Di-tert-butyl azodicarboxylate → HCID 90315915, compound

HRID 869062Notes

Reaction equation

HRID 869062 reaction equation
C([Mg]Cl)(C)C.[Cl-].[Li+].Br[C:9]1[CH:10]=[C:11]([CH:14]=[CH:15][C:16]=1[O:17][CH3:18])[C:12]#[N:13].[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-].[NH4+]>[CH3:34][C:31]([O:30][C:28]([N:19]([C:9]1[CH:10]=[C:11]([C:12]#[N:13])[CH:14]=[CH:15][C:16]=1[O:17][CH3:18])[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 7360493-Bromo-4-methoxybenzonitrileHCID 178461733HCID 178461733, compound

Product 1

HCID 90315915HCID 90315915, compoundYield 64.2%

Reagents, catalysts & solvents 2

HCID 8028TetrahydrofuranSolventHCID 25517Ammonium ChlorideSolvent

Procedure

Isopropylmagnesium chloride-lithium chloride complex (1.3 M in THF, 21.8 mL, 28.3 mmol) was added dropwise to a cold (−78° C.) solution of 3-bromo-4-methoxybenzonitrile (5 g, 23.6 mmol) in THF (100 mL), under argon. The reaction mixture was allowed to warm to rt. Di-tertbutyl azodicarboxylate (5.43 g, 23.58 mmol) was added. The reaction mixture was stirred for 3 h at rt, diluted with a saturated aqueous solution of ammonium chloride (175 mL), and extracted with EtOAc. The organic layers were combined, washed with a saturated solution of sodium bicarbonate, dried (Na2SO4), and concentrated. The residue was purified by silica gel column chromatography (hexane/EtOAc, 95:5→7:3) to provide 5.5 g of the title compound. tR: 1.16 min (LC-MS 4); ESI-MS: 362.2 [M−H]− (LC-MS 4); Rf=0.55 (hexane/EtOAc, 1:1).

Workup

  1. extractionextracted with EtOAc
  2. washwashed with a saturated solution of sodium bicarbonate
  3. dry with materialdried (Na2SO4)
  4. concentrationconcentrated
  5. customThe residue was purified by silica gel column chromatography (hexane/EtOAc, 95:5→7:3)

Sources & evidence

ORD record
ord-4322370d256a411ea6515cb25dc33a52
Source dataset
uspto-grants-2015_03
Patent number
US08969341B2

Reaction notes

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