2-Chloro-3-nitropyridine → HCID 18967512, compound

HRID 235143Notes

Reaction equation

HRID 235143 reaction equation
[NH2:1][C:2]1[CH:11]=[C:10]2[C:5]([CH:6]=[CH:7][CH:8]=[C:9]2[CH:12]2[CH2:17][CH2:16][N:15]([CH3:18])[CH2:14][CH2:13]2)=[CH:4][CH:3]=1.Cl[C:20]1[C:25]([N+:26]([O-:28])=[O:27])=[CH:24][CH:23]=[CH:22][N:21]=1>CN(C)C1C=CN=CC=1.CN(C)C=O>[N+:26]([C:25]1[C:20]([NH:1][C:2]2[CH:11]=[C:10]3[C:5]([CH:6]=[CH:7][CH:8]=[C:9]3[CH:12]3[CH2:13][CH2:14][N:15]([CH3:18])[CH2:16][CH2:17]3)=[CH:4][CH:3]=2)=[N:21][CH:22]=[CH:23][CH:24]=1)([O-:28])=[O:27]

Participants

5

Reactant 2

HCID 796132-Chloro-3-nitropyridineHCID 18967546HCID 18967546, compound

Product 1

HCID 18967512HCID 18967512, compoundYield 33.5%

Reagents, catalysts & solvents 2

HCID 142844-(Dimethylamino)pyridineCatalystHCID 6228DimethylformamideSolvent

Procedure

A mixture of the product from Example 57 (0.338 g, 1.4 mmol), 2-chloro-3-nitropyridine (0.446 g, 2.81 mmol), and 4-dimethylaminopyridine (0.172 g, 1.4 mmol) in dimethylformamide (6 mL) was refluxed 5 hours. The solvent was removed at reduced pressure and the residue was taken up in methylene chloride. The organic phase was washed with 1N sodium hydroxide and brine, then it was concentrated onto silica gel and flash chromatographed (1×4 inches silica gel). The elution proceeded as follows: 75% methylene chloride/hexane (175 mL) nil; methylene chloride (250 mL) unweighed excess 2-chloro-3-nitropyridine; 2% methanol/methylene chloride (200 mL) nil, (550 mL) 0.373 g of crude product contaminated with 4-dimethylamino-pyridine. This material was triturated with ether and filtered to give 0.17 g of title product as orange crystals. 1H NMR δ 10.34 (br s, 1 H), 8.59 (dd, J=2, 8.5 Hz, 1 H), 8.54-8.50 (m, 2 H), 7.88 (d, J=9 Hz, 1 H), 7.72-7.70 (m, 1 H), 7.66 (dd, J=2, 9 Hz, 1H), 7.45-7.41 (m, 2 H), 6.89 (dd, J=4.5, 8.5 Hz, 1 H), 3.27 (tt, J=4, 11.5 Hz, 1 H), 3.11 (long range coupled d, J=11.5 Hz, 1 H), 2.41 (s, 3 H), 2.27 (dt, J=2.5, 11.5 Hz, 2 H), 2.09-1.89 (m, 4 H).

Workup

  1. temperaturewas refluxed 5 hours
  2. customThe solvent was removed at reduced pressure
  3. washThe organic phase was washed with 1N sodium hydroxide and brine
  4. concentrationit was concentrated onto silica gel and flash
  5. customchromatographed (1×4 inches silica gel)
  6. washThe elution
  7. customThis material was triturated with ether
  8. filtrationfiltered

Sources & evidence

ORD record
ord-b0d0531f814d4028ae897729a0d88066
Source dataset
uspto-grants-1997_01
Patent number
US05597826

Reaction notes

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