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Acetic Acid → N-methyl 3-(4,6-dimethoxy-2-pyrimidinylmethyl)-4-isothiazolecarboxanilide

HRID 1720228
Notizen
Druckvorschau

Reaktionsgleichung

Reaktionsgleichung von HRID 1720228
[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
KomponentenVersuchsvorschriftAufarbeitungQuellen und NachweiseNotizen zur Reaktion

Komponenten

6

Edukt 3

HCID 176Acetic AcidHCID 6344DichloromethaneHCID 19050656N-methyl 3-(4,6-dimethoxy-2-pyrimidinylmethyl)-5-trimethylsilyl-4-isothiazolecarboxanilide

Produkt 1

HCID 19050650N-methyl 3-(4,6-dimethoxy-2-pyrimidinylmethyl)-4-isothiazolecarboxanilide

Reagenzien, Katalysatoren, Lösungsmittel 2

HCID 160554manganese(III) acetate dihydrate
Katalysator
HCID 1140TolueneLösungsmittel

Versuchsvorschrift

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).

Aufarbeitung

  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

Quellen und Nachweise

ORD-Eintrag
ord-c4d547f9ac9a44629bc91981b64d43a2
Quelldatensatz
uspto-grants-1996_04
DOI
10.6084/m9.figshare.5104873.v1
Patentnummer
US05506192

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