Acetic Acid → HCID 20163049, compound

HRID 246844Notes

Reaction equation

HRID 246844 reaction equation
[C:1]1([CH3:11])[CH:6]=[CH:5][CH:4]=[CH:3][C:2]=1[CH2:7][C:8]([OH:10])=[O:9].C([Li])CCC.[CH:17]([CH2:19][CH2:20][CH2:21][CH2:22][CH2:23][CH2:24][C:25]([O:27][CH3:28])=[O:26])=[O:18].C(O)(=O)C>C1COCC1.CCCCCC>[C:8]([CH:7]([C:2]1[CH:3]=[CH:4][CH:5]=[CH:6][C:1]=1[CH3:11])[CH:17]([OH:18])[CH2:19][CH2:20][CH2:21][CH2:22][CH2:23][CH2:24][C:25]([O:27][CH3:28])=[O:26])([OH:10])=[O:9]

Participants

7

Reactant 4

HCID 176Acetic AcidHCID 69519o-Tolylacetic acidHCID 535040Methyl 8-oxooctanoateHCID 178418339Butyllithium

Product 1

HCID 20163049HCID 20163049, compound

Reagents, catalysts & solvents 2

HCID 8028TetrahydrofuranSolvent2×HCID 8058HexaneSolvent

Procedure

o-Tolylacetic acid (4.56 g.) in THF (50 ml.) was treated at 5°-10° C. under argon with a 1.6M solution (36.0 ml.) of butyllithium in hexane. After 1 hour the solution obtained was added dropwise to a solution of methyl 7-formylheptanoate (5.68 g.) in dry THF (50 ml.) at -30 ° to -50° C. during 30 minutes. The mixture was stirred for 1.5 hours at the same temperature. Acetic acid (3.5 ml. ) was then added carefully and the mixture was evaporated. The residue was partitioned between ether (100 ml.) and saturated sodium bicarbonate solution (50 ml.). The aqueous layer was acidified to pH 4 (HCl) and extracted thoroughly with ether. The combined extracts were washed with water, dried (MgSO4) and evaporated. The residual oil was purified by medium pressure liquid chromatography on silica (190 g.), eluting with 30% v/v ethyl acetate/hexane, to give methyl 9-carboxy-8-hydroxy-9-o-tolylnonanoate (A) as an oil (1.94 g., single diastereoisomer);NMR : 1-1.7 (10H,m), 2.1-2.5 (5H,m), 3.6 (3H,s), 3.8-4.3 (2H,m), 6.7 (2H,br s), 7.2 (4H,s); m/e (chemical ionisation): 323 (M+ +H), 340 (M+ +NH4).

Workup

  1. customAfter 1 hour the solution obtained
  2. customthe mixture was evaporated
  3. customThe residue was partitioned between ether (100 ml.) and saturated sodium bicarbonate solution (50 ml.)
  4. extractionextracted thoroughly with ether
  5. washThe combined extracts were washed with water
  6. dry with materialdried (MgSO4)
  7. customevaporated
  8. customThe residual oil was purified by medium pressure liquid chromatography on silica (190 g.)
  9. washeluting with 30% v/v ethyl acetate/hexane

Sources & evidence

ORD record
ord-596996d6df234f4396d66ed5bab2cd8f
Source dataset
uspto-grants-1987_11
Patent number
US04704399

Reaction notes

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