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Organic Synteses vol 69 - Paquette L.A.

Paquette L.A., Boecman R.K. Organic Synteses vol 69 - John Wiley & Sons, 1990. - 174 p.
ISBN 0-471-54560-0
Download (direct link): organicsynthesesvol691990.pdf
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dry ether is added dropwise over 30 min through the addition funnel while maintaining the temperature at -15°C. Then the stirred mixture is allowed to warm to room temperature over 1 hr (Note 10). The resulting white suspension containing the lithium acetylide 2 is carefully poured into 450 mL of ice water slurry, the aqueous layer is saturated with sodium chloride, and the product is extracted with four 100-mL portions of ether. The combined extracts are dried over anhydrous magnesium sulfate, the drying agent is removed by filtration, and the solvent is distilled at atmospheric pressure using a 25-cm Vigreux column. The residue is distilled through a short-path distillation apparatus to afford 10.5-11.2 g (79-89% yield) of (E)-6,10-dimethyl-5,9-undecadien-1-yne, bp 103-107°C (10 mm) (Note 11).
B. (E)-7,11-Dimethyl-6,10-dodecadien-2-yn-1-ol. To the suspension containing the acetylide intermediate 2, as prepared in part A, is added 14 g (460 mmol) of paraformaldehyde (Note 12) in portions (Note 13) over 10 min (Note 14). After stirrini the mixture for 24 hr, the resulting suspension is poured into 450 mL of ice-cold watei (Note 15), the aqueous layer is saturated with sodium chloride, and the product is extracted with four 100-mL portions of ether. The combined organic extracts are dried over magnesium sulfate, the drying agent is removed by filtration, and the solvent is removed at room temperature on a rotary evaporator. The residue is distilled through a short-path distillation apparatus to provide a forerun of 2-butyn-1-ol (bp 42-46°C, 6 mm), followed by 10.5 g (68% yield) of (E)-7,11-dimethyl-6,10-dodecadien-2-yn-1-ol as a colorless liquid, bp 120-124°C (0.5 mm) (Note 16).
2. Notes
1. All glassware is dried in an oven at 125°C and assembled while warm.
2. Although the reaction mixture will become heterogeneous, mechanical stirring is unnecessary on this scale.
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3. A stainless steel cannula Inserted through this septum Is connected by means of tygon tubing to a mercury bubbler.
4. Ethyl ether is freshly distilled from the sodium ketyl of benzophenone.
5. This is an adaptation of the method used to condense methyl chloride, illustrated in Figure 1 of an Organic Syntheses procedure (Lusch, M. J.; Phillips, W. V.; Sieloff, R. F.; Nomura, G. S.; House, H. O. Org. Synth., Coll. Vol. 7,1990, 347).
6. The submitters used allene purchased from Matheson Gas Products, Inc. The checkers found that an old lecture bottle of allene from this source gave unsatisfactory results, affording a crude product that contained up to 20% of unchanged geranyl chloride. Other lecture bottles of allene from Matheson or Pfaltz and Bauer were satisfactory.
7. All temperatures recorded are external bath temperatures.
8. A solution of butyllithium in hexane was purchased from Foote Mineral Company. Before use the concentration is determined by titration according to the procedure of Watson and Eastham.3
9. Geranyl chloride was prepared by treating geraniol, available from Aldrich Chemical Company, Inc., with carbon tetrachloride and triphenylphosphine according to an Organic Syntheses procedure.4
10. If dienyne product containing less than 1% of geranyl chloride is required, the checkers suggest the following treatment at this point to destroy any remaining geranyl chloride: The addition funnel is removed and a gentle stream of argon is bubbled through the stirred reaction mixture for 15 min to remove excess allene. Additional butyllithium (40 mmol in hexane) is added and the resulting mixture is stirred for 3 hr at room temperature prior to hydrolytic work up. If this modification is employed the subsequent hydrolysis step should be done slowly. The Erlenmeyer flask (1 L) containing the ice/water mixture is best cooled externally with an ice bath during the hydrolysis.
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The checkers also report that (E)-6,10-dimethyl-5,9-undecadien-1-yne containing < 1% geranyl chloride is produced in 78-90% yield when 2.0 mmol of butyllithium per mmol of allene is employed.
11. Capillary GC analysis of the product using a 25-m fused silica DB-5 column shows the presence of 5% geranyl chloride which is eluted at a slightly shorter retention time than the enyne product. Similar analysis of the product produced (in 89% yield) by the modification reported in Note 10 showed that the product was > 96% pure and contained < 1% of geranyl chloride. Spectral properties for (E)-6,10-dimethyl-5,9-undecadien-1-yne are: IR (thin film) cm-1: 3312, 2119, 1665; 1H NMR (300 MHz, CDCI3) 8: 1.58 (s, 3 H), 1.60 (s, 3 H), 1.66 (s, 3 H), 1.97-2.14 (m, 4 H), 2.22 (narrow m, 4 H), 5.11 (m, 2 H), 5.19 (m, 1 H).
12. Paraformaldehyde is dried over P2O5 in a vacuum desiccator for 24 hr prior to use.
13. The dropping funnel is removed and replaced by a 250-mL Erlenmeyer flask containing the paraformaldehyde. This is connected to the reaction vessel by rubber tubing. The cannula previously attached to the mercury bubbler is inserted through the septum of the dry ice condenser.
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