N-octylaniline

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

Procedure: To a solution of 2′-amino-3,3″-bis-trifluoromethyl-[1,1′:3′1″]terphenyl-5′-carboxylic acid (0.113 g, 0.27 mmol 1 eq) in DMP (2.7 mL) was added 1,1′-carbonyldiimidazole (0.120 g, 0.74 mmol 2.7 eq) and phenyl octylamine (0.070 mL, 0.35 mmol, 1.3 eq) and the reaction was stirred overnight at rt. Additional 1,1′-carbonyldiidazole (0.124 g, 0.76 mmol 2.8 eq) and phenyl octylamine (0.070 mL, 0.35 mmol, 1.3 eq) was added and stirring was continued overnight. The solids were then filtered off and washed with EtOAc. The filtrate was washed with saturated NaHCO3 solution, 0.1 N HCl and brine. It was dried over MgSO4 and concentrated in vacuo. The residue was purified by flash chromatography (20% EtOAc:Hexane+1% Formic acid) to afford the title compound (0.150 g, 37%) as a light yellow oil. 1H NMR (DMSO-d6 δ8.20 (t, 1H); 7.81-7.70 (m, 8H); 7.61 (s, 2H); 7.25-7.12 (m, 5H); 4.87 (s, 2H); 3.19 (dd, 2H); 2.52 (t, 2H); 1.50 (m, 4H); 1.28 (m, 8H); IR (KBr) 3540, 3350, 2950, 2850, 1620, 1545, 1480, 1420, 1325, 1180, 1120, 1110, 1080 cm−1; mass spectrum [(+)APCI], m/z 613 (M+H)+; Anal. Calcd. for C35H34F6N2O: C, 68.62; H, 5.59; N, 4.57, Found: C, 67.66; H, 5.96; N, 4.33. stirring was continued overnight The solids were then filtered off washed with EtOAc The filtrate was washed with saturated NaHCO3 solution, 0.1 N HCl and brine It was dried over MgSO4 concentrated in vacuo The residue was purified by flash chromatography (20% EtOAc:Hexane+1% Formic acid)

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

Procedure: To 3,5-bis-(m-trifluoromethylphenyl)-4-hydroxy-benzoic acid ethyl ester (0.315 g, 0.74 mmol, 1 eq) was added thionyl chloride (2 mL) and the reaction was stirred overnight at rt and concentrated in vacuo. It was then added to a solution of phenyl octyl amine (0.222 mL, 1.12 mmol, 1 .51 eq) and triethylamine (0.470 mL, 3.37 mmol, 4.6 eq). The reaction was stirred at rt 1 h, poured into 0.1 N HCl solution and extracted with Et2O. The combined organics were washed with 1N HCl (×3), dried over MgSO4 and concentrated in vacuo. The residue was purified by flash chromatography (20% EtOAc:hexane) to afford title compound (0.393 g, 86%) as a colorless oil. 1H NMR (DMSO-d6) δ9.30 (s, 1H); 8.42 (t, 1H); 7.91-7.85 (m, 4H); 7.82 (s, 2H); 7.75-7.65 (m, 4H); 7.26-7.10 (m, 5H); 3.23 (dd, 2H); 2.52 (t, 2H); 1.52 (m, 4H); 1.27 (m, 8H); IR (film) 3330, 2980, 2840, 1640, 1600, 1550, 1470, 1320, 1180, 1120, 1080, 900, 805 cm−1; mass spectrum [(+)APCI], m/z 614 (M+H)+; Anal. Calcd. for C35H33F6NO2: C, 68.51; H, 5.42; N, 2.28, Found: C, 66.76; H, 5.46; N, 2.18. concentrated in vacuo The reaction was stirred at rt 1 h extracted with Et2O The combined organics were washed with 1N HCl (×3) dried over MgSO4 concentrated in vacuo The residue was purified by flash chromatography (20% EtOAc:hexane)

