Bromide ion → HCID 67604791, compound

HRID 361303Notes

Reaction equation

HRID 361303 reaction equation
[Mg].II.Br[CH2:5][CH2:6][CH:7]1[O:11][CH2:10][CH2:9][O:8]1.[Br-].[N+:13]([CH:16]=[CH:17][C:18]1[CH:23]=[CH:22][C:21]([O:24][CH3:25])=[C:20]([O:26][CH3:27])[C:19]=1[O:28][CH3:29])([O-:15])=[O:14]>C1COCC1>[CH2:9]1[CH2:10][O:11][CH:7]([CH2:6][CH2:5][CH:17]([C:18]2[CH:23]=[CH:22][C:21]([O:24][CH3:25])=[C:20]([O:26][CH3:27])[C:19]=2[O:28][CH3:29])[CH2:16][N+:13]([O-:15])=[O:14])[O:8]1

Participants

7

Reactant 5

HCID 259Bromide ionHCID 807IodineHCID 877762-(2-Bromoethyl)-1,3-dioxolaneHCID 304735HCID 304735, compoundHCID 5462224Magnesium

Product 1

HCID 67604791HCID 67604791, compound

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent3×

Procedure

A 2.16 g (90 mmol) portion of magnesium turnings was stirred vigorously under nitrogen with a Teflon coated magnetic stir bar for 16 h. A crystal of iodine and 10 mL of dry THF were added. About 10% of 10 mL of 2-(2-bromoethyl)-1,3-dioxolane was added. An exothermic reaction occurred. The mixture was diluted with an additional 90 mL of THF and the remaining 90% of the bromide was added dropwise over 45 min, The mixture was stirred for a further 3 h at room temperature and added dropwise over 20 min to an ice-cold solution of 18.48 g (77.3 mmol) of 1-nitro-2-(2,3,4-trimethoxyphenyl)ethene in 100 mL of THF. The cooling bath was removed, the mixture was stirred at room temperature for 20 h, poured into 500 mL of ice cold 3% aqueous HCl and extracted with three 200 mL portions of ether. The combined ether extracts were washed with 200 mL of saturated aqueous NaHCO3 and 200 mL of brine and dried over MgSO4. Removal of the solvent in vacuo left 17.14 g of an orange oil. This material was purified by flash chromatography on a column of 100 g of silica gel eluted successively with 250 mL portions of 0, 10, 20, 30, 40, 50, 60, 70, 80 and 100% ether in hexanes and 75 mL fractions were collected. Fractions 23-27 were combined and evaporated in vacuo to afford 5.53 g of 1,1-ethylenedioxy-5-nitro-4-(2,3,4-trimethoxyphenyl)pentane as an oil. 1H NMR (CDCl3) -- 1.5-1.9 (m, 4H), 3.7-4.0 (1 m, 14H), 4.6 (m, 2H), 4.85 (m, 1H), 6.6 (d, 1H), 6.8 (d, 1H).

Workup

  1. customAn exothermic reaction
  2. customThe cooling bath was removed
  3. stirringthe mixture was stirred at room temperature for 20 h
  4. additionpoured into 500 mL of ice cold 3% aqueous HCl
  5. extractionextracted with three 200 mL portions of ether
  6. washThe combined ether extracts were washed with 200 mL of saturated aqueous NaHCO3 and 200 mL of brine
  7. dry with materialdried over MgSO4
  8. customRemoval of the solvent in vacuo
  9. waitleft 17.14 g of an orange oil
  10. customThis material was purified by flash chromatography on a column of 100 g of silica gel
  11. washeluted successively with 250 mL portions of 0, 10, 20, 30, 40, 50, 60, 70, 80 and 100% ether in hexanes and 75 mL fractions
  12. customwere collected
  13. customevaporated in vacuo

Sources & evidence

ORD record
ord-a6dd3e82848446b383146a418d7babbd
Source dataset
uspto-grants-1999_02
Patent number
US05866513

Reaction notes

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