Allyl bromide → 2,6,6-Trimethyl-1-(1-hydroxy-3-butenyl)-1-cyclohexene

HRID 1579794Notes

Reaction equation

HRID 1579794 reaction equation
[CH2:1](Br)[CH:2]=[CH2:3].[CH3:5][C:6]1[CH2:11][CH2:10][CH2:9][C:8]([CH3:13])([CH3:12])[C:7]=1[CH:14]=[O:15].[NH4+].[Cl-]>CCOCC>[CH3:5][C:6]1[CH2:11][CH2:10][CH2:9][C:8]([CH3:12])([CH3:13])[C:7]=1[CH:14]([OH:15])[CH2:3][CH:2]=[CH2:1]

Participants

5

Reactant 3

HCID 7841Allyl bromide2×HCID 9895beta-CyclocitralHCID 25517Ammonium Chloride

Product 1

HCID 124203212,6,6-Trimethyl-1-(1-hydroxy-3-butenyl)-1-cyclohexeneYield 57%

Reagents, catalysts & solvents 1

HCID 3283Diethyl EtherSolvent3×

Procedure

In a typical experiment 10.7 g. of Mg turnings and 5 g. of allyl bromide were allowed to react in 70 ml. of dry ether. The reaction was exothermic and the temperature of the reaction mixture increased up to the boiling point of the solvent. To this solution allyl bromide (46 g.) and β-cyclocitral (61 g.) in 160 ml. of ether were added with vigorous stirring at such a rate as to maintain the ether at the boiling temperature. The reaction mixture was then kept at reflux during 6 hours and after cooling it was poured into a ice-cold concentrated aqueous solution of NH4Cl. The ethereal layer after the usual treatments gave 2,6,6-trimethyl-1-[1-hydroxy-3-butenyl]-1-cyclohexene (44.5 g.; 57 % yield): B.p. 60°-2°/0.001 Torr; nD20 = 1.4964; d420 = 0.9398; NMR spectrum (CCl4): 0.98 (3 H, s); 1.10 (3 H, s); 1.82 (3 H, s); 1.20-2.80 (9 H, m); 4.22 (1 H, m); 5.04 (2 H, d, J = 15 cps); 5.88 (1 H, m) δ ppm.

Workup

  1. customto react in 70 ml
  2. temperaturethe temperature of the reaction mixture increased up to the boiling point of the solvent
  3. temperatureat reflux during 6 hours
  4. temperatureafter cooling it

Sources & evidence

ORD record
ord-7a7bf897b05e429f9efc5d343d046447
Source dataset
uspto-grants-1976_01
Patent number
US03931326

Reaction notes

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