2-Bromo-4'-methylacetophenone → HCID 86696593, compound

HRID 2276339Notes

Reaction equation

HRID 2276339 reaction equation
[NH:1]1[CH2:6][CH2:5][CH2:4][CH2:3][C:2]1=[N:7][C:8]#[N:9].[K].Br[CH2:12][C:13]([C:15]1[CH:20]=[CH:19][C:18]([CH3:21])=[CH:17][CH:16]=1)=[O:14]>C(#N)C>[O:14]=[C:13]([C:15]1[CH:20]=[CH:19][C:18]([CH3:21])=[CH:17][CH:16]=1)[CH2:12][N:1]1[CH2:6][CH2:5][CH2:4][CH2:3][C:2]1=[N:7][C:8]#[N:9]

Participants

5

Reactant 3

HCID 692722-Bromo-4'-methylacetophenone2×HCID 5462222PotassiumHCID 178512034HCID 178512034, compound

Product 1

HCID 86696593HCID 86696593, compoundYield 59.5%

Reagents, catalysts & solvents 1

HCID 6342AcetonitrileSolvent

Procedure

A suspension of N-(piperidin-2-ylidene)cyanamide (1.23 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 then 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 1.52 g (59%) of N-(1-(2-oxo-2-p-tolylethyl)piperidin-2-ylidene)cyanamide as an orange solid. ESI/APCI(+): 256 (M+H). 1H NMR (CDI3) δ 7.83 (d, J=8.22 Hz, 2H, Harom.); 7.29 (d, J=8.04 Hz, 2H, Harom.); 4.89 (s, 2H, COCH2); 3.43 (m, 2H, CH2); 2.89 (m, 2H, CH2); 2.43 (s, 3H, CH3); 1.92 (m, 4H, 2×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-26ee5e4da4e04ea4877b6d6194b831a7
Source dataset
uspto-grants-2015_09
Patent number
US09132129B2

Reaction notes

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