Thallium reagents oxidants

Both the submitters and the checkers used thallium(III) tri-fluoroacetate prepared from thallium(III) oxide and trifluoroacetic acid.3 Although this material may be purchased from Aldrich Chemical Company, Inc. and Eastman Organic Chemicals, the submitters recommend that the reagent be freshly prepared prior to use. 

Littler has studied the oxidation of cyclohexanone with lead(IV), thallium(III), and mercury(II) salts (84), and found that, with all three reagents the rates of oxidation are independent of the concentration of oxidant. Oxidation by thallium(III) and mercury(II) in 35% aqueous perchloric acid showed first-order dependence on [H" ], and Littler suggested that the results were best interpreted in terms of the reaction sequence shown in Scheme 27. The major product of thallium(III) oxidation of... 

The reactions of aromatic substrates with thallium reagents is a fascinating subject which has been reviewed by McKillop and Taylor,two of the prime contributors to this field of chemistry. Two types of reaction are possible, both of which are important for the introduction of oxygen functionality. Tlie fu t is electrophilic aromatic thallation, whilst the second involves one-electron oxidation. 

Other oxidants like thallium(III) oxide, vanadium(V) oxyfluoride, palladium ) acetate, and ruthenium(IV) tetrakis(trifluoracetate) have been developed as powerful tools for the intramolecular biaryl coupling reaction [7,93,113]. Nevertheless, DDQ is still one of the most versatile reagents in oxidative coupling reactions (see Scheme 14 and 29 [82,114]). The highly strained dioxa[8](2,7)pyrenophane (65), portraying an overall curvature of nearly 90° for the pyrene subunit, was finally obtained from the mefa-cyclophanediene (66) by dehydrogenation with DDQ in refluxing benzene in 67% yield [114]. 

Sasaki and co-workers have investigated the reactions of the diene (186) with lead tetra-acetate and thallium(iii) reagents. Oxidation with lead tetra-acetate in... 

For thallium on the other hand, the monovalent state is the stable state and the trivalent state is oxidizing one and prone to reductive elimination, thanks to the inert pair effect. Nevertheless, in spite of their toxicity, trivalent thallium reagents enjoy some unique applications as oxidants in organic chemistry. 

The synthesis of some naturally occurring fused tetrahydrofurans has been elaborated using the well-known thallium reagent. Compounds of this type (47) exhibit a number of inhibitory actions and are prepared in reasonable yield by oxidative dimerization of p-alkoxycinnamic acids. 

In small-scale syntheses, a wide variety of oxidants have been employed in the preparation of quinones from phenols. Of these reagents, chromic acid, ferric ion, and silver oxide show outstanding usefulness in the oxidation of hydroquinones. Thallium (ITT) triduoroacetate converts 4-halo- or 4-/ f2 -butylphenols to l,4-ben2oquinones in high yield (110). For example, 2-bromo-3-methyl-5-/-butyl-l,4-ben2oquinone [25441-20-3] (107) has been made by this route. 

ThaUous sulfate, thaUous nitrate, and thaUous and thaUic oxide are the main compounds produced in bulk quantities by Noah Chemical. Approximately 20 other thallium compounds are also available commercially from Noah Chemical, Cooper Chemical, and Alfa Products, Ventron Division, Thiokol Corporation, in research and production quantities. However, demand for thallium compounds is small and limited to such appHcations as synthetic or analytical reagents. 

Uses. Tballium compounds have limited use in industrial appHcations. The use of thaHous sulfate in rodenticides and insecticides has been replaced by other compounds less harmful to animals (see Insect control technology Pesticides). Tb allium sulfide has been used in photoelectric cells (see Photovoltaic cells). A thallium bromide—thallium iodide mixture is used to transmit infrared radiation for signal systems. ThaHous oxide is used in the manufacture of glass (qv) that has a high coefficient of refraction. Tb allium formate—malonate aqueous solutions (Cletici s solution) have been used in mineral separations. Many thallium compounds have been used as reagents in organic synthesis in researchlaboratoti.es. 

Trifluoroacetates of silver, mercury(II), thallium(lll), lead(IV), and lodme(III) are synthetically valuable reagents that combine the properties of strong electrophiles, oxidizers, and Lewis acids Furthermore, trifluoroacetate anions are stable to oxidation, are weak nucleophiles, and usually do not cause any contamination of the reaction mixture... 

The mechanism of oxidation probably involves in most cases the initial formation of a glycol (15-35) or cyclic ester,and then further oxidation as in 19-7. In line with the electrophilic attack on the alkene, triple-bonds are more resistant to oxidation than double bonds. Terminal triple-bond compounds can be cleaved to carboxylic acids (RC=CHRCOOH) with thallium(III) nitrate or with [bis(trifluoroacetoxy)iodo]pentafluorobenzene, that is, C6F5l(OCOCF3)2, among other reagents. 

The reactions of TTN with a variety of unsaturated systems have been studied systematically during the last two years, and the results obtained clearly establish the synthetic utility of the reagent as a specific oxidant. Attempts were made in 1966 by Uemura et al. 162) to oxidize a,)8-unsatur-ated carbonyl compounds with thallium(III) acetate, but were unsuccessful. In 1970, however, Ollis and his co-workers 121-123) reported that prolonged treatment of highly activated chalcones (Scheme 20) with thal-... 

Symmetrical and unsymmetrical benzoins have been rapidly oxidized to benzils in high yields using solid reagent systems, copper(II) sulfate-alumina [105] or Oxone-wet alumina [105, 106] under the influence of microwaves (Scheme 6.32). Conventionally, the oxidative transformation of a-hydroxy ketones to 1,2-diketones is accomplished by reagents such as nitric acid, Fehling s solution, thallium(III) nitrate (TTN), ytterbium(III) nitrate, ammonium chlorochromate-alumina and dayfen. In addition to the extended reaction time, most of these processes suffer from drawbacks such as the use of corrosive acids and toxic metals that generate undesirable waste products. 

Oxidative coupling of aryl tetrahydroisoquinolines. This reagent is superior to thallium(III) trifluoroacetate or vanadium oxyfluoride for nonphenolic oxidative coupling of substrates such as 2 to provide aporphines and homoaporphines (3). 

Biaryl phenol coupling.1 The natural dibenzylbutanolide lignans, prestegane A (la) and B (lb), are converted to the corresponding bisbenzocyclooctadiene lactones (2) by oxidation with Ru02 in TFA-TFAA in 80-85% yield. The usual reagent for this oxidation, thallium tris(trifluoroacetate), is less efficient (45-50% yields). 

Much of the experience gained in the field of solution-phase oxidative deprotection of cysteine peptides can be applied to solid-phase chemistry. For this purpose the iodine, thallium(III), and chlorosilane/sulfoxide procedures have been usually employed,163 107-1121 generally, the results obtained with the thallium(III) reagent are better than with iodine. 

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