Water → 2-Amino-3-nitro-5-p-tolylpyridine

HRID 722070Notes

Reaction equation

HRID 722070 reaction equation
[C:1]1([CH3:10])[CH:6]=[CH:5][C:4](B(O)O)=[CH:3][CH:2]=1.C(=O)([O-])[O-].[Na+].[Na+].[NH2:17][C:18]1[C:23]([N+:24]([O-:26])=[O:25])=[CH:22][C:21](Br)=[CH:20][N:19]=1.O>O1CCOCC1.C1CCC(P(C2CCCCC2)C2CCCCC2)CC1.C1CCC(P(C2CCCCC2)C2CCCCC2)CC1.Cl[Pd]Cl>[NH2:17][C:18]1[C:23]([N+:24]([O-:26])=[O:25])=[CH:22][C:21]([C:4]2[CH:5]=[CH:6][C:1]([CH3:10])=[CH:2][CH:3]=2)=[CH:20][N:19]=1

Participants

7

Reactant 4

HCID 962WaterHCID 10340Sodium CarbonateHCID 79799Tolylboronic acidHCID 1388782-Amino-5-bromo-3-nitropyridine

Product 1

HCID 218827162-Amino-3-nitro-5-p-tolylpyridine

Reagents, catalysts & solvents 2

HCID 11050900Dichlorobis(tricyclohexylphosphine)pallium (II)CatalystHCID 312751,4-DioxaneSolvent

Procedure

0.19 g of dichlorobis(tricyclohexylphosphine)palladium, 0.754 g of 4-tolyl-boronic acid and 12.5 ml of a 2N sodium carbonate solution are added to a solution of 0.93 g of 2-amino-5-bromo-3-nitropyridine in 20 ml of degassed dioxane. The mixture is heated to reflux under N2 for 2.5 hours and, after cooling and addition of water, extracted three times with dichloromethane. The combined organic phases are dried over sodium sulfate and concentrated until a solid begins to precipitate. After addition of petroleum ether, the orange solid is isolated by suction, washed with petroleum ether and dried in vacuo. This gives 0.73 g of the title compound of m.p. 183–184° C. The mass spectrum shows the molecular peak MH+ at 230.1 Da.

Workup

  1. temperatureThe mixture is heated
  2. temperatureto reflux under N2 for 2.5 hours
  3. temperatureafter cooling
  4. extractionextracted three times with dichloromethane
  5. dry with materialThe combined organic phases are dried over sodium sulfate
  6. concentrationconcentrated until a solid
  7. customto precipitate
  8. additionAfter addition of petroleum ether
  9. customthe orange solid is isolated by suction
  10. washwashed with petroleum ether
  11. customdried in vacuo

Sources & evidence

ORD record
ord-1969f66519f14cab80bd060758c0999d
Source dataset
uspto-grants-2006_11
Patent number
US07138399B2

Reaction notes

Loading…