Sulfuric Acid → methyl 2-hydroxy-2-(6-methyl-7-oxo-4-(p-tolyl)-6,7-dihydro-1H-pyrrolo[2,3-c]pyridin-5-yl)acetate

HRID 1473212Notizen

Reaktionsgleichung

Reaktionsgleichung von HRID 1473212
[OH:1][CH:2]([C:7]1[N:12]([CH3:13])[C:11](=[O:14])[C:10]2[N:15](CC3C=CC(OC)=CC=3)[CH:16]=[CH:17][C:9]=2[C:8]=1[C:27]1[CH:32]=[CH:31][C:30]([CH3:33])=[CH:29][CH:28]=1)[C:3]([O:5][CH3:6])=[O:4].OS(O)(=O)=O.C1(OC)C=CC=CC=1>FC(F)(F)C(O)=O>[OH:1][CH:2]([C:7]1[N:12]([CH3:13])[C:11](=[O:14])[C:10]2[NH:15][CH:16]=[CH:17][C:9]=2[C:8]=1[C:27]1[CH:28]=[CH:29][C:30]([CH3:33])=[CH:31][CH:32]=1)[C:3]([O:5][CH3:6])=[O:4]

Komponenten

5

Edukt 3

HCID 1118Sulfuric AcidHCID 7519AnisoleHCID 89463201methyl 2-hydroxy-2-(1-(4-methoxybenzyl)-6-methyl-7-oxo-4-(p-tolyl)-6,7-dihydro-1H-pyrrolo[2,3-c]pyridin-5-yl)acetate

Produkt 1

HCID 89473317methyl 2-hydroxy-2-(6-methyl-7-oxo-4-(p-tolyl)-6,7-dihydro-1H-pyrrolo[2,3-c]pyridin-5-yl)acetateAusbeute 66,9 %

Reagenzien, Katalysatoren, Lösungsmittel 1

HCID 6422Trifluoroacetic acidLösungsmittel

Versuchsvorschrift

An ice cold solution of methyl 2-hydroxy-2-(1-(4-methoxybenzyl)-6-methyl-7-oxo-4-(p-tolyl)-6,7-dihydro-1H-pyrrolo[2,3-c]pyridin-5-yl)acetate (266 mg, 0.596 mmol) in Trifluoroacetic acid (TFA) (2.5 mL) was treated with conc. H2SO4 (185 μl, 3.47 mmol), and anisole (370 μl, 3.39 mmol). After stirring for 1 hour, the reaction was warmed to rt for 2 hours, and then quenched with sat. NaHCO3 until neutral. The mixture was extracted with EtOAc, washed with Brine, dried with Na2SO4, filtered, and concentrated. Purification with column chromatography (0-100% EtOAc/Hexane) afforded methyl 2-hydroxy-2-(6-methyl-7-oxo-4-(p-tolyl)-6,7-dihydro-1H-pyrrolo[2,3-c]pyridin-5-yl)acetate (130.1 mg, 0.399 mmol, 66.9% yield) as off-white solid. 1H NMR (400 MHz, CHLOROFORM-d) ppm 10.94 (br. s., 1H), 7.36 (dd, J=7.3, 12.5 Hz, 2H), 7.30-7.20 (m, 3H), 6.12-6.03 (m, 1H), 5.42 (s, 1H), 3.82-3.73 (m, 4H), 3.67 (s, 3H), 2.42 (s, 3H); LCMS (m/z) ES+=327 (M+1).

Aufarbeitung

  1. customquenched with sat. NaHCO3 until neutral
  2. extractionThe mixture was extracted with EtOAc
  3. washwashed with Brine
  4. dry with materialdried with Na2SO4
  5. filtrationfiltered
  6. concentrationconcentrated
  7. customPurification with column chromatography (0-100% EtOAc/Hexane)

Quellen und Nachweise

ORD-Eintrag
ord-a1fd6a5909a140138900a9f116655d0b
Quelldatensatz
uspto-grants-2015_04
Patentnummer
US09012642B2

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