Triethylamine → HCID 58137741, compound

HRID 2189453Notes

Reaction equation

HRID 2189453 reaction equation
[C]=O.Cl[C:4]1[C:5]2[N:6]([C:10]([C:13]3[CH:18]=[CH:17][C:16]([NH:19][C:20](=[O:26])[O:21][C:22]([CH3:25])([CH3:24])[CH3:23])=[CH:15][CH:14]=3)=[N:11][N:12]=2)[CH:7]=[CH:8][N:9]=1.C1C=CC(P(C2C=CC=CC=2)CCCP(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1.CCN(CC)CC>CCOC(C)=O.CC([O-])=O.CC([O-])=O.[Pd+2].CO.CS(C)=O>[C:22]([O:21][C:20]([NH:19][C:16]1[CH:17]=[CH:18][C:13]([C:10]2[N:6]3[CH:7]=[CH:8][N:9]=[C:4]([C:20]([O:21][CH3:22])=[O:26])[C:5]3=[N:12][N:11]=2)=[CH:14][CH:15]=1)=[O:26])([CH3:25])([CH3:24])[CH3:23]

Participants

9

Reactant 4

HCID 8471TriethylamineHCID 812191,3-Bis(diphenylphosphino)propaneHCID 58137776HCID 58137776, compoundHCID 178418416HCID 178418416, compound

Product 1

HCID 58137741HCID 58137741, compoundYield 27%

Reagents, catalysts & solvents 4

HCID 167845palladium(II) acetateCatalystHCID 679Dimethyl SulfoxideSolventHCID 887MethanolSolventHCID 8857Ethyl AcetateSolvent

Conditions

Temperature
75 °C

Procedure

Carbon monoxide gas was charged into a pressure bottle containing a mixture of tert-butyl 4-(8-chloro-[1,2,4]triazolo[4,3-a]pyrazin-3-yl)phenylcarbamate (61C) (714 mg, 2.065 mmol), Pd(OAc)2 (185 mg, 0.826 mmol), dppp (341 mg, 0.826 mmol), Et3N (1.15 mL, 8.26 mmol), DMSO (12 mL) and MeOH (6 mL) until the pressure reached to 30 psi. The bottle was then sealed and heated at 75° C. for 4 h. After cooling to room temperature, the reaction was diluted with EtOAc, washed with water (3×), saturated aqueous NaCl, dried (Na2SO4) and concentrated under reduced pressure. The crude product was purified using a silica gel cartridge eluting with a gradient of EtOAc in hexanes to afford 103 mg (17%) of the title compound. HPLC/MS (Method C): retention time=1.72 min, [M+H]+=370.4; 1H NMR (500 MHz, DMSO-d6): δ 9.75 (s, 1H), 8.78 (d, J=4.95 Hz, 1H), 8.04 (d, J=4.95 Hz, 1H), 7.86 (d, J=8.80 Hz, 2H), 7.73 (d, J=8.80 Hz, 2H), 4.02 (s, 3H), 1.47 (s, 9H).

Workup

  1. additioncontaining
  2. customThe bottle was then sealed
  3. temperatureAfter cooling to room temperature
  4. washwashed with water (3×), saturated aqueous NaCl
  5. dry with materialdried (Na2SO4)
  6. concentrationconcentrated under reduced pressure
  7. customThe crude product was purified
  8. washeluting with a gradient of EtOAc in hexanes

Sources & evidence

ORD record
ord-78ddf111f20643638bb6c9dedf049b68
Source dataset
uspto-grants-2012_12
Patent number
US08324241B2

Reaction notes

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