Acetic Acid → HCID 19050650, compound

HRID 863760Notes

Reaction equation

HRID 863760 reaction equation
[CH3:1][N:2]([C:9]([C:11]1[C:12]([CH2:20][C:21]2[N:26]=[C:25]([O:27][CH3:28])[CH:24]=[C:23]([O:29][CH3:30])[N:22]=2)=[N:13][S:14][C:15]=1[Si](C)(C)C)=[O:10])[C:3]1[CH:8]=[CH:7][CH:6]=[CH:5][CH:4]=1.C(O)(=O)C.C(Cl)Cl>C1(C)C=CC=CC=1.C([O-])(=O)C.C([O-])(=O)C.C([O-])(=O)C.[Mn+3]>[CH3:1][N:2]([C:9]([C:11]1[C:12]([CH2:20][C:21]2[N:26]=[C:25]([O:27][CH3:28])[CH:24]=[C:23]([O:29][CH3:30])[N:22]=2)=[N:13][S:14][CH:15]=1)=[O:10])[C:3]1[CH:4]=[CH:5][CH:6]=[CH:7][CH:8]=1

Participants

6

Reactant 3

HCID 176Acetic AcidHCID 6344DichloromethaneHCID 19050656HCID 19050656, compound

Product 1

HCID 19050650HCID 19050650, compound

Reagents, catalysts & solvents 2

HCID 160554manganese(III) acetate dihydrateCatalystHCID 1140TolueneSolvent

Procedure

A mixture of 2.0 g of N-methyl 3-(4,6-dimethoxy-2-pyrimidinylmethyl)-5-trimethylsilyl-4-isothiazolecarboxanilide, 1.5 g of manganese (III) triacetate, 20 ml of acetic acid and 30 ml of methylene dichloride is stirred at RT for 48 hours. The resulting suspension is suction filtered through filter aid and the filter cake washed with water and methylene dichloride. The organic layer is separated, dried and concentrated. The concentrate is flash chromatographed through 300 ml silica gel, 230-400 mesh, using 1 l 70/30 hexane/ethyl acetate, 500 ml 50/50 hexane/ethyl acetate taking 30×50 ml fractions. Fractions 10-15 give a mixture of two components which is heated with boron trifluoride methanol complex (4 drops) in 50 ml of toluene at 80° C. for 2 hrs. The reaction mixture is washed with 30 ml of 15% sodium bicarbonate solution, dried, and concentrated. The concentrate is flash chromatographed through 300 ml silica gel, 230-400 mesh, using 1 l 60/40 hexane/ethyl acetate, 500 ml 40/60 hexane/ethyl acetate and 200 ml ethyl acetate taking 34×50 ml fractions. Fractions 20-23 give N-methyl 3-(4,6-dimethoxy-2-pyrimidinylmethyl)-4-isothiazolecarboxanilide, 0.12 g, mp 92°-93° (Table F, cpd. no. 513). Fractions 24-28 give N-methyl 3-(4,6-dimethoxy-2-pyrimidinylcarbonyl)-4-isothiazolecarboxanilide, 0.3 g, mp 140°-142° C. (Table F, cpd. no. 514).

Workup

  1. filtrationfiltered
  2. filtrationthrough filter aid
  3. washthe filter cake washed with water and methylene dichloride
  4. customThe organic layer is separated
  5. customdried
  6. concentrationconcentrated
  7. customchromatographed through 300 ml silica gel, 230-400 mesh
  8. customFractions 10-15 give
  9. additiona mixture of two components which
  10. washThe reaction mixture is washed with 30 ml of 15% sodium bicarbonate solution
  11. customdried
  12. concentrationconcentrated
  13. customchromatographed through 300 ml silica gel, 230-400 mesh

Sources & evidence

ORD record
ord-704f4c7d0efa4ec18b937c91041ab820
Source dataset
uspto-grants-1996_10
Patent number
US05561101

Reaction notes

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