4-Methylmorpholine → N-[3-Cyano-4-[[(dimethylamino)methylene]amino]phenyl]-2-butynamide

HRID 583101Notes

Reaction equation

HRID 583101 reaction equation
[C:1]([OH:6])(=O)[C:2]#[C:3][CH3:4].ClC(OCC(C)C)=O.CN1CCOCC1.[NH2:22][C:23]1[CH:28]=[CH:27][C:26]([N:29]=[CH:30][N:31]([CH3:33])[CH3:32])=[C:25]([C:34]#[N:35])[CH:24]=1.C(=O)(O)[O-].[Na+]>O1CCCC1.C(OCC)(=O)C.[Cl-].[Na+].O>[C:34]([C:25]1[CH:24]=[C:23]([NH:22][C:1](=[O:6])[C:2]#[C:3][CH3:4])[CH:28]=[CH:27][C:26]=1[N:29]=[CH:30][N:31]([CH3:32])[CH3:33])#[N:35]

Participants

9

Reactant 5

HCID 79724-Methylmorpholine2×HCID 62365Isobutyl chloroformateHCID 685352-Butynoic acidHCID 516892Sodium BicarbonateHCID 11263933(E)-N'-(4-Amino-2-cyanophenyl)-N,N-dimethylformimidamide

Product 1

HCID 18350692N-[3-Cyano-4-[[(dimethylamino)methylene]amino]phenyl]-2-butynamideYield 89%

Reagents, catalysts & solvents 3

HCID 8028TetrahydrofuranSolvent2×HCID 8857Ethyl AcetateSolventHCID 57417360Sodium chloride; waterSolvent

Procedure

To a solution of 2.01 g (23.9 mmol) of 2-butynoic acid and 2.9 ml (22.3 mmol) isobutyl chloroformate in 30 ml tetrahydrofuran was stirred at 0° C. under nitrogen as 2.42 g (2.63 ml, 22.3 mmol) of N-methyl morpholine was added over 3 min. After stirring for 15 min., a solution of N'-(4-amino-2-cyanophenyl)-N,N-dimethylformamidine and 1.6 g (1.75 ml, 15.9 mmol) of N-methyl morpholine in 25 ml tetrahydrofuran was added over 4 min. The mixture was stirred 30 min. at 0° C. and 30 min. at room temperature. The mixture was diluted with 70 ml of ethyl acetate and poured into a mixture of brine and saturated sodium bicarbonate. The organic layer was dried (MgSO4) and filtered through a pad of silica gel. The solvent was removed and the residue was stirred with 50 ml of ether. The suspended solid was collected to give 3.61 g (89%) of an off-white solid. mass spectrum (m/e): 255.0 (M+H, electrospray).

Workup

  1. additionwas added over 3 min
  2. stirringThe mixture was stirred 30 min. at 0° C. and 30 min. at room temperature
  3. dry with materialThe organic layer was dried (MgSO4)
  4. filtrationfiltered through a pad of silica gel
  5. customThe solvent was removed
  6. stirringthe residue was stirred with 50 ml of ether
  7. customThe suspended solid was collected

Sources & evidence

ORD record
ord-07a9a542b1654bb29ad329e06359b547
Source dataset
uspto-grants-1999_07
Patent number
US05929080

Reaction notes

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