Hydrochloric Acid → 4-Amino-4'-chlorobenzophenone

HRID 1778210Notes

Reaction equation

HRID 1778210 reaction equation
[Cl:1][C:2]1[CH:7]=[CH:6][C:5]([C:8]([C:10]2[CH:15]=[CH:14][C:13]([N+:16]([O-])=O)=[CH:12][CH:11]=2)=[O:9])=[CH:4][CH:3]=1.Cl.Cl[Sn]Cl.[OH-].[Na+]>O>[NH2:16][C:13]1[CH:14]=[CH:15][C:10]([C:8]([C:5]2[CH:6]=[CH:7][C:2]([Cl:1])=[CH:3][CH:4]=2)=[O:9])=[CH:11][CH:12]=1

Participants

6

Reactant 4

HCID 313Hydrochloric AcidHCID 14798Sodium Hydroxide2×HCID 24479Stannous ChlorideHCID 3477714-Chloro-4'-nitrobenzophenone

Product 1

HCID 35287064-Amino-4'-chlorobenzophenone

Reagents, catalysts & solvents 1

HCID 962WaterSolvent

Conditions

Temperature
36 °C

Procedure

A 3-L 3-neck flask equipped with a thermocouple controller, a mechanical stirrer, a condenser, and a nitrogen inlet/outlet adapter was charged with (4-chlorophenyl)(4-nitrophenyl)methanone (132.0 g, 504.5 mmol), concentrated aqueous HCl (693.3 mL, 8.1 mol), and SnCl2 (313.3 g, 1.62 mol). The yellowish suspension was carefully heated to 36° C. with fast agitation (1000 rmp). The electric power to the heating mantle was turned off at 36° C. A moderate exotherm was observed, which gradually increased to 77° C. over 1 h with gas evolution to form a foamy suspension. The electric power was turned on at 77° C. again and gradually heated to 100° C. over 30 min and refluxed for 2 h. The reaction was cooled to 10° C., slowly poured into a mixture of ice (1 L) and 33% NaOH (1 L, 8.25 M) with fast stirring in an ice-water bath. The resulting yellowish slurry (pH=2-3) was adjusted to pH=9-10 with 50% NaOH. The resulting solid was collected by filtration and washed with deionized water (100 mL). The filtration cake was dried under air-suction at 20° C. overnight and then in a vacuum oven at 60° C. for 24 h to yield a yellowish solid. The yellowish solid (322 g) was suspended in deionized water (2 L) and extracted with EtOAc (2 L×3). The combined organic phases were washed with brine (1 L/each). The solvent was concentrated at 60° C. to yield (4-aminophenyl)(4-chlorophenyl)methanone as a slightly yellowish crystalline solid. (ES, m/z) 232, 234 (M+H)+

Workup

  1. customA 3-L 3-neck flask equipped with a thermocouple controller, a mechanical stirrer, a condenser, and a nitrogen inlet/outlet adapter
  2. customwas turned off at 36° C
  3. temperaturewhich gradually increased to 77° C. over 1 h with gas evolution
  4. customto form a foamy suspension
  5. customwas turned on at 77° C.
  6. temperaturegradually heated to 100° C. over 30 min
  7. temperaturerefluxed for 2 h
  8. temperatureThe reaction was cooled to 10° C.
  9. filtrationThe resulting solid was collected by filtration
  10. washwashed with deionized water (100 mL)
  11. customThe filtration cake was dried under air-suction at 20° C. overnight
  12. customin a vacuum oven at 60° C. for 24 h to yield a yellowish solid
  13. extractionextracted with EtOAc (2 L×3)
  14. washThe combined organic phases were washed with brine (1 L/each)
  15. concentrationThe solvent was concentrated at 60° C.

Sources & evidence

ORD record
ord-b5cd8cbb3aff45dea6035636abbd0e34
Source dataset
uspto-grants-2016_02
Patent number
US09266835B2

Reaction notes

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