Reduction, by amalgamated zinc and

Reduction, by amalgamated zinc and hydrodiloric acid, benzoin to stil-bene, 23, 86... 

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... 

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... 

The most important side-chain conversion involves reduction of ketones either by amalgamated zinc and HCl (Clemmensen reduction) or by hydrazine and strong base Wolff-Kishner reduction). This method is important because the necessary ketones are readily available through a modification of the Friedel-Crafts reaction that involves acid chlorides (see Sec. 19.6). Unlike alkylation by the Friedel-Crafts reaction, this method does not involve rearrangement. 

Reductive cleavage of attylic alcohols, ethers, or acetates by amalgamated zinc and HCl., 4 Amalgamated zinc is prepared by treatment of zinc powder with an aqueous solution of HgCl2- The resulting amalgam is washed with distilled water, ethanol, and... 

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. 

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) ... 

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. 

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]. 

Carbonation of the lithium derivative of 2-methoxybenzo[6]thio-phene affords the corresponding 3-carboxylic acid.183 2-Methylbenzo-[6]thiophene-3-carboxylic acid has been obtained (45%) by carbonation of 2-benzo[6]thienylmethylmagnesium chloride (Section VI,D, 4).528 re-Butyllithium reacts selectively with the bromine atom in 3-bromo-2-fluorobenzo[b]thiophene to give a product, which on carbonation affords 2-fluorobenzo[6]thiophene-3-carboxylic acid.482 Benzo[6]thiophene-7-carboxylic acid is obtained by reduction of the corresponding thioindoxyl with amalgamated zinc and acetic acid.315 Benzo[6]thiophene-3-carboxylic acid and its 2-ethyl derivative have been prepared in high yield by treatment of the pyridinium salt of the 3-chloroacetyl derivative with alkali.132... 

Several procedures can be used to convert the carbonyl group of an aldehyde or ketone to a methylene group. One reaction, known as the Clemmensen reduction, employs amalgamated zinc (zinc plus mercury) and hydrochloric acid as the reducing agent. An example is provided by the following equation ... 

Another demonstration of the strength of the Ru-S bond and also one of the few examples of oxygen removal from coordinated SO2 is seen in the reduction of the RU-SO2 complexes by amalgamated zinc to disulfur-bridged binuclear species, e.g. trans-[RU2Cl2(S2)(NH3)8]Cl2 >. 

There are two main synthetic routes to naphthalene the Haworth synthesis and a Diels-Alder approach. In the Haworth synthesis (Scheme 12.1), benzene is reacted under Friedel-Crafts conditions with succinic anhydride (butanedioic anhydride) to produce 4-oxo-4-phenylbutanoic acid, which is reduced with either amalgamated zinc and HCl (the Clemmensen reduction) or hydrazine, ethane-1,2-diol and potassium hydroxide (the Wolff-Kischner reaction) to 4-phenylbutanoic acid. Ring closure is achieved by heating in polyphosphoric acid (PPA). The product is 1-tetraione and reduction of the carbonyl group then gives 1,2,3,4-tetrahydronaphthalene (tetralin). Aromatization is achieved by dehydrogenation over a palladium catalyst. 

Aldehydes and ketones can be reduced to hydrocarbons by the action (a) of amalgamated zinc and concentrated hydrochloric acid, the Clemmensen reduction or (b) of hydrazine, NH2NH2, and a strong base like KCm or potassium teh-butoxide, the Wolff-Kishner reduction. These are particularly important when applied to the al faTryl ketones obtailTed from Friedel-Crafts acylation, since this reaction sequence permits, indirectly, the attachment of straight alkyl chains to the benzene ring. For example ... 

In the various solvent-extraction circuits employed in this process, use is made of a solution of D2EHPA in kerosene as the extractant. The selective recovery of the various metals is achieved by careful control of the equiUbrium pH value of the aqueous phases in the multistage extraction and stripping operations. After the leach liquor has passed through two separate circuits, each of which comprises five stages of extraction and four of stripping, the europium product is obtained initially as a solution of europium(III) chloride. Further purification of the product is accomplished by reduction with amalgamated zinc to Eu +, which is by far the most stable of the divalent lanthanide ions with respect to the reduction of water cf. the redox potentials of the Eu /Eu and Sm /Sm + couples, which are —0.43 and —1.55 V respectively ). Sulfuric acid is added to the... 

Clemmensen reaction. The Clemmensen method of reduction (1913) consists in refluxing a ketone with amalgamated zinc and hydrochloric acid. Acetophenone, for example, is reduced to ethylbenzene. The method is applicable to the reduction of most aromatic-aliphatic ketones to at least some aliphatic and alicyclic ketones, to the y-keto acids obtainable by Friedel-Crafts condensations with succinic anhydride (succinolylation), and to the cyclic ketones formed by intramolecular condensation. 

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