Benzoyl Peroxide → HCID 58567061, compound

HRID 1620361Notes

Reaction equation

HRID 1620361 reaction equation
[Br:1]N1C(=O)CCC1=O.[C:9]([O:13][C:14](=[O:22])[C:15]1[CH:20]=[CH:19][CH:18]=[C:17]([CH3:21])[N:16]=1)([CH3:12])([CH3:11])[CH3:10].C(OOC(=O)C1C=CC=CC=1)(=O)C1C=CC=CC=1.CCCCCC>C(Cl)(Cl)(Cl)Cl.C(OCC)(=O)C>[Br:1][CH2:21][C:17]1[N:16]=[C:15]([C:14]([O:13][C:9]([CH3:12])([CH3:11])[CH3:10])=[O:22])[CH:20]=[CH:19][CH:18]=1

Participants

7

Reactant 4

HCID 7187Benzoyl PeroxideHCID 8058HexaneHCID 67184N-bromobutanimideHCID 585670962-Pyridinecarboxylic acid, 6-Methyl-, 1,1-diMethylethyl ester

Product 1

HCID 58567061HCID 58567061, compoundYield 17.2%

Reagents, catalysts & solvents 2

HCID 5943Carbon TetrachlorideSolventHCID 8857Ethyl AcetateSolvent

Procedure

N-bromosuccinimide (1.95 g, 10.99 mmol), 6-methylpicolinic acid tert-butyl ester (2.1175 g, 10.96 mmol), and benzoyl peroxide (0.27 g, 1.10 mmol, 0.1 eq.) were dissolved in CCl4 (150 mL) and refluxed for 6.5 hours while monitored by TLC (3:1 hexane: ethyl acetate, Rf=0.28). The reaction mixture was filtered and the solvent was removed in vacuo. The light orange oil was redissolved in DCM and extracted three times with an aqueous solution of saturated NaHCO3 (50 mL). The organic layer was dried with MgSO4 and the solvent was removed in vacuo. The crude product was recrystallised twice from a hexane/ethyl acetate mixture (3:1) in the freezer afford the mono-brominated product as small off-white crystals (0.511 g, 1.88 mmol, 17.1%). 1H NMR (300 MHz, CDCl3, δ): 7.92 (d, 1H, ortho-H), 7.82 (t, 1H, meta-H), 7.65 (d, 1H, ortho-H), 4.65 (s, 2H, CH2), 1.64 (s, 9H, tBu-CH3). 13C NMR (300 MHz, CDCl3, δ): 171.0, 161.0, 157.9, 138.4, 127.0, 124.4, 60.9, 33.9, 28.6.

Workup

  1. temperaturerefluxed for 6.5 hours
  2. filtrationThe reaction mixture was filtered
  3. customthe solvent was removed in vacuo
  4. dissolutionThe light orange oil was redissolved in DCM
  5. extractionextracted three times with an aqueous solution of saturated NaHCO3 (50 mL)
  6. dry with materialThe organic layer was dried with MgSO4
  7. customthe solvent was removed in vacuo
  8. customThe crude product was recrystallised twice from a hexane/ethyl acetate mixture (3:1) in the freezer

Sources & evidence

ORD record
ord-1c06b2501d944ff793da1ce902fcbe6c
Source dataset
uspto-grants-2014_07
Patent number
US08772446B2

Reaction notes

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