Hydrochloric Acid → Methyl 2-(5-hydroxy-6-nitro-1,3-dioxoisoindolin-2-yl)acetate

HRID 571244

반응식

HRID 571244 반응식
Cl[C:2]1[CH:3]=[C:4]2[C:8](=[CH:9][C:10]=1Cl)[C:7](=[O:12])[N:6]([CH2:13][C:14]([O:16][CH3:17])=[O:15])[C:5]2=[O:18].[N:19]([O-:21])=[O:20].[K+].Cl.CN(C=[O:28])C>>[OH:28][C:2]1[CH:3]=[C:4]2[C:8](=[CH:9][C:10]=1[N+:19]([O-:21])=[O:20])[C:7](=[O:12])[N:6]([CH2:13][C:14]([O:16][CH3:17])=[O:15])[C:5]2=[O:18]

참가 물질

5

반응물 4

HCID 313Hydrochloric AcidHCID 6228DimethylformamideHCID 516910Potassium nitriteHCID 3710015Methyl 2-(5,6-dichloro-1,3-dioxoisoindolin-2-yl)acetate

생성물 1

HCID 15932847Methyl 2-(5-hydroxy-6-nitro-1,3-dioxoisoindolin-2-yl)acetate

실험 절차

A mixture of methyl 2-(5,6-dichloro-1,3-dioxoisoindolin-2-yl)acetate (1.420 g, 4.927 mmol) and potassium nitrite (1.678 g, 19.72 mmol) in dry DMF (23 ml) was heated to reflux for 5 hours. The reaction was cooled to room temperature, poured into 0.5N HCl (100 ml) and extracted twice with diethyl ether (2×100 ml). The combined organic layers were washed with 0.5N HCl (120 ml), with brine (100 ml) and dried over sodium sulfate. The solvent was removed, and the crude was purified by chromatography on silica gel cartridge (petroleum ether:ethyl acetate from 90:10 to 100% ethyl acetate). Two different impure fractions of desired compound were isolated. The first fraction was purified by trituration with MeOH affording 0.250 g of title compound. The second fraction was purified by flash chromatography on silica gel cartridge (petroleum ether:ethyl acetate:TFA from 80:20:0.2 to ethyl acetate:TFA=100:0.2) to obtain 0.160 g of title compound. The two clean portions of desired compound were mixed affording methyl 2-(5-hydroxy-6-nitro-1,3-dioxoisoindolin-2-yl)acetate (0.410 g, 1.463 mmol, 30% yield). MS/ESI+ 281.1 [MH]+.

후처리

  1. temperaturewas heated
  2. temperatureto reflux for 5 hours
  3. extractionextracted twice with diethyl ether (2×100 ml)
  4. washThe combined organic layers were washed with 0.5N HCl (120 ml), with brine (100 ml)
  5. dry with materialdried over sodium sulfate
  6. customThe solvent was removed
  7. customthe crude was purified by chromatography on silica gel cartridge (petroleum ether:ethyl acetate from 90:10 to 100% ethyl acetate)

출처 및 근거

ORD 기록
ord-79e48c8dfb0b42f686aa6bf7b6ab8259
출처 데이터셋
uspto-grants-2015_05
특허 번호
US09024027B2

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