Ethyl formate → HCID 13231875, compound

HRID 1980221Notes

Reaction equation

HRID 1980221 reaction equation
[Cl:1][C:2]1[CH2:3][C:4]2[C:9]([CH:10]=1)=[CH:8][CH:7]=[CH:6][CH:5]=2.[CH:11](OCC)=[O:12].[H-].[Na+].[H][H].[BH4-].[Na+]>C(O)(=O)C.O.CCOCC>[Cl:1][C:2]1[CH:3]([CH2:11][OH:12])[C:4]2[C:9]([CH:10]=1)=[CH:8][CH:7]=[CH:6][CH:5]=2

Participants

9

Reactant 5

HCID 8025Ethyl formateHCID 24758Sodium hydride2×HCID 4311764Sodium borohydrideHCID 12611492HCID 12611492, compoundHCID 178418361HCID 178418361, compound2×

Product 1

HCID 13231875HCID 13231875, compound

Reagents, catalysts & solvents 3

HCID 176Acetic AcidSolventHCID 962WaterSolvent2×HCID 3283Diethyl EtherSolvent

Procedure

A flask is charged with 75 gr (0.5 mol) 2-chloroindene, 50 ml (0.6 mol) ethyl formate, 400 ml dry ether and 23 gr (0.6 mol) sodium hydride (55-60% dispersion in oil). The mixture is heated to reflux to start the reaction, as indicated by a vigorous hydrogen evolution. The flask is cooled in an ice water bath, until hydrogen evolution subsides, then refluxed again for an additional ten minutes. Excess sodium hydride is carefully decomposed with water, and more water is added to form two layers. The aldehyde dissolves in the aqueous basic solution which is extracted several times with ether. To the aqueous solution are added 19 gr (0.5 mol) sodium borohydride. With vigorous stirring and cooling in an ice water bath, glacial acetic acid is added dropwise at a rate of a drop per second, until the mixture becomes acidic. The alcohol is extracted with ether and the organic solution dried and evaporated. The crude alcohol (75 gr, 83%) is recrystallized from carbon tetrachloride, to give white crystals, m.p. 104°-105° C. Elemental analysis: Calc. for C10H5ClO: C, 66.49%. H, 5.02%. Cl, 19.63% Found: C, 66.20%. H, 5.02%. Cl, 19.90. NMR spectrum (CDCl3, δppm): 2.05 (s, 1H), 3.50 (s, 2H), 4.65 (t, 2H), 7.1-7.6 (m, 4H).

Workup

  1. temperatureThe mixture is heated
  2. temperatureto reflux
  3. customthe reaction
  4. temperaturerefluxed again for an additional ten minutes
  5. additionis added
  6. customto form two layers
  7. extractionis extracted several times with ether
  8. temperaturecooling in an ice water bath
  9. extractionThe alcohol is extracted with ether
  10. customthe organic solution dried
  11. customevaporated
  12. customThe crude alcohol (75 gr, 83%) is recrystallized from carbon tetrachloride
  13. customto give white crystals, m.p. 104°-105° C

Sources & evidence

ORD record
ord-6bbde9e1ebc44d3ea4a82c402ae4c170
Source dataset
uspto-grants-1985_04
Patent number
US04508657

Reaction notes

Loading…