N,N-dihexylaniline

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

Procedure: To a solution of N,N-dihexylaniline (12.02 g, 4.60×10−2 mol) in anhydrous 1,2-dichloroethane (200 ml) at room temperature were successively added anhydrous DMF (3.60 ml, 4.65×10−2 mol) and POCl3 (5.20 ml, 5.58×10−2 mol), and the mixture was refluxed for 5.5 h. After cooling, 2M aqueous NaOAc solution (200 ml) was added and the reaction mixture was stirred overnight. The product was extracted three times with CHCl3 and the combined organic layers were dried over Na2SO4. The residue was chromatographed on silica gel with 1:1 hexane:CHCl3 as the eluent. Yield=10.793 g (81% based on 12.02 g of N,N-dihexylaniline). 1H NMR (250 MHz, CDCl3): δ 9.69 (s, 1H, —CHO), 7.70 (dd, 2H, J=8.9 Hz, Ph), 6.63 (d, 2H, J=9.0 Hz, Ph), 3.34 (t, 4H, J=7.8 Hz, —NCH2—), 1.48-1.70 (m, 4H, —NCH2CH2—), 1.19-1.41 (m, 12H, —CH2—), 0.91 (t, 6H, J=6.6 Hz, —CH3). CI MS m/z: 290.247 ((M+H)+) (calcd 290.248). at room temperature the mixture was refluxed for 5.5 h After cooling The product was extracted three times with CHCl3 the combined organic layers were dried over Na2SO4 The residue was chromatographed on silica gel with 1:1 hexane

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

Procedure: A mixture of aniline (5.90 ml, 6.47×10−2 mol), 1-iodohexane (20.0 ml, 0.136 mol) and K2CO3 (18.80 g, 0.136 mol) in 80 ml of EtOH was refluxed for 27 h under Ar. The precipitate was filtered off and washed with CH2Cl2. The filtrate was washed with water and dried over Na2SO4. The residue was chromatographed on silica gel with 4:1 hexane:CHCl3 as the eluent. Yield=14.735 g (87% based on 5.90 ml of aniline). 1H NMR (250 MHz, CDCl3): δ 7.20 (dd, 2H, J=7.1, 8.8 Hz, Ph), 6.57-6.66 (m, 3H, Ph), 3.24 (t, 4H, J=7.7 Hz, —NCH2—), 1.48-1.65 (m, 4H, —NCH2CH2—), 1.22-1.40 (m, 12H, —CH2—), 0.90 (t, 6H, J=6.6 Hz, —CH3). CI MS m/z: 262.253 ((M+H)+) (calcd 262.253). was refluxed for 27 h under Ar The precipitate was filtered off washed with CH2Cl2 The filtrate was washed with water dried over Na2SO4 The residue was chromatographed on silica gel with 4:1 hexane