Malonic Acid → 2-Propen-1-ol, 3-(3-pyridinyl)-

HRID 1974504Notes

Reaction equation

HRID 1974504 reaction equation
ClC(OCC)=O.[N:7]1[CH:12]=[CH:11][CH:10]=[C:9]([CH:13]=[CH:14][C:15](O)=[O:16])[CH:8]=1.N1C=CC=C(C=O)C=1.C(O)(=O)CC(O)=O>O1CCCC1.C(N(CC)CC)C>[N:7]1[CH:12]=[CH:11][CH:10]=[C:9]([CH:13]=[CH:14][CH2:15][OH:16])[CH:8]=1

Participants

7

Reactant 4

HCID 867Malonic AcidHCID 103713-PyridinecarboxaldehydeHCID 10928Ethyl chloroformateHCID 1019843-(3-Pyridinyl)-2-propenoic acid

Product 1

HCID 35635042-Propen-1-ol, 3-(3-pyridinyl)-

Reagents, catalysts & solvents 2

HCID 8028TetrahydrofuranSolventHCID 8471TriethylamineSolvent

Conditions

Temperature
-15 °C

Procedure

Triethylamine (1.4 ml) and ethyl chloroformate (0.94 ml) were added in succession to a stirred suspension of 3-(3-pyridyl)propenoic acid [1.49 g; prepared from pyridine-3-carbaldehyde and malonic acid using the general method described in Organic Synthesis, Coll, Vol. 4, 1963, 730] in tetrahydrofuran (40 ml) which had been cooled to -15° C. The mixture was stirred at this temperature for 30 minutes and then filtered. The filtrate was added over 15 minutes to a stirred solution of sodium borohydride (0.94 g) in water (8 ml) which had been cooled in an ice-bath. The mixture was stirred at ambient temperature for 3 hours then partitioned between diethyl ether and a dilute aqueous sodium hydroxide solution. The aqueous layer was extracted with diethyl ether and ethyl acetate. The combined organic extracts were washed with a saturated aqueous sodium chloride solution, dried (Na2SO4) and evaporated. The residue was purified by column chromatography eluting with toluene/ethyl acetate (1/1 v/v) to give 3-(3-pyridyl)prop-2-en-1-ol as an oil (0.84 g).

Workup

  1. filtrationfiltered
  2. additionThe filtrate was added over 15 minutes to a stirred solution of sodium borohydride (0.94 g) in water (8 ml) which
  3. temperaturehad been cooled in an ice-bath
  4. stirringThe mixture was stirred at ambient temperature for 3 hours
  5. customthen partitioned between diethyl ether
  6. extractionThe aqueous layer was extracted with diethyl ether and ethyl acetate
  7. washThe combined organic extracts were washed with a saturated aqueous sodium chloride solution
  8. dry with materialdried (Na2SO4)
  9. customevaporated
  10. customThe residue was purified by column chromatography
  11. washeluting with toluene/ethyl acetate (1/1 v/v)

Sources & evidence

ORD record
ord-d581718850834b509bbb2734c338e330
Source dataset
uspto-grants-1994_02
Patent number
US05283245

Reaction notes

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