Stannous chloride dihydrate → HCID 66665987, compound

HRID 522431Notes

Reaction equation

HRID 522431 reaction equation
[C:1]([C:5]1[N:10]=[CH:9][N:8]=[C:7]([NH2:11])[CH:6]=1)([CH3:4])([CH3:3])[CH3:2].Br[CH2:13][C:14]([C:16]1[CH:21]=[CH:20][CH:19]=[CH:18][C:17]=1[N+:22]([O-])=O)=O.O.O.[Sn](Cl)Cl.C(=O)([O-])O.[Na+]>C(O)C.C(OCC)(=O)C>[C:1]([C:5]1[N:10]=[CH:9][N:8]2[CH:13]=[C:14]([C:16]3[CH:21]=[CH:20][CH:19]=[CH:18][C:17]=3[NH2:22])[N:11]=[C:7]2[CH:6]=1)([CH3:4])([CH3:2])[CH3:3]

Participants

7

Reactant 4

HCID 61436Stannous chloride dihydrateHCID 2440252-Bromo-2'-nitroacetophenoneHCID 516892Sodium BicarbonateHCID 7137446-tert-butylpyrimidin-4-amine

Product 1

HCID 66665987HCID 66665987, compound

Reagents, catalysts & solvents 2

HCID 702EthanolSolventHCID 8857Ethyl AcetateSolvent

Procedure

A solution of 15.1 g (100 mmol) of 6-tert-butylpyrimidin-4-ylamine [3435-27-6] and 24.4 g (100 mmol) of 2-bromo-1-(2-nitrophenyl)ethanone [6851-99-6] in 300 ml of ethanol is heated under reflux for 8 h. The solvent is removed in vacuo, the residue is taken up in 200 ml of water, the mixture is rendered alkaline by addition of 2 N NaOH, the aqueous phase is extracted three times with 100 ml of dichloromethane each time, the organic phase is washed once with 100 ml of saturated sodium chloride solution, and the dichloromethane is removed in vacuo. The oily residue is dissolved in 500 ml of ethanol, 112.8 g (500 mmol) of tin(II) chloride dihydrate are added, and the mixture is heated under reflux for 2 h. After cooling, the reaction mixture is poured into 1000 ml of ice-water, the mixture is rendered weakly alkaline by addition of saturated sodium hydrogencarbonate solution, 500 ml of ethyl acetate are added, the mixture is filtered through a short Celite bed, the organic phase is separated off, washed once with 300 ml of water and once with 300 ml of saturated sodium chloride solution, and the solvent is then removed in vacuo. The 2-(7-tert-butylimidazo[1,2-c]pyrimidin-2-yl)phenylamine obtained in this way is reacted further as described in Example 1 with 42.1 g (500 mmol) of 2,2-dimethylpropanal [630-19-3] and 1.9 g (10 mmol) of p-toluenesulfonic acid hydrate. Yield: 9.0 g (27 mmol), 27%, purity: about 99.5% (NMR).

Workup

  1. temperatureunder reflux for 8 h
  2. customThe solvent is removed in vacuo
  3. additionby addition of 2 N NaOH
  4. extractionthe aqueous phase is extracted three times with 100 ml of dichloromethane each time
  5. washthe organic phase is washed once with 100 ml of saturated sodium chloride solution
  6. customthe dichloromethane is removed in vacuo
  7. dissolutionThe oily residue is dissolved in 500 ml of ethanol
  8. temperaturethe mixture is heated
  9. temperatureunder reflux for 2 h
  10. temperatureAfter cooling
  11. additionare added
  12. filtrationthe mixture is filtered through a short Celite bed
  13. customthe organic phase is separated off
  14. washwashed once with 300 ml of water and once with 300 ml of saturated sodium chloride solution
  15. customthe solvent is then removed in vacuo

Sources & evidence

ORD record
ord-86225cf91d6f462a87770de3f7892605
Source dataset
uspto-grants-2016_05
Patent number
US09331290B2

Reaction notes

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