Hydrochloric Acid → HCID 21855806, compound

HRID 614188Notes

Reaction equation

HRID 614188 reaction equation
C1([Mg]Br)C=CC=CC=1.[C:9]([CH2:11][C:12]([O:14][CH2:15][CH3:16])=[O:13])#[N:10].Br[C:18]1[CH:19]=[C:20]([CH3:24])[CH:21]=[CH:22][CH:23]=1.[Mg].[NH4+].[Cl-].Cl>CCOCC.O>[NH2:10][C:9]([C:18]1[CH:23]=[CH:22][CH:21]=[C:20]([CH3:24])[CH:19]=1)=[CH:11][C:12]([O:14][CH2:15][CH3:16])=[O:13]

Participants

9

Reactant 6

HCID 313Hydrochloric AcidHCID 7764Ethyl cyanoacetateHCID 115603-BromotolueneHCID 25517Ammonium ChlorideHCID 5462224MagnesiumHCID 178418255HCID 178418255, compound

Product 1

HCID 21855806HCID 21855806, compoundYield 65.3%

Reagents, catalysts & solvents 2

HCID 962WaterSolventHCID 3283Diethyl EtherSolvent3×

Procedure

To 202 ml of 2.9 M phenylmagnesium bromide in ether (0.585 mol) was aded 100 ml of ether. Then, 66.1 g (0.585 mol) of ethyl cyanoacetate was added over a few minutes with stirring at -40° to -15°. A heavy, thick precipitate formed that made stirring difficult. The mixture was allowed to warm slowly to 20°. Then, the Grignard reagent prepared from 100 g (0.585 mol) of 3-bromotoluene and 14.4 g (0.593 mol) of magnesium turnings in 300 ml of ether was added. The mixture was stirred at reflux for 4 hours, cooled, and poured slowly with stirring into 1 l. of ice-water mixture in which 62.6 g (1.17 mol) of NH4Cl was dissolved. Then, an ice-cold solution of 1.17 mol of HCl in 300 ml of water was added with stirring. The two layers were shaken together and separated. The aqueous layer was extracted with two 200-ml portions of ether. The ether layers were combined, dried (CaSO4), and concentrated under aspirator vacuum to 112.0 g of oil that contained 78.4 g (65% yield) of product (gas chromatography assay with internal standard). The oil was distilled to give 83.2 g of 89% pure product (62% yield of ester), boiling point 120°-130° (0.08 torr). Redistillation of the product through a fractionating column gave 57.2 g (48%) of 97% pure product, boiling point 118° (0.05 torr). A small sample was redistilled to give 100% pure material, boiling point 118° (0.1 torr).

Workup

  1. customA heavy, thick precipitate formed
  2. stirringthat made stirring difficult
  3. temperatureto warm slowly to 20°
  4. additionwas added
  5. stirringThe mixture was stirred
  6. temperatureat reflux for 4 hours
  7. temperaturecooled
  8. additionpoured slowly
  9. stirringwith stirring into 1 l
  10. stirringwith stirring
  11. stirringThe two layers were shaken together
  12. customseparated
  13. extractionThe aqueous layer was extracted with two 200-ml portions of ether
  14. dry with materialdried (CaSO4)
  15. concentrationconcentrated under aspirator vacuum to 112.0 g of oil that

Sources & evidence

ORD record
ord-db960153bb564626961012441d06ee7f
Source dataset
uspto-grants-1979_03
Patent number
US04144047

Reaction notes

Loading…