Hydrochloric Acid → HCID 22621249, compound

HRID 841192Notes

Reaction equation

HRID 841192 reaction equation
N[C:2]1[CH:7]=[C:6]([S:8][C:9]2[CH:14]=[CH:13][C:12]([Br:15])=[CH:11][CH:10]=2)[CH:5]=[CH:4][C:3]=1[N+:16]([O-:18])=[O:17].N([O-])=O.[Na+].S(=O)(=O)(O)N.C1(C)C=CC=CC=1.[ClH:35]>C(O)(=O)C.O>[Br:15][C:12]1[CH:13]=[CH:14][C:9]([S:8][C:6]2[CH:5]=[CH:4][C:3]([N+:16]([O-:18])=[O:17])=[C:2]([Cl:35])[CH:7]=2)=[CH:10][CH:11]=1

Participants

8

Reactant 5

HCID 313Hydrochloric Acid2×HCID 1140TolueneHCID 5987Sulfamic AcidHCID 22621246HCID 22621246, compoundHCID 23668193Sodium Nitrite

Product 1

HCID 22621249HCID 22621249, compound

Reagents, catalysts & solvents 2

HCID 176Acetic AcidSolventHCID 962WaterSolvent2×

Procedure

A solution of 2-amino-4-(4-bromophenylthio)nitrobenzene (Method 15) (2.25 g) in warm glacial acetic acid (13 ml) was poured onto ice (20 ml). Concentrated hydrochloric acid (3.95 ml) was added and the mixture was stirred and cooled to <5° C. A solution of sodium nitrite (0.524 g) in water (5 ml) was added over 7 minutes and the mixture was stirred for 2 hours at 0-5° C. Aqueous sulphamic acid solution (10% w/v) was added until a negative starch iodide test was observed. Meanwhile toluene was added to a solution of cuprous chloride (0.745 g) in water (1 ml) and concentrated hydrochloric acid (1.15 ml) and the mixture was cooled to <0° C. The first preparation (diazonium salt) was then added to the cold cuprous chloride mixture over 5 minutes and the resultant mixture was stirred at ambient temperature for 18 hours. The organic layer was separated and the aqueous layer was extracted with toluene (3×10 ml). The organic extracts were combined, washed with water and brine then dried. Volatile material was removed by evaporation and the residue was purified by chromatography on a silica gel Mega Bond Elut column eluting with 0-15% ethyl acetate/hexane to give the title compound (0.644 g). MS: 343 (M+).

Workup

  1. temperaturecooled to <5° C
  2. stirringthe mixture was stirred for 2 hours at 0-5° C
  3. temperaturethe mixture was cooled to <0° C
  4. customThe organic layer was separated
  5. extractionthe aqueous layer was extracted with toluene (3×10 ml)
  6. washwashed with water and brine
  7. customthen dried
  8. customVolatile material was removed by evaporation
  9. customthe residue was purified by chromatography on a silica gel Mega Bond Elut column
  10. washeluting with 0-15% ethyl acetate/hexane

Sources & evidence

ORD record
ord-c6bf945722314ae4b3e0a3cbef1901d8
Source dataset
uspto-grants-2002_04
Patent number
US06369273B1

Reaction notes

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