1,4-丁二醇单乙酸酯

反应条件: temp:0.00; pressure:0.00; stir:

反应条件: temp:0.00; pressure:0.00; stir:

反应条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: The procedure in Example 1 was followed but instead of the acetoxybutyraldehyde isomer mixture, 4-acetoxybutyraldehyde was employed and the hydrogenation was carried out in the presence of 5% by weight of methanol. After a hydrogenation time of 35 minutes, and after filtering off the catalyst and freeing the filtrate from methanol, 4-acetoxybutan-1-ol was obtained in 99% yield. After a hydrogenation time of 35 minutes, and after filtering off the catalyst

反应条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: 1,4-Butanediol (0.90 ml, 10.16 mmol) was added to a stirred suspension of NaH (246 mg, 10.25 mmol) in THF (20 ml) at room temperature and stirred for 30 minutes. Acetyl chloride (0.70 mL, 9.84 mmol) was then added to the thick white slurry. Following 45 minutes of stirring, the solution was diluted with diethyl ether (30 mL) and 10 w/v % K2CO3 (aq). The phases were separated and the organic phase washed with 10% K2CO3 (1×15 mL) and brine (1×15 mL). The combined aqueous phase was extracted with diethyl ether (1×30 mL). The organic phase was dried (MgSO4) and concentrated to afford 933 mg crude product as a colourless liquid. Purification by column chromatography (25 g silica, 2:1 hexanes:ethyl acetate) afforded 686 mg of acetic acid 4-hydroxy-butyl ester (51%). 1H NMR (CDCl3) δ 1.58-1.77 (m, 4H), 2.05 (s, 3H), 3.68 (t, 2H, J=6.1 Hz), 4.10 (t, 2H, J=6.4 Hz). Following 45 minutes of stirring The phases were separated the organic phase washed with 10% K2CO3 (1×15 mL) and brine (1×15 mL) The combined aqueous phase was extracted with diethyl ether (1×30 mL) The organic phase was dried (MgSO4) concentrated to afford 933 mg crude product as a colourless liquid Purification by column chromatography (25 g silica, 2:1 hexanes:ethyl acetate)

反应条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: 1,4-Butanediol (0.90 ml, 10.16 mmol) was added to a stirred suspension of NaH (246 mg, 10.25 mmol) in THF (20 ml) at room temperature and stirred for 30 minutes. Acetyl chloride (0.70 mL, 9.84 mmol) was then added to the thick white slurry. Following 45 minutes of stirring, the solution was diluted with diethyl ether (30 mL) and 10 w/v % K2CO3 (aq). The phases were separated and the organic phase washed with 10% K2CO3 (1×15 mL) and brine (1×15 mL). The combined aqueous phase was extracted with diethyl ether (1×30 mL). The organic phase was dried (MgSO4) and concentrated to afford 933 mg crude product as a colourless liquid. Purification by column chromatography (25 g silica, 2:1 hexanes:ethyl acetate) afforded 686 mg of acetic acid 4-hydroxy-butyl ester (51%). 1H NMR (CDCl3) δ 1.58-1.77 (m, 4H), 2.05 (s, 3H), 3.68 (t, 2H, J=6.1 Hz), 4.10 (t, 2H, J=6.4 Hz). Following 45 minutes of stirring The phases were separated the organic phase washed with 10% K2CO3 (1×15 mL) and brine (1×15 mL) The combined aqueous phase was extracted with diethyl ether (1×30 mL) The organic phase was dried (MgSO4) concentrated to afford 933 mg crude product as a colourless liquid Purification by column chromatography (25 g silica, 2:1 hexanes:ethyl acetate)

反应条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: The tube reactor is charged with 85 grams of silica-magnesia catalyst (70% silica -- 30% magnesia, 3/16 inch × 3/16 inch pills, Davison Chemical) and maintained at 220°-250° C. As in Example 1, 50.0 grams of 1,4-butanediol diacetate and 50 ml. of water are copassed over one hour. The effluent contains, as shown by quantitative glpc analysis, 12.2 grams of the unconverted butanediol diacetate (24% recovery), 15.1 grams of tetrahydrofuran and 24.4 grams of acetic acid (96% and 93% yields, respectively, based on 76% conversion), and 0.1 grams of 4-acetoxybutanol (0.3% yield). The tube reactor is charged with 85 grams of silica-magnesia catalyst (70% silica -- 30% magnesia, 3/16 inch × 3/16 inch pills, Davison Chemical) maintained at 220°-250° C yields

反应条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: The tube reactor is charged with 85 grams of silica-magnesia catalyst (70% silica -- 30% magnesia, 3/16 inch × 3/16 inch pills, Davison Chemical) and maintained at 220°-250° C. As in Example 1, 50.0 grams of 1,4-butanediol diacetate and 50 ml. of water are copassed over one hour. The effluent contains, as shown by quantitative glpc analysis, 12.2 grams of the unconverted butanediol diacetate (24% recovery), 15.1 grams of tetrahydrofuran and 24.4 grams of acetic acid (96% and 93% yields, respectively, based on 76% conversion), and 0.1 grams of 4-acetoxybutanol (0.3% yield). The tube reactor is charged with 85 grams of silica-magnesia catalyst (70% silica -- 30% magnesia, 3/16 inch × 3/16 inch pills, Davison Chemical) maintained at 220°-250° C yields

反应条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: The procedure in Example 1 was followed but instead of the acetoxybutyraldehyde isomer mixture, 4-acetoxybutyraldehyde was employed and the hydrogenation was carried out in the presence of 5% by weight of methanol. After a hydrogenation time of 35 minutes, and after filtering off the catalyst and freeing the filtrate from methanol, 4-acetoxybutan-1-ol was obtained in 99% yield. After a hydrogenation time of 35 minutes, and after filtering off the catalyst

反应条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: The procedure in Example 1 was followed but instead of the acetoxybutyraldehyde isomer mixture, 4-acetoxybutyraldehyde was employed and the hydrogenation was carried out in the presence of 5% by weight of methanol. After a hydrogenation time of 35 minutes, and after filtering off the catalyst and freeing the filtrate from methanol, 4-acetoxybutan-1-ol was obtained in 99% yield. After a hydrogenation time of 35 minutes, and after filtering off the catalyst

反应条件: temp:0.00; pressure:0.00; stir:

反应条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: The anhydride may be, but not limited to, acetic acid anhydride, propionic anhydride, butyric anhydride, pentanoic anhydride or hexanoic anhydride. Preferably, the anhydride is acetic acid anhydride. According to an embodiment, the esterification of 1,4-bunediol is performed with acetic acid anhydride to form CH3C(O)O—(CH2)4—OH.

反应条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: Alternatively, at least a portion of the 4-acetoxybutyraldehyde reaction product may be preferably converted to produce tetrahydrofuran (THF). Preferably, the 4-acetoxybutyraldehyde is hydrogenated to produce 4-acetoxybutanol, which then is dehydroacetoxylated to produce THF. The hydrogenation to produce 4-acetoxybutanol is preferably conducted according to the conditions described above. The 4-acetoxybutanol can then undergo a dehydroacetoxylation reaction to produce THF and acetic acid. The dehydroacetoxylation step is preferably performed at temperatures in the range of from 20 to 300° C. in the presence of a dehydroacetoxylation catalyst, such as silica, silica-alumina, and/or tungsten oxide. A final hydrolysis step may be performed to convert any 3-acetoxy-2-methylpropanol, formed by the hydrogenation of 3-acetoxy-2-methylpropionaldehyde, to 2-methyl-1,3-propanediol (MPD) a dehydroacetoxylation reaction A final hydrolysis step