Hydrochloric Acid → HCID 86614388, compound

HRID 1673309Notes

Reaction equation

HRID 1673309 reaction equation
[C:1]([CH2:4][CH2:5][CH2:6][N:7]1[C:11]2=[N:12][CH:13]=[CH:14][C:15]([CH2:16][CH2:17][C:18]3[CH:23]=[CH:22][C:21]([O:24][C:25](=[O:30])[C:26]([CH3:29])([CH3:28])[CH3:27])=[CH:20][CH:19]=3)=[C:10]2[C:9]([O:31][C@@H:32]2[O:58][C@H:57]([CH2:59][O:60][C:61](=[O:66])[C:62]([CH3:65])([CH3:64])[CH3:63])[C@@H:49]([O:50][C:51](=[O:56])[C:52]([CH3:55])([CH3:54])[CH3:53])[C@H:41]([O:42][C:43](=[O:48])[C:44]([CH3:47])([CH3:46])[CH3:45])[C@H:33]2[O:34][C:35](=[O:40])[C:36]([CH3:39])([CH3:38])[CH3:37])=[N:8]1)([OH:3])=O.C(OC(OC(OC(C)(C)C)=O)=O)(C)(C)C.C(=O)([O-])O.[NH4+:86].Cl>CN(C)C=O.N1C=CC=CC=1>[C:1]([CH2:4][CH2:5][CH2:6][N:7]1[C:11]2=[N:12][CH:13]=[CH:14][C:15]([CH2:16][CH2:17][C:18]3[CH:19]=[CH:20][C:21]([O:24][C:25](=[O:30])[C:26]([CH3:28])([CH3:27])[CH3:29])=[CH:22][CH:23]=3)=[C:10]2[C:9]([O:31][C@@H:32]2[O:58][C@H:57]([CH2:59][O:60][C:61](=[O:66])[C:62]([CH3:64])([CH3:65])[CH3:63])[C@@H:49]([O:50][C:51](=[O:56])[C:52]([CH3:54])([CH3:53])[CH3:55])[C@H:41]([O:42][C:43](=[O:48])[C:44]([CH3:45])([CH3:47])[CH3:46])[C@H:33]2[O:34][C:35](=[O:40])[C:36]([CH3:37])([CH3:38])[CH3:39])=[N:8]1)(=[O:3])[NH2:86]

Participants

7

Reactant 4

HCID 313Hydrochloric AcidHCID 14013Ammonium BicarbonateHCID 90495Di-tert-butyl dicarbonateHCID 86614389HCID 86614389, compound

Product 1

HCID 86614388HCID 86614388, compoundYield 84.3%

Reagents, catalysts & solvents 2

HCID 1049PyridineSolventHCID 6228DimethylformamideSolvent

Procedure

To a solution of 1-(3-carboxypropyl)-3-(2,3,4,6-tetra-O-pivaloyl-β-D-glucopyranosyloxy)-4-[2-(4-pivaloyloxyphenyl)-ethyl]-1H-pyrazolo[3,4-b]pyridine (95 mg) in N,N-dimethyl-formamide (2 mL) were added di(tert-butyl)dicarbonate (90 mg), pyridine (0.033 mL) and ammonium hydrogen carbonate (33 mg), and the mixture was stirred at room temperature for 3 hours. The reaction mixture was poured into 0.5 mol/L hydrochloric acid, and the resulting mixture was extracted with ethyl acetate. The extract was washed with water, a saturated aqueous sodium hydrogen carbonate solution and brine successively, and dried over anhydrous sodium sulfate. The solvent was removed under reduced pressure, and the residue was purified by column chromatography on silica gel (eluent: n-hexane/ethyl acetate=1/2-dichloromethane/methanol=15/1) to give 1-(3-carbamoylpropyl)-3-(2,3,4,6-tetra-O-pivaloyl-β-D-glucopyranosyloxy)-4-[2-(4-pivaloyloxyphenyl)ethyl]-1H-pyrazolo[3,4-b]pyridine (80 mg). This material was dissolved in methanol (2 mL). To the solution was added sodium methoxide (0.05 mL), and the mixture was stirred at 60° C. overnight. To the reaction mixture was added acetic acid (0.025 mL), and the resulting mixture was concentrated under reduced pressure. The residue was dissolved in a saturated aqueous potassium carbonate solution, and the solution was purified by solid phase extraction on ODS (washing solvent: distilled water, eluent: methanol) to give the product. The product was further purified by column chromatography on silica gel (eluent: dichloromethane/methanol=5/1-3/1) to give the title compound (23 mg).

Workup

  1. extractionthe resulting mixture was extracted with ethyl acetate
  2. washThe extract was washed with water
  3. dry with materiala saturated aqueous sodium hydrogen carbonate solution and brine successively, and dried over anhydrous sodium sulfate
  4. customThe solvent was removed under reduced pressure
  5. customthe residue was purified by column chromatography on silica gel (eluent: n-hexane/ethyl acetate=1/2-dichloromethane/methanol=15/1)

Sources & evidence

ORD record
ord-fef152abde9344c28cc109d30fcfa2db
Source dataset
uspto-grants-2011_08
Patent number
US07998975B2

Reaction notes

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