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

HRID 1908958노트

반응식

HRID 1908958 반응식
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

참가 물질

5

반응물 2

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

생성물 1

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

시약·촉매·용매 2

HCID 23938Palladium촉매HCID 887Methanol용매2회

실험 절차

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)+

후처리

  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

출처 및 근거

ORD 기록
ord-ff39310cbf9b4ffeae75d7f1c5107b64
출처 데이터셋
uspto-grants-2013_12
특허 번호
US08598342B2

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