Dimethylformamide → 2-Oxo-1,2,3,4-tetrahydroquinoline-7-carbonitrile

HRID 1256264Notes

Reaction equation

HRID 1256264 reaction equation
[CH3:1][N:2](C=O)C.Br[C:7]1[CH:16]=[C:15]2[C:10]([CH2:11][CH2:12][C:13](=[O:17])[NH:14]2)=[CH:9][CH:8]=1.CC1(C)C2C(=C(P(C3C=CC=CC=3)C3C=CC=CC=3)C=CC=2)OC2C(P(C3C=CC=CC=3)C3C=CC=CC=3)=CC=CC1=2.CN(CCN(C)C)C>[C-]#N.[Zn+2].[C-]#N.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.[Pd].[Pd].CCOC(C)=O.C(Cl)(Cl)Cl>[O:17]=[C:13]1[CH2:12][CH2:11][C:10]2[C:15](=[CH:16][C:7]([C:1]#[N:2])=[CH:8][CH:9]=2)[NH:14]1

Participants

9

Reactant 4

HCID 6228DimethylformamideHCID 8037N,N,N',N'-TetramethylethylenediamineHCID 6360441,1'-(9,9-Dimethyl-9H-xanthene-4,5-diyl)bis(1,1-diphenylphosphine)HCID 272818447-Bromo-1,2,3,4-tetrahydroquinolin-2-one

Product 1

HCID 586868452-Oxo-1,2,3,4-tetrahydroquinoline-7-carbonitrile

Reagents, catalysts & solvents 4

HCID 11186Zinc cyanide (Zn(CN)2)CatalystHCID 9811564Bis(dibenzylideneacetone)palladiumCatalystHCID 6212ChloroformSolventHCID 8857Ethyl AcetateSolvent

Conditions

Temperature
180 °C

Procedure

To a DMF solution (14.5 mL) of the compound (3.00 g) obtained in Step 1-2, zinc cyanide (1.04 g), Pd2(dba)3 (122 mg), Xantphos (154 mg) and TMEDA (590 μL) were added and the mixture was stirred under microwave irradiation (180° C.) for 5 minutes. To the reaction mixture, CHCl3 was added and the mixture was filtrated by Celite and washed with DMF. The filtrate was concentrated under reduced pressure. The residue was purified by column chromatography (silica gel 60 N, mobile phase: EtOAc/hexane=50/50 to 100/0; v/v). To the solid substance obtained, EtOAc was added at room temperature and the mixture was stirred for 30 minutes. A solid substance was obtained by filtration and washed with EtOAc to obtain 2-oxo-1,2,3,4-tetrahydroquinoline-7-carbonitrile (15.5 g, a light yellow solid).

Workup

  1. filtrationthe mixture was filtrated by Celite
  2. washwashed with DMF
  3. concentrationThe filtrate was concentrated under reduced pressure
  4. customThe residue was purified by column chromatography (silica gel 60 N, mobile phase: EtOAc/hexane=50/50 to 100/0; v/v)
  5. customTo the solid substance obtained
  6. stirringthe mixture was stirred for 30 minutes
  7. customA solid substance was obtained by filtration
  8. washwashed with EtOAc

Sources & evidence

ORD record
ord-d4ca4a8f32e04ec0a9afec4685e2576f
Source dataset
uspto-grants-2013_06
Patent number
US08461182B2

Reaction notes

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