Phosphate → HCID 14486197, compound

HRID 1461465Notes

Reaction equation

HRID 1461465 reaction equation
P([O-])([O-])([O-])=O.I([O-])(=O)(=O)=O.[Na+].[CH3:12][S:13]([C@H:16]1[N:19](C(C(OC)=O)=C(C)C)[C:18](=[O:28])[C@H:17]1[C@H:29]([O:31][Si:32]([C:35]([CH3:38])([CH3:37])[CH3:36])([CH3:34])[CH3:33])[CH3:30])(=[O:15])=[O:14].[Mn]([O-])(=O)(=O)=O.[K+]>CC(C)=O.[Mn]([O-])(=O)(=O)=O.[K+].C(OCC)(=O)C.O>[Si:32]([O:31][C@@H:29]([C@H:17]1[C@@H:16]([S:13]([CH3:12])(=[O:15])=[O:14])[NH:19][C:18]1=[O:28])[CH3:30])([C:35]([CH3:36])([CH3:37])[CH3:38])([CH3:34])[CH3:33]

Participants

9

Reactant 4

HCID 1061PhosphateHCID 516875Potassium Permanganate2×HCID 14486194HCID 14486194, compoundHCID 23667635Sodium periodate

Product 1

HCID 14486197HCID 14486197, compoundYield 92.3%

Reagents, catalysts & solvents 4

HCID 516875Potassium PermanganateCatalystHCID 180AcetoneSolvent2×HCID 962WaterSolventHCID 8857Ethyl AcetateSolvent

Conditions

Temperature
0 °C

Procedure

Phosphate buffer (pH 7, 680 ml), potassium permanganate (0.98 g, 0.006 mole), sodium periodate (87.3 g, 0.41 mole) and acetone (320 ml) were combined at ambient temperature and then cooled to 0° C. Over 8 minutes unsaturated ester of Example 1 (33.6 g, 0.08 mole) in acetone (320 ml) was added. The reaction was stirred 30 minutes at 0°-5° C. and then allowed to warm to ambient temperature. Over 1 hour reaction time the purple solution had changed to a pink color, and 30 ml of aqueous potassium permanganate (15 g, 0.095 mole in 500 ml water) was added. At 1 hour intervals, two more portions (50 ml and 75 ml) of aqueous potassium permanganate were added. The reaction was complete after 6 hours. Water (500 ml) and ethyl acetate were added, and the phases separated. The aqueous phase was extracted with ethyl acetate (3×250 ml). The combined organic layers were washed with water (2×500 ml), dried with sodium sulfate, and solvent removed under vacuum yielding 22.7 g (92%) of a thick colorless oil. Crystals formed on standing at 0° C.; m.p. 101°-102° C. IR(CHCl3) 3404, 2950, 2930, 2886, 2856, 1793, 1463, 1321, 1145, 1128 cm-1. NMR(250 MHz) 6.53 (bs, 1H), 4.74 (d, J=2.1 Hz, 1H), 4.32 (m, 1H), 3.56 (t, J=2.5 Hz, 1H), 2.96 (s, 3H), 1.26 (d, J=6 Hz, 3H), 0.86 (s, 9H), 0.07 (s, 3H), 0.05 (s, 3H).

Workup

  1. customwere combined at ambient temperature
  2. temperatureto warm to ambient temperature
  3. customOver 1 hour reaction time the purple solution
  4. additionwas added
  5. waitThe reaction was complete after 6 hours
  6. customthe phases separated
  7. extractionThe aqueous phase was extracted with ethyl acetate (3×250 ml)
  8. washThe combined organic layers were washed with water (2×500 ml)
  9. dry with materialdried with sodium sulfate, and solvent
  10. customremoved under vacuum

Sources & evidence

ORD record
ord-3cd7287525e843f4a76e5138607eacc9
Source dataset
uspto-grants-1991_12
Patent number
US05075439

Reaction notes

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