3070 Notes
Macromolecules, Vol. 37, No. 8, 2004
(75 MHz, CDCl3): δ 55.3, 105.9, 121.7, 123.7, 125.7, 126.8,
127.8, 132.7, 139.8, 141.7, 144.1. MS (EI): calcd for C22H16
(M+), 280.1247; found, 280.1246.
Exp er im en ta l Section
Gen er a l Meth od s a n d In str u m en ta tion . All chemicals
were of reagent grade from Aldrich Chemical Co. (St. Louis,
MO) and used as received. All synthetic manipulations were
performed under an argon atmosphere using standard Schlenk
techniques unless otherwise noted. Glassware was oven dried
before use. Column chromatography was performed using
Baker 40 µm silica gel. All organic extracts were dried over
MgSO4 and filtered prior to removal with a rotary evaporator.
Monomers 47 and 66 were synthesized according to literature
procedures with a number of trivial modifications. NMR
spectra were obtained on Varian Unity 300 MHz and Varian
Mercury 300 MHz instruments. NMR chemical shifts are
P olym er iza tion of 4. Into a 25 mL Schlenk tube under
argon was added 4 (99 mg, 0.4 mmol). The compound was
slowly stirred and heated to 165 °C for 1 h. After cooling to
room temperature, the polymeric product was dissolved in a
small amount of THF and then precipitated into MeOH. The
white precipitate was isolated by centrifugation and dried
under vacuum to give 1 (70% yield). 1H NMR (300 MHz,
CDCl3): δ 2.13 (s, 4H), 4.70 (s, 2H), 6.88 (m, 2H), 7.11 (m,
2H). 13C NMR (75 MHz, CDCl3): δ 29.2, 55.4, 122.7, 124.6,
143.2, 146.4.
P olym er iza tion of 5. Into a 25 mL Schlenk tube under
argon was added 5 (102 mg, 0.4 mmol). The compound was
slowly stirred and heated to 165 °C for 1 h. After cooling to
room temperature, the sparingly soluble polymeric product was
partially dissolved in THF by sonication. After removal of the
insoluble polymer by filtration, the soluble fraction was then
precipitated into MeOH. The white precipitate was isolated
by centrifugation and dried under vacuum to give polymer 2
(32% yield). 1H NMR (300 MHz, CDCl3): δ 1.91-2.15 (m, 4H),
4.55-4.70 (m, 2H), 6.84-6.96 (m, 2H), 6.99 (s, 2H), 7.02-7.22
(m, 2H), 7.28-7.46 (m, 2H), 7.54-7.70 (m, 2H). 13C NMR (75
MHz, CDCl3): δ 55.3, 105.9, 121.7, 123.7, 125.1, 125.7, 126.8,
127.8, 144.1.
referenced to CHCl3/TMS (7.27 ppm for H, 77.23 ppm for 13C).
1
Mass spectra (MS) were obtained at the MIT Department of
Chemistry Instrumentation Facility (DCIF) using a peak-
matching protocol to determine the mass and error range of
the molecular ion. All polymer solutions were filtered through
0.45 µm syringe filters prior to use. Polymer molecular weights
were determined on a HP series 1100 GPC system in THF (1,
0.5, and 0.1 mg/mL sample concentrations) at room temper-
ature vs polystyrene standards. Transition temperatures were
determined by differential scanning calorimetry using a TA
Instruments (New Castle, DE) Q1000 DSC at scan rates of 10
°C/min. Film thicknesses were measured using a Veeco (Wood-
bury, NY) Dektak 6M Stylus profilometer. Ellipsometry was
performed on polymer films spin-coated onto silicon substrates
with a Gaertner Scientific (Chicago, IL) three-wavelength
variable-angle ellipsometer. Melting points were measured
with a Meltemp II apparatus and are reported uncorrected.
13,14-Dich lor om eth yl-5,12-d ih yd r o-5,12-eth a n on a p h -
th a cen e. Into a 100 mL heavy-walled glass tube were added
tetracene (0.81 g, 4 mmol) and 1,4-dichloro-2-butene (13.35 g,
107 mmol) under Ar. The tube was sealed and heated to 190
°C for 48 h. The dark mixture was then cooled to room
temperature. The solvent was distilled off (75 mTorr, 75 °C),
and the black residue was purified by column chromatography
(silica gel) with hexane-methylene chloride (2:1) as eluent to
yield 1.36 g as a crude mixture of cis, trans, exo, and endo
isomers. The compound was used without additional purifica-
P olym er iza tion of 6. Into a 25 mL Schlenk tube under
argon were added 6 (58 mg, 0.1 mmol) and a minimal amount
of THF (0.2 mL). The reaction was heated to 165 °C for 24 h.
