2-methyl-6-propan-2-ylaniline

反応条件: temp:0.00; pressure:0.00; stir:

反応条件: temp:0.00; pressure:0.00; stir:

反応条件: temp:0.00; pressure:0.00; stir:

反応条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: Procedure as described for Amidine I using the following amounts: 7.80 mL of 2-isopropyl-6-methylaniline (50.0 mmol); 25.0 mL of 2.0 M butyllithium (50.0 mmol), 5.86 g of 4-methylbenzonitrile (50.0 mmol). After refluxing overnight, the solution was dark brown. Addition of water yielded an orange-brown solution with suspended solid. Solution was filtered and taken to dryness. The residue was treated with 100 mL of pentane stirred overnight and filtered yielding 10.98 g (83%) of beige material. 1H NMR (400 MHz, CDCl3): 7.82 (d, 2H), 7.26 (d, 2H), 7.15 (d, 1H), 7.05 (d, 1H), 6.98 (t, 1 H), 4.56 (s, 2H), 3.09 (septet, 1H), 2.42 (s, 3H), 2.15 (s, 3H), 1.21 (d, 3H), 1.16 (d, 3H). After refluxing overnight yielded an orange-brown solution Solution was filtered The residue was treated with 100 mL of pentane filtered

反応条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: 1-(6-Acetyl-pyridin-2-yl)-ethanone 2 (35.54 g, 0.22 mol), 25.0 g (0.168 mol) of 2-Isopropyl-6-methyl-phenylamine 14, 350 ml of n-propanol, and a few crystals of p-toluenesulfonic acid were stirred at room temperature for 36 h in a 500 ml flask under a flow of the nitrogen. The resultant yellow precipitate was filtered and washed by 20 ml of methanol. It was then dried at 1-mm vacuum overnight. The yield of 1-{6-[1-(2-Isopropyl-6-methyl-phenylimino)-ethyl]-pyridin-2-yl}-ethanone 15 was 13.35 g (27%) as a yellow solid. The resultant yellow precipitate was filtered washed by 20 ml of methanol It was then dried at 1-mm vacuum overnight

反応条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: 1-(6-Acetyl-pyridin-2-yl)-ethanone 2 (35.54 g, 0.22 mol), 25.0 g (0.168 mol) of 2-Isopropyl-6-methyl-phenylamine 14, 350 ml of n-propanol, and a few crystals of p-toluenesulfonic acid were stirred at room temperature for 36 h in a 500 ml flask under a flow of the nitrogen. The resultant yellow precipitate was filtered and washed by 20 ml of methanol. It was then dried at 1-mm vacuum overnight. The yield of 1-{6-[1-(2-Isopropyl-6-methyl-phenylimino)-ethyl]-pyridin-2-yl}-ethanone 15 was 13.35 g (27%) as a yellow solid. The resultant yellow precipitate was filtered washed by 20 ml of methanol It was then dried at 1-mm vacuum overnight

反応条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: 2-Methyl-6-isopropyl aniline was prepared by the method of Example 2 using an H-Y zeolite catalyst for the condensation of aniline and propylene. The ortho-toluidine and propylene were fed to the reactor in a 1:5 molar ratio and at an LHSV of 0.25 based on o-toluidine. The reaction was conducted at 250° C. and 861 psig. The effluent product stream was analyzed by gas chromatography. Conversion of o-toluidine was 81.5%. was conducted at 250° C.

反応条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: There were supplied 325 mg of 2,6-diacetylpyridine manufactured by Aldrich Chemical Company to a 25 mL-Schlenk tube. Thereto, 5 mL of anhydrous ethanol manufactured by Kanto Chemical Co., Inc., 0.62 mL of 2-methyl-6-isopropylaniline manufactured by Tokyo Chemical Industry Co., Ltd., and a few drops of acetic acid manufactured by Kanto Chemical Co., Inc. were added. The obtained mixture was refluxed for 24 hours. Then, the solvent contained in the mixture was distilled off, and the resultant mixture was subjected to recrystallization with methanol, thereby obtaining 298 mg (yield: 35%) of 2,6-bis[1-(2-methyl-6-isopropylphenylimino)ethyl]pyridine as a yellow powder. were added The obtained mixture was refluxed for 24 hours was distilled off the resultant mixture was subjected to recrystallization with methanol

反応条件: temp:5.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: 2-isopropyl-6-methylanilin (14.9 g, 0.1 mol) was solved in conc hydrobromic acid (40 ml) and the mixture was cooled to 5° C. Sodium nitrite (7.0 g, 0.1 mol) in water (15 ml) was added so that the temperature was below 10° C. A solution of copper(I)bromide in conc hydrobromic acid (10 ml) was added to the reaction mixture and the temperature was allowed to raise to room temperature. The mixture was stirred for 1 h. at room temperature and 30 min at 40° C. Hexane was added and the organic layer was separated and evaporated under reduced pressure. Purification by column chromatography on silica gel using hexane as eluent gave 6.9 g (32%) of the title compound as an oil. was below 10° C to raise to room temperature the organic layer was separated evaporated under reduced pressure Purification by column chromatography on silica gel

反応条件: temp:0.00; pressure:0.00; stir:

反応条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: 2-Isopropyl-6-methyl-phenylamine (5 g, 33.5 mmol) was dissolved in acetic acid (20 mL). To this solution was added a solution of bromine (1.8 mL, 35.14 mmol) in acetic acid (5 mL) dropwise over 10 min. After stirring for 1 h at room temperature, the reaction mixture was diluted with methylene chloride, washed with water (2×), saturated sodium thiosulfate (2×), saturated sodium bicarbonate (2×), and brine. The organic phase was dried over sodium sulfate, filtered, and concentrated. Purification by flash chromatography on silica gel afforded 7.6 g (quantitative) of the desired product. LC/MS: tR=1.37 min, 230.07 (MH)+. washed with water (2×), saturated sodium thiosulfate (2×), saturated sodium bicarbonate (2×), and brine The organic phase was dried over sodium sulfate filtered concentrated Purification by flash chromatography on silica gel

反応条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: 2-Isopropyl-6-methyl-phenylamine (5 g, 33.5 mmol) was dissolved in acetic acid (20 mL). To this solution was added a solution of bromine (1.8 mL, 35.14 mmol) in acetic acid (5 mL) dropwise over 10 min. After stirring for 1 h at room temperature, the reaction mixture was diluted with methylene chloride, washed with water (2×), saturated sodium thiosulfate (2×), saturated sodium bicarbonate (2×), and brine. The organic phase was dried over sodium sulfate, filtered, and concentrated. Purification by flash chromatography on silica gel afforded 7.6 g (quantitative) of the desired product. LC/MS: tR=1.37 min, 230.07 (MH)+. washed with water (2×), saturated sodium thiosulfate (2×), saturated sodium bicarbonate (2×), and brine The organic phase was dried over sodium sulfate filtered concentrated Purification by flash chromatography on silica gel