4-(dimethylamino)butan-2-one

Conditions: temp:0.00; pressure:0.00; stir:

Conditions: temp:0.00; pressure:0.00; stir:

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

Procedure: By following the procedure of Example 2(a) but using as starting material in Example 2(a) an appropriate starting material of formula II, for example, those described in Examples 2 to 14 and an appropriate aminoketone of formula III in which R2 and n are as described above and A is CH2NR4R5 wherein R4 and R5 are as described above, the amino compounds of formula I listed in Examples 31 to 46 are obtained. For example, according to the present procedure 2-phenyl-4-(β-hydroxyethyl)thiazole condenses with 1-(N,N-dimethylamino)-3-butanone to give the title compound, identical to the amine described in Example 31. are obtained

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

Procedure: By following the procedure of Example 2(a) but using as starting material in Example 2(a) an appropriate starting material of formula II, for example, those described in Examples 2 to 14 and an appropriate aminoketone of formula III in which R2 and n are as described above and A is CH2NR4R5 wherein R4 and R5 are as described above, the amino compounds of formula I listed in Examples 31 to 46 are obtained. For example, according to the present procedure 2-phenyl-4-(β-hydroxyethyl)thiazole condenses with 1-(N,N-dimethylamino)-3-butanone to give the title compound, identical to the amine described in Example 31. are obtained

Conditions: temp:-5.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: Sodium hydride (0.7 g) is added in small portions at a temperature in the region of -5° C. to a solution, maintained under an argon atmosphere, of 3-hydroxy-2-(7-methoxy-1,8-naphthyridin-2-yl)-1-isoindolinone (8.0 g) in anhydrous dimethylformamide (125 cc). The suspension obtained is stirred for 30 minutes at a temperature in the region of -5° C. and then treated with a solution of 4-dimethylamino-2-butanone (3.5 g) in anhydrous dimethylformamide (5 cc). The mixture is stirred for 3 hours at a temperature in the region of 20° C., and is then poured into distilled water (500 cc) and extracted with dichloromethane (3×200 cc). The organic phases are combined, washed with distilled water (4×25 cc), dried over magnesium sulphate, filtered and then concentrated to dryness under reduced pressure (2.7 kPa) at 40° C. The oily residue obtained is dissolved in ethyl acetate (400 cc) and the solution obtained is extracted with 1 N aqueous hydrochloric acid solution (2×100 cc). The aqueous phases are combined, washed with ethyl acetate (50 cc), alkalinized with 10 N aqueous sodium hydroxide solution to a pH in the region of 11 and extracted with ethyl acetate (2×250 cc). The organic phases are combined, washed with distilled water (3×30 cc), dried over magnesium sulphate, filtered and then concentrated to dryness under reduced pressure (2.7 kPa) at 60° C. After recrystallization in acetonitrile, 3-(4-dimethylamino-2-oxobutyl)-2-(7-methoxy-1,8-naphthyridin-2-yl)-1-isoindolinone (2.6 g), m.p. 140° C., is obtained. The suspension obtained The mixture is stirred for 3 hours at a temperature in the region of 20° C. is then poured into distilled water (500 cc) extracted with dichloromethane (3×200 cc) washed with distilled water (4×25 cc) dried over magnesium sulphate filtered concentrated to dryness under reduced pressure (2.7 kPa) at 40° C The oily residue obtained the solution obtained is extracted with 1 N aqueous hydrochloric acid solution (2×100 cc) washed with ethyl acetate (50 cc) extracted with ethyl acetate (2×250 cc) washed with distilled water (3×30 cc) dried over magnesium sulphate filtered concentrated to dryness under reduced pressure (2.7 kPa) at 60° C After recrystallization in acetonitrile

