N-bromobutanimide → Benzyl 4-amino-3-bromo-6-(4-chloro-2-fluoro-3-methoxyphenyl)-5-fluoropicolinate

HRID 1754146

Reaktionsgleichung

[Br:1]N1C(=O)CCC1=O.[NH2:9][C:10]1[C:15]([F:16])=[C:14]([C:17]2[CH:22]=[CH:21][C:20]([Cl:23])=[C:19]([O:24][CH3:25])[C:18]=2[F:26])[N:13]=[C:12]([C:27]([O:29][CH2:30][C:31]2[CH:36]=[CH:35][CH:34]=[CH:33][CH:32]=2)=[O:28])[CH:11]=1>ClCCCl>[NH2:9][C:10]1[C:15]([F:16])=[C:14]([C:17]2[CH:22]=[CH:21][C:20]([Cl:23])=[C:19]([O:24][CH3:25])[C:18]=2[F:26])[N:13]=[C:12]([C:27]([O:29][CH2:30][C:31]2[CH:32]=[CH:33][CH:34]=[CH:35][CH:36]=2)=[O:28])[C:11]=1[Br:1]

Komponenten

Reaktionsbedingungen

Temperatur: 23 °C

Versuchsvorschrift

N-Bromosuccinimide (NBS; 580 mg, 3.3 mmol, 1.1 equiv) was added to a stirred suspension of benzyl 4-amino-6-(4-chloro-2-fluoro-3-methoxyphenyl)-5-fluoropicolinate (1.2 g, 3.0 mmol, 1.0 equiv) in 1,2-dichloroethane (15 mL) at 23° C. The resulting bright yellow mixture was stirred at 23° C. for 72 h. The brown reaction mixture was concentrated by N2 stream and the residue was purified by silica gel column chromatography (eluting with 29% EtOAc/hexane) to afford the desired product, benzyl 4-amino-3-bromo-6-(4-chloro-2-fluoro-3-methoxyphenyl)-5-fluoropicolinate as a tan powder (1.3 g, 93%): mp 144-146° C.; IR (thin film) 3370 (s), 3225 (w), 3190 (w), 3093 (w), 3066 (w), 3037 (w), 2948 (w), 1731 (s), 1616 (s) cm−1; 1H NMR (400 MHz, CDCl3) δ 7.47 (m, 2H), 7.41-7.33 (m, 3H), 7.26-7.22 (m, 2H), 5.42 (s, 2H), 4.98 (br s, 2H), 3.96 (d, J=1 Hz, 3H); ESIMS m/z 485 ([M+H]+).

Aufarbeitung

concentrationThe brown reaction mixture was concentrated by N2 stream
customthe residue was purified by silica gel column chromatography (eluting with 29% EtOAc/hexane)

Quellen und Nachweise

ORD-Eintrag: ord-2ec9f9852fd14dddb52c69fdb4fb0e97
Quelldatensatz: uspto-grants-2015_10
DOI: 10.6084/m9.figshare.5104873.v1
Patentnummer: US09169217B2

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