3,5-dibromobenzaldehyde

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:

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

Conditions: temp:130.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: A mixture of 3,5-dibromobenzaldehyde (8.21 g, 31.1 mmoles), 3,5-bis(3′,5′-di-t-butylstyryl)styrene (41.4 g, 77.7 mmoles), anhydrous sodium carbonate (6.59 g, 62.2 mmoles), trans-di(μ-acetato)-bis[o-(di-o-tolylphosphino)benzyl]dipalladium (II) (58.3 mg, 0.062 mmoles, 0.1 mole %), 2,6-di-t-butylcresol (1.71 g, 7.77 mmoles) and anhydrous N,N-dimethylacetamide (100 mL) was degassed extremely thoroughly whilst stirring under oil-pump vacuum, purging with argon. The reaction mixture was then heated under argon at 130° C. for 17 hours. After further addition of anhydrous N,N-dimethylacetamide (100 mL), the reaction mixture was degassed for a second time and then heated at 130° C. for a further 5.5 hours. Further anhydrous N,N-dimethylacetamide (100 mL) was then added and the reaction was continued for a further 1 hour. The resulting sludge was washed with distilled water (3×250 mL) and dissolved in dichloromethane (1500 mL). The organic fraction was washed with distilled water (500 mL), dried over anhydrous sodium sulphate and evaporated to give a cream solid. The crude product was recrystallized from dichloromethane/pet. ether (60-80) three times before chromatography on flash silica using chloroform-pet.ether (60-80) (2:3) as the eluent gave a white solid of 3,5-bis[3′,5′-bis(3″,5-″-di-t-butylstyryl)styryl]benzaldehyde (25.2 g, 69%); δH(500 MHz; CDCl1) 1.41 (72H, s, t-Bu), 7.20 and 7.32 (8H, d, J 16, G-2 vinyl H), 7.34 and 7.38 (4H, d, J 16.5, G-1 vinyl H), 7.42 (4H, dd, J 2, sp H), 7.46 (8H, d, J 2, sp H), 7.67 (4H, s, G-1 bp H), 7.69 (2H, s, G-1 bp H), 8.00 (3H, s, cp H) and 10.14 (1H, s, CHO) which is identical to that reported. was degassed extremely thoroughly purging with argon After further addition of anhydrous N,N-dimethylacetamide (100 mL) the reaction mixture was degassed for a second time heated at 130° C. for a further 5.5 hours Further anhydrous N,N-dimethylacetamide (100 mL) was then added The resulting sludge was washed with distilled water (3×250 mL) dissolved in dichloromethane (1500 mL) The organic fraction was washed with distilled water (500 mL) dried over anhydrous sodium sulphate evaporated to give a cream solid The crude product was recrystallized from dichloromethane/pet. ether (60-80) three times before chromatography on flash silica

Conditions: temp:130.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: A mixture of 3,5-dibromobenzaldehyde (31.7 g, 120 mmoles), 3,5-di-t-butylstyrene (65.0 g, 301 mmoles), anhydrous sodium carbonate (31.9 g, 301 mmoles), trans-di(μ-acetato)-bis[o-(di-o-tolylphosphino)benzyl]dipalladium (II) (244 mg, 0.26 mmoles, 0.1 mole %), 2,6-di-t-butylcresol (13.3 g, 60 mmoles) and anhydrous N,N-dimethylacetamide (130 mL) was degassed thoroughly whilst stirring under oil-pump vacuum, purging with argon. The reaction mixture was then heated under argon at 130° C. for 26.5 h. After cooling, ether (250 mL) and hydrochloric acid (1.5 M, 150 mL) were added carefully. A suspension remained in the organic layer, which was washed with distilled water (5×125 mL) and evaporated. The combined aqueous layers were extracted with ether (100 mL) and this organic extract was washed with distilled water (4×30 mL) and combined with the main organic fraction. The crude product was triturated thoroughly with cold pet. ether (40-60), filtered and recrystallized from dichloromethane/pet. ether (60-80) to give colourless crystals of 3,5-bis(3′,5′-di-t-butylstyryl)benzaldehyde (44.61 g, 69%), m.p. 217-219° C. (Found: C, 87.7; H, 9.7. C39H50O requires C, 87.6; H, 9.4%); νmax (CHCl3)/cm−1 1698s (C═O), 1596s (C═C) and 964s (C═C—H trans); λmax (CHCl3)/nm 316 (log ε/dm3 mol−1 cm−1 4.65); δH(500 MHz; CDCl3) 1.41 (36H, s, t-Bu), 7.20 and 7.34 (4H, d, J 16, vinyl H), 7.43 (2H, dd, J 2, sp H), 7.44 (4H, d, J 2, sp H), 7.94 (1H, m, cp H), 7.95 (2H, d, J 1.5, cp H) and 10.11 (1H, s, CHO); m/z (APCI+) 535 (M+, 100%). was degassed thoroughly purging with argon After cooling ether (250 mL) and hydrochloric acid (1.5 M, 150 mL) were added carefully was washed with distilled water (5×125 mL) evaporated The combined aqueous layers were extracted with ether (100 mL) this organic extract was washed with distilled water (4×30 mL) The crude product was triturated thoroughly with cold pet. ether (40-60) filtered recrystallized from dichloromethane/pet. ether (60-80)

