Methyl 2-ethoxy-4-nitrobenzoate → 2-Ethoxy-4-aminobenzoic acid

HRID 467808

반응식

HRID 467808 반응식
[CH2:1]([O:3][C:4]1[CH:13]=[C:12]([N+:14]([O-])=O)[CH:11]=[CH:10][C:5]=1[C:6]([O:8]C)=[O:7])[CH3:2]>CO.[Ni]>[CH2:1]([O:3][C:4]1[CH:13]=[C:12]([NH2:14])[CH:11]=[CH:10][C:5]=1[C:6]([OH:8])=[O:7])[CH3:2]

참가 물질

4

반응물 1

HCID 9964566Methyl 2-ethoxy-4-nitrobenzoate

생성물 1

HCID 101763852-Ethoxy-4-aminobenzoic acid수율 108%

시약·촉매·용매 2

HCID 935Nickel촉매HCID 887Methanol용매

실험 절차

4.05 g (21.7 mmol, 1 eq) 2-hydroxy-4-nitro-benzoic acid are dissolved in 40 mL MeOH and 1.8 mL (24.8 mmol, 1.14 eq) thionyl chloride are slowly added dropwise. The mixture is refluxed for 2 h at 50° C. and stirred for another 2 h. After cooling the volatile constituents are eliminated in vacuo and 4.36 g of the crude methyl 2-hydroxy-4-nitro-benzoate are obtained, which are reacted without further purification. 1 g (5.1 mmol, 1 eq) of the methyl ester are dissolved in 25 mL DMF, 2.1 g (15.3 mmol, 3 eq) potassium carbonate are added and then 1.4 mL (18.8 mmol, 3.7 eq) bromoethane are added dropwise. The reaction mixture is stirred for 16 h at RT, then poured into 100 mL water and the pH is adjusted with concentrated aqueous hydrochloric acid to pH 3. It is extracted twice with 100 mL EE, dried on MgSO4 and after the elimination of all the volatile constituents in vacuo 1.28 g of methyl 2-ethoxy-4-nitro-benzoate are obtained. 1.28 g (5.06 mmol, 1 eq) of the nitro compound are dissolved in 50 mL MeOH, a spatula tip of Raney nickel is added and the reaction mixture is stirred in the autoclave under a hydrogen pressure of 4 bar for 16 h. The catalyst is filtered off through Celite® and the filtrate is freed in vacuo of all the volatile constituents. 0.99 g of the aniline are obtained [MS-ESI+: 351 (M+H)+].

후처리

  1. filtrationThe catalyst is filtered off through Celite®

출처 및 근거

ORD 기록
ord-894e0d98b9024962912db9c3abb6445b
출처 데이터셋
uspto-grants-2014_01
특허 번호
US08623887B2

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