Synthesis of photo-crosslinkable hole-transport polymers with tunable oxidation potentials and their use in organic light-emitting diodes

Article abstract of DOI:10.1055/s-2002-32533

A series of photo-crosslinkable arylamine-based hole-transport copolymers has been synthesized. The synthetic methodology employed allows for the redox potential of the polymer to be tuned by the incorporation of electron-donating or -withdrawing moieties. Upon exposure to ultraviolet radiation, the polymers become insoluble, as evidenced by UV/Vis absorption spectroscopy, a feature that is useful for the fabrication of multilayer organic light-emitting diodes (OLEDs) by solution processing techniques. OLEDs based on these hole-transport polymers have been fabricated and the performance of the devices has been evaluated. The photo-crosslinking process has been optimized so that it no longer adversely impacts device performance.

Full text of DOI:10.1055/s-2002-32533

PAPER
1201
Synthesis of Photo-Crosslinkable Hole-Transport Polymers with Tunable
Oxidation Potentials And Their Use In Organic Light-Emitting Diodes
S
ynthesis of Phot
i
o-Cros
c
slinkable
H
h
ole-Transpo
a
rt Polymer
s
rd D. Hreha,a Ya-Dong Zhang,a Benoit Domercq,b Nathalie Larribeau,b Joshua N. Haddock,b
Bernard Kippelen,*b Seth R. Marder*a,b
a
Department of Chemistry, The University of Arizona, Tucson, AZ 85721, USA
b
Optical Sciences Center, The University of Arizona, Tucson, AZ 85721, USA
E-mail: smarder@u.arizona.edu
Received 19 March 2002
work, the efficiency of devices was impaired by the pho-
to-crosslinking step. Here we report an extension of this
work entailing the synthesis and characterization of a new
set of variable-redox-potential photo-crosslinkable side-
Abstract: A series of photo-crosslinkable arylamine-based hole-
transport copolymers has been synthesized. The synthetic method-
ology employed allows for the redox potential of the polymer to be
tuned by the incorporation of electron-donating or -withdrawing
moieties. Upon exposure to ultraviolet radiation, the polymers be- chain acrylate polymers. We also describe fabrication of
come insoluble, as evidenced by UV/Vis absorption spectroscopy,
OLED devices based upon these new polymers. The de-
a feature that is useful for the fabrication of multilayer organic light-
vice fabrication conditions have been optimized using
emitting diodes (OLEDs) by solution processing techniques.
these new polymers to minimize the decrease in the de-
OLEDs based on these hole-transport polymers have been fabricat-
vice performance that had been previously reported.15
ed and the performance of the devices has been evaluated. The pho-
to-crosslinking process has been optimized so that it no longer
adversely impacts device performance.
Results and Discussion
Key words: hole-transport agents, photo-crosslinked polymers, or-
ganic light-emitting diodes, bis(diarylamino)biphenyls
We designed a series of methacrylate-based photo-
crosslinkable polymers in which bis(diarylamino)biphe-
nyl moieties are the hole-transport agent. As in our previ-
ous work,4,15 this group was chosen since such molecules
are widely used in vapor-deposited small-molecule-based
OLEDs due to their high hole mobilities and their tunable
orbital energies. Since we have previously found the de-
vice characteristics of bis(diarylamino)biphenyl-styrene
polymers to depend strongly on the orbital energies of the
polymers,4 we designed the new polymers to have a varie-
ty of redox potentials to allow tuning of the relative rates
of injection of holes into the polymer. The new polymers
also differ from those in reference15 in the linker between
the bis(diarylamino)biphenyl and the acrylate polymer
backbone.
Introduction
Light-emitting diodes (LEDs) based on organic small
molecules1,2 or polymeric materials3,4 have recently at-
tracted considerable interest due to their potential applica-
tion in flat-panel displays.5 To date, the most efficient
devices are multilayer structures composed of hole-trans-
port, emitting, and electron-transport layers sandwiched
between an anode and a cathode.6 Multilayer organic
light-emitting diodes (OLEDs) based on small molecules
can be fabricated by sequential vapor deposition of each
layer in high vacuum. However, OLED fabrication using
solution-based methods must be used for non-volatile
polymeric materials. However, for solution-based fabrica-
tion of multilayer OLEDs it is necessary that the first layer
is not dissolved during the deposition of a subsequent lay-
er. One approach that has been employed to circumvent
this problem is to render a material insoluble subsequent
to application by using either photo-induced or thermal
crosslinking reactions.7 Recently, photo-crosslinkable
polymers, as well as thermally crosslinkable oligomers,
for OLEDs have been reported.8–10 Recently, we reported
on a series of photo-crosslinkable side-chain acrylate
polymers containing a bis(diarylamino)biphenyl hole-
transport agent and cinnamate11,12 and chalcone13,14
groups as photo-crosslinking groups.15 In this earlier
The syntheses and molecular structures of the hole-trans-
port methacrylate-type monomers and the photo-
crosslinkable monomers are shown in Schemes 1–3. The
monomers 1-OMe, 1-Me, 1-F and 1-F2 were synthesized
from hydroxyl-containing compounds by reaction with
methacrylic acid using 1,3–dicyclohexylcarbodiimide
(DCC) as a dehydrating agent and 4-dimethylaminopyri-
dine (DMAP) as a catalyst. The monomers 1-Me, 1-F2,
and 12 were obtained in pure form by column chromato-
graphy on silica gel, eluting with a 7:3 ratio of dichlor-
omethane–hexanes; monomer 1-OMe was purified by
column chromatography on silica gel, eluting with
dichloromethane. Pure monomer 1-F was obtained by re-
precipitation of the crude product from tetrahydrofuran
(THF) into methanol (purification on silica gel was initial-
ly avoided as similar compounds reportedly decompose
on silica gel; however, this was not observed with com-
pounds 1-OMe, 1-Me, and 1-F2).15 The cores of the hole-
Synthesis 2002, No. 9, Print: 01 07 2002.
Art Id.1437-210X,E;2002,0,09,1201,1212,ftx,en;C11302SS.pdf.
© Georg Thieme Verlag Stuttgart · New York
ISSN 0039-7881

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R. D. Hreha et al.
PAPER
transport monomers were built up from compound 2, mophenol respectively, which was reacted with 3-bro-
which was obtained from the iodination of 4-bromobiphe- mopropanol under nucleophilic substitution conditions.
nyl using iodine and nitric acid. The amines 7-OMe, 7- The alcohol was then converted to the silyl ether 4 or the
Me, 7-F, 7-F2 were coupled to compound 2 selectively at trityl ether 5. The tert-butyldimethylsilyl (TBDMS) pro-
the iodine functionality using tris(dibenzylideneace- tecting group is preferred due to the ease which it can be
tone)dipalladium [Pd2(dba)3] and 1,1 -bis(diphenylphos- installed and removed. Monomer 1-OMe, was homopoly-
phino)ferrocene (DPPF) as the catalyst system in the merized and monomers 1-OMe, 1-Me, 1-F and 1-F2 were
presence of sodium t-butoxide.16 In our previous work copolymerized with 30% (mole ratio) of crosslinkable
with 4,4 -dibromobiphenyl we observed coupling of pri- monomer 12 using 2,2 -azobis(isobutyronitrile) (AIBN)
mary amines at both bromine positions leading to N,N - as an initiator under argon at 60 °C for 60 hours (as shown
diphenyl-1,1 -biphenyl-3,4-diamine structures.15 When in Scheme 4). The polymers were obtained in pure form
compound 2 is coupled to one equivalent of an amine as white powders by precipitation three times, once from
there appears to be complete selectivity for reaction at the benzene into methanol and twice from THF into metha-
iodine as none of the bromine-coupling product was seen. nol. The structure of the compounds and polymers were
The amines 6-OMe, 6-Me, 6-F and 6-F2 were then cou- confirmed by NMR spectroscopy and elemental analysis
1
pled at the bromine using the same conditions. The sec- (as shown in the experimental section). The H NMR
ondary amines 6-OMe, 6-Me, 6-F, 6-F2, 7-OMe, 7-Me, spectra of the copolymers exhibited extensive broadening
7-F, and 7-F2 were themselves synthesized under the of the peaks leading to peak overlap and undiscernible
same conditions (as shown in Scheme 3). The alcohols 3 multiplicities.
and 3-Br were synthesized from 4-iodophenol or 4-bro-
Scheme 1 Synthesis of monomers 1-OMe, 1-Me, 1-F, and 1-F2
Synthesis 2002, No. 9, 1201–1212 ISSN 0039-7881 © Thieme Stuttgart · New York

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Synthesis of Photo-Crosslinkable Hole-Transport Polymers
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Scheme 2 Synthesis of secondary amines
Scheme 3 Synthesis of monomer 12 with crosslinkable units
Scheme 4 Synthesis of the polymers
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R. D. Hreha et al.
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Each of the polymers was readily soluble in common or- crosslinkable units, and homopolymer 14, which has no
ganic solvents including THF, chloroform, toluene, ben- bis(diarylamino)biphenyl units, were synthesized for
zene and dichloromethane. The glass-transition comparison with 13-OMe and subjected to the same
temperatures (Tg) of the polymers were determined by dif- crosslinking conditions as 13-OMe. The homopolymer 14
ferential scanning calorimetry (DSC). The glass-transi- exhibited a decrease in absorbance at 310 nm similar to
tion temperatures of polymers 13-OMe, 13-Me, 13-F, 13- that seen for 13-OMe, while there was no decrease in ab-
F2 and 15-OMe are 97, 108, 99, 97, and 123 °C respec- sorbance of 15-OMe, confirming that the decrease in ab-
tively. There was no evidence of other thermal process in sorption is predominantly due to the [2+2] cycloaddition
the temperature range investigated (from 25 to 250 °C), reaction and that the bis(diarylamino)biphenyl moieties
suggesting that the polymers prepared are amorphous.
are relatively stable under the crosslinking conditions.
