Diisopropylethylamine → 5-Bromo-N-methyl-N-(2,2,6,6-tetramethylpiperidin-4-yl)-1,3,4-thiadiazol-2-amine
Reaktionsgleichung
[Br:1][C:2]1[S:3][C:4](Br)=[N:5][N:6]=1.[CH3:8][NH:9][CH:10]1[CH2:15][C:14]([CH3:17])([CH3:16])[NH:13][C:12]([CH3:19])([CH3:18])[CH2:11]1.CCN(C(C)C)C(C)C>O1CCOCC1>[Br:1][C:2]1[S:3][C:4]([N:9]([CH3:8])[CH:10]2[CH2:11][C:12]([CH3:18])([CH3:19])[NH:13][C:14]([CH3:17])([CH3:16])[CH2:15]2)=[N:5][N:6]=1Komponenten
Edukt 3
Produkt 1
Reagenzien, Katalysatoren, Lösungsmittel 1
Reaktionsbedingungen
- Temperatur
- 120 °C
Versuchsvorschrift
To a stirred solution of 2,5-dibromo-1,3,4-thiadiazole (2.975 g, 12.2 mmol) and N,2,2,6,6-pentamethylpiperidin-4-amine (2.493 g, 14.64 mmol) in dioxane (40 mL) was added DIPEA (10.65 mL, 61 mmol) and the resulting mixture refluxed at 120° C. for 16 hours. The reaction mixture was cooled to room temperature then filtered under vacuum, rinsed with dioxane, and the filtrate concentrated in vacuo to afford the crude product as a pink/red oil. The crude material was purified by flash chromatography using 3% [7M NH3 in MeOH]/DCM as the eluent to afford the title compound as a pink/red solid (2.924 g, 72% yield). LC-MS: Rt 0.70 min; MS m/z 335.2 [M+2H]+ [Method A]. 1H NMR (400 MHz, DMSO-d6) δ ppm 4.13-4.03 (m, 1H), 2.92 (s, 3H), 1.57 (dd, J=12.13, 3.54 Hz, 2H), 1.39 (t, J=12.13 Hz, 2H), 1.26 (br. s., 1H), 1.16 (s, 6H), 1.06 (s, 6H). LC-MS: Rt 1.12 min; MS m/z 335.2 [M+H]+ [Method B].
Aufarbeitung
- temperatureThe reaction mixture was cooled to room temperature
- filtrationthen filtered under vacuum
- washrinsed with dioxane
- concentrationthe filtrate concentrated in vacuo
- customto afford the crude product as a pink/red oil
- customThe crude material was purified by flash chromatography
Quellen und Nachweise
- ORD-Eintrag
- ord-29f8cd7043c74086980a58b9355d0ce2
- Quelldatensatz
- uspto-grants-2015_05
- Patentnummer
- US09040712B2
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