Benzoyl Peroxide → (E)-Ethyl 4-Bromo-3-methyl-2-butenoate

HRID 373203Notes

Reaction equation

HRID 373203 reaction equation
[CH3:1][C:2]([CH3:9])=[CH:3][C:4]([O:6][CH2:7][CH3:8])=[O:5].[Br:10]N1C(=O)CCC1=O.C(OOC(=O)C1C=CC=CC=1)(=O)C1C=CC=CC=1>C1C=CC=CC=1>[Br:10][CH2:1]/[C:2](/[CH3:9])=[CH:3]/[C:4]([O:6][CH2:7][CH3:8])=[O:5]

Participants

5

Reactant 3

HCID 7187Benzoyl PeroxideHCID 12516Ethyl 3,3-dimethylacrylateHCID 67184N-bromobutanimide

Product 1

HCID 11095793(E)-Ethyl 4-Bromo-3-methyl-2-butenoate

Reagents, catalysts & solvents 1

HCID 241BenzeneSolvent

Procedure

A mixture of ethyl 3,3-dimethylacrylate (12.8g, 100 mmol), N-bromosuccinimide (11.8g, 66 mmol), dry benzene (50 ml) and benzoyl peroxide (20 mg) was heated under reflux for 0.5h. After cooling, filtration, concentration and distillation, ethyl 4-bromo-3-methylcrotonate was obtained. The latter (33.8 mmol) was added dropwise to triethylphosphite (47.17 mmol) at 100°. The mixture was warmed to 150o and the residue purified by distillation to give triethyl 4-phosphono-3-methylcrotonate (b.p. 120° at 0.5 mm.Hg) as a cis/trans mixture.

Workup

  1. temperaturewas heated
  2. temperatureunder reflux for 0.5h
  3. temperatureAfter cooling
  4. filtrationfiltration, concentration and distillation

Sources & evidence

ORD record
ord-e9742e99a8f04a57b372f8fea82a5f85
Source dataset
uspto-grants-1992_11
Patent number
US05162367

Reaction notes

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