Ninhydrin → HCID 178527045, compound

HRID 1993111Notes

Reaction equation

HRID 1993111 reaction equation
[CH2:1]([O:3][PH:4](=[O:8])[O:5][CH2:6][CH3:7])[CH3:2].[O-]S(C(F)(F)F)(=O)=O.C(=O)([O-])[O-].[Cs+].[Cs+].C1C=[C:27]2[C:29]([C:31](O)(O)[C:32](=O)[C:26]2=CC=1)=O>O1CCCC1.ClCCl.O.CO>[CH2:1]([O:3][PH:4](=[O:8])[O:5][CH2:6][C:7]1[CH:27]=[CH:29][CH:31]=[CH:32][CH:26]=1)[C:2]1[CH:31]=[CH:32][CH:26]=[CH:27][CH:29]=1

Participants

9

Reactant 4

HCID 10236NinhydrinHCID 10796Cesium carbonate2×HCID 2758875TrifluoromethanesulfonateHCID 178476833HCID 178476833, compound

Product 1

HCID 178527045HCID 178527045, compoundYield 90%

Reagents, catalysts & solvents 4

HCID 887MethanolSolventHCID 962WaterSolventHCID 6344DichloromethaneSolventHCID 8028TetrahydrofuranSolvent

Procedure

To a solution of phenol 11 (6.45 g, 11.8 mmol) in tetrahydrofuran (161 mL) at room temperature was charged triflate reagent 12 (6.48 g, 15.3 mmol). Cesium carbonate (11.5 g, 35.3 mmol) was added and the mixture was stirred and monitored by TLC assay (SiO2, 5% methanol in dichloromethane as eluent, dibenzyl product Rf=0.26, visualization by UV or ninhydrin stain and heat). Additional Cs2CO3 was added until the reaction was judged complete. To the reaction contents was charged water (160 mL) and the mixture extracted with ethyl acetate (2×160 mL). The combined organic layer was dried over sodium sulfate, filtered, and concentrated via rotary evaporator to afford a viscous oil. The crude oil was purified by silica gel column chromatography using a gradient of 100% dichloromethane to 1% methanol in dichloromethane to afford product 9 as a white foam (8.68 g, 90% yield). 1H NMR (CDCl3) δ 7.75 (d, 2H), 7.40-7.20 (m, 16H), 6.95 (d, 2H), 5.65 (d, 1H), 5.20-4.90 (m, 6H), 4.25 (d, 2H), 4.00-3.80 (m, 4H), 3.75-3.65 (m, 3H), 3.20-2.75 (m, 7H), 1.90-1.75 (m, 1H), 1.30-1.20 (m, 1H), 0.90 (d, 3H), 0.85 (d, 3H). 31P NMR (CDCl3) δ 19.1.

Workup

  1. customTo the reaction contents
  2. extractionthe mixture extracted with ethyl acetate (2×160 mL)
  3. dry with materialThe combined organic layer was dried over sodium sulfate
  4. filtrationfiltered
  5. concentrationconcentrated via rotary evaporator
  6. customto afford a viscous oil
  7. customThe crude oil was purified by silica gel column chromatography

Sources & evidence

ORD record
ord-af19117ea04e475d8f27ff10dcee797f
Source dataset
uspto-grants-2010_01
Patent number
US07649015B2

Reaction notes

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