Ethanol → HCID 19075898, compound

HRID 2257240Notes

Reaction equation

HRID 2257240 reaction equation
O1CCCCC1[O:7][CH:8]([C:14]([O-:16])=[O:15])[C:9]([O:11][CH2:12][CH3:13])=[O:10].Cl.[N:18]1[CH:23]=[CH:22][CH:21]=[C:20]([CH2:24]Cl)[CH:19]=1.[CH3:26][CH2:27]O>>[N:18]1[CH:23]=[CH:22][CH:21]=[C:20]([CH2:24][C:8]([OH:7])([C:9]([O:11][CH2:12][CH3:13])=[O:10])[C:14]([O:16][CH2:26][CH3:27])=[O:15])[CH:19]=1

Participants

4

Reactant 3

HCID 702EthanolHCID 233943-(Chloromethyl)pyridine hydrochlorideHCID 86751148HCID 86751148, compound

Product 1

HCID 19075898HCID 19075898, compound

Procedure

4.3 g of ethyl 2-(2-tetrahydropyranyloxy)-1,3-propanedioate are added to 11 ml of a Na ethoxide solution (prepared from 0.72 g of Na) under stirring, shielding from humidity, keeping the temperature at 0° to 5° C. After 1 h, a solution of 2.4 g of 3-pyridylmethyl chloride hydrochloride in 8 ml of EtOH is dropped therein. The reaction mixture, which turns suddenly red, is kept under stirring at r.t. for 24 hours more. EtOH is evaporated off and the residue is partitioned between AcOEt and a 20% solution of monobasic potassium phosphate in water. The organic phase is separated, evaporated to dryness and the residue (about 4 g) is dissolved with 16 ml of 2N HCl, keeping r.t. for 4 hours; ethyl tartronate is removed by extraction with AcOEt. From the aqueous phases after alkalization to pH 8-8.5, subsequent extraction with AcOEt, the usual work up of the organic extract and subsequent chromatography on silica gel, 1.8 g of ethyl 3-(pyrid-3-yl)-2-hydroxy-2-ethoxycarbonyl-propanoate are obtained, oil, I.R.: 3500, 3000, 1740, 1590 cm-1, TLC (SiO2 : one spot Rf : 0.24 eluent AcOEt), H-NMR(CDCl3) δ (TMS): 1.2-1.3 t, 3.3 s , 4.15-4.3 q, 7.1-7.2 q, 7.6-7.65 m, 8.4-8.5 m.

Workup

  1. customat 0° to 5° C
  2. stirringunder stirring at r.t. for 24 hours more
  3. customEtOH is evaporated off
  4. customthe residue is partitioned between AcOEt
  5. customThe organic phase is separated
  6. customevaporated to dryness
  7. dissolutionthe residue (about 4 g) is dissolved with 16 ml of 2N HCl
  8. waitkeeping r.t. for 4 hours
  9. customethyl tartronate is removed by extraction with AcOEt
  10. extractionFrom the aqueous phases after alkalization to pH 8-8.5, subsequent extraction with AcOEt
  11. extractionthe usual work up of the organic extract

Sources & evidence

ORD record
ord-5503636018b140acaa96be9df1731479
Source dataset
uspto-grants-1997_08
Patent number
US05656656

Reaction notes

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