Yeonsuk Roh, Nathan L. Bauld
FULL PAPERS
butyllithium [based upon a 100% conversion of the 9-(3'-
bromocarbazolyl) group] was added during 15 minutes. After
3 h at this temperature, 0.32 mL of N,N-dimethylformamide
was slowly added and the mixture stirred for another 5 h. The
reaction mixture was carefully quenched by the addition of
saturated NH4Cl at 0 8C, until the solution became acidic.
After extraction with dichloromethane, the solution was
washed successively with water, with saturated NaHCO3 and
with saturated NaCl solution. After drying over anhydrous Na2
SO4, the solvent was evaporated to provide the corresponding
carbonyl product. The polymer products were dissolved in
dichloromethane and precipitated by dropwise addition of a
concentrated solution into a vigorously stirred excess of
methanol. The precipitate was isolated by filtration and dried
under vacuum at room temperature. These procedures were
done two more times to give the product; yield: 1.40 g (80.1%);
MW 43,700 and PDI 1.57 (vs. linear polystyrene standards);
1H NMR (300 MHz, CDCl3): d 0.7 3.4 (br), 4.3 5.8 (br),
7.0 7.6 (br), 7.8 8.4 (br), 10.0 10.3 (br); 13C NMR
(500 MHz, CDCl3): d 15.4, 16.8, 37.9 40.0 (complexmulti-
plicity), 41.1, 41.9, 43.3, 49.1, 65.8, 108.7, 111.5 112.5 (complex
multiplicity), 118.7, 120.1, 122.7, 123.7, 125.1, 130.6, 133.0,
139.9, 141.9, 191.5; UV (dichloromethane): lmax 266, 295,
346 nm.
Introduction of the NLO Functionality into the Block
Copolymer
To a mixture of malononitrile (0.15 mL) and dry pyridine
(0.2 mL) in 30 mL of dry benzene stirred at ambient temper-
ature for 30 minutes under nitrogen the previous block
copolymer containing the aldehyde functionality (1.42 g) was
added. The reaction mixture was heated under reflux for 22 h
and cooled to room temperature followed by washing with
water, drying with sodium sulfate and evaporating. The
polymer products were dissolved in dichloromethane and
precipitated by dropwise addition of a concentrated solution
into a vigorously stirred excess of hexane. The precipitate was
collected by filtration, dried, re-dissolved in dichloromethane
and re-precipitated by dropwise addition of a concentrated
solution into a vigorously stirred excess of hexane. The
precipitate was isolated by filtration and dried under vacuum
at room temperature. This procedure was done three more
times to give the product; yield: 1.49 g (81%); Mw 42,000 and
PDI 3.01 (vs. linear polystyrene standards); 1H NMR
(300 MHz, CDCl3): d 0.7 3.4 (br), 4.3 5.8 (br), 7.0 7.6
(br), 7.8 8.3 (br); 13C NMR (500 MHz, CDCl3): d 15.4, 16.6,
38.5, 41.0, 41.8, 43.3, 49.0, 65.8, 108.7, 111.5 112.5 (complex
multiplicity), 118.6, 119.8, 122.6, 123.7, 125.0, 125.5, 130.7,
133.1, 139.9, 141.9; IR (KBr pellet): n 1596 (nCC, aromatic),
1626 (nCC, alkene), 2223 cmÀ1 (nC8N, nitrile); UV (dichloro-
methane): lmax 266, 295, 331, 346, 413 nm; Tg 242.1 8C under
nitrogen and Td (onset, 0.6 wt% loss) 368.4 8C under nitrogen.
Introduction of the NLO Functionality into the
Random Copolymer
To a mixture of malononitrile (0.15 mL) and dry pyridine
(0.2 mL) in 30 mL of dry benzene stirred at ambient temper-
ature for 30 minutes under nitrogen the previous random
copolymer (1.30 g) was added. The reaction mixture was
heated under refluxfor 22 h and cooled to room temperature
followed by washing with water, drying with sodium sulfate and
evaporating. The polymer products were dissolved in dichloro-
methane and precipitated by dropwise addition of a concen-
trated solution into a vigorously stirred excess of hexane. The
precipitate was collected by filtration, dried, re-dissolved in
dichloromethane and re-precipitated by dropwise addition of a
concentrated solution into a vigorously stirred excess of
hexane. The precipitate was isolated by filtration and dried
under vacuum at room temperature. These procedures were
done three more times to give the product; yield: 1.24 g
(67.6%); MW 44,100 and PDI 1.62 (vs. linear polystyrene
standards); 1H NMR (300 MHz, CDCl3): d 0.7 3.4 (br),
4.3 5.8 (br), 7.0 7.6 (br), 7.8 8.3 (br); 13C NMR (500 MHz,
CDCl3): d 15.4, 16.8, 36.5 39.4 (complexmultiplicity), 41.1,
41.9, 43.6, 49.2, 65.8, 108.7, 111.5 112.5 (complexmultiplicity),
118.8, 120.0, 122.6, 123.7, 125.5, 130.6, 133.0, 139.9, 141.9; IR
(KBr pellet): n 1594 (nCC, aromatic), 1624 (nCC, alkene),
2223 cmÀ1 (nC8N, nitrile);UV (dichloromethane): lmax 266,
295, 331, 346, 415 nm; Tg 238.5 8C under nitrogen and Td (onset,
1.4 wt% loss) 374.0 8C under nitrogen.
Random Copolymerization of endo-5-(9-Carbazolyl)-
trans-6-methyl-2-norbornene and endo-5-[9-(3'-
Bromocarbazolyl)]-trans-6-methyl-2-norbornene
A solution of catalyst RuCl2( CHPh)(PCy3)2 (68 mg, 8.02 Â
10À5 mol) in 3 mL of dichloromethane and the mixture of
monomers, endo-5-(9-carbazolyl)-trans-6-methyl-2-norbor-
nene (1.12 g, 4.10 Â 10À3 mol) and endo-5-[9-(3'-bromocarba-
zolyl)]-trans-6-methyl-2-norbornene
(723 mg,
2.05 Â
10À3 mol), in 12 mL of dichloromethane were prepared in
different flasks in nitrogen-filled glove-box. The catalyst
solution was injected into the monomer solution by syringe.
The reaction was carried out at ambient temperature for 3.25 h
before termination as described above. The polymer was
precipitated in methanol. The precipitate was collected by
filtration, dried, re-dissolved in dichloromethane and re-
precipitated by dropwise addition of a concentrated solution
into a vigorously stirred excess of methanol. This procedure
was done one more time, and the polymer products were
isolated by filtration and dried under vacuum at room temper-
ature; yield: 1.81 g (98%); MW 31,600 and PDI 1.35 (vs.
1
linear polystyrene standards); H NMR (300 MHz, CDCl3):
d 0.7 3.4 (br), 4.3 5.8 (br), 7.0 7.6 (br), 7.8 8.3 (br);
13C NMR (500 MHz, CDCl3): d 15.4, 16.8, 37.9 39.5 (com-
plexmultiplicity), 41.0, 41.9, 43.6, 49.0, 65.8, 108.7, 111.6 112.5
(complexmultiplicity), 118.7, 120.1, 122.7, 123.7, 125.1, 128.2,
130.7, 133.0, 139.8, 141.9.
Acknowledgements
Formylation of the Random Copolymer
A stirred solution of 1.73 g of random copolymer in 30 mL of
dry benzene was kept at room temperature while 2.6 mL of n-
The authors thank the Robert A. Welch Foundation (Grant f-
149) for support of this research.
198
Adv. Synth. Catal. 2002, 344, 192 199