Hydrochloric Acid → HCID 86641128, compound

HRID 2191053Notes

Reaction equation

HRID 2191053 reaction equation
[N:1]([C@@:4]1([CH2:32]O)[C@H:8]2[O:9][C:10]([CH3:13])([CH3:12])[O:11][C@H:7]2[C@H:6]([N:14]2[CH:22]=[N:21][C:20]3[C:15]2=[N:16][CH:17]=[N:18][C:19]=3[NH:23][C:24](=[O:31])[C:25]2[CH:30]=[CH:29][CH:28]=[CH:27][CH:26]=2)[O:5]1)=[N+:2]=[N-:3].[C:34]([OH:40])([C:36](F)(F)F)=O.N1C=CC=CC=1.C1CCC(N=C=NC2CCCCC2)CC1.[P:62]([CH2:70]P(OCC)(OCC)=O)(OCC)([O:64][CH2:65][CH3:66])=[O:63].CC([O-])(C)C.[K+].C1COCC1.Cl>CS(C)=O.CCOC(C)=O>[N:1]([C@@:4]1(/[CH:32]=[CH:70]/[P:62](=[O:63])([O:40][CH2:34][CH3:36])[O:64][CH2:65][CH3:66])[C@@H:8]2[C@@H:7]([O:11][C:10]([CH3:13])([CH3:12])[O:9]2)[C@H:6]([N:14]2[CH:22]=[N:21][C:20]3[C:15]2=[N:16][CH:17]=[N:18][C:19]=3[NH:23][C:24](=[O:31])[C:25]2[CH:30]=[CH:29][CH:28]=[CH:27][CH:26]=2)[O:5]1)=[N+:2]=[N-:3]

Participants

11

Reactant 8

HCID 313Hydrochloric AcidHCID 1049PyridineHCID 6422Trifluoroacetic acidHCID 8028TetrahydrofuranHCID 10868DicyclohexylcarbodiimideHCID 15455Tetraethyl methylenediphosphonateHCID 23665647Potassium tert-butoxideHCID 89246847HCID 89246847, compound

Product 1

HCID 86641128HCID 86641128, compoundYield 81%

Reagents, catalysts & solvents 2

HCID 679Dimethyl SulfoxideSolventHCID 8857Ethyl AcetateSolvent

Procedure

Compound 36.3 (129 mg, 0.22 mmol) was dissolved in 2.2 mL anhydrous DMSO, treated with TFA.Pyridine (11 mg, 0.056 mmol) and DCC (69 mg, 0.33 mmol). The mixture was stirred at r.t. for 14 h, and then cooled to 0° C. Premixed (EtO)2P(O)CH2P(O)(OEt)2 with 1 M t-BuOK in THF (0.345 mL, 0.34 mmol) at 0° C., the mixture was stirred for 5 min and then added to the oxidized reaction mixture, warmed to r.t. and stirred for 3 h. The mixture was then cooled to 0° C., treated with 0.4 mL 1N HCl, diluted with EtOAc. The organic layer was washed with saturated NaHCO3, brine, dried over MgSO4, filtered and concentrated under reduced pressure. The residue was subjected to a silica gel column chromatography eluting with EtOAc to give compound 36.4 (124 mg, 81% yield).

Workup

  1. temperaturecooled to 0° C
  2. additionadded to the oxidized reaction mixture
  3. temperaturewarmed to r.t.
  4. stirringstirred for 3 h
  5. temperatureThe mixture was then cooled to 0° C.
  6. washThe organic layer was washed with saturated NaHCO3, brine
  7. dry with materialdried over MgSO4
  8. filtrationfiltered
  9. concentrationconcentrated under reduced pressure
  10. washeluting with EtOAc

Sources & evidence

ORD record
ord-53221c247c8b482c9f2891c3e033e3f9
Source dataset
uspto-grants-2012_12
Patent number
US08324179B2

Reaction notes

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