Acetic Acid → HCID 86584459, compound

HRID 2271256Notes

Reaction equation

HRID 2271256 reaction equation
[C:1]([C@:3]1([CH2:28][O:29][CH2:30][C:31]2[CH:36]=[CH:35][CH:34]=[CH:33][CH:32]=2)[O:7][C@@H:6]([N:8]2[CH:15]=[CH:14][C:12](=[O:13])[NH:11][C:9]2=[O:10])[C@H:5]([O:16][C:17](=[O:19])[CH3:18])[C@@H:4]1[O:20][CH2:21][C:22]1[CH:27]=[CH:26][CH:25]=[CH:24][CH:23]=1)#[CH:2].[OH-].[Na+].C(O)(=O)C.CS(Cl)(=O)=O>CO.C(OCC)(=O)C.O>[C:1]([C@:3]1([CH2:28][O:29][CH2:30][C:31]2[CH:36]=[CH:35][CH:34]=[CH:33][CH:32]=2)[O:7][C@@H:6]([N:8]2[CH:15]=[CH:14][C:12](=[O:13])[NH:11][C:9]2=[O:10])[C@@H:5]([O:16][C:17](=[O:19])[CH3:18])[C@@H:4]1[O:20][CH2:21][C:22]1[CH:23]=[CH:24][CH:25]=[CH:26][CH:27]=1)#[CH:2]

Participants

8

Reactant 4

HCID 176Acetic AcidHCID 14798Sodium HydroxideHCID 31297Methanesulfonyl chlorideHCID 9870192HCID 9870192, compound

Product 1

HCID 86584459HCID 86584459, compound

Reagents, catalysts & solvents 3

HCID 887MethanolSolventHCID 962WaterSolventHCID 8857Ethyl AcetateSolvent2×

Procedure

Compound 15 (2.30 g, 4.69 mmol) was dissolved in methanol (90.0 ml), and a 1 N aqueous solution of sodium hydroxide (10.0 ml) was added to the solution, followed by stirring for two hours at room temperature. The reaction mixture was neutralized with acetic acid and then brought to dryness under reduced pressure. The residue was dissolved in ethyl acetate. The organic layer was washed with water, dried over anhydrous magnesium sulfate, and brought to dryness under reduced pressure. The residue was concentrated by co-boiling with a small amount of pyridine three times. The product was dissolved in pyridine (50.0 ml), and methanesulfonyl chloride (0.73 ml, 9.41 mmol) was added to the solution under cooling, followed by stirring for three hours. A small amount of water was added to the reaction mixture, and the mixture was brought to dryness under reduced pressure. The residue was dissolved in ethyl acetate, followed by washing with water. The organic layer was dried over anhydrous magnesium sulfate and then brought to dryness under reduced pressure. The residue was dissolved in tetrahydrofuran (30.0 ml), and a 1 N aqueous solution of sodium hydroxide (50.0 ml) was added to the solution, followed by refluxing for one hour. After the reaction mixture was neutralized with acetic acid, the target compound was taken up through extraction with ethyl acetate. The organic layers were combined and dried over anhydrous magnesium sulfate. The organic layer was brought to dryness under reduced pressure, and the residue was purified by means of silica gel column chromatography (silica gel 250 ml, eluent; n-hexane:ethyl acetate=1:2), to thereby yield a white powder compound (Compound 16; 1.54 g, 3.43 mmol, 73.1%).

Workup

  1. washThe organic layer was washed with water
  2. dry with materialdried over anhydrous magnesium sulfate
  3. concentrationThe residue was concentrated by co-boiling with a small amount of pyridine three times
  4. dissolutionThe product was dissolved in pyridine (50.0 ml)
  5. temperatureunder cooling
  6. stirringby stirring for three hours
  7. washby washing with water
  8. dry with materialThe organic layer was dried over anhydrous magnesium sulfate
  9. dissolutionThe residue was dissolved in tetrahydrofuran (30.0 ml)
  10. additiona 1 N aqueous solution of sodium hydroxide (50.0 ml) was added to the solution
  11. temperatureby refluxing for one hour
  12. extractionthe target compound was taken up through extraction with ethyl acetate
  13. dry with materialdried over anhydrous magnesium sulfate
  14. customthe residue was purified by means of silica gel column chromatography (silica gel 250 ml, eluent; n-hexane:ethyl acetate=1:2)

Sources & evidence

ORD record
ord-292150a9166446aeb0f063f01be4a59f
Source dataset
uspto-grants-2001_12
Patent number
US06333315B1

Reaction notes

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