Methyl Nicotinate → HCID 14576266, compound

HRID 2294603Notes

Reaction equation

HRID 2294603 reaction equation
CC(C)([O-])C.[K+].[C:7]([O:15]C)(=O)[C:8]1[CH:13]=[CH:12][CH:11]=[N:10][CH:9]=1.C1(=O)[O:22][CH2:21][CH2:20][CH2:19][CH2:18]1>O1CCCC1.O>[N:10]1[CH:11]=[CH:12][CH:13]=[C:8]([C:7]([CH2:18][CH2:19][CH2:20][CH2:21][OH:22])=[O:15])[CH:9]=1

Participants

6

Reactant 3

HCID 7151Methyl NicotinateHCID 10953Delta-ValerolactoneHCID 23665647Potassium tert-butoxide

Product 1

HCID 14576266HCID 14576266, compoundYield 68.3%

Reagents, catalysts & solvents 2

HCID 962WaterSolventHCID 8028TetrahydrofuranSolvent2×

Conditions

Temperature
23 °C

Procedure

A solution of potassium tert-butoxide (83.55 g) in tetrahydrofuran (500 ml) at 22° C. is treated, dropwise, with a solution of methyl nicotinate (68.5 g) and delta-valerolactone (75.0 g) in tetrahydrofuran (125 ml) during a period of 1 hour. The solution is then stirred at 23° C. for 2 hours. The reaction mixture is diluted with water and washed with toluene (125 ml). The organic phase is discarded and the aqueous phase is treated dropwise with concentrated hydrochloric acid (400 ml; 37% w/v). The solution is stirred for a further 2 hours. The solution is then washed with dichloromethane (250 ml). The organic phase is discarded and the aqueous phase is treated with aqueous sodium hydroxide solution to bring it to between pH8 and pH9. The aqueous phase is then washed with toluene (125 ml) and the organic phase is back washed with water (3×100 ml). The two aqueous phases are combined and extracted with dichloro- methane. The dichloromethane extract is dried over magnesium sulphate, and evaporated to dryness, to give 4-hydroxybutyl 3-pyridyl ketone (61.1 g) in the form of an oil which crystallises to form a pale brown solid, m.p. 36°-38° C. [NMR (CDCl3): 1.7(m,2H), 1.9(m,2H), 3.1(t,2H), 3.7(t,2H), 7.4(m,1H), 8.2(dt,1H), 8.8(m, 1H), 9.2(m, 1H)].

Workup

  1. washwashed with toluene (125 ml)
  2. additionthe aqueous phase is treated dropwise with concentrated hydrochloric acid (400 ml; 37% w/v)
  3. stirringThe solution is stirred for a further 2 hours
  4. washThe solution is then washed with dichloromethane (250 ml)
  5. additionthe aqueous phase is treated with aqueous sodium hydroxide solution
  6. washThe aqueous phase is then washed with toluene (125 ml)
  7. washthe organic phase is back washed with water (3×100 ml)
  8. extractionextracted with dichloro- methane
  9. extractionThe dichloromethane extract
  10. dry with materialis dried over magnesium sulphate
  11. customevaporated to dryness

Sources & evidence

ORD record
ord-a003e5d072274194b106735551cdc898
Source dataset
uspto-grants-1997_11
Patent number
US05688954

Reaction notes

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