Ammonia → HCID 57825125, compound

HRID 1668703Notes

Reaction equation

HRID 1668703 reaction equation
II.[Br:3][C:4]1[CH:5]=[C:6]([C:10]([C:12]2[CH:17]=[CH:16][C:15]([O:18][CH3:19])=[C:14]([CH3:20])[CH:13]=2)=[CH2:11])[CH:7]=[CH:8][CH:9]=1.N.[NH2:22][C:23]([NH2:25])=[O:24]>C(OCC)(=O)C.C(#N)C.[Ag]OC#N.ClCCl>[Br:3][C:4]1[CH:5]=[C:6]([C:10]2([C:12]3[CH:17]=[CH:16][C:15]([O:18][CH3:19])=[C:14]([CH3:20])[CH:13]=3)[CH2:11][O:24][C:23]([NH2:25])=[N:22]2)[CH:7]=[CH:8][CH:9]=1

Participants

9

Reactant 4

HCID 222AmmoniaHCID 807IodineHCID 1176UreaHCID 57825032HCID 57825032, compound

Product 1

HCID 57825125HCID 57825125, compoundYield 40%

Reagents, catalysts & solvents 4

HCID 178513473HCID 178513473, compoundCatalystHCID 6342AcetonitrileSolventHCID 6344DichloromethaneSolventHCID 8857Ethyl AcetateSolvent2×

Procedure

A solution of iodine (1.92 g, 7.59 mmol) in ethyl acetate (50 mL) was added dropwise over 25 min to a mixture of 4-[1-(3-bromo-phenyl)-vinyl]-1-methoxy-2-methyl-benzene (2.1 g, 6.9 mmol) and silver cyanate (1.24 g, 8.28 mmol) in acetonitrile (19 mL) and ethyl acetate (9 mL), cooled in an ice bath. After complete addition, the reaction suspension was stirred for another 15 min at room temperature when TLC indicated the complete conversion of starting material. The reaction mixture was filtered, and the filtrate concentrated to give a dark grey oil. 50 mL of aqueous ammonia (25%) was added to the oil, and the mixture was stirred and warmed to 60° C. for 4 hours. LC-MS at this point indicated complete conversion of the intermediate urea to the desired aminoxazoline, dichloromethane (40 mL) was added to the crude and the two phases were separated. The organic layer was collected, dried over anhydrous magnesium sulfate, filtered and evaporated under reduced pressure. Crude was purified by silica gel chromatography eluting with dichloromethane/methanol (gradient 0-2%) to give 1.0 g of the desired product as yellow gum (40%)

Workup

  1. temperaturecooled in an ice bath
  2. additionAfter complete addition
  3. filtrationThe reaction mixture was filtered
  4. concentrationthe filtrate concentrated
  5. customto give a dark grey oil
  6. stirringthe mixture was stirred
  7. temperaturewarmed to 60° C. for 4 hours
  8. additionwas added to the crude
  9. customthe two phases were separated
  10. customThe organic layer was collected
  11. dry with materialdried over anhydrous magnesium sulfate
  12. filtrationfiltered
  13. customevaporated under reduced pressure
  14. customCrude was purified by silica gel chromatography
  15. washeluting with dichloromethane/methanol (gradient 0-2%)

Sources & evidence

ORD record
ord-3af9e0cf9ef046b1abe267ab143c9849
Source dataset
uspto-grants-2011_08
Patent number
US07989449B2

Reaction notes

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