HCID 22646671, compound → HCID 22009952, compound

HRID 850675Notes

Reaction equation

HRID 850675 reaction equation
[NH2:1][C:2]1[CH:7]=[CH:6][C:5]([C:8]([CH3:15])([CH3:14])[C:9]([O:11][CH2:12][CH3:13])=[O:10])=[CH:4][C:3]=1[Br:16].[N:17]([O-])=O.[Na+]>Cl.O>[Br:16][C:3]1[CH:4]=[C:5]([C:8]([CH3:15])([CH3:14])[C:9]([O:11][CH2:12][CH3:13])=[O:10])[CH:6]=[CH:7][C:2]=1[NH:1][NH2:17]

Participants

5

Reactant 2

HCID 22646671HCID 22646671, compoundHCID 23668193Sodium Nitrite

Product 1

HCID 22009952HCID 22009952, compound

Reagents, catalysts & solvents 2

HCID 313Hydrochloric AcidSolventHCID 962WaterSolvent

Procedure

A solution of 0.091 g of ethyl 2-(4-amino-3-bromophenyl)-2-methylpropionate in 0.32 mL of concentrated hydrochloric acid was stirred at -10 to -5° C. in an ice-acetone bath as a solution of 0.023 g of sodium nitrite in 0.20 mL of water was added dropwise over about 15 minutes. Stirring was continued at this temperature for an additional 30 minutes. Next, the supernatant was removed by syringe and added dropwise over 10 minutes to a solution of 0.36 g of stannous chloride dihydrate in 0.25 mL of concentrated hydrochloric acid stirred under nitrogen in an ice-acetone bath. The addition was carried out at such a rate that the internal temperature remained at about -5° C. A gummy material separated during the addition. After completion of the addition, stirring was continued at -10 to -5° C. for 1 hour. The mixture was then diluted with 60 mL ethyl acetate and washed with sodium carbonate. The organic layer was washed with water and brine then dried over magnesium sulfate. Concentration in vacuo gave the crude title compound.

Workup

  1. additionwas added dropwise over about 15 minutes
  2. customNext, the supernatant was removed by syringe
  3. additionadded dropwise over 10 minutes to a solution of 0.36 g of stannous chloride dihydrate in 0.25 mL of concentrated hydrochloric acid
  4. stirringstirred under nitrogen in an ice-acetone bath
  5. additionThe addition
  6. customremained at about -5° C
  7. customA gummy material separated during the addition
  8. additionAfter completion of the addition
  9. stirringstirring
  10. waitwas continued at -10 to -5° C. for 1 hour
  11. additionThe mixture was then diluted with 60 mL ethyl acetate
  12. washwashed with sodium carbonate
  13. washThe organic layer was washed with water and brine
  14. dry with materialthen dried over magnesium sulfate
  15. concentrationConcentration in vacuo

Sources & evidence

ORD record
ord-f4d68be7b1594a7584788d1eb3a96984
Source dataset
uspto-grants-2000_01
Patent number
US06017944

Reaction notes

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