methyl 2-hydroxy-2-methoxyacetate

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: To a solution of 2-hydroxy-2-methoxyacetic acid methyl ester (151 g) in toluene (300 mL), was added (R)-(+)-1-phenylethylamine (150 g) dropwise. The mixture was then stirred for 1 hr at room temperature. The resulting mixture was extracted with ethyl acetate. The organic layer was washed with water and brine, dried over magnesium sulfate, and evaporated to obtain the target compound as a yellow oil. The target compound was used in the next step without further purification. The resulting mixture was extracted with ethyl acetate The organic layer was washed with water and brine dried over magnesium sulfate evaporated

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

実験手順: Benzhydrylamine (48.8 g, 0.266 mol) was added drop wise to a solution of glyoxylic acid methyl ester methyl hemiacetal (32 g, 0.266 mol) in methylene chloride (300 mL). The mixture was stirred for 3 hours at room temperature and then dried over magnesium sulfate. The mixture was filtered and the solvent was removed from the filtrate under reduced pressure to yield a viscous oil. Trituration with diisopropyl ether/heptane gave methyl 2-(benzhydrylimino)acetate (53.4 g, 79%) as an off white solid. 1H-NMR (400 MHz, CDCl3): δ=3.82 (s, 3H), 7.17-7.31 (m, 10H), 7.73 (s, 1H). dried over magnesium sulfate The mixture was filtered the solvent was removed from the filtrate under reduced pressure to yield a viscous oil

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

実験手順: A solution of 3-amino-2-cyclohexyl-1-propanol (1 g, 6.37 mmole) and methyl glyoxylate methylhemiacetal (790 mg, 6.56 mmole; see Tetrahedron, 881, 1977) in methanol (9 ml) was stirred at room temperature under argon for 24 hours. The resulting solution was transferred to a Parr bottle, treated with additional methanol (22 ml), acetic acid (3.6 ml), and 10% Pd on carbon (857 mg) and hydrogenated at 50 psi overnight. The catalyst was filtered off and the filtrate was concentrated in vacuo. Acetic acid was removed by evaporation from toluene. The residue was partitioned between ethyl acetate and 1N HCl. The organic layer was extracted with additional HCl and the combined aqueous extracts were washed with ethyl acetate. The pH of the product rich aqueous solution was raised to 10.2, and sodium chloride was added to saturation. Extraction with ethyl acetate followed by drying (sodium sulfate), filtration and concentration in vacuo produced 780 mg (53%) of the title compound as an oil. The catalyst was filtered off the filtrate was concentrated in vacuo Acetic acid was removed by evaporation from toluene The residue was partitioned between ethyl acetate and 1N HCl The organic layer was extracted with additional HCl the combined aqueous extracts were washed with ethyl acetate The pH of the product rich aqueous solution was raised to 10.2, and sodium chloride was added to saturation Extraction with ethyl acetate by drying (sodium sulfate), filtration and concentration in vacuo

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

実験手順: 3 g (0.025 mol) of di-n-butylamine were added at 20° C. to a stirred mixture of 120 g (1 mol) of methyl 2-methoxy-2-hydroxyacetate and 58 g (1 mol) of propionaldehyde. An exothermic reaction started immediately and the temperature of the reaction mixture rose to about 90° C., and it boiled vigorously. After about 10 min the temperature started to fall again and reached room temperature after about 1.5 h. Distillation of the reaction mixture yielded 66.4 g of methyl 3-formylcrotonate of b.p. 45°-58° C./8-9 mbar, corresponding to a yield of 52%. The trans/cis ratio was determined by gas chromatography to be 91/9. An exothermic reaction rose to about 90° C. reached room temperature after about 1.5 h Distillation of the reaction mixture

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

実験手順: 3.2 g (0.025 mol) of di-n-butylamine were added to a boiling, at 70° C., mixture of 120 g (1 mol) of methyl 2-methoxy-2-hydroxyacetate and 58 g (1 mol) of propionaldehyde. An exothermic reaction started immediately and the temperature rose to 100° C., when part of the reaction mixture boiled out of the flask. The temperature slowly fell to 90° C. and was maintained at this for 30 min. Fractional distillation of the reaction mixture yielded 38.9 g of methyl 3-formylcrotonate of boiling point (b.p.) 56°-68° C./10 mbar, corresponding to a yield of 30.4% of theory. The trans/cis ratio was determined by gas chromatography to be 83/17. An exothermic reaction rose to 100° C. slowly fell to 90° C. was maintained at this for 30 min Fractional distillation of the reaction mixture

