Water → [(7S,9Z,11S,12R,13S,14R,15R,16R,17S,18S,19Z,21Z)-2,15,17,29-tetrahydroxy-11-methoxy-3,7,12,14,16,18,22-heptamethyl-6,23,26,27-tetraoxo-8,30-dioxa-24-azatetracyclo[23.3.1.14,7.05,28]triaconta-1(28),2,4,9,19,21,25(29)-heptaen-13-yl] acetate

HRID 1701846Notes

Reaction equation

HRID 1701846 reaction equation
[CH3:1][C@@H:2]1[C@H:37]([OH:38])[C@@H:36]([CH3:39])[C@@H:35]([OH:40])[C@@H:34]([CH3:41])[C@H:33]([O:42][C:43]([CH3:45])=[O:44])[C@H:32]([CH3:46])[C@@H:31]([O:47][CH3:48])[CH:30]=[CH:29][O:28][C@:25]2([CH3:49])[C:26](=[O:27])[C:15]3[C:16]([O:24]2)=[C:17]([CH3:23])[C:18]([OH:22])=[C:19]2[C:20](=[O:21])[C:10](=[C:11](Br)[C:12]([C:14]=32)=[O:13])[NH:9][C:7](=[O:8])[C:6]([CH3:51])=[CH:5][CH:4]=[CH:3]1.[OH:52]P([O-])(O)=O.[K+].O>CO.P([O-])([O-])([O-])=O.[Fe-3](C#N)(C#N)(C#N)(C#N)(C#N)C#N.[K+].[K+].[K+]>[CH3:1][C@@H:2]1[C@H:37]([OH:38])[C@@H:36]([CH3:39])[C@@H:35]([OH:40])[C@@H:34]([CH3:41])[C@H:33]([O:42][C:43]([CH3:45])=[O:44])[C@H:32]([CH3:46])[C@@H:31]([O:47][CH3:48])[CH:30]=[CH:29][O:28][C@@:25]2([CH3:49])[O:24][C:16]3[C:15]([C:26]2=[O:27])=[C:14]2[C:12]([C:11](=[O:52])[C:10](=[C:20]([OH:21])[C:19]2=[C:18]([OH:22])[C:17]=3[CH3:23])[NH:9][C:7](=[O:8])[C:6]([CH3:51])=[CH:5][CH:4]=[CH:3]1)=[O:13]

Participants

7

Reactant 3

HCID 962WaterHCID 516951Monobasic potassium phosphateHCID 128896153-Bromorifamycin S

Product 1

HCID 102115525[(7S,9Z,11S,12R,13S,14R,15R,16R,17S,18S,19Z,21Z)-2,15,17,29-tetrahydroxy-11-methoxy-3,7,12,14,16,18,22-heptamethyl-6,23,26,27-tetraoxo-8,30-dioxa-24-azatetracyclo[23.3.1.14,7.05,28]triaconta-1(28),2,4,9,19,21,25(29)-heptaen-13-yl] acetate

Reagents, catalysts & solvents 3

HCID 178511488HCID 178511488, compoundCatalystHCID 887MethanolSolventHCID 1061PhosphateSolvent

Procedure

A solution of 3.0 g of 3-bromorifamycin S in 50 ml of methanol and 70 ml of phosphate buffer of pH 8.0 (0.065 mole of Na2HPO4 and 0.004 mole of KH2PO4 per liter of water) is refluxed for 4 hours. The colour of the reaction solution changes during this time from blue-violet to yellow-brown. The reaction solution is then oxidised with excess potassium ferricyanide and, after acidification to pH ~3, is extracted with chloroform. After drying and concentration by evaporation of the chloroform extract, the residue is dissolved in ether and the ether solution is exhaustively extracted with phosphate buffer of pH=6. The wine-red aqueous buffer extract is acidified until the colour changes to yellow, and the precipitated 3-hydroxyrifamycin S is taken up with chloroform. After evaporating off the chloroform, 3-hydroxyrifamycin S is obtained in the form of a yellow foam, and the fact that it is identical with the fermentation product obtained earlier can be verified by thin-layer chromatography, 360-MHz-1H-NMR spectra, and by UV and IR spectra.

Workup

  1. extractionafter acidification to pH ~3, is extracted with chloroform
  2. customAfter drying
  3. concentrationconcentration
  4. customby evaporation of the chloroform
  5. extractionextract
  6. dissolutionthe residue is dissolved in ether
  7. extractionthe ether solution is exhaustively extracted with phosphate buffer of pH=6
  8. extractionThe wine-red aqueous buffer extract
  9. customAfter evaporating off the chloroform

Sources & evidence

ORD record
ord-1ad5c8326f464baf9514fe23c48b4a0e
Source dataset
uspto-grants-1983_04
Patent number
US04379149

Reaction notes

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