Sulfuric Acid → 16-(m-Methylphenoxy)hexadeca-5,8,11,14-tetraynoic acid methyl ester

HRID 1607804Notes

Reaction equation

HRID 1607804 reaction equation
C([Mg]Br)C.[CH3:5][C:6]1[CH:7]=[C:8]([CH:19]=[CH:20][CH:21]=1)[O:9][CH2:10][C:11]#[C:12][CH2:13][C:14]#[C:15][CH2:16][C:17]#[CH:18].[CH3:22][O:23][C:24](=[O:32])[CH2:25][CH2:26][CH2:27][C:28]#[C:29][CH2:30]I.S(=O)(=O)(O)O>CCOCC.O1CCCC1>[CH3:22][O:23][C:24](=[O:32])[CH2:25][CH2:26][CH2:27][C:28]#[C:29][CH2:30][C:18]#[C:17][CH2:16][C:15]#[C:14][CH2:13][C:12]#[C:11][CH2:10][O:9][C:8]1[CH:19]=[CH:20][CH:21]=[C:6]([CH3:5])[CH:7]=1

Participants

7

Reactant 4

HCID 1118Sulfuric AcidHCID 10901527Methyl 7-iodohept-5-ynoateHCID 145789739-(m-Methylphenoxy)-1,4,7-nonatriyneHCID 178418443HCID 178418443, compound

Product 1

HCID 1457897416-(m-Methylphenoxy)hexadeca-5,8,11,14-tetraynoic acid methyl ester

Reagents, catalysts & solvents 2

HCID 3283Diethyl EtherSolventHCID 8028TetrahydrofuranSolvent

Conditions

Temperature
0 °C

Procedure

1.61 ml (751 mg, 5.6 mmol) of 3.6N ethylmagnesium bromide in ether was added dropwise, under argon to a solution of 1.34 g (6 mmol) of 9-(m-methylphenoxy)-1,4,7-nonatriyne in 20 ml of anhydrous tetrahydrofuran. The temperature was maintained at 0° C. The reaction mixture was stirred for one hour further at 0° C., then allowed to warm to room temperature, and then 50 mg of cuprous cyanide wasadded. The mixture was stirred for 20 minutes, heated to 40° C. and then 1 g (3.75 mmol) of 7-iodo-5-heptynoic acid methyl ester was added. The resulting mixture was stirred during 4 hours at 40° C. The reaction mixture was then poured into 60 ml of 1N sulfuric acid and ice and the product extracted with ether (3×100 ml). The combined organic extract was concentrated to about 1/5 its original volume and washed several times with EDTA and water, dried over sodium sulfate and evaporated in vacuo. The crude material was purified by column chromatography on 75 g of silica gel, using hexane:ethyl acetate (85:15) as eluant, to obtain 16-(m-methylphenoxy)hexadeca-5,8,11,14-tetraynoic acid methyl ester, as an oil. The product was stored in dry ice.

Workup

  1. temperatureto warm to room temperature
  2. stirringThe mixture was stirred for 20 minutes
  3. temperatureheated to 40° C.
  4. stirringThe resulting mixture was stirred during 4 hours at 40° C
  5. extractionthe product extracted with ether (3×100 ml)
  6. extractionThe combined organic extract
  7. concentrationwas concentrated to about 1/5 its original volume
  8. washwashed several times with EDTA and water
  9. dry with materialdried over sodium sulfate
  10. customevaporated in vacuo
  11. customThe crude material was purified by column chromatography on 75 g of silica gel

Sources & evidence

ORD record
ord-a02baf2b8ebc4dba88a78f697c7979e4
Source dataset
uspto-grants-1989_09
Patent number
US04867915

Reaction notes

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