2-amino-4-methoxybenzaldehyde

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

Procedure: To a stirred solution of 2-amino-4-methoxybenzaldehyde (6 g, 39.7 mmol) in dichloromethane (100 mL) was added N-bromosuccinimide (7 g, 39.7 mmol). LCMS monitored the reaction until the starting material consumed completely. The reaction mixture was diluted with dichloromethane and water. The separated organic layer was dried sodium sulfate, filtered and concentrated to give the title compound (5 g, 56%) as a yellow solid. MS (ES+) C8H8BrNO2 requires: 229, 231. found: 230, 232 [M+H]+. the reaction until the starting material consumed completely The reaction mixture was diluted with dichloromethane and water filtered concentrated

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

Procedure: A mixture of (2-amino-4-methoxyphenyl)methanol (20 g, 131.0 mmol) and manganese oxide (68 g, 786.0 mmol) in dichloromethane (300 mL) was stirred at RT overnight. LCMS showed the reaction was completed. The solid was filtered off, and the filtrate was concentrated. The residue was purified by silica gel chromatography (petroleum ether:ethyl acetate=6:1) to give the title compound (7 g, 35%) as a yellow solid. MS (ES+) C8H9NO2 requires: 151. found: 152 [M+H]+. The solid was filtered off the filtrate was concentrated The residue was purified by silica gel chromatography (petroleum ether:ethyl acetate=6:1)

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

Procedure: A mixture of (2-amino-4-methoxyphenyl)methanol (20 g, 131.0 mmol) and manganese oxide (68 g, 786.0 mmol) in dichloromethane (300 mL) was stirred at RT overnight. LCMS showed the reaction was completed. The solid was filtered off, and the filtrate was concentrated. The residue was purified by silica gel chromatography (petroleum ether:ethyl acetate=6:1) to give the title compound (7 g, 35%) as a yellow solid. MS (ES+) C8H9NO2 requires: 151. found: 152 [M+H]+. The solid was filtered off the filtrate was concentrated The residue was purified by silica gel chromatography (petroleum ether:ethyl acetate=6:1)

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

Procedure: To a stirred solution of 2-amino-4-methoxybenzaldehyde (6 g, 39.7 mmol) in dichloromethane (100 mL) was added N-bromosuccinimide (7 g, 39.7 mmol). The reaction mixture was diluted with dichloromethane and water. The separated organic layer was dried sodium sulfate, filtered and concentrated to give the title compound (5 g, 56%) as a yellow solid. MS (ES+) C8H8BrNO2 requires: 229, 231, found: 230, 232 [M+H]+. filtered concentrated

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

Procedure: A mixture of (2-amino-4-methoxyphenyl)methanol (20 g, 131.0 mmol) and manganese oxide (68 g, 786.0 mmol) in dichloromethane (300 mL) was stirred at room temperature overnight. The solid was filtered off, and the filtrate was concentrated. The residue was purified by silica gel chromatography (petroleum ether:ethyl acetate=6:1) to give the title compound (7 g, 35%) as a yellow solid. MS (ES+) C8H9NO2 requires: 151, found: 152 [M+H]+. The solid was filtered off the filtrate was concentrated The residue was purified by silica gel chromatography (petroleum ether:ethyl acetate=6:1)

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

Procedure: To a stirred solution of 2-amino-4-methoxybenzaldehyde (6 g, 39.7 mmol) in dichloromethane (100 mL) was added N-bromosuccinimide (7 g, 39.7 mmol). The reaction mixture was diluted with dichloromethane and water. The separated organic layer was dried sodium sulfate, filtered and concentrated to give the title compound (5 g, 56%) as a yellow solid. MS (ES+) C8H8BrNO2 requires: 229, 231, found: 230, 232 [M+H]+. filtered concentrated

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

Procedure: A mixture of (2-amino-4-methoxyphenyl)methanol (20 g, 131.0 mmol) and manganese oxide (68 g, 786.0 mmol) in dichloromethane (300 mL) was stirred at room temperature overnight. The solid was filtered off, and the filtrate was concentrated. The residue was purified by silica gel chromatography (petroleum ether:ethyl acetate=6:1) to give the title compound (7 g, 35%) as a yellow solid. MS (ES+) C8H9NO2 requires: 151, found: 152 [M+H]+. The solid was filtered off the filtrate was concentrated The residue was purified by silica gel chromatography (petroleum ether:ethyl acetate=6:1)

