Trifluoroacetic anhydride → HCID 13392516, compound

HRID 638251Notes

Reaction equation

HRID 638251 reaction equation
O[CH:2]([C:6]1[CH:21]=[CH:20][C:9]([O:10][CH2:11][C:12]2[CH:16]=[CH:15][S:14][C:13]=2[C:17]([OH:19])=O)=[CH:8][CH:7]=1)[CH2:3][CH2:4][CH3:5].[F:22][C:23]([F:34])([F:33])[C:24]([O:26]C(=O)C(F)(F)F)=[O:25].[K+].[Br-]>ClCCl.C(OCC)(=O)C>[F:22][C:23]([F:34])([F:33])[C:24]([O:26][CH2:5][CH2:4][CH2:3][CH2:2][C:6]1[CH:7]=[CH:8][C:9]2[O:10][CH2:11][C:12]3[CH:16]=[CH:15][S:14][C:13]=3[C:17](=[O:19])[C:20]=2[CH:21]=1)=[O:25]

Participants

6

Reactant 3

HCID 9845Trifluoroacetic anhydrideHCID 253877Potassium BromideHCID 20253975HCID 20253975, compound

Product 1

HCID 13392516HCID 13392516, compound

Reagents, catalysts & solvents 2

HCID 6344DichloromethaneSolvent2×HCID 8857Ethyl AcetateSolvent

Procedure

A stirred suspension of 14.33 g (0.468 mol) of 3-[4-(1-hydroxybutyl)phenoxy]methyl-2-thiophenecarboxylic acid and 150 ml of anhydrous CH2Cl2 was treated with one portion of trifluoroacetic anhydride (22.60 g, 0.107 mol). The suspended material rapidly dissolved and the stirred solution was heated under reflux for four hours. After standing two days at ambient temperature, the reaction was quenched with water (70 ml) and washed with 50 ml of 5% NaHCO3 solution. The dried (Na2SO4) organic phase was concentrated to an oil, which was further dried by azeotropic distillation of toluene. The oil was dissolved in approximately 15 ml of isopropanol, seeded with product previously prepared on a smaller scale, and stirred until a thick crystalline mass formed. The mass was triturated with isopropanol, followed by vacuum filtration. The filter cake was dried in vacuo at 40° C. to afford 15.08 g (83.8%) of almost colorless crystals, m.p. 65.5°-67° C. The material appeared pure by TLC (siica gel, ethyl acetate, Rf =0.70; dichloromethane, Rf =0.51) and the IR (KBr), 1H-NMR (CDCl3) and MS (M+, 384) were consistent with structure.

Workup

  1. dissolutionThe suspended material rapidly dissolved
  2. temperaturethe stirred solution was heated
  3. temperatureunder reflux for four hours
  4. customthe reaction was quenched with water (70 ml)
  5. washwashed with 50 ml of 5% NaHCO3 solution
  6. dry with materialThe dried (Na2SO4) organic phase
  7. concentrationwas concentrated to an oil, which
  8. dry with materialwas further dried by azeotropic distillation of toluene
  9. dissolutionThe oil was dissolved in approximately 15 ml of isopropanol
  10. custompreviously prepared on a smaller scale
  11. customformed
  12. customThe mass was triturated with isopropanol
  13. filtrationfollowed by vacuum filtration
  14. customThe filter cake was dried in vacuo at 40° C.
  15. customto afford 15.08 g (83.8%) of almost colorless crystals, m.p. 65.5°-67° C

Sources & evidence

ORD record
ord-4c19a1196c874417b99b57f5347dfc2c
Source dataset
uspto-grants-1985_12
Patent number
US04560701

Reaction notes

Loading…