The redox potentials of the monomers 1-OMe, 1-Me, 1-F The irradiated polymer 13-OMe, 13-Me, 13-F, 13-F2, and
and 1-F2 versus ferrocenium/ferrocene were determined 14 films on quartz substrates were used to demonstrate the
by cyclic voltammetry in dichloromethane (Table). The insolubility of the polymers after UV irradiation. The UV
cyclic voltammograms show two sequential reversible absorption spectra were acquired after dipping the films in
one-electron processes corresponding to the successive THF for increasing lengths of time. Even after soaking the
removal of two electrons from the bis(diarylamino)biphe- films up to 80 minutes, no measurable decrease (<1%
nyl unit. The compounds 1-OMe, 1-Me, 1-F and 1-F2 change in absorbance) in absorption was observed sug-
demonstrate the expected trend of increasing redox poten- gesting that the polymers were crosslinked. In compari-
tial as the electron-donating substituents on the bis(diary- son, for non-irradiated films of 13-OMe, 13-Me, 13-F,
lamino)biphenyl moiety are replaced with electron- 13-F2, and 14 on quartz, it was found that the absorption
withdrawing substituents. The effects of the substituents intensities dramatically decreased after dipping the films
parallel those seen in similarly substituted non-polymeriz- in THF for 1 minute. The same large decrease in absorp-
able molecular bis(diarylamino)biphenyls and bis(diaryl- tion was found for an exposed film of 15-OMe on a quartz
amino)biphenyl-functionalized polyolefins.4 However, substrate. These observations indicate that the crosslinked
the potentials in the present compounds are somewhat copolymers are insoluble in THF and that the insolubility
lower, presumably due to the electron-donating nature of is not a result of the exposure of the bis(diarylamino)bi-
the ether linkage to the polymerizable group.
phenyl moiety to UV light, but due to the [2+2] cycload-
dition reaction of the cinnamate moiety.
a
Table Redox Potentials of Hole-Transport Monomers in CH2Cl2
In subsequent studies, copolymers containing 70 mol% of
these monomers and 30 mol% of cinnamate substituted
acrylate monomer could be photo-crosslinked using the
UV radiation (350 nm) provided by a standard UV-mask
aligner. As was the case with the handheld UV source ex-
periments (see above), the absorption band characteristic
of the bis(diarylamino)biphenyl moiety at 353 nm does
not vary upon UV exposure, whereas the cinnamate ab-
sorption band at 312 nm decreases as a function of UV ex-
posure (Figure 1). To efficiently crosslink the polymer
and make it insoluble, a minimum of 20 mJ/cm2 of UV ex-
posure was found to be required. We have been able to use
standard lithographic techniques to pattern these materi-
als. For instance, using a negative photolithography mask,
we have been able to define features ranging from 50 to
10 m as shown in Figure 1b.
Monomer
1-OMe
1-Me
1E1/2(mV)
105
2E1/2(mV)
360
190
470
1-F
300
540
1-F2
320
595
a Values are reported relative to the ferrocenium/ferrocene couple.
The crosslinking of the polymers upon UV-irradiation
was monitored by UV spectroscopy. In initial experi-
ments, thin films of polymers 13-OMe, 13-Me, 13-F, 13-
F2, 14 and 15-OMe were obtained on a quartz substrate by
spin-coating at 3000 rpm from THF solution (20 mg in 1
mL of THF). The polymer films were irradiated with an
unfiltered handheld UV source (365 nm, 7 W, UVGL-25)
for visualizing thin layer chromatography plates. The
films were kept 1.7 cm from the UV lamp. The progress
of the crosslinking was monitored by UV/Vis spectrosco-
py; the absorbance at 310 nm, attributed to the cinnamate
group, was found to decrease, whilst that at 353 nm, at-
tributed to the bis(diarylamino)biphenyl moiety remained
constant, suggesting that the cinnamate moieties undergo
[2+2] cycloaddition without photo-induced damage to the
hole-transport groups. To confirm these attributions and
this hypothesis, and to remove complications in interpre-
tation arising from some overlap between the 310 and 353
nm absorptions, homopolymer 15-OMe, which has no
Fabrication and Characterization of Light-Emitting
Devices
To investigate the performance of the hole-transport poly-
mers 13-OMe, 13-Me, 13-F, and 13-F2, 15-OMe in de-
vice geometry, we fabricated OLEDs with the following
structure: ITO/polymer (13-OMe or 13-Me or 13-F or 13-
F2,)/AlQ3/Mg:Ag. AlQ3 [aluminum tris(8-hydroxyquino-
linate)] was chosen as an electron-transport and emitting
material because its performance when combined with
other hole-transport materials is well documented. The
films of about 50 to 60 nm thickness were prepared by
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Synthesis of Photo-Crosslinkable Hole-Transport Polymers
1205
Figure 1 (a) Evolution of the absorption spectra of a 50 nm thick film of 13-OMe under UV exposure. (b) Photograph of 50 m sized features
obtained after photo-crosslinking (25 mJ/cm2) of a 60 nm thin film of 13-OMe. (c) Evolution of the absorption spectra of a film of 14 under
UV exposure. (d) Evolution of the absorption spectra of a film of 15 under UV exposure.
spin coating polymers 13-OMe, 13-Me, 13-F and 13-F2 Figure 2 shows the typical characteristic of an ITO/ 13-F
onto O2-plasma-treated ITO with sheet resistance of 20 /AlQ3/Mg:Ag device. The current density exhibits a typi-
/p (Colorado Concept Coatings, L.L.C.) from toluene cal diode behavior with a strong rectification above 2 V.
solutions. Then, 60 nm-thick AlQ3 films were vapor de- The light is first detected around 3 V. The external quan-
posited at a rate of 1 Å/s under a pressure of 1 10–6 Torr tum efficiency for 13-F-based devices reaches a maxi-
on top of the hole-transport layer. The metal cathode, a mum value of 1.2% at around 8 V with a luminance of
1:10 alloy of silver and magnesium, was deposited 1320 cd/m2.
through a mask to define five devices, each with an emis-
Upon crosslinking, we have previously reported that the
sive area of 0.1 cm2.
performance of OLEDs devices decreases significantly.15
OLED devices using these new polymers exhibit perfor- Optimization of UV exposure to minimize any adverse ef-
mances comparable to those of their wholly vapor-depos- fects is, therefore, critical for device performance. We
ited equivalents. The light emission of all the devices have investigated the dependence of the device perfor-
corresponds to the typical AlQ3 emission spectrum. mance as a function of the UV exposure for devices with
Figure 2 (a) Current density, and (b) luminance and external quantum efficiency as a function of applied voltage for a ITO/13-F /AlQ3/Mg:Ag
[50 nm/50 nm/300 nm (10:1)] device.
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R. D. Hreha et al.
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eluting with EtOAc–CH2Cl2 (1:49). The solvent was removed under
reduced pressure and the residual solvent was removed in vacuo.
The yield of the desired product, isolated as white crystals, was
26.30 g (84%).
1H NMR (500 MHz, CDCl3): = 1.69 (s, 1 H), 2.04 (quint, J = 6.0
Hz, 2 H), 3.86 (t, J = 6.0 Hz, 2 H), 4.09 (t, J = 6.0 Hz, 2 H), 6.69 (d,
J = 7.0 Hz, 2 H), 7.56 (d, J = 7.0 Hz, 2 H).
structure ITO/13-F/AlQ3/Mg:Ag. For each device, the
hole-transport polymer was spin-coated and crosslinked
using different UV energy densities ranging from 0 mJ/
cm2 to 180 mJ/cm2. The AlQ3 layer was then deposited on
all the samples during the same deposition run. We found
that for UV exposure energies of up to 30 mJ/cm2, which
are adequate to render the films insoluble; there is no mea-
surable decrease in the performance of the devices relative
to the uncrosslinked material. Presumably this level of
UV dosage leads to sufficient cross-linking to confer in-
solubility, yet insufficient decomposition of the
bis(diarylamino)biphenyl moities to adversely affect fac-
tors governing device performance, such as charge mobil-
ity. Detailed device fabrication and characterization
studies are currently in progress, and will be published in
due course.
13C NMR (125 MHz, CDCl3): = 31.8, 60.2, 65.6, 82.9, 116.8,
138.2, 158.56.
3-(4-Bromophenoxy)propan-1-ol (3-Br)19
To a 500 mL round bottom flask was added 4-bromophenol (32.22
g, 186 mmol), 3-bromopropanol (31.06 g, 224 mmol), DMF (50
mL) and K2CO3 (43.2 g, 313 mmol). The reaction mixture was
stirred at r.t. and the reaction was followed by TLC. Upon the dis-
appearance of 4-iodophenol, the mixture was poured into a separa-
tory funnel containing H2O (100 mL). The product was extracted
with EtOAc and the organic layer was washed with cold water (3
50 mL) and brine (50 mL). The solvent was removed under reduced
pressure and the residue was purified by flash chromatography on
silica gel, eluting with CH2Cl2. The solvent was removed under re-
duced pressure and the residual solvent was removed in vacuo. The
yield of the desired product, isolated as white crystals, was 37.2 g
(93%).
1H NMR (500 MHz, CDCl3): = 2.01 (quint, J = 6.0 Hz, 2 H), 2.25
(s, 1 H), 3.82 (t, J = 6.0 Hz, 2 H), 4.05 (t, J = 6.0 Hz, 2 H), 6.77 (d,
J = 9.0 Hz, 2 H), 7.35 (d, J = 9.0 Hz, 2 H).
13C NMR (125 MHz, CDCl3): = 31.9, 59.9, 65.6, 112.9, 116.2,
132.2, 157.8.
Chemicals received from commercial sources were used without
further purification. The synthesis of compound 11 was reported
previously.15 NMR spectra were recorded with a Varian Unity Plus
spectrometer at 500 MHz (1H) and 126 MHz (13C) in CDCl3 or ac-
etone-d6 unless otherwise stated. Spectra were internally referenced
1
relative to TMS [ (1H) = 0; (13C) = 0] using either the TMS H
resonance or the 13C resonance of the solvent. UV/Vis spectra were
recorded as thin films on quartz substrates with a Hewlett Packard
8453 spectrometer. GC-MS spectra were run on a Hewlett Packard
HP6890 GC with a Hewlett Packard 5973 mass spectrometer. The
glass-transition temperatures were determined by thermal analysis
using a Shimadzu DSC-50 differential scanning calorimeter run at
10°/min. Cyclic voltammetry was performed under argon using ca.
