Electro-organic synthetic

We are well aware that this discussion of the electrode material and its role in electro-organic chemistry is severely limited, both with respect to the number of examples quoted and to the number of possible factors involved. However, we think that the mere fact that hardly any synthetic investigations dealing with the problem have adequately characterized the surfaces of the electrode materials used gives us a good excuse for refraining from such a discussion. Let us first get the experimental facts on this point ... 

Conductive coatings may also find extensive use for product-selective synthetic electro-organic applications. Thus, conductive coatings might be used to affect oxidation or reduction of specific electroactive centers in a molecule and not of others. Such selectivity not only would improve the current efficiency for specific products but... 

Limitations to the acceptance of organic electrochemistry, particularly as a synthetic technique, may have been connected with the fact that electrode reactions are normally two-dimensional, i.e., they are restricted to a surface and therefore require mass transport (see elsewhere in this chapter) and also because many reactions yield a complex mixture of products when the electrolyses are carried out using a constant current. However, as early as 1898, Haber had pointed out the importance of control of the electrode potential for the overall process, in his work where nitrosobenzene, phenylhy-droxylamine and aniline were isolated selectively from the reduction of nitrobenzene. However, design of suitable controlled-potential equipment proved to be a practical barrier, even in laboratory studies, until 1942, when the potentiostat—an instrument capable of automatically controlling the electrode potential—was introduced.Without question, this instrument has facilitated electro-organic syntheses, mechanistic studies, and specific electrooxidation and electroreduction processes. More modern and electronically... 

Discoveries of new types of electro-organic reactions based on coupling and substitution reactions, cyclization and elimination reactions, electrochemically promoted rearrangements, recent advances in selective electrochemical fluorination, electrochemical versions of the classical synthetic reactions, and successful use of these reactions in multistep targeted synthesis allow the synthetic chemist to consider electrochemical methods as one of the powerful tools of organic synthesis. 

Mousty, C., Therias, S., Forano, C. and Besse, J. P. (1994). Anion-exchanging clay-modified electrodes - synthetic layered double hydroxides intercalated with electroactive organic-anions. J. Electro anal. Chem. 374, 63. 

Iodine — Iodine, L, is a halogen which occurs naturally mainly as iodide, I- [i]. Iodine (Greek ioeides for colored violet ) is a black solid with a melting point of 113.6 °C which is readily undergoing sublimation to form a violet gas. Iodine occurs in the oxidation states -1,0, +1, +3, +5, +7 and it possesses a rich redox chemistry [ii]. In aqueous solution the formation of I2 from I- occurs with a standard potential of 0.621V vs. SHE and this oxidation process is preceded by the formation of I3 with a standard potential of 0.536 V vs. SHE. For the reaction I2(cryst) + 2e - 21 E = 0.535 V. The I—/I3 redox couple is employed, for example, in solar cells [iii] and in long-lived lithium-iodine battery systems. The oxidation of I2 in organic solvents results formally in I+ intermediates which is a powerful oxidant and useful, for example, in electro-synthetic chemical processes [ii]. 

The properties of zeotype host-guest composites described above - i e, spatial organization, protection and stabilization of guest species - will become more important as molecules exhibit further properties that are essential for their use as materials. The well-developed synthetic methods for molecular compounds allow the preparation of designed molecular entities that possess predictable properties. However, no such thoroughly elaborated synthetic methods are available for the construction of organized arrays of functional molecules in their solid structures [36]. This is cumbersome since often the arrangement of the molecules in their solid compounds is detrimental to the effects (e g. non-linear optical, ferroelectric, electro-optical) that are to be exploited in materials. For example, many structures of molecules in the solid state are centrosymmetric. Also, molecular... 

Although the effect of temperature on each of the steps in an overall electrode process is readily predictable, it is surprising to find in the literature very few systematic studies of this variable or attempts to use it to change the rate, products or selectivity of an organic electro-synthetic process. A recent paper has, however, discussed equipment and suitable solvents for low-temperature electrochemistry (Van Dyne and Reilley, 1972a). 

Yoshida K (1984) Electro-oxidation in organic chemistry the role of cation-radicals as synthetic intermediates. Wiley, New York... 

Published data in this field of synthetic inorganic polymers exhibiting metallic-type conductivity continues at a rapidly increasing rate, particularly in the elucidation of molecular structure and the modification of polymers to produce greatly enhanced electrical characteristics. A comprehensive review of (SN) polymers, covering the preparation, structure, and properties, has been published which also includes coverage of comparable electro-active organic polymers. "... 

Kapalka A, Baltruschat H, Corrmineffis C (2011) Electrochemical oxidation of organic compounds induced by electro-generated free hydroxyl radicals on BDD electrodes. In Brillas E, Martinez-Huitle CA (eds) Synthetic diamond films preparation, electrochemistry, characterization and applications. Wiley, Hoboken/New Jersey... 

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