Acetic Acid → HCID 12377875, compound

HRID 262336Notes

Reaction equation

HRID 262336 reaction equation
[C:1]([C:9]1[CH:14]=[C:13](N)[CH:12]=[CH:11][C:10]=1[N:16]1[C:20]([C:21]([O:23][CH3:24])=[O:22])=[CH:19][C:18]([C:25]([O:27][CH3:28])=[O:26])=[N:17]1)(=[O:8])[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1.CC(O)=O.N([O-])=O.[Na+].[NH4+].[OH-].[ClH:39]>O>[C:1]([C:9]1[CH:14]=[C:13]([Cl:39])[CH:12]=[CH:11][C:10]=1[N:16]1[C:20]([C:21]([O:23][CH3:24])=[O:22])=[CH:19][C:18]([C:25]([O:27][CH3:28])=[O:26])=[N:17]1)(=[O:8])[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1

Participants

7

Reactant 5

HCID 176Acetic AcidHCID 313Hydrochloric Acid2×HCID 14923Ammonium HydroxideHCID 12377874HCID 12377874, compoundHCID 23668193Sodium Nitrite

Product 1

HCID 12377875HCID 12377875, compound

Reagents, catalysts & solvents 1

HCID 962WaterSolvent2×

Procedure

To a solution of 13.1 g. (34.5 mmol) of the final product of Example 2 in 50 ml. HOAc and 75 ml. of 3N HCl, stirred at 3°, was added dropwise so as to maintain a temperature of 3°-6°, a solution of 2.50 g. (36.3 mmol) of sodium nitrite in 25 ml. H2O. When the addition was complete, the reaction was stirred at 3° for 20 minutes. A fresh solution of cuprous chloride in concentrated hydrochloric acid (prepared from 27 g. cupric sulfate pentahydrate*) was mixed with an equal volume of water and cooled to 3°. The diazotized solution, which had to be kept cold (<5°) at all times, was slowly poured into the vigorously stirred 5° cuprous chloride solution in several portions, in order to control foaming. When addition was complete, the reaction was stirred for one hour while slowly warming to room temperature, then heated on a steam bath to an internal temperature of 95°. After cooling to room temperature, the reaction was made basic with NH4OH and extracted well with CH2Cl2. The combined extracts were washed with brine, dried (Na2SO4) and concentrated in vacuo to a brown oil. This crude product was chromatographed on silica gel using a 2% EtOAc in benzene solution as eluent to give the final product. An analytical sample was prepared by recrystallization from ether/hexane and was obtained as colorless crystals: mp 118°-120°.

Workup

  1. additionwas added dropwise so as
  2. temperatureto maintain a temperature of 3°-6°
  3. additionWhen the addition
  4. temperaturecooled to 3°
  5. custom(<5°)
  6. additionWhen addition
  7. stirringthe reaction was stirred for one hour
  8. temperatureheated on a steam bath to an internal temperature of 95°
  9. temperatureAfter cooling to room temperature
  10. extractionextracted well with CH2Cl2
  11. washThe combined extracts were washed with brine
  12. dry with materialdried (Na2SO4)
  13. concentrationconcentrated in vacuo to a brown oil
  14. customThis crude product was chromatographed on silica gel using a 2% EtOAc in benzene solution as eluent

Sources & evidence

ORD record
ord-b533c751c009422da94c305a754f3133
Source dataset
uspto-grants-1979_05
Patent number
US04153799

Reaction notes

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