10–4 M solutions in sample and 0.1 M in Bu4N+PF6– using a glassy-
carbon working electrode, a platinum auxiliary electrode, a AgCl/
Ag pseudo-reference electrode, and a BAS 100B potentiostat. Po-
tentials were referenced by the addition of ferrocene to the cell, and
are quoted to the nearest 5 mV relative to the ferrocenium/ferrocene
couple at 0 V.
tert-Butyl[3-(4-iodophenoxy)propoxy]dimethylsilane (4)
To a dry 250 mL round bottom flask under N2 was added 3 (26.3 g,
94.5 mmol), tert-butyldimethylsilyl chloride (17.82 g, 118.2
mmol), imidazole (8.1 g, 118.2 mmol) and DMF (50 mL). The re-
action mixture was stirred while the progress of the reaction was
monitored by TLC. Upon the disappearance of the starting material,
the mixture was poured into a separatory funnel containing cold wa-
ter (100 mL). The product was extracted with Et2O (3 50 mL). The
Et2O layers were combined and washed with cold water (3 100
mL) and brine (3 45 mL). The solvent was removed under reduced
pressure and the residue was purified by flash chromatography elut-
ing with 1:4 CH2Cl2–hexanes. The solvent was removed under re-
duced pressure and the residual solvent was removed in vacuo. The
mass of the purified product isolated as colorless oil was 37.08 g
( 100%). The purity of the product was estimated to be greater than
95% by 1H NMR and was used in the next step without further pu-
rification.
4-Bromo-4 -iodo-1,1 -biphenyl (2)17
4-Bromobiphenyl (49.83 g, 214 mmol), I2 (32.5 g, 128.4 mmol) and
CCl4 (100 mL) were added to a 500 mL round bottom flask
equipped with an efficient reflux condenser. The mixture was heat-
ed to 50 °C and was stirred while concd HNO3 (24.0 g, 385 mmol,
17.0 mL) was added over 30 min. After all the HNO3 was added, the
mixture was gently refluxed until GC-MS showed none of the 4-
bromobiphenyl. The mixture was extracted with toluene and the
oily layer was washed with conc. HNO3 (3 10 mL). The material
was washed with 10% aq NaOH (50 mL) and dried (MgSO4). The
solvent was removed under reduced pressure and the pale brown
crystals were recrystallized from hot hexanes. The purified product
was isolated as white crystals (58.61 g, 77%).
1H NMR (500 MHz, CDCl3): = 0.58 (s, 6 H), 0.88 (s, 9 H), 1.97
(quint, J = 6.0 Hz, 2 H), 3.79 (t, J = 6.0 Hz, 2 H), 4.03 (t, J = 6.0 Hz,
2 H), 6.69 (d, J = 9.0 Hz, 2 H), 7.54 (d, J = 9.0 Hz, 2 H).
13C NMR (125 MHz, (CDCl3): = –2.98, 18.29, 25.89, 32.18,
59.28, 64.47, 82.48, 116.85, 139.11, 158.89.
1H NMR (500 MHz, CDCl3): = 7.29 (d, J = 8.0 Hz, 2 H), 7.42 (d,
J = 8.0 Hz, 2 H), 7.57 (d, J = 8.0 Hz, 2 H), 7.77 (d, J = 8.0 Hz, 2 H).
GC-MS: m/z (rel. int., %) = 358, 360 (1:1, 100, M+).
HRMS: m/z calcd for C15H26IO2Si 393.0747, found 393.0754.
1-Bromo-4-[3-(trityloxy)propoxy]benzene (5)
3-(4-Iodophenoxy)propan-1-ol (3)18
To a solution of 3-Br (18.0 g, 78.0 mmol) and triphenylmethyl-
chloride (21.77 g, 78 mmol) in pyridine (40 mL) under N2, was add-
ed 4-dimethylaminopyridine (150 mg, 1.2 mmol). The solution was
stirred at 70 °C for 32 h and the progress of the reaction was moni-
tored by TLC. The pyridine was removed under reduced pressure
and the material was dissolved in CH2Cl2 (100 mL) and the CH2Cl2
layer was washed with cold water (3 50 mL). The crude material
was purified by flash chromatography on silica gel, eluting with
CH2Cl2. The material was further purified by column chromatogra-
phy on silica gel, eluting with hexanes–EtOAc (3:1). The solvent
To a 500 mL round bottom flask was added 4-iodophenol (24.9 g,
113 mmol), 3-bromopropanol (18.9 g, 136 mmol), DMF (100 mL)
and K2CO3 (31.2 g, 226 mmol). The reaction mixture was stirred at
r.t. and the reaction was followed by TLC. Upon the disappearance
of 4-iodophenol, the mixture was poured into a separatory funnel
containing H2O (100 mL). The product was extracted with EtOAc
and the organic layer was washed with cold water (3 50 mL) and
brine (50 mL). The solvent was removed under reduced pressure
and the residue was purified by flash chromatography on silica gel,
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Synthesis of Photo-Crosslinkable Hole-Transport Polymers
3-Fluoro-N-{4-[3-(trityloxy)propoxy]phenyl}aniline (6-F)
1207
was removed under reduced pressure and the residual solvent was
removed in vacuo. The yield of product isolated as a viscous oil was
37.1 g ( 100%). The purity of the product was estimated greater
than 95% by 1H NMR and was used in the next step without further
purification.
1H NMR (500 MHz, CDCl3): = 2.06 (quint J = 6 Hz, 2 H), 3.28 (t,
J = 6 Hz, 2 H), 4.10 (t, J = 6 Hz, 2 H), 6.76 (d, J = 9 Hz, 2 H), 7.26
(m, 9 H), 7.37 (d, J = 9 Hz, 6 H), 7.43 (m, 6 H).
To a dry 250 mL round bottom flask under argon, were added 3-flu-
oroaniline (4.3 g, 38 mmol), 5 (14.58 g, 31 mmol) and toluene (50
mL). The mixture was deoxygenated for 10 min and then Pd2(dba)3
(0.6 g, 0.7 mmol) and DPPF (0.6 g, 1.1 mmol) were added. After
stirring for 10 min, t-BuONa (4.8 g, 50 mmol) was added. The tem-
perature was increased to 90 °C using an oil bath and the reaction
mixture was stirred while the progress of the reaction was moni-
tored by TLC. Upon the disappearance of the starting material the
mixture was filtered through a plug of silica gel eluting with
CH2Cl2. The product was purified by column chromatography on
silica gel, eluting with toluene. The solvent was removed under re-
duced pressure. The residual solvent was removed in vacuo; pale
yellow glass; yield: 12.71 g (83%).
13C NMR (75 MHz, (CDCl3): = 29.76, 59.73, 65.02, 86.45,
112.59, 116.27, 126.88, 127.21, 127.70, 127.88, 128.58,
132.11,144.11, 157.96.
HRMS: m/z calcd for C28H25BrO2 472.1038, found 472.1034.
1H NMR (500 MHz, CDCl3): = 2.10 (quint, J = 6.0 Hz, 2 H), 3.32
(t, J = 6.5 Hz, 2 H), 4.15 (t, J = 6.5 Hz, 2 H), 5.58 (s, 1 H), 6.51 (dt,
J = 2.5 Hz, 9.0 Hz, 1 H), 6.20 (m, 2 H), 6.88 (d, J = 7.5 Hz, 2 H),
7.10 (d, J = 8.5 Hz, 2 H), 7.14 (q, J = 8.0 Hz, 1 H), 7.26 (m, 9 H),
7.46 (d, J = 7.0 Hz, 6 H).
13C NMR (125 MHz, CDCl3): = 29.94, 59.94, 65.18, 86.48,
101.45, 101.65, 105.50, 105.67, 110.67, 115.37, 123.40, 126.90,
127.74, 128.66, 130.34, 130.41, 134.34, 144.21, 147.41, 147.48,
155.31, 162.95, 164.88.
N-[4-(3-{tert-Butyl(dimethyl)silyl]oxy}propoxy)phenyl]-3-
methylaniline (6-Me)
To a dry 500 mL round bottom flask under argon were added 4
(13.64 g, 35.8 mmol), m-toluidine (4.5 g, 41.2 mmol), and toluene
(100 mL). The mixture was deoxygenated for 10 min and then
Pd2(dba)3 (0.4 g, 0.44 mmol) and DPPF (0.5 g, 0.88 mmol) were
added. After stirring for 10 min, t-BuONa (3.9 g, 41.2 mmol) was
added. The reaction mixture was heated to 90 °C and stirred while
the progress of the reaction was monitored by TLC. Upon the dis-
appearance of the starting material, the mixture was filtered through
a plug of silica gel eluting with CH2Cl2. The product was purified
by flash chromatography eluting with CH2Cl2–hexanes (1:1). The
solvent was removed in vacuo to give 10.26 g (77%) of the desired
product as a brown oil.
Anal. Calcd for C34H30FNO2: C, 81.09; H, 6.00; N, 2.76. Found: C,
81.42; H, 6.12; N, 2.98.
HRMS: m/z calcd for C34H30FNO2 503.2261, found 503.2245.
1H NMR (500 MHz, CDCl3): = 0.70 (s, 6 H), 0.91 (s, 9 H), 2.00
(quint, J = 6 Hz, 2 H), 2.29 (s, 3 H), 3.82 (t, J = 6 Hz, 2 H), 4.06 (t,
J = 6 Hz, 2 H), 5.46 (s, 1 H), 6.67 (d, J = 7 Hz, 1 H), 6.73 (d, J = 7
Hz, 2 H), 6.87 (d, J = 9 Hz, 2 H), 7.06 (d, J = 8 Hz, 2 H), 7.11 (t,
J = 8 Hz, 1 H).
13C NMR (125 MHz, CDCl3): = –5.15, 18.55, 21.77, 26.14, 32.70,
59.80, 65.05, 112.91, 115.47, 116.43, 120.58, 122.44, 129.33,
135.87, 145.39,154.89.
N-[4-(3-{tert-Butyl(dimethyl)silyl]oxy}propoxy)phenyl]-2,4-dif-
luoroaniline (6-F2)
To a dry 500 mL round bottom flask under argon, were added 4
(18.44 g, 47.0 mmol), 2,4-difluoroaniline (6.5 g, 51.0 mmol), and
toluene (100 mL). The mixture was deoxygenated for 10 min and
then Pd2(dba)3 (0.65 g, 0.71 mmol) and DPPF (0.8 g, 1.40 mmol)
were added. After stirring for 10 min, t-BuONa (5.1 g, 54.0 mmol)
was added. The temperature was raised to 90 °C and the reaction
mixture was stirred while the progress of the reaction was followed
by TLC. Upon the disappearance of the starting material, the mix-
ture was filtered through a plug of silica gel eluting with CH2Cl2.
