Silver perchlorate, reaction with

When triphenylbismuth dichloride, ia acetone, is treated with silver perchlorate, ia absolute ethanol, tetraphenylbismuthonium perchlorate [43047-28-5], C24H2QBiC104, is formed (165). If, however, the same reaction is carried out only ia acetone, the following reaction occurs (166) ... 

Analogous to the oxidation of hydrazones to azo compounds, A-unsubstituted pyrazolidines are oxidized to A -pyrazolines. For example, the blcyclic pyrazolidine (415) when treated with silver oxide yields the pyrazoline (416) (65JA3023). Pyrazolidine (417) is transformed into the perchlorate of the pyrazolium salt (411) by reaction with mercury(II) acetate in ethanol followed by addition of sodium perchlorate (69JOU1480). 

A similar transformation results when trimethylsilyloxy-substituted allylic halides react with silver perchlorate in nitromethane. The resulting allylic cation gives cycloaddition reactions with dienes such as cyclopentadiene. The isolated products result from desilyla-tion of the initial adducts ... 

Bromo-A-homo-estra-4y5 0)-diene-3, l-dione (49). A solution of silver perchlorate (0.55 g, 5 mole-eq) in acetone (2 ml) is added to a refluxing solution of monoadduct (48 0.28 g) in acetone (30 ml) containing water (0.5 ml). After being heated at reflux for 25 min the reaction mixture is cooled and the precipitated silver bromide is removed by filtration, yield about 0.11 g. The filtrate is diluted with water (500 ml) and is thoroughly extracted with chloroform. The chloroform extracts are washed with water and saturated salt solution, dried over anhydrous magnesium sulfate, and evaporated at... 

A -Arylisotellurazolium perchlorates were prepared in 78-86% yields by the reaction of (3-bromotellurenylvinylaldimines 8 with silver perchlorate in DMSO or acetone [97DOK(357)504],... 

Benzo-l,2,3-telluradiazolium perchlorate 87 is the only compound known so far containing a 1,2,3-telluradiazole ring. It was obtained in 65% yield by reaction of the tellurenyl chloride 88 with silver perchlorate (88KGS1426). 

Reaction of the 3,4-dimethyl-1-phenylphosphole (L) complex [PdLjClj] with 1-vinylimidazole in the presence of silver perchlorate carried out in... 

In the case of 60, the ion has been prepared and has been shown to be a diradical in the ground state, as predicted by the discussion on page 58. Evidence that 60 is not only nonaromatic but also antiaromatic comes from studies on 64 and 66. When 64 is treated with silver perchlorate in propionic acid, the molecule is rapidly solvolyzed (a reaction in which the intermediate 65 is formed see Chapter 5). Under the same conditions, 66 undergoes no solvolysis at all that is, 60 does not form. If 60 were merely nonaromatic, it should be about as stable as 65 (which of course has no resonance stabilization at all). The fact that it is so much more reluctant to form indicates that 60 is much less stable than 65. It is noted that under certain conditions, 65 can be generated solvolytically. ... 

The reaction of silver perchlorate with the complex [Au(C6F5)(Ph2PCHPPh2Me)j gives the trinuclear heterometallic cationic complex [ (C6F5)AuPh2PCH(PPh2Me) 2Ag CIO4 [84]. 

A highly explosive liquid [1]. Early attempts failed to isolate it but prepared numerous other explosive compounds. Reaction of dichlorine hexoxide with silicon tetrachloride or tetrabromide gave an explosive solid, apparently a perchlorato oligosiloxane. Silver perchlorate and silicon tetrahalides in ether gave explosive volatile organics, perhaps ethyl perchlorate. Replacing ether by acetonitrile as solvent, a solid (di)acetonitrile adduct of the tetraperchlorate precipitated, described as exceptionally explosive even in the smallest quantities [2],... 

Not only water and alcohols, but also other oxygen compounds, are able to react covalently with acylium ions. In the case of hydroxy compounds the product is stabilized by loss of the proton from the hydroxyl group, but certain ethers give an analogous reaction in which the product is stabilized by loss of a carbonium ion.288 Using acetyl chloride with silver perchlorate in nitromethane as the source of acetyl... 

Problems of dilution and pH sensitivity have also been encountered in the synthesis of cts-[Pt(S-R2SO)(olefin)Cl2] complexes (85), where deoxygenation of the sulfoxide with concomitant oxidation of the metal center occurs at low pH. The reactions of [M(Ph2PCH2CH2PPh2)Cl2] (M = Pd, Pt) with one equivalent of silver perchlorate in the presence of Me2SO yield either the O-Me O complex or its deoxygenation product, depending upon reaction conditions. A sequence of reactions, Eq. (27), has been proposed (143). 

Since we could not prepare a stable solution of the ester, we attempted its preparation in the styrene solution to be polymerised. Silver perchlorate was dissolved in this and the reaction was started by the crushing of a phial containing 1-phenylethyl bromide (under our conditions styrene was not polymerised by the silver perchlorate alone). The solutions became cloudy because of the formation of colloidal silver bromide, but no colour formation could be observed until the end of the polymerisation then the solutions became yellow, very like the reaction mixtures in which perchloric acid had been used as catalyst. The ester was found to be as effective a catalyst as anhydrous perchloric acid. Equal concentrations of the ester and the acid produced very similar polymerisations as shown in the Figure. The accelerating parts of the curves obtained with the ester as catalyst are readily explained by the fact that the reaction between silver perchlorate and 1-phenylethyl bromide is not instantaneous and therefore a steady increase in catalyst concentration characterises the first part of the polymerisation. 

The ester hypothesis is supported by experiments in which the ester was formed in situ by the reaction of 1-phenylethyl bromide with silver perchlorate in the presence of styrene. These gave results in close agreement with those obtained with perchloric acid [6]. Propagation by the ester is envisaged as addition of the two parts of the ester across the double bond of the monomer in modern terminology this is an insertion . 

Dibenzothiophene 5-oxide is sufficiently nucleophilic to be alkylated at the oxygen atom by alkyl halides in the presence of silver perchlorate (96). Such compounds were found to be readily hydrolyzed back to the sulfoxide. The reaction of 96 with amines is discussed in Section VI, E, 3. 

Glycosyl perchlorates are formed on treating glycosyl halides with silver perchlorate in inert solvents, and react readily with alcohols to give glycosides, but they have been reported to explode when heated > so their use in direct displacement reactions has understandably been limited. These esters have, however, presumably been present as intermediates in the many reactions of glycosyl halides with alcohols in which silver perchlorate was used as a catalyst (e.g. Ref. s )). 

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