Phosphoric Acid → {([2,3-Bis(nitrooxy)propoxy]carbonyl}oxy)-3-[4-(methylsulfonyl)phenyl]-2-phenylbut-2-enoic acid

HRID 1437592Notes

Reaction equation

HRID 1437592 reaction equation
[C:1](=[O:36])([O:14][CH2:15]/[C:16](/[C:26]1[CH:31]=[CH:30][C:29]([S:32]([CH3:35])(=[O:34])=[O:33])=[CH:28][CH:27]=1)=[C:17](/[C:20]1[CH:25]=[CH:24][CH:23]=[CH:22][CH:21]=1)\[CH2:18][OH:19])[O:2][CH2:3][CH:4]([O:10][N+:11]([O-:13])=[O:12])[CH2:5][O:6][N+:7]([O-:9])=[O:8].CC(OI1(OC(C)=O)(OC(C)=O)OC(=O)C2C=CC=CC1=2)=[O:39].CC(=CC)C.P(=O)(O)(O)O.[O-]Cl=O.[Na+]>ClCCl.C1COCC1.CC(O)(C)C.O>[N+:11]([O:10][CH:4]([CH2:5][O:6][N+:7]([O-:9])=[O:8])[CH2:3][O:2][C:1]([O:14][CH2:15][C:16]([C:26]1[CH:31]=[CH:30][C:29]([S:32]([CH3:35])(=[O:33])=[O:34])=[CH:28][CH:27]=1)=[C:17]([C:20]1[CH:25]=[CH:24][CH:23]=[CH:22][CH:21]=1)[C:18]([OH:39])=[O:19])=[O:36])([O-:13])=[O:12]

Participants

10

Reactant 5

HCID 1004Phosphoric AcidHCID 105532-Methyl-2-buteneHCID 159087TriacetoxyperiodinaneHCID 23668197Sodium ChloriteHCID 866234342,3-bis(nitrooxy)propyl (2Z)-4-hydroxy-2-[4-(methylsulfonyl)phenyl]-3-phenylbut-2-en-1-yl carbonate

Product 1

HCID 76653544{([2,3-Bis(nitrooxy)propoxy]carbonyl}oxy)-3-[4-(methylsulfonyl)phenyl]-2-phenylbut-2-enoic acidYield 38.7%

Reagents, catalysts & solvents 4

HCID 962WaterSolventHCID 6344DichloromethaneSolventHCID 6386tert-ButanolSolventHCID 8028TetrahydrofuranSolvent

Procedure

To a solution of 3.1 g of 2,3-bis(nitrooxy)propyl (2Z)-4-hydroxy-2-[4-(methylsulfonyl)phenyl]-3-phenylbut-2-en-1-yl carbonate in 30 mL of dichloromethane was added 3.1 g of Dess-Martin reagent and the resultant mixture was stirred at rt for 2 h. Then 3 mL of water was added and the resultant mixture was stirred at rt for 0.5 h. The cloudy mixture was then filtered and filtrate extracted 3× with EtOAc. The organic layers were combined, dried (Na2SO4), filtered and concentrated in vacuo to give a pale yellow residue. The crude material was then dissolved in a solvent mixture of 5 mL of THF with 5 mL of t-BuOH and to this was added 2 mL of 2-methyl-2-butene followed by the addition of 2 mL of 1 M of phosphoric acid and 1.16 g of NaClO2. The reaction mixture was stirred at rt for 3.5 h. The organic phase was separated and the aqueous phase was extracted with EtOAc. The combined organic layer was dried (Na2SO4), filtered, and then concentrated in vacuo. The crude was purified by recrystallization from warm ether to afford 1.23 g of the title compound as a white solid. 1H NMR (500 MHz, acetone-d6): δ 7.79 (d, 2H), 7.47 (d, 2H), 7.22-7.14 (m, 5H), 5.75-5.72 (m, 1H), 5.43 (s, 2H), 5.03 (dd, 1H), 4.83 (dd, 1H), 4.63 (dd, 1H), 4.47 (dd, 1H), 3.08 (s, 3H).

Workup

  1. filtrationThe cloudy mixture was then filtered
  2. extractionfiltrate extracted 3× with EtOAc
  3. dry with materialdried (Na2SO4)
  4. filtrationfiltered
  5. concentrationconcentrated in vacuo
  6. customto give a pale yellow residue
  7. customThe organic phase was separated
  8. extractionthe aqueous phase was extracted with EtOAc
  9. dry with materialThe combined organic layer was dried (Na2SO4)
  10. filtrationfiltered
  11. concentrationconcentrated in vacuo
  12. customThe crude was purified by recrystallization
  13. temperaturefrom warm ether

Sources & evidence

ORD record
ord-0f11c6e899404362b783d5cdef3ce089
Source dataset
uspto-grants-2009_11
Patent number
US07622501B2

Reaction notes

Loading…