Reactions with lead acetates

The above proposal is supported by the lack of reaction of electron-deficient arylamines, such as p-N02-aniline and p-Et02C-aniline, in the copper-mediated reactions with lead acetates because of the inability of the amines to reduce Cu(II) to Cu(I). This lack of reduction is indicated by the lack of a color change upon addition of Cu(OAc)2 to a solution of either of the amines. Further, the presence of Cu(III) species may be responsible for the formation of arenes and polymeric species during the A-arylation of anilines that are easily oxidized (Scheme 11). 

A direct method for introduction of a C-21 acetoxyl group into a 20-keto-pregnane is by reaction with lead tetraacetate at room temperature. Although originally the reaction carried out in hot acetic acid gave low yields, a careful study by Henbest has defined conditions so that yields as high as 86 % can be obtained at room temperature. The preferred solvent is 5 % methanol in benzene, with boron trifluoride etherate as catalyst. With either methanol or benzene, the yield is less than 4%. 

Excretion of hydrogen sulfide was documented after dermal exposure in rabbits. Trunk fiir of rabbits was clipped and left intact or abraded for exposure to hydrogen sulfide gas (unknown concentrations) for 1.5-2 hours the animals then breathed clean air (Laug and Draize 1942). Evidence for the excretion of hydrogen sulfide by the rabbits was a sulfide reaction of the expired air with lead acetate paper (Laug and Draize 1942). Sulfides in the expired air were noted in one rabbit with intact skin after 7 minutes of exposure. This study was limited by the lack of measurement of exposure concentrations and the small number of animals used. 

Reaction with hydrogen sulfide forms black precipitate of lead sulfide, PbS. A paper soaked with lead acetate solution turns black on exposure to H2S, a test often used to detect sulfide. 

V to IX), the copper complexes of the imidazoles also precipitated from the reaction mixture, and were filtered off. Oxalic acid and 4(5)-imidazole (30) were determined in the filtrate.11 40,41 The complex was suspended in hot water,11,29 32-40,41,43 47 50 53,88 dilute sulfuric acid,48,49 or dilute hydrochloric acid,44 the copper was removed as the sulfide, with hydrogen sulfide or sodium sulfide,49 and the excess of hydrogen sulfide was removed with lead acetate.11 40 41,50 The clear... 

Woodward hydroxylation of 256 leads mainly to sterically disfavored products having cis-oriented substituents at C-2 and C-3, and C-2 and C-4. In fact, in this case also, the attack of I4 occurs from the less-hindered side. The iodonium ion (284) is then opened by the acetate anion, to afford iodo acetate 285 which, in the following substitution reaction with silver acetate, gives the more-hindered, c/.y-hydroxylation product 286. 

For analysis by titration with Fehling s solution, the sample is treated with lead acetate to precipitate protein and fat, filtered, and the filtrate titrated with alkaline CuS04, while heating. The reactions involved are summarized in Figure 2.37. 

The basic salt is formed by the reaction of lead acetate with sodium or magnesium styphnate. The chemical composition of the basic salts formed depends upon the reaction conditions. The basic salt is usually credited with the structural formula (II), corresponding to the dibasic salt ... 

Alkalies. — The solution of 2 gm. of ammonium phosphate in 100 cc. of water is treated with lead acetate solution in slight excess to precipitate the phosphoric acid, and is then filtered. The excess of lead in the filtrate is then precipitated with hydrogen sulphide, the liquid filtered, the filtrate evaporated to dryness, and the residue ignited. The residue should not be soluble in water, nor should it have an alkaline reaction. 

ANALYZER (Reagent-Tape). The key to chemical analysis by this method is a tape (paper or fabric) that has been impregnated with a chemical substance that reacts with the unknown to form a reaction product on the tape which lias some special characteristic, e.g., color, increased or decreased opacity, change in electrical conductance, or increased or lessened fluorescence. Small pieces of paper treated with lead acetate, for example, have, been used manually by chemists for many years to determine the presence of hydrogen sulfide in a solution or in the atmosphere. This basic concept forms the foundation for a number of sophisticated instruments that may pietreat a sample gas, pass it over a cyclically advanced tape, and, for example, photo-metrically sense the color of the exposed tape, to establish a relationship between color and gas concentration. Depending upon tile type uf reactiun involved, the tape may he wet or dry and it may be advanced continuously or periodically. Obviously, there are many possible variations within the framework of this general concept. 

