Di-tert-butyl dicarbonate → Tert-butyl(6-bromo-3-methoxypyridin-2-yl)carbamate

HRID 1772885Notes

Reaction equation

HRID 1772885 reaction equation
BrC1N=C(N)C(OC)=CC=1.CC(OC(OC(OC(C)(C)C)=O)=O)(C)C.[C:26]([O:30][C:31]([N:33]([C:41]1[C:46]([O:47][CH3:48])=[CH:45][CH:44]=[C:43]([Br:49])[N:42]=1)C(OC(C)(C)C)=O)=[O:32])([CH3:29])([CH3:28])[CH3:27]>CN(C)C1C=CN=CC=1.CC#N>[C:26]([O:30][C:31](=[O:32])[NH:33][C:41]1[C:46]([O:47][CH3:48])=[CH:45][CH:44]=[C:43]([Br:49])[N:42]=1)([CH3:29])([CH3:27])[CH3:28]

Participants

6

Reactant 3

HCID 90495Di-tert-butyl dicarbonateHCID 575629062-Amino-6-bromo-3-methoxypyridineHCID 118685198Di-tert-butyl(6-bromo-3-methoxypyridin-2-yl)imidodicarbonate

Product 1

HCID 131734688Tert-butyl(6-bromo-3-methoxypyridin-2-yl)carbamate

Reagents, catalysts & solvents 2

HCID 142844-(Dimethylamino)pyridineCatalystHCID 6342AcetonitrileSolvent

Procedure

A mixture of 6-bromo-3-methoxypyridin-2-amine (10.2 g, 50.2 mmol), Boc2O (38.2 g, 0.18 mol) and 4-(dimethylamino)pyridine (1.2 g, 9.82 mmol) in MeCN (550 mL) was refluxed for 2 h. After cooling to rt and concentration in vacuo EtOAc (500 mL) was added and the organic phase washed with water (100 mL) and brine (50 mL). The organic phase was dried (MgSO4), filtered and the filtrate concentrated in vacuo. Purification by chromatography eluting with 4:1 DCM-heptane yielded a mixture of the title compound and di-tert-butyl(6-bromo-3-methoxypyridin-2-yl)imidodicarbonate (10.6 g) in an approximate ratio of 55:45.

Workup

  1. temperaturewas refluxed for 2 h
  2. concentrationconcentration in vacuo EtOAc (500 mL)
  3. additionwas added
  4. washthe organic phase washed with water (100 mL) and brine (50 mL)
  5. dry with materialThe organic phase was dried (MgSO4)
  6. filtrationfiltered
  7. concentrationthe filtrate concentrated in vacuo
  8. customPurification by chromatography
  9. washeluting with 4:1 DCM-heptane
  10. customyielded

Sources & evidence

ORD record
ord-0c5f5d9864ed461fa7bcf07e8b4192b3
Source dataset
uspto-grants-2016_02
Patent number
US09249160B2

Reaction notes

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