Conditions: temp:105.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: To N-acetyl-N-octylaniline (48.4 g, 196 mmol) there was added 4N hydrochloric acid (100 mL) and the mixture heated to 100-110° C. and stirred at this temperature for 4 days. The reaction mixture was cooled to ambient temperature, diluted with water (100 mL), and hexanes (200 mL). The pH of the reaction mixture was brought to pH 14 by addition of 45% potassium hydroxide with cooling by an ice bath. The layers were separated and the aqueous layer washed with hexanes (100 mL). The combined organic layers were dried over sodium sulfate and concentrated by rotary evaporation to give the desired product as a light brown oil (40 g, 195 mmol, 99%). The product was identified by NMR spectroscopy and mass spectrometry and in general was used without further purification. Analytically pure product was obtained by distillation at reduced pressure: by 145-150° C. (0.5 mm). The reaction mixture was cooled to ambient temperature with cooling by an ice bath The layers were separated the aqueous layer washed with hexanes (100 mL) The combined organic layers were dried over sodium sulfate concentrated by rotary evaporation

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

Procedure: To a solution of 2′-amino-3,3″-bis-trifluoromethyl-[1,1′:3′1″]terphenyl-5′-carboxylic acid (0.113 g, 0.27 mmol 1 eq) in DMP (2.7 mL) was added 1,1′-carbonyldiimidazole (0.120 g, 0.74 mmol 2.7 eq) and phenyl octylamine (0.070 mL, 0.35 mmol, 1.3 eq) and the reaction was stirred overnight at rt. Additional 1,1′-carbonyldiidazole (0.124 g, 0.76 mmol 2.8 eq) and phenyl octylamine (0.070 mL, 0.35 mmol, 1.3 eq) was added and stirring was continued overnight. The solids were then filtered off and washed with EtOAc. The filtrate was washed with saturated NaHCO3 solution, 0.1 N HCl and brine. It was dried over MgSO4 and concentrated in vacuo. The residue was purified by flash chromatography (20% EtOAc:Hexane+1% Formic acid) to afford the title compound (0.150 g, 37%) as a light yellow oil. 1H NMR (DMSO-d6 δ8.20 (t, 1H); 7.81-7.70 (m, 8H); 7.61 (s, 2H); 7.25-7.12 (m, 5H); 4.87 (s, 2H); 3.19 (dd, 2H); 2.52 (t, 2H); 1.50 (m, 4H); 1.28 (m, 8H); IR (KBr) 3540, 3350, 2950, 2850, 1620, 1545, 1480, 1420, 1325, 1180, 1120, 1110, 1080 cm−1; mass spectrum [(+)APCI], m/z 613 (M+H)+; Anal. Calcd. for C35H34F6N2O: C, 68.62; H, 5.59; N, 4.57, Found: C, 67.66; H, 5.96; N, 4.33. stirring was continued overnight The solids were then filtered off washed with EtOAc The filtrate was washed with saturated NaHCO3 solution, 0.1 N HCl and brine It was dried over MgSO4 concentrated in vacuo The residue was purified by flash chromatography (20% EtOAc:Hexane+1% Formic acid)

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

Procedure: To a solution of 2′-amino-3,3″-bis-trifluoromethyl-[1,1′:3′1″]terphenyl-5′-carboxylic acid (0.113 g, 0.27 mmol 1 eq) in DMP (2.7 mL) was added 1,1′-carbonyldiimidazole (0.120 g, 0.74 mmol 2.7 eq) and phenyl octylamine (0.070 mL, 0.35 mmol, 1.3 eq) and the reaction was stirred overnight at rt. Additional 1,1′-carbonyldiidazole (0.124 g, 0.76 mmol 2.8 eq) and phenyl octylamine (0.070 mL, 0.35 mmol, 1.3 eq) was added and stirring was continued overnight. The solids were then filtered off and washed with EtOAc. The filtrate was washed with saturated NaHCO3 solution, 0.1 N HCl and brine. It was dried over MgSO4 and concentrated in vacuo. The residue was purified by flash chromatography (20% EtOAc:Hexane+1% Formic acid) to afford the title compound (0.150 g, 37%) as a light yellow oil. 1H NMR (DMSO-d6 δ8.20 (t, 1H); 7.81-7.70 (m, 8H); 7.61 (s, 2H); 7.25-7.12 (m, 5H); 4.87 (s, 2H); 3.19 (dd, 2H); 2.52 (t, 2H); 1.50 (m, 4H); 1.28 (m, 8H); IR (KBr) 3540, 3350, 2950, 2850, 1620, 1545, 1480, 1420, 1325, 1180, 1120, 1110, 1080 cm−1; mass spectrum [(+)APCI], m/z 613 (M+H)+; Anal. Calcd. for C35H34F6N2O: C, 68.62; H, 5.59; N, 4.57, Found: C, 67.66; H, 5.96; N, 4.33. stirring was continued overnight The solids were then filtered off washed with EtOAc The filtrate was washed with saturated NaHCO3 solution, 0.1 N HCl and brine It was dried over MgSO4 concentrated in vacuo The residue was purified by flash chromatography (20% EtOAc:Hexane+1% Formic acid)

