Oxalic Acid → HCID 22715177, compound

HRID 352128Notes

Reaction equation

HRID 352128 reaction equation
[C:1]([OH:6])(=[O:5])[C:2]([OH:4])=[O:3].[Cl:7][C:8]1[CH:15]=[CH:14][C:11]([C:12]#[N:13])=[C:10]([O:16][CH:17]([C:23]2[CH:27]=[CH:26][O:25][CH:24]=2)[CH2:18][CH2:19][CH2:20][NH:21]C)[CH:9]=1.[N-]=[N+]=[N-].[Na+].C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.C(=O)(O)[O-].[Na+].C(O)(=O)C(O)=O>CS(C)=O.O.O1CCCC1>[C:1]([OH:6])(=[O:5])[C:2]([OH:4])=[O:3].[NH2:21][CH2:20][CH2:19][CH2:18][CH:17]([C:23]1[CH:27]=[CH:26][O:25][CH:24]=1)[O:16][C:10]1[CH:9]=[C:8]([Cl:7])[CH:15]=[CH:14][C:11]=1[C:12]#[N:13]

Participants

9

Reactant 5

HCID 971Oxalic AcidHCID 11776TriphenylphosphineHCID 33557Sodium AzideHCID 516892Sodium BicarbonateHCID 22715166HCID 22715166, compound

Product 1

HCID 22715177HCID 22715177, compoundYield 48.1%

Reagents, catalysts & solvents 3

HCID 679Dimethyl SulfoxideSolventHCID 962WaterSolventHCID 8028TetrahydrofuranSolvent

Procedure

To a tetrahydrofuran solution of the iodo intermediate from Example 27 step (e) (30 ml, 1.42 mmol), was added dropwise a solution of sodium azide (0.28 g, 4.26 mmol) in dimethyl sulphoxide (5 ml). The reaction was then stirred for 22hat room temperature. The solution was then treated with triphenylphosphine (1.12 g, 4.26 mmol) and water (5 ml) and stirred for 24hat room temperature. Aqueous saturated sodium bicarbonate solution (30 ml) was added and the mixture extracted with ethyl acetate (3×70 ml). The combined extracts were washed with water (2×30 ml), dried (sodium sulphate) and evaporated. The residue was dissolved in methanol, applied to a CC SCX resin, washed with methanol (200 ml) and then eluted with 7N ammonia in methanol (100 ml). The solvent was removed in vacuo and the residue-chromatographed on flash silica, eluting with 7% 7N ammonia in methanol in dichloromethane. The product was dissolved in methanol, treated with one equivalent of oxalic acid, stirred for ten minutes and then the solvent was removed in vacuo. The solid residue was recrystallised from isopropanol to give the title compound as a white solid (0.26 g, 47%).

Workup

  1. stirringstirred for 24hat room temperature
  2. extractionthe mixture extracted with ethyl acetate (3×70 ml)
  3. washThe combined extracts were washed with water (2×30 ml)
  4. dry with materialdried (sodium sulphate)
  5. customevaporated
  6. dissolutionThe residue was dissolved in methanol
  7. washwashed with methanol (200 ml)
  8. washeluted with 7N ammonia in methanol (100 ml)
  9. customThe solvent was removed in vacuo
  10. customthe residue-chromatographed on flash silica
  11. washeluting with 7% 7N ammonia in methanol in dichloromethane
  12. dissolutionThe product was dissolved in methanol
  13. stirringstirred for ten minutes
  14. customthe solvent was removed in vacuo
  15. customThe solid residue was recrystallised from isopropanol

Sources & evidence

ORD record
ord-32f27880b706484da2a2ba68eb8e28ad
Source dataset
uspto-grants-2004_06
Patent number
US06743939B2

Reaction notes

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