Sulfuric Acid → 9-(m-Methylphenoxy)-1,4,7-nonatriyne

HRID 1607803Notes

Reaction equation

HRID 1607803 reaction equation
[CH2:1]([Mg]Br)C.C[C:6]1[CH:15]=[CH:14][CH:13]=[CH:12][C:7]=1[O:8][CH2:9][C:10]#[CH:11].Br[CH2:17][C:18]#[C:19][CH2:20][C:21]#[CH:22].S(=O)(=O)(O)O>CCOCC.O1CCCC1>[CH3:1][C:13]1[CH:12]=[C:7]([CH:6]=[CH:15][CH:14]=1)[O:8][CH2:9][C:10]#[C:11][CH2:17][C:18]#[C:19][CH2:20][C:21]#[CH:22]

Participants

7

Reactant 4

HCID 1118Sulfuric AcidHCID 123605171-Methyl-2-(prop-2-yn-1-yloxy)benzeneHCID 145789641-Bromo-2,5-hexadiyneHCID 178418443HCID 178418443, compound

Product 1

HCID 145789739-(m-Methylphenoxy)-1,4,7-nonatriyne

Reagents, catalysts & solvents 2

HCID 3283Diethyl EtherSolventHCID 8028TetrahydrofuranSolvent2×

Conditions

Temperature
0 °C

Procedure

14.55 ml (6.79 g, 50.9 mmol) of a 3.5N solution of ethylmagnesium bromide in ether was added dropwise, under argon to a cold (0°-5° C.) solution of 7.82 g (53 mmol) of 3-(methylphenoxy)-1-propyne (C.A. 82, 155636 d) in 150 ml of anhydrous tetrahydrofuran at such a rate to maintain the temperature at 0° C.Thereafter, the reaction mixture was stirred for 1 hour further at 0°-5° C. Then, 246 mg of cuprous cyanide was added. After stirring 20 minutes more, a solution of 4 g (25.4 mmol) of 1-bromo-2,5-hexadiyne in 25 ml of anhydrous tetrahydrofuran was added dropwise, maintaining the temperature between 0°-5° C. The mixture was stirred at room temperature for 3 additional hours, and pouredinto 200 ml of 1N sulfuric acid and ice. After extraction with ether (3×100 ml) the combined organic extracts were concentrated in vacuo to a small volume, and washed several times with EDTA, to remove the copper salts, and then with water, dried over sodium sulfate and evaporated. The crude material was purified by column chromatography on 250 g of silica gel, using hexane as eluant, to yield 9-(m-methylphenoxy)-1,4,7-nonatriyne, as an oil. The product was stored indry ice.

Workup

  1. stirringAfter stirring 20 minutes more
  2. temperaturemaintaining the temperature between 0°-5° C
  3. stirringThe mixture was stirred at room temperature for 3 additional hours
  4. extractionAfter extraction with ether (3×100 ml) the combined organic extracts
  5. concentrationwere concentrated in vacuo to a small volume
  6. washwashed several times with EDTA
  7. customto remove the copper salts
  8. dry with materialwith water, dried over sodium sulfate
  9. customevaporated
  10. customThe crude material was purified by column chromatography on 250 g of silica gel

Sources & evidence

ORD record
ord-2754473fd89f4f3db0f79b21050614e4
Source dataset
uspto-grants-1989_09
Patent number
US04867915

Reaction notes

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