The product was purified by column chromatography eluting with
CH2Cl2–hexanes (1:4). The solvent was removed under reduced
pressure. The residual solvent was removed in vacuo to furnish 5.09
g (28%) of the desired product as a brown oil.
1H NMR (500 MHz, CDCl3): = 0.05 (s, 6 H), 0.88 (s, 9 H), 1.99
(quint, J = 6 Hz, 2 H), 3.81 (t, J = 6 Hz, 2 H), 4.05 (t, J = 6 Hz, 2 H),
5.43 (s, 1 H), 6.72 (tq, J = 8.5 Hz, 1.5 Hz, 1H), 6.87 (m, 3 H), 7.01
(m, 3 H).
13C NMR (125 MHz, (CDCl3): = –5.18, 18.52, 26.12, 32.64,
59.71, 65.02, 103.88, 104.06, 104.26, 110.76, 110.79, 110.94,
110.96, 115.59, 116.26, 116.29, 116.33, 116.36, 122.41, 130.22,
130.31, 135.00, 151.09, 151.18, 153.03, 153.11, 154.79, 154.88,
155.29, 156.71, 156.80.
Anal. Calcd for C22H33NO2Si Found: C, 70.84; H, 8.84; N, 3.80.
HRMS: m/z calcd for C22H33NO2Si 372.2359, found 372.2348.
N-[4-(3-{tert-Butyl(dimethyl)silyl]oxy}propoxy)phenyl]-4-
methoxyaniline (6-OMe)
To a dry 500 mL round bottom flask under argon, were added 4
(13.84 g, 35.3 mmol), 4-methoxyaniline (5.1 g, 41.0 mmol), and tol-
uene (100 mL). The mixture was deoxygenated for 10 min and then
Pd2(dba)3 (0.61 g, 0.56 mmol) and DPPF (0.7 g, 1.12 mmol) were
added. After stirring for 10 min, t-BuONa (4.3 g, 45.0 mmol) was
added. The reaction mixture was heated to 90 °C and was stirred
while the progress of the reaction was followed by TLC. Upon the
disappearance of the starting material, the mixture was filtered
through a plug of silica gel eluting with CH2Cl2. The product was
purified by flash chromatography eluting with CH2Cl2–hexanes
(7:3). The solvent was removed in vacuo to afford 8.50 g (62%) of
the product as a brown oil.
HRMS: m/z calcd for C21H29F2NO2Si 393.1936, found 393.1939.
1H NMR (500 MHz, acetone-d6): = 0.07 (s, 6 H), 0.90 (s, 9 H),
1.94 (quint, J = 6 Hz, 2 H), 3.74 (s, 3 H), 3.83 (t, J = 6 Hz, 2 H), 4.04
(t, J = 6 Hz, 2 H), 6.79 (s, 1 H), 6.84 (m, 4 H), 6.97 (m, 4 H).
13C NMR (125 MHz, acetone-d6): = –2.88, 21.11, 28.60, 35.66,
57.99, 62.45, 67.64, 117.61, 118.35, 121.75, 121.82, 125.71,
141.56, 156.29, 156.93.
Anal. Calcd for C21H29F2NO2Si: C, 64.09; H, 7.43; N, 3.56. Found:
C, 64.22; H, 7.52; N, 3.58.
N-(4-Methoxyphenyl)-3-methylaniline (7-OMe)20
To a dry 500 mL round bottom flask under argon were added 4-io-
doanisole (14.7 g, 67.1 mmol), m-toluidine (7.5 g, 70.0 mmol), and
toluene (100 mL). The mixture was deoxygenated for 10 min and
then Pd2(dba)3 (1.2 g, 1.3 mmol) and DPPF (1.5 g, 2.7 mmol) were
added. After stirring for 10 min, t-BuONa (12.5 g, 127 mmol) was
added. The temperature was raised to 90 °C and the reaction mix-
ture was stirred while the progress of the reaction was followed by
TLC. Upon the disappearance of the starting material, the reaction
Anal. Calcd for C22H33NO3Si: C, 68.17; H, 8.58; N, 3.61. Found: C,
68.19; H, 8.38; N, 3.63.
HRMS: m/z calcd for C22H33NO3Si 387.2230, found 387.2231.
Synthesis 2002, No. 9, 1201–1212 ISSN 0039-7881 © Thieme Stuttgart · New York

1208
R. D. Hreha et al.
PAPER
mixture was filtered through a plug of silica gel, eluting with
CH2Cl2. The product was purified by flash chromatography eluting,
with CH2Cl2–hexanes (3:7). The solvent was removed under re-
duced pressure. The residual solvent was removed in vacuo to give
7.80 g (59%) of the desired product as a pale yellow oil.
1H NMR (500 MHz, CDCl3): = 2.30 (s, 3 H), 3.81 (s, 3 H), 5.47
(s, 1 H), 6.68 (m, 2 H) 6.87 (d, J = 7.5 Hz, 2 H), 7.12 (m, 3 H).
N-(3-Methylphenyl)-N-phenyl-4-bromo-1,1 -biphenyl-4 -amine
(8-Me)21
To a dry 250 mL round bottom flask under argon were added 3-me-
thyldiphenylamine (8.41 g 47.0 mmol), 2 (20.0 g, 55.9 mmol) and
toluene (50 mL). The mixture was deoxygenated for 10 min and
then Pd2(dba)3 (0.77 g, 0.8 mmol) and DPPF (0.93 g, 1.6 mmol)
were added. After stirring for 10 min, t-BuONa (5.6 g, 58 mmol)
was added. The temperature of the reaction was raised to 90 °C
while the progress of the reaction was monitored by TLC. Upon the
disappearance of the starting material, the mixture was filtered
through a plug of silica gel, eluting with CH2Cl2. The product was
purified by flash chromatography, eluting with a solution of hex-
anes–CH2Cl2 (1:1). The solvent was removed under reduced pres-
sure. The residual solvent was removed in vacuo to afford 6.76 g
(35%) of the desired product as white crystals.
1H NMR (500 MHz, CDCl3): = 2.29 (s, 3 H), 6.88 (d, J = 7.5 Hz,
1 H), 6.93 (m, 2 H), 7.05 (t, J = 7.5 Hz, 1 H), 7.12 (m, 4 H), 7.17 (t,
7.5 Hz, 1 H), 7.28 (m, 2 H), 7.44 (m, 4 H), 7.54 (d, J = 7.5 Hz, 2 H).
13C NMR (125 MHz, CDCl3): = 21.40, 120.80, 121.88, 122.91,
123.53, 124.10, 124.43, 127.46, 125.32, 127.46, 128.14, 129.10,
129.23, 131.76, 133.36, 139.19, 139.54, 147.39, 147.57.
13C NMR (125 MHz, CDCl3): = 21.56, 55.54, 112.72, 114.60,
116.26, 120.43, 122.18, 129.13, 139.14.
N-(3-Fluorophenyl)-N-(3-methylphenyl)amine (7-F)
To a dry 500 mL round bottom flask under argon were added 1-flu-
oro-3-iodobenzene (22.1 g, 100 mmol), m-toluidine (12.5 g, 116
mmol), and toluene (100 mL). The mixture was deoxygenated for
10 min and then Pd2(dba)3 (1.2 g, 1.3 mmol) and DPPF (1.5 g, 2.7
mmol) were added. After stirring for 10 min, t-BuONa (12.5 g, 127
mmol) was added. The reaction mixture was stirred while the
progress of the reaction was followed by TLC. Upon the disappear-
ance of the starting material, the mixture was filtered through a plug
of silica gel, eluting with CH2Cl2. The product was purified by flash
chromatography, eluting with CH2Cl2–hexanes (3:2). The solvent
was removed under reduced pressure. The residual solvent was re-
moved in vacuo and 18.62 g (93%) of the product was isolated as a
pale yellow oil.
N-(4 -Bromo-1,1 -biphenyl-4-yl)-N-(4-methoxyphenyl)-N-(3-
methylphenyl)amine (8-OMe)
To a dry 250 mL round bottom flask under argon were added 7-
OMe (7.78 g 36.5 mmol), 2 (14.3 g, 40.0 mmol) and toluene (50
mL). The mixture was deoxygenated for 10 min and Pd2(dba)3 (0.55
g, 0.6 mmol) and DPPF (0.6 g, 1.2 mmol) were added. After stirring
for 10 min, t-BuONa (3.9 g, 40 mmol) was added. The temperature
was raised to 90 °C and the reaction mixture was stirred while the
progress of the reaction was monitored by TLC. Upon the disap-
pearance of the starting material the mixture was filtered through a
plug of silica gel, eluting with CH2Cl2. The product was purified by
flash chromatography, eluting with hexanes–CH2Cl2 (7:3). The sol-
vent was removed under reduced pressure. The residual solvent was
removed in vacuo to give 9.82 g (61%) of the desired product as
white crystals.
1H NMR (500 MHz, CDCl3): = 2.27 (s, 3 H), 3.82 (s, 3 H), 6.82
(d, J = 7.0 Hz, 1 H), 6.90 (m, 4 H), 7.05 (d, J = 9.0 Hz, 2 H), 7.12
(m, 3 H), 7.41 (q, J = 3 Hz, 4 H), 7.52 (d, J = 9.0 Hz, 2 H).
13C NMR (125 MHz, CDCl3): = 21.43, 55.44, 114.74, 120.63,
120.76, 122.17, 123.37, 124.20, 127.34, 127.44, 128.06, 128.97,
131.73, 132.46, 139.04, 139.62, 140.43, 147.64, 147.97, 156.25.
1H NMR (500 MHz, (CDCl3): = 2.35 (s, 3 H), 5.74 (s, 1 H), 6.59
(t, J = 9.0 Hz, 1 H), 6.78 (d, J = 7.0 Hz, 2 H), 6.84 (d, J = 7.5 Hz, 1
H), 6.94 (s, 2 H), 7.22 (m, 2 H).
13C NMR (125 MHz, (CDCl3): = 21.50, 103.36, 103.56, 106.77,
106.94, 112.46, 116.09, 119.70, 122.94, 129.25 130.38, 130.45,
139.37, 141.85, 145.39, 145.47, 162.79, 164.72.
