Sodium Chloride → 2-Amino-3-cyano-4-methyl-5-phenylcarbonylpyridine

HRID 1078244Notes

Reaction equation

HRID 1078244 reaction equation
[NH2:1][C:2]1[C:7]([C:8]#[N:9])=[C:6]([CH3:10])[C:5](I)=[CH:4][N:3]=1.[C]=O.[C:14]1(B(O)O)[CH:19]=[CH:18][CH:17]=[CH:16][CH:15]=1.C(N(CC)CC)C.[Cl-].[Na+].[O:32]1CCOC[CH2:33]1>C([O-])(=O)C.[Pd+2].C([O-])(=O)C.O>[NH2:1][C:2]1[C:7]([C:8]#[N:9])=[C:6]([CH3:10])[C:5]([C:33]([C:14]2[CH:19]=[CH:18][CH:17]=[CH:16][CH:15]=2)=[O:32])=[CH:4][N:3]=1

Participants

9

Reactant 6

HCID 5234Sodium ChlorideHCID 8471TriethylamineHCID 312751,4-DioxaneHCID 66827Phenylboronic AcidHCID 113912652-Amino-5-iodo-4-methylnicotinonitrileHCID 178418416HCID 178418416, compound3×

Product 1

HCID 197072072-Amino-3-cyano-4-methyl-5-phenylcarbonylpyridine

Reagents, catalysts & solvents 2

HCID 167845palladium(II) acetateCatalystHCID 962WaterSolvent

Conditions

Temperature
65 °C

Procedure

A solution of 4.9 grams (0.019 mole) of 2-amino-3-cyano-5-iodo-4-methylpyridine (prepared as in Step E of Example 9) in 75 mL of dioxane is stirred, and gaseous carbon monoxide is bubbled in during a 15 minute period. While maintaining a carbon monoxide atmosphere, 4.7 grams (0.039 mole) of phenylboronic acid (commercially available), 6.8 mL (0.048 mole) of triethylamine, and 0.5 gram (catalyst) of palladium(11) acetate are in turn added. To maintain the carbon monoxide atmosphere, a balloon filled with carbon monoxide gas is then attached to the reaction vessel. The reaction mixture is then warmed to 65° C. where it is stirred for about 20 hours. The reaction mixture is then poured into a mixture of 300 mL of water and 100 mL of aqueous saturated sodium chloride solution. This mixture is extracted with two 150 mL portions of ethyl acetate. The combined extracts are dried with magnesium sulfate and filtered. The filtrate is concentrated under reduced pressure to a residue. The residue is purified using column chromatography, yielding 2-amino-3-cyano-4-methyl-5-phenylcarbonylpyridine.

Workup

  1. customgaseous carbon monoxide is bubbled in during a 15 minute period
  2. additionadded
  3. extractionThis mixture is extracted with two 150 mL portions of ethyl acetate
  4. dry with materialThe combined extracts are dried with magnesium sulfate
  5. filtrationfiltered
  6. concentrationThe filtrate is concentrated under reduced pressure to a residue
  7. customThe residue is purified

Sources & evidence

ORD record
ord-aec492bf9d124c1290afc042175c25fb
Source dataset
uspto-grants-1996_08
Patent number
US05547954

Reaction notes

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