Hexane → 2-(2-Bromo-5-methoxy-4-(methoxycarbonyl)phenyl)acetic acid

HRID 730624Notes

Reaction equation

[C:1]([CH2:4][C:5]1[CH:14]=[CH:13][C:8]([C:9]([O:11][CH3:12])=[O:10])=[C:7]([O:15][CH3:16])[CH:6]=1)([OH:3])=[O:2].[Br:17]Br.CCCCCC>CC(O)=O>[Br:17][C:14]1[C:5]([CH2:4][C:1]([OH:3])=[O:2])=[CH:6][C:7]([O:15][CH3:16])=[C:8]([CH:13]=1)[C:9]([O:11][CH3:12])=[O:10]

Participants

Conditions

Temperature: 22.5 °C

Procedure

Methyl 4-carboxymethyl-2-methoxybenzoate 10c (12.7 g, 0.0567 mol) was dissolved in glacial AcOH (100 mL) and bromine (3.2 mL, 0.0624 mol, 1.1 eq) was added drop wise via a syringe, while maintaining the internal temperature between 20-25° C. After stirring for 4 h at RT, the AcOH was evaporated and the orange oil co-evaporated twice with toluene to give an orange solid. This material was triturated with CH2Cl2 and some of the precipitated product was removed by filtration. The rest of the product which remained in the filtrate was then concentrated, loaded on a silica gel column and eluted with 1% AcOH in EtOAc:hexane (6:4 ratio). The product was further purified by a second chromatography and re-crystallization from EtOAc:hexane to give pure methyl 5-bromo-4-carboxymethyl-2-methoxybenzoate as white solid 10d (total amount 9 g, 52% yield).

Workup

customthe AcOH was evaporated
customto give an orange solid
customThis material was triturated with CH2Cl2
customsome of the precipitated product was removed by filtration
concentrationwas then concentrated
washeluted with 1% AcOH in EtOAc:hexane (6:4 ratio)
customThe product was further purified by a second chromatography and re-crystallization from EtOAc

Sources & evidence

ORD record: ord-48b86d1b42cb44d7b10991a9ab5ef0e6
Source dataset: uspto-grants-2009_09
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US07582766B2

Reaction notes

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