Hydrochloric Acid → 2-Trimethylsilanyl-ethyl 4-[3-(8,8-dimethyl-5-p-tolyl-7,8-dihydro-naphthalen-2-yl)-3-oxo-propenyl]-benzoate

HRID 853193Notes

Reaction equation

HRID 853193 reaction equation
[CH:1]([C:3]1[CH:12]=[CH:11][C:6]([C:7]([O:9][CH3:10])=[O:8])=[CH:5][CH:4]=1)=O.[CH3:13][C:14]1([CH3:34])[C:23]2[CH:22]=[C:21]([C:24](=[O:26])[CH3:25])[CH:20]=[CH:19][C:18]=2[C:17]([C:27]2[CH:32]=[CH:31][C:30]([CH3:33])=[CH:29][CH:28]=2)=[CH:16][CH2:15]1.Cl.[CH3:36][Si:37]([CH:40](O)C)([CH3:39])[CH3:38].Cl.CN(C)CCCN=C=NCC>[OH-].[Na+].CO.ClCCl.CN(C)C1C=CN=CC=1>[CH3:13][C:14]1([CH3:34])[C:23]2[CH:22]=[C:21]([C:24](=[O:26])[CH:25]=[CH:1][C:3]3[CH:12]=[CH:11][C:6]([C:7]([O:9][CH2:10][CH2:36][Si:37]([CH3:40])([CH3:39])[CH3:38])=[O:8])=[CH:5][CH:4]=3)[CH:20]=[CH:19][C:18]=2[C:17]([C:27]2[CH:28]=[CH:29][C:30]([CH3:33])=[CH:31][CH:32]=2)=[CH:16][CH2:15]1

Participants

10

Reactant 5

HCID 313Hydrochloric AcidHCID 15294Methyl 4-FormylbenzoateHCID 27239391,3-Propanediamine, N'-(ethylcarbonimidoyl)-N,N-dimethyl-, monohydrochlorideHCID 124478981-(Trimethylsilyl)ethanolHCID 223237763,4-Dihydro-1-(4-methylphenyl)-4,4-dimethyl-6-acetylnaphthalene2×

Product 1

HCID 688321412-Trimethylsilanyl-ethyl 4-[3-(8,8-dimethyl-5-p-tolyl-7,8-dihydro-naphthalen-2-yl)-3-oxo-propenyl]-benzoateYield 43%

Reagents, catalysts & solvents 4

HCID 142844-(Dimethylamino)pyridineCatalystHCID 887MethanolSolventHCID 6344DichloromethaneSolventHCID 14798Sodium HydroxideSolvent

Procedure

Methyl 4-formylbenzoate (available from Aldrich, 113 mg, 0.69 mmol) was added to a solution of 1-(8,8-dimethyl-5-p-tolyl-7,8-dihydro-naphthalen-2-yl)-ethanone (Compound 5, 200 mg, 0.69 mmol) in 10 mL of 1 N NaOH and 20 mL of methanol. After stirring at room temperature for 18 h, the reaction mixture was acidified with 1N HCl and extracted with ethyl acetate (3×10 mL). The combined organic layer was washed with brine (1×10 mL), dried (MgSO4) and concentrated at reduced pressure to give a yellow crude solid. This crude solid was then dissolved in 10 mL of dichloromethane and 1 mL of trimethylsilylethanol at 0° C. 1-(3-dimethylaminopropyl)-3-ethylcarbodimide hydrochloride (EDCI) (265 mg, 1.38 mmol) and 4-dimethylaminopyridine (DMAP) (6 mg, 0.07 mmol) were added. After stirring at room temperature for 18 h, the reaction was quenched with water (10 mL), extracted with dichloromethane (3×10 mL), washed with brine (1×10 mL), dried (MgSO4) and concentrated at reduced pressure. Purification by flash chromatography (90:10 hexane/ethyl acetate) yielded the title compound (155 mg, 43% yield) as a yellow oil:

Workup

  1. extractionextracted with ethyl acetate (3×10 mL)
  2. washThe combined organic layer was washed with brine (1×10 mL)
  3. dry with materialdried (MgSO4)
  4. concentrationconcentrated at reduced pressure
  5. customto give a yellow crude solid
  6. customat 0° C
  7. stirringAfter stirring at room temperature for 18 h
  8. customthe reaction was quenched with water (10 mL)
  9. extractionextracted with dichloromethane (3×10 mL)
  10. washwashed with brine (1×10 mL)
  11. dry with materialdried (MgSO4)
  12. concentrationconcentrated at reduced pressure
  13. customPurification by flash chromatography (90:10 hexane/ethyl acetate)

Sources & evidence

ORD record
ord-79daae1565ed4931828e536a5f052b7c
Source dataset
uspto-grants-2007_08
Patent number
US07253319B2

Reaction notes

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