1-methylazepan-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:; See reaction.notes.procedure_details.

実験手順: A solution of 15.7% of methyl 6-aminocaproate and 8.2% of caprolactam in water was pumped through a 40 ml tube reactor at 270° C. and 100 bar with a residence time of 4.2 minutes. The exit stream contained according to quantitative gas chromatography 14.98% by weight of caprolactam, corresponding to a yield of 55.4%, based on methyl 6-aminocaproate. N-methylcaprolactam was formed as a by-product in a 4.5% yield. with a residence time of 4.2 minutes

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

実験手順: A solution of 18.28% of methyl 6-aminocaproate and 5.75% of caprolactam in water was pumped through a 40 ml tube reactor at 300° C. and 100 bar with a residence time of 15 minutes. The exit stream contained according to quantitative gas chromatography 15.09% by weight of caprolactam, corresponding to a yield of 65.6%, based on methyl 6-aminocaproate. N-methylcaprolactam was formed as a by-product in a 5.8% yield. with a residence time of 15 minutes

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

実験手順: A mercerised cotton fabric is padded with a dyeing liquor which contains, per liter, 30 g of the direct dyestuff C.I. No. 35,780 and 100 g of N-methylcaprolactam, squeezed off to a liquor pick-up of 80% and then dried for 2 minutes at 150°. It is then rinsed. A deep red dyeing is obtained. Comparably good results are obtained if instead of N-methylcaprolactam 100 g of N-hydroxyethyl-oxazolidone per liter or 150 g of N-methyloxazolidone per liter are used. dried for 2 minutes at 150° It is then rinsed A deep red dyeing is obtained Comparably good results

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

実験手順: Thus after 2 times recycle of the distillation residue, an overall caprolactam yield of 91.2 mol % had been achieved based on the initial amount of M5FV. In the first cyclization pass, where still some methanol was present, 5.1 mol % of the unwanted by-product N-methyl caprolactam was formed. The approximated caprolactam yield per pass was 61.2% in the first pass, 66.5% in the second pass (first recycle of distillation residue) and 66.4% in the third pass (second recycle of distillation residue). Thus, it was proven that after distillative caprolactam recovery the remaining distillation residue can be successfully recycled to the cyclization reactor resulting in a high overall caprolactam yield.

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

実験手順: Following the procedure of Example 3, reaction of the lithium anion of N-methylcaprolactam with m-triphenylsiloxybenzyne (from o-chlorotriphenylsilyloxybenzene and lithium tetramethylpiperidide) followed by workup with aqueous acid gives the title compound m.p. 192°-3° C. (ethylacetate).

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

実験手順: Diisopropylamine (152 g) in tetrahydrofuran (150 ml) was added over 30 minutes to 15% butyl lithium in hexane (641 g, 1.50 mole) under nitrogen at 20°-25° C. with cooling and the mixture stirred 30 minutes at room temperature. N-methylcaprolactam (63.6 g) in tetrahydrofuran (60 ml) was added over 5 minutes below 25° C. with cooling, the mixture was stirred for one hour at room temperature and then o-chloroanisole (71.3 g) was added over 20 minutes keeping the temperature below 30° C. The reaction mixture was stirred for two hours, water (2. l.) was added, the product was extracted into ethyl acetate (2×1 l.), the extracts were combined, washed with 2 N hydrochloric acid (1. l.) and water (500 ml) and evaporated under reduced pressure to give 27.1 g oil. with cooling with cooling the mixture was stirred for one hour at room temperature the temperature below 30° C The reaction mixture was stirred for two hours the product was extracted into ethyl acetate (2×1 l.) washed with 2 N hydrochloric acid (1. l.) and water (500 ml) evaporated under reduced pressure

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

実験手順: A solution of butyl lithium (0.05 moles) in hexane (31.25 ml), was treated with 2,2,6,6-tetramethylpiperidine (8.5 ml), followed by THF (100 ml) under an inert atmosphere at 0° C. A solution of N-methylcaprolactam (6.25 ml, 50 mM) in THF (20 ml) was added, the mixture stirred for 30 minutes and treated with a solution of butyl lithium (0.05 mole) in hexane (31.25 ml). After 15 minutes, o-chloroanisole (6.2 ml) was added and the mixture stirred for fifteen hours at ambient temperature. After 15 minutes the mixture stirred for fifteen hours at ambient temperature

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

実験手順: A solution of butyl lithium (0.05 mole) in hexane (34.4 ml), was treated with 2,2,6,6-tetramethylpiperidine (9.3 ml) followed by dry THF (100 ml) under an inert atmosphere at 0° C. The mixture was treated with N-methylcaprolactam (6.9 ml, 55 mM) and stirred for 30 minutes. A solution of butyl lithium (0.05 mole) in hexane (34.4 ml) was added, the reaction mixture stirred 15 minutes then treated with o-chloroanisole (3.1 ml). After 30 minutes a solution of butyl lithium (0.05 moles) in hexane (31.25 ml) was added, the mixture stirred for 15 minutes and treated with o-chloroanisole (3.1 ml). After a further 30 minutes, the reaction was quenched with water (100 ml) and the solvents removed under reduced pressure. The residue was partitioned between 5 N HCl (100 ml) and toluene (250 ml). The organic phase was washed with brine, dried and the solvents removed under reduced pressure. the reaction mixture stirred 15 minutes the mixture stirred for 15 minutes After a further 30 minutes the reaction was quenched with water (100 ml) the solvents removed under reduced pressure The residue was partitioned between 5 N HCl (100 ml) and toluene (250 ml) The organic phase was washed with brine dried the solvents removed under reduced pressure

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

実験手順: A solution of butyl lithium (0.05 mole) in hexane (34.4 ml), was treated with 2,2,6,6-tetramethylpiperidine (9.3 ml) followed by dry THF (100 ml) under an inert atmosphere at 0° C. The mixture was treated with N-methylcaprolactam (6.9 ml, 55 mM) and stirred for 30 minutes. A solution of butyl lithium (0.05 mole) in hexane (34.4 ml) was added, the reaction mixture stirred 15 minutes then treated with o-chloroanisole (3.1 ml). After 30 minutes a solution of butyl lithium (0.05 moles) in hexane (31.25 ml) was added, the mixture stirred for 15 minutes and treated with o-chloroanisole (3.1 ml). After a further 30 minutes, the reaction was quenched with water (100 ml) and the solvents removed under reduced pressure. The residue was partitioned between 5 N HCl (100 ml) and toluene (250 ml). The organic phase was washed with brine, dried and the solvents removed under reduced pressure. the reaction mixture stirred 15 minutes the mixture stirred for 15 minutes After a further 30 minutes the reaction was quenched with water (100 ml) the solvents removed under reduced pressure The residue was partitioned between 5 N HCl (100 ml) and toluene (250 ml) The organic phase was washed with brine dried the solvents removed under reduced pressure