Ammonium Chloride → HCID 12882214, compound

HRID 1165708Notes

Reaction equation

HRID 1165708 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 the above solution. 50 ml of a 15% strength solution of n-butyllithium in n-hexane was then slowly added dropwise to the mixture at -120° C. The mixture was first stirred for 2 hours at a temperature of approximately -110° C., and was thereafter stirred overnight at -78° C. The reaction mixture was warmed to room temperature and 100 ml of 10% strength ammonium chloride solution and 200 ml of ethyl acetate were added to it, and the aqueous phase was separated off. The organic phase was washed successively once with 1N hydrochloric acid and twice with saturated sodium chloride solution, and was dried over sodium sulphate and concentrated. The residue was suspended in ether, and the solid material was filtered off under suction and recrystallized from acetonitrile. 12.3 g (50% of theory relative to n-butyllithium) of 1-(4-chlorophenoxy)-3,3-dimethyl-2-(pyrimidin-5-yl)-butan-2-ol of melting point 172°-174° C. were obtained.

Workup

  1. stirringwas thereafter stirred overnight at -78° C
  2. temperatureThe reaction mixture was warmed to room temperature
  3. customthe aqueous phase was separated off
  4. washThe organic phase was washed successively once with 1N hydrochloric acid and twice with saturated sodium chloride solution
  5. dry with materialwas dried over sodium sulphate
  6. concentrationconcentrated
  7. filtrationthe solid material was filtered off under suction
  8. customrecrystallized from acetonitrile

Sources & evidence

ORD record
ord-915e67bb739f44daa1524ecb22bec7a6
Source dataset
uspto-grants-1990_03
Patent number
US04911750

Reaction notes

Loading…