Thionyl Chloride → HCID 178458474, compound

HRID 277621Notes

Reaction equation

HRID 277621 reaction equation
C(O[C:5]1[CH:20]=[CH:19][CH:18]=[CH:17][C:6]=1[C:7]([O:9][C@H:10]1[CH2:15][CH2:14][C@H:13](O)[CH2:12][CH2:11]1)=[O:8])C=C.[Br:21][CH2:22][CH2:23][CH2:24][CH2:25][CH2:26][C:27](Cl)=[O:28].S(Cl)(Cl)=O>C1(C)C=CC=CC=1>[CH2:7]([O:8][C:19]1[CH:20]=[CH:5][C:6]([C:7]([O:9][C@H:10]2[CH2:11][CH2:12][C@H:13]([C:27](=[O:28])[CH2:26][CH2:25][CH2:24][CH2:23][CH2:22][Br:21])[CH2:14][CH2:15]2)=[O:8])=[CH:17][CH:18]=1)[CH:6]=[CH2:5]

Participants

5

Reactant 3

HCID 24386Thionyl ChlorideHCID 898486-Bromohexanoyl chlorideHCID 178458322HCID 178458322, compound

Product 1

HCID 178458474HCID 178458474, compoundYield 189.8%

Reagents, catalysts & solvents 1

HCID 1140TolueneSolvent

Procedure

55.2 g (0.2 mol) of trans-4-hydroxycyclohexyl allyloxybenzoate prepared as described in Example 1 were dissolved in 300 ml of dry toluene, and 43 g (0.205 mol) of 6-bromohexanoyl chloride (prepared from the free acid by conventional reaction with thionyl chloride; b.p. 60-62° C. at 0.04 mbar) were added dropwise at 105° C. over the course of 60 minutes with stirring. After the mixture had been stirred at 105° C. for a further 90 minutes, the solvent was stripped off under reduced pressure, and the residue was crystallized out using petroleum benzine/methyl tert-butyl ether (20:1), giving 83 g (92%) of trans-[4-(6-bromo-hexanoyl)cyclohexyl] 4-allyloxybenzoate, melting point 56° C. 79 g (0.174 mol) of this ester, 25 g (0.21 mol) of potassium methacrylate and 0.2 g of 2,6-di-tert-butyl-4-methylphenol (stabilizer) were dissolved in 400 ml of dimethylformamide, and the mixture was heated at 70-75° C. for 3 hours with stirring. The solvent was then distilled off under reduced pressure, the residue was taken up in 400 ml of methyl tert-butyl ether, and the solution was washed with water, 0.05 N NaOH, and again with water, dried and evaporated. The residue was recrystallized from methanol, yielding 70 g (87.5%) of the title compound, which melts at 50° C. and clears at 55° C.

Workup

  1. additionb.p. 60-62° C. at 0.04 mbar) were added dropwise at 105° C. over the course of 60 minutes
  2. stirringAfter the mixture had been stirred at 105° C. for a further 90 minutes
  3. customthe residue was crystallized out

Sources & evidence

ORD record
ord-2a0d393a64954f6e8482a3ba135358a5
Source dataset
uspto-grants-2002_03
Patent number
US06358574B1

Reaction notes

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