Triphenylphosphine → 2-Bromo-4-methyl-1-((3-methylpent-4-en-2-yl)oxy)benzene

HRID 1400757Notes

Reaction equation

HRID 1400757 reaction equation
[Br:1][C:2]1[CH:7]=[C:6]([CH3:8])[CH:5]=[CH:4][C:3]=1[OH:9].[CH3:10][CH:11]([CH:15]=[CH2:16])[CH:12](O)[CH3:13].C1C=CC(P(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1.CCOC(/N=N/C(OCC)=O)=O>C1COCC1.O>[Br:1][C:2]1[CH:7]=[C:6]([CH3:8])[CH:5]=[CH:4][C:3]=1[O:9][CH:15]([CH:11]([CH3:10])[CH:12]=[CH2:13])[CH3:16]

Participants

7

Reactant 4

HCID 11776TriphenylphosphineHCID 231092-Bromo-4-methylphenolHCID 5447013-Methyl-4-penten-2-olHCID 5462977Diethyl azodicarboxylate

Product 1

HCID 867108152-Bromo-4-methyl-1-((3-methylpent-4-en-2-yl)oxy)benzeneYield 59.8%

Reagents, catalysts & solvents 2

HCID 962WaterSolventHCID 8028TetrahydrofuranSolvent

Procedure

To a solution of 2-bromo-4-methylphenol (1 g, 5.35 mmol) and 3-methylpent-4-en-2-ol (2.68 g, 26.7 mmol) in THF (20 mL) was added Ph3P (7.01 g, 26.7 mmol) followed by DEAD (4.23 mL, 26.7 mmol) and the resulting mixture was stirred at room temp for 16 h. Water was then added and the mixture was extracted with ether (2×50 mL), dried (Na2SO4), filtered and concentrated. The residue was then purified by Biotage (0-20% EtOAc/hexane) to afford 2-bromo-4-methyl-1-((3-methylpent-4-en-2-yl)oxy)benzene (860 mg, 3.19 mmol, 59.8% yield) as yellow oil. Product is approx 2:1 mixture of trans/cis isomers. 1H NMR (400 MHz, CDCl3) δ 7.38 (d, J=2.0 Hz, 1H), 7.08-7.01 (m, 1H), 6.83-6.79 (m, 1H), 6.02-5.89 (m, 1H), 5.16 (q, J=1.8 Hz, 0.5H), 5.14-5.08 (m, 1.5H), 4.31-4.37 (m, 0.3H), 4.28-4.19 (m, 0.7H), 2.64-2.50 (m, 1H), 2.29 (s, 3H), 1.30-1.24 (m, 3H), 1.19-1.14 (m, 3H).

Workup

  1. extractionthe mixture was extracted with ether (2×50 mL)
  2. dry with materialdried (Na2SO4)
  3. filtrationfiltered
  4. concentrationconcentrated
  5. customThe residue was then purified by Biotage (0-20% EtOAc/hexane)

Sources & evidence

ORD record
ord-8e105f46896141aeb7dfda9e017486b6
Source dataset
uspto-grants-2014_12
Patent number
US08906929B2

Reaction notes

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