Acetic Acid → methyl 5-((4-fluorophenylamino)methyl)-2,2-dimethyl-4H-[1,3]dioxino[4,5-c]pyridine-8-carboxylate

HRID 402570ノート

反応式

HRID 402570 の反応式
C(O)(=O)C.[CH3:5][O:6][C:7]([C:9]1[N:10]=[CH:11][C:12]([CH:21]=O)=[C:13]2[CH2:18][O:17][C:16]([CH3:20])([CH3:19])[O:15][C:14]=12)=[O:8].[F:23][C:24]1[CH:30]=[CH:29][C:27]([NH2:28])=[CH:26][CH:25]=1.C([BH3-])#N.[Na+]>CO>[F:23][C:24]1[CH:30]=[CH:29][C:27]([NH:28][CH2:21][C:12]2[CH:11]=[N:10][C:9]([C:7]([O:6][CH3:5])=[O:8])=[C:14]3[O:15][C:16]([CH3:19])([CH3:20])[O:17][CH2:18][C:13]=23)=[CH:26][CH:25]=1

参加物

6

反応物 4

HCID 176Acetic AcidHCID 97314-FluoroanilineHCID 5003444Sodium cyanoborohydrideHCID 58360280methyl 5-formyl-2,2-dimethyl-4H-[1,3]dioxino[4,5-c]pyridine-8-carboxylate

生成物 1

HCID 58360284methyl 5-((4-fluorophenylamino)methyl)-2,2-dimethyl-4H-[1,3]dioxino[4,5-c]pyridine-8-carboxylate収率 96.2%

試薬・触媒・溶媒 1

HCID 887Methanol溶媒

実験手順

Acetic acid (50 μL, 0.87 mmol) was added to a mixture of 5-Formyl-2,2-dimethyl-4H-[1,3]dioxino[4,5-c]pyridine-8-carboxylic acid methyl ester [J. Org. Chem. 1999, 64, 4537] (220 mg, 0.87 mmol) and 4-fluoroaniline (125 μL, 1.3 mmol) in dry methanol (4 mL) and stirred at room temperature for 15 min. and sodium cyanoborohydride (72 mg, 1.3 mmol) was added. This mixture was stirred at room temperature for 3 h followed by evaporation of 90% of the methanol volume under reduced pressure. The residue was extracted with dichloromethane (3×25 mL) and the combined organic layers were dried (anh. Na2SO4), filtered and concentrated under reduced pressure. The crude product was purified by silica gel (methanol/dichloromethane, 0 to 10% methanol) to give 0.290 g of methyl 5-((4-fluorophenylamino)methyl)-2,2-dimethyl-4H-[1,3]dioxino[4,5-c]pyridine-8-carboxylate (compound 21a) (96%) as a white solid MS-ESI m/z 347 [MI-1]+.

後処理

  1. stirringThis mixture was stirred at room temperature for 3 h
  2. customfollowed by evaporation of 90% of the methanol volume under reduced pressure
  3. extractionThe residue was extracted with dichloromethane (3×25 mL)
  4. dry with materialthe combined organic layers were dried (anh. Na2SO4)
  5. filtrationfiltered
  6. concentrationconcentrated under reduced pressure
  7. customThe crude product was purified by silica gel (methanol/dichloromethane, 0 to 10% methanol)

出典と根拠

ORDレコード
ord-616e42faea6749c2ba1b68b1d3431c79
出典データセット
uspto-grants-2014_06
特許番号
US08742123B2

反応ノート

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