Sodium periodate → Methyl 5-bromo-1-(2,2-dihydroxyethyl)-4-oxo-3-[(phenylmethyl)oxy]-1,4-dihydro-2-pyridinecarboxylate

HRID 406920Notes

Reaction equation

HRID 406920 reaction equation
I([O-])(=O)(=O)=[O:2].[Na+].[Br:7][C:8]1[C:9](=[O:31])[C:10]([O:23][CH2:24][C:25]2[CH:30]=[CH:29][CH:28]=[CH:27][CH:26]=2)=[C:11]([C:19]([O:21][CH3:22])=[O:20])[N:12]([CH2:14][CH:15]([OH:18])CO)[CH:13]=1>O>[Br:7][C:8]1[C:9](=[O:31])[C:10]([O:23][CH2:24][C:25]2[CH:30]=[CH:29][CH:28]=[CH:27][CH:26]=2)=[C:11]([C:19]([O:21][CH3:22])=[O:20])[N:12]([CH2:14][CH:15]([OH:2])[OH:18])[CH:13]=1

Participants

4

Reactant 2

HCID 23667635Sodium periodateHCID 58277229Methyl 5-bromo-1-(2,3-dihydroxypropyl)-4-oxo-3-[(phenylmethyl)oxy]-1,4-dihydro-2-pyridinecarboxylate

Product 1

HCID 58277223Methyl 5-bromo-1-(2,2-dihydroxyethyl)-4-oxo-3-[(phenylmethyl)oxy]-1,4-dihydro-2-pyridinecarboxylateYield 88%

Reagents, catalysts & solvents 1

HCID 962WaterSolvent

Procedure

A reactor was charged with sodium periodate (1.67 kg, 7.8 mol) and 44 L of deionized water. To the agitated mixture was added 8.5 kg of ice. This was stirred until all the ice melted and the mixture temperature was 1.4° C. To this was added methyl 5-bromo-1-(2,3-dihydroxypropyl)-4-oxo-3-[(phenylmethyl)oxy]-1,4-dihydro-2-pyridinecarboxylate 19 (2.73 kg, 6.62 mol) via a powder addition funnel. The mixture was allowed to warm to rt and the slurry was stirred for 16 h. A sample was monitored by 1H NMR and showed the disappearance of starting material. The mixture was filtered and the cake washed with 20 kg of deionized water. This was repeated until a negative starch/iodide paper result was obtained (4×20 L washes). The solids were dried in a vacuum oven at 45-55° C. to provide methyl 5-bromo-1-(2,2-dihydroxyethyl)-4-oxo-3-[(phenylmethyl)oxy]-1,4-dihydro-2-pyridinecarboxylate 20 (2.176 kg, 88%) as a mixture with the corresponding aldehyde form 21. Purity was determined to be 99.5% by HPLC. 1H NMR (300 MHz, acetone-d6) δ 8.12 (s, 1H), 7.49-7.30°(m, 5H), 5.56 (dd, J=6.0, 2.4 Hz, 1H), 5.23 (m, 1H), 5.20 (s, 2H), 3.97 (d, J=5.1 Hz, 2H), 3.87 (s, 3H).

Workup

  1. customwas 1.4° C
  2. additionvia a powder addition funnel
  3. filtrationThe mixture was filtered
  4. washthe cake washed with 20 kg of deionized water
  5. customresult
  6. customwas obtained (4×20 L washes)
  7. customThe solids were dried in a vacuum oven at 45-55° C.

Sources & evidence

ORD record
ord-a519b87b72f144dab8c76a2d2fd7f55b
Source dataset
uspto-grants-2014_06
Patent number
US08754214B2

Reaction notes

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