Dichloromethane → (+/-)-2-(Hydroxymethyl)-6,8-dihydrospiro[cyclopenta[g]quinoxaline-7,3'-pyrrolo[2,3-b]pyridin]-2'(1'H)-one

HRID 551102Notizen

Reaktionsgleichung

Reaktionsgleichung von HRID 551102
[NH2:1][C:2]1[CH:3]=[C:4]2[C:17](=[CH:18][C:19]=1[N+:20]([O-])=O)[CH2:16][C@:6]1([C:14]3[C:9](=[N:10][CH:11]=[CH:12][CH:13]=3)[NH:8][C:7]1=[O:15])[CH2:5]2.[O-]S([O-])(=O)=O.[Mg+2].[CH2:29]([O-:31])[CH3:30].[CH2:32](Cl)Cl>CO>[OH:31][CH2:29][C:30]1[CH:32]=[N:1][C:2]2[CH:3]=[C:4]3[CH2:5][C:6]4([C:14]5[C:9](=[N:10][CH:11]=[CH:12][CH:13]=5)[NH:8][C:7]4=[O:15])[CH2:16][C:17]3=[CH:18][C:19]=2[N:20]=1

Komponenten

6

Edukt 4

HCID 6344DichloromethaneHCID 24083Sulfuric acid magnesium salt (1:1)HCID 1194401-Hydroxyethyl radical2×HCID 67174155(S)-5-Amino-6-nitro-1,3-dihydrospiro[indene-2,3'-pyrrolo[2,3-b]pyridin]-2'(1'H)-one2×

Produkt 1

HCID 67173211(+/-)-2-(Hydroxymethyl)-6,8-dihydrospiro[cyclopenta[g]quinoxaline-7,3'-pyrrolo[2,3-b]pyridin]-2'(1'H)-one

Reagenzien, Katalysatoren, Lösungsmittel 1

HCID 887MethanolLösungsmittel

Versuchsvorschrift

To a stirred solution of 5,6-diamino-1,3-dihydrospiro[indene-2,3′-pyrrolo[2,3-b]pyridin]-2′(1′H)-one (320 mg, 1.20 mmol, described in Intermediate 13) and MgSO4 (1.06 g, 8.81 mmol) in CH2Cl2 (15 mL) and CH3OH (15 mL) was added the ethanolate of hydroxypyruvic aldehyde trimer [Evans et al., J. Am. Chem. Soc. 1938, 60, 1628-1629] (320 mg, 1.0 mmol). After 4 h, more of the ethanolate of hydroxypyruvic aldehyde trimer (340 mg, 1.1 mmol) was added and the mixture was heated to reflux for 2 h. The reaction mixture was partitioned between brine (50 mL) and EtOAc (150 mL). The organic layer was removed and the aqueous layer was extracted further with EtOAc (2×100 mL). The combined organic extracts were dried over Na2SO4, filtered, and concentrated in vacuo. The crude product was purified by silica gel chromatography, eluting with a gradient of CH2Cl2:MeOH—100:0 to 90:10, to give the title compound. MS: m/z=319 (M+1).

Aufarbeitung

  1. temperaturethe mixture was heated
  2. temperatureto reflux for 2 h
  3. customThe reaction mixture was partitioned between brine (50 mL) and EtOAc (150 mL)
  4. customThe organic layer was removed
  5. extractionthe aqueous layer was extracted further with EtOAc (2×100 mL)
  6. dry with materialThe combined organic extracts were dried over Na2SO4
  7. filtrationfiltered
  8. concentrationconcentrated in vacuo
  9. customThe crude product was purified by silica gel chromatography
  10. washeluting with a gradient of CH2Cl2

Quellen und Nachweise

ORD-Eintrag
ord-cda2bd18f09a4bf5adebc046295b1016
Quelldatensatz
uspto-grants-2011_05
Patentnummer
US07947677B2

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