Diisopropylamine → HCID 12665522, compound

HRID 2049333Notes

Reaction equation

HRID 2049333 reaction equation
[C:1]1([CH2:7][N:8]2[CH2:14][CH2:13][CH2:12][CH2:11][CH2:10][C:9]2=[O:15])[CH:6]=[CH:5][CH:4]=[CH:3][CH:2]=1.C([N-]C(C)C)(C)C.[Li+].C(NC(C)C)(C)C.C([Li])CCC.C[O:37][C:38]1[CH2:43][CH2:42][CH2:41][C:40](=O)[CH:39]=1.[Br-].[Li+]>C1COCC1.C(#N)C.C(Cl)(Cl)Cl>[OH:37][C:38]1[CH:39]=[C:40]([CH:10]2[CH2:11][CH2:12][CH2:13][CH2:14][N:8]([CH2:7][C:1]3[CH:2]=[CH:3][CH:4]=[CH:5][CH:6]=3)[C:9]2=[O:15])[CH:41]=[CH:42][CH:43]=1

Participants

10

Reactant 6

HCID 7912DiisopropylamineHCID 82050Lithium BromideHCID 855973-Methoxycyclohex-2-en-1-oneHCID 14910681-Benzylazepan-2-oneHCID 2724682Lithium diisopropylamideHCID 178418339Butyllithium

Product 1

HCID 12665522HCID 12665522, compoundYield 20.3%

Reagents, catalysts & solvents 3

HCID 6212ChloroformSolventHCID 6342AcetonitrileSolventHCID 8028TetrahydrofuranSolvent2×

Procedure

A solution of hexahydro-1-phenylmethyl-2H-azepin-2-one (5.68 g) in dry THF was added at -10° C. to lithium diisopropylamide (0.032 mm) prepared from diisopropylamine (4.4 ml) and butyl lithium (22.9 ml of 1.4 M solution in hexane). The mixture was stirred for 30 minutes and then treated with a solution of 3-methoxy-2-cyclohexenone (2.53 g) in THF. After 5 hours at ambient temperature the mixture was poured onto ice-cold concentrated hydrochloric acid (100 ml). After vigorously stirring for 12 hours the solution was shaken with several portions of chloroform. The combined chloroform layers were evaporated to give an orange oil. This was refluxed with cupric bromide (8.95 g) and lithium bromide (1.74 g; 0.02 m) in acetonitrile for 1 hour. Removal of the solvent left a black oil that was triturated with excess 2 N sodium hydroxide solution. The filtrate, after removal of the orange precipitate, was extracted with methylene chloride. The organic layer was acidified (conc.HCl) and the white suspension shaken with several portions of chloroform and were evaporated to leave a dark red oil (1.2 g) that crystallised from ethyl acetate to give the title compound (0.35 g) m.p. 160°-166° C.

Workup

  1. additionAfter 5 hours at ambient temperature the mixture was poured onto ice-cold concentrated hydrochloric acid (100 ml)
  2. stirringAfter vigorously stirring for 12 hours the solution
  3. customThe combined chloroform layers were evaporated
  4. customto give an orange oil
  5. customRemoval of the solvent
  6. waitleft a black oil that
  7. customwas triturated with excess 2 N sodium hydroxide solution
  8. customThe filtrate, after removal of the orange precipitate
  9. extractionwas extracted with methylene chloride
  10. stirringthe white suspension shaken with several portions of chloroform
  11. customwere evaporated

Sources & evidence

ORD record
ord-c2a01360bcb7442b81800bbab85547f3
Source dataset
uspto-grants-1980_04
Patent number
US04197241

Reaction notes

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