Acetone dissolving metals

Carbanions occasionally react with aryl halides spontaneously, mostly under irradiation, or by supplying electrons either from dissolved metals or from a cathode. However, certain Fe+2 salts catalyse the S l reactions with carbanions. That was the case for the reaction of PhBr or Phi with acetone or pinacolone enolate ions in liquid ammonia or DMS0172a, as well as for the reaction of the enolate ion of several carbanions with several aryl and hetaryl halides in DMS0172b. Since these reactions are inhibited byp-DNB andp-cymene, and the relative reactivity of nucleophiles is similar to that determined in photo-stimulated or spontaneous reactions, it seems that FeCl2 initiates the S l process. 

The metal-NHs reductions of carbonyl groups are exceedingly fast reactions for the reaction of acetone with an ammoniated electron the rate is 9 x 10 M" s". Although many, particularly older, published experimental procedures for the metal-NHs reduction of ketones employ prolonged reaction times with excess metal, these conditions are unnecessarily harsh. The reactions of carbonyl compounds with metals in NH3 are effectively instantaneous and by using short reaction times it appears that reduction of terminal alkenes and disubstituted alkynes can be avoided.In addition to the functional groups mentioned above, alcohols, amines and ethers, other than epoxides, are usually stable to reductions of aldehydes and ketones by dissolving metals. " ... 

Internal alkynes can be converted to trans alkenes using sodium (or lithium) in liquid ammonia. The reaction stops at the alkene stage because sodium (or lithium) reacts more rapidly with triple bonds than with double bonds. This reaction is called a dissolving metal reduction. Ammonia is a gas at room temperature (bp = — 33 °C), so it is kept in the liquid state by cooling the reaction flask in a dry ice/acetone mixture, which has a temperature of -78 °C. 

Since reductions by metal atoms often occur as one-electron processes, intermediate radicals are frequently involved in dissolving-metal reductions. When the reaction conditions are adjusted so that coupling of these intermediates competes favorably with other processes, the formation of carbon-carbon bonds will occur. A useful example which has been known for a long time is the reductive coupling of acetone to 2,3-dimethylbutane-2,3-diol (pinacol). Considerable effort has been... 

Two double salts of potassium dichloroisocyanurate [PDCC, KCl2(NCO)3] and TCCA are known, ie, Cl3(NCO)3 KCl2(NCO)3 [30622-37-8] and Cl2(NCO)2 4KCl2(NCO)2 [30622-37-8]. The latter is produced commercially. It can be prepared by reaction of TCCA dissolved iu acetone with aqueous PDCC (39), reaction of TCCA with saturated KCl or potassium salts of organic acids (34), or by reaction of CA with KOCl (40). A number of mixed metal... 

Acetylene Acetylene is used primarily in operations requiring high flame temperature, such as welding and metal cutting. To transport acetylene, it is dissolved in acetone under pressure and drawn into small containers filled with porous material. 

Sodium alginate [9005-38-3]. Freed from heavy metal impurities by treatment with ion-exchange resins (Na -form), or with a dilute solution of the sodium salt of EDTA. Also dissolved in 0. IM NaCl, centrifuged and fractionally ppted by gradual addition of EtOH or 4M NaCl. The resulting gels were centrifuged off, washed with aq EtOH or acetone, and dried under vacuum. [Buchner, Cooper and Wassermann J Chem Soc 3974 7967.]... 

The general reaction procedure and apparatus used are exactly as described in Procedure 2. Ammonia (465 ml) is distilled into a 2-liter reaction flask and to this is added 165mlofisopropylalcoholandasolutionof30g(0.195 mole) of 17/ -estradiol 3-methyl ether (mp 118.5-120°) in 180 ml of tetrahydrofuran. The steroid is only partially soluble in the mixture. A 5 g portion of sodium (26 g, 1.13 g-atoms total) is added to the stirred mixture and the solid dissolves in the light blue solution within several min. As additional metal is added, the mixture becomes dark blue and a solid (matted needles) separates. Stirring is inefficient for a few minutes until the mass of crystals breaks down. All of the sodium is consumed after 1 hr and 120 ml of methanol is then added to the mixture with care. The product is isolated as in Procedure 4h 2. After being air-dried, the solid weighs 32.5 g (ca. 100% for a monohydrate). A sample of the material is dried for analysis and analyzed as described in Procedure 2 enol ether, 91% unreduced aromatics, 0.3%. The crude product may be crystallized from acetone-water or preferably from hexane. 

I have found that a mixture of citral and acetone, if it is subjected, in the presence of water, for a suffieiently long time to the action of hydrates of alkaline earths or of hydrates of alkali metals, or of other alkaline agents, is eondensed to a ketone of the formula CjjH pO. This substanee, which I term Pseudo-ionone," may be produced lor instance in shaking together for several days equal parts of citral and acetone with a solution of hydrate of barium, and in dissolving the products of this reaction in ether. 

Theory. Conventional anion and cation exchange resins appear to be of limited use for concentrating trace metals from saline solutions such as sea water. The introduction of chelating resins, particularly those based on iminodiacetic acid, makes it possible to concentrate trace metals from brine solutions and separate them from the major components of the solution. Thus the elements cadmium, copper, cobalt, nickel and zinc are selectively retained by the resin Chelex-100 and can be recovered subsequently for determination by atomic absorption spectrophotometry.45 To enhance the sensitivity of the AAS procedure the eluate is evaporated to dryness and the residue dissolved in 90 per cent aqueous acetone. The use of the chelating resin offers the advantage over concentration by solvent extraction that, in principle, there is no limit to the volume of sample which can be used. 

Reagents. Standard copper (II) solutions. Dissolve 100 mg of spectroscopically pure copper metal in a slight excess of nitric acid and dilute to 1 L in a graduated flask with de-ionised water. Pipette a 10 mL aliquot into a 100 mL graduated flask and make up to the mark with acetone (analytical grade) the resultant solution contains 10 g of copper per mL. Use this stock solution to... 

Under N2, clean Li metal (0.17 g, 25 mmol) was placed in a round-bottom flask with a solvent mixture of MeOH (3 mL) and pcntan-t-ol (17 mL). The mixture was heated under N, until the reaction with Li was complete. Then, naphthalene-2,3-dicarbonitrilc (2 g, 11 mmol) was added to the mixture which turned green-brown the mixture was refluxed for 3h. The brown powder, obtained after cooling and removal of the solvent under reduced pressure, was dissolved in anhyd acetone (20 mL) and then hexane (70 mL) was added. The green precipitate was separated from the brown solution by filtration. This purification by precipitation was repeated twice. The green precipitate was placed in a Soxhlet extractor and extracted for 3 h with acetone (200 mL) in order to separate the product from the insoluble metal-free species and LiOH. The acetone solution was evaporated down to a volume of 20 mL. The product precipitated after the addition of hexane (70 mL). This latter purification step was performed several times yield 1.29 g (64%). 

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