Cesium carbonate → HCID 66706786, compound

HRID 911258Notes

Reaction equation

HRID 911258 reaction equation
Br[C:2]1[CH:9]=[CH:8][CH:7]=[CH:6][C:3]=1[C:4]#[N:5].C[C:11]([CH3:22])([C:13](=O)[CH2:14][C:15](=[O:20])[C:16]([CH3:19])(C)C)C.C(=O)([O-])[O-].[Cs+].[Cs+].C[N:30]1C(=O)CCC1>[Cu]Cl>[NH2:5][CH2:4][C:3]1[CH:6]=[CH:7][C:8]([O:20][C:15]2[CH:14]=[CH:13][CH:11]=[CH:22][C:16]=2[C:19]#[N:30])=[CH:9][CH:2]=1

Participants

6

Reactant 4

HCID 10796Cesium carbonateHCID 13387N-methyl-2-pyrrolidoneHCID 162722-BromobenzonitrileHCID 707002,2,6,6-Tetramethyl-3,5-heptanedione

Product 1

HCID 66706786HCID 66706786, compoundYield 38%

Reagents, catalysts & solvents 1

HCID 62652Cuprous chlorideCatalyst

Conditions

Temperature
120 °C

Procedure

Mix under argon (4-hydroxybenzyl)-carbamic acid tert-butyl ester (1.5 g, 6.7 mmol), 2-bromobenzonitrile (813 mg, 4.5 mmol), 2,2,6,6-tetramethylheptane-3,5-dione (83 mg, 0.45 mmol), and cesium carbonate (2.2 g, 6.7 mmol) in anhydrous NMP (8.5 mL). Degas the flask and fill with argon. Add copper(I) chloride (223 mg, 2.25 mmol) quickly. Degas the flask, fill with argon and heat at 120° C. for 3 h. Cool to ambient temperature, dilute with EtOAc, filter and concentrate in vacuo. Purify by chromatography on silica gel eluting with hexane/EtOAc (1:0, 9:1 and 3:1). Evaporate the solvent and dissolve the residue in DCM (100 mL). Add trifluoroacetic acid (20 mL) and stir at ambient temperature for 16 h. Concentrate in vacuo, dissolve the residue in EtOAc and wash with 1N aqueous NaOH. Dry over Na2SO4 and concentrate in vacuo. Purify by SCX chromatography to obtain the title compound (385 mg, 38%). MS (ES+) m/z: 225 (M+H)+.

Workup

  1. additionMix under argon (4-hydroxybenzyl)-carbamic acid tert-butyl ester (1.5 g, 6.7 mmol)
  2. customDegas the flask
  3. customDegas the flask
  4. temperatureCool to ambient temperature
  5. additiondilute with EtOAc
  6. filtrationfilter
  7. concentrationconcentrate in vacuo
  8. customPurify by chromatography on silica gel eluting with hexane/EtOAc (1:0, 9:1 and 3:1)
  9. customEvaporate the solvent
  10. dissolutiondissolve the residue in DCM (100 mL)
  11. concentrationConcentrate in vacuo
  12. dissolutiondissolve the residue in EtOAc
  13. washwash with 1N aqueous NaOH
  14. dry with materialDry over Na2SO4
  15. concentrationconcentrate in vacuo
  16. customPurify by SCX chromatography

Sources & evidence

ORD record
ord-63c4450beb9d4750acbff3f0e46d64d5
Source dataset
uspto-grants-2011_09
Patent number
US08022062B2

Reaction notes

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