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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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KOH
EtOH
NhUOAc. HOAc Cu(OAc)2 • H20
c6o
c.
oéo
Oxone (KHSO5)
aS5
D.
1.Ac20
2. HCI, H20
3. NaOH, H20
Submitted by Thomas W. Bell, Young-Moon Cho, Albert Firestone, Karin Healy, Jia Liu, Richard Ludwig and Scott D. Rothenberger.1 Checked by Edward R. Holler, Jr. and Bruce E. Smart.
226
1. Procedure
A 8-n-Butyl-2-hydroxytricyclo[7.3.1.02<7]tridecan-13-one. A 2-L, three-necked, round-bottomed flask is equipped with a magnetic stirring bar, thermometer, 500-mL pressure equalizing dropping funnel, and a reflux condenser fitted with a nitrogen gas inlet tube which is attached to a mineral oil bubbler. The flask is flushed with nitrogen and then charged with 1.0 L (947 g, 9.65 mol) of cyclohexanone (Note 1). The cyclohexanone is stirred and heated to 70-75°C under nitrogen, a solution of 9.0 g (0.14 mol) of potassium hydroxide (Note 2) in 85 mL of absolute ethanol is added in one portion, and then a solution of 150 mL (122 g, 1.4 mol) of pentanal (Note 3) in 140 mL of absolute ethanol is added dropwise over a period of 8 hr while maintaining the reaction mixture at 70-75°C. The reaction mixture is stirred and held at 70-75°C for an additional 12 hr, and then allowed to cool to room temperature. The reaction flask is immersed in an ice bath, the inner wall of the flask is scratched with a glass rod to initiate crystallization, and the mixture is kept at 0°C for 4 hr to complete the crystallization. The colorless crude product is collected by vacuum filtration and washed with 200 mL of cold ether. The filtrates are combined and concentrated to approximately 200 mL with a rotary evaporator. The precipitated white solid is collected by filtration and washed with water (2 x 200 mL) and 200 mL of cold ether to give a second crop of crude product. The two crops are combined and recrystallized from 750 mL of methanol, washed with water, and dried at 60°C under vacuum (1 mm) to give 228-230 g (61-62%) of 8-n-butyl-2-hydroxytricyclo[7.3.1.02>7]tridecan-13-one, mp 140-141 °C (Note 4).
B. 9-n-Butyl-1,2,3,4,5,6,7,8-octahydroacridine. A 1-L, three-necked, round-bottomed flask equipped with a mechanical stirrer, glass stopper, and a reflux condenser fitted with a nitrogen gas inlet tube which is attached to a mineral oil bubbler is flushed with nitrogen and then charged with 17.0 g (0.22 mol) of ammonium
227
acetate, 82 g (0.41 mol) of cupric acetate monohydrate (Note 5), and 200 ml. of glacial acetic acid. The mixture is stirred and heated at reflux for 15 min under a static atmosphere of nitrogen. The resulting solution is allowed to cool below reflux and 53 g (0.20 mol) of 8-n-butyl-2-hydroxytricyclo[7.3.1.02'7]tridecan-13-one is added in several portions. The blue-green reaction mixture is then refluxed under nitrogen for 3 hr with efficient stirring to control foaming. The mixture is allowed to cool to room temperature and then chilled in an ice bath for 3 hr. The precipitated cuprous acetate is collected by vacuum filtration using a fritted glass funnel (medium porosity) and washed with 100 mL of acetic acid. The combined filtrates are diluted with 500 mL of water, cooled in an ice bath, and carefully neutralized by slowly adding 33.3% (w/w) aqueous sodium hydroxide (Note 6). The resulting cloudy mixture is transferred to a separatory funnel and extracted with ether (400 mL, then 2 x 200 mL). The combined ether extracts are washed successively with 140 mL of 3% aqueous sodium hydroxide and 70 mL of saturated aqueous sodium chloride, and then dried over anhydrous magnesium sulfate along with 1 g of decolorizing charcoal (Norit). The solids are removed by filtration and washed with 200 mL of ether. The combined filtrates are concentrated to minimum volume with a rotary evaporator, and the residual solid is dried to a constant weight under vacuum (1 mm) to give 44.3-47.0 g (91-96%) of beige, crystalline product, mp 36-38°C. The product is further purified by adding a solution of 44.3 g of material in 90 mL of dichloromethane to a column of Woelm neutral alumina (75 x 28 mm), and eluting with an additional 300 mL of dichloromethane. The solvent is removed on a rotary evaporator to give 42.1 g (86%) of white crystalline solid, mp 41-43°C (Note 7).
C. 9-n-Butyl-1,2,3,4,5,6,7,8-octahydroacridine N-oxide. A 2-L, round-bottomed flask equipped with a magnetic stirrer and a reflux condenser litted with a nitrogen inlet tube is flushed with nitrogen and charged with 790 mL of methanol, 240 mL of water,
38.0 g (0.16 mol) of purified 9-n-butyl-1,2,3,4,5,6,7,8-octahydroacridine, 28.5 g (0.34
228
mol) of sodium bicarbonate, and 72.0 g (0.12 mol) of Oxone® (Note 8). The suspension is stirred under nitrogen at 45-50°C for 24 hr (Note 9). The mixture is cooled to room temperature, filtered, and the filtercake is washed with methanol (2 x 50 mL). The methanol is removed from the combined filtrates with a rotary evaporator, and the resulting mixture is extracted with dichloromethane (3 x 100 mL). The combined extracts are washed with water (2 x 50 mL) and dried over magnesium sulfate. The drying agent is removed by filtration, the filtrate is concentrated with a rotary evaporator, and the residual solid is dried under vacuum (0.1-0.5 mm) to give
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