Selenium, acetals

It is possible to form, and cyclise, tertiary alkyllithiums, provided they are benzylic or allylic, by starting with a selenide. Krief has used selenium acetals to construct the starting materials 249 and 252, and on treatment with n-BuLi an extremely rapid (less than 20 min even at -110 °C effectively instantaneous at -78 °C) selenium-lithium exchange ensues to give tertiary organolithiums 250 and 253. Cyclisation to give 251 or 254 takes half an hour at -78 °C, and... 

Procedures which utilize selenides are similar, but a-lithio selenides are not generally preparable via simple deprotonation chemistry, due to facile selenium-lithium exchange. - Selenium-stabilized anions are available, however, by transmetalladon reactions of selenium acetals and add readily to carbonyl compounds. The use of branched selenium-stabilized anions has been shown to result exclusively in 1,2-addidon to unhindered cyclohexenones, in contrast to the analogous sulfur ylides. The resulting 3-hydroxy selenides undergo elimination by treatment with base after activation by alkylation or oxidation (Scheme 10). An alternative method of activating either p-hydroxy selenides or sulfides toward elimination involves treatment of a chloroform solution of the adduct with thallium ethoxide (Scheme 11). A mechanism involving the intermediacy of a selenium ylide is proposed. 

Sesquiterpene, cedrol 19 and its derivatives are functionalized at remote carbons to produce 20 and 21 using DIB, diphenylselenium acetate and iodine or HgO and bromine. The use of HgO/Br2 and selenium acetate improves the yield of the reaction [14, 15]. 

When camphor (I) is heated with selenium dioxide in acetic acid, the methylene group next to the carbonyl group is oxidised also to a carbonyl group, to form camphorquinone (II). Note that the compound (II) is not a true quinone but a 1,2-diketone ... 

Place a mixture of 5 g. of camphor, 6 g. of powdered selenium dioxide and 5 ml. of acetic anhydride in flask fitted with a reflux water-condenser. Heat the flask in an oil-bath for 3 hours at 140-150 so that gentle boiling occurs shake the mixture from time to time. 

Then cool the reaction-mixture, filter it at the pump, leaving a black residue of selenium, and wash out the flask twice with 2x5 ml. of acetic acid, passing the washings also through the filter. Dilute the united filtrates with water, and make the solution alkaline with 10% aqueous sodium hydroxide, which precipitates the camphorquinone. Cool, filter off the yellow camphorquinone at the pump, wash with water and drain thoroughly. 

Ninhydrin (also named 1 2 3-triketoindane or 1 2 3-triketohydrindene hydrate) is prepared most simply from the inexpensive phthahc anhydride (I). The latter is condensed with acetic anhydride In the presence of potassium acetate to give phthalylacetlc acid (II) reaction of the latter with sodium methoxide in methanol yields 1 3-indanedionecarboxyhc acid, which is decomposed upon warming with dilute hydrochloric or sulphuric acid to indane-1 3-dione (or 1 3-diketohydrindene) (HI). Selenium dioxide oxidation of (III) afibrds indane-1 2 3-trione hydrate (ninhydrin) (IV). 

Chromic(VI) acid Acetic acid, acetic anhydride, acetone, alcohols, alkali metals, ammonia, dimethylformamide, camphor, glycerol, hydrogen sulflde, phosphorus, pyridine, selenium, sulfur, turpentine, flammable liquids in general... 

Vitamin E acetate [58-95-7] serves primarily as an antioxidant and is closely associated with selenium. Vitamin E usually is present in... 

Alkyl Isoquinolines. Coal tar contains small amounts of l-methylisoquinoline [1721-93-3] 3-methylisoquinoline [1125-80-0] and 1,3-dimetliylisoquinoline [1721-94-4J. The 1- and 3-methyl groups are more reactive than others in the isoquinoline nucleus and readily oxidize with selenium dioxide to form the corresponding isoquinoline aldehydes (174). These compounds can also be obtained by the hydrolysis of the dihalomethyl group. The 1- and 3-methyhsoquinolines condense with benzaldehyde in the presence of zinc chloride or acetic anhydride to produce 1- and 3-styryhsoquinolines. Radicals formed by decarboxylation of carboxyUc acids react to produce 1-aIkyhsoquinolines. 

