Acetic Acid → (1-{6-[Trifluoromethyl]pyridin-3-yl}ethyl)(methyl)lambda4-sulfanylidenecyanamide
Reaction equation
[CH3:1][S:2][CH:3]([C:5]1[CH:6]=[N:7][C:8]([C:11]([F:14])([F:13])[F:12])=[CH:9][CH:10]=1)[CH3:4].[N:15]#[C:16][NH2:17].[O-]Cl.[Na+].S(S([O-])=O)([O-])(=O)=O.[Na+].[Na+].C(O)(=O)C>C(#N)C>[F:12][C:11]([F:14])([F:13])[C:8]1[N:7]=[CH:6][C:5]([CH:3]([S:2]([CH3:1])=[N:17][C:16]#[N:15])[CH3:4])=[CH:10][CH:9]=1Participants
Reactant 5
Product 1
Reagents, catalysts & solvents 1
Conditions
- Temperature
- -5 °C
Procedure
A solution of 22.1 g (0.1 mol) of 3-[1-(methylthio)ethyl]-6-(trifluoromethyl)pyridine and 5.04 g (0.12 mol) of cyanamide in 150 mL of acetonitrile was cooled to −5° C. To this solution was added 150 g (0.115 mol, Clorox™ 5.7% wt) of aqueous NaOCl dropwise over 15 min. The reaction mixture was allowed to stir at −5° C. for 45 min, and then allowed to warm to 5° C. To the mixture was added 5 mL of 25% aq sodium metabisulfite and the two phase mixture was allowed to settle. To the organic phase was added 5.7 mL (0.1 mol) of glacial acetic acid, and the solution concentrated in vacuo to an oil. This oil was dissolved in 70 mL of CH2Cl2 and washed with 50 mL of water. The aqueous layer was re-extracted with 30 mL of CH2Cl2. The organics were combined and dried over MgSO4. After filtration, the dichloromethane solution was analyzed by LC and contained 42:52 (area) ratio of isomers A and B above.
Workup
- temperatureto warm to 5° C
- concentrationthe solution concentrated in vacuo to an oil
- dissolutionThis oil was dissolved in 70 mL of CH2Cl2
- washwashed with 50 mL of water
- extractionThe aqueous layer was re-extracted with 30 mL of CH2Cl2
- dry with materialdried over MgSO4
- filtrationAfter filtration
Sources & evidence
- ORD record
- ord-375c129aae414cc7b7b740ac3b8122af
- Source dataset
- uspto-grants-2012_06
- Patent number
- US08193222B1
Reaction notes
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