Aniline → Dimethyl 2-anilinobenzene-1,4-dicarboxylate

Temperatur

100 °C

To a mixture of dimethyl bromoterephthalate (4.5 g, 16.0 mmol), aniline (2.2 mL, 24.0 mmol), (S)-(−)-2,2′-bis(diphenylphosphino)-1,1′-binaphthyl (922 mg, 1.48 mmol), and toluene (50 mL) was added cesium carbonate (7.53 g, 23.1 mmol), followed by palladium(II) acetate (0.22 g, 1.0 mmol). The mixture was heated to 100° C. for 24 h. HPLC indicated that the reaction was complete. The reaction mixture was cooled to room temperature, diluted with diethyl ether and filtered under reduced pressure through a pad of Celite. The filtrate was concentrated under reduced pressure and purified by silica gel chromatography using a 1:10 mixture of EtOAc and hexane to give 4.58 (97%) of 1A as a bright yellow solid. HPLC retention time=3.74 min. (Condition A) and LC/MS M++1=286+. 1H-NMR (400 MHz, CDCl3): δ 9.50 (bs, 1H), 8.01 (d, J=8.30, 1H), 7.91 (d, J=1.50, 1H), 7.32-7.40 (m, 4H), 7.25 (m, 1H), 7.13 (m, 1H), 3.93 (s, 3H), 3.88 (s, 3H).

1. temperatureThe reaction mixture was cooled to room temperature
2. filtrationfiltered under reduced pressure through a pad of Celite
3. concentrationThe filtrate was concentrated under reduced pressure
4. custompurified by silica gel chromatography
5. additiona 1:10 mixture of EtOAc and hexane

ORD-Eintrag

ord-0bf03931b142489ebaac81ba47c01ea0

Quelldatensatz

uspto-grants-2007_12

DOI

10.6084/m9.figshare.5104873.v1

Patentnummer

US07312209B2