Iodoethane → HCID 54308167, compound

HRID 1938503Notes

Reaction equation

HRID 1938503 reaction equation
C(OC([N:8]1[C:17]2[C:12](=[CH:13][CH:14]=[CH:15][CH:16]=2)[C:11](=[O:18])[CH2:10][C:9]1([CH3:20])[CH3:19])=O)(C)(C)C.I[CH2:22][CH3:23].[H-].[Na+].C(O)(C(F)(F)F)=O.[OH-].[Na+]>CN(C=O)C.C(Cl)Cl.CCOC(C)=O.CCCCCC>[CH2:22]([CH:10]1[C:11](=[O:18])[C:12]2[C:17](=[CH:16][CH:15]=[CH:14][CH:13]=2)[NH:8][C:9]1([CH3:19])[CH3:20])[CH3:23]

Participants

9

Reactant 5

HCID 6340IodoethaneHCID 6422Trifluoroacetic acidHCID 14798Sodium HydroxideHCID 24758Sodium hydrideHCID 10612446tert-Butyl 2,2-dimethyl-4-oxo-3,4-dihydroquinoline-1(2H)-carboxylate

Product 1

HCID 54308167HCID 54308167, compoundYield 41.7%

Reagents, catalysts & solvents 3

HCID 6228DimethylformamideSolventHCID 6344DichloromethaneSolventHCID 21226206Ethyl acetate hexaneSolvent

Procedure

To a solution of 1-tert-butoxycarbonyl-1,2,3,4-tetrahydro-2,2-dimethyl-4-quinolinone (EXAMPLE 325) (0.10 g, 0.36 mmol) and iodoethane (0.50 mL, 6.3 mmol) in DMF (5 mL ) was added NaH (60% in mineral oil, 40 mg, 1.0 mmol) and the resulting mixture was stirred at rt for 15 h. The reaction was quenched with water (5 mL ) and was extracted with EtOAc (2×15 mL ). Removal of solvent and chromatography of the crude residue on a silica gel column using a 10% mixture of EtOAc and hexane as solvents afforded a mixture of products, which was treated with TFA (0.50 mL ) in methylene chloride (1.0 mL ) for 3 h. The reaction was neutralized to pH 10 by 5% NaOH and was extracted with EtOAc (2×20 mL ). Chromatography (silica gel, EtOAc/hexane, 3/7) afforded 30 mg (41%) of (R/S)-3-ethyl-1,2,3,4-tetrahydro-2,2-dimethyl-4-quinolinone (30 mg, 0.15 mmol) as a colorless oil. The quinolinone (30 mg, 0.15 mmol) was treated with Et3SiH (1.0 mL ) and BF3 -OEt2 (0.05 mL, 0.4 mmol) in CH2Cl2 (1.0 mL ) at 100° C. for 15 h in a sealed tube. Purification of the crude product by chromatography (silica gel, EtOAc/hexane, 1/9) afforded 20 mg (71%) of (R/S)-3-ethyl-1,2,3,4-tetrahydro-2,2-dimethylquinoline. Data for (R/S)-3-ethyl-1,2,3,4-tetrahydro-2,2-dimethylquinoline: 1H NMR (400 MHz, CDCl3) 6.98 (d, J=7.5, 1H), 6.96 (t, J=7.5, 1H), 6.61 (t, J=7.5, 1H), 6.44 (d, J=7.5, 1H), 3.60 (s, 1H), 2.90 (dd, J=16.7, 5.2, 1H), 2.41 (dd, J=16.7, 10.7, 1H), 1.68 (m, 1H), 1.52 (m, 1H), 1.23 (m, 1H), 1.22 (s, 3H), 1.05 (s, 3H).

Workup

  1. customThe reaction was quenched with water (5 mL )
  2. extractionwas extracted with EtOAc (2×15 mL )
  3. customRemoval of solvent and chromatography of the crude residue on a silica gel column
  4. customafforded
  5. additiona mixture of products, which
  6. extractionwas extracted with EtOAc (2×20 mL )

Sources & evidence

ORD record
ord-b863aaa7a87d4bedb7600a0ccc3ab7ff
Source dataset
uspto-grants-1997_12
Patent number
US05693647

Reaction notes

Loading…