1-Bromonaphthalene → 1-n-Octylnaphthalene

In a dry N2 purged flask, octylmagnesium bromide (100 mmol), Ni(dppp)Cl2 (0.4 g, 1 mol %), zinc chloride (10.2 g, 75 mmol), and THF (100 mL) were added and allowed to stir for 30 minutes before 1-bromonapthalene (10.43 mL, 75 mmol) was added slowly. The solution was then heated to reflux overnight before being quenched with saturated ammonia chloride (150 mL). The crude 1-octylnapthalene was then extracted with hexanes (3×50 mL), washed with H2O (100 mL), and dried with anhydrous magnesium sulfate. The solvent was filtered and removed via rotary evaporation. The resulting oil was diluted with hexanes (10 mL) and purified by column chromatography (silica, hexanes) yielding 1-octylnapthalene as a colorless oil (16.9 g, 93%). 1H NMR: δ 8.09 (d, J=8.4 Hz, 1H), 7.89 (d, J=8 Hz, 1H), 7.24 (d, J=8 Hz, 1H), 7.518 (m, 2H), 7.430 (dt, J=8.4 Hz, 6.8 Hz, 1H), 7.36 (d, J=6.8 Hz, 1H), 3.10 (t, J=8 Hz, 2H), 1.79 (p, J=8.0 Hz, 2H), 1.48 (m), 1.34 (m), 0.93 (t, J=7.2 Hz, 6.8 Hz, 3H). 13C NMR: δ 139.3, 134.1, 132.2, 129.0, 126.6, 126.1, 125.8, 125.7, 125.6, 124.2, 33.4, 32.2, 31.1, 30.1, 29.8, 29.6, 22.9, 14.4 5-Octylacenapthylene-1,2-dione (18, Scheme 5, wherein R=octyl). Oxalyl chloride (6.47 g, 50 mmol) was added to a stirred suspension of AlCl3 (13.3 g, 100 mmol) in dichloromethane (300 mL) under N2 at −5° C. After drop wise addition of 1-octylnapthalene (12.02 g, 50 mmol) was diluted in dichloromethane (100 mL) and added dropwise to the reaction mixture. The new mixture was allowed to stir for an additional 5 hours making sure the temperature did not get above 0° C. The reaction mixture was then quenched by pouring over ice (200 g). The quenched solution was allowed to warm to room temperature and the resulting layers separated. The organic layer was washed with a saturated solution of sodium bicarbonate (1×100 mL) and water (1×100 mL) after which it was dried with anhydrous magnesium sulfate. The solvent was filtered and removed by rotary evaporation resulting in the crude product. The product was purified by column chromatography (silica, 10% EtOAc in Hexanes) yielding a yellow solid of 5-octylacenapthylene-1,2-dione (3.74 g, 30%). 1H NMR: δ 8.33 (d, J=8.4 Hz, 1H), 8.01 (d, J=6.8 Hz, 1H), 7.98 (d, J=7.2 Hz, 1H), 7.80 (dt, J=7.2 Hz, 6.8 Hz, 1H), 7.62 (d, J=7.2 Hz, 1H), 3.16 (t, J=8 Hz, 2H) 1.78 (p, J=8 Hz, 2H), 1.44 (m, 2H), 1.25 (m, 8H), 0.85 (t, J=7.2 Hz, 3H). 13C NMR: δ 189.1, 187.9, 147.8, 146.4, 130.1, 129.9, 129.1, 128.1, 127.2, 126.8, 122.4, 121.7, 33.3, 32.0, 30.8, 29.9, 29.6, 29.4, 22.8, 14.3. 5-Octylacenaptho[1,2-b]thieno[5,4-e]pyrazine (3k, Scheme 5, wherein R=octyl). Diaminothiophene 1 (0.507 g, 5.0 mmol) was dissolved in 50 mL of absolute ethanol. Octylacenapthylene dione (1.246 g, 5.0 mmol) was then added and the solution was heated at reflux for 3 hours. The mixture was then cooled to room temperature, diluted with 100 mL of water, and extracted with dichlormethane. The combined organic layers were dried with anhydrous magnesium sulfate and the solvent removed by rotary evaporation. The resulting oily solid was then purified by column chromatography (50% CH2Cl2 in hexanes) yielding a yellow solid of 5-octylacenaptho[1,2-b]thieno[5,4-e]pyrazine (0.37 g, 20%. 1H NMR: δ 8.3 (d, J=6.8 Hz, 1H), 8.22 (dd, J=8.0 Hz, 7.2 Hz, 2H), 7.98 (dd, J=8.4 Hz, 8.0 Hz, 2H), 7.82 (t, J=6.8 Hz, 1H), 7.63 (d, J=7.2 Hz, 1H) 3.192 (t, J=7.6 Hz, 2H), 1.83 (p, J=7.6 Hz, 2H), 1.47 (m, 2H) 1.31 (m, 8H), 0.83 (t, J=7.2 Hz, 3H). 13C NMR: 154.7, 154.4, 143.6, 142.1, 142.0, 138.0, 132.0, 129.6, 129.5, 128.4, 128.3, 126.4, 121.2, 120.7, 117.6, 117.3, 32.8, 32.1, 31.6, 30.0, 29.7, 29.5, 22.9, 14.3. Polymer (20). Electropolymerization experiments were carried out in a three-electrode cell consisting of a platinum disc working electrode, a platinum wire auxiliary electrode, and a silver wire quasi-reference electrode. Solutions consisted of monomer 3k (0.05 M) dissolved in anhydrous CH3CN. The supporting electrolyte was 0.10 M TBAPF6. The solutions were deoxygenated by sparging with argon prior to each scan and blanketed with argon during the polymerizations. The platinum disc working electrode was polished with 0.05 mm alumina and washed well with deionized water and dry CH3CN prior to each film growth. The films were grown at a constant potential corresponding to the monomer Epa. The polymer-coated electrode was then removed, washed with CH3CN and placed in a cell with a fresh electrolyte solution for cyclic voltammetry measurements.

1. additionwas added slowly
2. temperatureThe solution was then heated
3. temperatureto reflux overnight
4. custombefore being quenched with saturated ammonia chloride (150 mL)
5. extractionThe crude 1-octylnapthalene was then extracted with hexanes (3×50 mL)
6. washwashed with H2O (100 mL)
7. dry with materialdried with anhydrous magnesium sulfate
8. filtrationThe solvent was filtered
9. customremoved via rotary evaporation
10. additionThe resulting oil was diluted with hexanes (10 mL)
11. custompurified by column chromatography (silica, hexanes)

ORD record

ord-8b2b2fdccec94a1a93b01bdacd5d682e

Source dataset

uspto-grants-2011_02

DOI

10.6084/m9.figshare.5104873.v1

Patent number

US07888452B2