Lithium acetone

The stereoselective enolization of 3-pentanone by LiTMP mixed aggregates with butyl-lithium was studied by Pratt and coworkers. The mixed aggregate resulted in a slightly higher stereoselectivity, which increased with decreasing amount of the lithium base. Semiempirical PM3 calculations were used in an attempt to determine the mechanism of ketone deprotonation by the mixed aggregate. Equations 20 and 21 show two alternative mechanisms for the formation of lithium acetone enolate in thf solution, involving... 

Use SpartanView to compare electrostatic potential maps of acetone enol and lithium acetone enolate. Which of the two has a more negative carbon ... 

After the air in the flask had been completely replaced with nitrogen, it was cooled in a liquid nitrogen bath and a solution of 25 g of acetylene in 160 ml of dry THF was introduced. The solution had been prepared by dissolving acetylene (freed from acetone by means of a cold trap) in THF cooled at -80 to -90°C. A solution of 0.21 mol of butyl lithium in about 150 ml of hexane was added in 5 min to the vigorously stirred solution. During this addition the temperature of the mixture was kept between -80 and -100°C by occasionally dipping the flask into the liquid nitrogen. To the white suspension were successively added at -80°C a solution of 10 g. of anhydrous lithium bromide (note 1) in 30 ml of THF and 0.20 mol of freshly distilled benzaldehyde. The reaction mixture was kept for 3 h at -69°C, after which the temperature was allowed to rise to +10°C over a period of 2 h. 

Difunctional target molecules are generally easily disconnected in a re/ro-Michael type transform. As an example we have chosen a simple symmetrical molecule, namely 4-(4-methoxyphenyl)-2,6-heptanedione. Only p-anisaldehyde and two acetone equivalents are needed as starting materials. The antithesis scheme given helow is self-explanatory. The aldol condensation product must be synthesized first and then be reacted under controlled conditions with a second enolate (e.g. a silyl enolate plus TiCl4 or a lithium enolate), enamine (M. Pfau, 1979), or best with acetoacetic ester anion as acetone equivalents. 

Iodoform Acetone, lithium, mercury(II) oxide, mercury(I) chloride, silver nitrate... 

Platinum Acetone, arsenic, hydrazine, lithium, proxosulfuric acid, phosphorus, selenium, tellurium... 

In the vapor phase, acetone vapor is passed over a catalyst bed of magnesium aluminate (206), 2iac oxide—bismuth oxide (207), calcium oxide (208), lithium or 2iac-doped mixed magnesia—alumina (209), calcium on alumina (210), or basic mixed-metal oxide catalysts (211—214). Temperatures ranging... 

In this process, the fine powder of lithium phosphate used as catalyst is dispersed, and propylene oxide is fed at 300°C to the reactor, and the product, ahyl alcohol, together with unreacted propylene oxide is removed by distihation (25). By-products such as acetone and propionaldehyde, which are isomers of propylene oxide, are formed, but the conversion of propylene oxide is 40% and the selectivity to ahyl alcohol reaches more than 90% (25). However, ahyl alcohol obtained by this process contains approximately 0.6% of propanol. Until 1984, ah ahyl alcohol manufacturers were using this process. Since 1985 Showa Denko K.K. has produced ahyl alcohol industriahy by a new process which they developed (6,7). This process, which was developed partiy for the purpose of producing epichlorohydrin via ahyl alcohol as the intermediate, has the potential to be the main process for production of ahyl alcohol. The reaction scheme is as fohows ... 

Isomerization and Hydrogenolysis. lsomeri2ation of propylene oxide to propionaldehyde and acetone occurs over a variety of catalysts, eg, pumice, siUca gel, sodium or potassium alum, and 2eohtes (80,81). Stronger acid catalysts favor acetone over propionaldehyde (81). AHyl alcohol yields of 90% are obtained from use of a supported lithium phosphate catalyst (82). 

The unsaturated tetraoxaquaterene (accompanied by linear condensation products) was first synthesized in 18.5% yield by the acid-catalyzed condensation of furan with acetone in the absence of added lithium salts. Other ketones also condensed with furan to give analogous products in 6-12% yield.A corresponding macrocycle was also prepared in 9% yield from pyrrole and cyclohexanone. The macrocyclic ether products have also been obtained by condensation of short linear condensation products having 2, 3, or 4 furan rings with a carbonyl compound. ... 

Chastrette and Chastrette showed that the cyclocooligomerization of furan and acetone was improved by the presence of lithium salts. Liotta and co-workers reported the synthesis of 12-crown-4 by a double Williamson approach in the presence of LiC104. They mention in a footnote that A run performed as detailed but without UCIO4 gave no product . Other inferential evidence has accumulated as well. 

Mobile phase Acetone — acetonitril — 0.1 mol/1 aqueous lithium chloride... 

