2-prop-2-enoxyacetic acid

反応条件: temp:65.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: Thionyl chloride (1.5 L) is added in one portion to a solution of 2-(allyloxy)acetic acid (2.2 Kg, 18.9 mol) in toluene (3.0 L), and the mixture is heated at 65° C. under a nitrogen atmosphere for 1 h. The mixture is cooled to room temperature and is added to a solution of N,O-dimethylhydroxylamine hydrochloride (2.1 Kg, 21.5 mol) and N-methyl morpholine (6.5 L, 59.2 mol) in dichloromethane (19 L) at 5° C. The reaction mixture is stirred at 25° C. for 16 h. Water is added, and the reaction mixture is extracted with dichloromethane. The combined organic phase is collected and washed with 1 M HCl (6 L), dried over magnesium sulfate and concentrated under reduced pressure. The residue is purified by silica gel chromatography eluting with ethyl acetate in hexanes to afford the title compound (1.49 Kg, 50%). ES/MS m/e: 160 (M+1). The mixture is cooled to room temperature the reaction mixture is extracted with dichloromethane The combined organic phase is collected washed with 1 M HCl (6 L) dried over magnesium sulfate concentrated under reduced pressure The residue is purified by silica gel chromatography eluting with ethyl acetate in hexanes

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

実験手順: 1.8 g of allyloxyacetic acid are placed in 15 mL dichloromethane, combined with 4.8 g of TBTU and 7.5 mL of ethyldiisopropylamine and stirred for 15 min. at RT. Then the mixture is cooled to −5° C. and 3.1 g of 1,2,3,4,5,6-hexahydro-6,11,11-trimethyl-2,6-methano-3-benzazocin-10-ol are added. The mixture is stirred for 30 min at 0° C., and for 1 h at RT. Then it is washed once with 100 ml of 2N HCL and 100ml of 10% potassium carbonate solution, dried and evaporated down in vacuo. The residue is taken up in 50 mL of THF and added dropwise under nitrogen to a suspension of 1.0 g of lithium aluminium hydride in 50 ml of THF (temp. increases to 35° C.). Then the mixture is heated to 50° C., stirred for 1 h, cooled and 1 ml of water is added dropwise at 0-10° C., the mixture is stirred for 30 min, 3 ml of NaOH are added and the mixture is stirred for another 30 min. The precipitate is suction filtered, the mother liquor is evaporated down in vacuo and the residue is filtered through a short column (about 75 ml of silica gel; dichloromethane 70, ethyl acetate 20, methanol 10). The appropriate fractions are evaporated down in vacuo, and crystallised from acetone+eth. HCl. Yield 2.8 g (77%), melting point: 236° C.; [α]D20=−78,3° (c=1; methanol). Then the mixture is cooled to −5° C. The mixture is stirred for 30 min at 0° C. for 1 h at RT Then it is washed once with 100 ml of 2N HCL and 100ml of 10% potassium carbonate solution dried evaporated down in vacuo added dropwise under nitrogen to a suspension of 1.0 g of lithium aluminium hydride in 50 ml of THF (temp. increases to 35° C.) Then the mixture is heated to 50° C. stirred for 1 h cooled 1 ml of water is added dropwise at 0-10° C. the mixture is stirred for 30 min 3 ml of NaOH are added the mixture is stirred for another 30 min filtered the mother liquor is evaporated down in vacuo the residue is filtered through a short column (about 75 ml of silica gel; dichloromethane 70, ethyl acetate 20, methanol 10) The appropriate fractions are evaporated down in vacuo crystallised from acetone+

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

実験手順: 2-(Allyloxy)acetic acid (0.500 g, 4.31 mmol) was dissolved in dichloromethane (20 ml), and 2-bromoacetonitrile (2.06 g, 17.18 mmol) and triethylamine (0.87 g, 8.61 mmol) were slowly added at room temperature. After stirring at room temperature for 3 hours, the reaction solution was concentrated under reduced pressure, and the resulting residue was purified by column chromatography (petroleum ether:ethyl acetate=20:1) to afford cyanomethyl 2-(allyloxy)acetate (0.40 g, 60%). the reaction solution was concentrated under reduced pressure the resulting residue was purified by column chromatography (petroleum ether:ethyl acetate=20:1)

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

実験手順: 2.5 g of crude 2-allyloxyacetic acid are introduced into 40 ml of toluene, and 4.7 g (30 mmol) of 9-decen-1-ol and 0.38 g (2.0 mmol) of p-toluenesulfonic acid are added. The mixture is then heated with a water separator until visible amounts of water no longer separate out. The mixture is then cooled, and the organic phase is washed once with saturated NaHCO3 solution, dried over Na2SO4 and filtered, and the product is freed from the solvent. Flash chromatography (cyclohexane/EtOAc=20:1, Rf=0.29) gives 3.1 g (62%) of dec-9-enyl 2-allyloxy-acetate as a colorless oil. are added no longer separate out The mixture is then cooled the organic phase is washed once with saturated NaHCO3 solution dried over Na2SO4 filtered