Polymerization of phenylacetylene by triethyl aluminum and titanium tetraethoxide

Abstract

The polymerization of phenylacetylene to polyphenylacetylene was accomplished with the combined catalysts triethyl aluminum and titanium tetraethoxide. The progress of the reaction was monitored by gas chromatography. The parameters included temperature (−80, 25, 140°C), solvent (benzene, chlorobenzene, toluene, cyclohexane, and nitrobenzene), mole ratio of catalysts (Al/Ti; 1.5, 3.0, 4.5, 6.0, and 9.0), aging times of catalysts (2, 10, and 40 min), and order of addition of reagents. Derivatives of polyphenylacetylene were obtained by the acylation of polyphenylacetylene with p‐nitrobenzoyl chloride, the sulfonation of polyphenylacetylene with benzenesulfonyl chloride, and the formation of polyphenylacetylene complexes with complexing agents such as bromine, iodine, iodine chloride, boron trifluoride, and ferric chloride. A new phenylacetylene‐acetylene product mixture was produced by the polymerization of phenylacetylene and acetylene at 25 and −80°C. The electrical conductivity of polyphenylacetylene and its derivatives is in the range of 10−10−10−3 Ω−1 cm−1.

The electrical properties of poly(5,6-dihydroxy-2-cyclohexen-1,4-ylene) derivatives

“…"From a comparison of the high-field resonance with the resonance of the side chain ester substituent. 6 Value cannot be calculated due to overlapping resonance of the acetate group. was prepared in several steps by the Wittig coupling of two allylic reactants followed by an electrocyclic ring closure.18…”

“…The mixture was then diluted with dichloromethane (200 mL) and washed with 10% hydrochloric acid solution (2 X 50 mL), water (50 mL), 5% sodium hydroxide solution (50 mL), water (50 mL), and saturated sodium chloride solution (50 mL). The organic phase was then dried (magnesium sulfate), concentrated, flash chromatographed (silica gel, 40% ether/hexane), recrystallized (ethanol/water), and dried to give 22 g (89%) of 5: mp 80-80.5 °C; IR (CHC13) 2880,1730,1385,1190,1020 cm"1; NMR (60 MHz) 2.4-2.S (m, 4 H), 5.62 (t, 2 H, J = 6 Hz), 5.78 (t, 2 H, J = 1 Hz), 7.45-7.70 (m, 6 ), 8.0-8.2 (m, 4 H). Anal.…”

“…The residue was dissolved in dichloromethane (50 mL) and washed with aqueous 10% hydrochloric acid solution (25 mL), water (25 mL), aqueous 5% sodium hydroxide solution (25 mL), water (25 mL), and aqueous saturated sodium chloride solution (25 mL). The dichloromethane solution was dried (magnesium sulfate), concentrated, and purified by flash chromatography (40% ether/hexane) to give 0.62 g (62%) of la: mp 91-92 °C (ethanol/water); IR (CC14) 1735,1520,1245 cm"1; NMR (270 MHz) 5.89 (br s, 2 ), 6.05-6.15 (m, 2 H), 6.15-6.3 (m, 2 H), 7.25-7.6 (m, 6 ), Anal. Caled for C2oH1604: C, 74.99; , 5.04.…”

“…Caled for C2oH1604: C, 74.99; , 5.04. Found: C, 74.80; , 5.08. cis-4,5-Bis(pivaloyloxy)cyclohexene (6). Pivaloyl chloride (13 g, 0.11 mol) followed by DMAP (1.3 g, 11 mmol) was added to a solution of 4 (4.0 g, 35 mmol) and triethylamine (17 mL, 0.12 mol) in dichloromethane (100 mL) at 0 °C.…”

“…The ethereal phase was washed with aqueous 10% hydrochloric acid solution (2 X 50 mL), water (50 mL), aqueous 5% sodium hydroxide solution (50 mL), water (50 mL), and aqueous sodium chloride solution (50 mL), then dried (magnesium sulfate), and concentrated to give 7.7 g (84%) of lb. The material was further purified by MPLC (4% ethyl acetate/hexane) and bulb-to-bulb distillation: bp 95 °C (0.01 mm); IR (neat) 3080, 3000,1750,1490, 1290, 1150 cm"1; NMR (270 MHz) 1.20 (s, 18 H), 5.49 (m, 2 H), 5.88 (m, 2 ), 6.07 (m, 2 H); 13C NMR (68 MHz) 27.0, 38.8, 67.2,125.7,125.9,175.5. Anal.…”