While keeping the collected deuterioammonia at dry ice-isopropyl alcohol temperature, lithium wire (10 mg) is added, followed by a solution of 3/3-hydroxy-5a-cholest-7-en-6-one (161 50 mg) in anhydrous tetrahydrofuran (4 ml). The reaction mixture is stirred for 20 min, the cooling bath is then removed and the ammonia is allowed to boil under reflux for 40 min. A saturated solution of ammonium chloride in tetrahydrofuran is added dropwise until the deep blue color disappears and then the ammonia is allowed to evaporate. The residue is extracted with ether and the organic layer washed with dilute hydrochloric acid and sodium bicarbonate solution and then with water. Drying and evaporation of the solvent gives a semicrystalline residue which is dissolved in acetone and oxidized with 8 N chromic acid solution. After the usual workup the residue is dissolved in methanol containing sodium hydroxide (0.2 g) and heated under reflux for 1 hr to remove any deuterium introduced at C-5 or C-7. (For workup, see section II-B). 

A suspension of lithium aluminum deuteride (1.6 g) in dry tetrahydrofuran (60 ml) is added dropwise to a stirred and cooled (with ice-salt bath) solution of 5a-androst-l4-ene-3j3,17j3-diol (179, 1.6 g) and boron trifluoride-etherate (13.3 g) in dry tetrahydrofuran (60 ml). The addition is carried out in a dry nitrogen atmosphere, over a period of 30 min. After an additional 30 min of cooling the stirring is continued at room temperature for 2 hr. The cooling is resumed in a dry ice-acetone bath and the excess deuteriodiborane is destroyed by the cautious addition of propionic acid. The tetrahydrofuran is then evaporated and the residue is dissolved in propionic acid and heated under reflux in a nitrogen atmosphere for 8 hr. After cooling, water is added and the product extracted with ether. The ether... 

A solution of 16jS-methyl-l la,17a,21-trihydroxy-5j5-pregnane-3,20-dione 21-acetate (52), 45 g, in dioxane (297 ml) is cooled to 15° and treated over a 5 min period with a solution of bromine (34.2 g) in dioxane (594 ml) precooled to 18°. After 2 min a solution of sodium acetate (60 g) in water (600 ml) is added and the mixture poured into ice water (8 liters). The precipitate is filtered off, washed to neutrality with water, and dried to give the crude dibromide (53), 55.7 g mp 125-126° (dec.) [aJu 58°. A mixture of dibromide (53), 55.5 g, lithium bromide (27.8 g), lithium carbonate (27.8 g) and DMF (1.11 liters) is refluxed under rapid stirring for 6 hr. The mixture is concentrated under vacuum to about 250 ml, poured into ice water (8 liters) containing hydrochloric acid (250 ml), and extracted with methylene dichloride. The extracts are washed to neutrality with water and evaporated to dryness. The residue is dissolved in acetone, evaporated to dryness under reduced pressure, redissolved in acetone and crystallized by the additon of hexane. This gives the dienone (54) 24.4 g, mp 236-239°. 

Some instances of incomplete debromination of 5,6-dibromo compounds may be due to the presence of 5j5,6a-isomer of wrong stereochemistry for anti-coplanar elimination. The higher temperature afforded by replacing acetone with refluxing cyclohexanone has proved advantageous in some cases. There is evidence that both the zinc and lithium aluminum hydride reductions of vicinal dihalides also proceed faster with diaxial isomers (ref. 266, cf. ref. 215, p. 136, ref. 265). The chromous reduction of vicinal dihalides appears to involve free radical intermediates produced by one electron transfer, and is not stereospecific but favors tra 5-elimination in the case of vic-di-bromides. Chromous ion complexed with ethylene diamine is more reactive than the uncomplexed ion in reduction of -substituted halides and epoxides to olefins. ... 

An ethereal solution approximately 2.5 molar in methyllithium is prepared from 17 ml of methyl iodide and 4 g of lithium metal in 200 ml of anhydrous ether. A mixture consisting of 150 ml anhydrous ether, 3 g (10 mmoles) of 3jS-hydroxy-5a-androstane-ll,17-dione and 60 ml (0.15 moles) of the above methyllithium solution are stirred at room temperature for 40 hr. The reaction mixture is diluted with 100 ml of water and the ether is removed by distillation. Filtration of the chilled aqueous phase yields 2.6 g (77%) of 1 la,17a-dimethyl-5a-androstane-3a,l l/ ,17j5-triol mp 149-154°. Recrystallization from acetone-hexane yields pure material mp 164-166° [a] —5° (CHCI3). 

A solution of 10 g of this compound in 80 ml of tetrahydrofuran is added, with cooling, during 5 min, to a solution of 4.8 g of lithium aluminum hydride in 60 ml of tetrahydrofuran, and the mixture refluxed for 2.25 hr then cooled in an ice bath and treated with 60 ml of acetone, followed by 200 ml of ether and 72 ml of 2 A sodium hydroxide. The mixture is filtered, the cake washed with 50 ml of acetone, and the combined filtrate washed with water, dried over sodium sulfate and evaporated under reduced pressure. The residue is crystallized from acetone to give 6.05 g (68 %) of the enamine. 

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