Hydrochloric Acid → 3-Chloronaphthalene-2-carboxylic acid

HRID 1270744Notes

Reaction equation

HRID 1270744 reaction equation
OS(O)(=O)=O.N([O-])=O.[Na+].N[C:11]1[C:12]([C:21]([OH:23])=[O:22])=[CH:13][C:14]2[C:19]([CH:20]=1)=[CH:18][CH:17]=[CH:16][CH:15]=2.O.[ClH:25]>CC(O)=O.C(Cl)Cl.Cl[Cu]>[Cl:25][C:11]1[C:12]([C:21]([OH:23])=[O:22])=[CH:13][C:14]2[C:19]([CH:20]=1)=[CH:18][CH:17]=[CH:16][CH:15]=2

Participants

9

Reactant 5

HCID 313Hydrochloric AcidHCID 962WaterHCID 1118Sulfuric AcidHCID 222443-Amino-2-naphthoic acidHCID 23668193Sodium Nitrite

Product 1

HCID 134630003-Chloronaphthalene-2-carboxylic acid

Reagents, catalysts & solvents 3

HCID 62652Cuprous chlorideCatalystHCID 176Acetic AcidSolventHCID 6344DichloromethaneSolvent

Procedure

To a flask containing 35 mL of concentrated H2SO4 is added 3.31 g NaNO2 (47.9 mmol) slowly over 15 minutes. The mixture is stirred an additional 15 minutes before being cooled to room temperature in a cold water bath. A solution of 8.14 g 3-amino-2-naphthoic acid (43.5 mmol) in 65 mL HOAc is added slowly dropwise, keeping the reaction temperature below 40° C. The mixture is stirred for 30 minutes and then poured carefully into an ice-cold solution of 10.14 g CuCl (102.2 mmol) in 65 mL of concentrated HCl. The mixture is heated to 80° C. and stirred for 30 minutes before adding 200 mL of H2O. After stirring an additional 15 minutes, the mixture is filtered and washed with H2O to give a gray solid. The solid is dissolved in 500 mL of CH2Cl2 and the solution is washed 2 times with 100 mL saturated aqueous brine and dried over Na2SO4. Evaporation of the solvents gives a solid that is dried in vacuo to give 3-chloro-2-naphthoic acid as a brown solid.

Workup

  1. customthe reaction temperature below 40° C
  2. stirringThe mixture is stirred for 30 minutes
  3. temperatureThe mixture is heated to 80° C.
  4. stirringstirred for 30 minutes
  5. stirringAfter stirring an additional 15 minutes
  6. filtrationthe mixture is filtered
  7. washwashed with H2O
  8. customto give a gray solid
  9. washthe solution is washed 2 times with 100 mL saturated aqueous brine
  10. dry with materialdried over Na2SO4
  11. customEvaporation of the solvents
  12. customgives a solid
  13. customthat is dried in vacuo

Sources & evidence

ORD record
ord-daf55847923d4e85851e97c039e4b5ad
Source dataset
uspto-grants-2007_04
Patent number
US07202364B2

Reaction notes

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