N-bromobutanimide → 5-Bromo-2-(bromomethyl)-1,3-benzothiazole

HRID 538548Notes

Reaction equation

HRID 538548 reaction equation
[Br:1]N1C(=O)CCC1=O.[Br:9][C:10]1[CH:11]=[CH:12][C:13]2[S:17][C:16]([CH3:18])=[N:15][C:14]=2[CH:19]=1>C(Cl)(Cl)(Cl)Cl>[Br:9][C:10]1[CH:11]=[CH:12][C:13]2[S:17][C:16]([CH2:18][Br:1])=[N:15][C:14]=2[CH:19]=1

Participants

4

Reactant 2

HCID 67184N-bromobutanimideHCID 30174575-Bromo-2-methylbenzothiazole

Product 1

HCID 144586425-Bromo-2-(bromomethyl)-1,3-benzothiazoleYield 39%

Reagents, catalysts & solvents 1

HCID 5943Carbon TetrachlorideSolvent

Procedure

N-Bromosuccinimide (4.45 g, 25 mmol, 1.4 equiv.) and subsequently α,α′-azoisobutyronitrile (110 mg, 0.7 mmol, 0.04 equiv.) were added to a solution of 5-bromo-2-methyl-benzothiazole (4.07 g, 17.85 mmol, 1 equiv.) in CCl4 (110 ml). The reaction mixture was stirred at reflux for 24 hrs. After cooling, succinimide was removed by filtration and was rinsed with CCl4 (100 ml). The filtrate was evaporated to dryness under reduced pressure and the orange solid residue was purified by column chromatography on silica, eluted with CH2Cl2/hexane (20%-70% gradient), to give the desired product as a white solid, 2.15 g (39% yield). Mp 116-117, HPLC-MS (method 1): m/z 308 [M+H]+, Rt=4.84 min. The reaction gave also 1.40 g (20% yield) of the by-product 5-bromo-2-dibromomethyl-benzothiazole, as well as 0.89 g (22%) of un-reacted starting material.

Workup

  1. temperatureat reflux for 24 hrs
  2. temperatureAfter cooling
  3. customsuccinimide was removed by filtration
  4. washwas rinsed with CCl4 (100 ml)
  5. customThe filtrate was evaporated to dryness under reduced pressure
  6. customthe orange solid residue was purified by column chromatography on silica
  7. washeluted with CH2Cl2/hexane (20%-70% gradient)

Sources & evidence

ORD record
ord-f66e3a1e75b04b5785bad9d6b155894b
Source dataset
uspto-grants-2014_10
Patent number
US08865736B2

Reaction notes

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