Trifluoroacetic anhydride → [1-Oxo-2-(3-hydroxyphenyl)-2-methyl-6,7-dichloro-5-indanyloxy]acetic acid

HRID 839706

Reaction equation

HRID 839706 reaction equation
[O:1]=[C:2]1[C:10]2[C:5](=[CH:6][C:7]([O:13][CH2:14][C:15]([O:17]CC)=[O:16])=[C:8]([Cl:12])[C:9]=2[Cl:11])[CH2:4][C:3]1([C:21]1[CH:26]=[CH:25][CH:24]=[CH:23][CH:22]=1)[CH3:20].[Pb]=O.FC(F)(F)C(OC(=O)C(F)(F)F)=[O:32]>FC(F)(F)C(O)=O>[O:1]=[C:2]1[C:10]2[C:5](=[CH:6][C:7]([O:13][CH2:14][C:15]([OH:17])=[O:16])=[C:8]([Cl:12])[C:9]=2[Cl:11])[CH2:4][C:3]1([C:21]1[CH:22]=[CH:23][CH:24]=[C:25]([OH:32])[CH:26]=1)[CH3:20]

Participants

5

Reactant 3

HCID 9845Trifluoroacetic anhydrideHCID 14827Lead monoxideHCID 20384378Ethyl(1-oxo-2-phenyl-2-methyl-6,7-dichloro-5-indanyloxy)acetate

Product 1

HCID 20378235[1-Oxo-2-(3-hydroxyphenyl)-2-methyl-6,7-dichloro-5-indanyloxy]acetic acidYield 60%

Reagents, catalysts & solvents 1

HCID 6422Trifluoroacetic acidSolvent2×

Conditions

Temperature
25 °C

Procedure

Ethyl (1-oxo-2-phenyl-2-methyl-6,7-dichloro-5-indanyloxy)acetate (18.95 g., 0.05 mole) dissolved in trifluoroacetic acid (100 ml.) is added portionwise at less than 10° C. to a stirred mixture of lead tetrakistrifluoroacetate (.055 mole) prepared by stirring lead oxide (37.5 g.), trifluoroacetic acid (85 ml.) and trifluoroaceticanhydride (75 g.) at 25° C. for 96 hrs. After stirring the reaction mixture at 25° C. for 6 hours it is poured into crushed ice-water (1 l.) to precipitate 19.7 g. of a mixture of esters which is hydrolyzed by heating at reflux with ethanol (400 ml.) -water (250 ml.) - 10N sodium hydroxide solution (40 ml.) for 3/4 hr. On addition to crushed ice-water (1 l.) -12N hydrochloric acid (50 ml.) a gummy product precipitates, is extracted with ether then concentrated to give 60% of [1-oxo-2-(3-hydroxyphenyl)-2-methyl-6,7-dichloro-5-indanyloxy]acetic acid and 20% of the 4-hydroxyphenyl derivative. Crystallization from acetic acid gives 2.6 g. of [1-oxo-2-(3-hydroxyphenyl)-2-methyl-6,7-dichloro-5-indanyloxy]acetic acid, m.p. 248° - 255° C.

Workup

  1. customprepared
  2. additionis poured
  3. customto precipitate 19.7 g
  4. additionof a mixture of esters which
  5. temperatureby heating
  6. temperatureat reflux with ethanol (400 ml.) -water (250 ml.) - 10N sodium hydroxide solution (40 ml.) for 3/4 hr
  7. additionOn addition
  8. customto crushed ice-water (1 l.) -12N hydrochloric acid (50 ml.) a gummy product
  9. customprecipitates
  10. extractionis extracted with ether
  11. concentrationthen concentrated

Sources & evidence

ORD record
ord-865229b663ff414d84814e8fc682df17
Source dataset
uspto-grants-1978_06
Patent number
US04096267

Linked notes

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