Bromine → N-(5-tert-butyl-1,3,4-thiadiazol-2-yl)-4-bromoacetoacetamide

HRID 261759Notes

Reaction equation

HRID 261759 reaction equation
[C:1]([C:5]1[S:9][C:8]([NH:10][C:11](=[O:16])[CH2:12][C:13]([CH3:15])=[O:14])=[N:7][N:6]=1)([CH3:4])([CH3:3])[CH3:2].[Br:17]Br>C(O)(=O)C>[C:1]([C:5]1[S:9][C:8]([NH:10][C:11](=[O:16])[CH2:12][C:13]([CH2:15][Br:17])=[O:14])=[N:7][N:6]=1)([CH3:4])([CH3:2])[CH3:3]

Participants

4

Reactant 2

HCID 24408BromineHCID 21321160N-(5-tert-butyl-1,3,4-thiadiazol-2-yl)acetoacetamide

Product 1

HCID 21321151N-(5-tert-butyl-1,3,4-thiadiazol-2-yl)-4-bromoacetoacetamideYield 46.6%

Reagents, catalysts & solvents 1

HCID 176Acetic AcidSolvent2×

Procedure

A reaction flask was charged with 14.3 g (0.059 mole) of N-(5-tert-butyl-1,3,4-thiadiazol-2-yl)acetoacetamide dissolved in 230 ml of acetic acid. With efficient stirring, there was added dropwise 9.4 g (0.059 mole) of bromine dissolved in 55 ml of acetic acid while controlling the temperature at 20°-25°. The reaction solution was allowed to stir overnight at ambient temperature. On the following morning a sample of the precipitated solids was withdrawn. By N.M.R. analysis, the material was determined to be the corresponding 2-bromoacetoacetamide, m.p. 128°-30°. The reaction mixture was heated at 75°-80° for twelve hours. The solution was cooled to 20° and the precipitated solid was collected on a vacuum filter. After washing the filter cake with water, the material was stirred with aqueous sodium bicarbonate. The product was isolated and dried. There was obtained 8.8 g (46.6%) of authentic N-(5-tert-butyl-1,3,4-thiadiazol-2-yl)-4-bromoacetoacetamide, m.p. 144°-46°. N.M.R. (CDCl3) ∂ 1.4 [C(CH3)3 ], 4.4 (CH2), 6.3 (CH, enol).

Workup

  1. customat 20°-25°
  2. customOn the following morning a sample of the precipitated solids was withdrawn
  3. temperatureThe reaction mixture was heated at 75°-80° for twelve hours
  4. temperatureThe solution was cooled to 20°
  5. customthe precipitated solid was collected on a vacuum
  6. filtrationfilter
  7. washAfter washing the filter cake with water
  8. stirringthe material was stirred with aqueous sodium bicarbonate
  9. customThe product was isolated
  10. customdried

Sources & evidence

ORD record
ord-6fbca97737484fc58206ccfcdcc1d0f0
Source dataset
uspto-grants-1979_05
Patent number
US04152329

Reaction notes

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