4-bromo-3-methyl-2,3-dihydro-1H-inden-1-one → 4-Cyano-3-methyl-1-indanone

HRID 1608583Notes

Reaction equation

HRID 1608583 reaction equation
Br[C:2]1[CH:10]=[CH:9][CH:8]=[C:7]2[C:3]=1[CH:4]([CH3:12])[CH2:5][C:6]2=[O:11].[Cu][C:14]#[N:15]>CN(C=O)C.O.Cl.C1(C)C=CC=CC=1.O.O.O.O.O.O.[Fe](Cl)(Cl)Cl>[C:14]([C:2]1[CH:10]=[CH:9][CH:8]=[C:7]2[C:3]=1[CH:4]([CH3:12])[CH2:5][C:6]2=[O:11])#[N:15]

Participants

8

Reactant 2

HCID 212173954-bromo-3-methyl-2,3-dihydro-1H-inden-1-oneHCID 178418546HCID 178418546, compound

Product 1

HCID 190423034-Cyano-3-methyl-1-indanone

Reagents, catalysts & solvents 5

HCID 16211236Trichloroiron;hexahydrateCatalystHCID 313Hydrochloric AcidSolventHCID 962WaterSolvent2×HCID 1140TolueneSolvent2×HCID 6228DimethylformamideSolvent

Procedure

A mixture of 2.6 g (11.5 mmol) of 4-bromo-3-methyl-1-indanone [J. Org. Chem. 22, 1019 (1957)] and 1.14 g (12.7 mmol) of copper(I) cyanide in 2.5 ml of DMF is stirred for 6 hours at 170°. The reaction mixture is then cooled to 100°, and 50 ml of toluene and a solution of 4.5 g (16.5 mmol) of iron(III) chloride hexahydrate in 7 ml of water and 1.7 ml of concentrated hydrochloric acid are added in succession thereto. The reaction mixture is stirred for 20 minutes at 70°, cooled and diluted with toluene and water. The organic phase is separated off, washed with water, a semi-saturated sodium hydrogen carbonate solution and again with water, dried and concentrated by evaporation. The residue is distilled at 100°-120°/0.05 mbar in a bulb tube still and corresponds to starting compound (a), m.p. 109°-111°; IR (CH2Cl2): 2220, 1710 cm-1 ; 1H-NMR (CDCl3): δ=7.92 (m,2H); 7.52 (t,1H); 3.73 (m,1H); 3.03 (q,1H); 2.40 (q,1H); 1.55 (d,3H).

Workup

  1. temperatureThe reaction mixture is then cooled to 100°
  2. stirringThe reaction mixture is stirred for 20 minutes at 70°
  3. temperaturecooled
  4. customThe organic phase is separated off
  5. washwashed with water
  6. dry with materiala semi-saturated sodium hydrogen carbonate solution and again with water, dried
  7. concentrationconcentrated by evaporation
  8. distillationThe residue is distilled at 100°-120°/0.05 mbar in a bulb tube still

Sources & evidence

ORD record
ord-726e2de009664db6897a5bad87502de9
Source dataset
uspto-grants-1995_03
Patent number
US05395855

Reaction notes

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