Sulfuric Acid → 16-Phenylthiohexadeca-5,8,11,14-tetraynoic acid ethyl ester

HRID 1607810Notes

Reaction equation

HRID 1607810 reaction equation
[CH2:1]([Mg]Br)[CH3:2].C1(S[CH2:12][C:13]#[C:14][CH2:15][C:16]#[C:17][CH2:18][C:19]#[CH:20])C=CC=CC=1.[CH2:21]([O:23][C:24](=O)[CH2:25][CH2:26][CH2:27][C:28]#[C:29][CH2:30]I)[CH3:22].[S:33](=O)(=O)(O)O.O1[CH2:42][CH2:41][CH2:40][CH2:39]1>>[CH2:21]([O:23][C:24](=[S:33])[CH2:25][CH2:26][CH2:27][C:28]#[C:29][CH2:30][C:12]#[C:13][CH2:14][C:15]#[C:16][CH2:17][C:18]#[C:19][CH2:20][C:2]1[CH:1]=[CH:42][CH:41]=[CH:40][CH:39]=1)[CH3:22]

Participants

6

Reactant 5

HCID 1118Sulfuric AcidHCID 8028Tetrahydrofuran2×HCID 117375597-Iodo-5-heptynoic acid ethyl esterHCID 145789959-Phenylthio-1,4,7-nonatriyneHCID 178418443HCID 178418443, compound

Product 1

HCID 8674338916-Phenylthiohexadeca-5,8,11,14-tetraynoic acid ethyl ester

Conditions

Temperature
-25 °C

Procedure

8.4 ml (4.254 g, 31 mmol) of 3.79N ethereal ethylmagnesium bromide was added dropwise, under argon to a solution of 6.5 g (29 mmol) of 9-phenylthio-1,4,7-nonatriyne in 20 ml of anhydrous tetrahydrofuran. The temperature was maintained at -25° C. After the addition, the reaction mixture was stirred for 1 hour further at the same temperature and then 285 mg of cuprous cyanide were added. After the addition, the mixture was stirred for 20 minutes more at 0° C. and then treated with 12.2 g (44 mmol) of 7-iodo-5-heptynoic acid ethyl ester in 15 ml of anhydrous tetrahydrofuran. After the addition, the solution was stirred for an additional 3 hours at room temperature. The reaction mixture was then poured into 150 ml of 1N sulfuric acid and ice and the product extracted with ether (3×150 ml). The combined organic extract was concentrated to about 1/3 its original volume and washed 3 times with EDTAand water, dried over sodium sulfate and evaporated in vacuo. The crude material was purified by column chromatography on 100 g of silica gel, using hexane-ethyl acetate (95:5) as eluant, to obtain 16-phenylthiohexadeca-5,8,11,14-tetraynoic acid ethyl ester, as an oil. The product was stored in dry ice.

Workup

  1. additionAfter the addition
  2. additionAfter the addition
  3. stirringthe mixture was stirred for 20 minutes more at 0° C.
  4. additionAfter the addition
  5. stirringthe solution was stirred for an additional 3 hours at room temperature
  6. extractionthe product extracted with ether (3×150 ml)
  7. extractionThe combined organic extract
  8. concentrationwas concentrated to about 1/3 its original volume
  9. washwashed 3 times with EDTAand water
  10. dry with materialdried over sodium sulfate
  11. customevaporated in vacuo
  12. customThe crude material was purified by column chromatography on 100 g of silica gel

Sources & evidence

ORD record
ord-f485e7e6cae8480694d2b974438ea748
Source dataset
uspto-grants-1989_09
Patent number
US04867915

Reaction notes

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