| 88% |
With Jones reagent In acetone at 0 - 20℃; for 0.5h; |
Dec-9-ynoic acid (EC2-094)
Jones reagent (2 M, 1.78 mL, 3.56 mmol, 1.1 eq.) was added dropwise to a solution of dec-9-yn-l-ol (500 mg, 3.24 mmol, 1.0 eq.) in acetone (32 mL) at 0 °C and the reaction was left stirring at this temperature for 30 minutes. The ice-bath was removed and the reaction was stirred for 1 hour at room temperature. The solvent was removed under reduced pressure, the residue partitioned between EtOAc (20 mL) and fhO (20 mL), the two phases separated and the organic phase washed with NaHCCL (3 x 20 mL). The aqueous phase was collected, acidified by addition of 1 M HC1 until pH = 1 and the residue re-extracted with EtOAc (3 x 20 mL). These organic extracts were dried (MgS04) and the solvent evaporated to give dec-9-ynoic acid (EC2-094) (480 mg, 88%) as a pale yellow oil. 1 H NMR (500 MHz, DCh-d) d 2.28 (t, J = 7.5 Hz, 2H), 2.11 (td, J = 7.1, 2.7 Hz, 2H), 1.87 (t, J = 2.7 Hz, 1H), 1.57 (p, J = 7.6 Hz, 2H), 1.50-1.41 (m, 2H), 1.38-1.20 (m, 6H). (See Morcillo, et al„ J. Org. Chem., 76:2277-81, 2011.) |
| 87% |
With tetrapropylammonium perruthennate; 4-methylmorpholine N-oxide In acetonitrile at 20℃; for 0.833333h; |
|
| 84% |
With sodium tungstate; dihydrogen peroxide; methyl tri-n-octyl ammonium hydrogen sulfate at 90 - 95℃; for 4h; |
|
| 81% |
With chromium(VI) oxide; sulfuric acid In water; acetone at -5 - 20℃; |
1.4.2 4.1.1.4.2. Dec-9-ynoic acid (9)
To a solution of 9-decyn-1-ol 8 (5 ml, 28.20 mmol) in acetone at -5 °C was slowly added chromic acid solution prepared from CrO3 (4.23 g, 42.30 mmol), water (4 ml), and conc. H2SO4 (3 ml) at 0 °C. The mixture was then stirred for 2 h and left overnight at room temperature, after which it was extracted with diethyl ether, washed with water and brine, dried over Na2SO4 and concentrated in vacuo. The residue was purified by silica gel flash column chromatography (n-hexane/EtOAc, 7:1) to yield dec-9-ynoic acid 9 (3.8 g, 81%) as clear oil. |
| 67% |
With dipyridinium dichromate In N,N-dimethyl-formamide for 72h; Inert atmosphere; |
|
| 61% |
With chromium(VI) oxide; sulfuric acid In water; acetone at -5℃; for 2.5h; |
|
|
With chromium(VI) oxide; sulfuric acid |
|
|
With jones' reagent In acetone at 0℃; for 2h; |
|
|
With sodium dichromate |
|
|
With jones reagent |
|
|
With jones reagent In acetone at 0℃; for 2h; |
|
|
With Jones reagent In acetone at 55℃; for 0.5h; |
|
|
With Jones reagent In acetone at 0 - 20℃; for 1.58333h; |
Methyl Dec-9-ynoate (6)
2-(Dec-9-yn-1-yloxy)tetrahydro-2H-pyran4 (5; 3.2 g, 13.4 mmol) was dissolved in MeOH (66 mL), and 5% aq H2SO4 (13.4 mL) was slowly added to the stirred solution at 5 °C. The mixture was stirred further 24 h at r.t. then neutralized with sat. aq NaHCO3 (12 mL), and concentrated in vacuo to remove the MeOH. The residue was extracted with Et2O (3 × 60 mL). The organic extract was washed with cold H2O (30 mL) and brine (60 mL), dried (MgSO4) and concentrated in vacuo to give a crude oily product (2.1 g). This was dissolved in acetone(24 mL) at 0 °C and treated by dropwise addition of Jones reagent 29(11.2 mL) over 50 min with vigorous stirring. The ice bath was removed, and the mixture was stirred for 45 min. The mixture was then poured into ice-water (70 mL) and extracted with Et2O (3 × 65mL). The organic layers were combined, washed with brine (2 × 60mL), dried (MgSO4), and concentrated in vacuo. The residue was dissolved in Et2O (50 mL) and a ~0.2 M solution of diazomethane30 inEt2O (70 mL) at 0 °C was added dropwise. Removal of the solvent gavean oil that was purified by column chromatography [silica gel, hexane-Et2O, (20:1)] as a colorless oil; yield: 2.2 g (90%). |
|
With chromium(VI) oxide; sulfuric acid In water; acetone at 25℃; |
|
|
With sodium hypochlorite; sodium chlorite; 2,2,6,6-Tetramethyl-1-piperidinyloxy free radical In acetonitrile at 20℃; |
2.5.4 2.5.4
Synthesis of dec-9-ynoic acid
A solution of NaClO2 (48.2 g, 536 mmol) and NaOCl (36.0 g, 48.7 mmol) was simultaneously added to a solution of dec-9-yn-1-ol (15 g, 97.4 mmol) and TEMPO (7.6 g, 48.7 mmol) in CH3CN (300 ml) and pH 4-buffer solution (75 ml). The reaction mixture was stirred at RT overnight, diluted with EA (900 ml), washed with water (900 ml) and brine, dried over Na2SO4, concentrated under vacuum. The crude was purified by silica gel chromatography (PE/EA=1/1) to afford the desired dec-9-ynoic acid (20 g, crude) as a colourless oil. 1H NMR (400 MHz, CDCl3) δ 2.36 (t, J=7.3 Hz, 2H), 2.18 (td, J=6.9, 2.3 Hz, 2H), 1.93 (t, J=2.3 Hz, 1H), 1.72-1.59 (m, 2H), 1.54 (td, J=14.1, 7.2 Hz, 2H), 1.48-1.30 (m, 6H) ppm. |
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