Dimethyl pyridine-2,6-carboxylate → Methyl 6-(hydroxymethyl)picolinate

HRID 1174155

反応式

HRID 1174155 の反応式
[N:1]1[C:6]([C:7](OC)=[O:8])=[CH:5][CH:4]=[CH:3][C:2]=1[C:11]([O:13][CH3:14])=[O:12].[BH4-].[Na+]>CO.O1CCCC1>[OH:8][CH2:7][C:6]1[N:1]=[C:2]([C:11]([O:13][CH3:14])=[O:12])[CH:3]=[CH:4][CH:5]=1

参加物

5

反応物 2

HCID 79549Dimethyl pyridine-2,6-carboxylateHCID 4311764Sodium borohydride

生成物 1

HCID 11513809Methyl 6-(hydroxymethyl)picolinate収率 86.1%

試薬・触媒・溶媒 2

HCID 887Methanol溶媒HCID 8028Tetrahydrofuran溶媒

反応条件

温度
25 °C

実験手順

A suspension of dimethyl 2,6-pyridine-dicarboxylate (50 g, 0.25 mol) in methanol (400 mL) and tetrahydrofuran (150 mL) was heated to dissolve and while the solution was still hot, it was treated in portions with sodium borohydride (9.1 g, 0.24 mol). The mixture was stirred for 1 hour after the addition, cooled to 25° C., quenched with 10% citric acid (80 mL), stirred for 15 minutes, filtered, and concentrated. A solution of the concentrate in dichloromethane was dried over sodium sulfate, filtered, and concentrated. A solution of the residue in hot ethyl acetate was allowed to stand for 16 hours at 25° C. The resulting precipitate (23 g) was collected by filtration. The mother liquor was concentrated and the resulting solid was purified by flash chromatography on silica gel eluting with 10% methanol in dichloromethane to give the crude white solid (24 g). The solid was crystallized in ethyl acetate to give a total yield of the title compound (36 g, 84% yield).

後処理

  1. temperaturewas heated
  2. dissolutionto dissolve and while the solution
  3. additionafter the addition
  4. customquenched with 10% citric acid (80 mL)
  5. stirringstirred for 15 minutes
  6. filtrationfiltered
  7. concentrationconcentrated
  8. concentrationA solution of the concentrate in dichloromethane
  9. dry with materialwas dried over sodium sulfate
  10. filtrationfiltered
  11. concentrationconcentrated
  12. waitto stand for 16 hours at 25° C
  13. filtrationThe resulting precipitate (23 g) was collected by filtration
  14. concentrationThe mother liquor was concentrated
  15. customthe resulting solid was purified by flash chromatography on silica gel eluting with 10% methanol in dichloromethane
  16. customto give the crude white solid (24 g)
  17. customThe solid was crystallized in ethyl acetate

出典と根拠

ORDレコード
ord-32c70c8863b74cf1b8f8f1c71fd9602e
出典データセット
uspto-grants-2010_11
特許番号
US07834043B2

関連ノート

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