Hydrochloric Acid → HCID 13139571, compound

HRID 2398774Notes

Reaction equation

HRID 2398774 reaction equation
N[C:2]1[CH:3]=[C:4]([CH:8]=[CH:9][C:10]=1[Cl:11])[C:5]([OH:7])=[O:6].Cl.N([O-])=O.[Na+].O(CC)C([S-])=[S:19].[K+]>O.[Ni](Cl)Cl>[Cl:11][C:10]1[CH:9]=[CH:8][C:4]([C:5]([OH:7])=[O:6])=[CH:3][C:2]=1[SH:19]

Participants

7

Reactant 4

HCID 313Hydrochloric AcidHCID 760923-Amino-4-chlorobenzoic acidHCID 2735045Potassium ethylxanthateHCID 23668193Sodium Nitrite

Product 1

HCID 13139571HCID 13139571, compound

Reagents, catalysts & solvents 2

HCID 24385Nickel DichlorideCatalystHCID 962WaterSolvent2×

Conditions

Temperature
0 °C

Procedure

3-Amino-4-chlorobenzoic acid (34.3g) was added to 5N hydrochloric acid (120 ml) and cooled to 0° C. To the stirred suspension was added a solution of sodium nitrite (14.5g) in water (35 ml) over 30 min. with the temperature maintained at 0° to 5° C. The yellow diazonium solution, containing some suspended solid was added to a solution of potassium ethyl xanthate (37.5g) in water (60 ml), containing 0.2g nickel chloride, at 45°-50° C. Nitrogen evolution occurred and the yellow solid which precipitated at first decomposed to a red oil which then solidified. When the addition was complete, the mixture was heated to 70° C., cooled, and the red solid filtered off and washed with water. It was then boiled with a solution of potassium hydroxide (60 g) in water (300 ml) for 2 hr., cooled, filtered and acidified with excess hydrochloric acid. Thin-layer chromatography indicated the presence of 2 components in the precipitated creamy solid. Recrystallisation from acetic acid yielded a by-product, m.p. 240°-290° C., and dilution of the recrystallisation liquors gave a solid which was recrystallised from aqueous ethanol yielding mainly 4-chloro-3-mercapto-benzoic acid, m.p. 209°-211° C.

Workup

  1. temperaturemaintained at 0° to 5° C
  2. customat 45°-50° C
  3. customthe yellow solid which precipitated
  4. additionWhen the addition
  5. temperaturethe mixture was heated to 70° C.
  6. temperaturecooled
  7. filtrationthe red solid filtered off
  8. washwashed with water
  9. temperature, cooled
  10. filtrationfiltered
  11. customRecrystallisation from acetic acid
  12. customyielded
  13. customa by-product, m.p. 240°-290° C., and dilution of the recrystallisation liquors
  14. customgave a solid which
  15. customwas recrystallised from aqueous ethanol yielding mainly 4-chloro-3-mercapto-benzoic acid, m.p. 209°-211° C.

Sources & evidence

ORD record
ord-d1bccde971f548989bbfa04fc3c4d2d9
Source dataset
uspto-grants-1977_05
Patent number
US04025635

Reaction notes

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