تفاعل #335966

معادلة التفاعل

1-chlorooctane

calcium

2-cyclohexen-1-one

calcium

→

3-octylcyclohexanone

المردود 87.0%

المذيبات

NH4Cl

ظروف التفاعل

المعالجة

1. 1
   أخرىAn organocalcium cuprate reagent was prepared
2. 2
   درجة الحرارةThe reaction mixture was cooled to -50° C.
3. 3
   درجة الحرارةThe resulting mixture was gradually warmed to room temperature
4. 4
   ترشيحThe reaction mixture was then filtered through a small pad of Celite™
5. 5
   ترشيحfilter agent
6. 6
   غسيلwas washed with Et2O (50 mL)
7. 7
   استخلاصThe aqueous layer was extracted with Et2O (2×30 mL)
8. 8
   غسيلThe combined organic phases were washed with H2O (3×15 mL)
9. 9
   تجفيفdried over anhydrous MgSO4
10. 10
    أخرىRemoval of solvent and flash-column chromatography on silica gel (70 g, 230-400 mesh
11. 11
    غسيلeluted sequentially with 50:1 hexanes/EtOAc and 10:1 hexanes/EtOAc)

الإجراء التجريبي

The following experimental procedure is representative of the reactions set forth below in Table III. The organocalcium reagent (2.66 mmol) was prepared from 1-chlorooctane (395 mg, 2.66 mmol) and highly reactive calcium (3.10 mmol) as described above. An organocalcium cuprate reagent was prepared by adding lithium 2-thienylcyanocuprate (Aldrich Chemical Co., Milwaukee, Wis., 0.25M in THF, 14 mL, 3.50 mmol) to the calcium reagent via a syringe at -50° C. The reaction mixture was gradually warmed to -35° C. over a 30 minute period. The reaction mixture was cooled to -50° C. and 2-cyclohexen-1-one (210 mg, 2.18 mmol) was added via a disposable syringe. The resulting mixture was gradually warmed to room temperature. Saturated aqueous NH4Cl solution (20 mL) was added at room temperature. The reaction mixture was then filtered through a small pad of Celite™ filter agent and was washed with Et2O (50 mL). The aqueous layer was extracted with Et2O (2×30 mL). The combined organic phases were washed with H2O (3×15 mL) and dried over anhydrous MgSO4. Removal of solvent and flash-column chromatography on silica gel (70 g, 230-400 mesh, eluted sequentially with 50:1 hexanes/EtOAc and 10:1 hexanes/EtOAc) gave 3-octylcyclohexanone (401 mg, 87% yield): IR (neat) 2954, 2925, 2854, 1714, 1458, 1225 cm-1 ; 1H NMR (200 MHz, CDCl3) δ 1.10-2.50 (m, 23 H), 0.88 t, J=6.4 Hz, 3 H); 13C NMR (50 MHz, CDCl3) δ 212.0, 48.2, 41.5, 39.1, 36.6, 31.8, 31.3, 29.7, 29.5, 29.2, 26.6, 25.3, 22.6, 14.1.

المصدر