4-Chloro-3-nitropyridine → 3-(3-Nitropyridin-4-yl)cyclohex-2-enone

HRID 1523412Notizen

Reaktionsgleichung

CC1(C)C(C)(C)OB([C:9]2[CH2:14][CH2:13][CH2:12][C:11](=[O:15])[CH:10]=2)O1.Cl[C:18]1[CH:23]=[CH:22][N:21]=[CH:20][C:19]=1[N+:24]([O-:26])=[O:25]>O1CCOCC1.C([O-])([O-])=O.[Na+].[Na+].CCOC(C)=O.C1C=CC(P(C2C=CC=CC=2)[C-]2C=CC=C2)=CC=1.C1C=CC(P(C2C=CC=CC=2)[C-]2C=CC=C2)=CC=1.Cl[Pd]Cl.[Fe+2].C(Cl)Cl>[N+:24]([C:19]1[CH:20]=[N:21][CH:22]=[CH:23][C:18]=1[C:9]1[CH2:14][CH2:13][CH2:12][C:11](=[O:15])[CH:10]=1)([O-:26])=[O:25]

Komponenten

Reaktionsbedingungen

Temperatur: 110 °C

Versuchsvorschrift

To a solution of 3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)cyclohex-2-enone (1.0 equiv.) in degassed dioxane and 2M Na2CO3 was added 4-chloro-3-nitropyridine (1.2 equiv.) and Pd(dppf)Cl2-DCM (0.05 equiv.). The reaction was heated in an oil bath to 110° C. for 2 hours. Cooled to room temperature, then diluted with EtOAc, added H2O— dark solution, lots of emulsions. Filtered to get rid of the solids, then extracted the organic phase, dried with Na2SO4, and concentrated. The crude was purified via silica gel chromatography eluting with ethyl acetate and hexanes (1:1) to yield 3-(3-nitropyridin-4-yl)cyclohex-2-enone (55%, 2 steps). LC/MS=219 (M+H), LC=2.294 min.

Aufarbeitung

temperatureCooled to room temperature
additionadded H2O— dark solution, lots of emulsions
filtrationFiltered
customto get rid of the solids
extractionextracted the organic phase
dry with materialdried with Na2SO4
concentrationconcentrated
customThe crude was purified via silica gel chromatography
washeluting with ethyl acetate and hexanes (1:1)

Quellen und Nachweise

ORD-Eintrag: ord-74bb4c80fe414fa78fff8fe595fb1195
Quelldatensatz: uspto-grants-2015_07
DOI: 10.6084/m9.figshare.5104873.v1
Patentnummer: US09079889B2

Notizen zur Reaktion

Wird geladen…