HRMS: m/z calcd for C13H12FN 201.0954, found 201.0957.
Anal. Calcd for C13H12FN: C, 77.59; H, 6.01; N, 6.96. Found: C,
77.70; H, 6.11; N, 7.10.
2,4-Difluoro-N-(3-methylphenyl)aniline (7-F2)
To a dry 500 mL round bottom flask under argon were added diflu-
oro-1-iodobenzene (14.15 g, 59 mmol), m-toluidine (8.03 g, 75
mmol), and toluene (100 mL). The mixture was deoxygenated for
10 min and Pd2(dba)3 (0.73 g, 0.8 mmol) and DPPF (0.87 g, 1.5
mmol) were added. After stirring for 10 min, t-BuONa (7.4 g, 77
mmol) was added. The reaction mixture was stirred while the
progress of the reaction was followed by TLC. Upon the disappear-
ance of starting material, the reaction mixture was carefully poured
into a separatory funnel containing H2O (50 mL). The product was
extracted with toluene (3 50 mL). The solvent was removed under
reduced pressure and the material was purified by flash chromatog-
raphy on silica gel, eluting with hexane–CH2Cl2 (7:3). The solvent
was removed under reduced pressure and the residual solvent was
removed in vacuo. The yield of the desired product isolated as a yel-
low oil was 11.46 g (88%).
1H NMR (500 MHz, CDCl3): = 2.33 (s, 3 H), 5.55 (s, 1 H), 6.85
(m, 5 H), 7.18 (t, J = 8.5 Hz, 1 H), 7.27 (m, 1 H).
13C NMR (125 MHz, CDCl3): = 21.50, 103.98, 104.16, 104.19.
104.38, 110.74, 110.89, 110.91, 114.61, 118.28, 119.30, 119.33,
119.37, 119.40, 122.28, 127.77, 129.23, 139.37, 142.61, 152.35,
154.20, 155.69, 155.78, 157.61.
HRMS: m/z calcd for C26H22BrNO 443.0885 found 443.0882.
Anal. Calcd for C26H22BrNO: C, 70.28; H, 4.99; N, 3.15. Found: C,
70.39; H, 5.04; N, 3.31.
N-(4 -Bromo-1,1 -biphenyl-4-yl)-N-(3-fluorophenyl)-N-(3-me-
thylphenyl)amine (8-F)
To a dry 250 mL round bottom flask under argon were added 7-F
(5.5 g, 27.5 mmol), 2 (8.5 g, 23.7 mmol) and toluene (50 mL). The
mixture was deoxygenated for 10 min and Pd2(dba)3 (0.4 g, 0.4
mmol) and DPPF (0.4 g, 0.7 mmol) were added. After stirring for
10 min, t-BuONa (3.4 g, 35 mmol) was added. The temperature was
raised to 90 °C and the reaction mixture was stirred while the
progress of the reaction was monitored by TLC. Upon the disap-
pearance of the starting material, the mixture was filtered through a
plug of silica gel, eluting with CH2Cl2. The product was purified by
column chromatography, eluting with hexanes–toluene (93:7). The
solvent was removed under reduced pressure. The residual solvent
was removed in vacuo to afford 6.88 g (67%) of the desired product
was isolated as a pale yellow glassy solid.
HRMS: m/z calcd for C13H11F2N 443.0885, found 443.0882.
Anal. Calcd for C13H11F2N: C, 71.22; H, 5.06; N, 6.39. Found: C,
71.35; H, 4.88; N, 6.44.
1H NMR (500 MHz, CDCl3): = 2.30 (s, 3 H), 6.90 (dt, J = 2.5 Hz,
5 Hz, 1 H), 6.78 (dt, J = 2.0 Hz, 9 Hz, 1 H), 6.86 (dd, J = 2.5 Hz, 8.5
Synthesis 2002, No. 9, 1201–1212 ISSN 0039-7881 © Thieme Stuttgart · New York

PAPER
Synthesis of Photo-Crosslinkable Hole-Transport Polymers
1209
Hz, 1 H), 6.95 (dd, J = 7.5 Hz, 16.5 Hz, 3 H), 7.17 (m, 4 H), 7.46
(m, 4 H), 7.50 (d, J = 7.5 Hz, 2 H).
Anal. Calcd for C59H48F2N2O2: C, 82.88; H, 5.66; N, 3.28. Found:
C, 83.18; H, 5.51; N, 3.36.
13C NMR (125 MHz, CDCl3): = 21.40, 108.84, 109.01, 109.90,
110.01, 118.54, 121.05, 122.48, 124.40, 124.89, 125.95, 127.67,
128.23, 129.29, 130.05, 130.12, 131.81, 134.35, 139.40, 139.44,
146.85, 146.95, 149.33, 162.46, 164.41.
3-[4-(3-Methyl{4 -[3-methyl(phenyl)anilino][1,1 -biphenyl]-4-
yl}anilino)phenoxy]propan-1-ol (10-Me)
To a dry 250 mL round bottom flask under argon were added 6-Me
(6.10 g 16.2 mmol), 8-Me (6.71 g, 16.3 mmol) and toluene (50 mL).
The mixture was deoxygenated by bubbling argon through the solu-
tion for 10 min, and then Pd2(dba)3 (0.22 g, 0.25 mmol) and DPPF
(0.27 g, 0.5 mmol) were added. After stirring for 10 min, t-BuONa
(2.0 g, 20 mmol) was added. The temperature of the reaction mix-
ture was raised to 100 °C while the progress of the reaction was
monitored by TLC. Upon the disappearance of the starting material,
the mixture was filtered through a fritted glass funnel. The solvent
was removed under reduced pressure to yield a brown viscous oil.
The material was dissolved in THF (30 mL) and a solution of 1 M
Bu4NF in THF was added. The mixture was allowed to stir while
being followed by TLC. Upon the disappearance of the TBDMS-
protected alcohol, the solution was poured into a 500 mL separatory
funnel containing H2O (100 mL). The product was extracted with
Et2O (3 50 mL). The organic layers were combined and the sol-
vent was removed under reduced pressure. The product was puri-
fied by flash chromatography, eluting with a solution of CH2Cl2–
EtOAc (9:1). The solvent was removed under reduced pressure. The
residual solvent was removed in vacuo to yield 9.13 g (95%) of the
product as a pale yellow glassy solid.
GC-MS: m/z (rel. int., %) = 431, 433 (1:1, 100, M+).
Anal. Calcd for C25H19BrFN: C, 69.45; H, 4.43; N, 3.24. Found: C,
69.42; H, 4.25; N, 3.25.
N-(4 -Bromo-1,1 -biphenyl-4-yl)-N-(2,4-difluorophenyl)-N-(3-
methylphenyl)amine (8-F2)
To a dry 250 mL round bottom flask under argon were added 7-F2
(9.5 g 43.4 mmol), 2 (16.8 g, 47.7 mmol) and toluene (50 mL). The
mixture was deoxygenated for 10 min and then Pd2(dba)3 (0.7 g, 0.7
mmol) and DPPF (0.8 g, 1.4 mmol) were added. After stirring for
10 min, t-BuONa (3.4 g, 35 mmol) was added. The temperature was
raised to 90 °C and the reaction mixture was stirred while the
progress of the reaction was monitored by TLC. Upon the disap-
pearance of the starting material, the mixture was filtered through a
plug of silica gel, eluting with CH2Cl2. The product was purified by
column chromatography, eluting with a solution of hexanes–
CH2Cl2 (95:5). The solvent was removed under reduced pressure.
The residual solvent was removed in vacuo to give 12.19 g (63%)
of the desired product was isolated as a pale yellow glass.
1H NMR (500 MHz, CDCl3): = 1.61 (s, 1 H), 2.06 (quint, J = 3.5
Hz, 2 H), 2.65 (d, J = 5.5 Hz, 6 H), 3.90 (t, J = 6.0 Hz, 2 H), 4.12 (t,
J = 6.5 Hz, 2 H), 6.80 (d, J = 7.0 Hz, 1 H), 6.90 (m, 7 H), 7.04 (t,
J = 7.0 Hz, 1 H), 7.12 (m, 10 H), 7.27 (m, 2 H), 7.43 (t, J = 8.5 Hz,
4 H).
13C NMR (125 MHz, CDCl3): = 21.44, 21.49, 31.99, 60.57, 66.02,
115.30, 120.47, 121.61, 122.58, 122.78, 123.06, 123.79, 123.90,
124.06, 124.14, 125.05, 127.13, 127.15, 127.23, 128.95, 129.06,
129.19, 133.75, 134.68, 138.97, 139.09, 140.91, 146.66, 147.11,
147.64, 147.81, 147.88, 155.21.
1H NMR (500 MHz, CDCl3): = 2.31 (s, 3 H), 6.90 (m, 5 H), 7.02
(d, J = 9 Hz, 2 H), 7.22 (m, 2 H), 7.44 (d, J = 9.0 Hz, 4 H), 7.54 (d,
J = 8.0 Hz, 2 H).
13C NMR (125 MHz, CDCl3): = 21.49, 105.31, 105.51, 105.71,
112.05, 112.02, 112.23, 120.02, 120.85, 121.26, 123.47, 124.04,
127.53, 128.17, 129.13, 130.44, 130.51, 131.80, 133.19, 139.25,
139.52, 146.61, 146.94, 157.63, 159.18, 159.26, 159.65, 161.24.
HRMS: m/z calcd for C25H18F2BrN: 451.0574, found 451.0577.
Anal. Calcd for C25H18F2BrN: C, 66.68; H, 4.03; N, 3.11. Found: C,
67.07; H, 3.98; N, 3.15.
HRMS: m/z calcd for C41H38N2O2: 590.2933, found 590.2933.
Anal. Calcd for C41H38N2O2: C, 83.36; H, 6.48; N, 4.74. Found: C,
83.35; H, 6.66; N, 4.90.
