Hydrazine hydrate (1:1) → Methyl 7-amino-2,3-dihydro-1,4-benzodioxin-6-carboxylate

HRID 1908958ノート

反応式

HRID 1908958 の反応式
O.NN.[N+:4]([C:7]1[C:8]([C:17]([O:19][CH3:20])=[O:18])=[CH:9][C:10]2[O:15][CH2:14][CH2:13][O:12][C:11]=2[CH:16]=1)([O-])=O>CO.[Pd]>[NH2:4][C:7]1[C:8]([C:17]([O:19][CH3:20])=[O:18])=[CH:9][C:10]2[O:15][CH2:14][CH2:13][O:12][C:11]=2[CH:16]=1

参加物

5

反応物 2

HCID 24654Hydrazine hydrate (1:1)HCID 10537941Methyl 7-Nitro-1,4-benzodioxane-6-carboxylate

生成物 1

HCID 3146109Methyl 7-amino-2,3-dihydro-1,4-benzodioxin-6-carboxylate収率 50.4%

試薬・触媒・溶媒 2

HCID 23938Palladium触媒HCID 887Methanol溶媒2 回

実験手順

A solution of hydrazine monohydrate (1.0 mL, 21 mmol) in MeOH (3 mL) was added dropwise to a refluxing suspension of methyl 7-nitro-2,3-dihydrobenzo[b][1,4]dioxine-6-carboxylate (889 mg, 3.7 mmol) and palladium on carbon (10%, 220 mg) in MeOH (25 mL) under N2. After refluxing overnight, the resulting mixture was cooled to room temperature, filtered through celite and the filter cake was washed with MeOH. The combined filtrates were concentrated under reduced pressure and the residue was purified by column chromatography on silica gel eluting with 30% ethyl acetate in hexane to yield methyl 7-amino-2,3-dihydrobenzo[b][1,4]dioxine-6-carboxylate (390 mg, 50%). 1H NMR (CDCl3, 600 MHz) δ 7.19 (s, 1H), 6.17 (s, 1H), 4.24-4.22 (m, 2H), 4.17-4.15 (m, 2H), 3.82 (s, 3H); MS (ES+) m/z 210.1 (M+H)+

後処理

  1. temperatureAfter refluxing overnight
  2. filtrationfiltered through celite
  3. washthe filter cake was washed with MeOH
  4. concentrationThe combined filtrates were concentrated under reduced pressure
  5. customthe residue was purified by column chromatography on silica gel eluting with 30% ethyl acetate in hexane

出典と根拠

ORDレコード
ord-ff39310cbf9b4ffeae75d7f1c5107b64
出典データセット
uspto-grants-2013_12
特許番号
US08598342B2

反応ノート

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