4-Bromophenol → 4-(1,1-Dimethyl-2-propynyloxy)bromobenzene

HRID 1073931Notes

Reaction equation

HRID 1073931 reaction equation
[CH:1]1[C:6]([OH:7])=[CH:5][CH:4]=[C:3]([Br:8])[CH:2]=1.[CH3:9][C:10](O)([C:12]#[CH:13])[CH3:11].N(C(OCC)=O)=NC(OCC)=O.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1>ClCCl>[CH3:9][C:10]([CH3:11])([O:7][C:6]1[CH:5]=[CH:4][C:3]([Br:8])=[CH:2][CH:1]=1)[C:12]#[CH:13]

Participants

6

Reactant 4

HCID 78084-BromophenolHCID 82582-Methyl-3-butyn-2-olHCID 11776TriphenylphosphineHCID 220568ethyl N-ethoxycarbonyliminocarbamate

Product 1

HCID 540101944-(1,1-Dimethyl-2-propynyloxy)bromobenzeneYield 15.1%

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent

Procedure

69.2 g of p-bromophenol and 33.6 g of 2-methylbut-3-yn-2-ol were dissolved in 600 ml of dichloromethane and 75 ml of diethyl azodicarboxylate were added. 126 g of triphenylphosphine were added portionwise and the mixture was stirred overnight. The mixture was washed with dilute hydrochloric acid and 2M sodium hydroxide solution, dried over sodium sulphate and evaporated. The residue was chromatographed on silica gel using ethyl acetate/petroleum ether (1:10) for the elution. There was obtained an oil which was distilled to give 14.4 g of 4-(1,1-dimethyl-2-propynyloxy)bromobenzene of boiling point 96°-106° C./1 mmHg.

Workup

  1. washThe mixture was washed with dilute hydrochloric acid and 2M sodium hydroxide solution
  2. dry with materialdried over sodium sulphate
  3. customevaporated
  4. customThe residue was chromatographed on silica gel
  5. washfor the elution
  6. customThere was obtained an oil which
  7. distillationwas distilled

Sources & evidence

ORD record
ord-c8ae302e66e9466182d94de4e4e16313
Source dataset
uspto-grants-1990_11
Patent number
US04971982

Reaction notes

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