2-Bromo-4'-methylacetophenone → HCID 86696592, compound

HRID 2276338Notes

Reaction equation

HRID 2276338 reaction equation
[NH:1]1[CH2:5][CH2:4][CH2:3][C:2]1=[N:6][C:7]#[N:8].[K].Br[CH2:11][C:12]([C:14]1[CH:19]=[CH:18][C:17]([CH3:20])=[CH:16][CH:15]=1)=[O:13]>C(#N)C>[O:13]=[C:12]([C:14]1[CH:19]=[CH:18][C:17]([CH3:20])=[CH:16][CH:15]=1)[CH2:11][N:1]1[CH2:5][CH2:4][CH2:3][C:2]1=[N:6][C:7]#[N:8]

Participants

5

Reactant 3

HCID 692722-Bromo-4'-methylacetophenone2×HCID 5462222PotassiumHCID 178512053HCID 178512053, compound

Product 1

HCID 86696592HCID 86696592, compoundYield 84%

Reagents, catalysts & solvents 1

HCID 6342AcetonitrileSolvent

Procedure

A suspension of N-(pyrrolidin-2-ylidene)cyanamide (1.09 g; 10 mmol) in acetonitrile (20 mL) was heated gently until dissolution and then potassium hydrogenocarbonate (1.66 g; 12 mmol) and 2-bromo-1-p-tolylethanone (2.98 g; 14 mmol) were added. The well stirred mixture was heated at reflux for 21 h and an extra amount of 2-bromo-1-p-tolylethanone (0.426 g; 2 mmol) was added. The reaction mixture was heated for 6 additional hours. After cooling, the precipitate was filtered, washed with dichloromethane and the filtrate was concentrated under reduced pressure. The crude residue was purified by flash-chromatography on silica gel using a gradient of ethyl acetate (1-20%) in dichloromethane to furnish 2.02 g (84%) of N-(1-(2-oxo-2-p-tolylethyl)pyrrolidin-2-ylidene)cyanamide as an orange solid. ESI/APCI(+): 242 (M+H). 1H NMR (CDI3) δ 7.83 (d, J=8.22 Hz, 2H, Harom.); 7.29 (d, J=8.04 Hz, 2H, Harom.); 4.81 (s, 2H, COCH2); 3.69 (m, 2H, CH2); 3.03 (m, 2H, CH2); 2.43 (s, 3H, CH3); 2.24 (m, 2H, CH2).

Workup

  1. temperaturewas heated gently until dissolution
  2. temperaturewas heated
  3. temperatureat reflux for 21 h
  4. temperatureThe reaction mixture was heated for 6 additional hours
  5. temperatureAfter cooling
  6. filtrationthe precipitate was filtered
  7. washwashed with dichloromethane
  8. concentrationthe filtrate was concentrated under reduced pressure
  9. customThe crude residue was purified by flash-chromatography on silica gel using a gradient of ethyl acetate (1-20%) in dichloromethane

Sources & evidence

ORD record
ord-c9c49356c7034fdab2e951194c83f14e
Source dataset
uspto-grants-2015_09
Patent number
US09132129B2

Reaction notes

Loading…