反应详情

1-Indanone (100 g, 0.757 mol) was dissolved in 2-methoxyethanol (600 mL) in a 2 L round bottom flask equipped with a overhead mechanical stirrer. The mixture was cooled over an ice bath, and concentrated aqueous HCl (200 mL) was added. Butyl nitrite (50 mL, 0.428 mol) was added, and after 1 minute when precipitate began to form, more butyl nitrite (50 mL, 0.428 mol) was added. The mixture was stirred for 15 min. more and then poured into ice water (8 L). The solid was filtered on a sintered funnel and rinsed with 8 L water. The solid was dissolved in 2.5 L hot methanol, seeded with pure oxime, then allowed to cool to room temperature then over an ice bath. The yellow crystals were collected on a sintered funnel, rinsed with cold methanol, then dried overnight under vacuum to yield 2-oximino-1-indanone (92.8 g, 76% yield). The finely ground oxime (80 g, 0.496 mol) was suspended in 35% formaldehyde solution (160 mL) and concentrated HCl (320 mL) in a 2 L round bottom flask equipped with an overhead mechanical stirrer. The temperature was maintained initially at 15° C. with an ice bath, then the bath was removed and the reaction mixture was stirred vigorously for 30 min. The mixture was poured onto 2 L ice, the solid filtered and then rinsed with water. The yellow powder was dried in a vacuum oven to yield 55.0 g product, which was recrystallized from ether (5 L, 3 crops) to afford after oven drying pure diketone (37.3 g, 51% yield). The aqueous mother liquor yielded crystals of the oxime (9.5 g, 12% recovered starting material).

1. customequipped with a overhead mechanical stirrer
2. temperatureThe mixture was cooled over an ice bath
3. customto form
4. filtrationThe solid was filtered on a sintered funnel
5. washrinsed with 8 L water
6. dissolutionThe solid was dissolved in 2.5 L hot methanol
7. customThe yellow crystals were collected on a sintered funnel
8. washrinsed with cold methanol
9. customdried overnight under vacuum