Iodination with silver perchlorate

Schwechten, 1926, 1927) of extracting the perchlorate from a precipitated mixture of the salt and silver iodide is increasingly being put to use today (Bell et al., 1969). When perchlorates were first made in this way it was thought that the effective oxidant wras chlorine tetroxide. The need to use fresh solutions of iodine-silver perchlorate was known, but the complexity of the reactions of iodine with silver perchlorate was not. These reactions vary with the solvent, and a prominent (but not the only) reaction in ether is the formation of iodine triperchlorate (21) (Alcock and Waddington,... 

Pleiadiene has been prepared by ring-expansion of (43), using a two-step procedure. Treatment of (43) with n-butyl-lithium and dichloromethane gave a mixture of bicyclobutane (44) and pleiadiene (total yield 68 %). Thermolysis, irradiation, treatment with silver perchlorate in benzene, and treatment with iodine in CCl (preferred) were all then used to convert this mixture into pleiadiene exclusively (60-80%). "... 

Benzene can be iodinated under anhydrous conditions with silver perchlorate as a catalyst. One suggested mechanism is ... 

C. HIO is prepared by oxidation of iodine with perchloric acid, nitric acid, or hydrogen peroxide or oxidation of iodine in aqueous suspension to iodic acid by silver nitrate. Iodic acid is also formed by anodic oxidation at a platinum electrode of iodine dissolved in hydrochloric acid (113,114). 

The detection and determination ot the perchlorates.—The perchlorates give no precipitates with silver nitrate or barium chloride soln. cone. soln. give a white crystalline precipitate with potassium chloride. Unlike all the other oxy-acids of chlorine, a soln. of indigo is not decolorized by perchloric acid, even after the addition of hydrochloric acid and they do not give the explosive chlorine dioxide when warmed with sulphuric acid unlike the chlorates, the perchlorates are not reduced by the copper-zinc couple, or sulphur dioxide. Perchloric acid can be titrated with —iV-alkali, using phenolphthalein as indicator. The perchlorates can be converted into chlorides by heat and the chlorides determined volumetrically or gravimetrically they can be reduced to chloride by titanous sulphate 28 and titration of the excess of titanous sulphate with standard permanganate they can be fused with zinc chloride and the amount of chlorine liberated can be measured in terms of the iodine set free from a soln. of potassium iodide and they can be... 

Perchlorates are unusual in that most are either extremely soluble or only sparingly soluble in water. Silver (I) perchlorate is one of the most soluble salts known, while its coordination compound with pyridine is so insoluble that pyridine can be precipitated quantitatively from aqueous solution by treatment with silver (I) perchlorate.1 Although several complexes of pyridine and silver (I) perchlorate have been described,1,2 the one in which silver(I) exhibits its common coordination number of two is the most stable. This compound provides a stable, nondeli-quescent starting material for synthesizing the perchlorates of the dipyridine complexes of unipositive bromine3 and iodine.4... 

The reaction of cyclohepta-1,4-diene and cycloocta-1,4-diene with electrophiles (bromine, iodine) results in transannular 7t-cyclization. Thus, reaction of cyclohepta-1,4-diene with silver(I) perchlorate and iodine in methanol gave /ranj-2,5-dimethoxybicyclo[4.1.0]heptane (26, n = 1) in 56% yield. Cycloocta-1,4-diene reacted similarly. ... 

Addition of (Z,Z)-cycloocta-l,4-diene to one equivalent of iodine and two equivalents of sil-ver(I) perchlorate in methanol, gave fra x-2,6-dimethoxybicyclo[5.1.0]octane (4) in 57% yield. Reaction of the dibromocyclooctane 2 with silver(I) perchlorate in methanol also gave the diether 4 in 56% yield. ... 

Bicyclobutane 12, obtained in one step from phenalene, was transformed to pleiadiene 13 in 60-80% yield under a variety of conditions, e.g. heating to 500 °C, or irradiation at 253.7 nm, or treatment with silver(I) perchlorate in benzene, or preferably treatment with a catalytic amount of iodine in carbon tetrachloride. ... 

Aromatic iodination [1, 497, after citation of ref. 12]. Polyalkylbenzenes having bulky groups are not reactive toward iodine alone but may react in the presence of an oxidizing agent. In a detailed study of agents used in this connection (silver perchlorate, mercuric oxide, iodic acid, potassium persulfate, etc.) Japanese investigators123 found the combination of iodine with periodic acid dihydrate to be the most satisfactory. 

METHYL SULFOXIDE (67-68-5) CjHjOS (CHjIjSO Combustible liquid [explosion limits in air (vol %) 2.6 to 63.0 flashpoint 203°F/95°C oc autoignition temp 419°F/215°C Fire Rating 2]. Violent or explosive reaction with strong oxidizers, acryl halides, aryl halides and related compounds, alkali metals p-bromobenzoyl acetanilide, boron compounds, especially hydrides iodine pentafluoride, magnesium perchlorate, methyl bromide, perchloric acid, periodic acid, silver fluoride, sodium... 

ABSOLUTE ALCOHOL or ABSOLUTE ETHANOL (64-17-5) Forms explosive mixture with air (flash point 55°F/13°C). Reacts, possibly violently, with strong oxidizers, bases, acetic anhydride, acetyl bromide, acetyl chloride, aliphatic amines, bromine pentafluoride, calcium oxide, cesium oxide, chloryl perchlorate, disulfuryl difluoride, ethylene glycol methyl ether. Iodine heptafluoride, isocyanates, nitrosyl perchlorate, perchlorates, platinum, potassium- er -butoxide, potassium, potassium oxide, potassium peroxide, phosphonis(III) oxide, silver nitrate, silver oxide, sulfuric acid, oleum, sodium, sodium hydrazide, sodium peroxide, sulfmyl cyanamide, tetrachlorosilane, i-triazine-2,4,6-triol, triethoxydialuminum tribromide, triethylaluminum, uranium fluoride, xenon tetrafluoride. Mixture with mercury nitrate(II) forms explosive mercury fulminate. Forms explosive complexes with perchlorates, magnesium perchlorate (forms ethyl perchlorate), silver perchlorate. Flow or agitation of substance may generate electrostatic charges due to low conductivity. 

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