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

HRID 571244

反応式

HRID 571244 の反応式
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]

参加物

5

反応物 4

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

生成物 1

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

実験手順

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]+.

後処理

  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)

出典と根拠

ORDレコード
ord-79e48c8dfb0b42f686aa6bf7b6ab8259
出典データセット
uspto-grants-2015_05
特許番号
US09024027B2

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