Potassium → HCID 22645915, compound

HRID 2414447Notes

Reaction equation

HRID 2414447 reaction equation
[C:1]([C:3]1[N:4]([CH2:10][CH2:11][CH2:12][C:13](=[O:15])[CH3:14])[C:5]([CH3:9])=[C:6]([CH3:8])[N:7]=1)#[N:2].[K]>O1CCCC1>[C:13]([C:12]1[CH2:11][CH2:10][N:4]2[C:5]([CH3:9])=[C:6]([CH3:8])[N:7]=[C:3]2[C:1]=1[NH2:2])(=[O:15])[CH3:14]

Participants

4

Reactant 2

HCID 5462222PotassiumHCID 9877708HCID 9877708, compound

Product 1

HCID 22645915HCID 22645915, compound

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent2×

Conditions

Temperature
0 °C

Procedure

102 g of 2-cyano-4,5-dimethyl-1-N-(pentan-2-on-5-yl)imidazole from Example 5 are dissolved in tetrahydrofuran (1.2 l) under a dry N 2 atmosphere and cooled in an ice bath to T=0° C. Potassium tern butoxide solution (1.0 M in THF, 640 ml) is then added dropwise over a period of about 15 min. After a further 15 min, the ice bath is removed so that the beige reaction suspension slowly warms to RT. It is then stirred vigorously for 2 h. After completion of the reaction (TLC toluene/acetone=4:1 and CH2Cl2/MeOH=9:1), saturated NH4Cl solution (about 140 ml) is added until the cessation of the reaction and tetrahydrofuran is distilled off. The residue is then dissolved in dichloromethane and extracted twice with saturated NH4Cl solution and once with saturated NaCl solution. The organic phase is dried (MgSO4), filtered off with suction and concentrated to dryness in a high vacuum. The title compound is obtained here as a crude product in the form of an amorphous solid (86 g). The crude product is dissolved in ethanol (90 ml) at a temperature of about 85° C. The solution is then cooled in an ice bath and diethyl ether (180 ml) is added. The product phase is allowed to stand overnight at T=4° C. The precipitate of product is filtered off with suction, washed with a little cold diethyl ether and the filtercake is dried in a high vacuum. The mother liquor is concentrated to dryness, then taken up in the solvent mixture toluenelacetone=5:1 and treated with 5 times the amount of flash silica gel (Mallinckrodt-Baker, 30-60 μm). After filtration and removal of the solvent by distillation, precipitation is carried out again as described above. The title compound (55 g) is obtained as a pure substance in the form of a yellow-orange, amorphous solid, which is sensitive to photooxidation and is stored under N2. TLC (CH2Cl2/MeOH=9:1), Rf=0.59; m.p.: 204° C. (decomposition).

Workup

  1. customthe ice bath is removed so that the beige reaction suspension
  2. customslowly warms to RT
  3. customAfter completion of the reaction (TLC toluene/acetone=4:1 and CH2Cl2/MeOH=9:1), saturated NH4Cl solution (about 140 ml)
  4. distillationis distilled off
  5. dissolutionThe residue is then dissolved in dichloromethane
  6. extractionextracted twice with saturated NH4Cl solution and once with saturated NaCl solution
  7. dry with materialThe organic phase is dried (MgSO4)
  8. filtrationfiltered off with suction
  9. concentrationconcentrated to dryness in a high vacuum

Sources & evidence

ORD record
ord-d4ca4a2da65249688d674a5e0a93976c
Source dataset
uspto-grants-2004_11
Patent number
US06812349B2

Reaction notes

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