Cyanide → 9-(m-Chlorophenoxy)-1,4,7-nonatriyne

HRID 1607808Notes

Reaction equation

HRID 1607808 reaction equation
C([Mg]Br)C.[Cl:5][C:6]1[CH:7]=[C:8]([CH:13]=[CH:14][CH:15]=1)[O:9][CH2:10][C:11]#[CH:12].[C-]#N.Br[CH2:19][C:20]#[C:21][CH2:22][C:23]#[CH:24]>CCOCC.O1CCCC1>[Cl:5][C:6]1[CH:7]=[C:8]([CH:13]=[CH:14][CH:15]=1)[O:9][CH2:10][C:11]#[C:12][CH2:19][C:20]#[C:21][CH2:22][C:23]#[CH:24]

Participants

7

Reactant 4

HCID 5975CyanideHCID 142239771-Chloro-3-(prop-2-yn-1-yloxy)benzeneHCID 145789641-Bromo-2,5-hexadiyneHCID 178418443HCID 178418443, compound

Product 1

HCID 145789879-(m-Chlorophenoxy)-1,4,7-nonatriyne

Reagents, catalysts & solvents 2

HCID 3283Diethyl EtherSolventHCID 8028TetrahydrofuranSolvent2×

Conditions

Temperature
0 °C

Procedure

21.76 ml (9.8 g, 0.735 mmol) of a 3.38N solution of ethylmagnesium bromide in ether was added dropwise, under argon to a cold (0°-5° C.) solution of 11.66 g (0.7 mol) of 3-(m-chlorophenoxy)-1-propyne [I. Iway, et al., Chem. Pharm. Bull., 11, 1042 (1963)] in 80 ml of anhydrous tetrahydrofuran. The rate was monitoredto maintain a temperature of 0° C. Thereafter, the reaction mixture was stirred for 1 hour further at 0°-5° C. Then, 31.35 mg ofcuprous cyanide were added and the mixtured stirred 20 minutes more. Then asolution of 5.5 g (0.035 mol) of 1-bromo-2,5-hexadiyne in 20 ml of anhydrous tetrahydrofuran was added dropwise to the mixture as the temperature was maintained at between 0°-5° C. Then the reaction was stirred at room temperature for 3 additional hours and quenched with 200 ml of 1N sulfuric acid and ice. After extraction with ether (3×200 ml), the combined organic extracts were concentrated invacuo to a small volume, and washed several times with EDTA and water, dried over sodium sulfate and evaporated in vacuo. The residue was purified by column chromatography on 350 g of silica gel, using hexane as eluant, and the product crystallized from methylene chloride-hexane, to yield 9-(m-chlorophenoxy)-1,4,7-nonatriyne, as an oil. The product was stored in dry ice.

Workup

  1. stirringthe mixtured stirred 20 minutes more
  2. temperaturewas maintained at between 0°-5° C
  3. stirringThen the reaction was stirred at room temperature for 3 additional hours
  4. customquenched with 200 ml of 1N sulfuric acid and ice
  5. extractionAfter extraction with ether (3×200 ml)
  6. concentrationthe combined organic extracts were concentrated invacuo to a small volume
  7. washwashed several times with EDTA and water
  8. dry with materialdried over sodium sulfate
  9. customevaporated in vacuo
  10. customThe residue was purified by column chromatography on 350 g of silica gel
  11. customthe product crystallized from methylene chloride-hexane

Sources & evidence

ORD record
ord-953ff14afdc84604b702b5e92042e464
Source dataset
uspto-grants-1989_09
Patent number
US04867915

Reaction notes

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