Benzoyl Peroxide → HCID 66742725, compound

HRID 1259343Notes

Reaction equation

HRID 1259343 reaction equation
[CH3:1][O:2][C:3]1[C:8]([C:9]([O:11][CH2:12][CH3:13])=[O:10])=[C:7]([CH3:14])[N:6]=[C:5]([C:15]2[CH:16]=[N:17][C:18]([O:23][CH3:24])=[C:19]([O:21][CH3:22])[CH:20]=2)[CH:4]=1.C1C(=O)N([Br:32])C(=O)C1.C(OOC(=O)C1C=CC=CC=1)(=O)C1C=CC=CC=1.C(=O)([O-])[O-].[K+].[K+]>C(Cl)(Cl)(Cl)Cl>[Br:32][CH2:14][C:7]1[N:6]=[C:5]([C:15]2[CH:16]=[N:17][C:18]([O:23][CH3:24])=[C:19]([O:21][CH3:22])[CH:20]=2)[CH:4]=[C:3]([O:2][CH3:1])[C:8]=1[C:9]([O:11][CH2:12][CH3:13])=[O:10]

Participants

6

Reactant 4

HCID 7187Benzoyl PeroxideHCID 11430Potassium CarbonateHCID 67184N-bromobutanimide2×HCID 66742834HCID 66742834, compound

Product 1

HCID 66742725HCID 66742725, compound

Reagents, catalysts & solvents 1

HCID 5943Carbon TetrachlorideSolvent

Conditions

Temperature
65 °C

Procedure

As shown in step 9-iv of Scheme 9, Compound 2032 (200 mg, 0.628 mmol) and NBS (112 mg, 0.63 mmol) were added to 15 mL of CCl4 and the solution purged with nitrogen for 5 minutes. Benzoyl peroxide (20 mole %) was added and the reaction mixture heated at 65° C. under nitrogen for 16 hours. An additional equivalent of NBS and 0.3 equivalents of benzoyl peroxide were added and heating continued for an additional hour. Potassium carbonate (1.0 g) was added as an acid scavenger and heating continued for an additional 24 hours. The reaction mixture was cooled and filtered through a cotton plug and the volatiles removed under reduced pressure. The residue was taken up in DCM and passed through a plug of silica gel, which was eluted with additional DCM. Elution with EtOAc recovered crude product, which was further purified by silica gel chromatography (DCM—1:1 EtOAc/DCM to give ethyl 6-(bromomethyl)-4,5′,6′-trimethoxy-2,3′-bipyridine-5-carboxylate (Compound 2033, 87 mg of white solid: ESMS (M+1) 397/399.

Workup

  1. customthe solution purged with nitrogen for 5 minutes
  2. additionBenzoyl peroxide (20 mole %) was added
  3. temperatureheating
  4. waitcontinued for an additional hour
  5. temperatureheating
  6. temperatureThe reaction mixture was cooled
  7. filtrationfiltered through a cotton plug
  8. customthe volatiles removed under reduced pressure
  9. washwas eluted with additional DCM
  10. washElution with EtOAc
  11. customrecovered crude product, which
  12. customwas further purified by silica gel chromatography (DCM—1:1 EtOAc/DCM

Sources & evidence

ORD record
ord-43606cfb9bd249138f0fdb75879b4325
Source dataset
uspto-grants-2013_06
Patent number
US08466288B2

Reaction notes

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