Triphenylphosphine → HCID 57748770, compound

HRID 1670639Notes

Reaction equation

HRID 1670639 reaction equation
Br[C:2]1[CH:7]=[CH:6][C:5]([NH:8][N:9]2[CH2:14][CH2:13][N:12]([CH3:15])[CH2:11][CH2:10]2)=[C:4]([N+:16]([O-:18])=[O:17])[CH:3]=1.[F:19][C:20]1[CH:21]=[CH:22][C:23]2=[C:24]([CH:45]=1)[O:25][CH2:26][C:27]1[C:43]([F:44])=[CH:42][CH:41]=[CH:40][C:28]=1/[C:29]/2=[CH:30]\B1OC(C)(C)C(C)(C)O1.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.C([O-])(=O)C.[K+]>O1CCOCC1.O.O.C([O-])(=O)C.[Pd+2].C([O-])(=O)C>[F:19][C:20]1[CH:21]=[CH:22][C:23]2=[C:24]([CH:45]=1)[O:25][CH2:26][C:27]1[C:43]([F:44])=[CH:42][CH:41]=[CH:40][C:28]=1/[C:29]/2=[CH:30]\[C:2]1[CH:7]=[CH:6][C:5]([NH:8][N:9]2[CH2:14][CH2:13][N:12]([CH3:15])[CH2:11][CH2:10]2)=[C:4]([N+:16]([O-:18])=[O:17])[CH:3]=1

Participants

8

Reactant 4

HCID 11776TriphenylphosphineHCID 517044Potassium AcetateHCID 67334316HCID 67334316, compoundHCID 67335785HCID 67335785, compound

Product 1

HCID 57748770HCID 57748770, compoundYield 55%

Reagents, catalysts & solvents 3

HCID 167845palladium(II) acetateCatalystHCID 962WaterSolventHCID 218864351,4-Dioxane--water (1/1)Solvent

Procedure

Degas three times a mixture of (4-bromo-2-nitro-phenyl)-(4-methyl-piperazin-1-yl)-amine (0.016 mol, 5.0 g), (E)-3,7-difluoro-11-(4,4,5,5-tetramethyl[1,3,2]dioxaborolan-2-ylmethylene)-6,11-dihydro-dibenzo[b,e]oxepine (0.017 mol, 6.4 g), triphenylphosphine (0.0028 mol, 0.74 g) and potassium acetate (0.0317 mol, 3.11 g) in dioxane/water (3:1) (200 mL) with nitrogen. Add palladium (II) acetate (0.5 mmol, 113 mg) to the reaction mixture and degas again three times with nitrogen. Heat the resulting reaction mixture at 85° C. for 16 h. Cool the reaction mixture to room temperature and dilute with water. Extract the mixture with ethyl acetate, combine organic layers, and wash with water and brine. Dry the organic phase over anhydrous sodium sulfate, filter, and concentrate. Crystallize the crude material from methanol, filter, and dry under vacuum to obtain the title compound (4.2 g, 55%) as an orange solid. ES-MS m/z 479 [M+1]+.

Workup

  1. customDegas three times
  2. temperatureHeat
  3. customthe resulting reaction mixture at 85° C. for 16 h
  4. extractionExtract the mixture with ethyl acetate
  5. washwash with water and brine
  6. dry with materialDry the organic phase over anhydrous sodium sulfate
  7. filtrationfilter
  8. concentrationconcentrate
  9. customCrystallize the crude material from methanol
  10. filtrationfilter
  11. customdry under vacuum

Sources & evidence

ORD record
ord-f4fa6ba0d41f41419c3feeda0dfa86f3
Source dataset
uspto-grants-2011_08
Patent number
US07994164B2

Reaction notes

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