Conditions: temp:-5.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: Sodium hydride (0.7 g) is added in small portions at a temperature in the region of -5° C. to a solution, maintained under an argon atmosphere, of 3-hydroxy-2-(7-methoxy-1,8-naphthyridin-2-yl)-1-isoindolinone (8.0 g) in anhydrous dimethylformamide (125 cc). The suspension obtained is stirred for 30 minutes at a temperature in the region of -5° C. and then treated with a solution of 4-dimethylamino-2-butanone (3.5 g) in anhydrous dimethylformamide (5 cc). The mixture is stirred for 3 hours at a temperature in the region of 20° C., and is then poured into distilled water (500 cc) and extracted with dichloromethane (3×200 cc). The organic phases are combined, washed with distilled water (4×25 cc), dried over magnesium sulphate, filtered and then concentrated to dryness under reduced pressure (2.7 kPa) at 40° C. The oily residue obtained is dissolved in ethyl acetate (400 cc) and the solution obtained is extracted with 1 N aqueous hydrochloric acid solution (2×100 cc). The aqueous phases are combined, washed with ethyl acetate (50 cc), alkalinized with 10 N aqueous sodium hydroxide solution to a pH in the region of 11 and extracted with ethyl acetate (2×250 cc). The organic phases are combined, washed with distilled water (3×30 cc), dried over magnesium sulphate, filtered and then concentrated to dryness under reduced pressure (2.7 kPa) at 60° C. After recrystallization in acetonitrile, 3-(4-dimethylamino-2-oxobutyl)-2-(7-methoxy-1,8-naphthyridin-2-yl)-1-isoindolinone (2.6 g), m.p. 140° C., is obtained. The suspension obtained The mixture is stirred for 3 hours at a temperature in the region of 20° C. is then poured into distilled water (500 cc) extracted with dichloromethane (3×200 cc) washed with distilled water (4×25 cc) dried over magnesium sulphate filtered concentrated to dryness under reduced pressure (2.7 kPa) at 40° C The oily residue obtained the solution obtained is extracted with 1 N aqueous hydrochloric acid solution (2×100 cc) washed with ethyl acetate (50 cc) extracted with ethyl acetate (2×250 cc) washed with distilled water (3×30 cc) dried over magnesium sulphate filtered concentrated to dryness under reduced pressure (2.7 kPa) at 60° C After recrystallization in acetonitrile

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

Procedure: By following the procedure of Example 2(a) but using as starting material in Example 2(a) an appropriate starting material of formula II, for example, those described in Examples 2 to 14 and an appropriate aminoketone of formula III in which R2 and n are as described above and A is CH2NR4R5 wherein R4 and R5 are as described above, the amino compounds of formula I listed in Examples 31 to 46 are obtained. For example, according to the present procedure 2-phenyl-4-(β-hydroxyethyl)thiazole condenses with 1-(N,N-dimethylamino)-3-butanone to give the title compound, identical to the amine described in Example 31. are obtained

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

Procedure: To a solution of 4-dimethylamino-2-butanone[34.5 g, 0.3 moles, described by E. C. du Feu et al., J. Chem. Soc., 56 (1937)] in dry isopropanol (120 ml), gaseous hydrogen chloride is introduced at 0° C. until the solution is acidic to congo red (ca. pH=4). Isopropanol saturated with hydrogen chloride (2 ml) is added. Isopropyl nitrite (29.4 g, 0.33 moles) is added dropwise with stirring while maintaining the reaction temperature at 30° to 35° C. After 30 min, diethyl ether (100 ml) is added and the mixture is stirred for 30 min. The precipitate is collected to obtain 47 g of the title compound, mp 188°-199° C. The latter precipitate is crystallized from ethanol-diethyl ether to obtain 32 g of title compound; mp 205°-206° C., nmr(DMSO-d6) δ 2.4(s), 2.75(s), 4.07(s) and 12.35(broad singlet). while maintaining the reaction temperature at 30° to 35° C the mixture is stirred for 30 min The precipitate is collected

