3-Aminopyridine → Methyl 2-cyano-3-(methylsulfanyl)-3-(3-pyridinylamino)-2-propenoate

HRID 1724644Notes

Reaction equation

HRID 1724644 reaction equation
[NH2:1][C:2]1[CH:3]=[N:4][CH:5]=[CH:6][CH:7]=1.C([Li])CCC.[CH3:13][S:14][C:15](SC)=[C:16]([C:21]#[N:22])[C:17]([O:19][CH3:20])=[O:18]>C1COCC1.CCCCCC>[C:21]([C:16](=[C:15]([S:14][CH3:13])[NH:1][C:2]1[CH:3]=[N:4][CH:5]=[CH:6][CH:7]=1)[C:17]([O:19][CH3:20])=[O:18])#[N:22]

Participants

6

Reactant 3

HCID 100093-AminopyridineHCID 319957Methyl 2-cyano-3,3-bis(methylsulfanyl)prop-2-enoateHCID 178418339Butyllithium

Product 1

HCID 68937763Methyl 2-cyano-3-(methylsulfanyl)-3-(3-pyridinylamino)-2-propenoate

Reagents, catalysts & solvents 2

HCID 8028TetrahydrofuranSolventHCID 8058HexaneSolvent

Conditions

Temperature
-20 °C

Procedure

1.39 g (14.8 mmol) of 3-aminopyridine are dissolved in 50 ml of THF, cooled to −20° C., and 7.4 ml of a 2M solution of n-butyllithium in hexane are added. After stirring for 15 min, 2.00 g (9.84 mmol) of methyl 3,3-bis(methylthio)-2-cyanoacrylate are added. The mixture is warmed to room temperature while stirring and then hydrolyzed with ice-water. The product is extracted with dichloromethane. After drying over sodium sulfate, the solvent is removed in vacuo and the residue is purified by preparative HPLC. 0.44 g (18.1% of theory) of the desired product is obtained.

Workup

  1. temperatureThe mixture is warmed to room temperature
  2. stirringwhile stirring
  3. extractionThe product is extracted with dichloromethane
  4. dry with materialAfter drying over sodium sulfate
  5. customthe solvent is removed in vacuo
  6. customthe residue is purified by preparative HPLC

Sources & evidence

ORD record
ord-3cf20e77010b4cb2b9a346e5b3f41dc0
Source dataset
uspto-grants-2009_02
Patent number
US07488733B2

Reaction notes

Loading…