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

Procedure: To 3,5-bis-(m-trifluoromethylphenyl)-4-hydroxy-benzoic acid ethyl ester (0.315 g, 0.74 mmol, 1 eq) was added thionyl chloride (2 mL) and the reaction was stirred overnight at rt and concentrated in vacuo. It was then added to a solution of phenyl octyl amine (0.222 mL, 1.12 mmol, 1 .51 eq) and triethylamine (0.470 mL, 3.37 mmol, 4.6 eq). The reaction was stirred at rt 1 h, poured into 0.1 N HCl solution and extracted with Et2O. The combined organics were washed with 1N HCl (×3), dried over MgSO4 and concentrated in vacuo. The residue was purified by flash chromatography (20% EtOAc:hexane) to afford title compound (0.393 g, 86%) as a colorless oil. 1H NMR (DMSO-d6) δ9.30 (s, 1H); 8.42 (t, 1H); 7.91-7.85 (m, 4H); 7.82 (s, 2H); 7.75-7.65 (m, 4H); 7.26-7.10 (m, 5H); 3.23 (dd, 2H); 2.52 (t, 2H); 1.52 (m, 4H); 1.27 (m, 8H); IR (film) 3330, 2980, 2840, 1640, 1600, 1550, 1470, 1320, 1180, 1120, 1080, 900, 805 cm−1; mass spectrum [(+)APCI], m/z 614 (M+H)+; Anal. Calcd. for C35H33F6NO2: C, 68.51; H, 5.42; N, 2.28, Found: C, 66.76; H, 5.46; N, 2.18. concentrated in vacuo The reaction was stirred at rt 1 h extracted with Et2O The combined organics were washed with 1N HCl (×3) dried over MgSO4 concentrated in vacuo The residue was purified by flash chromatography (20% EtOAc:hexane)

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

Procedure: To 3,5-bis-(m-trifluoromethylphenyl)-4-hydroxy-benzoic acid ethyl ester (0.315 g, 0.74 mmol, 1 eq) was added thionyl chloride (2 mL) and the reaction was stirred overnight at rt and concentrated in vacuo. It was then added to a solution of phenyl octyl amine (0.222 mL, 1.12 mmol, 1 .51 eq) and triethylamine (0.470 mL, 3.37 mmol, 4.6 eq). The reaction was stirred at rt 1 h, poured into 0.1 N HCl solution and extracted with Et2O. The combined organics were washed with 1N HCl (×3), dried over MgSO4 and concentrated in vacuo. The residue was purified by flash chromatography (20% EtOAc:hexane) to afford title compound (0.393 g, 86%) as a colorless oil. 1H NMR (DMSO-d6) δ9.30 (s, 1H); 8.42 (t, 1H); 7.91-7.85 (m, 4H); 7.82 (s, 2H); 7.75-7.65 (m, 4H); 7.26-7.10 (m, 5H); 3.23 (dd, 2H); 2.52 (t, 2H); 1.52 (m, 4H); 1.27 (m, 8H); IR (film) 3330, 2980, 2840, 1640, 1600, 1550, 1470, 1320, 1180, 1120, 1080, 900, 805 cm−1; mass spectrum [(+)APCI], m/z 614 (M+H)+; Anal. Calcd. for C35H33F6NO2: C, 68.51; H, 5.42; N, 2.28, Found: C, 66.76; H, 5.46; N, 2.18. concentrated in vacuo The reaction was stirred at rt 1 h extracted with Et2O The combined organics were washed with 1N HCl (×3) dried over MgSO4 concentrated in vacuo The residue was purified by flash chromatography (20% EtOAc:hexane)

