((Dimethylamino)methyl)phenol

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

実験手順: 2-(Dimethylaminomethyl)phenyltributylstannyl Ether is prepared as follows: 59.6 gm (0.1 mole) bis(tributyltin) oxide and 30.0 gm (0.2 mole) 2-dimethylaminomethyl phenol (as just prepared) are placed in 200 ml benzene. This is slowly heated to reflux in a system equipped with a Dean-Starke tube. After about 30 minutes water began to separate in the Dean-Starke tube. After 72 hours at reflux 1.9 ml of water had separated (theory 1.8 ml). A clear straw colored reaction mixture resulted and benzene is evaporated therefrom on a rotating evaporator to provide 87.7 gm of a yellow liquid. This is fractionated at reduced pressure. The product collected at 165°-168° C. at 0.5 mm is 75.0 gm of a straw colored liquid (Percent yield - 82). Infrared spectral analysis provided bands characteristic of the desired product. This is slowly heated to reflux in a system equipped with a Dean-Starke tube to separate in the Dean-Starke tube After 72 hours at reflux 1.9 ml of water had separated (theory 1.8 ml) A clear straw colored reaction mixture resulted benzene is evaporated on a rotating evaporator

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

実験手順: 2-Dimethylaminomethyl phenol was prepared by the method of S. Cavitt, "J. Org. Chem.", 27, 1211 (1962). 61.0 gm salicylaldehyde, 127 gm 25% by wt dimethylamine in water and 1.2 gm 10% by wt palladium on charcoal are placed in a pressure bottle of a Parr hydrogenator and hydrogenated until 41.7 lbs of hydrogen are taken up. The experiment is repeated and reaction mixtures combined. The catalyst is filtered off and the filtrate made acidic (pH 2), extracted with ether, and the ether discarded. The aqueous phase is adjusted to pH 8 with NaOH and extracted with ether. The aqueous phase is adjusted to pH 9 with NaOH and extracted with ether. The ether extracts are combined, dried over MgSO4, filtered, and evaporated on a rotating evaporator. There results 111.7 gm of an orange liquid (Percent crude yield - 75). This is fractionated at reduced pressure. The product is collected at 60°-63° C. at 0.5 mm to provide 99.1 gm of a yellow liquid (Percent yield - 65). reaction mixtures The catalyst is filtered off extracted with ether extracted with ether extracted with ether dried over MgSO4 filtered evaporated on a rotating evaporator

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

実験手順: 2-(Dimethylaminomethyl)phenyltributylstannyl Ether is prepared as follows: 59.6 gm (0.1 mole) bis(tributyltin) oxide and 30.0 gm (0.2 mole) 2-dimethylaminomethyl phenol (as just prepared) are placed in 200 ml benzene. This is slowly heated to reflux in a system equipped with a Dean-Starke tube. After about 30 minutes water began to separate in the Dean-Starke tube. After 72 hours at reflux 1.9 ml of water had separated (theory 1.8 ml). A clear straw colored reaction mixture resulted and benzene is evaporated therefrom on a rotating evaporator to provide 87.7 gm of a yellow liquid. This is fractionated at reduced pressure. The product collected at 165°-168° C. at 0.5 mm is 75.0 gm of a straw colored liquid (Percent yield - 82). Infrared spectral analysis provided bands characteristic of the desired product. This is slowly heated to reflux in a system equipped with a Dean-Starke tube to separate in the Dean-Starke tube After 72 hours at reflux 1.9 ml of water had separated (theory 1.8 ml) A clear straw colored reaction mixture resulted benzene is evaporated on a rotating evaporator

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

実験手順: 2-Dimethylaminomethyl phenol was prepared by the method of S. Cavitt, "J. Org. Chem.", 27, 1211 (1962). 61.0 gm salicylaldehyde, 127 gm 25% by wt dimethylamine in water and 1.2 gm 10% by wt palladium on charcoal are placed in a pressure bottle of a Parr hydrogenator and hydrogenated until 41.7 lbs of hydrogen are taken up. The experiment is repeated and reaction mixtures combined. The catalyst is filtered off and the filtrate made acidic (pH 2), extracted with ether, and the ether discarded. The aqueous phase is adjusted to pH 8 with NaOH and extracted with ether. The aqueous phase is adjusted to pH 9 with NaOH and extracted with ether. The ether extracts are combined, dried over MgSO4, filtered, and evaporated on a rotating evaporator. There results 111.7 gm of an orange liquid (Percent crude yield - 75). This is fractionated at reduced pressure. The product is collected at 60°-63° C. at 0.5 mm to provide 99.1 gm of a yellow liquid (Percent yield - 65). reaction mixtures The catalyst is filtered off extracted with ether extracted with ether extracted with ether dried over MgSO4 filtered evaporated on a rotating evaporator

