Sodium Chloride → HCID 7017105, compound

HRID 1155669Notes

Reaction equation

HRID 1155669 reaction equation
C([Li])CCC.[C:6]1([CH2:12][C:13]2[S:14][CH:15]=[CH:16][CH:17]=2)[CH:11]=[CH:10][CH:9]=[CH:8][CH:7]=1.CN(C)[CH:20]=[O:21].[Cl-].[Na+]>CCCCCC.C(OCC)C>[C:6]1([CH2:12][C:13]2[S:14][C:15]([CH:20]=[O:21])=[CH:16][CH:17]=2)[CH:7]=[CH:8][CH:9]=[CH:10][CH:11]=1

Participants

7

Reactant 4

HCID 5234Sodium ChlorideHCID 6228DimethylformamideHCID 139391Thiophene, 2-(phenylmethyl)-HCID 178418339Butyllithium

Product 1

HCID 7017105HCID 7017105, compoundYield 86.8%

Reagents, catalysts & solvents 2

HCID 3283Diethyl EtherSolvent3×HCID 8058HexaneSolvent

Procedure

Under a nitrogen atmosphere, 25.7 grams (0.40 mole) of n-butyllithium in 168 ml of hexane was added by syringe to 300 ml of diethyl ether. The stirred solution was cooled in an ice-water bath and 70.0 grams (0.40 mole) of 2-(phenylmethyl)thiophene in 100 ml of diethyl ether was added dropwise during a 0.75 hour period. Upon complete addition, the cooling bath was removed and the reaction mixture stirred for 1.5 hours, then transferred to a Morton flask using a nitrogen pressure differential and tubing connecting the reaction vessel with the Morton flask. A solution of 32.3 grams (0.44 mole) of dimethylformamide in 200 ml of diethyl ether was added dropwise. During the addition the reaction mixture was allowed to warm to reflux temperature, then was stirred for 4.5 hours while cooling to ambient temperature. Stirring was continued for an additional 16 hours. The reaction mixture was poured into 400 grams of ice, and solid sodium chloride was added to saturation. After an additional 0.25 hour stirring, the organic layer was separated and the aqueous layer was extracted with two portions of 400 ml each of diethyl ether. The extracts and the organic layer above were combined and washed, in succession, with one portion of 300 ml of a saturated aqueous solution of sodium chloride, one portion of 300 ml of aqueous 2 N hydrochloric acid, one portion of 300 ml of a saturated aqueous solution of sodium chloride, one portion of 300 ml of a saturated aqueous solution of sodium bicarbonate, and finally, one portion of 300 ml of a saturated aqueous solution of sodium chloride. The organic layer was dried with magnesium sulfate, filtered and the filtrate concentrated under reduced pressure to give a residual oil. The residual oil was distilled under reduced pressure using a Kugelrohr distilling system to give 70.2 grams of 5-(phenylmethyl)thiophene-2-carboxaldehyde; b.p. 105° C./0.25 mm.

Workup

  1. temperatureThe stirred solution was cooled in an ice-water bath
  2. additionUpon complete addition
  3. customthe cooling bath was removed
  4. additionDuring the addition the reaction mixture
  5. temperatureto warm
  6. temperatureto reflux temperature
  7. stirringwas stirred for 4.5 hours
  8. stirringStirring
  9. waitwas continued for an additional 16 hours
  10. additionwas added to saturation
  11. stirringAfter an additional 0.25 hour stirring
  12. customthe organic layer was separated
  13. extractionthe aqueous layer was extracted with two portions of 400 ml each of diethyl ether
  14. washwashed, in succession, with one portion of 300 ml of a saturated aqueous solution of sodium chloride, one portion of 300 ml of aqueous 2 N hydrochloric acid, one portion of 300 ml of a saturated aqueous solution of sodium chloride, one portion of 300 ml of a saturated aqueous solution of sodium bicarbonate
  15. dry with materialThe organic layer was dried with magnesium sulfate
  16. filtrationfiltered
  17. concentrationthe filtrate concentrated under reduced pressure
  18. customto give a residual oil
  19. distillationThe residual oil was distilled under reduced pressure
  20. distillationdistilling system

Sources & evidence

ORD record
ord-754154d8b3054ea4ac070d227303a4f1
Source dataset
uspto-grants-1982_06
Patent number
US04332815

Reaction notes

Loading…