Sulfuric Acid → 9-Phenoxy-1,4,7-nonatriyne

HRID 1607806Notes

Reaction equation

HRID 1607806 reaction equation
C([Mg]Br)C.[O:5]([CH2:12][C:13]#[CH:14])[C:6]1[CH:11]=[CH:10][CH:9]=[CH:8][CH:7]=1.Br[CH2:16][C:17]#[C:18][CH2:19][C:20]#[CH:21].S(=O)(=O)(O)O>CCOCC.O1CCCC1>[O:5]([CH2:12][C:13]#[C:14][CH2:16][C:17]#[C:18][CH2:19][C:20]#[CH:21])[C:6]1[CH:11]=[CH:10][CH:9]=[CH:8][CH:7]=1

Participants

7

Reactant 4

HCID 1118Sulfuric AcidHCID 83613(Prop-2-ynyloxy)benzeneHCID 145789641-Bromo-2,5-hexadiyneHCID 178418443HCID 178418443, compound

Product 1

HCID 145789809-Phenoxy-1,4,7-nonatriyne

Reagents, catalysts & solvents 2

HCID 3283Diethyl EtherSolventHCID 8028TetrahydrofuranSolvent2×

Conditions

Temperature
0 °C

Procedure

4.81 ml (1.92 g, 14.4 mmol) of a 3N solution of ethylmagnesium bromide in ether was added dropwise under argon to a solution of 2 g (15.15 mmol) of 3-phenoxy-1-propyne (G. Pourcelot, et al., Bull. Soc. Chim., France, (1966), pp 3016-24, in 15 ml of anhydrous tetrahydrofuran. The rate of addition was adjusted to maintain the temperature at 0° C. Thereafter, the reaction mixture was stirred for 1 hour further at 0°-5° C. Then, 77 mg of cuprous cyanide was added. After stirring 20 minutes more, a solution of 1.13 g (7.22 mmol) of 1-bromo-2,5-hexadiyne in 10 ml of anhydrous tetrahydrofuran was added dropwise. The temperature was maintained at between 0°-5° C.The resulting mixture was stirred at room temperature for 3 additional hours, then poured into 60 ml of 1N sulfuric acid and ice, and the resulting solution extracted with ether (3×100 ml). The combined organic extracts were concentrated in vacuo to a small volume, and washed several times with EDTA and water, dried over sodium sulfate and evaporated. The crude material was purified by TLC using hexane:methylene chloride (80:20) as the eluant, and the product crystallized from methylene chloride-hexane, to yield 9-phenoxy-1,4,7-nonatriyne, as an oil.The product was stored in dry ice.

Workup

  1. additionThe rate of addition
  2. stirringAfter stirring 20 minutes more
  3. temperatureThe temperature was maintained at between 0°-5° C
  4. stirringThe resulting mixture was stirred at room temperature for 3 additional hours
  5. extractionthe resulting solution extracted with ether (3×100 ml)
  6. concentrationThe combined organic extracts were concentrated in vacuo to a small volume
  7. washwashed several times with EDTA and water
  8. dry with materialdried over sodium sulfate
  9. customevaporated
  10. customThe crude material was purified by TLC
  11. customthe product crystallized from methylene chloride-hexane

Sources & evidence

ORD record
ord-1256b646e0204c22b877bde436d2afc0
Source dataset
uspto-grants-1989_09
Patent number
US04867915

Reaction notes

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