Phosphoric Acid → (Z)-4-Acetoxy-3-(4-(methylsulfonyl) phenyl)-2-phenylbut-2-enoic acid

HRID 1375706Notes

Reaction equation

HRID 1375706 reaction equation
[C:1]([O:4][CH2:5]/[C:6](/[C:16]1[CH:21]=[CH:20][C:19]([S:22]([CH3:25])(=[O:24])=[O:23])=[CH:18][CH:17]=1)=[C:7](/[C:10]1[CH:15]=[CH:14][CH:13]=[CH:12][CH:11]=1)\[CH2:8][OH:9])(=[O:3])[CH3:2].CC(OI1(OC(C)=O)(OC(C)=O)OC(=O)C2C=CC=CC1=2)=[O:28].CC(=CC)C.P(=O)(O)(O)O.[O-]Cl=O.[Na+]>ClCCl.C1COCC1.CC(O)(C)C.O>[C:1]([O:4][CH2:5]/[C:6](/[C:16]1[CH:17]=[CH:18][C:19]([S:22]([CH3:25])(=[O:24])=[O:23])=[CH:20][CH:21]=1)=[C:7](/[C:10]1[CH:15]=[CH:14][CH:13]=[CH:12][CH:11]=1)\[C:8]([OH:28])=[O:9])(=[O:3])[CH3:2]

Participants

10

Reactant 5

HCID 1004Phosphoric AcidHCID 105532-Methyl-2-buteneHCID 159087TriacetoxyperiodinaneHCID 23668197Sodium ChloriteHCID 58787789(2Z)-4-hydroxy-2-[4-(methylsulfonyl)phenyl]-3-phenylbut-2-enyl acetate

Product 1

HCID 11617716(Z)-4-Acetoxy-3-(4-(methylsulfonyl) phenyl)-2-phenylbut-2-enoic acidYield 93%

Reagents, catalysts & solvents 4

HCID 962WaterSolventHCID 6344DichloromethaneSolventHCID 6386tert-ButanolSolventHCID 8028TetrahydrofuranSolvent

Procedure

To a solution of 38.3 g of (2Z)-4-hydroxy-2-[4-(methylsulfonyl)phenyl]-3-phenylbut-2-enyl acetate in 500 mL of dichloromethane, 47 g of Dess-Martin reagent was added and the resulted mixture was stirred at rt for 2 hr. Then 2 mL of water was added and the resulted mixture was stirred at rt for 1 hr. Then the mixture was filtered and evaporated. The crude thus obtained was dissolved in a solvent mixture of 200 mL of THF with 200 mL of t-BuOH. To the resulting mixture, 30 mL of 2-methyl-2-butene was added and followed by the addition of 200 mL of 1.2 M of phosphoric acid and 200 mL of 1 M of NaClO2. The resulting mixture was stirred at rt for 30 min. The organic phase was separated and the aqueous phase was extracted with EtOAc. The organic phase was combined, dried over Na2SO4, filtered, and then evaporated. The crude was purified by recrystallization from ether to afford 37 g of the titled compound as white solid. 1H NMR (acetone-d6, 500 M Hz): δ 7.76 (d, 2H), 7.43 (d, 2H), 7.18–7.12 (m, 3H), 7.12–7.08 (m, 2H), 5.24 (s, 2H), 3.05 (s, 3H), 1.88 (s, 3H).

Workup

  1. stirringthe resulted mixture was stirred at rt for 1 hr
  2. filtrationThen the mixture was filtered
  3. customevaporated
  4. customThe crude thus obtained
  5. stirringThe resulting mixture was stirred at rt for 30 min
  6. customThe organic phase was separated
  7. extractionthe aqueous phase was extracted with EtOAc
  8. dry with materialdried over Na2SO4
  9. filtrationfiltered
  10. customevaporated
  11. customThe crude was purified by recrystallization from ether

Sources & evidence

ORD record
ord-eb8b01a0dd8d4c03a3dd1e2966a3e83f
Source dataset
uspto-grants-2007_01
Patent number
US07169809B2

Reaction notes

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