Phosphoric Acid → HCID 58841168, compound

HRID 1269347Notes

Reaction equation

HRID 1269347 reaction equation
[C:1](=[O:30])([O:8][CH2:9]/[C:10](/[C:20]1[CH:25]=[CH:24][C:23]([S:26]([CH3:29])(=[O:28])=[O:27])=[CH:22][CH:21]=1)=[C:11](/[C:14]1[CH:19]=[CH:18][CH:17]=[CH:16][CH:15]=1)\[CH2:12][OH:13])[O:2][CH2:3][CH2:4][CH2:5][CH2:6][Br:7].C[C:32](OI1(OC(C)=O)(OC(C)=O)OC(=O)C2C=CC=CC1=2)=[O:33].CC(=CC)C.P(=O)(O)(O)O.[O-]Cl=O.[Na+]>ClCCl.C1COCC1.CC(O)(C)C.O>[Br:7][CH2:6][CH2:5][CH2:4][CH2:3][O:2][C:1]([O:8][CH2:9]/[C:10](/[C:20]1[CH:25]=[CH:24][C:23]([S:26]([CH3:29])(=[O:27])=[O:28])=[CH:22][CH:21]=1)=[C:11](/[C:14]1[CH:19]=[CH:18][CH:17]=[CH:16][CH:15]=1)\[C:12]([O:33][CH3:32])=[O:13])=[O:30]

Participants

10

Reactant 5

HCID 1004Phosphoric AcidHCID 105532-Methyl-2-buteneHCID 159087TriacetoxyperiodinaneHCID 23668197Sodium ChloriteHCID 57446831HCID 57446831, compound

Product 1

HCID 58841168HCID 58841168, compoundYield 87.7%

Reagents, catalysts & solvents 4

HCID 962WaterSolventHCID 6344DichloromethaneSolventHCID 6386tert-ButanolSolventHCID 8028TetrahydrofuranSolvent

Procedure

To a solution of 4.2 g of 4-bromobutyl (2Z)-4-hydroxy-2-[4-(methylsulfonyl)phenyl]-3-phenylbut-2-enyl carbonate in 50 mL of dichloromethane, 4.2 g of Dess-Martin reagent was added and the mixture was stirred at rt for 1 hr. Then 0.5 mL of water was added and the mixture was stirred at rt for 0.5 hr. The resulting mixture was filtered and evaporated. The crude thus obtained was dissolved in a solvent mixture of 30 mL of THF with 30 mL of t-BuOH. To this mixture, 5 mL of 2-methyl-2-butene was added followed by the addition of 50 mL of 1 M phosphoric acid and 25 mL of 1 M of NaClO2. The resulting mixture was stirred at rt for 15 min. The organic phase was separated and the aqueous phase was extracted with EtOAc. The organic phase was combined, dried over Na2SO4, filtered, treated with CH2N2, and then evaporated. The crude was purified by flash chromatography over silica gel (5–50% EtOAc/hexane) to afford 3.89 g of the titled compound as a clear oil. The solvent was evaporated and the residue was purified by flash chromatograph over silica gel to afford 4.3 g of the titled compound. 1H NMR (acetone-d6, 500 M Hz): δ 7.80 (d, 2 H), 7.47 (d, 2 H), 7.22–7.15 (m, 3 H), 7.12–7.05 (m, 2 H), 5.30 (s, 2 H), 4.14 (t, 2 H), 3.82 (s, 3 H), 3.53 (t, 2 H), 3.09 (s, 3 H), 1.91–1.86 (m, 2H), 1.81–1.70 (m, 2H).

Workup

  1. stirringthe mixture was stirred at rt for 0.5 hr
  2. filtrationThe resulting mixture was filtered
  3. customevaporated
  4. customThe crude thus obtained
  5. stirringThe resulting mixture was stirred at rt for 15 min
  6. customThe organic phase was separated
  7. extractionthe aqueous phase was extracted with EtOAc
  8. dry with materialdried over Na2SO4
  9. filtrationfiltered
  10. additiontreated with CH2N2
  11. customevaporated
  12. customThe crude was purified by flash chromatography over silica gel (5–50% EtOAc/hexane)

Sources & evidence

ORD record
ord-258679c415ef407e8cdf6616b2763342
Source dataset
uspto-grants-2007_04
Patent number
US07199154B2

Reaction notes

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