Sulfuric Acid → 9-(p-Methylthiophenoxy)-1,4,7-nonatriyne

HRID 1607812Notes

Reaction equation

HRID 1607812 reaction equation
C([Mg]Br)C.[CH3:5][C:6]1[CH:15]=[CH:14][C:9]([S:10][CH2:11][C:12]#[CH:13])=[CH:8][CH:7]=1.Br[CH2:17][C:18]#[C:19][CH2:20][C:21]#[CH:22].S(=O)(=O)(O)O>CCOCC.O1CCCC1>[CH3:5][C:6]1[CH:15]=[CH:14][C:9]([S:10][CH2:11][C:12]#[C:13][CH2:17][C:18]#[C:19][CH2:20][C:21]#[CH:22])=[CH:8][CH:7]=1

Participants

7

Reactant 4

HCID 1118Sulfuric AcidHCID 110301514-Methyl-1-prop-2-ynylthiobenzeneHCID 145789641-Bromo-2,5-hexadiyneHCID 178418443HCID 178418443, compound

Product 1

HCID 867433919-(p-Methylthiophenoxy)-1,4,7-nonatriyne

Reagents, catalysts & solvents 2

HCID 3283Diethyl EtherSolventHCID 8028TetrahydrofuranSolvent

Conditions

Temperature
-10 °C

Procedure

27.15 ml (13.75 g, 0.103 mol) of a 3.8N solution of ethylmagnesium bromide in ether was added dropwise under argon to a cold solution of 15.3g (0.085 mol) of 3-(p-methylthiophenoxy)-1-propyne in 80 ml of anhydrous tetrahydrofuran, at such a rate to maintain the temperature at -10°C. The resulting mixture was stirred for 1 hour and then treated with 677.2mg of cuprous cyanide. After stirring 20 minutes more, a solution of 10.8 g(0.0687 mol) of 1-bromo-2,5-hexadiyne in 25 ml of anhydrous tetrahydrofuranwas added dropwise, maintaining the temperature between 0°-5°C. The reaction mixture was stirred at room temperature for 3 additional hours, and then poured into 150 ml of 1N sulfuric acid and ice. After extraction with ether (3×150 ml) the combined organic extracts were concentrated in vacuo to a small volume, and washed several times with EDTA and then with water, dried over sodium sulfate and evaporated. The crude material was purified by column chromatography on 200 g of silica gel, using hexane:ethyl acetate (95:5) as eluant, and the product crystallized from methylene-chloride-hexane, to yield 9-(p-methylthiophenoxy)-1,4,7-nonatriyne, as an oil. The product was stored in dry ice.

Workup

  1. stirringAfter stirring 20 minutes more
  2. temperaturemaintaining the temperature between 0°-5°C
  3. stirringThe reaction mixture was stirred at room temperature for 3 additional hours
  4. extractionAfter extraction with ether (3×150 ml) the combined organic extracts
  5. concentrationwere concentrated in vacuo to a small volume
  6. washwashed several times with EDTA
  7. dry with materialwith water, dried over sodium sulfate
  8. customevaporated
  9. customThe crude material was purified by column chromatography on 200 g of silica gel
  10. customthe product crystallized from methylene-chloride-hexane

Sources & evidence

ORD record
ord-f0b5c352400c49c3bb5e4be5719a6039
Source dataset
uspto-grants-1989_09
Patent number
US04867915

Reaction notes

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