Ammonium Chloride → HCID 12882214, compound

HRID 1248518Notes

Reaction equation

HRID 1248518 reaction equation
[Cl:1][C:2]1[CH:15]=[CH:14][C:5]([O:6][CH2:7][C:8](=[O:13])[C:9]([CH3:12])([CH3:11])[CH3:10])=[CH:4][CH:3]=1.Br[C:17]1[CH:18]=[N:19][CH:20]=[N:21][CH:22]=1.C([Li])CCC.[Cl-].[NH4+]>O1CCCC1.CCOCC.CCCCCC.C(OCC)(=O)C>[Cl:1][C:2]1[CH:15]=[CH:14][C:5]([O:6][CH2:7][C:8]([C:17]2[CH:18]=[N:19][CH:20]=[N:21][CH:22]=2)([OH:13])[C:9]([CH3:11])([CH3:12])[CH3:10])=[CH:4][CH:3]=1

Participants

9

Reactant 4

HCID 25517Ammonium ChlorideHCID 783445-BromopyrimidineHCID 905182-Butanone, 1-(4-chlorophenoxy)-3,3-dimethyl-HCID 178418339Butyllithium

Product 1

HCID 12882214HCID 12882214, compoundYield 50%

Reagents, catalysts & solvents 4

HCID 3283Diethyl EtherSolventHCID 8028TetrahydrofuranSolvent2×HCID 8058HexaneSolventHCID 8857Ethyl AcetateSolvent

Conditions

Temperature
-110 °C

Procedure

A solution of 22.65 g (0.1 mol) of 1-(4-chlorophenoxy)-3,3-dimethyl-butan-2-one in 110 ml of absolute tetrahydrofuran and 70 ml of absolute ether was cooled to -120° C. under a dry nitrogen atmosphere. A solution of 15.9 g (0.1 mol) of 5-bromopyrimidine in 50 ml of absolute tetrahydrofuran was added dropwise to this solution. 50 ml of a 15% strength solution of n-butyl-lithium in n-hexane were then slowly added dropwise at -120° C. The mixture was subsequently stirred, first at a temperature of about -110° C. for 2 hours and then at -78° C. overnight. The reaction mixture was warmed to room temperature, 100 ml of 10% strength ammonium chloride solution and 200 ml of ethyl acetate were added and the aqueous phase was separated off. The organic phase was washed once with 1 N hydrochloric acid and then twice with saturated sodium chloride solution, dried over sodium sulphate and concentrated. The residue was suspended in ether and the solid was filtered off and recrystallised from acetonitrile. 12.3 g (50% of theory, relative to n-butyl-lithium) of 1-(4-chlorophenoxy)-3,3-dimethyl-2-(pyrimidin-5-yl)-butan-2-ol of melting point 172°-174° C. were obtained.

Workup

  1. customat -78° C.
  2. customovernight
  3. temperatureThe reaction mixture was warmed to room temperature
  4. customthe aqueous phase was separated off
  5. washThe organic phase was washed once with 1 N hydrochloric acid
  6. dry with materialtwice with saturated sodium chloride solution, dried over sodium sulphate
  7. concentrationconcentrated
  8. filtrationthe solid was filtered off
  9. customrecrystallised from acetonitrile

Sources & evidence

ORD record
ord-f762298bd2bd482fa6d7c5f83b3185cb
Source dataset
uspto-grants-1985_06
Patent number
US04525204

Reaction notes

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