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

Procedure: A process for the production of 2,3,6-trimethylphenol which comprises reacting a carbonyl compound selected from the group consisting of methyl vinyl ketone, methyl β-hydroxyethyl ketone, methyl β-methoxyethyl ketone, methyl β-phenoxyethyl ketone, methyl β-acetyloxyethyl ketone, methyl β-benzoyloxyethyl ketone, methyl β-methyl-sulfonyloxyethyl ketone, methyl β-phenylsulfonyloxyethyl ketone, methyl β-dimethylaminoethyl ketone, methyl β-chloroethyl ketone, dimethyl-(β-acetylethyl)-sulfonium bromide or trimethyl-(β-acetylethyl)-ammonium iodide to a mixture of diethyl ketone and a basic reagent selected from the group consisting of an alkali metal, an alkaline earth metal, a hydroxide, oxide, alcoholate, amide, hydride or organo metallic compound of an alkali metal or alkaline earth metal, and a quaternary ammonium hydroxide, the amount of said diethyl ketone being in the molar ratio of 1:1 to 50:1 with respect to the total amount of carbonyl compound added, at a reaction temperature of 20° to 150° C. to produce 2,3,6-trimethyl-2-cyclohexen-1-one, and dehydrogenating the latter to produce 2,3,6-trimethylphenol.

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

Procedure: To a solution of 4-dimethylamino-2-butanone[34.5 g, 0.3 moles, described by E. C. du Feu et al., J. Chem. Soc., 56 (1937)] in dry isopropanol (120 ml), gaseous hydrogen chloride is introduced at 0° C. until the solution is acidic to congo red (ca. pH=4). Isopropanol saturated with hydrogen chloride (2 ml) is added. Isopropyl nitrite (29.4 g, 0.33 moles) is added dropwise with stirring while maintaining the reaction temperature at 30° to 35° C. After 30 min, diethyl ether (100 ml) is added and the mixture is stirred for 30 min. The precipitate is collected to obtain 47 g of the title compound, mp 188°-199° C. The latter precipitate is crystallized from ethanol-diethyl ether to obtain 32 g of title compound; mp 205°-206° C., nmr(DMSO-d6) δ 2.4(s), 2.75(s), 4.07(s) and 12.35(broad singlet). while maintaining the reaction temperature at 30° to 35° C the mixture is stirred for 30 min The precipitate is collected

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

Procedure: A process for the production of 2,3,6-trimethylphenol which comprises reacting a carbonyl compound selected from the group consisting of methyl vinyl ketone, methyl β-hydroxyethyl ketone, methyl β-methoxyethyl ketone, methyl β-phenoxyethyl ketone, methyl β-acetyloxyethyl ketone, methyl β-benzoyloxyethyl ketone, methyl β-methyl-sulfonyloxyethyl ketone, methyl β-phenylsulfonyloxyethyl ketone, methyl β-dimethylaminoethyl ketone, methyl β-chloroethyl ketone, dimethyl-(β-acetylethyl)-sulfonium bromide or trimethyl-(β-acetylethyl)-ammonium iodide to a mixture of diethyl ketone and a basic reagent selected from the group consisting of an alkali metal, an alkaline earth metal, a hydroxide, oxide, alcoholate, amide, hydride or organo metallic compound of an alkali metal or alkaline earth metal, and a quaternary ammonium hydroxide, the amount of said diethyl ketone being in the molar ratio of 1:1 to 50:1 with respect to the total amount of carbonyl compound added, at a reaction temperature of 20° to 150° C. to produce 2,3,6-trimethyl-2-cyclohexen-1-one, and dehydrogenating the latter to produce 2,3,6-trimethylphenol.

Conditions: temp:80.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: To a solution of 1-dimethylamino-3-butanone (1.0 g) dissolved in toluene (10 ml), p-toluenesulfonic acid (1.3 g) is added. The suspension is stirred for 10 min. Indene-3-ethanol (1.0 g) in toluene (5 ml) is added to the suspension and the resulting solution stirred for 2 hr. Boron trifluoride etherate (0.25 ml) is added together with ca. 0.5 g of hydrated alkali-aluminum silicate. The mixture is heated at 80° C for 30 min. The mixture is cooled and diluted with water. The organic layer is separated and the aqueous layer extracted with toluene. The organic layers are washed with water. The combined aqueous phase is rendered alkaline with conc.NH4OH and extracted with toluene. The latter extract is treated with charcoal and then concentrated to afford the title compound, identical to the compound of the same name described in Example 284. the resulting solution stirred for 2 hr The mixture is cooled The organic layer is separated the aqueous layer extracted with toluene The organic layers are washed with water NH4OH and extracted with toluene The latter extract is treated with charcoal concentrated