Sulfuric Acid → (6-Methyl-3-nitropyridin-2-yl)acetonitrile

HRID 1681279Notes

Reaction equation

HRID 1681279 reaction equation
[N+:1]([C:4]1[C:5]([CH2:25][C:26]#[N:27])=[N:6][C:7]([CH:10](C(OC(C)(C)C)=O)C(OC(C)(C)C)=O)=[CH:8][CH:9]=1)([O-:3])=[O:2].S(=O)(=O)(O)O.C(=O)([O-])[O-].[Na+].[Na+]>O1CCOCC1>[CH3:10][C:7]1[N:6]=[C:5]([CH2:25][C:26]#[N:27])[C:4]([N+:1]([O-:3])=[O:2])=[CH:9][CH:8]=1

Participants

5

Reactant 3

HCID 1118Sulfuric AcidHCID 10340Sodium CarbonateHCID 15009581HCID 15009581, compound

Product 1

HCID 14822074(6-Methyl-3-nitropyridin-2-yl)acetonitrileYield 59.3%

Reagents, catalysts & solvents 1

HCID 312751,4-DioxaneSolvent

Procedure

A mixture of (3-nitro-6-(dicarbo-t-butoxymethyl)-2-pyridyl)acetonitrile (6.85 g, 18.2 mmol), dioxane (150 mL), and 2M sulfuric acid (25 mL) was heated at reflux for 12 hours. The resulting solution was cooled, neutralized with sodium carbonate, and extracted with ethyl acetate (3×50 mL). These extracts were combined, dried (MgSO4), and evaporated under reduced pressure to yield an oil. This oil was passed through a silica gel filter (approximately 100 g) followed by methylene chloride. This filtrate was evaporated under reduced pressure to afford (6-methyl-3-nitro-2-pyridyl)acetonitrile (1.91 g, 10.8 mmol, 59%) as an off-white solid: mp, 70°-72° C.; IR (KBr) 2,245, 1,595, 1,580, 1,515, 1,450, 1,370, 1,340 cm-1 ; 1H NMR (CDCl3) δ 8.38 (d, J=8.4 Hz, 1H), 7.37 (d, J=8.4 Hz, 1H), 4.39 (s, 2H), 2.70 (s, 3H); 13C NMR (CDCl3) δ 164.7, 145.3, 142.1, 133.8, 123.9, 115.1, 27.1, 24.7; LRMS (m/z, relative intensity) 178 (29), 177 (M+, 93), 160 (16), 132 (26), 131 (92), 105 (37), 104 (100), 92 (32), 79 (50), 78 (51), 77 (81), 63 (54); HRMS 3.98; N, 23.72; found: C, 53.90; H, 3.95; N, 23.47.

Workup

  1. temperaturewas heated
  2. temperatureat reflux for 12 hours
  3. temperatureThe resulting solution was cooled
  4. extractionextracted with ethyl acetate (3×50 mL)
  5. dry with materialdried (MgSO4)
  6. customevaporated under reduced pressure
  7. customto yield an oil
  8. filtrationfilter (approximately 100 g)
  9. customThis filtrate was evaporated under reduced pressure

Sources & evidence

ORD record
ord-e2ec631dd4f5473080e0c9155423442f
Source dataset
uspto-grants-1992_12
Patent number
US05169947

Reaction notes

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