Acetic Acid → p-Chloro-beta-nitrostyrene

HRID 1184980Notes

Reaction equation

HRID 1184980 reaction equation
C(O)(=O)C.[Cl:5][C:6]1[CH:13]=[CH:12][C:9]([CH:10]=O)=[CH:8][CH:7]=1.C(N)C1C=CC=CC=1.[N+:22]([CH3:25])([O-:24])=[O:23]>O>[Cl:5][C:6]1[CH:13]=[CH:12][C:9]([CH:10]=[CH:25][N+:22]([O-:24])=[O:23])=[CH:8][CH:7]=1

Participants

6

Reactant 4

HCID 176Acetic AcidHCID 6375NitromethaneHCID 7504BenzylamineHCID 77264-Chlorobenzaldehyde

Product 1

HCID 95339p-Chloro-beta-nitrostyrene

Reagents, catalysts & solvents 1

HCID 962WaterSolvent

Conditions

Temperature
78 °C

Procedure

To 1066.8 g of acetic acid were added 200.14 g (1.356 mol) of 4-chlorobenzaldehyde, and 153.4 g (1.429 mol) of benzylamine, and the added components were dissolved in the acid. This solution was heated to 78° C., and 325.7 g (5.336 mol) of nitromethane was dropwise added thereto at 78 to 80° C. over 2 hours and 50 minutes. Thereafter, the solution was stirred at about 79° C. for 40 minutes. Next, 1016 g of water was dropwise added thereto at about 50° C. over 2 hours and 25 minutes. The mixture was cooled to about 10° C. and was stirred at 6 to 10° C. for 1 hour and 50 minutes. The obtained crystals were filtrated, and washed with 1016.2 g of water. The wet crystals were dissolved into 572.8 g of toluene at about 50° C. The resultant was separated into two phases, and the water phase thereof was removed. The remaining phase was washed with 330.8 g of water. By HPLC, 803.24 g of the toluene phase was analyzed. As a result, the phase contained 253.8 g of 4-chloro-β-nitrostyrene. The yield thereof was 97.1%.

Workup

  1. dissolutionthe added components were dissolved in the acid
  2. custom50 minutes
  3. waitat about 50° C. over 2 hours
  4. custom25 minutes
  5. temperatureThe mixture was cooled to about 10° C.
  6. stirringwas stirred at 6 to 10° C. for 1 hour and 50 minutes
  7. filtrationThe obtained crystals were filtrated
  8. washwashed with 1016.2 g of water
  9. dissolutionThe wet crystals were dissolved into 572.8 g of toluene at about 50° C
  10. customThe resultant was separated into two phases
  11. customthe water phase thereof was removed
  12. washThe remaining phase was washed with 330.8 g of water
  13. customThe yield

Sources & evidence

ORD record
ord-12f2b8e7cce5436ea4331fdebc3519ae
Source dataset
uspto-grants-2014_03
Patent number
US08669395B2

Reaction notes

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