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

HRID 1779294
ノート
印刷プレビュー

反応式

HRID 1779294 の反応式
[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
参加物実験手順後処理出典と根拠反応ノート

参加物

6

反応物 3

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

生成物 1

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

試薬・触媒・溶媒 2

HCID 160554manganese(III) acetate dihydrate触媒
HCID 1140
Toluene
溶媒

実験手順

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).

後処理

  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

出典と根拠

ORDレコード
ord-fbe92b78eb394d03a1ab8828b483e7e5
出典データセット
uspto-grants-1997_05
DOI
10.6084/m9.figshare.5104873.v1
特許番号
US05627138

反応ノート

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