Iodine → Methyl 7-bromoquinoline-3-carboxylate

HRID 2423394Notes

Reaction equation

[Br:1][C:2]1[CH:7]=[CH:6][C:5](/[CH:8]=[C:9](\[CH2:14][NH:15]S(C2C=CC(C)=CC=2)(=O)=O)/[C:10]([O:12][CH3:13])=[O:11])=[CH:4][CH:3]=1.C(OI(OC(=O)C)C1C=CC=CC=1)(=O)C.II.C([O-])([O-])=O.[K+].[K+]>ClCCCl.CCOC(C)=O>[Br:1][C:2]1[CH:7]=[C:6]2[C:5]([CH:8]=[C:9]([C:10]([O:12][CH3:13])=[O:11])[CH:14]=[N:15]2)=[CH:4][CH:3]=1

Participants

Conditions

Temperature: 120 °C

Procedure

A solution of 820 mg (1.93 mmol) of methyl (2E)-3-(4-bromophenyl)-2-({[(4-methylphenyl)sulfonyl]amino}methyl)-2-propenoate, 995 mg (3.09 mmol) of bis(acetyloxy)(phenyl)-λ3-iodane and 490 mg (1.93 mmol) of iodine in 35 mL of 1,2-dichloroethane were stirred at 70° C. for 30 min. The solvent was evaporated and the residue taken up in 25 mL DMF and 1.07 g (7.73 mmol) of K2CO3 was added. The mixture was stirred at 120° C. for 6 hr. EtOAc was added and the organics were washed with three portions of H2O then brine. The solution was then concentrated and the residue purified by silica gel chromatography (40 g of silica gel eluting with 0-40% EtOAc in hexanes over 45 minutes) to give 80 mg (16%) of methyl 7-bromo-3-quinolinecarboxylate as an off-white solid. 1H NMR (400 MHz, CDCl3): δ 9.34 (s, 1H), 8.81 (s, 1H), 8.35 (s, 1H), 7.80 (d, J=9 Hz, 1H), 7.73 (d, J=9 Hz, 1H), 4.02 (s, 3H). ESI-LCMS m/z 267 (M+H)+.

Workup

customThe solvent was evaporated
washthe organics were washed with three portions of H2O
concentrationThe solution was then concentrated
customthe residue purified by silica gel chromatography (40 g of silica gel eluting with 0-40% EtOAc in hexanes over 45 minutes)

Sources & evidence

ORD record: ord-12644c96ebfa473dbc52688b1147c93f
Source dataset: uspto-grants-2011_06
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US07960552B2

Reaction notes

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