18-Crown-6 → Methyl 3-chloro-5-(4-methoxyphenyl)-1,2-thiazole-4-carboxylate

HRID 2177269Notes

Reaction equation

[Cl:1][C:2]1[C:6]([C:7]([O:9][CH3:10])=[O:8])=[C:5](Cl)[S:4][N:3]=1.[CH3:12][O:13][C:14]1[CH:19]=[CH:18][C:17](B(O)O)=[CH:16][CH:15]=1.[F-].[K+].C1OCCOCCOCCOCCOCCOC1>CC([O-])=O.CC([O-])=O.[Pd+2]>[Cl:1][C:2]1[C:6]([C:7]([O:9][CH3:10])=[O:8])=[C:5]([C:17]2[CH:18]=[CH:19][C:14]([O:13][CH3:12])=[CH:15][CH:16]=2)[S:4][N:3]=1

Participants

Conditions

Temperature: 110 °C

Procedure

Into a 25-mL round-bottom flask purged and maintained with an inert atmosphere of nitrogen, was placed a solution of methyl 3,5-dichloro-1,2-thiazole-4-carboxylate (300 mg, 1.41 mmol, 1.00 equiv) in Tol (5 mL), (4-methoxyphenyl)boronic acid (270 mg, 1.78 mmol, 1.26 equiv), Pd(OAc)2 (17 mg, 0.08 mmol, 0.05 equiv), KF (260 mg), 18-Crown-6 (180 mg, 0.68 mmol, 0.48 equiv). The resulting solution was stirred for 2 h at 110° C. in an oil bath. The resulting mixture was concentrated under vacuum. The residue was applied onto a silica gel column with ethyl acetate/petroleum ether (1:19). This resulted in 330 mg (74%) of methyl 3-chloro-5-(4-methoxyphenyl)-1,2-thiazole-4-carboxylate as a white crystal.

Workup

customInto a 25-mL round-bottom flask purged
temperaturemaintained with an inert atmosphere of nitrogen
concentrationThe resulting mixture was concentrated under vacuum
customThis resulted in 330 mg (74%) of methyl 3-chloro-5-(4-methoxyphenyl)-1,2-thiazole-4-carboxylate as a white crystal

Sources & evidence

ORD record: ord-1e8969db023c402aac3f9259905b0ec9
Source dataset: uspto-grants-2015_06
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US09067898B1

Reaction notes

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