Pyridine → HCID 22117060, compound

HRID 1275526Notes

Reaction equation

HRID 1275526 reaction equation
[C:1]1([O:7][C:8]([C:10]2([Si](C)(C)C)[C:23]3[CH:22]=[C:21]([O:24][Si](C(C)(C)C)(C)C)[CH:20]=[CH:19][C:18]=3[O:17][C:16]3[C:11]2=[CH:12][CH:13]=[CH:14][CH:15]=3)=[O:9])[CH:6]=[CH:5][CH:4]=[CH:3][CH:2]=1.N1C=CC=CC=1>CC#N>[OH:24][C:21]1[CH:20]=[CH:19][C:18]2[O:17][C:16]3[C:11](=[CH:12][CH:13]=[CH:14][CH:15]=3)[CH:10]([C:8]([O:7][C:1]3[CH:2]=[CH:3][CH:4]=[CH:5][CH:6]=3)=[O:9])[C:23]=2[CH:22]=1

Participants

4

Reactant 2

HCID 1049PyridineHCID 53851273HCID 53851273, compound2×

Product 1

HCID 22117060HCID 22117060, compound

Reagents, catalysts & solvents 1

HCID 6342AcetonitrileSolvent

Procedure

A suspended mixture of 2-tert-butyldimethylsiloxy-9-trimethylsilyl-9-xanthene-carboxylic acid phenyl ester, 6 (570 mg, 1.13 mmole), in CH3CN (10 ml) and pyridine (2 ml) became a clear yellow solution after a brief stirring at room temperature. The mixture was treated with 20 drops of 48% HF from a pipette and stirred for 3 hrs at room temperature. The reaction mixture was quenched with dilute HCL solution, followed by two extractions with 30% EtOAc-hexanes. The combined organic layers were washed with water, dried over anhydrous Na2SO4 and concentrated. The residue was dissolved in a minimum amount of 2% MeOH-CH2Cl2 and chromatographed on a silica gel column, eluting with CH2Cl2 to 2% MeOH-CH2Cl2. The relatively clean fractions were pooled and concentrated. The impure yellow product was further purified by trituration first with 5% EtOAc-hexanes followed by hexanes, yielding pure phenyl 2-hydroxy-9H-9-xanthene-carboxylate 7 ((173.5 mg, 48.3%) as a slightly yellow solid: mp 182-184° C.; 1H NMR (DMSO-d6): delta 7.33-7.40 (3H, m), 7.24 (1H, m), 7.13-7.17 (2H, m), 7.04 (1H, d, J=8.8 Hz), 6.95-6.98 (2H, m), 6.90 (1H, d, J=2.6 Hz), 6.78 (1H, dd, J=8.8, 2.6 Hz) and 5.40 (1H, s).

Workup

  1. additionThe mixture was treated with 20 drops of 48% HF from a pipette
  2. stirringstirred for 3 hrs at room temperature
  3. customThe reaction mixture was quenched with dilute HCL solution
  4. extractionfollowed by two extractions with 30% EtOAc-hexanes
  5. washThe combined organic layers were washed with water
  6. dry with materialdried over anhydrous Na2SO4
  7. concentrationconcentrated
  8. dissolutionThe residue was dissolved in a minimum amount of 2% MeOH-CH2Cl2
  9. customchromatographed on a silica gel column
  10. washeluting with CH2Cl2 to 2% MeOH-CH2Cl2
  11. concentrationconcentrated
  12. customThe impure yellow product was further purified by trituration first with 5% EtOAc-hexanes

Sources & evidence

ORD record
ord-81b3593326174f4a8256f4a7c0d5d0b2
Source dataset
uspto-grants-2000_12
Patent number
US06162610

Reaction notes

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