2-fluoro-6-propan-2-ylaniline

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

Procedure: The procedure of Example 6 was repeated, except that ortho-fluoroaniline was substituted for ortho-toluidine. An LHSV of 0.125 hr.-1 and an N/R ratio of amine to olefin was 1:3. Table 4 sets forth the reaction conditions and results. An LHSV of 0.125 hr Table 4 sets forth the reaction conditions results

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

Procedure: 2-fluoro-6-isopropyl aniline was prepared by the method of Example 2 using an H-Y zeolite catalyst for the condensation of 2-aniline and propylene. In this reaction 2-fluoroaniline and propylene were fed to a reactor in a 1:5 mole ratio and LHSV of 0.25 based on 2-fluoroaniline. The reaction was conducted at 255° C. and 879 psig. The effluent product stream was analyzed by gas chromatography. Conversion of 2-fluoroaniline was 71.2%. were fed to a reactor in a 1 was conducted at 255° C.

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

Procedure: 2-fluoro-6-isopropyl aniline was prepared by the method of Example 2 using an H-Y zeolite catalyst for the condensation of 2-aniline and propylene. In this reaction 2-fluoroaniline and propylene were fed to a reactor in a 1:5 mole ratio and LHSV of 0.25 based on 2-fluoroaniline. The reaction was conducted at 255° C. and 879 psig. The effluent product stream was analyzed by gas chromatography. Conversion of 2-fluoroaniline was 71.2%. were fed to a reactor in a 1 was conducted at 255° C.

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

Procedure: To a 100 mL round-bottomed flask equipped with a stir bar and nitrogen inlet were added 2-fluoro-6-isopropylaniline (0.415 g, 2.71 mmol), dichloromethane (13.6 mL), water (6.78 mL), and sodium bicarbonate (0.683 g, 8.13 mmol). To this biphasic mixture was added thiophosgene (0.199 mL, 2.60 mmol) and the reaction was stirred vigorously for 2 hours. The suspension was filtered through a phase separator cartridge and the organic phase was concentrated in a 100 mL round-bottomed flask. The flask was equipped with a magnetic stir bar and nitrogen inlet and the residue was dissolved in ethanol (6.78 mL). To the resulting solution was added hydrazine hydrate (0.131 mL, 2.71 mmol) and the reaction was stirred at room temperature for 2 days. The solution was concentrated and the resulting residue was suspended in a mixture of diethyl ether and hexanes and reconcentrated to give a solid. The solid was suspended in a minimal amount of diethyl ether and the mixture was diluted with hexanes. The majority of the diethyl ether was evaporated and the resulting solid was collected by vacuum filtration, washed with hexanes and then dried under house vacuum to provide the title compound (0.518 g, 2.28 mmol, 84% yield) as a white solid: mp 122-124° C.; 1H NMR (400 MHz, CDCl3) δ 8.56 (bs, 1H), 7.52 (bs, 1H), 7.32 (td, J=8.1, 5.6 Hz, 1H), 7.17-7.12 (m, 1H), 7.00 (ddd, J=9.5, 8.2, 1.4 Hz, 1H), 4.07 (bs, 2H), 3.15 (hept, J=7.0 Hz, 1H), 1.24 (d, J=6.9 Hz, 6H); ESIMS m/z 229 ([M+H]+). To a 100 mL round-bottomed flask equipped with a stir bar and nitrogen inlet The suspension was filtered through a phase separator cartridge the organic phase was concentrated in a 100 mL round-bottomed flask The flask was equipped with a magnetic stir bar and nitrogen inlet the residue was dissolved in ethanol (6.78 mL) the reaction was stirred at room temperature for 2 days The solution was concentrated the resulting residue was suspended in a mixture of diethyl ether and hexanes to give a solid The majority of the diethyl ether was evaporated the resulting solid was collected by vacuum filtration washed with hexanes dried under house vacuum

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

Procedure: To a solution of 1-fluoro-2-nitro-3-(prop-1-en-2-yl)benzene (0.590 g, 3.26 mmol) in ethyl acetate (32.6 mL) in a 250 mL round-bottomed flask equipped with a magnetic stir bar and nitrogen inlet was added palladium on carbon (5% Pd/C, 0.693 g, 0.326 mmol). The reaction flask was evacuated and purged with hydrogen (2×) and then placed under 1 atmosphere (atm) of hydrogen and stirred at room temperature overnight. The reaction was filtered through Celite® and the pad was washed with ethyl acetate. The filtrate was concentrated to give the title compound (0.423 g, 2.76 mmol, 85% yield) as clear and colorless oil: IR (neat) 3476 (m), 3392 (m), 2966 (m), 2872 (m), 1628 (s), 1474 (s), 1270 (m) cm−1; 1H NMR (400 MHz, CDCl3) δ 6.92 (dt, J=7.7, 1.2 Hz, 1H), 6.86 (ddd, J=10.8, 8.1, 1.4 Hz, 1H), 6.69 (td, J=8.0, 5.6 Hz, 1H), 3.71 (bs, 2H), 2.92 (hept, J=6.8 Hz, 1H), 1.26 (d, J=6.8 Hz, 6H); 13C NMR (101 MHz, CDCl3) δ 151.91 (d, J=237.6 Hz), 135.10 (d, J=2.3 Hz), 131.60 (d, J=11.8 Hz), 120.52 (d, J=3.0 Hz), 117.99 (d, J=8.0 Hz), 112.28 (d, J=19.6 Hz), 27.77 (d, J=2.9 Hz), 22.22. The reaction flask was evacuated purged with hydrogen (2×) The reaction was filtered through Celite® the pad was washed with ethyl acetate The filtrate was concentrated

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

Procedure: The procedure of Example 6 was repeated, except that ortho-fluoroaniline was substituted for ortho-toluidine. An LHSV of 0.125 hr.-1 and an N/R ratio of amine to olefin was 1:3. Table 4 sets forth the reaction conditions and results. An LHSV of 0.125 hr Table 4 sets forth the reaction conditions results

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

Procedure: 2-fluoro-6-isopropyl aniline was prepared by the method of Example 2 using an H-Y zeolite catalyst for the condensation of 2-aniline and propylene. In this reaction 2-fluoroaniline and propylene were fed to a reactor in a 1:5 mole ratio and LHSV of 0.25 based on 2-fluoroaniline. The reaction was conducted at 255° C. and 879 psig. The effluent product stream was analyzed by gas chromatography. Conversion of 2-fluoroaniline was 71.2%. were fed to a reactor in a 1 was conducted at 255° C.