Bromoacetyl bromide → N-(4-(2-bromoacetyl)phenyl)methanesulfonamide

HRID 466349Notes

Reaction equation

HRID 466349 reaction equation
[CH3:1][S:2]([NH:5][C:6]1[CH:11]=[CH:10][CH:9]=[CH:8][CH:7]=1)(=[O:4])=[O:3].[Br:12][CH2:13][C:14](Br)=[O:15].[Cl-].[Al+3].[Cl-].[Cl-]>C(=S)=S>[Br:12][CH2:13][C:14]([C:9]1[CH:8]=[CH:7][C:6]([NH:5][S:2]([CH3:1])(=[O:4])=[O:3])=[CH:11][CH:10]=1)=[O:15]

Participants

5

Reactant 3

HCID 61147Bromoacetyl bromideHCID 70970Methanesulfonamide, N-phenyl-HCID 6451240Aluminum(III) Chloride

Product 1

HCID 15592151N-(4-(2-bromoacetyl)phenyl)methanesulfonamide

Reagents, catalysts & solvents 1

HCID 6348Carbon DisulfideSolvent

Procedure

Methanesulfonanilide as prepared in Preparation 1 (172.0 g, 1.0 mole), bromoacetylbromide (363.35 g, 1.8 mole), and 1 liter of carbon disulfide is combined under N2 with vigorous mechanical stirring. Anhydrous aluminum chloride (400.0 g, 3.0 mole) is added in portions to this mixture over 11/2 hour resulting in a deep red color and separation of the reaction mixture into two layers. Following the addition, the reaction is stirred at ambient temperature for 45 minutes and is then heated to reflux. After refluxing for 1 hour the oil bath is removed and the reaction is stirred at room temperature overnight. The two layers are allowed to separate and the upper layer is decanted. The viscous dark brown layer remaining is slowly poured over a mixture of crushed ice and 400 ml of concentrated HCl. This results in decomposition of the dark material with violent fuming, and yellow precipitate formation. The resulting precipitate is filtered then washed with H2O, a small volume of EtOH, and ether. The remaining solid is crystallized from large volumes of CH2Cl2 containing a small amount of MeOH to aid in solubility which yielded 3 crops of the title compound, m.p. 186°-188° C.; [according to the literature, R. H. Uloth, et al., J. Med. Chem. 9, p. 88 (1966), m.p. 190°-191° C. dec⟧

Workup

  1. customresulting in a deep red color and separation of the reaction mixture into two layers
  2. additionthe addition
  3. temperatureis then heated to reflux
  4. temperatureAfter refluxing for 1 hour the oil bath
  5. customis removed
  6. stirringthe reaction is stirred at room temperature overnight
  7. customto separate
  8. customthe upper layer is decanted
  9. additionThe viscous dark brown layer remaining is slowly poured over a mixture of crushed ice and 400 ml of concentrated HCl
  10. customThis results in decomposition of the dark material with violent fuming, and yellow precipitate formation
  11. filtrationThe resulting precipitate is filtered
  12. washthen washed with H2O
  13. customThe remaining solid is crystallized from large volumes of CH2Cl2 containing a small amount of MeOH

Sources & evidence

ORD record
ord-1743b1e02214454c98a7ac710939b887
Source dataset
uspto-grants-1992_10
Patent number
US05155268

Reaction notes

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