8-Nonynoic acid → HCID 20396622, compound

HRID 972106Notes

Reaction equation

HRID 972106 reaction equation
[C:1]([OH:11])(=[O:10])[CH2:2][CH2:3][CH2:4][CH2:5][CH2:6][CH2:7][C:8]#[CH:9].C([Mg]Br)C.Br[CH2:17][C:18]#[C:19][CH2:20][C:21]#[C:22][CH2:23][CH2:24][CH2:25][CH2:26][CH2:27][CH3:28]>O1CCCC1>[C:1]([OH:11])(=[O:10])[CH2:2][CH2:3][CH2:4][CH2:5][CH2:6][CH2:7][C:8]#[C:9][CH2:17][C:18]#[C:19][CH2:20][C:21]#[C:22][CH2:23][CH2:24][CH2:25][CH2:26][CH2:27][CH3:28]

Participants

5

Reactant 3

HCID 356988-Nonynoic acidHCID 20396624HCID 20396624, compoundHCID 178418443HCID 178418443, compound

Product 1

HCID 20396622HCID 20396622, compoundYield 48%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent3×

Procedure

To a solution of non-8-ynoic acid (nD25 1.4529, m.p. 20°-2°; 30.8 g, 0.2 mol) in tetrahydrofuran (100 ml) was added a 1.45 M solution (275 ml) of ethylmagnesium bromide in tetrahydrofuran during 30 minutes at 0°. The resulting mixture was stirred for 21/2 hours, after which cuprous cyanide (720 mg, 4 mmol) was added and stirring was continued for 10 minutes. A solution of 1-bromododeca-2,5-diyne (Struyk et al., loc.cit., b.p. 78°-80°/0.001 mm Hg, nD25 1.5055; 36.2 g, 0.15 mol) in tetrahydrofuran (75 ml) was then added during 10 minutes, and the stirred mixture heated to boiling and boiled under reflux for 15 hours: at the end of the first 4 hours another portion of cuprous cyanide (360 mg) was added. After refluxing was completed the bulk of the solvent present was distilled off under reduced pressure and to the cooled residue were added ether (100 ml) and aqueous 2N sulphuric acid. The mixture was thoroughly shaken, the ether layer which formed on standing was separated off and the aqueous layer extracted with ether; the combined ether layers were washed with saturated aqueous ammonium chloride solution, then with water, dried with anhydrous sodium sulphate and evaporated. The residue was dissolved in a small quantity of light petroleum and the solution chromatographed on a column (30 cm length and 2.2 cm diameter) of silica gel using as eluant mixtures of light petroleum and ether commencing with a proportion by volume of 95:5 and proceeding with increasing proportions of ether, with a final proportion of 40:60. The eluted fractions found to contain acid were combined and evaporated: the residue was crystallised from a mixture of light petroleum and ether (85:15 by volume) at -5° to give heneicosa-8,11,14-triynoic acid (22.7 g, 48%), m.p. 57°-8°; infrared absorption peaks at 1690 (--COOH) and 1309 cm-1 (--CH2C≡C--). The acid was converted by reaction with an ether solution of diazomethane to its methyl ester which was submitted to GLC and shown to be of 99.5% purity; mass spectrum parent peak m/e=328.

Workup

  1. stirringstirring
  2. waitwas continued for 10 minutes
  3. temperaturethe stirred mixture heated
  4. temperatureunder reflux for 15 hours
  5. temperatureAfter refluxing
  6. distillationwas distilled off under reduced pressure and to the cooled residue
  7. additionwere added ether (100 ml) and aqueous 2N sulphuric acid
  8. stirringThe mixture was thoroughly shaken
  9. customthe ether layer which formed on standing
  10. customwas separated off
  11. extractionthe aqueous layer extracted with ether
  12. washthe combined ether layers were washed with saturated aqueous ammonium chloride solution
  13. dry with materialwith water, dried with anhydrous sodium sulphate
  14. customevaporated
  15. dissolutionThe residue was dissolved in a small quantity of light petroleum
  16. customthe solution chromatographed on a column (30 cm length and 2.2 cm diameter) of silica gel using as eluant mixtures of light petroleum and ether commencing with a proportion by volume of 95:5
  17. customevaporated
  18. customthe residue was crystallised from a mixture of light petroleum and ether (85:15 by volume) at -5°

Sources & evidence

ORD record
ord-483289f17fc745408c95a1be510266b1
Source dataset
uspto-grants-1979_07
Patent number
US04163108

Reaction notes

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