Acetic Acid → 7-Bromodibenzothiophene-3-yl-amine

HRID 720762Notes

Reaction equation

HRID 720762 reaction equation
[Br:1][C:2]1[CH:3]=[CH:4][C:5]2[C:9]3[CH:10]=[CH:11][C:12]([N+:14]([O-])=O)=[CH:13][C:8]=3[S:7](=O)[C:6]=2[CH:18]=1.C(O)(=O)C.O.O.Cl[Sn]Cl>Cl>[Br:1][C:2]1[CH:3]=[CH:4][C:5]2[C:9]3[CH:10]=[CH:11][C:12]([NH2:14])=[CH:13][C:8]=3[S:7][C:6]=2[CH:18]=1

Participants

5

Reactant 3

HCID 176Acetic AcidHCID 61436Stannous chloride dihydrateHCID 218950963-Bromo-7-nitrodibenzothiophene-5-oxide

Product 1

HCID 218950877-Bromodibenzothiophene-3-yl-amine

Reagents, catalysts & solvents 1

HCID 313Hydrochloric AcidSolvent

Procedure

A flask equipped with a stirrer and a thermometer was charged with 26.98 g of the intermediate 3-bromo-7-nitrodibenzothiophene-5-oxide prepared in Example 1-2 and 269.8 g of glacial acetic acid in a nitrogen atmosphere. 112.7 g of SnCl2.2H2O dissolved in 158 g of concentrated hydrochloric acid was added dropwise at 14 to 18° C. over 1 hour, and stirred overnight at room temperature. The resulting reactant was filtered, washed with 1:1 glacial acetic acid/concentrated hydrochloric acid, and neutralized with 1100 g of a 7 wt % aqueous solution of sodium hydroxide. The reactant was extracted with ethyl acetate, washed with water, concentrated, and purified by silica gel chromatography using 1:1 hexane/chloroform mixed with 0.1 wt % triethylamine as an eluting solvent, to thereby obtain 17.31 g of objective 7-bromodibenzothiophene-3-yl-amine. The product was subjected to elemental analysis, the results of which are as follows:

Workup

  1. customA flask equipped with a stirrer
  2. additionwas added dropwise at 14 to 18° C. over 1 hour
  3. filtrationThe resulting reactant was filtered
  4. washwashed with 1:1 glacial acetic acid/concentrated hydrochloric acid
  5. extractionThe reactant was extracted with ethyl acetate
  6. washwashed with water
  7. concentrationconcentrated
  8. custompurified by silica gel chromatography
  9. additionmixed with 0.1 wt % triethylamine as an eluting solvent

Sources & evidence

ORD record
ord-09f00bf0e5be4b3a93ce977cbdef6043
Source dataset
uspto-grants-2006_11
Patent number
US07135579B2

Reaction notes

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