The direct combination of selenium and acetylene provides the most convenient source of selenophene (76JHC1319). Lesser amounts of many other compounds are formed concurrently and include 2- and 3-alkylselenophenes, benzo[6]selenophene and isomeric selenoloselenophenes (76CS(10)159). The commercial availability of thiophene makes comparable reactions of little interest for the obtention of the parent heterocycle in the laboratory. However, the reaction of substituted acetylenes with morpholinyl disulfide is of some synthetic value. The process, which appears to entail the initial formation of thionitroxyl radicals, converts phenylacetylene into a 3 1 mixture of 2,4- and 2,5-diphenylthiophene, methyl propiolate into dimethyl thiophene-2,5-dicarboxylate, and ethyl phenylpropiolate into diethyl 3,4-diphenylthiophene-2,5-dicarboxylate (Scheme 83a) (77TL3413). Dimethyl thiophene-2,4-dicarboxylate is obtained from methyl propiolate by treatment with dimethyl sulfoxide and thionyl chloride (Scheme 83b) (66CB1558). The rhodium carbonyl catalyzed carbonylation of alkynes in alcohols provides 5-alkoxy-2(5//)-furanones (Scheme 83c) (81CL993). The inclusion of ethylene provides 5-ethyl-2(5//)-furanones instead (82NKK242). The nickel acetate catalyzed addition of r-butyl isocyanide to alkynes provides access to 2-aminopyrroles (Scheme 83d) (70S593). 

Hexahydrobenzoyloxodedelphonine acetate (VI) was dehydrogenated by selenium at 330° and gave as chief product a hydrocarbon, b.p. 90°/0-02 mm., whose composition, ultra-violet absorption spectrum and chemical properties, so far as examined, indicate that it may be a bicyclopentenobenzene and therefore in a different category from the phenanthrene hydrocarbons yielded by the atisine group of bases. 

Ketohydroxycassanic acid, C20H32O4, has also been used for another mode of degradation by Ruzicka, Dalma and Scott (1941). On oxidation by chromic acid in acetic acid it yields diketocassanic acid, C20H30O4, m.p. 225°, [a]u ° — 44° (EtOH), which forms a methyl ester, m.p. 108°, (EtOH), and is reduced by sodium amyloxide at 220° to cassanic acid, C20H34O2, m.p. 224°, [a]f - - 3° (CHCI3), which on selenium dehydrogenation also yields 1 7 8-trimethylphenanthrene. 

Diseleno Acetals and Ketals R2C(SeR )2 Selenium compounds are generally HIGHLY TOXIC. 

In a 100-ml flask is placed a mixture of 19.5 g (0.18 mole) of freshly sublimed, pulverized selenium dioxide, 15 g (0.10 mole) of df/-camphor and 15 ml of acetic anhydride. The flask is fitted with a magnetic stirrer and a condenser, and the mixture is heated to 135° on an oil bath with stirring for 16 hours. After cooling, the mixture is diluted with ether to precipitate selenium, which is then filtered off, and the volatile materials are removed under reduced pressure. The residue is dissolved in ether (200 ml), washed four times with 50-ml portions of water and then washed several times with saturated sodium bicarbonate solution (until the washes are basic). The ether solution is finally washed several times with water, then dried, and the ether is evaporated. The residue may be purified by sublimation at reduced pressure or recrystallized from aqueous ethanol (with clarification by Norit, if necessary). The product is yellow, mp 197-199°. 

Preparation of 9a-F uoro-11, 17a,21 -Trihydroxy-16 Methy -1,4-Pregnadiene-3,20-Dione 21-Acetate 100 mg of 9a-f uoro-11(3,17a,21-trihydroxy-16(3-methyl-4-pregnene-3,20-dione 21-acetate was treated with selenium dioxide to produce the corresponding 9a-fluoro-11(3, 17a,21-trihydroxy-16(3-methyl-1,4-pregnadiene-3,20-dione 21-acetate. Alternately, Bacillus sphaericus may be utilized. 

A mixture of 290 mg of the 16,21-diacetate of 6a,9a-difluoro-16o --hYdroxY-hYdrocortisone, 30 cc of t-butanol, 0.5 cc of pyridine and 150 mg of selenium dioxide was refluxed for 53 hours under an atmosphere of nitrogen and cooled ethyl acetate was added and filtered through celite the solvent was evaporated to dryness under reduced pressure, the residue... 

An alternative synthetic route is described in U.S, Patent 2,900,398 as follows. A suspension of 30 g of 17a-methyI-testosterone and 10 g of selenium dioxide in 600 cc of tertiary amyl alcohol is treated with 60 g of magnesium powder and 6 cc of glacial acetic acid. 

The ethyl acetate solution is then washed with water, dried and evaporated. To remove any selenium still present, the residue is dissolved in 200 cc of methanol and mixed with 100 g of iron powder and 2 g of active carbon. The mixture is heated for 30 minutes with stirring under reflux, then filtered with suction, washed with methanol and the solution evaporated in vacuo. The residue is then chromatographed on 900 g of aluminum oxide. The residues of the evaporated benzene and ether fractions are treated with active carbon in methanol or acetone, evaporated again, and the residue recrystallized from a mixture of acetone and ether. There are obtained 17.5 g of pure 1-dehydro-17a-methyl-testosterone which melts at 163° to 164°C. 

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