Water → ethyl 6-chloro-5-azido-2-(trifluoromethyl)-2H-chromene-3-carboxylate

HRID 855145Notes

Reaction equation

HRID 855145 reaction equation
[Cl:1][C:2]1[C:3](F)=[C:4]2[C:9](=[CH:10][CH:11]=1)[O:8][CH:7]([C:12]([F:15])([F:14])[F:13])[C:6]([C:16]([O:18][CH2:19][CH3:20])=[O:17])=[CH:5]2.[N-:22]=[N+:23]=[N-:24].[Na+].O.C(OCC)(=O)C>CS(C)=O>[Cl:1][C:2]1[C:3]([N:22]=[N+:23]=[N-:24])=[C:4]2[C:9](=[CH:10][CH:11]=1)[O:8][CH:7]([C:12]([F:15])([F:14])[F:13])[C:6]([C:16]([O:18][CH2:19][CH3:20])=[O:17])=[CH:5]2

Participants

6

Reactant 4

HCID 962WaterHCID 8857Ethyl AcetateHCID 33557Sodium AzideHCID 58934464ethyl 6-chloro-5-fluoro-2-(trifluoromethyl)-2H-chromene-3-carboxylate

Product 1

HCID 58934903ethyl 6-chloro-5-azido-2-(trifluoromethyl)-2H-chromene-3-carboxylateYield 74.2%

Reagents, catalysts & solvents 1

HCID 679Dimethyl SulfoxideSolvent

Conditions

Temperature
85 °C

Procedure

To the solution of ethyl 6-chloro-5-fluoro-2-(trifluoromethyl)-2H-chromene-3-carboxylate (1.0 g, 3.1 mmol) in 20 mL of DMSO was added a solution of sodium azide (1.0 g, 5 mmol) in minimum amount of water. The reaction was then heated to 85° C. for 15 hrs. After cooling to room temperature, to the reaction was added 200 mL of ethyl acetate. The resulting suspension was then washed with brine, and dried over anhydrous magnesium sulfate. After removing the solvents, the residue was purified on silica gel column with ethyl acetate/hexane, it gave 0.8 g of a yellow oil. Part of the product was purified on reverse phase HPLC for further analytical characterization. It gave a pink solid. LC-MS(ES+) 348.3(M+1, 70), 320.2(M−27, 100). 1H NMR(CDCl3/400 MHz) 7.99(s, 1H), 7.24(d, J=8.8 Hz, 1H), 6.75(d, J=8.8 Hz, 1H), 5.67(q, J=6.8 Hz, 1H), 4.32(m, 2H), 1.35(t, J=7.2 Hz, 3H). 19F NMR(CDCl3/400 Hz) −78.71(d, J=6.8 Hz). 13C NMR(CDCl3/400 Hz) 163.7, 152.7, 134.4, 133.9, 131.9,123.3(q, J=287.3 Hz), 122.6, 117.7, 114.6, 114.2, 70.6(q, J=33.3 Hz), 61.9, 14.4. HRSM(EI+) m/e calc. for (C13H9ClF3N3O3) 347.0285(M+), found: 347.0294(M+).

Workup

  1. temperatureAfter cooling to room temperature, to the reaction
  2. washThe resulting suspension was then washed with brine
  3. dry with materialdried over anhydrous magnesium sulfate
  4. customAfter removing the solvents
  5. customthe residue was purified on silica gel column with ethyl acetate/hexane, it

Sources & evidence

ORD record
ord-c883b330260a4918a515d110219af48e
Source dataset
uspto-grants-2007_08
Patent number
US07259266B2

Reaction notes

Loading…