Chemistry of the Podocarpaceae. XX. Epoxides of ring-A-unsaturated 12-Methoxypodocarpa-8,11,13-trienes

Canbie, RC; Denny, W. A.

doi:10.1071/ch9691699

Cited by 11 publications

(8 citation statements)

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“…Found: C, 69.92; H, 6.85. 3,4,5,6,7,-one-7-carboxylic Acid (3).-A solution of 9.60 g of 8-methoxytetralin-2-carboxylic acid in 487 ml of dry ethanol was added with stirring to 390 ml of liquid ammonia. To this solution was added 45.8 g of sodium spheres in four portions.…”

Section: Experimental Section12mentioning

confidence: 99%

“…The solvent was removed and 70.3 ml of water was added. The pH was quickly adjusted to [5][6] with sodium carbonate and the solution was extracted with three portions of ether. The aqueous layer was allowed to stand for 12 hr at room temperature and extracted with four portions of ether.…”

Section: Experimental Section12mentioning

confidence: 99%

“…Caled for C,8H20NA: C, 55.67; , 5.19;N,14.43. Found: C,55.50; , 5.30;N,4,4a,5,6,7,8,-one-7-carboxylic Acid.-To a rapidly stirred mixture of 3.93 g of cuprous iodide in 79 ml of anhydrous ether at 0°under nitrogen was added slowly over a 10-min period, 15-17 ml of a 2 A ethereal solution of methyllithium. The solution was allowed to stir for 5 min, and 1 g of 3,4,5,6,7,8-hexahydronaphthalen-l(2H)-one-7carboxylic acid (3) in 100 ml of dry ether was added and rinsed in with two 10-ml portions of the same solvent.…”

Section: Experimental Section12mentioning

confidence: 99%

“…Caled for Ci6H240: C, 81.76; H, 10.98. Found: C, 81.87; H, 10.77. epf-Widdrol (5).-A mixture of 1.44 g (6.54 mmol) of epoxide 23, 1.17 g (31 mmol) of LiAlH4, and 125 ml of glyme was heated under reflux in a nitrogen atmosphere for 16 hr. The cooled mixture was diluted with ether and water carefully added until a clear organic layer was obtained.…”

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confidence: 99%

“…A suitable starting point for the preparation of 3 seemed to be the readily available 5-methoxytetralone-3-carboxylic acid (4). 4 Clemmensen reduction of 4 afforded 8-methoxytetralin-2-carboxylic acid (5), which on Birch reduction followed by acid hydrolysis of the crude reaction products6 gave a mixture of four acids. Separation of this mixture by chromatography (4) A. Sieglitz and C. Jordanides, Justus Liebigs Ann.…”

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confidence: 99%

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Stereoselective nonannelation synthesis of eudalene sesquiterpenes

Huffman¹,

Mole²

1972

J. Org. Chem.

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13 nmr (CCl4) S 7.45-7.87 (3 H, m), 7.20-7.27 (2 H, m), 5.43 (2 H, q, J = 8 and 6 Hz), 2.53-2.78 (2 H, m), 1.57 (3 H, s), 1.20 (3 H, s), 1.09 (6 H, 8).Anal. Calcd for C22Hs002: C, 80.94; H, 9.26. Found: C, 81.22; H, 9.01. 1,4,8, undeca-3,6-diene (22)-A mixture of 3.8 g of widdrol benzoate and 100 ml of freshly distilled N , Ndimethylaniline was heated under reflux for 40 hr, diluted with 500 ml of 2 N aqueous hydrochloric acid, and extracted three times with hexane. The hexane extract was washed with saturated aqueous sodium bicarbonate solution and dried, and the solvent was rotary evaporated to give 3.1 g of oily material.Glpc analysis (20v0 DEGS, Chromosorb P, HMDS, 130°, 5 ft X 0.25 in.) indicated three hydrocarbons in a ratio of 70, 25, and 5% yields. This crude material after filtration through Woelm neutral alumina (activity 11) was used directly in the next experiment.A 250-mg portion was chromatographed on 20 g of silica gel impregnated with 22% silver nitrate. Elution with 72 ml of hexane-benzene (9: 1) afforded a total of 185 mg of the diene 22 in six fractions. The major product from the middle chromatography fraction was still impure as indicated by a low residual uv absorption in the 255-273-nm region. No further purification was attempted and the purified diene had the following properties: uv max (cyclohexane) 185 nm (e 17,400), 254 (1120), 263 (1240), 273 (860); nmr (CC1,) 6 5.17-5.83 (2 H, poorly formed quartet, J = 7 and 3 Ha), 3.17 (1 H, d, J = 20 Ha), 1.72 (3 H, narrow multiplet), 1.10 (3 H , s), 1.08 (3 H, s), 1.09 (3 H, s). Anal. Calcd for ClaHa4: C, 88.16; HI 11.84. Found: C, 88.20; H , 11.67. 1,4,8,8-Tetramethyl[S.4.0]undeca-4,6-diene @).-To a solution of 2.0 g (72% pure) of diene 22 in 2 ml of dry benzene and 100 ml of dry dimethyl sulfoxide (distilled from calcium hydride) was added 3.1 g of potassium tert-butoxide. The dark red solution was stirred a t room temperature for 6 hr, poured into water, and processed in the usual fashion. The crude product was chromatographed on 20 g of Woelm neutral alumina (activity 11) to give 1.7 g (85%) of hydrocarbon mixture which upon glpc analysis showed two peaks (78 and 22%). The minor product has a retention time identical with starting diene 22. The dominant reaction product was purified by preparative glpc; the retention time and all spectra were identical with those of diene 8 prepared from trans-thujopsene.3~,4~-O~a-lor,4~~,8,8-tetramethylbicyclo[ 5.4 .O] undec-6-ene (23).-A solution of 469 mg (2.24 mmol) of 82.5% m-chloroperbenzoic acid in 7 ml of chloroform was slowly added to a solution of 551 mg (2.70 mmol) of diene 22 (70% purity) in 5 ml of chloroform at 0'. The reaction was allowed to proceed for 3.5 hr at 0", diluted with pentane, and worked up in the standard fashion. The crude product was chromatographed on 25 g of Woelm neutral alumina (activity 11). Elution with 32 ml of hexane gave 100 mg of unreacted hydrocarbon; elution with hexane-ether (increasingly greater amounts of ether) gave two products. The first product was 70 mg (14%...

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Section: Experimental Section12mentioning

confidence: 99%

Section: Experimental Section12mentioning

confidence: 99%