Hydrochloric Acid → 2-(3-Nitro-phenylamino)-pyridine-3-carbaldehyde

HRID 1241709Notes

Reaction equation

HRID 1241709 reaction equation
Br[C:2]1[N:9]=[CH:8][CH:7]=[CH:6][C:3]=1[CH:4]=[O:5].[N+:10]([C:13]1[CH:14]=[C:15]([CH:17]=[CH:18][CH:19]=1)[NH2:16])([O-:12])=[O:11].C(=O)([O-])[O-].[Cs+].[Cs+].Cl>C1(C)C=CC=CC=1.O.C([O-])(=O)C.[Pd+2].C([O-])(=O)C.C1(P(C2C=CC=CC=2)CCCP(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.ClCCl>[N+:10]([C:13]1[CH:14]=[C:15]([NH:16][C:2]2[N:9]=[CH:8][CH:7]=[CH:6][C:3]=2[CH:4]=[O:5])[CH:17]=[CH:18][CH:19]=1)([O-:12])=[O:11]

Participants

10

Reactant 4

HCID 313Hydrochloric AcidHCID 74233-NitroanilineHCID 10796Cesium carbonateHCID 47149512-Bromonicotinaldehyde

Product 1

HCID 121149522-(3-Nitro-phenylamino)-pyridine-3-carbaldehydeYield 83.1%

Reagents, catalysts & solvents 5

HCID 812191,3-Bis(diphenylphosphino)propaneCatalystHCID 167845palladium(II) acetateCatalystHCID 962WaterSolventHCID 1140TolueneSolventHCID 6344DichloromethaneSolvent

Conditions

Temperature
100 °C

Procedure

A suspension of 2-bromonicotinaldehyde (2.54 g, 13.6 mmol; synthesized according to SYNTHETIC COMMUNICATIONS, 23(19): 2727–2730 (1993)), 3-nitroaniline (2.26 g, 1.2 eq.), palladium acetate (123 mg, 0.04 eq.), 1,3-bis(diphenyl-phosphino)propane (341 mg, 0.06 eq.), and cesium carbonate (6.22 g, 1.4 eq.) in toluene (30 ml) was stirred at 100° C. for 4 hours under nitrogen atmosphere, and cooled to room temperature, followed by addition of 10% hydrochloric acid (50 ml) and dichloromethane. The mixture was stirred for 1 hr, then diluted with water (50 ml), and extracted with dichloromethane. The extract was dried, and then evaporated. To the residue was added hexane to precipitate crystals, filtered off, washed with hexane, and dried under reduced pressure to afford 2-(3-nitrophenylamino)-nicotinaldehyde as a yellow powder (2.75 g, 74%).

Workup

  1. temperaturecooled to room temperature
  2. stirringThe mixture was stirred for 1 hr
  3. extractionextracted with dichloromethane
  4. customThe extract was dried
  5. customevaporated
  6. additionTo the residue was added hexane
  7. customto precipitate crystals
  8. filtrationfiltered off
  9. washwashed with hexane
  10. customdried under reduced pressure

Sources & evidence

ORD record
ord-8c7355841fd547908b661b08dbd8ec8f
Source dataset
uspto-grants-2006_10
Patent number
US07115623B2

Reaction notes

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