N,N -Bis(3-fluorophenyl)-N-(3-methylphenyl)-N -{4-[3-(trityl-
oxy)propoxy]phenyl}-1,1 -biphenyl-4,4 -diamine (9-F)
To a dry 500 mL round bottom flask under argon was added 6-F
(12.34 g, 24.51 mmol), 8-F (11.40 g, 26.4 mmol), and toluene (100
mL). The mixture was deoxygenated for 10 min and then Pd2(dba)3
(0.2 g, 0.2 mmol) and DPPF (0.2 g, 0.3 mmol) were added. After
stirring for 10 min, t-BuONa (3.1 g, 32 mmol) was added. The tem-
perature was raised to 90 °C and the reaction mixture was stirred
while the progress of the reaction was followed by TLC. Upon the
disappearance of the starting material the mixture was filtered
through a plug of silica gel, eluting with CH2Cl2. The product was
purified by column chromatography, eluting with hexanes–CH2Cl2
(70:30). The solvent was removed under reduced pressure and the
residual solvent was removed in vacuo to give 19.31 g (92%) of the
desired product as a pale yellow glassy solid.
1H NMR (500 MHz, acetone-d6): = 2.06 (quint, J = 7.0 Hz, 2 H),
2.26 (s, 3 H), 3.29 (t, J = 6.0 Hz, 2 H), 4.18 (t, J = 6.0 Hz, 2 H), 6.70
(m, 4 H), 6.80 (dd, J = 3.0 Hz, 8.5 Hz, 2 H), 6.94 (m, 5 H), 7.11 (m,
6 H), 7.25 (m, 12 H), 7.46 (d, J = 8.0 Hz, 6 H), 7.57 (m, 4 H).
13C NMR (125 MHz, acetone-d6): = 11.65, 11.78, 20.50, 26.51,
59.81, 64.80, 86.36, 100.28, 107.43,m 107.60, 107.76, 108.23,
108.41, 108.82, 109.02, 115.63, 116.88, 118.11, 122.47, 123.87,
124.72, 124.96, 125.88, 126.88, 127.33, 127.35, 127.70, 127.99,
128.56, 129.43, 130.36, 130.45, 134.66, 135.27, 139.39, 139.48,
144.37, 146.19, 146.43, 146.95, 149.70, 150.06, 156.51, 162.40,
164.32.
3-[4-(4-Methoxy{4 -[4-methoxy(3-methylphenyl)anilino][1,1 -
biphenyl]-4-yl}anilino)phenoxy]propan-1-ol (10-OMe)
To a dry 250 mL round bottom flask under argon were added 6-
OMe (7.95 g 20.5 mmol), 8-OMe (9.59 g, 21.6 mmol) and toluene
(50 mL). The mixture was deoxygenated and then Pd2(dba)3 (0.30
g, 0.32 mmol) and DPPF (0.40 g, 0.64 mmol) were added. After stir-
ring for 10 min, t-BuONa (1.4 g, 25 mmol) was added The temper-
ature of the reaction mixture was raised to 100 °C while the progress
of the reaction was monitored by TLC. Upon the disappearance of
the starting material the mixture was filtered through a fritted glass
funnel. The solvent was removed under reduced pressure to yield a
brown viscous oil. The material was dissolved in THF (30 mL) and
a 1 M solution of Bu4NF in THF (20 mL) was added. The mixture
was allowed to stir while the reaction was followed by TLC. Upon
the disappearance of the TBDMS protected alcohol, the solution
was poured into a 500 mL separatory funnel containing H2O (100
mL). The product was extracted with Et2O (3 50 mL). The organic
layers were combined and the solvent was removed under reduced
pressure. The product was purified by flash chromatography, elut-
ing with a solution of CH2Cl2–EtOAc (19:1). The solvent was re-
moved under reduced pressure. The residual solvent was removed
in vacuo to give 11.27 g (86%) of the product as a pale yellow
glassy solid.
1H NMR (500 MHz, acetone-d6): = 1.98 (quint, 6 Hz, 2 H), 2.35
(s, 3 H), 2.86 (s, 1 H), 3.75 (t, J = 6 Hz, 2 H), 3.79 (s, 3 H), 3.80 (s,
HRMS: m/z calcd for C59H48F2N2O2 854.3684, found 854.3693.
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R. D. Hreha et al.
PAPER
3 H), 4.11 (t, J = 6 Hz, 2 H), 6.82 (t, J = 6.5 Hz, 2 H), 6.94 (m, 9 H),
7.00 (d, J = 8.5 Hz, 2 H), 7.06 (m, 6 H), 7.15 (t, J = 8.0 Hz, 1 H),
7.47 (dd, J = 3.5 Hz, 9.0 Hz, 4 H).
13C NMR (125 MHz, acetone-d6): = 20.59, 32.48, 54.80, 64.85,
114.67, 114.76, 115.26, 120.17, 120.43, 122.57, 122.93, 123.54,
126.54, 126.72, 127.28, 128.99, 132.31, 133.79, 138.75, 140.48,
140.64, 140.74, 146.95, 147.78, 148.04, 155.62, 156.12, 156.47.
2 H), 6.80 (m, 11 H), 7.01 (d, J = 8.5 Hz, 2 H), 7.08 (d, J = 8.5 Hz,
2 H), 7.19 (m, 3 H), 7.41 (t, J = 9.0 Hz, 4 H).
13C NMR (125 MHz, CDCl3): = 21.46, 31.94, 60.57, 66.04,
105.21, 105.40, 105.61, 111.92, 112.03, 115.24, 119.36, 119.61,
121.85, 122.81, 123.49, 125.78, 127.11, 128.99, 129.91, 130.35,
133.19, 134.45, 139.08, 139.95, 145.90, 146.73, 146.88, 155.26.
HRMS: m/z calcd for C40H32FN2O2: 648.2400, found 648.2400.
HRMS: m/z calcd for C42H40N2O4: 636.2988, found 636.2992.
Anal. Calcd for C40H32F4N2O2: C, 74.06; H, 4.97; N, 4.32. Found:
C, 73.83; H, 4.81; N, 4.50.
Anal Calcd for C42H40N2O4: C, 79.22; H, 6.33; N, 4.40. Found: C,
79.12; H, 6.15; N, 4.43.
3-[4-(3-Methyl{4 -[3-methyl(phenyl)anilino][1,1 -biphenyl]-4-
yl}anilino)phenoxy]propyl 2-Methacrylate (1-Me)
3-[4-(3-Fluoro{4 -[3-fluoro(3-methylphenyl)anilino][1,1 -biphe-
nyl]-4-yl}anilino)phenoxy]propan-1-ol (10-F)
To a dry 250 mL round bottom flask under argon were added 10-Me
(7.72 g, 13.1 mmol), dicyclohexylcarbodiimide (4.20 g, 20.0
mmol), methacrylic acid (1.50 g, 17.0 mmol), and THF (50 mL).
The solution was cooled to 0 °C and 4-dimethylaminopyridine (0.2
g, 1.7 mmol) was added. The temperature was allowed to rise to r.t.
while the progress of the reaction was followed by TLC. Upon the
disappearance of the starting material, the mixture was poured into
cold water (200 mL). The product was extracted with Et2O (3 50
mL). The organic layers were combined and the solvent was re-
moved under reduced pressure. The product was purified by flash
chromatography over silica gel, eluting with CH2Cl2–hexanes (7:3).
The solvent was removed under reduced pressure. The residual sol-
vent was removed in vacuo to furnish 8.07 g (94%) of the desired
product as a pale yellow glassy solid.
1H NMR (500 MHz, CDCl3): = 1.99 (s, 3 H), 2.21 (quint, J = 6.5
Hz, 2 H), 2.29 (s, 3 H), 2.30 (s, 3 H), 4.10 (t, J = 6.0 Hz, 2 H), 4.40
(t, J = 6.0 Hz, 2 H), 5.61 (s, 1 H), 6.16 (s, 1 H), 6.83 (d, J = 7.5 Hz,
1 H), 6.88 (d, J = 9.5 Hz, 3 H), 6.94 (m, 4 H), 7.03 (t, J = 7.5 Hz, 1
H), 7.14 (m, 10 H), 7.28 (t, J = 8.0 Hz, 2 H), 7.46 (t, J = 8.0 Hz, 4
H).
To a 1000 mL round bottom flask, was added 9-F (18.69, 21.86
mmol), Et2O (360 mL) and 95% formic acid (190 mL). The solution
was stirred for 4 h while the progress of the reaction was monitored
by TLC. Upon the disappearance of the starting material, the mix-
ture was carefully poured into a separatory funnel containing H2O
(50 mL). The product was extracted with Et2O (3 50 mL). The or-
ganic layers were combined and washed with aq sat. NaHCO3 (5
50 mL). The excess solvent was removed under reduced pressure
and the residue was purified by column chromatography over silica
gel, eluting with CH2Cl2. The solvent was removed under reduced
pressure and the residual solvent was removed in vacuo to afford
5.43 g (41%) of the desired product as a pale yellow glassy solid.
1H NMR (500 MHz, acetone-d6): = 1.98 (quint, 6 Hz, 2 H), 2.26
(s, 3 H), 3.70 (s, 1 H), 3.75 (t, J = 6 Hz, 2 H), 4.11 (t, J = 6 Hz, 2 H),
6.69 (m, 4 H), 6.80 (m, 2 H), 6.95 (m, 5 H), 7.11 (m, 6 H), 7.22 (m,
3 H), 7.59 (m, 4 H).
13C NMR (125 MHz, CDCl3): = 20.51, 32.42, 58.11, 64.87,
107.43, 107.57, 107.60, 107.76, 108.25, 108.42, 108.85, 109.04,
115.57, 116.88, 118.14, 122.47, 123.84, 124.72, 124.95, 125.86,
127.31, 127.35, 128.01, 129.45, 130.36, 130.44, 130.46, 130.55,
134.65, 135.27, 139.39, 146.19, 146.43, 146.95, 149.70, 149.77,
149.99, 150.06, 156.70, 162.40, 162.37, 164.32.
13C NMR (125 Hz, CDCl3): = 18.37, 21.44, 28.74, 55.36, 61.56,
64.59, 115.29, 120.46, 121.61, 122.58, 122.77, 123.04, 123.79,
123.89, 124.06, 124.14, 125.05, 125.58, 127.11, 127.15, 127.24,
128.95, 129.05, 129.18, 133.73, 134.68, 136.30, 138.95, 139.09,
140.84, 146.65, 147.14, 147.64, 147.81, 147.90, 155.26, 167.39.
HRMS: m/z calcd for C40H34F2N2O5 613.2667, found 613.2697
Anal. Calcd for C40H34F2N2O5: C, 78.41; H, 5.59; N, 4.57. Found:
C, 78.20; H, 5.62; N, 4.52.
HRMS: m/z calcd for C45H42N2O3: 658.3195, found 658.3190.
