Phenol → 1-Chloro-2-(3-methyl-2-butenyloxy)-4-nitrobenzene

HRID 50012

Reaction equation

HRID 50012 reaction equation
[Cl:1][C:2]1[CH:7]=[CH:6][C:5]([N+:8]([O-:10])=[O:9])=[CH:4][C:3]=1[OH:11].C(=O)([O-])[O-].[K+].[K+].Br[CH2:19][CH:20]=[C:21]([CH3:23])[CH3:22].C1(O)C=CC=CC=1>[Br-].C([N+](CCCC)(CCCC)CCCC)CCC.C(C(C)=O)C>[Cl:1][C:2]1[CH:7]=[CH:6][C:5]([N+:8]([O-:10])=[O:9])=[CH:4][C:3]=1[O:11][CH2:19][CH:20]=[C:21]([CH3:23])[CH3:22]

Participants

7

Reactant 4

HCID 996PhenolHCID 11430Potassium CarbonateHCID 692642-Chloro-5-nitrophenolHCID 700922-Butene, 1-bromo-3-methyl-2×

Product 1

HCID 129856901-Chloro-2-(3-methyl-2-butenyloxy)-4-nitrobenzene

Reagents, catalysts & solvents 2

HCID 74236Tetrabutylammonium BromideCatalystHCID 6569Methyl Ethyl KetoneSolvent

Procedure

A reaction mixture of 2-chloro-5-nitrophenol (50.6 g), anhydrous potassium carbonate (44.5 g), tetrabutylammonium bromide (4.7 g) and 4-bromo-2-methyl-2-butene (53.3 g, 90%) in methyl ethyl ketone (263 mL) was stirred at ambient temperature overnight. TLC of the reaction mixture showed traces of phenol remaining. Additional prenyl bromide (1 mL) was then added to the reaction mixture and stirred for 2 hours. The solvent was then removed from the reaction mixture. The residue of the reaction mixture was then treated with water and extracted into diethyl ether. The extract was washed with 2N sodium hydroxide and water, dried (MgSO4), filtered, and evaporated, to leave a brown solid which was recrystallised from ethyl acetate/isopropyl alcohol to give 1-chloro-2-(3-methyl-2-butenyloxy)-4-nitrobenzene, 49.5 g, a beige solid, a single spot on TLC (ethyl acetate:hexane, 20:80).

Workup

  1. stirringstirred for 2 hours
  2. customThe solvent was then removed from the reaction mixture
  3. additionThe residue of the reaction mixture was then treated with water
  4. extractionextracted into diethyl ether
  5. washThe extract was washed with 2N sodium hydroxide and water
  6. dry with materialdried (MgSO4)
  7. filtrationfiltered
  8. customevaporated
  9. customto leave a brown solid which
  10. customwas recrystallised from ethyl acetate/isopropyl alcohol

Sources & evidence

ORD record
ord-838b54af43ff4a799efbc77e83ff702c
Source dataset
uspto-grants-2004_03
Patent number
US06710077B1

Linked notes

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