1-Chloro-3-phenylpropan-2-one → 4-(4-Benzyl-1,3-thiazol-2-yl)-2-bromoaniline

HRID 233762Notes

Reaction equation

HRID 233762 reaction equation
[NH2:1][C:2]1[CH:10]=[CH:9][C:5]([C:6](=[S:8])[NH2:7])=[CH:4][C:3]=1[Br:11].Cl[CH2:13][C:14]([CH2:16][C:17]1[CH:22]=[CH:21][CH:20]=[CH:19][CH:18]=1)=O>C(O)C>[CH2:16]([C:14]1[N:7]=[C:6]([C:5]2[CH:9]=[CH:10][C:2]([NH2:1])=[C:3]([Br:11])[CH:4]=2)[S:8][CH:13]=1)[C:17]1[CH:22]=[CH:21][CH:20]=[CH:19][CH:18]=1

Participants

4

Reactant 2

HCID 2363491-Chloro-3-phenylpropan-2-oneHCID 197021324-Amino-3-bromobenzthioamide

Product 1

HCID 197021424-(4-Benzyl-1,3-thiazol-2-yl)-2-bromoanilineYield 68%

Reagents, catalysts & solvents 1

HCID 702EthanolSolvent

Procedure

A mixture of 4-amino-3-bromobenzthioamide (1.66 g, 7.18 mmol) and 1-chloro-3-phenylacetone [Tarhouni, R. et al., Tetrahedron Letters, 835 (1964)] (1.36 g, 8.07 mmol, 1.1 eq) in absolute ethanol (18 mL) was heated at reflux under nitrogen for 2.5 hours. The resulting reaction mixture was evaporated under reduced pressure, and the residue was partitioned between ethyl acetate (20 mL) and a saturated solution of sodium hydrogen carbonate (20 mL). The ethyl acetate layer was removed, and the aqueous layer was extracted with ethyl acetate (2×20 mL). The organic extracts were combined, dried (MgSO4), and evaporated under reduced pressure. The residual solid was chromatographed using silica gel (approximately 175 g) and elution with an ethyl acetate gradient in hexanes [1:4 to 1:1] to afford the title compound (68%) as a pale yellow solid: top, 110°-115° C.; 13C NMR (CDCl3) δ 166.8, 157.1, 145.6, 139.1, 130.7, 129.1, 128.6, 126.9, 126.4, 125.4, 115.3, 113.2, 109.2, 38.0. Anal. calcd for C16H13BrN2S: C, 55.66; H, 3.79; N, 8.11. Found: C, 55.36; H, 3.71; N, 7.92.

Workup

  1. temperaturewas heated
  2. temperatureat reflux under nitrogen for 2.5 hours
  3. customThe resulting reaction mixture
  4. customwas evaporated under reduced pressure
  5. customthe residue was partitioned between ethyl acetate (20 mL)
  6. customThe ethyl acetate layer was removed
  7. extractionthe aqueous layer was extracted with ethyl acetate (2×20 mL)
  8. dry with materialdried (MgSO4)
  9. customevaporated under reduced pressure
  10. customThe residual solid was chromatographed
  11. washsilica gel (approximately 175 g) and elution with an ethyl acetate gradient in hexanes [1:4 to 1:1]

Sources & evidence

ORD record
ord-44e4e8f3364e415c8010518f8afcf793
Source dataset
uspto-grants-1997_01
Patent number
US05594014

Reaction notes

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