Anal. Calcd for C45H42N2O3: C, 82.04; H, 6.43; N, 4.25. Found: C,
82.05; H, 6.40; N, 4.32.
3-[4-({4 -[2,4-Difluoro(3-methylphenyl)anilino][1,1 -biphenyl]-
4-yl}-2,4-difluoroanilino)phenoxy]propan-1-ol (10-F2)
To a dry 250 mL round bottom flask under argon were added 6-F2
(4.52 g 11.49 mmol), 8-F2 (6.21 g, 13.8 mmol) and toluene (50 mL).
The mixture was deoxygenated and then Pd2(dba)3 (0.19 g, 0.2
mmol) and DPPF (0.23 g, 0.4 mmol) were added. After stirring for
10 min, t-BuONa (1.4 g, 15 mmol) was added. The temperature of
the reaction was raised to 100 °C while the progress of the reaction
was monitored by TLC. Upon the disappearance of the starting ma-
terial, the mixture was filtered through a fritted glass funnel. The
solvent was removed under reduced pressure to yield a brown vis-
cous oil. The material was dissolved in THF (30 mL) and a 1 M so-
lution of Bu4NF in THF (20 mL) was added. The mixture was
allowed to stir while the progress of the reaction was followed by
TLC. Upon the disappearance of the TBDMS protected alcohol, the
solution was poured into a 500 mL separatory funnel containing
H2O (100 mL). The product was extracted with Et2O (3 50 mL).
The organic layers were combined and the solvent was removed un-
der reduced pressure. The product was purified by flash chromatog-
raphy, eluting with CH2Cl2. The solvent was removed under
reduced pressure. The residual solvent was removed in vacuo to
give 5.93 g (80%) of the product as a pale yellow glassy solid.
3-[4-(4-Methoxy{4 -4[4-methoxy(3-methylphenyl)anilino][1,1 -
biphenyl]-4-yl)anilino)phenoxy]propyl 2-Methacrylate (1-
OMe)
To a dry 250 mL round bottom flask under argon were added 10-
OMe (11.22 g, 17.6 mmol), dicyclohexylcarbodiimide (5.09 g, 24.7
mmol), methacrylic acid (1.82 g, 21.1 mmol), and THF (50 mL).
The solution was cooled to 0 °C and 4-dimethylaminopyridine
(0.2g, 1.7 mmol) was added. The temperature was allowed to raise
to r.t. while the reaction was followed by TLC. Upon the disappear-
ance of the starting material, the mixture was poured into cold water
(200 mL). The product was extracted with Et2O (3 50 mL). The
organic layers were combined and the solvent was removed under
reduced pressure. The product was purified by column chromatog-
raphy over silica gel, eluting with CH2Cl2. The solvent was removed
under reduced pressure. The residual solvent was removed in vacuo
to afford 11.21 g (90%) of the desired product as a pale yellow
glassy solid.
1H NMR (500 MHz, acetone-d6): = 1.93 (s, 3 H), 2.17 (quint,
J = 6.5 Hz, 2 H), 2.24 (s, 3 H), 3.8 (d, J = 5.5 Hz, 6 H), 4.14 (t,
J = 6.0 Hz, 2 H), 4.34 (t, J = 6.0 Hz, 2 H), 5.63 (s, 1 H), 6.10 (s, 1
H), 6.83 (m, 2 H), 6.93 (m, 9 H), 7.00 (d, J = 8.5 Hz, 2 H), 7.08 (m,
6 H), 7.16 (t, J = 8.0 Hz, 1 H), 7.49 (dd, J = 11.5 Hz, 8.5 Hz, 4 H).
1H NMR (500 MHz, CDCl3): = 1.67 (s, 1 H), 2.06 (quint, J = 6.0
Hz, 2 H), 3.28 (s, 3 H), 3.87 (t, J = 6.0 Hz, 2 H), 4.13 (t, J = 6.0 Hz,
Synthesis 2002, No. 9, 1201–1212 ISSN 0039-7881 © Thieme Stuttgart · New York

PAPER
Synthesis of Photo-Crosslinkable Hole-Transport Polymers
1211
13C NMR (125 MHz, CD2Cl2): = 18.05, 21.11, 28.65, 55.36,
61.41, 64.72, 114.60, 115.17, 120.25, 122.64, 122.88, 123.69,
125.02, 126.74, 127.28, 127.70, 128.80, 133.78, 136.49, 138.98,
146.93, 156.25, 167.10.
3-{4-[(E)-3-Methoxy-3-oxoprop-1-enyl]phenoxy}propyl 2-
Methacrylate (12)15
To a dry 250 mL round bottom flask under argon were added 11
(9.18 g, 39.0 mmol), dicyclohexylcarbodiimide (9.6 g, 46.8 mmol),
methacrylic acid (4.02 g, 46.8 mmol), and THF (50 mL). The solu-
tion was cooled to 0 °C in an ice-bath and 4-dimethylaminopyridine
(0.2 g, 1.7 mmol) was added. The temperature was allowed to in-
crease to r.t. while the reaction was followed by TLC. Upon the dis-
appearance of the starting material the mixture was filtered through
a fritted glass funnel. The solid was rinsed with THF (3 10 mL)
and the solution was transferred to a round bottom flask and the sol-
vent was removed under reduced pressure. The product was puri-
fied by flash chromatography over silica gel, eluting with CH2Cl2–
hexanes (7:3). The solvent was removed under reduced pressure.
The residual solvent was removed in vacuo to give 7.81 g (66%) of
the desired product as white crystals.
1H NMR (500 MHz, CDCl3): = 1.94 (s, 3 H), 2.18 (quint, J = 6.0
Hz, 2 H), 3.79 (s, 3 H), 4.09 (t, J = 6.5 Hz, 2 H), 4.34 (t, J = 6.5 Hz,
2 H), 5.57 (s, 1 H), 6.10 (s, 1 H), 6.30 (d, J = 16 Hz, 1 H), 6.89 (d,
J = 8.5 Hz, 2 H), 7.46 (d, J = 9.0 Hz, 2 H), 7.64 (d, J = 16 Hz, 1 H).
13C NMR (125 MHz, CDCl3): = 18.28, 28.51, 51.56, 61.32, 64.49,
114.73, 115.26, 125.58, 127.15, 129.69, 136.18, 144.44, 160.51,
167.29, 167.72.
HRMS: m/z calcd for C46H44N2O5: 705.3328, found 705.3346.
Anal. Calcd for C46H44N2O5: C, 78.38; H, 6.29; N, 3.97. Found: C,
78.41; H, 6.12; N, 4.03.
3-[4-(3-Fluoro{4 -[3-fluoro(3-methylphenyl)anilino][1,1 -biphe-
nyl]-4-yl}anilino)phenoxy]propyl 2-Methacrylate (1-F)
To a dry 250 mL round bottom flask under argon were added 10-F
(5.01 g, 8.18 mmol), dicyclohexylcarbodiimide (2.0 g, 9.8 mmol),
methacrylic acid (0.9 g, 9.8 mmol), and THF (50 mL). The solution
was cooled to 0 °C and 4-dimethylaminopyridine (0.3 g, 2.5 mmol)
was added. The temperature was allowed to raise to r.t. while the re-
action was followed by TLC. Upon the disappearance of the starting
material, the mixture was poured into cold MeOH (200 mL). The
white crystals were collected by vacuum filtration and recrystal-
lized from a mixture of THF and MeOH. The white powder was
dried under vacuum; yield: 4.75 g (85%).
1H NMR (500 MHz, acetone-d6): = 1.93 (s, 3 H), 2.17 (quint,
J = 6.5 Hz, 2 H), 2.27 (s, 3 H), 4.15 (t, J = 6.0 Hz, 2 H), 4.34 (t,
J = 6.0 Hz, 2 H), 5.63 (quint, J = 2.0 Hz, 1 H), 6.09 (q, J = 1 Hz, 1
H), 6.73 (m, 6 H), 6.95 (m, 5 H), 7.12 (m, 6 H), 7.24 (quint, J = 6.5
Hz, 3 H), 7.59 (m, 4 H).
Polymer 13-OMe
To a thick-walled glass tube containing argon and a stir bar was add-
ed 1-OMe (2.00 g, 23.04 mmol), 12 (0.40 g, 1.30 mmol), and AIBN
(0.007 g, 0.04 mmol). The tube was again pump-filled with argon
and deoxygenated anhyd benzene (10 mL) was added. The tube was
sealed and heated at 60 °C for 72 h. The reaction mixture was al-
lowed to cool and was poured into MeOH (100 mL). The white sol-
id was collected by vacuum filtration and was dissolved in THF,
followed by precipitation in MeOH. The process was repeated three
times. The product was collected as a white powder by vacuum fil-
tration; yield: 1.90 g (79%).
1H NMR (500 MHz, CDCl3): = 0.89 (s, 2 H), 1.02 (s, 2 H), 1.26
(s, 1 H), 1.56 (s, 2 H), 1.99 (s, 6H), 2.13 (s, 3 H), 2.19 (s, 6 H), 3.66
(s, 2 H), 3.89 (s, 4 H), 4.07 (s, 4 H), 6.21 (s, J = 1.5 Hz, 1 H), 6.88
(m, 33 H), 7.16 (s, 3 H), 7.27 (s, 8 H) 7.54, (d, J = 1.5 Hz, 1 H).
13C NMR (125 MHz, CD2Cl2): = 17.53, 20.48, 61.25, 64.62,
107.46, 107.59, 107.63, 107.79, 108.23, 108.41, 108.81, 109.01.
115.62, 116.89, 118.12, 118.09, 122.47, 123.90, 124.72, 124.96,
125.88, 127.33, 127.35, 127.99, 129.43, 130.38, 130.45, 130.55,
134.71, 135.28, 136.51, 139.41, 139.65, 146.20, 146.42, 146.95,
149.70, 149.79, 150.04, 156.41, 162.40, 164.32, 166.51.
HRMS: m/z calcd for C44H38F4N2O3: 680.2850, found 680.2856.
Anal. Calcd for C44H38F2N2O3: C, 77.63; H, 5.63; N, 4.11. Found:
C, 77.57; H, 5.46; N, 4.03.
