Cesium carbonate → 4-Isopropyl-6-methoxy-2-saccharinylmethyl 3,5-dichloro-2-[2-(dimethylamino)ethoxy]pyridine-4-carboxylate

HRID 864758ノート

反応式

HRID 864758 の反応式
Cl.[Cl:2][C:3]1[C:4]([O:13][CH2:14][CH2:15][N:16]([CH3:18])[CH3:17])=[N:5][CH:6]=[C:7]([Cl:12])[C:8]=1[C:9]([OH:11])=[O:10].C(=O)([O-])[O-].[Cs+].[Cs+].Cl[CH2:26][N:27]1[C:37](=[O:38])[C:36]2[C:31](=[CH:32][C:33]([O:42][CH3:43])=[CH:34][C:35]=2[CH:39]([CH3:41])[CH3:40])[S:28]1(=[O:30])=[O:29]>[Br-].C([N+](CCCC)(CCCC)CCCC)CCC.CN(C=O)C>[Cl:2][C:3]1[C:4]([O:13][CH2:14][CH2:15][N:16]([CH3:18])[CH3:17])=[N:5][CH:6]=[C:7]([Cl:12])[C:8]=1[C:9]([O:11][CH2:26][N:27]1[C:37](=[O:38])[C:36]2[C:31](=[CH:32][C:33]([O:42][CH3:43])=[CH:34][C:35]=2[CH:39]([CH3:41])[CH3:40])[S:28]1(=[O:29])=[O:30])=[O:10]

参加物

6

反応物 3

HCID 10796Cesium carbonateHCID 99951732-(Chloromethyl)-4-isopropyl-6-methoxybenzo[D]isothiazol-3(2H)-one 1,1-dioxideHCID 70048173HCID 70048173、化合物

生成物 1

HCID 152255214-Isopropyl-6-methoxy-2-saccharinylmethyl 3,5-dichloro-2-[2-(dimethylamino)ethoxy]pyridine-4-carboxylate収率 2.1%

試薬・触媒・溶媒 2

HCID 74236Tetrabutylammonium Bromide触媒HCID 6228Dimethylformamide溶媒

反応条件

温度
80 °C

実験手順

A mixture of 3,5-dichloro-2-[2-(dimethylamino)ethoxy)-pyridine-4-carboxylic acid hydrochloride (2.65 g, 0.0084 mol), cesium carbonate (4.1 g, 0.013 mol), tetrabutylammonium bromide (1.0 g, 0.003 mol) and DMF (25 ml) was stirred for 10 minutes, then 2-chloromethyl-4-isopropyl-6-methoxysaccharin (2.4 g, 0.0084 mol) was added. The mixture was heated to 80° C. and stirred for 1 hour. The solvent was removed in vacuo and the residue was partitioned between water/methylene chloride. The organic layer was separated, washed with water, dried over anhydrous MgSO4 and concentrated in vacuo. The residue was dissolved in ethyl acetate and filtered through a plug of silica. Ethereal HCl was added to the filtrate and the solvent was removed in vacuo. The residue was washed with ether (50 ml), treated with saturated NaHCO3 and extracted with methylene chloride. The solvent was removed in vacuo, the residue was triturated with methanol and an off-white solid was collected by filtration. The product was dried in high vacuum to afford 0.096 g (2.1%) of 4-isopropyl-6-methoxy-2-saccharinylmethyl 3,5-dichloro-2-[2-(dimethylamino)ethoxy]pyridine-4-carboxylate, m.p. 155°-160° C. (dec).

後処理

  1. stirringstirred for 1 hour
  2. customThe solvent was removed in vacuo
  3. customthe residue was partitioned between water/methylene chloride
  4. customThe organic layer was separated
  5. washwashed with water
  6. dry with materialdried over anhydrous MgSO4
  7. concentrationconcentrated in vacuo
  8. dissolutionThe residue was dissolved in ethyl acetate
  9. filtrationfiltered through a plug of silica
  10. additionEthereal HCl was added to the filtrate
  11. customthe solvent was removed in vacuo
  12. washThe residue was washed with ether (50 ml)
  13. additiontreated with saturated NaHCO3
  14. extractionextracted with methylene chloride
  15. customThe solvent was removed in vacuo
  16. customthe residue was triturated with methanol
  17. filtrationan off-white solid was collected by filtration
  18. customThe product was dried in high vacuum

出典と根拠

ORDレコード
ord-0dd6ba8d706f48269116ca9f2a40743c
出典データセット
uspto-grants-1996_10
特許番号
US05563163

反応ノート

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