甲基2-己酸乙酯

反应条件: temp:-20.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: 47 ml (0.334 mol) of diisopropylamine are added dropwise at −20° C. to a solution of 118 ml (0.319 mol) of n-butyllithium (2.7 M in heptane) in 118 ml of THF, and the mixture is stirred at −20° C. for 30 min. Within approx. 15 min, 48 g (0.304 mol) of methyl 2-ethylhexanoate are added dropwise at −20° C., and the mixture is stirred at −20° C. for a further 30 min and subsequently admixed with 18 g (0.60 mol) of paraformaldehyde. After 30 min at −20° C., the mixture is stirred at 0° C. for 2 h. After addition of 100 ml of MTBE and 100 ml of saturated aqueous solution of ammonium chloride, the mixture is stirred at RT for 2 h. The organic phase is removed, the aqueous phase is re-extracted 1×with 100 ml of MTBE and the combined organic phases are concentrated on a rotary evaporator. The crude product (97% conversion based on methyl 2-ethylhexanoate) can be purified by distillation to obtain methyl 2-ethyl-2-hydroxymethylhexanoate (b.p.: 100° C., 6 mbar) in 91% yield with a purity of >99%. Within approx. 15 min the mixture is stirred at −20° C. for a further 30 min After 30 min at −20° C. the mixture is stirred at 0° C. for 2 h the mixture is stirred at RT for 2 h The organic phase is removed the aqueous phase is re-extracted 1×with 100 ml of MTBE the combined organic phases are concentrated on a rotary evaporator The crude product (97% conversion based on methyl 2-ethylhexanoate) can be purified by distillation

反应条件: temp:-20.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: 9.8 ml (0.070 mol) of diisopropylamine are added dropwise at 20° C. to a solution of 24.4 ml (0.065 mol) of n-butyllithium (2.7 M in heptane) in 25 ml of MTBE, and the mixture is stirred at −20° C. for 30 min. Within approx. 10 min, 10 g (0.063 mol) of methyl 2-ethylhexanoate are added dropwise at −20° C., and the mixture is stirred at 20° C. for a further 30 min and subsequently admixed with 5.7 g (0.19 mol) of paraformaldehyde. After 30 min at −20° C., the mixture is stirred at 0° C. for 2 h. After the removal of the solvent at 20° C. and 20 mbar, 20 ml of MTBE and 40 ml of saturated aqueous solution of ammonium chloride are added to the oily residue (approx. 20 g) and the mixture is stirred at RT for 2 h. The organic phase is removed, the aqueous phase is re-extracted 1× with 20 ml of MTBE and the combined organic phases are concentrated on a rotary evaporator. The yield of pure product is 86% (GC). Within approx. 10 min the mixture is stirred at 20° C. for a further 30 min After 30 min at −20° C. the mixture is stirred at 0° C. for 2 h After the removal of the solvent at 20° C. 20 mbar, 20 ml of MTBE and 40 ml of saturated aqueous solution of ammonium chloride are added to the oily residue (approx. 20 g) the mixture is stirred at RT for 2 h The organic phase is removed the aqueous phase is re-extracted 1× with 20 ml of MTBE the combined organic phases are concentrated on a rotary evaporator

反应条件: temp:20.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: 5.2 ml (0.037 mol) of diisopropylamine are added dropwise at 20° C. to a solution of 12.9 ml (0.035 mol) of n-butyllithium (2.7 M in heptane) in 17 ml of THF, and the mixture is stirred at 20° C. for 15 min. Within approx. 10 min, 5 g (0.032 mol) of methyl 2-ethylhexanoate are added dropwise at 20° C., and the mixture is stirred at 20° C. for a further 30 min and subsequently admixed with 2.9 g (0.097 mol) of paraformaldehyde. After stirring at 20° C. for 2 hours, a saturated aqueous solution of ammonium chloride (20 ml) is added and the mixture is stirred at RT for 2 h. The organic phase is removed, the aqueous phase is re-extracted 1× with 20 ml of MTBE and the combined organic phases are concentrated on a rotary evaporator. The yield of pure product is 77% (GC). Within approx. 10 min the mixture is stirred at 20° C. for a further 30 min After stirring at 20° C. for 2 hours the mixture is stirred at RT for 2 h The organic phase is removed the aqueous phase is re-extracted 1× with 20 ml of MTBE the combined organic phases are concentrated on a rotary evaporator