3-[4-{4 -[2,4-difluoro(3-methylphenyl)anilino][1,1 -biphenyl]-4-
yl}-2,4-difluoroanilino)phenoxy]propyl 2-Methacrylate (1-F2)
To a dry 250 mL round bottom flask under argon were 10-F2 (2.88
g, 14 mmol), methacrylic acid (1.00 g, 11.1 mmol), and THF (50
mL). The solution was cooled to 0 °C and 4-dimethylaminopyridine
(0.2 g, 1.7 mmol) was added. The temperature was allowed to raise
to r.t. while the reaction was followed by TLC. Upon the disappear-
ance of the starting material the mixture was poured into cold water
(200 mL). The product was extracted with Et2O (3 50 mL). The
organic layers were combined and the solvent was removed under
reduced pressure. The product was purified by flash chromatogra-
phy on silica gel, eluting with CH2Cl2–hexanes (7:3). The solvent
was removed under reduced pressure. The residual solvent was re-
moved in vacuo to yield 11.21 g (90%) of the desired product as a
pale yellow glass.
1H NMR (500 MHz, CDCl3): = 1.96 (s, 3 H), 2.18 (quint, J = 6.5
Hz, 2 H), 2.23 (s, 3 H), 4.05 (t, J = 6.0 Hz, 2 H), 4.37 (t, J = 6.0 Hz,
2 H), 5.58 (s, 1 H), 6.76 (t, J = 8.0 Hz, 1 H), 6.87 (m, 11 H), 7.00
(d, J = 8.0 Hz, 2 H), 7.01 (d, J = 8.5 Hz, 2 H), 7.23 (m, 3 H), 7.41
(t, J = 9.0 Hz, 4 H).
13C NMR (125 MHz, CDCl3): = 18.36, 21.49, 28.71, 61.52, 64.60,
105.21, 105.42, 105.63, 111.95, 112.12, 115.26, 119.39, 119.60,
121.88. 122.84, 123.53, 125.58, 125.85, 127.14, 129.02, 129.88,
130.44, 130.82, 133.17, 134.49, 136.29, 139.09, 139.90, 145.92,
148.79, 146.92, 155.35, 167.36.
Anal. Calcd: C, 79.54; H, 6.46; N, 3.54. Found: C, 79.18; H, 6.27;
N, 3.45.
Polymer 13-Me
To a thick-walled glass tube containing argon and a stir bar was add-
ed 1-Me (1.20 g, 1.70 mmol), 12 (0.22 g, 0.73 mmol) and AIBN
(0.0039 g, 0.024 mmol). The tube was pump-filled with argon and
deoxygenated anhyd benzene (10 mL) was added. The tube was
sealed and heated at 60 °C for 82 h. The reaction mixture was al-
lowed to cool and was poured into MeOH (100 mL). The white sol-
id was collected by vacuum filtration and was dissolved in THF
followed by reprecipitation in MeOH. The process was repeated
three times. The product isolated as a white powder was collected
vacuum filtration; yield: 0.95 g (67%).
1H NMR (500 MHz, CDCl3): = 0.89 (s, 3 H), 1.02 (s, 3 H), 1.26
(s, 1 H), 1.57 (s, 5 H), 1.98 (s, 8H), 2.18 (s, 5 H), 3.69 (m, 15 H),
3.86 (m, 9 H), 6.22 (d, J = 15.5 Hz 1 H), 6.83 (m, 4 H), 7.42 (m, 10
H), 7.55 (d, J = 16.0 Hz, 1 H).
Anal. Calcd: C, 76.63; H, 6.34; N, 3.35. Found: C, 76.33; H, 6.36;
N, 3.38.
Polymer 13-F
To a thick-walled glass tube containing argon and a stir bar was add-
ed 1-F (1.50 g, 2.2 mmol), 12 (0.29 g, 0.94 mmol) and AIBN (0.005
g, 0.031 mmol). The tube was pump-filled with argon and deoxy-
genated anhyd benzene (10 mL) was added. The tube was sealed
HRMS: m/z calcd for C44H36F4N2O3: 716.2662, found 716.2665.
Anal. Calcd for C46H36F4N2O3: C, 73.73; H, 5.06; N, 3.91. Found:
C, 73.78; H, 5.11; N, 3.96.
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1212
R. D. Hreha et al.
PAPER
and heated at 60 °C for 72 h. The reaction mixture was allowed to
cool and was poured into MeOH (100 mL). The white solid was col-
lected by vacuum filtration and was dissolved in THF and then re-
precipitated from MeOH. The process was repeated three times.
The product isolated as a white powder was collected by vacuum
filtration; yield: 1.41 g (79%).
1H NMR (500 MHz, CDCl3): = 0.89–2.21 (br overlapping peaks
36 H), 3.67–4.09 (br overlapping peaks 18 H), 6.22 (d, J = 15.5 Hz,
1 H), 6.69–7.30 (br overlapping peaks, 55 H), 7.56 (d, J = 15.5 Hz,
1 H).
13C NMR (125 MHz, C4D8O): = 21.64, 55.67, 115.54, 116.16,
121.19, 121.89, 123.63, 123.70, 124.53, 127.36, 127.66, 128.07,
129.75, 133.63, 134.94, 139.55, 141.62, 141.83, 141.99, 147.88,
148.58, 149.11, 155.98, 157.00, 157.37.
Anal. Calcd: C, 78.38; H, 6.29; N, 3.97. Found: C, 78.03; H, 6.30;
N, 4.06.
Acknoweldgements
This work was funded by NSF through a CAREER grant (B. K.), by
AFOSR, ONR, NASA through the University of Alabama at Hunts-
ville, Durel Corporation, and through a 3M young faculty award (B.
K.). R.D.H acknowledges a University of Arizona Proposition 301
fellowship. The authors are grateful to Steve Barlow for his contri-
butions to the preparation of this manuscript.
Anal. Calcd: C, 75.96; H, 5.79; N, 3.44. Found: C, 75.68; H, 5.57;
N, 3.39.
Polymer (13-F2)
To a thick-walled glass tube containing argon and a stir bar was add-
ed 1-F2 (1.70 g, 2.37 mmol), 12 (0.32 g, 1.02 mmol) and AIBN
(0.0056 g, 0.034 mmol). The tube was again pump filled with argon
and deoxygenated anhyd benzene (10 mL) was added. The tube was
sealed and heated at 60 °C for 82 h. The reaction mixture was al-
lowed to cool and was poured into MeOH (100 mL). The white sol-
id was collected by vacuum filtration and was dissolved in THF
followed by precipitation from MeOH. The process was repeated
twice followed by reprecipitation from THF into MeOH. The prod-
uct was collected as a white powder by vacuum filtration; yield:
1.82 g (90%).
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(13) Rami Reddy, A. V.; Subramanian, K.; Krishnasamy, V.;
Ravichandran, J. Eur. Polym. J. 1996, 32, 916.
(14) Subramanian, K.; Krishnasamy, V.; Nanjundan, S.; Rami
Reddy, A. V. Eur. Polym. J. 2000, 36, 2343.
Polymer 14
To a thick-walled glass tube containing argon and a stir bar was add-
ed 12 (0.50 g, 1.64 mmol) and AIBN (0.0021 g, 0.0014 mmol). The
tube was pump-filled with argon and deoxygenated anhyd benzene
(10 mL) was added. The tube was sealed and heated at 60 °C for 82
h. The reaction mixture was allowed to cool and was poured into
MeOH (100 mL). The white solid was collected by vacuum filtra-
tion and was dissolved in THF and then precipitated from MeOH.
The process was repeated twice followed by reprecipitation in ace-
tone from THF. The product was collected as a white powder by
vacuum filtration; yield: 0.42 g (84%).
1H NMR (500 MHz, (CDCl3): = 0.84 (m, 2 H), 1.88 (m, 3 H), 1.99
(s, 3 H), 3.76 (s, 3 H), 3.94 (s, 2 H), 4.04 (s, 2 H), 6.25 (d, J = 27 Hz
1 H), 6.81 (d, J = 13.0 Hz, 4 H), 7.39 (d, J = 13.5 Hz, 2 H), 7.58 (d,
J = 26.0 Hz, 1 H).
(15) Zhang, Y. D.; Hreha, R. D.; Marder, S. R.; Jabbour, G. E.;
Kippelen, B.; Peyghambarian, N. J. Mater. Chem. 2002, 12,
1703.
Anal. Calcd: C, 67.09; H, 6.62. Found: C, 66.81; H, 6.40.
Polymer 15-OMe
(16) Hartwig, J. F. Angew. Chem. Int. Ed. 1998, 37, 2046.
(17) Hu, N. X.; Ong, B. S.; Xie, S.; Popovic, Z. D.; Hor, A. M.
Eur. Pat. Appl. 827367, 1998; Chem. Abstr. 1998, 128,
223711.
(18) Hansen, H. C.; Olsson, R.; Croston, G.; Andersson, C. M.
Bioorg. Med. Chem. Lett. 2000, 21, 2435.
(19) Hsieh, C. J.; Wu, S. H.; Hsiue, G. H.; Hsu, C. S.; Chain, S.
J. Polym. Sci., Part A: Polym. Chem. 1994, 32, 1077.
(20) Guram, A. S.; Buchwald, S. L. J. Am. Chem. Soc. 1994, 116,
7901.
To a thick-walled glass tube containing argon and a stir bar was add-
ed 1-OMe (1.00 g, 1.41 mmol) and AIBN (0.0023 g, 0.0014 mmol).
The tube was pump-filled with argon and deoxygenated anhyd ben-
zene (10 mL). The tube was sealed and heated at 60 °C for 82 h. The
reaction mixture was allowed to cool and was poured into MeOH
(100 mL). The white solid was collected by vacuum filtration and
was dissolved in THF and then precipitated in MeOH. The process
was repeated twice followed by reprecipitation in acetone from
THF. The product was collected as a white powder by vacuum fil-
tration; yield: 0.80 g (80%).
(21) Goodbrand, H. B.; Hu, N. X. J. Org. Chem. 1999, 64, 670.
1H NMR (500 MHz, CDCl3): = 0.96 (s, 2 H), 1.65 (s, 1 H), 1.99
(s, 3 H), 2.19 (s, 3 H), 3.62 (s, 3H), 3.71 (s, 3 H), 3.90 (m, 4 H), 6.83
(m, 20 H), 7.02 (m, 4 H).
Synthesis 2002, No. 9, 1201–1212 ISSN 0039-7881 © Thieme Stuttgart · New York