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

Procedure: Ethyl N-(4-ethoxycarbonylphenyl)formimidate (Example Ia) (6.6 g, 0.03 mol) and N-octylaniline (6.2 g, 0.03 mol) were heated at 180° until 1.7 ml of ethanol had been collected by distillation. The resulting pale yellow oil was flash distilled to yield the desired product, bp≈235° C. (0.05 mm). ##STR15## had been collected by distillation distilled

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

Procedure: To a solution of 2′-amino-3,3″-bis-trifluoromethyl-[1,1′:3′1″]terphenyl-5′-carboxylic acid (0.113 g, 0.27 mmol 1 eq) in DMF (2.7 mL) was added 1,1′-carbonyldiimidazole (0.120 g, 0.74 mmol 2.7 eq) and phenyl octylamine (0.070 mL, 0.35 mmol, 1.3 eq) and the reaction was stirred overnight at rt. Additional 1,1′-carbonyldimidazole (0.124 g, 0.76 mmol 2.8 eq) and phenyl octylamine (0.070 mL, 0.35 mmol, 1.3 eq) was added and stirring was continued overnight. The solids were then filtered off and washed with EtOAc. The filtrate was washed with saturated NaHCO3 solution, 0.1 N HCl and brine. It was dried over MgSO4 and concentrated in vacuo. The residue was purified by flash chromatography (20% EtOAc:Hexane +1% Formic acid) to afford the title compound (0.150 g, 37%) as a light yellow oil. 1H NMR (DMSO-d6 5 8.20 (t, 1H); 7.81-7.70 (m, 8H); 7.61 (s, 2H); 7.25-7.12 (m, 5H); 4.87 (s, 2H); 3.19 (dd, 2H); 2.52 (t, 2H); 1.50 (m, 4H); 1.28 (m, 8H); IR (KBr) 3540, 3350, 2950, 2850, 1620, 1545, 1480, 1420, 1325, 1180, 1120, 1110, 1080 cm−1; mass spectrum [(+)APCI], m/z 613 (M+H)+; Anal. Calcd. for C35H34F6N2O: C, 68.62; H, 5.59; N, 4.57, Found: C, 67.66; H, 5.96; N, 4.33. stirring was continued overnight The solids were then filtered off washed with EtOAc The filtrate was washed with saturated NaHCO3 solution, 0.1 N HCl and brine It was dried over MgSO4 concentrated in vacuo The residue was purified by flash chromatography (20% EtOAc:Hexane +1% Formic acid)

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

Procedure: To a solution of 2′-amino-3,3″-bis-trifluoromethyl-[1,1′:3′1″]terphenyl-5′-carboxylic acid (0.113 g, 0.27 mmol 1 eq) in DMF (2.7 mL) was added 1,1′-carbonyldiimidazole (0.120 g, 0.74 mmol 2.7 eq) and phenyl octylamine (0.070 mL, 0.35 mmol, 1.3 eq) and the reaction was stirred overnight at rt. Additional 1,1′-carbonyldiimidazole (0.124 g, 0.76 mmol 2.8 eq) and phenyl octylamine (0.070 mL, 0.35 mmol, 1.3 eq) was added and stirring was continued overnight. The solids were then filtered off and washed with EtOAc. The filtrate was washed with saturated NaHCO3 solution, 0.1 N HCl and brine. It was dried over MgSO4 and concentrated in vacuo. The residue was purified by flash chromatography (20% EtOAc: Hexane+1% Formic acid) to afford the title compound (0.150 g, 37%) as a light yellow oil. 1H NMR (DMSO-d6 δ 8.20 (t, 1H); 7.81–7.70 (m, 8H); 7.61 (s, 2H); 7.25–7.12 (m, 5H); 4.87 (s, 2H); 3.19 (dd, 2H); 2.52 (t, 2H); 1.50 (m, 4H); 1.28 (m, 8H); IR (KBr) 3540, 3350, 2950, 2850, 1620, 1545, 1480, 1420, 1325, 1180, 1120, 1110, 1080 cm−1; mass spectrum [(+)APCI], m/z 613 (M+H)+; Anal. Calcd. for C35H34F6N2O: C, 68.62; H, 5.59; N, 4.57. Found: C, 67.66; H, 5.96; N, 4.33. stirring was continued overnight The solids were then filtered off washed with EtOAc The filtrate was washed with saturated NaHCO3 solution, 0.1 N HCl and brine It was dried over MgSO4 concentrated in vacuo The residue was purified by flash chromatography (20% EtOAc: Hexane+1% Formic acid)

