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Radical coupling dioxide

The photoextrusion of sulphur dioxide to form cyclophanes or other novel aromatic molecules has been reviewed and studied by Givens208-210, while the photodecomposition of aromatic sulphones to form products of radical coupling reactions has recently also received attention211. [Pg.962]

The reduction of carbon dioxide (Section 2.5.4) raises the question of possible competition between a radical-radical coupling and a radical-substrate coupling according to Scheme 6.3, in which the competition shown in the upper part of Scheme 2.34 is represented symbolically. [Pg.421]

Perhaps the best-known and most widely appreciated electrochemical transformation is the Kolbe oxidation (see also Chapter 6) [1, 2, 31]. The process involves the one electron oxidation of the salt of a carboxylic acid, and the loss of carbon dioxide to afford a radical, R, that subsequently engages in coupling reactions. Both symmetrical (R + R ) and nonsym-metrical (R + R ) radical couplings are known and are illustrated in the following discussion. The nonsymmetrical variety (often referred to as a mixed or hetero coupling) is remarkable given that it requires the cogeneration and reaction of more than one reactive intermediate. [Pg.324]

The ESR spectrum of the thioxanthene S, S-dioxide radical anion itself shows that the two possible conformers coexist, since the two methylene protons are not equivalent. In the case of the 9-monoalkyl derivatives, the large coupling constant observed for the 9-proton leads to the conclusion that the 9-substituent is in the boat equatorial position as in II1 F Thus the radical anions and the neutral molecule display different conformations. The protons in the 9-position of the radical anions of cis-9-methylthioxanthene S-oxides (2, n — 1, R1 = H, R2 = CH3) have an appreciable coupling constant10 which suggests that these radical anions have the substituent in the pseudo-axial position. Furthermore, in the radical anions the S—O bond is pseudo-axial. These situations are exactly the opposite of that observed for the neutral compound. [Pg.1051]

Today the coupled product is described as being formed by union of two alkyl radicals fonned by loss of one electron and carbon dioxide from the carboxylate ion. Extensive early use of the Kolbe reaction was made for the synthesis of long chain a,co-dicarboxylate esters starting from the half esters of shorter chain a,03-diacids [49]. [Pg.312]

When 151 is caused to react with terf-butyl chloride, a coupling occurs in high yield [Eq. (99)] the substitution seems neither to be an SN1 nor an SN2 reaction but was suggested to occur via an initial electron transfer from 151 to f-BuCl, followed by coupling of the two radicals [Eq. (99)].37 Anion 151 also reacts with carbon dioxide, forming a spiro derivative of malonic acid. [Pg.294]


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See also in sourсe #XX -- [ Pg.973 ]




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