1,4-Dioxane → 2-(4-Bromo-2-nitrothiophen-3-yl)thiazole

HRID 1519923Notes

Reaction equation

Br[C:2]1[C:6]([Br:7])=[CH:5][S:4][C:3]=1[N+:8]([O-:10])=[O:9].C([Sn](CCCC)(CCCC)[C:16]1[S:17][CH:18]=[CH:19][N:20]=1)CCC.O1CCOCC1>C1C=CC([P]([Pd]([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)[P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1.CCOC(C)=O>[Br:7][C:6]1[C:2]([C:16]2[S:17][CH:18]=[CH:19][N:20]=2)=[C:3]([N+:8]([O-:10])=[O:9])[S:4][CH:5]=1

Participants

Conditions

Temperature: 130 °C

Procedure

A mixture of 3,4-dibromo-2-nitrothiophene (242 mg, 0.85 mmol), 2-(tributylstannyl)thiazole (315 mg, 0.84 mmol), Pd(Ph3P)4 catalyst (194 mg, 0.17 mmol) and dioxane (0.9 mL) was heated in the microwave to 130° C. for 25 min. The reaction mixture was diluted with EtOAc and filtered to remove solids. The remaining organic solution was washed with saturated, aqueous solutions of sodium bicarbonate and salt before drying over sodium sulfate. The organic was concentrated under reduced pressure to give a dark oil. The crude product was purified by column chromatography (30% EtOAc/hexanes) to give 2-(4-bromo-2-nitrothiophen-3-yl)thiazole (210 mg). LCMS m/z of 289.1/291.1 with a retention time of 2.043 min on the [1] method.

Workup

filtrationfiltered
customto remove solids
washThe remaining organic solution was washed with saturated, aqueous solutions of sodium bicarbonate and salt
dry with materialbefore drying over sodium sulfate
concentrationThe organic was concentrated under reduced pressure
customto give a dark oil
customThe crude product was purified by column chromatography (30% EtOAc/hexanes)

Sources & evidence

ORD record: ord-8286b25c748f453b9564fd2da27acab0
Source dataset: uspto-grants-2015_07
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US09073891B2

Reaction notes

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