Diethyl Ether → 85081-69-2

HRID 1754886Notes

Reaction equation

HRID 1754886 reaction equation
[CH:1]1([OH:9])[CH2:8][CH2:7][CH2:6][CH:5]=[CH:4][CH2:3][CH2:2]1.C(OC)(=O)C1C=CC=CC=1.[OH-].[NH4+].C(OCC)C>C1CCCCC1.C(OCC)C.[N+]([O-])([O-])=O.[Ag+]>[CH:1]1([OH:9])[CH2:8][CH2:7][CH2:6][CH:5]=[CH:4][CH2:3][CH2:2]1

Participants

7

Reactant 4

HCID 3283Diethyl EtherHCID 7150Methyl BenzoateHCID 14923Ammonium HydroxideHCID 53815104-Cycloocten-1-ol2×

Product 1

HCID 1238561585081-69-2

Reagents, catalysts & solvents 2

HCID 24470Silver NitrateCatalystHCID 21895417Cyclohexane diethyletherSolvent

Procedure

(E)-cyclooct-4-enol was synthesized from (Z)-cyclooct-4-enol (H. Meier, W. Mayer, H. Kolshorn, Chem. Ber. 1987, 120, 685-689) by modification of previously published procedures (M. Royzen, G. P. A. Yap, J. M. Fox, J. Am. Chem. Soc. 2008, 130, 3760-3761; N. K. Devaraj, R. Upadhyay, J. B. Haun, S. A. Hilderbrand, R. Weissleder, Angew. Chem. 2009, 48, 7013-7016). 2 g (15.9 mmol) (Z)-cyclooct-4-enol and 2.2 g (16.3 mmol) methyl benzoate were dissolved in 250 mL cyclohexane/diethyl ether=1:9. The Petri dish was placed in an UVP-CL-1000-ultraviolet crosslinker reactor and irradiated for eight hours under ice-cooling. In intervals of 25-30 minutes the reaction mixture was passed through a column packed with 27 g of silver nitrate (10%) impregnated silica (commercially available from Aldrich). The mixture passing through the column was placed back into the UV crosslinker for further irradiation. After eight hours the irradiation was stopped and the silica was added to an ammonium hydroxide solution (28%, 160 ml). The suspension was stirred for 5 minutes, 160 ml of diethylether were added and stirring continued for 5 minutes. The aqueous layer was extracted with ether, the combined organic phases were washed with water and dried over magnesium sulfate. After evaporation of the solvents and flash chromatography (cyclohexane/ethyl acetate=1:1) two separated diastereomers of the product could be isolated. The main product 8b was obtained as a colourless oil (455 mg, 3.61 mmol, 23%) and used for further steps.

Workup

  1. customThe Petri dish was placed in an UVP-CL-1000-ultraviolet crosslinker reactor
  2. customirradiated for eight hours under ice-
  3. temperaturecooling
  4. customIn intervals of 25-30 minutes
  5. customwas placed back into the UV crosslinker for further irradiation
  6. customAfter eight hours the irradiation
  7. stirringstirring
  8. waitcontinued for 5 minutes
  9. extractionThe aqueous layer was extracted with ether
  10. washthe combined organic phases were washed with water
  11. dry with materialdried over magnesium sulfate
  12. customAfter evaporation of the solvents and flash chromatography (cyclohexane/ethyl acetate=1:1) two separated diastereomers of the product
  13. customcould be isolated

Sources & evidence

ORD record
ord-ddd949c74fa84519a80347cac737c587
Source dataset
uspto-grants-2015_10
Patent number
US09169283B2

Reaction notes

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