The former is deposited in yellow crystals, mixed with sulphur when acetoxime is treated with phosphorus pentasulphide in carbon bisulphide soln. the insoluble product extracted with alcohol and the alcoholic soln. heated to boiling the compound separates from cold water in large, transparent, seemingly monoclinic prisms, melts at 146° 150° with decomposition, and is readily soluble in water, but only sparingly in alcohol, and insoluble in ether and carbon bisulphide. It decomposes carbonates, gives a colourless precipitate with lead acetate, and is decomposed by hot dilute nitric acid with separation of sulphur and formation of phosphoric acid it is also decomposed by mercuric oxide, the filtrate from the precipitated mercury sulphide giving all the reactions of phosphoric acid. 

Acyl-2-methylthio-l,6,6a lv-trithiapentalenes, on reaction with mercuric acetate, undergo a degradation leading to a dithiolylidene ketone (Eq. 16).46... 

Zinc 2-ethylhexanoate was prepared in refluxing toluene from the reaction of 2-ethylhexanoic acid with zinc oxide. The lead salt was prepared in methanol by the reaction of lead acetate with 2-ethylhexanoic acid. The reaction of barium oxide with 2-ethylhexanoic acid in toluene provided the barium salt. 

The characteristic colours and solubilities of many metallic sulphides have already been discussed in connection with the reactions of the cations in Chapter III. The sulphides of iron, manganese, zinc, and the alkali metals are decomposed by dilute hydrochloric acid with the evolution of hydrogen sulphide those of lead, cadmium, nickel, cobalt, antimony, and tin(IV) require concentrated hydrochloric acid for decomposition others, such as mercury(II) sulphide, are insoluble in concentrated hydrochloric acid, but dissolve in aqua regia with the separation of sulphur. The presence of sulphide in insoluble sulphides may be detected by reduction with nascent hydrogen (derived from zinc or tin and hydrochloric acid) to the metal and hydrogen sulphide, the latter being identified with lead acetate paper (see reaction 1 below). An alternative method is to fuse the sulphide with anhydrous sodium carbonate, extract the mass with water, and to treat the filtered solution with freshly prepared sodium nitroprusside solution, when a purple colour will be obtained the sodium carbonate solution may also be treated with lead nitrate solution when black lead sulphide is precipitated. 

The test is usually carried out by adding the reagent to the solution acidified with dilute hydrochloric acid carbonates, sulphites, and phosphates are not precipitated under these conditions. Concentrated hydrochloric acid or concentrated nitric acid should not be used, as a precipitate of barium chloride or of barium nitrate may form these dissolve, however, upon dilution with water. The barium sulphate precipitate may be filtered from the hot solution and fused on charcoal with sodium carbonate, when sodium sulphide will be formed. The latter may be extracted with water, and the extract filtered into a freshly prepared solution of sodium nitroprusside, when a transient, purple colouration is obtained (see under Sulphides, Section IV.6, reaction 5). An alternative method is to add a few drops of very dilute hydrochloric acid to the fused mass, and to cover the latter with lead acetate paper a black stain of lead sulphide is produced on the paper. The so-called Hepar reaction, which is less sensitive than the above two tests, consists of placing the fusion product on a silver coin and moistening with a little water a brownish-black stain of silver sulphide results. 

Thus, reactions of carbonyl compounds with hydrogen peroxide and acids lead to products similar to those obtained by the ozonization of olefins (Section III), which also yields 1,2,4-trioxolans and 1,2,4,5-tetroxans. The similarity of the two reactions is understandable, since the intermediates )C+—OO- in the ozonization27a and )C+—OOH in the hydrogen peroxide reactions are related as a conjugate base-acid pair. A number of cyclic peroxides of structure 7 are prepared from bis(hydroperoxy)dialkyl peroxides (5) by reaction with lead(IV) acetate, as described by Criegee et al.la This reaction is also thought to involve a carbonium ion intermediate,31 which reacts with the second OOH group. 

The conversion to primary acetates is carried out in higher yield if the hydroalumination is conducted with only 2 equiv. of the alkene followed by reaction with lead tetraacetate (equation II). ... 

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