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

Procedure: A mixture of (2-amino-4-methoxyphenyl)methanol (20 g, 131.0 mmol) and manganese oxide (68 g, 786.0 mmol) in dichloromethane (300 mL) was stirred at RT overnight. LCMS showed the reaction was completed. The solid was filtered off, and the filtrate was concentrated. The residue was purified by silica gel chromatography (petroleum ether:ethyl acetate=6:1) to give the title compound (7 g, 35%) as a yellow solid. MS (ES+) C8H9NO2 requires: 151. found: 152 [M+H]+. Synthesis of 2-amino-5-bromo-4-methoxybenzaldehyde The solid was filtered off the filtrate was concentrated The residue was purified by silica gel chromatography (petroleum ether:ethyl acetate=6:1)

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

Procedure: To a stirred solution of 2-amino-4-methoxybenzaldehyde (6 g, 39.7 mmol) in dichloromethane (100 mL) was added N-bromosuccinimide (7 g, 39.7 mmol). LCMS monitored the reaction until the starting material consumed completely. The reaction mixture was diluted with dichloromethane and water. The separated organic layer was dried sodium sulfate, filtered and concentrated to give the title compound (5 g, 56%) as a yellow solid. MS (ES+) C8H8BrNO2 requires: 229, 231. Found: 230, 232 [M+H]+. the reaction until the starting material consumed completely The reaction mixture was diluted with dichloromethane and water filtered concentrated

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

Procedure: A mixture of (2-amino-4-methoxyphenyl)methanol (20 g, 131.0 mmol) and manganese oxide (68 g, 786.0 mmol) in dichloromethane (300 mL) was stirred at RT overnight. LCMS showed the reaction was completed. The solid was filtered off, and the filtrate was concentrated. The residue was purified by silica gel chromatography (petroleum ether:ethyl acetate=6:1) to give the title compound (7 g, 35%) as a yellow solid. MS (ES+) C8H9NO2 requires: 151. Found: 152 [M+H]+. The solid was filtered off the filtrate was concentrated The residue was purified by silica gel chromatography (petroleum ether:ethyl acetate=6:1)

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

Procedure: To a stirred solution of 2-amino-4-methoxybenzaldehyde (6 g, 39.7 mmol) in dichloromethane (100 mL) was added N-bromosuccinimide (7 g, 39.7 mmol). LCMS monitored the reaction until the starting material consumed completely. The reaction mixture was diluted with dichloromethane and water. The separated organic layer was dried sodium sulfate, filtered and concentrated to give the title compound (5 g, 56%) as a yellow solid. MS (ES+) C8H8BrNO2 requires: 229, 231. Found: 230, 232 [M+H]+. the reaction until the starting material consumed completely The reaction mixture was diluted with dichloromethane and water filtered concentrated

Conditions: temp:175.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: 2-Formyl-5-methoxyaniline (11.93 g, 79.5 mmol, 1.0 eq) and urea (38.0 g, 0.636 mol, 8.0 eq) were mixed, ground into a fine powder and placed into a 1 L 2-neck flask equipped with a mechanical stirrer and an air condenser. The flask was placed into a preheated (160° C.) oil bath. The reaction mixture melted and was stirred at 170-180° C. for 1 hour until it solidified forming yellowish-brown solid. The reaction mixture was cooled to RT, crushed, mixed with 70 mL of H2O and stirred for ˜1 hour at RT. The solid was filtered, washed with 150 mL of H2O and 20 mL of ice cold Et2O. The yellow solid thus obtained was dried over P4O10 under high vacuum for several hours and the crude material (12.57 g) was used for the next step without purification. equipped with a mechanical stirrer and an air condenser was placed into a preheated (160° C.) oil bath solidified forming yellowish-brown solid The reaction mixture was cooled to RT crushed stirred for ˜1 hour at RT The solid was filtered washed with 150 mL of H2O and 20 mL of ice cold Et2O The yellow solid thus obtained was dried over P4O10 under high vacuum for several hours the crude material (12.57 g) was used for the next step without purification