yield: 3.54 g (3.57 mmol, 91%)
of a colorless solid. M.p.: 89 ꢀC (ethyl acetate/acetone). 1H NMR
(400 MHz, CD2Cl2): δ = 7.01 (t, 7JPH = 1.9 Hz, 1H, CH), 4.04
(m, 8H, OCH2CH3), 3.73 (d, 2JPH = 22.5 Hz, 4H, CH2), 1.24 (td,
3JHH = 7.1 Hz, 4JPH = 1.3 Hz, 12H, OCH2CH3). 13C NMR (101
MHz, CDCl3, P decoupled): δ = 136.8 (quart.), 136.66 (quart.),
136.63 (quart.), 135.0 (CCl), 134.78 (CCl), 134.76 (2C, CCl), 134.7
(CCl), 133.9 (CCl), 133.75 (CCl), 133.72 (CCl), 133.68 (CCl),
133.67 (CCl), 133.52 (CCl), 133.47 (CCl), 132.69 (quart.), 132.67
(quart.), 132.4 (CCl), 62.5 (4C, OCH2CH3), 56.7 (CH), 33.1 (2C,
CH2), 16.33 (2C, OCH2CH3), 16.32 (2C, OCH2CH3). 31P NMR
(162 MHz, CDCl3): δ = 21.9. ESI pos. (high resolution): calcd for
[Bis(4-methyl-2,3,5,6-tetrachlorophenyl)-(2,3,4,5,6-pentachloro-
phenyl)]methane 2. To a hot solution (70 ꢀC) of S2Cl2 (3.42 g,
25.3 mmol) and anhydrous AlCl3 (1.73 g, 13.0 mmol) in SO2Cl2
(400 mL) a solution of 1 (9.07 g, 33.3 mmol) in SO2Cl2 (200 mL)
was added dropwise over the course of 1 h. After 8 h of heating,
during which the reaction volume was kept constant by addition
of further SO2Cl2, the latter was removed by distillation first
at atmospheric pressure and then in vacuum. Water (500 mL)
was added and the mixture was made basic by the addition of
NaHCO3, whereupon it was heated to reflux during 1 h. The
cooled mixture was acidified with conc. HCl (ca. 50 mL) and the
solid was filtered off and washed with water. The crude product
was repeatedly heated to reflux in n-hexane and filtered off until
the n-hexane filtrate remained colorless. Yield: 15.0 g (20.8 mmol,
63%) of a gray solid. Decomposition: 313 ꢀC (n-hexane). 1H NMR
Xþ6 of [M þ NH4
]
þ þ = C29H29Cl13NO6P2þ, 1009.73325; found,
1009.73317 (Δ = 0.08 ppm).
Poly{[((bis(2,3,5,6-tetrachlorophenyl)-2,3,4,5,6-pentachloro-
phenyl)methane)-4,40-diyl]-alt-[4,40-bis(vinylphenyl)-4-(2-ethyl-
hexyloxy)phenylamine]} 7. Under a nitrogen atmosphere, 4 (475mg,
479 μmol) and 656,57 (200 mg, 466 μmol) were dissolved in dry THF
(4.65 mL). To the yellow solution was added KOtBu (113 mg,
1.01 mmol) in four portions and the mixture was stirred at r.t. for 3 h.
The resulting black, viscous liquid was poured onto 100 mL of
0.01 M HCl to give a yellow precipitate that was stirred for a few
minutes, filtered off, and washed with water and acetone. The crude
product was washed in a Soxhlet apparatus with acetone overnight,
dried, dissolved in THF and precipitated by dropwise addition of the
concentrated THF solution into n-hexane. Yield: 378 mg (339 μmol,
73%) of a yellow solid. Decomposition: 293 ꢀC (THF/n-hexane).
1H NMR (600 MHz, [D8]THF): δ = 7.47 (AA0, 4H, phenyl),
7.13 (s, 1H, CHPCTM), 7.12-7.01 (10H, AA0, BB0 and C-CH=
(600 MHz, CDCl3): δ = 6.99 (s, 1H, CH), 2.62 (s, 6H, CH3). 13
C
NMR (151 MHz, CDCl3): δ = 137.2 (quart.), 137.11 (quart.),
137.09 (quart.), 135.53 (quart.), 135.49 (quart.), 135.2 (CCl),
134.3 (CCl), 134.224 (CCl), 134.220 (CCl), 134.1 (CCl), 134.0
(CCl), 133.32 (CCl), 133.25 (CCl), 133.24 (CCl), 133.22
(CCl), 133.11 (CCl), 133.05 (CCl), 132.2 (CCl), 56.4 (CH),
20.633 (CH3), 20.631(CH3). APCI neg. (high-resolution):
3
CH-C), 6.92 (BB0, 2H, phenyl), 3.88 (d, JHH = 5.6 Hz, 2H,
OCH2(ethylhexyl)), 1.72 (s, 1H, CH(ethylhexyl)),58 1.59-1.30 (m, 8H,
(56) Karastatiris, P.; Mikroyannidis, J. A.; Spiliopoulos, I. K. J. Polym.
Sci. A: Polym. Chem. 2008, 46, 2367–2378.
(57) Hua, J.; Meng, F.; Li, J.; Ding, F.; Fan, X.; Tian, H. Eur. Polym. J.
2006, 42, 2686–2694.
(58) The signal is hidden below the THF signal as confirmed by
comparison with the spectrum in CD2Cl2.
(55) Brook, A. G.; Gilman, H.; Miller, L. S. J. Am. Chem. Soc. 1953, 75,
4759–4765.