Sulfuric Acid → 16-(p-Methylthiophenoxy)-hexadeca-5,8,11,14-tetraynoic acid ethyl ester

HRID 1607813Notes

Reaction equation

HRID 1607813 reaction equation
C([Mg]Br)C.[CH3:5][C:6]1[CH:21]=[CH:20][C:9]([S:10][CH2:11][C:12]#[C:13][CH2:14][C:15]#[C:16][CH2:17][C:18]#[CH:19])=[CH:8][CH:7]=1.[CH2:22]([O:24][C:25](=[O:33])[CH2:26][CH2:27][CH2:28][C:29]#[C:30][CH2:31]I)[CH3:23].S(=O)(=O)(O)O>CCOCC.O1CCCC1>[CH2:22]([O:24][C:25](=[O:33])[CH2:26][CH2:27][CH2:28][C:29]#[C:30][CH2:31][C:19]#[C:18][CH2:17][C:16]#[C:15][CH2:14][C:13]#[C:12][CH2:11][S:10][C:9]1[CH:20]=[CH:21][C:6]([CH3:5])=[CH:7][CH:8]=1)[CH3:23]

Participants

7

Reactant 4

HCID 1118Sulfuric AcidHCID 117375597-Iodo-5-heptynoic acid ethyl esterHCID 867433919-(p-Methylthiophenoxy)-1,4,7-nonatriyneHCID 178418443HCID 178418443, compound

Product 1

HCID 7039536816-(p-Methylthiophenoxy)-hexadeca-5,8,11,14-tetraynoic acid ethyl ester

Reagents, catalysts & solvents 2

HCID 3283Diethyl EtherSolventHCID 8028TetrahydrofuranSolvent2×

Conditions

Temperature
-10 °C

Procedure

12.03 ml (6.077 g, 0.0455 mol) of 3.8N ethylmagnesium bromide in ether was added dropwise to a solution of 9.65 g (0.0379 mol) of 9-(p-methylthiophenoxy)-1,4,7-nonatriyne in 80 ml of anhydrous tetrahydrofuran. The temperature was maintained at -10° C. The reaction mixture was stirred for 1 hour further at 0° C., allowed to warm to room temperature, and then 374 mg of cuprous cyanide were added. The mixture was stirred for 20 additional minutes, heated to 40° C. and then treated with 13.83 g (49.38 mmol) of 7-iodo-5-heptynoic acid ethyl ester in 30 ml of anhydrous tetrahydrofuran.The resulting mixture was stirred for 3 additional hours at 40° C., then poured on to 300 ml of 1N sulfuric acid and ice. After extraction with ether (3×150 ml), the combined extract was concentrated to a small volume and washed several times with Versene solution and water, dried and evaporated in vacuo. The crude material was purified by column chromatography on 125 g of silica gel, using hexane:ethyl acetate (95:5) as eluant, to obtain 16-(p-methylthiophenoxy)-hexadeca-5,8,11,14-tetraynoic acid ethyl 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 additional minutes
  3. temperatureheated to 40° C.
  4. stirringThe resulting mixture was stirred for 3 additional hours at 40° C.
  5. extractionAfter extraction with ether (3×150 ml)
  6. extractionthe combined extract
  7. concentrationwas concentrated to a small volume
  8. washwashed several times with Versene solution and water
  9. customdried
  10. customevaporated in vacuo
  11. customThe crude material was purified by column chromatography on 125 g of silica gel

Sources & evidence

ORD record
ord-e0d78c79c1a84b03a517da1aa93d27cc
Source dataset
uspto-grants-1989_09
Patent number
US04867915

Reaction notes

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