Ammonia → HCID 66941707, compound

HRID 1616654Notes

Reaction equation

HRID 1616654 reaction equation
[CH2:1]([N:8]1[CH2:15][CH2:14][C@:13]2([CH3:19])[C:16]([CH3:18])([CH3:17])[C@H:9]1[CH2:10][C:11]1C(OS(C(F)(F)F)(=O)=O)=[CH:22][CH:21]=[CH:20][C:12]=12)[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1.O.[NH3:33].C(O[CH2:38][CH3:39])(=O)C>CN(C)C=O.C1C=CC([P]([Pd]([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)[P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1.[C-]#N.[Zn+2].[C-]#N>[CH2:1]([N:8]1[CH2:15][CH2:14][C@:13]2([CH3:19])[C:16]([CH3:18])([CH3:17])[C@H:9]1[CH2:10][C:11]1[C:39]([C:38]#[N:33])=[CH:22][CH:21]=[CH:20][C:12]=12)[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1

Participants

8

Reactant 4

HCID 222AmmoniaHCID 962WaterHCID 8857Ethyl AcetateHCID 58123948HCID 58123948, compound

Product 1

HCID 66941707HCID 66941707, compound

Reagents, catalysts & solvents 3

HCID 11186Zinc cyanide (Zn(CN)2)CatalystHCID 178418397HCID 178418397, compoundCatalystHCID 6228DimethylformamideSolvent

Conditions

Temperature
100 °C

Procedure

Tetrakis(triphenylphosphine)palladium(0) (2.79 g) is added to a mixture of (2R,6S)-trifluoro-methanesulfonic acid 3-benzyl-6,11,11-trimethyl-1,2,3,4,5,6-hexahydro-2,6-methano-benzo[d]azocin-10-yl ester (7.30 g) and zinc cyanide (2.85 g) in N,N-dimethylformamide (35 mL) kept in argon atmosphere. The resulting mixture is stirred at 100° C. for 6 h. After cooling to room temperature, water (300 mL), concentrated ammonia solution (10 mL), and ethyl acetate (150 mL) are added and the forming precipitate is separated by filtration. The organic layer of the filtrate is separated and the aqueous layer is extracted twice with ethyl acetate. The combined organic phases are washed with brine and dried (MgSO4). The solvent is removed under reduced pressure and the residue is purified by chromatography on silica gel (cyclohexane/ethyl acetate 19:1) to give the product.

Workup

  1. temperatureAfter cooling to room temperature
  2. customthe forming precipitate is separated by filtration
  3. customThe organic layer of the filtrate is separated
  4. extractionthe aqueous layer is extracted twice with ethyl acetate
  5. washThe combined organic phases are washed with brine
  6. dry with materialdried (MgSO4)
  7. customThe solvent is removed under reduced pressure
  8. customthe residue is purified by chromatography on silica gel (cyclohexane/ethyl acetate 19:1)
  9. customto give the product

Sources & evidence

ORD record
ord-eb73e008eec642d89d66fda4c84ad5d5
Source dataset
uspto-grants-2014_07
Patent number
US08765780B2

Reaction notes

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