Toluene → 4-broMo-2-phenylthiazole

HRID 2041869Notes

Reaction equation

HRID 2041869 reaction equation
[C:1]1(B(O)O)[CH:6]=[CH:5][CH:4]=[CH:3][CH:2]=1.Br[C:11]1[S:12][CH:13]=[C:14]([Br:16])[N:15]=1.C1(C)C=CC=CC=1.C(=O)([O-])[O-].[Na+].[Na+]>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.O.C(O)C>[C:1]1([C:11]2[S:12][CH:13]=[C:14]([Br:16])[N:15]=2)[CH:6]=[CH:5][CH:4]=[CH:3][CH:2]=1

Participants

8

Reactant 4

HCID 1140TolueneHCID 10340Sodium CarbonateHCID 66827Phenylboronic AcidHCID 27632972,4-Dibromo-1,3-thiazole

Product 1

HCID 118315284-broMo-2-phenylthiazoleYield 71.8%

Reagents, catalysts & solvents 3

HCID 178418397HCID 178418397, compoundCatalystHCID 702EthanolSolventHCID 962WaterSolvent

Procedure

A flask containing 238 mg of tetrakis(triphenylphosphine)palladium, 0.55 g of phenyl boronic acid and 1.00 g of 2,4-dibromothiazole was subjected to nitrogen substitution. To this flask, 30 ml of toluene, 6.1 ml of ethanol, and 9.1 ml of a 2 M sodium carbonate aqueous solution were added, and the obtained mixture was then stirred under reflux for 6 hours. Thereafter, the reaction solution was cooled to a room temperature, and 50 ml of water was then added thereto, followed by extraction with 50 ml of ethyl acetate twice. The organic layer was washed with 30 ml of a saturated brine, and it was then dried over magnesium sulfate. The magnesium sulfate was filtrated, and the organic layer was then concentrated. The residue was then purified by column chromatography (Wako Gel C-200; hexane:ethyl acetate=14:1), so as to obtain 0.71 g of 2-phenyl-4-bromothiazole.

Workup

  1. temperatureunder reflux for 6 hours
  2. extractionfollowed by extraction with 50 ml of ethyl acetate twice
  3. washThe organic layer was washed with 30 ml of a saturated brine, and it
  4. dry with materialwas then dried over magnesium sulfate
  5. filtrationThe magnesium sulfate was filtrated
  6. concentrationthe organic layer was then concentrated
  7. customThe residue was then purified by column chromatography (Wako Gel C-200; hexane:ethyl acetate=14:1)

Sources & evidence

ORD record
ord-b83bdf959e124a62afc93b9691cb68d8
Source dataset
uspto-grants-2013_11
Patent number
US08586505B2

Reaction notes

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