Carbon tetrabromide → HCID 11543102, compound

HRID 1272182Notes

Reaction equation

HRID 1272182 reaction equation
C(OC([N:8]1[CH2:20][C@@H:19]([CH3:21])[N:18]2[C@H:10]([CH2:11][C:12]3[C:17]2=[N:16][CH:15]=[C:14]([F:22])[C:13]=3[CH2:23]O)[CH2:9]1)=O)(C)(C)C.BrC(Br)(Br)Br.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1>ClCCl.O1CCCC1.C([O-])(=O)C.[Pd+2].C([O-])(=O)C>[NH3:8].[F:22][C:14]1[C:13]([CH3:23])=[C:12]2[C:17]([N:18]3[C@H:10]([CH2:11]2)[CH2:9][NH:8][CH2:20][C@H:19]3[CH3:21])=[N:16][CH:15]=1

Participants

8

Reactant 3

HCID 11205Carbon tetrabromideHCID 11776TriphenylphosphineHCID 11667216HCID 11667216, compound

Product 2

HCID 222AmmoniaYield 25%HCID 11543102HCID 11543102, compoundYield 143.5%

Reagents, catalysts & solvents 3

HCID 167845palladium(II) acetateCatalystHCID 6344DichloromethaneSolventHCID 8028TetrahydrofuranSolvent

Procedure

To a solution of 0.068 g (4R,9aR)-7-fluoro-8-hydroxymethyl-4-methyl-3,4,9,9a-tetrahydro-1H-2,4a,5-triaza-fluorene-2-carboxylic acid tert-butyl ester in 3 mL of dichloromethane was added 0.0995 g tetrabromomethane and 0.0786 g triphenylphosphine and the mixture was stirred at ambient temperature for 2.5 h The reaction mixture was concentrated and the residue was purified by chromatography on silica gel with a mixture of heptane:ethyl acetate (1:1) to yield 0.0695 g of a slightly yellow oil. This oil was dissolved in 1 mL tetrahydrofuran and 3.0 mg palladium acetate was added. To the resulting mixture was added 0.05 mL polymethylhydrosiloxane and the mixture was stirred at room temperature for 0.5 h. The reaction mixture was partitioned between water and ethyl acetate. The organic phase was washed with water and dried over sodium sulfate and evaporated. The residue was dissolved in 0.60 mL trifluoroacetic acid and stirred at room temperature for 0.5 h. The solvent was evaporated and the residue was purified by chromatography on silica gel with dichloromethane:methanol:ammonia (25% in water) (9:1:0.1) to yield 0.032 g (4R,9aR)-7-fluoro-4,8-dimethyl-1,2,3,4,9,9a-hexahydro-2,4a,5-triaza-fluorene as a slightly yellow oil.

Workup

  1. concentrationwas concentrated
  2. customthe residue was purified by chromatography on silica gel with a mixture of heptane:ethyl acetate (1:1)
  3. customto yield 0.0695 g of a slightly yellow oil
  4. stirringthe mixture was stirred at room temperature for 0.5 h
  5. customThe reaction mixture was partitioned between water and ethyl acetate
  6. washThe organic phase was washed with water
  7. dry with materialdried over sodium sulfate
  8. customevaporated
  9. dissolutionThe residue was dissolved in 0.60 mL trifluoroacetic acid
  10. stirringstirred at room temperature for 0.5 h
  11. customThe solvent was evaporated
  12. customthe residue was purified by chromatography on silica gel with dichloromethane

Sources & evidence

ORD record
ord-f34cfcee20794af1866f9efe16be0907
Source dataset
uspto-grants-2007_04
Patent number
US07208494B2

Reaction notes

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