2-phenylmethoxybenzaldehyde

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:0.00; pressure:0.00; stir:

Conditions: temp:70.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: 185 g of dimethylformamide and 82.8 g (0.6 mol) of potassium carbonate were placed in a flask, and 61 g (0.5 mol) of salicylaldehyde were added dropwise thereto. 75.9 g (0.6 mol) of benzyl chloride were then added dropwise to the resulting mixture at a temperature of 50° C. for one hour. After the addition, the mixture was stirred at a temperature of 70° C. for two hours. The resulting reaction mixture was washed with 185 g of toluene and 330 g of water. The solvent was distilled out of the mixture at an inside temperature of 90° C. under a reduced pressure of 10 mmHg thereby providing 104.5 g of 2-benzyloxybenzaldehyde as bottom in the form of brown liquid having a purity 97.9% in a yield of 96.5%. After the addition The resulting reaction mixture was washed with 185 g of toluene and 330 g of water The solvent was distilled out of the mixture at an inside temperature of 90° C. under a reduced pressure of 10 mmHg

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

Procedure: 2-(benzyloxy)benzaldehyde (5g, 23.6 mmol) was reacted with vinylmagnesium bromide in THF (90 ml) at 0 C. The reaction was quenched with 2 N HCl and the product was extracted in i-PrOAc, dried over Na2SO4 and purified by flash chromatography with EtOAc:toluene 2.5:97.5. The reaction was quenched with 2 N HCl the product was extracted in i-PrOAc dried over Na2SO4 purified by flash chromatography with EtOAc:toluene 2.5:97.5

Conditions: temp:60.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: In methanol (20 ml) were dissolved 2-amino-5-chloro-α-(3-tert-butoxycarbonylaminomethylphenyl)benzyl alcohol (0.5 g) obtained in Example 1 (2) and 2-benzyloxybenzaldehyde (0.7 g). To the solution were added acetic acid (0.15 g) and cyano sodium borohydride (0.16 g). The mixture was stirred for 40 minutes at 60° C. The reaction mixture was concentrated, to which were added water (50 ml) and ethyl acetate (60 ml), followed by subjecting the mixture to extraction. The organic layer was separated, washed with water and dried over anhydrous sodium sulfate. The solvent was distilled off, and the residue was purified by means of a silica gel column chromatography to give 2-(2-benzyloxybenzylamino)-5-chloro-α-(3-tert-butoxycarbonylaminomethylphenyl)benzyl alcohol (1.05 g) as a colorless oily product. The reaction mixture was concentrated, to which were added water (50 ml) and ethyl acetate (60 ml) to extraction The organic layer was separated washed with water dried over anhydrous sodium sulfate The solvent was distilled off the residue was purified by means of a silica gel column chromatography

Conditions: temp:60.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: In methanol (20 ml) were dissolved 2-amino-5-chloro-α-(3-tert-butoxycarbonylaminomethylphenyl)benzyl alcohol (0.5 g) obtained in Example 1 (2) and 2-benzyloxybenzaldehyde (0.7 g). To the solution were added acetic acid (0.15 g) and cyano sodium borohydride (0.16 g). The mixture was stirred for 40 minutes at 60° C. The reaction mixture was concentrated, to which were added water (50 ml) and ethyl acetate (60 ml), followed by subjecting the mixture to extraction. The organic layer was separated, washed with water and dried over anhydrous sodium sulfate. The solvent was distilled off, and the residue was purified by means of a silica gel column chromatography to give 2-(2-benzyloxybenzylamino)-5-chloro-α-(3-tert-butoxycarbonylaminomethylphenyl)benzyl alcohol (1.05 g) as a colorless oily product. The reaction mixture was concentrated, to which were added water (50 ml) and ethyl acetate (60 ml) to extraction The organic layer was separated washed with water dried over anhydrous sodium sulfate The solvent was distilled off the residue was purified by means of a silica gel column chromatography

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

Procedure: Salicylaldehyde (50 mmoles) was dissolved in dry dimethylformamide (DMF) (100 ml) at room temperature. Benzyl bromide (75 mmoles) was then added followed by the potassium carbonate (125 mmoles) and the mixture stirred at room temperature for 48 h. The mixture is then filtered to remove the potassium carbonate and the filtrate is mixed with ethyl acetate. The organic phase is washed with water (3×200 ml), brine and dried over MgSO4. The solution is then filtered and evaporated in vacuo to provide the crude material. Solid products are washed with ethyl ether to provide the clean desired product or in the case of aldehydes which are oils, they are purified by silica gel chromatography. The mixture is then filtered to remove the potassium carbonate the filtrate is mixed with ethyl acetate The organic phase is washed with water (3×200 ml), brine dried over MgSO4 The solution is then filtered evaporated in vacuo to provide the crude material Solid products are washed with ethyl ether

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

Procedure: Salicylaldehyde (50 mmoles) was dissolved in dry dimethylformamide (DMF) (100 ml) at room temperature. Benzyl bromide (75 mmoles) was then added followed by the potassium carbonate (125 mmoles) and the mixture stirred at room temperature for 48 h. The mixture is then filtered to remove the potassium carbonate and the filtrate is mixed with ethyl acetate. The organic phase is washed with water (3×200 ml), brine and dried over MgSO4. The solution is then filtered and evaporated in vacuo to provide the crude material. Solid products are washed with ethyl ether to provide the clean desired product or in the case of aldehydes which are oils, they are purified by silica gel chromatography. The mixture is then filtered to remove the potassium carbonate the filtrate is mixed with ethyl acetate The organic phase is washed with water (3×200 ml), brine dried over MgSO4 The solution is then filtered evaporated in vacuo to provide the crude material Solid products are washed with ethyl ether