Water → HCID 118622718, compound

HRID 2202281Notes

Reaction equation

HRID 2202281 reaction equation
[C:1]([C:3]1[CH:4]=[C:5]2[C:10](=[CH:11][CH:12]=1)[CH:9]([C:13]([O:15][CH2:16][CH3:17])=[O:14])[N:8]([C:18]([O:20][C:21]([CH3:24])([CH3:23])[CH3:22])=[O:19])[CH2:7][CH2:6]2)#N.O.O.[PH2]([O-])=[O:28].[Na+]>C(O)(=O)C.N1C=CC=CC=1.[Ni]>[CH:1]([C:3]1[CH:4]=[C:5]2[C:10](=[CH:11][CH:12]=1)[CH:9]([C:13]([O:15][CH2:16][CH3:17])=[O:14])[N:8]([C:18]([O:20][C:21]([CH3:24])([CH3:23])[CH3:22])=[O:19])[CH2:7][CH2:6]2)=[O:28]

Participants

7

Reactant 3

HCID 962WaterHCID 118622773HCID 118622773, compoundHCID 178418950HCID 178418950, compound

Product 1

HCID 118622718HCID 118622718, compoundYield 85.4%

Reagents, catalysts & solvents 3

HCID 935NickelCatalystHCID 176Acetic AcidSolventHCID 1049PyridineSolvent

Conditions

Temperature
60 °C

Procedure

To a solution of 1-ethyl 2-tert-butyl 6-cyano-3,4-dihydroisoquinoline-1,2(1H)-dicarboxylate (0.5 g, 1.51 mmol) in acetic acid (5.00 mL) and pyridine (10 mL) was added a mixture of Raney-nickel (0.5 g, 1.51 mmol) and water (5 mL), and then sodium hypophosphite monohydrate (2.5 g, 23.59 mmol) was added thereto under argon atmosphere. The mixture was stirred at 60° C. for 3 hr, and then overnight at 100° C. The reaction mixture was filtered through Celite, and the filtrate was diluted with ethyl acetate. The mixture was washed with aqueous ammonium chloride solution, aqueous sodium hydrogencarbonate solution and brine, and dried over magnesium sulfate, and the solvent was evaporated under reduced pressure. The obtained residue was purified by silica gel column chromatography (solvent gradient; 5→70% ethyl acetate/hexane) to give 1-ethyl 2-tert-butyl 6-formyl-3,4-dihydroisoquinoline-1,2(1H)-dicarboxylate (0.430 g, 1.290 mmol, 85%) as a colorless oil.

Workup

  1. customovernight
  2. customat 100° C
  3. filtrationThe reaction mixture was filtered through Celite
  4. additionthe filtrate was diluted with ethyl acetate
  5. washThe mixture was washed with aqueous ammonium chloride solution, aqueous sodium hydrogencarbonate solution and brine
  6. dry with materialdried over magnesium sulfate
  7. customthe solvent was evaporated under reduced pressure
  8. customThe obtained residue was purified by silica gel column chromatography (solvent gradient; 5→70% ethyl acetate/hexane)

Sources & evidence

ORD record
ord-48b8c9ac02f346fda594132a53965126
Source dataset
uspto-grants-2016_06
Patent number
US09365520B2

Reaction notes

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