Water → HCID 67281724, compound

HRID 1958096Notes

Reaction equation

HRID 1958096 reaction equation
[H-].[Na+].[CH:3]1([CH2:6][OH:7])[CH2:5][CH2:4]1.[Br:8][C:9]1[C:10]([Cl:18])=[N:11][CH:12]=[C:13]([N+:15]([O-:17])=[O:16])[CH:14]=1.O>CN(C=O)C>[Br:8][C:9]1[C:10]([O:7][CH2:6][CH:3]2[CH2:5][CH2:4]2)=[N:11][CH:12]=[C:13]([N+:15]([O-:17])=[O:16])[CH:14]=1.[Br:8][C:9]1[C:10]([Cl:18])=[N:11][CH:12]=[C:13]([N+:15]([O-:17])=[O:16])[CH:14]=1

Participants

7

Reactant 4

HCID 962WaterHCID 24758Sodium hydrideHCID 75644CyclopropanemethanolHCID 2308893-Bromo-2-chloro-5-nitropyridine

Product 2

HCID 2308893-Bromo-2-chloro-5-nitropyridineHCID 67281724HCID 67281724, compoundYield 32%

Reagents, catalysts & solvents 1

HCID 6228DimethylformamideSolvent

Conditions

Temperature
25 °C

Procedure

To a solution of sodium hydride (2.21 g, 55.34 mmol) in anhydrous DMF (20 ml) was added cyclopropylmethanol (CAS Registry No. 2516-33-8) (12.45 ml, 153.2 mmol) under nitrogen at 0° C. and the reaction mixture was stirred at 25° C. for 30 minutes. Then 3-bromo-2-chloro-5-nitropyridine (CAS Registry No. 5470-17-7) (7.3 g, 30.74 mmol) was added drop wise at 0° C. and stirred for two hours at 25° C. Water (60m1) was added to the reaction mixture and extracted with ethyl acetate (3×100 ml). The combined organic layers were washed with water and brine, dried over Na2SO4 and evaporated under reduced pressure to get the crude residue (12 g). The crude was purified by column chromatography (2% ethyl acetate/hexane) to get the desired product (2.06 g, 32%) as light yellow solid and 1.7 g of unreacted 3-bromo-2-chloro-5-nitropyridine was recovered. MS (LC/MS): not responding, NMR is in agreement with the structure: 1H-NMR (400 MHz, CDCl3): δ 0.41 (m, 2H), 0.65 (m, 2H), 1.32 (m, 1H), 4.34 (d, 2H), 8.60 (d, 1H), 8.96 (d, 1H).

Workup

  1. addition5470-17-7) (7.3 g, 30.74 mmol) was added drop wise at 0° C.
  2. stirringstirred for two hours at 25° C
  3. extractionextracted with ethyl acetate (3×100 ml)
  4. washThe combined organic layers were washed with water and brine
  5. dry with materialdried over Na2SO4
  6. customevaporated under reduced pressure
  7. customto get the crude residue (12 g)
  8. customThe crude was purified by column chromatography (2% ethyl acetate/hexane)

Sources & evidence

ORD record
ord-17f6cfacb1d8430ab8550b9e9bb743c0
Source dataset
uspto-grants-2013_04
Patent number
US08410107B2

Reaction notes

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