2,4-Dimethylthiazole → 5-(2-Methoxy-4-nitro-phenyl)-2,4-dimethyl-thiazole

HRID 2076130Notes

Reaction equation

HRID 2076130 reaction equation
Br[C:2]1[CH:7]=[CH:6][C:5]([N+:8]([O-:10])=[O:9])=[CH:4][C:3]=1[O:11][CH3:12].C([O-])(=O)C.[K+].[CH3:18][C:19]1[S:20][CH:21]=[C:22]([CH3:24])[N:23]=1>CN(C)C(=O)C.[Pd].C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1>[CH3:12][O:11][C:3]1[CH:4]=[C:5]([N+:8]([O-:10])=[O:9])[CH:6]=[CH:7][C:2]=1[C:21]1[S:20][C:19]([CH3:18])=[N:23][C:22]=1[CH3:24]

Participants

6

Reactant 3

HCID 109342,4-DimethylthiazoleHCID 1012932-Bromo-5-nitroanisoleHCID 517044Potassium Acetate

Product 1

HCID 670961295-(2-Methoxy-4-nitro-phenyl)-2,4-dimethyl-thiazoleYield 62.1%

Reagents, catalysts & solvents 2

HCID 11979704Tetrakis(triphenylphosphine)palladiumCatalystHCID 31374DimethylacetamideSolvent

Procedure

In a microwave vial a mixture of 2-bromo-5-nitroanisole (600 mg, 2.53 mmol), potassium acetate (377 mg, 3.80 mmol) and tetrakis(triphenylphosphine)-palladium(0) (148 mg, 0.13 mmol) in N,N-dimethylacetamide (8 mL) was flushed with nitrogene while 2,4-dimethylthiazole (1.47 g, 12.7 mmol) was added. The tube was sealed and the mixture irradiated for 30 minutes at 170° C. The red-brown mixture was partitioned between ethyl acetate and water. The aqueous layer was re-extracted with ethyl acetate. The combined organic phases were washed with water, with brine, dried with magnesium sulfate and the solvent was evaporated to dryness. Column chromatography (40 g silica, heptane/ethyl acetate 7:3 v/v) afforded the title compound (415 mg, 62%) as a yellow solid. MS ISP (m/e): 265.1 (100) [(M+H)+]. 1H NMR (CDCl3, 300 MHz): δ (ppm)=7.90 (dd, 1H), 7.81 (d, 1H), 7.45 (d, 1H), 3.95 (s, 3H), 2.71 (s, 3H), 2.35 (s, 3H). mp 123-125° C.

Workup

  1. additionwas added
  2. customThe tube was sealed
  3. customthe mixture irradiated for 30 minutes at 170° C
  4. customThe red-brown mixture was partitioned between ethyl acetate and water
  5. extractionThe aqueous layer was re-extracted with ethyl acetate
  6. washThe combined organic phases were washed with water, with brine
  7. dry with materialdried with magnesium sulfate
  8. customthe solvent was evaporated to dryness

Sources & evidence

ORD record
ord-17767fb3db9b407ca09ec20f44737c7b
Source dataset
uspto-grants-2011_04
Patent number
US07923450B2

Reaction notes

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