Water → HCID 15572418, compound

HRID 443407Notes

Reaction equation

HRID 443407 reaction equation
[CH3:1][C:2]1[CH:7]=[CH:6][C:5]([OH:8])=[CH:4][N:3]=1.[CH3:9][C:10](N(C)C)=[O:11].O.[O:16]1CC[CH2:18][CH2:17]1>C([Li])CCC.CCCCCC>[C:10]([O:8][C:5]1[CH:6]=[CH:7][C:2]([CH2:1][C:17](=[O:16])[CH3:18])=[N:3][CH:4]=1)(=[O:11])[CH3:9]

Participants

7

Reactant 4

HCID 962WaterHCID 8028Tetrahydrofuran2×HCID 142752-Methyl-5-hydroxypyridineHCID 31374Dimethylacetamide

Product 1

HCID 15572418HCID 15572418, compound

Reagents, catalysts & solvents 2

HCID 8058HexaneSolventHCID 178418339ButyllithiumSolvent

Procedure

The starting material is prepared as follows: To the suspension of 32.7 g of 2-methyl-5-pyridinol in 400 ml of tetrahydrofuran, 400 ml of 1.6 molar n-butyllithium in hexane are added during 1 hour while stirring under nitrogen and cooling with ice to maintain the temperature below 10°. Thereupon 29 g of dimethylacetamide in 50 ml of tetrahydrofuran are added during 15 minutes, the mixture is stirred for 2 hours at room temperature and poured into 700 ml of water. It is thoroughly shaken, the aqueous layer separated, washed with diethyl ether, acidified with hydrochloric acid and again washed with diethyl ether. Its pH is adjusted to 5.0 with aqueous sodium bicarbonate and after saturation with sodium chloride the mixture is extracted with ethyl acetate-isopropanol (1:1). The extract is evaporated azeotropically with the aid of benzene and the residue is taken up in 100 ml of acetic anhydride. The mixture is stirred for 30 minutes at the steam bath, evaporated, the residue distilled and the fraction boiling at 130°-138°/0.9 mmHg collected, to yield the 5-acetoxy-2-pyridylacetone; its hydrochloride melts at 69°-72° and the oxime thereof at 149°-150°.

Workup

  1. customThe starting material is prepared
  2. additionare added during 1 hour
  3. temperaturecooling with ice
  4. temperatureto maintain the temperature below 10°
  5. stirringthe mixture is stirred for 2 hours at room temperature
  6. stirringIt is thoroughly shaken
  7. customthe aqueous layer separated
  8. washwashed with diethyl ether
  9. washagain washed with diethyl ether
  10. extractionafter saturation with sodium chloride the mixture is extracted with ethyl acetate-isopropanol (1:1)
  11. customThe extract is evaporated azeotropically with the aid of benzene
  12. stirringThe mixture is stirred for 30 minutes at the steam bath
  13. customevaporated
  14. distillationthe residue distilled
  15. customthe fraction boiling at 130°-138°/0.9 mmHg collected

Sources & evidence

ORD record
ord-25ac389068174f31bcbd17df83b2b181
Source dataset
uspto-grants-1981_04
Patent number
US04260619

Reaction notes

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