Hydrochloric Acid → 1-Methyl-3-(3-oxocyclohex-1-en-1-yl)azepan-2-one

HRID 2049320Notes

Reaction equation

HRID 2049320 reaction equation
C(NC(C)C)(C)C.C([Li])CCC.[CH3:13][N:14]1[C:20](=[O:21])[CH2:19][CH2:18][CH2:17][CH2:16][CH2:15]1.C[O:23][C:24]1[CH2:29][CH2:28][CH2:27][C:26](=O)[CH:25]=1.Cl>O1CCCC1>[CH3:13][N:14]1[CH2:15][CH2:16][CH2:17][CH2:18][CH:19]([C:26]2[CH2:27][CH2:28][CH2:29][C:24](=[O:23])[CH:25]=2)[C:20]1=[O:21]

Participants

7

Reactant 5

HCID 313Hydrochloric AcidHCID 7912DiisopropylamineHCID 17369N-MethylcaprolactamHCID 855973-Methoxycyclohex-2-en-1-oneHCID 178418339Butyllithium

Product 1

HCID 119705831-Methyl-3-(3-oxocyclohex-1-en-1-yl)azepan-2-oneYield 85.8%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent3×

Conditions

Temperature
0 °C

Procedure

Diisopropylamine (12.14 g, 17.0 ml) in dry tetrahydrofuran (THF 20 ml) was added dropwise to a stirred cooled (-10° C.) solution of butyl lithium (86 ml of 1.4 molar solution in hexane) under nitrogen. After 10 minutes Gilman test was negative. 1-Methylcaprolactam (14.19 g) in THF (20 ml) was added, also at -10° C. Reaction was stirred for 10 minutes at 0° C. and 3-methoxy-2-cyclohexenone (12.6 g, 0.1 mole) in THF (20 ml) was added. The mixture was allowed to warm to room temperature and stirred at room temperature for 1.5 hours, then cooled to -10° C. and decomposed by addition of 2 N HCl (125 ml) rapidly but not allowing temperature to exceed 0° C. The mixture was stirred at room temperature for 30 minutes. The aqueous layer was separated and extracted with dichloromethane. The combined organic extracts were dried over anhydrous magnesium sulphate and evaporated to an oil which crystallised from toluene-light petroleum (b.p. 60°-80° C.) affording the title compound (18.99 g), m.p. 109°-110° C.

Workup

  1. customReaction
  2. temperatureto warm to room temperature
  3. stirringstirred at room temperature for 1.5 hours
  4. temperaturecooled to -10° C.
  5. customto exceed 0° C
  6. stirringThe mixture was stirred at room temperature for 30 minutes
  7. customThe aqueous layer was separated
  8. extractionextracted with dichloromethane
  9. dry with materialThe combined organic extracts were dried over anhydrous magnesium sulphate
  10. customevaporated to an oil which
  11. customcrystallised from toluene-light petroleum (b.p. 60°-80° C.)

Sources & evidence

ORD record
ord-ff49906d34c141f59e52d57dd6d79a4a
Source dataset
uspto-grants-1980_04
Patent number
US04197241

Reaction notes

Loading…