Methyl morpholine oxide → HCID 58979077, compound

HRID 1181092Notes

Reaction equation

HRID 1181092 reaction equation
[CH2:1]([O:3][C:4](=[O:26])[C:5]([O:8][C:9]1[CH:14]=[CH:13][C:12]([O:15][CH2:16][C:17]2[CH:22]=[CH:21][CH:20]=[CH:19][CH:18]=2)=[CH:11][C:10]=1CC=C)([CH3:7])[CH3:6])[CH3:2].C[N+]1([O-])[CH2:33][CH2:32][O:31]CC1.I([O-])(=O)(=O)=[O:36].[Na+].Cl([O-])=O.[Na+]>CC(C)=O.O.CCOC(C)=O.[Os](=O)=O.C1COCC1>[CH2:1]([O:3][C:4](=[O:26])[C:5]([O:8][C:9]1[CH:14]=[CH:13][C:12]([O:15][CH2:16][C:17]2[CH:18]=[CH:19][CH:20]=[CH:21][CH:22]=2)=[CH:11][C:10]=1[CH2:33][C:32]([OH:36])=[O:31])([CH3:6])[CH3:7])[CH3:2]

Participants

10

Reactant 4

HCID 82029Methyl morpholine oxideHCID 23667635Sodium periodateHCID 23668197Sodium ChloriteHCID 58979392HCID 58979392, compound

Product 1

HCID 58979077HCID 58979077, compound

Reagents, catalysts & solvents 5

HCID 18757412036-02-1CatalystHCID 180AcetoneSolventHCID 962WaterSolvent4×HCID 8028TetrahydrofuranSolventHCID 8857Ethyl AcetateSolvent

Procedure

A solution of 2-(2-allyl-4-benzyloxy-phenoxy)-2-methyl-propionic acid ethyl ester (8.07 g, 22.8 mmol) in acetone (85 mL) and water (8.5 mL) was treated with 4-methyl-morpholine 4-oxide (3.68 g, 27.2 mmol) then osmium (IV) oxide (2 chips). The flask was covered with foil and stirred 5 h. The solution was diluted with EtOAc (600 mL) and washed with 1N Na2S2O3 (2×75 mL) and brine (75 mL). The organic layer was concentrated to a tan oil (8.74 g). The oil was dissolved in THF (54 mL) and water (36 mL), and sodium periodate (15.4 g, 72.0 mmol) was added. THF (54 mL) and water (36 mL) were added. The thick white slurry was stirred for 3 h and filtered. The filtrate was extracted with EtOAc (500 mL). The organic layer was washed successively with brine, 1N Na2S2O3, and brine (75 mL each) and was concentrated to an orange oil (7.65 g). The oil was diluted with tert-butanol (180 mL) and 2-methyl-2-butene (60 mL) and was cooled in an ice bath. The mixture was treated with sodium chlorite (19 g, 0.21 mol), and a solution of NaH2PO4 (19 g, 0.14 mol) in water (120 mL) was added over 5 min. After 15 min, the ice bath was removed. The mixture was stirred for 2 h and was partitioned between EtOAc (500 mL) and water (50 mL). The organic layer was washed with 1N Na2S2O3 (75 mL) and brine (75 mL), dried (NaSO4), and concentrated to the title compound as a pale yellow solid (6.52 g, 77%). This material was used in subsequent reactions without further purification.

Workup

  1. washwashed with 1N Na2S2O3 (2×75 mL) and brine (75 mL)
  2. concentrationThe organic layer was concentrated to a tan oil (8.74 g)
  3. dissolutionThe oil was dissolved in THF (54 mL)
  4. stirringThe thick white slurry was stirred for 3 h
  5. filtrationfiltered
  6. extractionThe filtrate was extracted with EtOAc (500 mL)
  7. washThe organic layer was washed successively with brine, 1N Na2S2O3, and brine (75 mL each)
  8. concentrationwas concentrated to an orange oil (7.65 g)
  9. additionThe oil was diluted with tert-butanol (180 mL) and 2-methyl-2-butene (60 mL)
  10. temperaturewas cooled in an ice bath
  11. waitAfter 15 min
  12. customthe ice bath was removed
  13. stirringThe mixture was stirred for 2 h
  14. customwas partitioned between EtOAc (500 mL) and water (50 mL)
  15. washThe organic layer was washed with 1N Na2S2O3 (75 mL) and brine (75 mL)
  16. dry with materialdried (NaSO4)
  17. concentrationconcentrated to the title compound as a pale yellow solid (6.52 g, 77%)
  18. customThis material was used in subsequent reactions without further purification

Sources & evidence

ORD record
ord-c290ef466be640ef81cf53f59aed2b1b
Source dataset
uspto-grants-2007_10
Patent number
US07282501B2

Reaction notes

Loading…