Oxalyl chloride → 819071-06-2

HRID 1592989Notes

Reaction equation

HRID 1592989 reaction equation
[CH2:1]([O:8][C:9]1C=[CH:16][CH:15]=[CH:14][C:10]=1[C:11]([OH:13])=[O:12])[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1.[C:18](Cl)(=O)C(Cl)=O.[OH2:24].C1(C)C=CC(S(O)(=O)=O)=CC=1.[Si]([CH:40]=[N+:41]=[N-])(C)(C)C>CN(C=O)C>[OH:24][C:3]1[CH:4]=[CH:5][CH:6]=[CH:7][C:2]=1[C:1]1[O:8][C:9]2[C:10]([C:11]([O:13][CH3:18])=[O:12])=[CH:14][CH:15]=[CH:16][C:40]=2[N:41]=1

Participants

6

Reactant 4

HCID 65578Oxalyl chlorideHCID 167693TrimethylsilyldiazomethaneHCID 521998p-Toluenesulfonic acid monohydrateHCID 18105812-Benzyloxybenzoic acid

Product 1

HCID 136027360819071-06-2Yield 36%

Reagents, catalysts & solvents 1

HCID 6228DimethylformamideCatalyst

Procedure

To a solution of 2-benzyloxybenzoic acid dry CH2Cl2 was added to 1 ml of freshly distilled oxalyl chloride. After stirring for 10 minutes, 1 drop of DMF was added to the reaction mixture. The reaction mixture was stirred for 2 hours at room temperature and the solvent was removed by evaporation. The resultant yellow oil was dried under vacuum for 3 hours. The yellow oil was then dissolved in 5 ml of dry xylenes and transferred via cannula to a solution of 3-aminosalacylic acid (g, 31.5 mmol) in xylenes. The mixture was stirred at room temperature for 1 h, then heated to reflux overnight. After the reaction mixture had cooled to room temperature, p-toluenesulfonic acid monohydrate (475 mg, 2.5 mmol) was added and the mixture heated to reflux for an additional 12 h. The reaction mixture was cooled to 0° C. and treated with an excess of TMSCHN2. The product was purified by column chromatography (20% EtOAc in hexane) to give a light yellow solid (42 mg, 36%): 1H NMR δ 4.04 (s, 3H, CH3), 7.00 (m, 1H), 7.10 (d, 1H, J=8.4 Hz), 7.4-7.5 (m, 2H), 7.87 (dd, 1H, J=8.1, 1.2 Hz), 7.97 (dd, 1H, J=7.5, 1.2 Hz), 8.06 (dd, 1H, J=8.1, 1.2 Hz); CIMS m/z 270 (MH+); HRMS m/z calc'd for C15H12NO4: 270.0763, found 270.0766.

Workup

  1. stirringThe reaction mixture was stirred for 2 hours at room temperature
  2. customthe solvent was removed by evaporation
  3. customThe resultant yellow oil was dried under vacuum for 3 hours
  4. dissolutionThe yellow oil was then dissolved in 5 ml of dry xylenes
  5. stirringThe mixture was stirred at room temperature for 1 h
  6. temperatureheated
  7. temperatureto reflux overnight
  8. temperaturethe mixture heated
  9. temperatureto reflux for an additional 12 h
  10. temperatureThe reaction mixture was cooled to 0° C.
  11. customThe product was purified by column chromatography (20% EtOAc in hexane)

Sources & evidence

ORD record
ord-1b8b9bb305d84659ab1f53a5209f4978
Source dataset
uspto-grants-2007_11
Patent number
US07294643B2

Reaction notes

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