Group amalgams

Rubidium can be liquid at room temperature. It is a soft, silvery-white metallic element of the alkali group and is the second most electropositive and alkaline element. It ignites spontaneously in air and reacts violently in water, setting fire to the liberated hydrogen. As with other alkali metals, it forms amalgams with mercury and it alloys with gold, cesium, sodium, and potassium. It colors a flame yellowish violet. Rubidium metal can be prepared by reducing rubidium chloride with calcium, and by a number of other methods. It must be kept under a dry mineral oil or in a vacuum or inert atmosphere. 

The methylthio group is removed by treatment with zinc powder in HCl (276) to give the 2-unsubstituted thiazole. The action of aluminum-mercury amalgam in methanol on various thioethers is reported to yield the expected thiazole (108) when Rj is an alkyl group and the corresponding A-4-thiazoline-2-thione (109) when Rj PhCH - (Scheme 55) (169). 

Two methods for converting carbonyl groups to methylene units are the Clem mensen reduction (zinc amalgam and con centrated hydrochloric acid) and the Wolff-Kishner reduction (heat with hydra zine and potassium hydroxide in a high boiling alcohol)... 

Metal Amalgams and Hydrides. Metal hydrides and amalgams are sometimes the preferred method of reducing various functional groups in the laboratory, especially when the necessary equipment for catalytic hydrogenations is unavailable. However, these reagents are usually too expensive to make their use on a large commercial scale feasible. 

Strontium [7440-24-6] Sr, is in Group 2 (IIA) of the Periodic Table, between calcium and barium. These three elements are called alkaline-earth metals because the chemical properties of the oxides fall between the hydroxides of alkaU metals, ie, sodium and potassium, and the oxides of earth metals, ie, magnesium, aluminum, and iron. Strontium was identified in the 1790s (1). The metal was first produced in 1808 in the form of a mercury amalgam. A few grams of the metal was produced in 1860—1861 by electrolysis of strontium chloride [10476-85-4]. 

Thione or alkylthio groups have also been involved in nucleophilic substitutions with hydrazine, or amines, and by desulfurization using Raney nickel or aluminum amalgam. 

This, on reduction with zinc dust and acetic acid, yielded the corresponding oxime, which was further reduced by sodium amalgam to -3 4 5-trimethoxyphenylethylamine, CgHjj(OMe)3. CH. CH. NHg, and this proved to be identical with mezcaline (I). Like the latter, it behaves on analysis as if it contained the grouping —NHMe but this had already been disproved by Heffter. Interest in the remarkable physiological properties attributed to mezcaline has led to many syntheses of this alkaloid and of its isomerides and analogues. ... 

Nitrogen cannot be eliminated from the latter by further methylation, but (VIII) on catalytic hydrogenation has its vinyl group converted into ethyl and the product, on methylation followed by reduction with sodium amalgam, yields 6-dimethylamino-3 4 3 4 -tetramethoxy-6 -ethyl-a)3-diphenylethane (X), and this, on repetition of the methylation, and reduc-... 

In these dithebainone products the pnra-position with reference to the hydroxyl group in ring I is assumed to be the point of junction (see dithebainone formula, p. 255), but an isomeride, is-8 -. 8 -dihydrothe-bainone, is obtained when thebainone is reduced with sodium amalgam (Goto and Ogawa ). 

The exchange of aromatic protons can be effected in the absence of any -OH or —NH2 activating group during the course of a Clemmensen reduction in deuteriochloric and deuterioacetic acid mixture (see section Ill-D). This reaction has been carried out with various tricyclic diterpenes and is best illustrated by the conversion of dehydroabietic acid into its 12,14-d2-labeled analog (40 -+ 41).Amalgamated zinc is reportedly necessary for the exchange reaction since the results are less satisfactory when a zinc chloride-mercuric chloride mixture is used. 

Hydrogen can be prepared by the reaction of water or dilute acids on electropositive metals such as the alkali metals, alkaline earth metals, the metals of Groups 3, 4 and the lanthanoids. The reaction can be explosively violent. Convenient laboratory methods employ sodium amalgam or calcium with water, or zinc with hydrochloric acid. The reaction of aluminium or ferrosilicon with aqueous sodium hydroxide has also been used. For small-scale preparations the hydrolysis of metal hydrides is convenient, and this generates twice the amount of hydrogen as contained in the hydride, e.g. ... 

Radium, the last element in the group, was isolated in trace amounts as the chloride by P. and M. Curie in 1898 after their historic processing of tonnes of pitchblende. It was named by Mme Curie in allusion to its radioactivity, a word also coined by her (Latin radius, a ray) the element itself was isolated electrolytically via an amalgam by M. Curie and A. Debieme in 1910 and its compounds give a carmine-red flame test. 

Because they possess an odd number of valence electrons the elements of this group can only satisfy the 18-electron rule in their carbonyls if M-M bonds are present. In accord with this, mononuclear carbonyls are not formed. Instead [M2(CO)s], [M4(CO)i2] and [M6(CO)i6] are the principal binary carbonyls of these elements. But reduction of [Co2(CO)g] with, for instance, sodium amalgam in benzene yields the monomeric and tetrahedral, 18-electron ion, [Co(CO)4] , acidification of which gives the pale yellow hydride, [HCo(CO)4]. Reductions employing Na metal in liquid NH3 yield the super-reduced [M(CO)3] (M = Co, Rh, Ir) containing these elements in their lowest formal oxidation state. 

Condensation of the intermediate, 16, with acetaldehyde rather than acetone gives the piperidone containing one less methyl group (22). Reduction of the ketone with sodium amalgam... 

---