HCID 13958724, compound → HCID 13958725, compound

HRID 255981Notes

Reaction equation

HRID 255981 reaction equation
[F:1][C:2]1[CH:7]=[CH:6][C:5]([N+:8]([O-])=O)=[CH:4][C:3]=1[C:11]1[CH:16]=[C:15]([CH3:17])[N:14]=[C:13]([CH3:18])[CH:12]=1.[H][H]>[Pt](=O)=O.C(O)(=O)C>[CH3:18][C:13]1[CH:12]=[C:11]([C:3]2[CH:4]=[C:5]([NH2:8])[CH:6]=[CH:7][C:2]=2[F:1])[CH:16]=[C:15]([CH3:17])[N:14]=1

Participants

5

Reactant 2

HCID 13958724HCID 13958724, compound2×HCID 178418361HCID 178418361, compound2×

Product 1

HCID 13958725HCID 13958725, compound

Reagents, catalysts & solvents 2

HCID 345198Adams' catalystCatalystHCID 176Acetic AcidSolvent

Procedure

4-(2-fluoro-5-nitrophenyl)-2,6-dimethylpyridine, 180 g, was divided into four equal portions and each portion was reduced separately as follows. A mixture containing 45 g of 4-(2-fluoro-5-nitrophenyl)-2,6-dimethylpyridine, 200 ml of acetic acid and 800 mg of platinum dioxide was catalytically hydrogenated until hydrogen uptake ceased, about 4 hours with little hydrogen uptake the last thirty minutes. The catalyst was filtered off, washed with 300 ml of water, and the filtrate made basic by adding aqueous ammonium hydroxide. The solution was cooled to yield a oily material which solidified. The solid was collected, washed with water and dried to yield the desired amine. The remaining three 45 g portions of 4-(2-fluoro-5-nitrophenyl)-2,6-dimethylpyridine were reduced in the same way and the combined amine products were dissolved in 600 ml of concentrated hydrochloric acid and heated on a steam bath with stirring for 4 and 1/2 hours and then treated with decolorizing charcoal and filtered. The filtrate was made basic by adding aqueous ammonia and the resulting mixture was chilled to yield an oil which crystallized. The crystalline material was collected, washed with water and dried in an oven to yield 164.9 g of gummy solid. The solid was dissolved in ether containing 5% methanol and the solution was filtered through silica gel to remove the gummy impurities. The ether-methanol solvent of the filtrate was distilled off in vacuo and the residue was recrystallized from ether-isopropyl alcohol to yield 80.9 g of 3-(2,6-dimethyl-4-pyridinyl)-4-fluorobenzeneamine, m.p. 142°-145° C. Concentration of the mother liquor yielded another 43.4 g of the product, m.p. 141°-144° C., thereby giving a total yield of 82%.

Workup

  1. filtrationThe catalyst was filtered off
  2. washwashed with 300 ml of water
  3. additionby adding aqueous ammonium hydroxide
  4. temperatureThe solution was cooled
  5. customto yield a oily material which
  6. customThe solid was collected
  7. washwashed with water
  8. customdried

Sources & evidence

ORD record
ord-2619388068e04252a0f7ebfcd23675a9
Source dataset
uspto-grants-1987_10
Patent number
US04699984

Reaction notes

Loading…