Water → 4-Methyl-6-(methylsulfonyl)pyridin-3-amine

HRID 1811567

Reaction equation

HRID 1811567 reaction equation
Cl[C:2]1[N:7]=[CH:6][C:5]([NH2:8])=[C:4]([CH3:9])[CH:3]=1.[CH3:10][S:11]([O-:13])=[O:12].[Na+].CNCCNC.O>[Cu].CS(C)=O>[CH3:10][S:11]([C:2]1[N:7]=[CH:6][C:5]([NH2:8])=[C:4]([CH3:9])[CH:3]=1)(=[O:13])=[O:12]

Participants

7

Reactant 4

HCID 962WaterHCID 8070N,N'-DimethylethylenediamineHCID 2733271Sodium methanesulfinateHCID 27344253-Amino-6-chloro-4-picoline

Product 1

HCID 586715824-Methyl-6-(methylsulfonyl)pyridin-3-amineYield 27%

Reagents, catalysts & solvents 2

HCID 23978CopperCatalystHCID 679Dimethyl SulfoxideSolvent

Conditions

Temperature
150 °C

Procedure

A mixture of 6-chloro-4-methyl-pyridin-3-ylamine (1.53 g, 11 mmol), sodium methanesulfinate (1.60 g, 16 mmol), copper catalyst (0.50 g, 0.99 mmol), and N1,N2-dimethylethane-1,2-diamine (0.214 mL, 2.0 mmol) in 20 mL DMSO was heated under microwave irradiation at 150° C. After 2 h, mixture was poured into ca. 200 mL water and extracted five times with ca. 200 mL AcOEt. Organic phases were dried over MgSO4, filtered, and concentrated. Residue was purified by column chromatography (AcOEt/hexane 5:1→AcOEt) to give 6-methanesulfonyl-4-methyl-pyridin-3-ylamine as a white solid (0.534 g, 27%). 1HNMR (DMSO-d6, 400 MHz) 32.4 (s, 3H), 3.08 (s, 3H), 6.08 (s, 2H), 7.59 (s, 1H), 7.97 (s, 1H). Exact mass calculated for C7H10N2O2S 186.05 found 187.0 (MH+).

Workup

  1. extractionextracted five times with ca. 200 mL AcOEt
  2. dry with materialOrganic phases were dried over MgSO4
  3. filtrationfiltered
  4. concentrationconcentrated
  5. customResidue was purified by column chromatography (AcOEt/hexane 5:1→AcOEt)

Sources & evidence

ORD record
ord-b197c6bfbf21446cb32f5e377ae6ff9e
Source dataset
uspto-grants-2013_01
Patent number
US08362248B2

Linked notes

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