Ethyl Acetate → 4,5,6-Trimethoxy-4'-nitrobiphenyl-2,2'-dicarbaldehyde

HRID 1925094노트

반응식

HRID 1925094 반응식
Br[C:2]1[C:9]([O:10][CH3:11])=[C:8]([O:12][CH3:13])[C:7]([O:14][CH3:15])=[CH:6][C:3]=1[CH:4]=[O:5].Cl[C:17]1[CH:24]=[CH:23][C:22]([N+:25]([O-:27])=[O:26])=[CH:21][C:18]=1[CH:19]=[O:20].C(OCC)(=O)C>CN(C=O)C.[Cu]>[CH3:15][O:14][C:7]1[CH:6]=[C:3]([CH:4]=[O:5])[C:2]([C:17]2[C:18]([CH:19]=[O:20])=[CH:21][C:22]([N+:25]([O-:27])=[O:26])=[CH:23][CH:24]=2)=[C:9]([O:10][CH3:11])[C:8]=1[O:12][CH3:13]

참가 물질

6

반응물 3

HCID 8857Ethyl AcetateHCID 729332-Chloro-5-nitrobenzaldehydeHCID 7780032-Bromo-3,4,5-trimethoxybenzaldehyde

생성물 1

HCID 866380424,5,6-Trimethoxy-4'-nitrobiphenyl-2,2'-dicarbaldehyde수율 57.7%

시약·촉매·용매 2

HCID 23978Copper촉매HCID 6228Dimethylformamide용매2회

실험 절차

A mixture of 2-bromo-3,4,5-trimethoxybenzaldehyde (prepared as described in Example 1, starting materials, 1.00 g, 3.64 mmol) and 2-chloro-5-nitrobenzaldehyde (obtained from Aldrich; 241.9 mg, 1.30 mmol) in dry DMF (2 mL) was added to a stirred, boiling suspension of copper bronze (0.91 g, 14.3 mmol) in dry DMF (5 mL) over a period of 30 minutes. After 8 hours TLC (petroleum ether-ethyl acetate 4:1) indicated the consumption of the starting materials. The mixture was cooled, passed through a Celite plug and diluted with toluene, which was distilled off to afford a dark oil. Column chromatography (petroleum ether 60-80°—ethyl acetate 2:1) afforded a sample of 4,5,6-trimethoxy-4′-nitrobiphenyl-2,2′-dicarbaldehyde (259 mg) containing traces of a second compound. This mixture was dissolved in ethanol (5 mL) and treated with a solution of sodium borohydride (0.2 g) in water (1.5 mL). After stirring for 40 minutes, the mixture was added to 1 M aqueous hydrochloric acid (20 mL). The precipitated product was collected on a filter, washed with water and recrystallised from ethanol, which gave the 2′-hydroxymethyl-4,5,6-trimethoxy-4′-nitrobiphenyl-2-yl)methanol as a white powder (113 mg, 25%), which was used for further reaction without further purification.

후처리

  1. additionwas added to a stirred
  2. customthe consumption of the starting materials
  3. temperatureThe mixture was cooled
  4. additiondiluted with toluene, which
  5. distillationwas distilled off
  6. customto afford a dark oil

출처 및 근거

ORD 기록
ord-48dc02c8160c4331b80fca2070b38131
출처 데이터셋
uspto-grants-2012_05
특허 번호
US08178578B2

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