Iodoethane → HCID 54308167, compound

HRID 1938433Notes

Reaction equation

HRID 1938433 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, 1 H), 6.96 (t, J=7.5, 1 H), 6.61 (t, J=7.5, 1 H), 6.44 (d, J=7.5, 1 H), 3.60 (s, 1 H), 2.90 (dd, J=16.7, 5.2, 1 H), 2.41 (dd, J=16.7, 10.7, 1 H), 1.68 (m, 1 H), 1.52 (m, 1 H), 1.23 (m, 1 H), 1.22 (s, 3 H), 1.05 (s, 3 H).

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-39a110a892cf4d6585aa5c876805e9d8
Source dataset
uspto-grants-1997_12
Patent number
US05693646

Reaction notes

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