4-(diethoxymethyl)benzaldehyde

Conditions: temp:0.00; pressure:0.00; stir:

Conditions: temp:0.00; pressure:0.00; stir:

Conditions: temp:0.00; pressure:0.00; stir:

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

Procedure: To a solution of 4-(diethoxymethyl)benzaldehyde (5.0 g, 24 mmol) in ether (65 ml), cooled to -10° C., was added dropwise a 1.5M toluene-THF methylmagnesium bromide solution (64 ml, 96 mmol) at such a rate that the temperature remains below 0° C. After the addition the reaction was quenched with saturated ammonium chloride (80 ml) and the solution was diluted with water (50 ml) and extracted with ether (2×75 ml). The combined extracts were washed with water (50 ml) and brine (50 ml), dried over sodium sulfate and concentrated in vacuo, leaving present title product (5.2 g, 97%) as an oil. remains below 0° C After the addition the reaction was quenched with saturated ammonium chloride (80 ml) the solution was diluted with water (50 ml) extracted with ether (2×75 ml) The combined extracts were washed with water (50 ml) and brine (50 ml) dried over sodium sulfate concentrated in vacuo

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

Procedure: To a solution of terephthalaldehyde mono(diethyl acetal) (1.9 ml, 9.6 mmol) in methanol (35 ml) was added sodium borohydride (1.1 g, 28.8 mmol) while cooling. After 5 minutes at room temperature the reaction was quenched with water (50 ml) and the mixture was extracted with ethyl acetate (2×50 ml). The combined extracts were washed with water and brine, dried over sodium sulfate and concentrated in vacuo, leaving title product as a colorless oil (1.81 g, 90%). while cooling After 5 minutes at room temperature the reaction was quenched with water (50 ml) the mixture was extracted with ethyl acetate (2×50 ml) The combined extracts were washed with water and brine dried over sodium sulfate concentrated in vacuo

Conditions: temp:0.00; pressure:0.00; stir:

Conditions: temp:0.00; pressure:0.00; stir:

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

Procedure: 4-(Diethoxymethyl)benzaldehyde (104 g, 0.5 mol) was dissolved in 300 ml of ether and the resulting solution cooled to -75° C. in an acetone-dry ice bath. With vigorous stirring, methyllithium (390 mL of 1.4M in ether, 0.55 mol) was added at a rate which maintained the temperature at less than -60° C. The reaction mixture was allowed to warm to room temperature, stirred for two hours at that temperature, poured into 500 mL of ice and water, stirred 10 minutes and the layers separated. The aqueous layer was extracted with 500 mL ether. The organic layers were combined, washed with 500 mL each of H2O and then brine dried (MgSO4) and stripped in vacuo to yield 110-111.5 (98-100%) of present title product as a viscous, light yellow oil. maintained the temperature at less than -60° C to warm to room temperature stirred 10 minutes the layers separated The aqueous layer was extracted with 500 mL ether washed with 500 mL each of H2O brine dried (MgSO4)

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

Procedure: 4-(Diethoxymethyl)benzaldehyde (104 g, 0.5 mol) was dissolved in 300 ml of ether and the resulting solution cooled to -75° C. in an acetone-dry ice bath. With vigorous stirring, methyllithium (390 mL of 1.4M in ether, 0.55 mol) was added at a rate which maintained the temperature at less than -60° C. The reaction mixture was allowed to warm to room temperature, stirred for two hours at that temperature, poured into 500 mL of ice and water, stirred 10 minutes and the layers separated. The aqueous layer was extracted with 500 mL ether. The organic layers were combined, washed with 500 mL each of H2O and then brine dried (MgSO4) and stripped in vacuo to yield 110-111.5 (98-100%) of present title product as a viscous, light yellow oil. maintained the temperature at less than -60° C to warm to room temperature stirred 10 minutes the layers separated The aqueous layer was extracted with 500 mL ether washed with 500 mL each of H2O brine dried (MgSO4)

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

Procedure: Potassium tert-butoxide (0.044 mol, 44mL 1M solution in THF) was added to a mixture of terephthalaldehyde mono-(diethyl acetal) (Sigma-Aldrich) (9.98 g, 0.048 mol) and 4-(diphenylamino)benzyltributylphosphonium bromide (21.6 g, 0.040 mol) in anhydrous THF (200 mL) in a 500 mL round bottom flask equipped with a reflux condenser, addition funnel and nitrogen inlet. After the addition was complete, the mixture was refluxed for 2 hours, and then cooled to RT. Aqueous HCl (20 mL, 3M) was then added and the mixture was stirred an additional hour. The product was extracted with methylene chloride (3×100 mL) and the combined organic solution dried with MgSO4. The solvent was removed by rotovaporization and the crude product purified by silica gel column chromatography (1:1 hexane:methylene chloride) yielding the pure product as a bright yellow solid (13 g, 87%). 1H NMR δ: 7.02-7.85 (m, 18 Ar—H, 2 vinyl H), 9.96 (s, 1H, CHO). equipped with a reflux condenser, addition funnel and nitrogen inlet After the addition the mixture was refluxed for 2 hours The product was extracted with methylene chloride (3×100 mL) the combined organic solution dried with MgSO4 The solvent was removed by rotovaporization the crude product purified by silica gel column chromatography (1:1 hexane:methylene chloride)

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

Procedure: Potassium tert-butoxide (0.044 mol, 44mL 1M solution in THF) was added to a mixture of terephthalaldehyde mono-(diethyl acetal) (Sigma-Aldrich) (9.98 g, 0.048 mol) and 4-(diphenylamino)benzyltributylphosphonium bromide (21.6 g, 0.040 mol) in anhydrous THF (200 mL) in a 500 mL round bottom flask equipped with a reflux condenser, addition funnel and nitrogen inlet. After the addition was complete, the mixture was refluxed for 2 hours, and then cooled to RT. Aqueous HCl (20 mL, 3M) was then added and the mixture was stirred an additional hour. The product was extracted with methylene chloride (3×100 mL) and the combined organic solution dried with MgSO4. The solvent was removed by rotovaporization and the crude product purified by silica gel column chromatography (1:1 hexane:methylene chloride) yielding the pure product as a bright yellow solid (13 g, 87%). 1H NMR δ: 7.02-7.85 (m, 18 Ar—H, 2 vinyl H), 9.96 (s, 1H, CHO). equipped with a reflux condenser, addition funnel and nitrogen inlet After the addition the mixture was refluxed for 2 hours The product was extracted with methylene chloride (3×100 mL) the combined organic solution dried with MgSO4 The solvent was removed by rotovaporization the crude product purified by silica gel column chromatography (1:1 hexane:methylene chloride)

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

Procedure: A mixture of terephthalaldehyde (10 g, 74.55 mmol), ammonium chloride (160 mg, 3.0 mmol) in ethanol (10.3 g, 223.6 mmol) was added dropwise triethoxymethane (12.15 g, 82 mmol) at 0° C. After the addition, the mixture was stirred at room temperature overnight. The mixture was concentrated, the residue was purified by silica gel chromatography to give the title compound (7.0 g, yield 50%) as a white solid. LC-MS (ESI) m/z: 209 (M+1)+. After the addition The mixture was concentrated the residue was purified by silica gel chromatography