反応条件: temp:60.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: 0.45 kg of dimethylamine was passed, under normal pressure and at a reaction temperature of 20°-25° C., in the course of 5 hours into a mixture of 1.0 kg of phenol, 0.30 kg of paraformaldehyde and 3.1 kg of methanol and the reaction mixture was then warmed to 60° C. for 1 hour. After distilling off methanol and water in vacuo, 1.551 kg of a mixture which contained 0.242 kg of phenol, 0.605 kg of o-dimethylaminomethylphenol, 0.030 kg of p-dimethylaminomethylphenol, 0.302 kg of bis- and tris-dimethylaminomethylphenol and 0.392 kg of condensation and resinification products was obtained and 0.595 kg (49% of theory, relative to converted phenol), of o-dimethylaminomethylphenol could be obtained from this mixture. After distilling off methanol and water in vacuo, 1.551 kg of a mixture which 0.242 kg of phenol, 0.605 kg of o-dimethylaminomethylphenol, 0.030 kg of p-dimethylaminomethylphenol, 0.302 kg of bis- and tris-dimethylaminomethylphenol and 0.392 kg of condensation resinification products was obtained

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

実験手順: A solution of 2-(N,N-dimethylaminomethyl)phenol (10.0 g, which contains 30% phenol by weight) in DMF (10 ml) was added dropwise with stirring to a suspension of sodium hydride (3.14 g, 60% dispersion in mineral oil) in DMF (75 ml) at ambient temperature under nitrogen. After the addition the mixture was stirred at ambient temperature for 30 minutes. A solution of 2-chloro-N,N-diethylethylamine in toluene (70 ml) [prepared by dissolving the hydrochloride (14.8 g) in water (20 ml), adding aqueous sodium hydroxide (5M) to basify the mixture and then extracting the mixture with toluene 3×20 ml, drying, filtering and then making up to 70 ml as required] was added dropwise over a period of 2 minutes and the resulting mixture heated on a steam bath for 18 hours under nitrogen. The mixture was poured into ice/water (500 ml) and sodium hydroxide solution was added until the mixture was basic (pH=14). The mixture was extracted with ether to give a residue which was distilled under vacuum. The highest boiling fraction (b.p. 105°-110° C. at 0.6 mbar) was dissolved in ether and acidified with ethereal hydrogen chloride. The solvent was removed under reduced pressure. The residue was dissolved in propan-2-ol and ether added to induce precipitation. The solid was collected by filtration and recrystallised from propan-2-ol to give 2-(2-diethylaminoethoxy)-N,N-dimethylbenzylamine dihydrochloride, m.p. 213°-214° C. After the addition the mixture extracting the mixture with toluene 3×20 ml drying filtering was added dropwise over a period of 2 minutes the resulting mixture heated on a steam bath for 18 hours under nitrogen The mixture was poured into ice/water (500 ml) and sodium hydroxide solution was added until the mixture The mixture was extracted with ether to give a residue which was distilled under vacuum The highest boiling fraction (b.p. 105°-110° C. at 0.6 mbar) was dissolved in ether The solvent was removed under reduced pressure The residue was dissolved in propan-2-ol ether added precipitation The solid was collected by filtration recrystallised from propan-2-ol

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

実験手順: 2-(Dimethylaminomethyl)phenyltributylstannyl Ether is prepared as follows: 59.6 gm (0.1 mole) bis(tributyltin) oxide and 30.0 gm (0.2 mole) 2-dimethylaminomethyl phenol (as just prepared) are placed in 200 ml benzene. This is slowly heated to reflux in a system equipped with a Dean-Starke tube. After about 30 minutes water began to separate in the Dean-Starke tube. After 72 hours at reflux 1.9 ml of water had separated (theory 1.8 ml). A clear straw colored reaction mixture resulted and benzene is evaporated therefrom on a rotating evaporator to provide 87.7 gm of a yellow liquid. This is fractionated at reduced pressure. The product collected at 165°-168° C. at 0.5 mm is 75.0 gm of a straw colored liquid (Percent yield - 82). Infrared spectral analysis provided bands characteristic of the desired product. This is slowly heated to reflux in a system equipped with a Dean-Starke tube to separate in the Dean-Starke tube After 72 hours at reflux 1.9 ml of water had separated (theory 1.8 ml) A clear straw colored reaction mixture resulted benzene is evaporated on a rotating evaporator

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

実験手順: 2-Dimethylaminomethyl phenol was prepared by the method of S. Cavitt, "J. Org. Chem.", 27, 1211 (1962). 61.0 gm salicylaldehyde, 127 gm 25% by wt dimethylamine in water and 1.2 gm 10% by wt palladium on charcoal are placed in a pressure bottle of a Parr hydrogenator and hydrogenated until 41.7 lbs of hydrogen are taken up. The experiment is repeated and reaction mixtures combined. The catalyst is filtered off and the filtrate made acidic (pH 2), extracted with ether, and the ether discarded. The aqueous phase is adjusted to pH 8 with NaOH and extracted with ether. The aqueous phase is adjusted to pH 9 with NaOH and extracted with ether. The ether extracts are combined, dried over MgSO4, filtered, and evaporated on a rotating evaporator. There results 111.7 gm of an orange liquid (Percent crude yield - 75). This is fractionated at reduced pressure. The product is collected at 60°-63° C. at 0.5 mm to provide 99.1 gm of a yellow liquid (Percent yield - 65). reaction mixtures The catalyst is filtered off extracted with ether extracted with ether extracted with ether dried over MgSO4 filtered evaporated on a rotating evaporator