反应条件: temp:0.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: 5.2 ml (0.037 mol) of diisopropylamine are added dropwise at 0° C. to a solution of 12.9 ml (0.035 mol) of n-butyllithium (2.7 M in heptane) in 17 ml of THF, and the mixture is stirred at 0° C. for 15 min. Within approx. 10 min, 5 g (0.032 mol) of methyl 2-ethylhexanoate are added dropwise at 0° C., and the mixture is stirred at 0° C. for 30 min and subsequently admixed with 2.9 g (0.097 mol) of paraformaldehyde. After stirring at 0° C for 2 hours, a saturated aqueous solution of ammonium chloride (20 ml) is added and the mixture is stirred at RT for 2 h. The organic phase is removed, the aqueous phase is re-extracted once with 20 ml of MTBE and the combined organic phases are concentrated on a rotary evaporator. The yield of pure product is 83% (GC). Within approx. 10 min the mixture is stirred at 0° C. for 30 min After stirring at 0° C for 2 hours the mixture is stirred at RT for 2 h The organic phase is removed the aqueous phase is re-extracted once with 20 ml of MTBE the combined organic phases are concentrated on a rotary evaporator

反应条件: temp:0.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: 5.2 ml (0.037 mol) of diisopropylamine are added dropwise at 0° C. to a solution of 12.9 ml (0.035 mol) of n-butyllithium (2.7 M in heptane) in 17 ml of THF, and the mixture is stirred at 0° C. for 15 min. Within approx. 10 min, 5 g (0.032 mol) of methyl 2-ethylhexanoate are added dropwise at 0° C., and the mixture is stirred at 0° C. for 30 min and subsequently admixed with 2.9 g (0.097 mol) of paraformaldehyde. After stirring at 0° C for 2 hours, a saturated aqueous solution of ammonium chloride (20 ml) is added and the mixture is stirred at RT for 2 h. The organic phase is removed, the aqueous phase is re-extracted once with 20 ml of MTBE and the combined organic phases are concentrated on a rotary evaporator. The yield of pure product is 83% (GC). Within approx. 10 min the mixture is stirred at 0° C. for 30 min After stirring at 0° C for 2 hours the mixture is stirred at RT for 2 h The organic phase is removed the aqueous phase is re-extracted once with 20 ml of MTBE the combined organic phases are concentrated on a rotary evaporator

反应条件: temp:20.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: 47 ml (0.334 mol) of diisopropylamine are added dropwise at 20° C. to a solution of 118 ml (0.319 mol) of n-butyllithium (2.7 M in heptane) in 118 ml of THF, and the mixture is stirred at 20° C. for 30 min. Within approx. 15 min, 48 g (0.304 mol) of methyl 2-ethylhexanoate are added dropwise at −20° C., and the mixture is stirred at −20° C. for 30 min and subsequently admixed with 27 g (0.90 mol) of paraformaldehyde. After 30 min at −20° C., the mixture is stirred at 0° C. for a further 2 h. After the solvent has been removed at 20° C. and 20 mbar (approx. 250 ml), 100 ml of MTBE and 200 ml of saturated aqueous solution of ammonium chloride are added to the oily residue and the mixture is stirred at RT for 2 h. The organic phase is removed, the aqueous phase is re-extracted 1× with 100 ml of MTBE and the combined organic phases are concentrated on a rotary evaporator. The crude product (97% conversion based on methyl 2-ethylhexanoate) can be purified by distillation to obtain methyl 2-ethyl-2-hydroxymethylhexanoate (b.p.: 100° C., 6 mbar) in 91% yield with a purity of >99%. Within approx. 15 min the mixture is stirred at −20° C. for 30 min After 30 min at −20° C. the mixture is stirred at 0° C. for a further 2 h After the solvent has been removed at 20° C. 20 mbar (approx. 250 ml), 100 ml of MTBE and 200 ml of saturated aqueous solution of ammonium chloride are added to the oily residue the mixture is stirred at RT for 2 h The organic phase is removed the aqueous phase is re-extracted 1× with 100 ml of MTBE the combined organic phases are concentrated on a rotary evaporator The crude product (97% conversion based on methyl 2-ethylhexanoate) can be purified by distillation

