p-Toluenesulfonic acid → HCID 15672406, compound

HRID 1653978Notes

Reaction equation

HRID 1653978 reaction equation
[CH:1]([C:3]1[CH:4]=[C:5]([C:13]([O:15][CH3:16])=[O:14])[C:6]([C:9]([O:11][CH3:12])=[O:10])=[N:7][CH:8]=1)=O.[CH3:17][NH:18][CH2:19][CH2:20][NH2:21].C1(C)C=CC(S(O)(=O)=O)=CC=1.C(O[C:37](=[O:39])[CH3:38])(=O)C>C1(C)C=CC=CC=1.N1C=CC=CC=1.C(Cl)Cl>[C:37]([N:21]1[CH2:20][CH2:19][N:18]([CH3:17])[CH:1]1[C:3]1[CH:4]=[C:5]([C:13]([O:15][CH3:16])=[O:14])[C:6]([C:9]([O:11][CH3:12])=[O:10])=[N:7][CH:8]=1)(=[O:39])[CH3:38]

Participants

8

Reactant 4

HCID 6101p-Toluenesulfonic acidHCID 7918Acetic AnhydrideHCID 8014N-MethylethylenediamineHCID 15672397HCID 15672397, compound

Product 1

HCID 15672406HCID 15672406, compoundYield 57.1%

Reagents, catalysts & solvents 3

HCID 1049PyridineSolventHCID 1140TolueneSolventHCID 6344DichloromethaneSolvent

Conditions

Temperature
0 °C

Procedure

A solution of dimethyl 5-formylpyridine-2,3-dicarboxylate (0.75 g, 0.0036 mol), N-methylethylene diamine (0.38 mL, 0.0044 mol) and a catalytic amount of para-toluenesulfonic acid in toluene (10 mL) is heated at reflux temperature for 3 hours. During this process, water is removed by placement of an addition funnel containing 3 angstrom molecular sieves between the reaction flask and the reflux condensor. The reaction mixture is concentrated in vacuo, dissolved in methylene chloride (30 mL) and is washed with saturated aqueous sodium bicarbonate solution. The organic solution is dried over anhydrous magnesium sulfate and concentrated in vacuo to give a residue. The residue is dissolved in pyridine (10 mL) at 0° C. and treated with acetic anhydride (0.34 mL, 0.0036 mol). The reaction mixture is stirred for 1 hour at 0° C. and for 66 hours at room temperature. The pyridine is removed in vacuo to yield an oil. The oil is dissolved in methylene chloride and washed with saturated aqueous sodium bicarbonate. The organic solution is dried over anhydrous magnesium sulfate, concentrated in vacuo and purified by chromatography using silica gel and 10% triethylamine in ethyl acetate as eluant to yield the title compound (0.66 g, 56%) as a yellow oil, identified by IR and NMR spectral analyses.

Workup

  1. temperatureat reflux temperature for 3 hours
  2. customDuring this process, water is removed by placement of an addition funnel
  3. additioncontaining 3 angstrom molecular sieves between the reaction flask
  4. concentrationThe reaction mixture is concentrated in vacuo
  5. dissolutiondissolved in methylene chloride (30 mL)
  6. washis washed with saturated aqueous sodium bicarbonate solution
  7. dry with materialThe organic solution is dried over anhydrous magnesium sulfate
  8. concentrationconcentrated in vacuo
  9. customto give a residue
  10. customThe pyridine is removed in vacuo
  11. customto yield an oil
  12. washwashed with saturated aqueous sodium bicarbonate
  13. dry with materialThe organic solution is dried over anhydrous magnesium sulfate
  14. concentrationconcentrated in vacuo
  15. custompurified by chromatography

Sources & evidence

ORD record
ord-77edf28c50e34be2a8a96a9d23d16ca0
Source dataset
uspto-grants-1995_04
Patent number
US05405827

Reaction notes

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