Hydrochloric Acid → HCID 178448044, compound

HRID 1590517Notes

Reaction equation

HRID 1590517 reaction equation
[Mg].II.[F:4][C:5]([F:16])([F:15])[O:6][C:7]1[CH:14]=[CH:13][C:10]([CH2:11]Br)=[CH:9][CH:8]=1.C(O[CH2:24]/[CH:25]=[CH:26]/[C@H:27]1[CH2:32][CH2:31][C@H:30]([C@H:33]2[CH2:38][CH2:37][C@H:36](/[CH:39]=[CH:40]/[CH3:41])[CH2:35][CH2:34]2)[CH2:29][CH2:28]1)(=O)C(C)(C)C.Cl>C(OCC)C.[Cu]Cl>[F:4][C:5]([F:16])([F:15])[O:6][C:7]1[CH:14]=[CH:13][C:10]([CH2:11][CH2:41]/[CH:40]=[CH:39]/[C@H:36]2[CH2:37][CH2:38][C@H:33]([C@H:30]3[CH2:29][CH2:28][C@H:27](/[CH:26]=[CH:25]/[CH3:24])[CH2:32][CH2:31]3)[CH2:34][CH2:35]2)=[CH:9][CH:8]=1

Participants

8

Reactant 5

HCID 313Hydrochloric AcidHCID 807IodineHCID 1427851-(Bromomethyl)-4-(trifluoromethoxy)benzeneHCID 5462224MagnesiumHCID 178448054HCID 178448054, compound

Product 1

HCID 178448044HCID 178448044, compoundYield 45.8%

Reagents, catalysts & solvents 2

HCID 62652Cuprous chlorideCatalystHCID 3283Diethyl EtherSolvent3×

Procedure

0.12 g of magnesium shavings were covered with 5 ml of absolute diethyl ether while gassing with nitrogen and then, after the addition of a crystal of iodine, covered with a solution of 1.3 g of 4-(trifluoromethoxy)benzyl bromide in 25 ml of diethyl ether. After completion of the addition the mixture was heated to reflux for a further 30 minutes. The reaction mixture was transferred into a dropping funnel and then added dropwise at 0° C. and while gassing with nitrogen to a solution of 0.9 g of 3E-[trans-4-(trans-4-[1E-propenyl]cyclohexyl)cyclohexyl]-allyl pivalate, 0.03 g of copper-(I) chloride and 25 ml of absolute diethyl ether. After completion of the addition the reaction mixture was stirred at room temperature for a further 30 minutes, then treated with 20 ml of 25% hydrochloric acid and the organic phase was separated. The aqueous phase was extracted three times with 50 ml of diethyl ether each time. The combined organic phases were washed in succession with 500 ml of water, 250 ml of concentrated potassium carbonate solution and again with 500 ml of water, dried over magnesium sulphate, filtered and subsequently concentrated. The residue was purified by chromatography on silica gel with hexane. Recrystallization from acetone gave 0.5 g of pure 1-trifluoromethoxy-4-[4E-(trans-4-(trans-4-[1E-propenyl]cyclohexyl)cyclohexyl)-3-butenyl]benzene with m.p. (C-N) 63° C. and cl.p. (N-1) 149° C.

Workup

  1. additionAfter completion of the addition the mixture
  2. temperaturewas heated
  3. temperatureto reflux for a further 30 minutes
  4. customThe reaction mixture was transferred into a dropping funnel
  5. additionadded dropwise at 0° C.
  6. additionAfter completion of the addition the reaction mixture
  7. customthe organic phase was separated
  8. extractionThe aqueous phase was extracted three times with 50 ml of diethyl ether each time
  9. washThe combined organic phases were washed in succession with 500 ml of water, 250 ml of concentrated potassium carbonate solution and again with 500 ml of water
  10. dry with materialdried over magnesium sulphate
  11. filtrationfiltered
  12. concentrationsubsequently concentrated
  13. customThe residue was purified by chromatography on silica gel with hexane
  14. customRecrystallization from acetone

Sources & evidence

ORD record
ord-fff3c0623fef43c3a0c762eb5a31a74f
Source dataset
uspto-grants-1993_04
Patent number
US05204018

Reaction notes

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