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

実験手順: 3 g (0.025 mol) of di-n-butylamine were added at 20° C. to a stirred mixture of 120 g (1 mol) of methyl 2-methoxy-2-hydroxyacetate and 58 g (1 mol) of propionaldehyde. An exothermic reaction started immediately and the temperature of the reaction mixture rose to about 90° C., and it boiled vigorously. After about 10 min the temperature started to fall again and reached room temperature after about 1.5 h. Distillation of the reaction mixture yielded 66.4 g of methyl 3-formylcrotonate of b.p. 45°-58° C./8-9 mbar, corresponding to a yield of 52%. The trans/cis ratio was determined by gas chromatography to be 91/9. An exothermic reaction rose to about 90° C. reached room temperature after about 1.5 h Distillation of the reaction mixture

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

実験手順: 3.2 g (0.025 mol) of di-n-butylamine were added to a boiling, at 70° C., mixture of 120 g (1 mol) of methyl 2-methoxy-2-hydroxyacetate and 58 g (1 mol) of propionaldehyde. An exothermic reaction started immediately and the temperature rose to 100° C., when part of the reaction mixture boiled out of the flask. The temperature slowly fell to 90° C. and was maintained at this for 30 min. Fractional distillation of the reaction mixture yielded 38.9 g of methyl 3-formylcrotonate of boiling point (b.p.) 56°-68° C./10 mbar, corresponding to a yield of 30.4% of theory. The trans/cis ratio was determined by gas chromatography to be 83/17. An exothermic reaction rose to 100° C. slowly fell to 90° C. was maintained at this for 30 min Fractional distillation of the reaction mixture

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

実験手順: A mixture of 4.4 g (26.1.10-3 mol) of 7-azidoheptanamide, 2.9 ml (29.2.10-3 mol) of methyl 2-hydroxy-2-methoxyacetate and 250 ml of dichloromethane is prepared and refluxed for 24 hours by means of a device which is such that the reflux condensate passes through a bed of 4 Å molecular sieves (about 30 g). After return to room temperature, the device for eliminating the methanol is removed and 2.29 ml (31.10-3 mol) of thionyl chloride are added to the reaction medium, which is then refluxed again for 1.75 h. The reaction mixture is subsequently concentrated under reduced pressure and then taken up with 50 ml of dichloromethane. A solution of 2.29 ml (31.10-3 mol) of triethylamine and 4.5 g (26.10-3 mol) of (S)-(-)-α-methyl-2-naphthalenemethanol [or 1-(S)-(naphthalen-2-yl)ethanol] in 50 ml of dichloromethane is added. The reaction mixture is stirred for 24 hours at room temperature and then washed successively with 100 ml of 1N hydrochloric acid and sodium chloride solution. After drying, the organic phase is concentrated under reduced pressure and the residue is purified by chromatography on silica gel using a hexane/2-propanol mixture (9/1 v/v) as the eluent to give 6.67 g of the expected product in the form of a colorless oil (yield=62%). is prepared refluxed for 24 hours by means of a device which to room temperature is removed is then refluxed again for 1.75 h The reaction mixture is subsequently concentrated under reduced pressure washed successively with 100 ml of 1N hydrochloric acid and sodium chloride solution After drying the organic phase is concentrated under reduced pressure the residue is purified by chromatography on silica gel using a hexane/2-propanol mixture (9/1 v/v) as the eluent

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

実験手順: To a solution of 2-hydroxy-2-methoxyacetic acid methyl ester (151 g) in toluene (300 mL), was added (R)-(+)-1-phenylethylamine (150 g) dropwise. The mixture was then stirred for 1 hr at room temperature. The resulting mixture was extracted with ethyl acetate. The organic layer was washed with water and brine, dried over magnesium sulfate, and evaporated to obtain the target compound as a yellow oil. The target compound was used in the next step without further purification. The resulting mixture was extracted with ethyl acetate The organic layer was washed with water and brine dried over magnesium sulfate evaporated