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

Procedure: To 3,5-bis-(m-trifluoromethylphenyl)-4-hydroxy-benzoic acid ethyl ester (0.315 g, 0.74 mmol, 1 eq) was added thionyl chloride (2 mL) and the reaction was stirred overnight at rt and concentrated in vacuo. It was then added to a solution of phenyl octyl amine (0.222 mL, 1.12 mmol, 1.51 eq) and triethylamine (0.470 mL, 3.37 mmol, 4.6 eq). The reaction was stirred at rt 1 h, poured into 0.1 N HCl solution and extracted with Et2O. The combined organics were washed with 1N HCl (×3), dried over MgSO4 and concentrated in vacuo. The residue was purified by flash chromatography (20% EtOAc:hexane) to afford title compound (0.393 g, 86%) as a colorless oil. 1H NMR (DMSO-d6) δ 9.30 (s, 1H); 8.42 (t, 1H); 7.91–7.85 (m, 4H); 7.82 (s, 2H); 7.75–7.65 (m, 4H); 7.26–7.10 (m, 5H); 3.23 (dd, 2H); 2.52 (t, 2H); 1.52 (m, 4H); 1.27 (m, 8H); IR (film) 3330, 2980, 2840, 1640, 1600, 1550, 1470, 1320, 1180, 1120, 1080, 900, 805 cm−1; mass spectrum [(+)APCI], m/z 614 (M+H)+; Anal. Calcd. for C35H33F6NO2: C, 68.51; H, 5.42; N, 2.28. Found: C, 66.76; H, 5.46; N, 2.18. concentrated in vacuo The reaction was stirred at rt 1 h extracted with Et2O The combined organics were washed with 1N HCl (×3) dried over MgSO4 concentrated in vacuo The residue was purified by flash chromatography (20% EtOAc:hexane)

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

Procedure: To a solution of 2′-amino-3,3″-bis-trifluoromethyl-[1,1′;3′1″]terphenyl-5′-carboxylic acid (0.113 g, 0.27 mmol 1 eq) in DMF (2.7 mL) was added 1,1′-carbonyldiimidazole (0.120 g, 0.74 mmol 2.7 eq) and phenyl octylamine (0.070 mL, 0.35 mmol, 1.3 eq) and the reaction was stirred overnight at rt. Additional 1,1′-carbonyldiimidazole (0.124 g, 0.76 mmol 2.8 eq) and phenyl octylamine (0.070 mL, 0.35 mmol, 1.3 eq) was added and stirring was continued overnight. The solids were then filtered off and washed with EtOAc. The filtrate was washed with saturated NaHCO3 solution, 0.1 N HCl and brine. It was dried over MgSO4 and concentrated in vacuo. The residue was purified by flash chromatography (20% EtOAc:Hexane+1% Formic acid) to afford the title compound (0.150 g, 37%) as a light yellow oil. 1H NMR (DMSO-d6 δ 8.20 (t, 1H); 7.81-7.70 (m, 8H); 7.61 (s, 2H); 7.25-7.12 (m, 5H); 4.87 (s, 2H); 3.19 (dd, 2H); 2.52 (t, 2H); 1.50 (m, 4H); 1.28 (m, 8H); IR (KBr) 3540, 3350, 2950, 2850, 1620, 1545, 1480, 1420, 1325, 1180, 1120, 1110, 1080 cm−1; mass spectrum [(+)APCI], m/z 613 (M+H)+; Anal. Calcd. for C35H34F6N2O: C, 68.62; H, 5.59; N, 4.57, Found: C, 67.66; H, 5.96; N, 4.33. stirring was continued overnight The solids were then filtered off washed with EtOAc The filtrate was washed with saturated NaHCO3 solution, 0.1 N HCl and brine It was dried over MgSO4 concentrated in vacuo The residue was purified by flash chromatography (20% EtOAc:Hexane+1% Formic acid)