4-(dihexylamino)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:95.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: To a solution of dry DMF (1.1. mL) under Argon at 0° C. was added of POC13(375 μL, 4 mmol). N,N-Dihexylaniline (1.04 g, 4 mmol) was added dropwise and the solution was mixed with rapid stirring to form a green solution. The reaction mixture was heated at 95° C. for 2 h. The solution quickly turned red/brown. After 2 h the solution was cooled. It was poured into ice/water 20 mL and aq. saturated NaOAc (20 mL) was added. The partially neutralized solution was partitioned between ether and water. The ether layer was washed with aq. saturated NaHCO3 and dried over sodium sulfate. After concentrating to approximately 20 mL. DMF oiled out of the solution. The solution was transferred from the oil and concentrated under reduced pressure. The resultant residue was purified via flash column chromatography, using a gradient of 0→20% ethyl acetate; petroleum ether as eluent to give N,N-Dihexyl-4-aminobenzaldehyde (32) (970 mg, 84%). 1H NMR (CDCl3) δ 9.72 (s, 1H CHO); 7.70 (d, 2H, ArH); 6.64 (d, 2H, ArH); 3.32 (t, 4H, 2×NCH2); 0.89 (t, 6H 2×CH2CH3). TLC (silica gel): Rf=0.75 (20% ethyl acetate;petroleum ether). the solution was mixed to form a green solution After 2 h the solution was cooled was added The partially neutralized solution was partitioned between ether and water The ether layer was washed with aq. saturated NaHCO3 dried over sodium sulfate After concentrating to approximately 20 mL concentrated under reduced pressure The resultant residue was purified via flash column chromatography

Conditions: temp:0.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: To Methyltriphenylphosphonium bromide (3.07 g, 8.59×10−3 mol) in 50 ml of dry THF was added w-BuLi (2.2 M solution in hexane, 4.00 ml, 8.80×10−3 mol) dropwise at −78° C. After 2.5 h, the reaction mixture was gradually warmed up to 0° C., and again cooled to −78° C. N,N-dihexyl-4-formylaniline (2.26 g, 7.81×10−3 mol) in 15 ml of dry THF was slowly added to the reaction mixture. The reaction mixture was stirred overnight and meanwhile gradually warmed up to 10° C. Aqueous NaCl was added to the reaction mixture and the organic layer was extracted with petroleum ether. The organic layer was dried over Na2SO4. After the solvent was evaporated, the residue was chromatographed on silica gel with 1:1 hexane:CHCl3. Yield=0.775 g (35% based on 2.26 g of N,N-dihexyl-4-formylaniline). 1H NMR (250 MHz, CDCl3): δ 7.27 (d, 2H, J=8.8 Hz, Ph-H), 6.61 (dd, 1H, J=10.9, 17.8 Hz, vinyl-H), 6.58 (d, 2H, J=8.9 Hz, Ph-H), 5.49 (dd, 1H, J=1.1, 17.6 Hz, vinyl-H), 4.97 (dd, 1H, J=0.9, 10.8 Hz, vinyl-H), 3.25 (t, 4H, J=1.7 Hz, NCH2), 1.48-1.66 (m, 4H, NCH2CH2—), 1.20-1.42 (m, 12H, —CH2—), 0.89 (t, 6H, J=6.6 Hz, —CH3). CI MS m/z: 288.269 ((M+H)+) (calcd 288.269). again cooled to −78° C meanwhile gradually warmed up to 10° C the organic layer was extracted with petroleum ether The organic layer was dried over Na2SO4 After the solvent was evaporated the residue was chromatographed on silica gel with 1:1 hexane