Dimethylacetamide → HCID 67406660, compound

HRID 625957Notes

Reaction equation

HRID 625957 reaction equation
Br[C:2]1[C:7]([Br:8])=[CH:6][C:5]([O:9][CH3:10])=[C:4]([O:11][CH3:12])[N:3]=1.C[C:14]([N:16](C)C)=O>[C-]#N.[C-]#N.[Zn+2].[Zn].C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.[Pd].[Pd].C1C=CC(P(C2C=CC=CC=2)[C-]2C=CC=C2)=CC=1.C1C=CC(P(C2C=CC=CC=2)[C-]2C=CC=C2)=CC=1.[Fe+2]>[Br:8][C:7]1[C:2]([C:14]#[N:16])=[N:3][C:4]([O:11][CH3:12])=[C:5]([O:9][CH3:10])[CH:6]=1

Participants

7

Reactant 2

HCID 31374DimethylacetamideHCID 23056693HCID 23056693, compound

Product 1

HCID 67406660HCID 67406660, compoundYield 26%

Reagents, catalysts & solvents 4

HCID 11186Zinc cyanide (Zn(CN)2)CatalystHCID 23994ZincCatalystHCID 635956Ferrocene-1,1'-bis-(diphenylphosphine)CatalystHCID 9811564Bis(dibenzylideneacetone)palladiumCatalyst

Conditions

Temperature
120 °C

Procedure

To a mixture of 2,3-dibromo-5,6-dimethoxypyridine (150 mg, 0.505 mmol), Zn(CN)2 (30 mg, 0.253 mmol), Zn powder (33 mg, 0.051 mmol), Pd2(dba)3 (13.9 mg, 0.015 mmol) and DPPF (8.4 mg, 0.015 mmol), under argon, was added DMA (1.5 mL) and stirred at 120° C. for 3.5 h. Cooled to room temperature, filtered and purified by preparative HPLC (10-95% CH3CN/H2O over 20 min, 0.05% added TFA). The desired fractions were loaded onto a Strata-X-C cation exchange column. After washing the column with water and MeOH, the column was eluted with 5% NH4OH in MeOH to give 32 mg (26%) of 3-bromo-5,6-dimethoxypyridine-2-carbonitrile as a tan solid. LC/MS (M+H)+ 243.1.

Workup

  1. temperatureCooled to room temperature
  2. filtrationfiltered
  3. custompurified by preparative HPLC (10-95% CH3CN/H2O over 20 min, 0.05% added TFA)
  4. washAfter washing the column with water and MeOH
  5. washthe column was eluted with 5% NH4OH in MeOH

Sources & evidence

ORD record
ord-fcbab253aa5d417faee2d236d0fcf5f6
Source dataset
uspto-grants-2016_04
Patent number
US09309199B2

Reaction notes

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