Boron tribromide → 3-(3-amino-5-methyl-1,2,4-benzotriazin-7-yl)-4-chlorophenol

HRID 273519Notes

Reaction equation

HRID 273519 reaction equation
[Cl:1][C:2]1[CH:7]=[CH:6][C:5]([O:8]C)=[CH:4][C:3]=1[C:10]1[CH:20]=[C:19]([CH3:21])[C:13]2[N:14]=[C:15]([NH2:18])[N:16]=[N:17][C:12]=2[CH:11]=1.B(Br)(Br)Br>C(Cl)Cl>[NH2:18][C:15]1[N:16]=[N:17][C:12]2[CH:11]=[C:10]([C:3]3[CH:4]=[C:5]([OH:8])[CH:6]=[CH:7][C:2]=3[Cl:1])[CH:20]=[C:19]([CH3:21])[C:13]=2[N:14]=1

Participants

4

Reactant 2

HCID 25134Boron tribromideHCID 248227537-(2-Chloro-5-methoxyphenyl)-5-methylbenzo[e][1,2,4]triazin-3-amine

Product 1

HCID 115075103-(3-amino-5-methyl-1,2,4-benzotriazin-7-yl)-4-chlorophenolYield 73%

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent2×

Conditions

Temperature
0 °C

Procedure

7-(2-chloro-5-methoxy-phenyl)-5-methyl-benzo[1,2,4]triazin-3-ylamine (0.158 g, 0.527 mmol, 1 equiv) was diluted with 10 mL DCM and chilled to 0° C. using an ice bath. A 1.0 M solution of BBr3 in DCM (3.16 mL, 3.16 mmol, 6.0 equiv) was then added in one portion resulting in a dark reaction mixture. The reaction was allowed to come to ambient temperature and stirred for 3.5 hours, then quenched by carefully pouring onto a saturated solution of sodium bicarbonate followed by sonication for 3-5 minutes. Additional DCM was added and this mixture was washed with sodium bicarbonate followed by brine. The organic phase was separated, dried over sodium sulfate (Na2SO4), filtered and evaporated to dryness. Solids were then diluted with minimum amount of ethyl acetate and precipitated out with hexanes. Product was filtered off and dried to yield a yellow solid (0.110 g, 73% yield). MS (ESI+): m/z 287.1, LC retention time: 2.46 min.

Workup

  1. customresulting in a dark reaction mixture
  2. customto come to ambient temperature
  3. customquenched
  4. additionby carefully pouring onto a saturated solution of sodium bicarbonate
  5. customfollowed by sonication for 3-5 minutes
  6. additionAdditional DCM was added
  7. washthis mixture was washed with sodium bicarbonate
  8. customThe organic phase was separated
  9. dry with materialdried over sodium sulfate (Na2SO4)
  10. filtrationfiltered
  11. customevaporated to dryness
  12. additionSolids were then diluted with minimum amount of ethyl acetate
  13. customprecipitated out with hexanes
  14. filtrationProduct was filtered off
  15. customdried

Sources & evidence

ORD record
ord-f410e96d1e754621a511c6059546ae66
Source dataset
uspto-grants-2008_11
Patent number
US07456176B2

Reaction notes

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