反应条件: temp:120.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: 173.0 g of a feed mixture consisting of 598.4 g of 2-ethyl-hexanoic acid, 397.8 g of methanol, and 3.8 g of concentrated sulfuric acid is placed in a 1-liter flask equipped with a bottom valve, a stirrer, an internal thermometer, and a Claisen bridge including a receiver. The flask contents are stirred for 30 minutes at 120° C. and the distilled amounts are collected in the receiver. While a temperature of 120° C. is maintained, the feed mixture is added continuously to the flask in an amount sufficient to maintain a constant reactor volume of 300 to 320 ml, allowing for the distilled amounts and amounts drawn off through the bottom valve. After the system has been adjusted to equilibrium, the following balance is obtained with a test period of 6 hours: is placed in a 1-liter flask equipped with a bottom valve, a stirrer the distilled amounts are collected in the receiver While a temperature of 120° C. is maintained the feed mixture is added continuously to the flask in an amount sufficient to maintain a constant reactor volume of 300 to 320 ml the following balance is obtained with a test period of 6 hours

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

实验步骤: The conditions of Example 1 were repeated except that the following amounts were used: 60% sodium hydride in mineral oil (200 g, 5.03 mol. 2.0 mol/mol acetophenone), methyl 2-ethylhexanoate (618 g, 3.91 mol, 1.5 mol/mol acetophenone), xylene (449 g), and then a solution of acetophenone (304 g, 2.53 mol) in xylene (180 g) was added over 1 h. The mixture was kept at reflux for an additional 30 min. Workup of the reaction mixture gave material having product in a crude yield of 89%. Vacuum distillation (200 mtorr) through a 15 cm Vigreux column yielded the product in the heart cut: 4-ethyl-1-phenyl-1,3-octadione (523 g, 97% pure, 2.06 mol; 81% yield; bp: 128-169° C.). Dypnone was undetectable in the product. at reflux for an additional 30 min Workup of the reaction mixture gave material Vacuum distillation (200 mtorr) through a 15 cm Vigreux column yielded the product in the heart cut

反应条件: temp:-20.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: 47 ml (0.334 mol) of diisopropylamine are added dropwise at −20° C. to a solution of 118 ml (0.319 mol) of n-butyllithium (2.7 M in heptane) in 118 ml of THF, and the mixture is stirred at −20° C. for 30 min. Within approx. 15 min, 48 g (0.304 mol) of methyl 2-ethylhexanoate are added dropwise at −20° C., and the mixture is stirred at −20° C. for a further 30 min and subsequently admixed with 18 g (0.60 mol) of paraformaldehyde. After 30 min at −20° C., the mixture is stirred at 0° C. for 2 h. After addition of 100 ml of MTBE and 100 ml of saturated aqueous solution of ammonium chloride, the mixture is stirred at RT for 2 h. The organic phase is removed, the aqueous phase is re-extracted 1×with 100 ml of MTBE and the combined organic phases are concentrated on a rotary evaporator. The crude product (97% conversion based on methyl 2-ethylhexanoate) can be purified by distillation to obtain methyl 2-ethyl-2-hydroxymethylhexanoate (b.p.: 100° C., 6 mbar) in 91% yield with a purity of >99%. Within approx. 15 min the mixture is stirred at −20° C. for a further 30 min After 30 min at −20° C. the mixture is stirred at 0° C. for 2 h the mixture is stirred at RT for 2 h The organic phase is removed the aqueous phase is re-extracted 1×with 100 ml of MTBE the combined organic phases are concentrated on a rotary evaporator The crude product (97% conversion based on methyl 2-ethylhexanoate) can be purified by distillation

