Benzenepropanoic acid → HCID 14423996, compound

HRID 621414Notes

Reaction equation

HRID 621414 reaction equation
[C:1]1([CH2:7][CH2:8][C:9]([OH:11])=O)[CH:6]=[CH:5][CH:4]=[CH:3][CH:2]=1.S(Cl)(Cl)=O.BrN1C(=O)CCC1=O.[NH2:24][C:25]1[CH:30]=[C:29]([N+:31]([O-:33])=[O:32])[CH:28]=[CH:27][C:26]=1[OH:34].CN(C)C1C=CC=CC=1>Br.O1CCCC1.C(Cl)(Cl)(Cl)Cl>[CH2:7]([CH:8]1[C:9](=[O:11])[NH:24][C:25]2[CH:30]=[C:29]([N+:31]([O-:33])=[O:32])[CH:28]=[CH:27][C:26]=2[O:34]1)[C:1]1[CH:2]=[CH:3][CH:4]=[CH:5][CH:6]=1

Participants

9

Reactant 5

HCID 107Benzenepropanoic acidHCID 949N,N-DimethylanilineHCID 24386Thionyl ChlorideHCID 67184N-bromobutanimideHCID 36133892-Amino-4-Nitrophenol

Product 1

HCID 14423996HCID 14423996, compoundYield 54%

Reagents, catalysts & solvents 3

HCID 260Hydrogen BromideCatalystHCID 5943Carbon TetrachlorideSolvent2×HCID 8028TetrahydrofuranSolvent2×

Conditions

Temperature
70 °C

Procedure

A mixture of 12.0 g of 3-phenylpropionic acid, 25 ml of thionylchloride and 8 ml of carbon tetrachloride are heated at 70° C. for 45 minutes. Then, 10.7 g of N-bromosuccinimide, 40 ml of carbon tetrachloride and 6 drops of 48% hydrobromic acid are further added thereto, and the mixture is heated for 1 hour. After cooling, insoluble materials are filtered off, and the filtrate is condensed to dryness. The residue is dissolved in 20 ml of tetrahydrofuran, and the mixture is added dropwise to 120 ml of a tetrahydrofuran solution containing 12.3 g of 2-amino-4-nitrophenol and 14.5 g of N,N-dimethylaniline under ice cooling. After stirring at room temperature for 40 minutes, the mixture is evaporated to remove the solvent. Water is added to the residue, and the mixture is extracted with ethyl acetate, dried and evaporated to remove the solvent. Then, the residue is dissolved in 200 ml of acetone. 41.4 g of potassium carbonate are added thereto, and the mixture is refluxed for 1 hour. After cooling, the reaction mixture is poured into water. Crystalline precipitates are collected by filtration, washed with water, dried and recrystallised from a mixture of ethyl acetate and n-hexane to give 12.25 g of 2-benzyl-6-nitro-3-oxo-1,4-benzoxazine.

Workup

  1. temperaturethe mixture is heated for 1 hour
  2. temperatureAfter cooling
  3. filtrationinsoluble materials are filtered off
  4. customcondensed to dryness
  5. customthe mixture is evaporated
  6. customto remove the solvent
  7. additionWater is added to the residue
  8. extractionthe mixture is extracted with ethyl acetate
  9. customdried
  10. customevaporated
  11. customto remove the solvent
  12. dissolutionThen, the residue is dissolved in 200 ml of acetone
  13. addition41.4 g of potassium carbonate are added
  14. temperaturethe mixture is refluxed for 1 hour
  15. temperatureAfter cooling
  16. additionthe reaction mixture is poured into water
  17. customCrystalline precipitates
  18. filtrationare collected by filtration
  19. washwashed with water
  20. customdried
  21. customrecrystallised from a mixture of ethyl acetate and n-hexane

Sources & evidence

ORD record
ord-69e5ee7f1a474f13bdc85b36a547a2ca
Source dataset
uspto-grants-1989_04
Patent number
US04824833

Reaction notes

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