Di-tert-butyl azodicarboxylate → Di-tert-butyl 1-(2,4-dimethoxypyrimidin-5-yl)hydrazine-1,2-dicarboxylate

HRID 869063

Reaction equation

HRID 869063 reaction equation
C([Mg]Cl)(C)C.[Cl-].[Li+].Br[C:9]1[C:10]([O:17][CH3:18])=[N:11][C:12]([O:15][CH3:16])=[N:13][CH:14]=1.[N:19]([C:28]([O:30][C:31]([CH3:34])([CH3:33])[CH3:32])=[O:29])=[N:20][C:21]([O:23][C:24]([CH3:27])([CH3:26])[CH3:25])=[O:22]>C1COCC1.[Cl-].[Na+].O>[CH3:34][C:31]([O:30][C:28]([N:19]([C:9]1[C:10]([O:17][CH3:18])=[N:11][C:12]([O:15][CH3:16])=[N:13][CH:14]=1)[NH:20][C:21]([O:23][C:24]([CH3:27])([CH3:26])[CH3:25])=[O:22])=[O:29])([CH3:32])[CH3:33]

Participants

6

Reactant 3

HCID 97268Di-tert-butyl azodicarboxylateHCID 2557195-Bromo-2,4-dimethoxypyrimidineHCID 178461733HCID 178461733, compound

Product 1

HCID 90303215Di-tert-butyl 1-(2,4-dimethoxypyrimidin-5-yl)hydrazine-1,2-dicarboxylateYield 100%

Reagents, catalysts & solvents 2

HCID 8028TetrahydrofuranSolventHCID 57417360Sodium chloride; waterSolvent

Procedure

Isopropylmagnesium chloride-lithium chloride complex (1.3 M in THF, 18.3 mL, 23.7 mmol) was added dropwise to a cold (0° C.) solution of 5-bromo-2,4-dimethoxypyrimidine (4 g, 18.3 mmol) in THF (50 mL), under argon. The reaction mixture was allowed to warm to rt and stirred for 1 h at this temperature. Di-tertbutyl azodicarboxylate (4.2 g, 18.3 mmol) was added portionwise. The reaction mixture was stirred for 1 h at rt, diluted with brine, and extracted with EtOAc. The organic layers were combined, washed with brine, dried (Na2SO4), and concentrated. The residue was purified by silica gel column chromatography (hexane/EtOAc, 9:1→7.3) to provide 6.78 g of the title compound. tR: 1.08 min (LC-MS 4); ESI-MS: 371.3 [M+H]+ (LC-MS 4); Rf=0.55 (hexane/EtOAc, 1:1).

Workup

  1. stirringThe reaction mixture was stirred for 1 h at rt
  2. extractionextracted with EtOAc
  3. washwashed with brine
  4. dry with materialdried (Na2SO4)
  5. concentrationconcentrated
  6. customThe residue was purified by silica gel column chromatography (hexane/EtOAc, 9:1→7.3)

Sources & evidence

ORD record
ord-0a93f58261644c23aaee87435155d431
Source dataset
uspto-grants-2015_03
Patent number
US08969341B2

Linked notes

Loading…