oxan-2-one

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:

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:0.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: To a stirred suspension of N,O-dimethylhydroxyamine hydrochloride (14.6 g, 150 mmol) in dry dichloromethane (150 mL) was added a solution of trimethylaluminum (2.0 M solution in toluene, 75 mL, 150 mmol) drop wise at room temperature. After stirring for 30 min, tetrahydropyran-2-one (10 g, 100 mmol) in dry dichloromethane (50 mL) was added drop wise. The reaction mixture was stirred over night. After cooling to 0° C., 1N HCl (80 mL, 80 mmol) was added slowly (exothermic reaction), diluted with dichloromethane (200 mL). The two layers were separated and the aqueous layer was extracted with dichloromethane twice. The combined organic phases were dried over sodium sulfate, filtered and concentrated. The residue was purified by column chromatography on silica gel (120 g column, 0% methanol in dichloromethane to 20% methanol in dichloromethane) to give product (9.7 g, 60%). 1H NMR (CDCl3) δ 3.68 (s, 3H), 3.63 (t, J=6.1 Hz, 2H), 3.17 (s, 3H), 2.46 (t, J=7.0 Hz, 2H), 1.69-1.74 (m, 2H), 1.58-1.64 (m, 2H). MS EI m/z 162 (M+H)+. The reaction mixture was stirred over night (exothermic reaction) The two layers were separated the aqueous layer was extracted with dichloromethane twice The combined organic phases were dried over sodium sulfate filtered concentrated The residue was purified by column chromatography on silica gel (120 g column, 0% methanol in dichloromethane to 20% methanol in dichloromethane)

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

実験手順: A solution of 1,5-dibromopentane (5 gms, 23.15 mmol) in dry THF (10 ml) was added slowly to a suspension of Magnesium turning (2.8 gms, 112 mmole) in dry THF (50 ml) and catalytic amount of iodine under nitrogen atmosphere. After the addition of about 3 ml of dibromopentane solution in THF, Grignard reaction was initiated. The addition was continued maintaining a gentle reflux. The mixture was refluxed for 16 hours to complete the formation of the Grignard reagent. To the reaction mixture was added a solution of a solution of δ-valerolactone (2.13 gms, 21.3 mmol) in dry THF (50 ml). The resulting mixture was refluxed for 6 hours under nitrogen and then quenched by addition of saturated solution of ammonium chloride at 0° C. The product was extracted in ethylacetate. Organic layer was washed with water, brine and dried over anh. Na2SO4. Drying agent was filtered off and the solvent was removed under vacuum to give 2.7 gms of diol (8), which was used without any further purification in the next step. The addition was continued maintaining a gentle reflux The mixture was refluxed for 16 hours The resulting mixture was refluxed for 6 hours under nitrogen quenched by addition of saturated solution of ammonium chloride at 0° C The product was extracted in ethylacetate Organic layer was washed with water, brine dried over anh. Na2SO4 Drying agent was filtered off the solvent was removed under vacuum

反応条件: temp:110.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: 1,4-Difluorobenzene (22 ml, 210 mmol) was mixed with □-valerolactone (4 ml, 42 mmol) and AlCl3 (28 g, 210 mmol) was added by portions to the stirred reaction mixture. The reaction mixture was then refluxed at stirring for 16 h (oil bath 110° C.). The reaction mixture was cooled down (ice/brine bath) and ice/conc. HCl was added and stirred until homogeneous mixture was obtained. The reaction mixture was then extracted into methylene chloride, washed with water (4×10 ml) and sodium bicarbonate solution (3×100 ml). The organic extract was dried over Na2SO4. Concentration by rotary evaporation gave 6.7 g of product as yellow powder. Yield 81%. was added by portions to the stirred reaction mixture The reaction mixture was then refluxed stirred until homogeneous mixture was obtained The reaction mixture was then extracted into methylene chloride washed with water (4×10 ml) and sodium bicarbonate solution (3×100 ml) The organic extract was dried over Na2SO4 Concentration by rotary evaporation

反応条件: temp:-78.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: δ-Valerolactone (7.14 g, 71.35 mmol) was slowly added to a flask containing freshly made LDA (80 mmol) in 200 ml of dry THF at -78° C. under N2. After stirring the solution for 40 min at -78° C., benzyl bromide (12.20 g, 71 mmol) was added. The bath was removed and the reaction was stirred at room temperature for 40 min. At the end, the crude mixture was poured to a slurry of AcOEt-Hexane and 0.5 N H2SO4. The organic layer was washed with brine, dried over MgSO4 and concentrated in vacuo. The crude product was then dissolved in 60 ml of MeOH and 10 ml of concentrated H2SO4. After stirring the solution at room temperature overnight, the acid was neutralized with aqueous NaHCO3. The crude product was extracted with AcOEt-Hexane and purified by column chromatography (silica gel, AcOEt-Hexane, 1:3) which gave 6.2 g (40% yield) of methyl 2-benzyl-5-hydroxy-pentanoate; 1H NMR (CDCl3, 300 MHz) δ: 7.30-7.10 (m,5H), 3.58 (s,3H,OCH3, 3.56 (t,J=6Hz,2H), 2.95 (dd,J=7,12Hz,1H), 2.75 (dd,J=6,12Hz,1H), 2.69 (m,1H), 2.15 (s,1H,-OH), and 1.70-1.50 (m,4H). The bath was removed the reaction was stirred at room temperature for 40 min At the end, the crude mixture was poured to a slurry of AcOEt-Hexane and 0.5 N H2SO4 The organic layer was washed with brine dried over MgSO4 concentrated in vacuo The crude product was then dissolved in 60 ml of MeOH After stirring the solution at room temperature overnight The crude product was extracted with AcOEt-Hexane purified by column chromatography (silica gel, AcOEt-Hexane, 1:3) which

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

実験手順: According to the ratio for charging as described in Table 2, oxetane and delta-valerolactone (referred to as VL in Table and Figure) were mixed, and polymerized in a bulk state at 60° C. for 24 hours using 0.2% by mol of a triethylaluminum-water (1/0.75) based complex as an initiator based on the total amount of the monomers. were mixed polymerized in a bulk state at 60° C. for 24 hours

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

実験手順: In a water separator, 5-fluoroindole (5.0 g, 37 mmol.), δ-valerolactone (3.83 ml, 42 mmol.), potassium hydroxide (3.09 g, 55 mmol.) in p-cymene (120 ml) were heated to boiling, with stirring. The water separation was stopped after 80 h. For working up, water (50 ml) was added to the mixture at RT and stirring was carried out for 30 min. The phases were then separated in a separating funnel. The aqueous phase was washed with ether (3×20 ml), adjusted to pH 1 with 2M HCl and extracted with ether (5×25 ml). The combined extracts were washed with water (5×10 ml), dried, filtered and concentrated. The residue was purified by flash chromatography on silica gel (375 g) (eluant: 2700 ml of cyclohexane/EE 4:1 followed by 1500 ml of cyclohexane/EE 1:1 and 650 ml of EE). 1.9 g of 5-(5-fluoro-1H-indol-3-yl)pentanoic acid were obtained (beige solid, m.p. 86–92° C.). The water separation water (50 ml) was added to the mixture at RT stirring was carried out for 30 min The phases were then separated in a separating funnel The aqueous phase was washed with ether (3×20 ml) extracted with ether (5×25 ml) The combined extracts were washed with water (5×10 ml) dried filtered concentrated The residue was purified by flash chromatography on silica gel (375 g) (eluant: 2700 ml of cyclohexane/EE 4:1 followed by 1500 ml of cyclohexane/EE 1:1 and 650 ml of EE)