Tert-Butyl nitrite → 2,3-Dichloro-5-(methylthio)pyridine

HRID 1279188Notes

Reaction equation

HRID 1279188 reaction equation
N[C:2]1[CH:3]=[N:4][C:5]([Cl:9])=[C:6]([Cl:8])[CH:7]=1.[CH3:10][S:11]SC.N(OC(C)(C)C)=O>C(Cl)Cl>[Cl:9][C:5]1[C:6]([Cl:8])=[CH:7][C:2]([S:11][CH3:10])=[CH:3][N:4]=1

Participants

5

Reactant 3

HCID 10906Tert-Butyl nitriteHCID 12232Dimethyl DisulfideHCID 145952195-Amino-2,3-dichloropyridine

Product 1

HCID 153764962,3-Dichloro-5-(methylthio)pyridineYield 62%

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent2×

Procedure

A solution of 50.6 g (0.3 mol) of 3-amino-5,6-dichloropyridine in 700 ml of methylene chloride was slowly added dropwise at 40° C. to a solution of 56.6 g (0.6 mol) of dimethyl disulfide and 46.7 g (0.45 mol) of tert-butyl nitrite in 320 ml of dry methylene chloride. The mixture was then stirred for 1 hour at 40° C. and subsequently for another approximately 15 hours at approximately 20° C., whereupon 500 ml of ice-water were added to the reaction mixture. The organic phase which was separated off was washed once with 1 N hydrochloric acid and once with water, dried over sodium sulfate and finally concentrated. After the crude product had been stirred with n-hexane, 21 g of a dark solid were obtained (purity 94% according to GC). After the hexane solution was concentrated, a further 21.3 g of product of value remained which had a purity of 77% (according to GC). Total yield: 62%; m.p.: 66-67° C.; 1H-NMR (in d6 dimethyl sulfoxide): δ [ppm]=2.6 (s, CH3); 8.1 and 8.3 (2×d, pyr H).

Workup

  1. additionwere added to the reaction mixture
  2. customThe organic phase which was separated off
  3. washwas washed once with 1 N hydrochloric acid and once with water
  4. dry with materialdried over sodium sulfate
  5. concentrationfinally concentrated

Sources & evidence

ORD record
ord-a0ccc401000d46aca956529fb60e1a5a
Source dataset
uspto-grants-2002_09
Patent number
US06448205B1

Reaction notes

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