Iodine → Dilinoleylmethyl Formate

HRID 713850Notes

Reaction equation

HRID 713850 reaction equation
II.[CH2:3](Br)[CH2:4][CH2:5][CH2:6][CH2:7][CH2:8][CH2:9][CH2:10]/[CH:11]=[CH:12]\[CH2:13]/[CH:14]=[CH:15]\[CH2:16][CH2:17][CH2:18][CH2:19][CH3:20].[CH:22]([O:24][CH2:25][CH3:26])=[O:23].OS(O)(=O)=O>CCOCC>[CH:22]([O:24][CH:25]([CH2:3][CH2:4][CH2:5][CH2:6][CH2:7][CH2:8][CH2:9][CH2:10]/[CH:11]=[CH:12]\[CH2:13]/[CH:14]=[CH:15]\[CH2:16][CH2:17][CH2:18][CH2:19][CH3:20])[CH2:26][CH2:3][CH2:4][CH2:5][CH2:6][CH2:7][CH2:8][CH2:9]/[CH:10]=[CH:11]\[CH2:12]/[CH:13]=[CH:14]\[CH2:15][CH2:16][CH2:17][CH2:18][CH3:19])=[O:23]

Participants

6

Reactant 4

HCID 807IodineHCID 1118Sulfuric AcidHCID 8025Ethyl formateHCID 10065142(6Z,9Z)-18-bromooctadeca-6,9-diene

Product 1

HCID 58264324Dilinoleylmethyl FormateYield 113.9%

Reagents, catalysts & solvents 1

HCID 3283Diethyl EtherSolvent2×

Procedure

To a suspension of Mg turnings (1.64 g, 67.4 mmol) with one crystal of iodine in 500 mL of anhydrous ether under nitrogen was added a solution of linoleyl bromide (II, 18.5 g, 56.1 mmol) in 250 mL of anhydrous ether at room temperature. The resulting mixture was refluxed under nitrogen overnight. The mixture was cooled to room temperature. To the cloudy mixture under nitrogen was added dropwise ethyl formate (4.24 g, 57.2 mmol). Upon addition, the mixture was stirred at room temperature overnight. The mixture was treated with 10% H2SO4 aqueous solution (250 mL). The ether phase was separated and aqueous phase extracted with ether (150 mL). The combined organic phase was washed with water (400 mL), brine (300 mL), and then dried over anhydrous Na2SO4. Evaporation of the solvent gave 17.8 g of yellowish oil as a crude product (III). The crude product was used directly in the following step without further purification.

Workup

  1. temperatureThe resulting mixture was refluxed under nitrogen overnight
  2. additionUpon addition
  3. customThe ether phase was separated
  4. extractionaqueous phase extracted with ether (150 mL)
  5. washThe combined organic phase was washed with water (400 mL), brine (300 mL)
  6. dry with materialdried over anhydrous Na2SO4
  7. customEvaporation of the solvent

Sources & evidence

ORD record
ord-76530a7f9e3f4a028295bd98604100bf
Source dataset
uspto-grants-2015_11
Patent number
US09186325B2

Reaction notes

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