Phenyl propargyl sulfide → 9-Phenylthio-1,4,7-nonatriyne

HRID 1607809Notes

Reaction equation

HRID 1607809 reaction equation
C([Mg]Br)C.[C:5]1([S:11][CH2:12][C:13]#[CH:14])[CH:10]=[CH:9][CH:8]=[CH:7][CH:6]=1.Br[CH2:16][C:17]#[C:18][CH2:19][C:20]#[CH:21]>CCOCC.O1CCCC1>[C:5]1([S:11][CH2:12][C:13]#[C:14][CH2:16][C:17]#[C:18][CH2:19][C:20]#[CH:21])[CH:10]=[CH:9][CH:8]=[CH:7][CH:6]=1

Participants

6

Reactant 3

HCID 4131667Phenyl propargyl sulfideHCID 145789641-Bromo-2,5-hexadiyneHCID 178418443HCID 178418443, compound

Product 1

HCID 145789959-Phenylthio-1,4,7-nonatriyne

Reagents, catalysts & solvents 2

HCID 3283Diethyl EtherSolventHCID 8028TetrahydrofuranSolvent2×

Procedure

24.64 ml (12.48 g, 0.0936 mol) of a 3.8N solution of ethylmagnesium bromide in ether was added dropwise, under argon to a cold solution of 13.2 g (0.089 mol) of 3-phenylthio-1-propyne (G. Pourcelot et al, vide supra) in 70 ml of anhydrous tetrahydrofuran. The temperature was maintained at 0°-5° C. Thereafter, the reaction mixture was stirred for 1 hour further at room temperature. Then, 440 mg of cuprous cyanide were added and the solution stirred for 20 minutes more. Then a solution of 7 g (0.0445 mol) of 1-bromo-2,5-hexadiyne in 20 ml of anhydrous tetrahydrofuran was added dropwise, maintaining the temperature between 0°-5° C. After the addition, the reaction mixture was stirred at room temperature for 3 additional hours, and then quenched with 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 150 g of silica gel, using hexane as eluant, to produce 9-phenylthio-1,4,7-nonatriyne, as an oil. The product was stored in dry ice.

Workup

  1. temperatureThe temperature was maintained at 0°-5° C
  2. stirringthe solution stirred for 20 minutes more
  3. temperaturemaintaining the temperature between 0°-5° C
  4. additionAfter the addition
  5. stirringthe reaction mixture was stirred at room temperature for 3 additional hours
  6. customquenched with 150 ml of 1N sulfuric acid and ice
  7. extractionAfter extraction with ether (3×150 ml) the combined organic extracts
  8. concentrationwere concentrated in vacuo to a small volume
  9. washwashed several times with EDTA
  10. customwith water,dried over sodium sulfate and evaporated
  11. customThe crude material was purified by column chromatography on 150 g of silica gel

Sources & evidence

ORD record
ord-9fceabef52f04751a98cab03af0d7b31
Source dataset
uspto-grants-1989_09
Patent number
US04867915

Reaction notes

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