The reaction mixture was then cooled to room temperature,
dissolved in additional THF, and slowly precipitated into
MeOH. The white precipitate was isolated by centrifugation
1
and dried under vacuum to give 3 (55% yield). H NMR (300
MHz, CDCl3): δ 2.20 (m, 4H), 4.79 (m, 2H), 5.25-5.42 (m, 2H)
6.85-7.50 (m, 14H). 13C NMR (75 MHz, CDCl3): δ 54.2, 118.1,
119.0, 122.4, 123.6, 125.3, 125.9, 142.1, 143.2, 145.7.
Ack n ow led gm en t. We thank the MIT Center for
Materials Science and Engineering for funding sup-
ported under the NSF MRSEC program. J .P.A. thanks
MIT for funding through a J ohn A. Lyons Graduate
Research Fellowship.
1
tion; mp 137-147 °C. H NMR (300 MHz, CDCl3) (note: the
spectrum is too complex to assign the individual isomers): δ
2.52-2.64 (m, 2H), 2.86-3.02 (m, 2H), 3.48-3.53 (dd, 2H, J
) 4, 11 Hz), 4.69-4.72 (dd, 2H, J ) 1, 6 Hz), 7.18-7.25 (m,
2H), 7.36-7.50 (m, 4H), 7.76-7.85 (m, 4H). 13C NMR (75 MHz,
CDCl3): δ 43.9, 44.5, 44.6, 44.7, 46.6, 46.7, 122.2, 124.2, 125.8,
125.9, 126.0, 126.7, 126.9, 127.8, 132.6, 137.6, 139.8, 140.6,
142.6. MS (EI): calcd for C22H18Cl2 (M+), 352.0780; found,
352.0790.
Refer en ces a n d Notes
(1) Yang, J .; Swager, T. M. J . Am. Chem. Soc. 1998, 120,
11864-11873.
(2) Williams, V. E.; Swager, T. M. Macromolecules 2000, 33,
4069-4073.
(3) Long, T. M.; Swager, T. M. J . Am. Chem. Soc. 2002, 124,
3826-3827.
13,14-Dim e t h yle n e -5,12-d ih yd r o-5,12-e t h a n on a p h -
th a cen e (5). Into a 250 mL round-bottom flask under Ar were
added potassium tert-butoxide (1.24 g, 11 mmol), 13,14-
dichloromethyl-5,12-dihydro-5,12-ethanonaphthacene (1.18 g,
3 mmol), THF (11 mL), and DMSO (22 mL). The dark green
mixture was stirred at room temperature for 36 h. The reaction
was quenched by pouring over ice water. The suspension was
extracted with ether (300 mL), washed with brine (100 mL),
and dried over MgSO4. After filtration and evaporation to
dryness, the product was purified by column chromatography
(silica gel) with hexane as eluent to give 0.70 g (75% yield) as
(4) Long, T. M.; Swager, T. M. Adv. Mater. 2001, 13, 601-604.
(5) Meek, J . S.; Stacy, R. D. J . Org. Chem. 1961, 26, 300-302.
(6) Luo, J .; Hart, H. J . Org. Chem. 1987, 52, 3631-3636.
(7) Butler, D. N.; Snow, R. A. Can. J . Chem. 1972, 50, 795-
802.
(8) Yates, P.; Eaton, P. J . J . Am. Chem. Soc. 1960, 82, 4436-
4437.
(9) Braillon, B.; Claire, J . C.; Saquet, M.; Thuillier, A. J . Chem.
Res. 1986, 98-99, 977-995.
(10) Patney, H. K. Synthesis 1991, 9, 694-696.
(11) Long, T. M.; Swager, T. M. J . Am. Chem. Soc. 2003, 125,
14113-14119.
1
a white powder; mp 153-156 °C. H NMR (300 MHz, CDCl3):
δ 5.01 (s, 2H), 5.21 (s, 2H), 5.36 (s, 2H), 7.15-7.17 (dd, 2H, J
) 3, 6 Hz), 7.36-7.43 (m, 4H), 7.76-7.79 (m, 4H). 13C NMR
MA0354694