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

Procedure: 10 g (37.9 mmol) of 3,5-dibromobenzaldehyde and 5 g (45.5 mmol) of 2-aminophenol were dissolved in 200 mL of acetic acid. The solution was agitated at room temperature for 30 minutes. Next, 20.2 g (45.5 mmol) of lead (IV) acetate was added thereto. The resulting product was agitated at 50° C. for 1 hour. Then, water was added to the acquired reactant. The mixture was extracted with ethyl acetate and treated under reduced pressure to remove the solvent, obtaining 5.7 g (Y=42%) of a white solid. The resulting product was agitated at 50° C. for 1 hour The mixture was extracted with ethyl acetate treated under reduced pressure to remove the solvent obtaining 5.7 g (Y=42%) of a white solid

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

Procedure: 5.03 g (19.1 mmol) of 3,5-dibromobenzaldehyde and 3.1 mL (28.6 mmol) of 2-aminothiophenol were dissolved in 60 mL of acetic acid. The solution was agitated at room temperature for 30 minutes. 9.78 g (21.0 mmol) of lead (IV) acetate was added thereto. The resulting mixture was agitated at 50° C. for 1 hour. Then, water was poured into the reactant. It was extracted with ethyl acetate. The extract was separated through a column and dried, obtaining 4.74 g (Y=67%) of a white solid. The resulting mixture was agitated at 50° C. for 1 hour It was extracted with ethyl acetate The extract was separated through a column dried obtaining 4.74 g (Y=67%) of a white solid

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

Procedure: 20 g (75.8 mmol) of 3,5-dibromobenzaldehyde and 16.8 g (90.9 mmol) of N-phenyl-o-phenylenediamine were dissolved in 150 mL of acetic acid. The solution was agitated at room temperature for 30 minutes. Next, 37 g (83.4 mmol) of lead (IV) acetate was added thereto. The resulting product was agitated at 50° C. for 1 hour. Then, water was poured into the acquired reactant. The resulting product was treated with ethyl acetate to perform extraction and the solvent was removed under reduced pressure. The extract was separated through a column and dried, gaining 9.5 g (Y=29%) of a yellow solid. The resulting product was agitated at 50° C. for 1 hour extraction the solvent was removed under reduced pressure The extract was separated through a column dried

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

Procedure: To 3,5-dibromobenzylbromide (Lancaster) (20 g, 0.061 mole) in H2O (27 mL) and glacial acetic acid (27 mL) was added hexamethylenetetramine (Aldrich). The reaction mixture was heated at reflux for 2 hours. Concentrated HCl (22 mL) was then added and the refluxing was continued for 30 minutes. After cooling to room temperature, the reaction mixture was poured into H2O (230 mL) and stirred for 10 minutes. The resulting precipitate was filtered, washed with H2O and dried to yield 3,5-dibromobenzaldehyde (11.45 g) as a white solid. MS and NMR were consistent with the desired structure. The reaction mixture was heated at reflux for 2 hours The resulting precipitate was filtered washed with H2O dried

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

Procedure: 3,5-Dibromobenzaldehyde (1 eq.), cyclopropylamine (2 eq.) and magnesium sulfate (1 eq.) were stirred in dichloromethane (0.1 M) for 20 h. The insolubles were then removed via filtration through a pad of celite and washed further with dichloromethane. The filtrate was concentrated in vacuo to afford the crude imine which was then immediately re-taken up in MeOH (0.1 M). To this solution was added sodium borohydride (5 eq.) portionwise and the resulting mixture was stirred at RT for 4 h. The reaction was quenched with 1 N aq. HCl, neutralized with 1 N aq. NaOH and extracted with ether. The combined organic extracts were then washed further with water and brine, dried over MgSO4, and filtered. Concentration of the filtrate in vacuo afforded the title compound as a pale yellow oil. The insolubles were then removed via filtration through a pad of celite washed further with dichloromethane The filtrate was concentrated in vacuo to afford the crude imine which The reaction was quenched with 1 N aq. HCl extracted with ether The combined organic extracts were then washed further with water and brine dried over MgSO4 filtered