反应条件: temp:-20.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: 9.8 ml (0.070 mol) of diisopropylamine are added dropwise at 20° C. to a solution of 24.4 ml (0.065 mol) of n-butyllithium (2.7 M in heptane) in 25 ml of MTBE, and the mixture is stirred at −20° C. for 30 min. Within approx. 10 min, 10 g (0.063 mol) of methyl 2-ethylhexanoate are added dropwise at −20° C., and the mixture is stirred at 20° C. for a further 30 min and subsequently admixed with 5.7 g (0.19 mol) of paraformaldehyde. After 30 min at −20° C., the mixture is stirred at 0° C. for 2 h. After the removal of the solvent at 20° C. and 20 mbar, 20 ml of MTBE and 40 ml of saturated aqueous solution of ammonium chloride are added to the oily residue (approx. 20 g) and the mixture is stirred at RT for 2 h. The organic phase is removed, the aqueous phase is re-extracted 1× with 20 ml of MTBE and the combined organic phases are concentrated on a rotary evaporator. The yield of pure product is 86% (GC). Within approx. 10 min the mixture is stirred at 20° C. for a further 30 min After 30 min at −20° C. the mixture is stirred at 0° C. for 2 h After the removal of the solvent at 20° C. 20 mbar, 20 ml of MTBE and 40 ml of saturated aqueous solution of ammonium chloride are added to the oily residue (approx. 20 g) the mixture is stirred at RT for 2 h The organic phase is removed the aqueous phase is re-extracted 1× with 20 ml of MTBE the combined organic phases are concentrated on a rotary evaporator

反应条件: temp:20.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: 5.2 ml (0.037 mol) of diisopropylamine are added dropwise at 20° C. to a solution of 12.9 ml (0.035 mol) of n-butyllithium (2.7 M in heptane) in 17 ml of THF, and the mixture is stirred at 20° C. for 15 min. Within approx. 10 min, 5 g (0.032 mol) of methyl 2-ethylhexanoate are added dropwise at 20° C., and the mixture is stirred at 20° C. for a further 30 min and subsequently admixed with 2.9 g (0.097 mol) of paraformaldehyde. After stirring at 20° C. for 2 hours, a saturated aqueous solution of ammonium chloride (20 ml) is added and the mixture is stirred at RT for 2 h. The organic phase is removed, the aqueous phase is re-extracted 1× with 20 ml of MTBE and the combined organic phases are concentrated on a rotary evaporator. The yield of pure product is 77% (GC). Within approx. 10 min the mixture is stirred at 20° C. for a further 30 min After stirring at 20° C. for 2 hours the mixture is stirred at RT for 2 h The organic phase is removed the aqueous phase is re-extracted 1× with 20 ml of MTBE the combined organic phases are concentrated on a rotary evaporator

反应条件: temp:0.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: 5.2 ml (0.037 mol) of diisopropylamine are added dropwise at 0° C. to a solution of 12.9 ml (0.035 mol) of n-butyllithium (2.7 M in heptane) in 17 ml of THF, and the mixture is stirred at 0° C. for 15 min. Within approx. 10 min, 5 g (0.032 mol) of methyl 2-ethylhexanoate are added dropwise at 0° C., and the mixture is stirred at 0° C. for 30 min and subsequently admixed with 2.9 g (0.097 mol) of paraformaldehyde. After stirring at 0° C for 2 hours, a saturated aqueous solution of ammonium chloride (20 ml) is added and the mixture is stirred at RT for 2 h. The organic phase is removed, the aqueous phase is re-extracted once with 20 ml of MTBE and the combined organic phases are concentrated on a rotary evaporator. The yield of pure product is 83% (GC). Within approx. 10 min the mixture is stirred at 0° C. for 30 min After stirring at 0° C for 2 hours the mixture is stirred at RT for 2 h The organic phase is removed the aqueous phase is re-extracted once with 20 ml of MTBE the combined organic phases are concentrated on a rotary evaporator