4,5-dihydroxybenzene-1,2-dicarbonitrile

Conditions: temp:75.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: To the mixture of 4,5-dihydroxy-phthalonitrile (2.50 g, 15.6 mmol), 2-(2,2-diethoxy-ethyl)-propane-1,3-diol (4.5 g, 23.4 mmol) and triphenylphosphine (6.138 g, 23.4 mmol) in THF (40 mL) was added diethyl azodicarboxylate (4.08 g, 23.4 mmol) and the resulting mixture heated at 75° C. overnight. The resulting mixture was then cooled to room temperature and evaporated in vacuo to yield a solid, which was purified via flash column chromatography (EA/Hex 2:3) to yield 3-(2,2-diethoxyethyl)-3,4-dihydro-2H-benzo[b][1,4]dioxepine-7,8-dicarbonitrile as a white solid. MS MH+=317, 1H NMR (CDCl3) δ 7.29 (s, 2H), 4.58 (m, 1H), 4.46 (m, 2H), 4.19 (m, 2H), 3.66 (m, 2H), 3.52 (m, 2H), 2.60 (m, 1H), 1.78 (m, 2H), 1.20 (t, J=7.0 Hz, 6H). The resulting mixture was then cooled to room temperature evaporated in vacuo to yield a solid, which was purified via flash column chromatography (EA/Hex 2:3)

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: A slurry of 4,5-bis-bromomethyl-phthalic acid dimethyl ester (1.57 g, 4.12 mmol), 4,5-dihydroxy-phthalonitrile (660 mg, 4.12 mmol) and potassium carbonate (1.1 g, 8.24 mmol) in DMF (20 mL) was heated to 60° C. for 1 h under an atmosphere of argon. The resulting slurry was cooled to room temperature and diluted with water. A white precipitate was collected via filtration and re-crystallized from EtOAc to yield 2,3-dicyano-6,11-dihydro-5,12-dioxa-dibenzo[a,e]cyclooctene-8,9-dicarboxylic acid dimethyl ester as a white solid. C20H14N2O6; MS (ESI) m/z 378.9 (MH)+. A white precipitate was collected via filtration re-crystallized from EtOAc