Reduction amalgamated zinc

Clemmensen reduction Aldehydes and ketones may generally be reduced to the corresponding hydrocarbons by healing with amalgamated zinc and hydrochloric acid. 

Aliphatic hydrocarbons can be prepared by the reduction of the readily accessible ketones with amalgamated zinc and concentrated hydrochloric acid (Clemmensen method of reduction). This procedure is particularly valuable for the prep>aration of hydrocarbons wdth an odd number of carbon atoms where the Wurtz reaction cannot be applied with the higher hydrocarbons some secondary alcohol is produced, which must be removed by repeated distillation from sodium. 

Clemmensen reduction of aldehydes and ketones. Upon reducing aldehydes or ketones with amalgamated zinc and concentrated hydrochloric acid, the main products are the hydrocarbons (>C=0 —> >CHj), but variable quantities of the secondary alcohols (in the case of ketones) and unsaturated substances are also formed. Examples are ... 

Secondary aisines, which can be synthesized by methods analogous to those used for piimaiy arsines, are obtained in good yields by the reduction of arsinic acids (44) or haloarsines (45) with amalgamated zinc and hydrochloric acid. They can also be prepared by the alkylation of primary arsenides (46) ... 

Clemmensen reaction is the reduction of carbonyl compounds with amalgamated zinc and concentrated hydrochloric acid... 

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. ... 

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. 

REDUCTION WITH AMALGAMATED ZINC THE JONES REDUCTOR 10.138... 

The silver reductor has a relatively low reduction potential (the Ag/AgCl electrode potential in 1M hydrochloric acid is 0.2245 volt), and consequently it is not able to effect many of the reductions which can be made with amalgamated zinc. The silver reductor is preferably used with hydrochloric acid solutions, and this is frequently an advantage. The various reductions which can be effected with the silver and the amalgamated zinc reductors are summarised in Table 10.11. ... 

The solutions of mer-OsCl3(PR3)3 undergo an interesting reduction with zinc amalgam [155] to form OsCl2(PR3)2L (Figure 1.62), where L is a molecule abstracted from the atmosphere in the reaction flask if a noble gas, incapable of coordination, is employed, coordinative saturation is obtained by dimerization to [(PR3)3OsCl3Os(PR3)3]+. 

Creosol (also called 2-methoxy-jb-cresol, 4-methylguaiacol, and 3-methoxy-4-hydroxytoluene) has been obtained by the fractionation of beach creosote tar,4 by the reduction of vanillin by electrolytic methods,6 6 by hydrogen and palladium on charcoal or barium sulfate,7 8 with hydrazine,9 and by amalgamated zinc and hydrochloric acid.3 10 11 It has also been prepared by methyl-ation of 4-methylcatechol with methyl iodide 12 13 or with methyl sulfate 14 and is reported to be formed by the distillation of the calcium salt of 3-methoxy-4-hydroxyphenylacetic acid.16... 

Amalgamated zinc residues isolated from Clemmensen reduction of an alkyl aryl ketone in glacial acetic acid were pyrophoric, and had to be immediately dumped into water after filtration to prevent ignition. 

Aluminum ethoxide, 21, 9 Aluminum isopropoxide, 21, 9 Amalgamated zinc, 20, 57 23, 86 Amide, 20, 37, 62, 66 preparation by ammonolysis, 20, 62 Amination, by reduction of a ketone in the presence of ammonia, 23, 68 of bromoacetal with use of high-pressure hydrogenation bomb, 24, 3 of a-bromoisocaproic acid, 21, 75 of a -bromo-/3-methylvaleric acid, 21, 62... 

The most stable of the germanium hydrides, R GcI I4 (n = 0,1,2,3), are the tri-organogermanium hydrides, which are prepared by the reduction of the corresponding halides with lithium alanate, or with amalgamated zinc and hydrochloric acid5-7. 

The neutralization values were influenced by reduction with strong reducing agents, lithium aluminum hydride, sodium borohydride, and amalgamated zinc plus hydrochloric acid (35, 46). For the most part, the consumption of NajCOj and of NaOEt decreased in equivalent amounts. This is further confirmation of the assumption that lactones of the fluorescein type or of the lactol type are present. The reaction with sodium ethoxide was shown to be no true neutralization, that is, exchange of H+for Na+, at all, but an addition reaction w ith the formation of the sodium salt of a semi-acetal or ketal ... 

A( ueous solutions of chromium(ll) sulfate have Ijeen prepared from chromium(lll) sulfate by reduction with zinc powder and from potassium dichromate by reduction with amalgamated zinc and sulfuric acid. Solid chromitim(II) sulfate penlahyrlrate can be obtained from the reaction of highly purified chromium metal... 

Reduction of aldehydes and ketones to the corresponding methylene compounds using amalgamated zinc and hydrogen chloride. 

Aqueous solutions of vanadous chloride (vanadium dichloride) are prepared by reduction of vanadium pentoxide with amalgamated zinc in hydrochloric acid [213], Reductions are carried out in solution in tetrahydrofuran at room temperature or under reflux. Vanadiiun dichloride reduces a-halo ketones to ketones [214], a-diketones to acyloins [215], quinones to hydroquinones [215], sulfoxides to sulfides [216] and azides to amines [217] (Procedure 40, p. 215). 

Reduction of saturated aliphatic aldehydes to alkanes was carried out by refluxing with amalgamated zinc and hydrochloric acid (Clemmensen reduction) [760, 758] (p. 28) or by heating with hydrazine and potassium hydroxide (Wolff-Kizhner reduction) [280, 759] (p. 34). Heptaldehyde gave heptane in 72% yield by the first and in 54% yield by the second method. 

Reduction of a,/3-unsaturated to saturated ketones was further achieved by electrolysis in a neutral medium using copper or lead cathodes (yields 55-75%) [766], with lithium in propylamine (yields 40-65%) [876], with potassium-graphite clathrate CgK (yields 57-85%) [807], and with zinc in acetic acid (yield 87%) [688]. Reduction with amalgamated zinc in hydrochloric acid (Clemmensen reduction) usually reduces both functions [877]. 

Clemmensen reduction can be effected either using amalgamated zinc or cadmium and hydrochloric acid, or in the equivalent electrochemical reaction at cathodes of cadmium or lead in 30 % sulphuric acid (see p. 344). Where the amino function is associated with a ring system, Clemmensen reduction of a-aminoketones gives rise to three types of product ... 

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