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Formate, electron donor

An important method for construction of functionalized 3-alkyl substituents involves introduction of a nucleophilic carbon synthon by displacement of an a-substituent. This corresponds to formation of a benzylic bond but the ability of the indole ring to act as an electron donor strongly influences the reaction pattern. Under many conditions displacement takes place by an elimination-addition sequence[l]. Substituents that are normally poor leaving groups, e.g. alkoxy or dialkylamino, exhibit a convenient level of reactivity. Conversely, the 3-(halomethyl)indoles are too reactive to be synthetically useful unless stabilized by a ring EW substituent. 3-(Dimethylaminomethyl)indoles (gramine derivatives) prepared by Mannich reactions or the derived quaternary salts are often the preferred starting material for the nucleophilic substitution reactions. [Pg.119]

Among the reagents that are classified as weak electrophiles, the best studied are the aromatic diazonium ions, which reagents react only with aromatic substrates having strong electron-donor substituents. The products are azo compounds. The aryl diazonium ions are usually generated by diazotization of aromatic amines. The mechanism of diazonium ion formation is discussed more completely in Section 11.2.1 of Part B. [Pg.587]

The reaction rates and product yields of [2+2] cycloadditions are expectedly enhanced by electronic factors that favor radical formation. Olefins with geminal capto-dative substituents are especially efficient partners (equations 33 and 34) because of the synergistic effect of the electron acceptor (capto) with the electron donor (dative) substituents on radical stability [95]... [Pg.779]

The charge-tranter concept of Mulliken was introduced to account for a type of molecular complex formation in which a new electronic absorption band, attributable to neither of the isolated interactants, is observed. The iodine (solute)— benzene (solvent) system studied by Benesi and Hildebrand shows such behavior. Let D represent an interactant capable of functioning as an electron donor and A an interactant that can serve as an electron acceptor. The ground state of the 1 1 complex of D and A is described by the wave function i [Pg.394]

Beeause the anion acts as an electron donor, we can find clues to its reactivity preferences by examining the shape of its HOMO. The HOMO is delocalized over several sites, but the largest contribution to the HOMO clearly comes from the terminal carbon atom. Therefore, we expect electron movement and bond formation to occur at this carbon, and lead to the product shown on the left. [Pg.21]

When equimolar quantities of 80a and its dication 110 are combined in acetonitrile, single electron transfer occurs and the coproportionation product was obtained (95TL2741).Tliis deeply red-colored, air-sensitive radical cation 111 showed a strong ESR signal (g = 2.0034). On the other hand, the excellent electron donor 80a could be prepared by electrolytic reduction starting from 110. It was necessary to carry out the reduction with scrupulous exclusion of oxygen. Tlius, the electrolysis of 110 at -1.10 V initially gave rise to an intense red color, which was presumably due to the formation of 111. Upon further reduction, the red color faded and the tetraaza-fulvalene 80a was isolated at a 62% yield (Scheme 45). [Pg.156]

The coupling of bromo- or iodobenzene to styrene yields regioselectively a mixture of E- and Z-stilbenes 12 and 13. An electron-withdrawing substituent at the olefinic double bond often improves the regioselectivity, while an electron-donor-substituted alkene gives rise to the formation of regioisomers. [Pg.156]

Let us consider the conditions which favor the formation and survival of the dimeric and polymeric radical ions. This might be achieved by keeping the concentration of monomer high, the concentration of monomer" ions low and by removing the radical ions as rapidly as possible from the zone containing the primary electron donors. Moreover, since the radical ions dimerize, their average life time increases as their concentration decreases. The following experiment should probably produce the best results. [Pg.153]

Finally, stereoregularity of the initial PAN also affects the disposition of a CTC obtained from this polymer to the formation of photoinduced states with complete charge transfer. Both the values of the stationary concentration of these states and the rate of growth to this level, are considerably higher for a PCS obtained from the polymer with elevated stereoregularity. All this characterizes the effect of PCS stereoregularity on their reactivity in the formation of a CTC. The semi-conductive properties of PCS complexes of various classes with electron donors have been studied267, 268 ... [Pg.34]

Monomers that are strong electron donors may undergo spontaneous oupolymeri/.aliun with strong electron acceptor monomers by a radical mechanism. In certain cases homopolymers formed by an ionic mechanism accompany copolymer formation.312,j2s... [Pg.110]

While there is clear evidence for complex formation between certain electron donor and electron acceptor monomers, the evidence for participation of such complexes in copolymerization is often less compelling. One of the most studied systems is S-.V1 Al I copolymerization/8 75 However, the models have been applied to many copolymerizations of donor-acceptor pairs. Acceptor monomers have substituents such as carboxy, anhydride, ester, amide, imide or nitrile on the double bond. Donor monomers have substituents such as alkyl, vinyl, aryl, ether, sulfide and silane. A partial list of donor and acceptor monomers is provided in Table 7.6.65.-... [Pg.351]

Salts of diazonium ions with certain arenesulfonate ions also have a relatively high stability in the solid state. They are also used for inhibiting the decomposition of diazonium ions in solution. The most recent experimental data (Roller and Zollinger, 1970 Kampar et al., 1977) point to the formation of molecular complexes of the diazonium ions with the arenesulfonates rather than to diazosulfonates (ArN2 —0S02Ar ) as previously thought. For a diazonium ion in acetic acid/water (4 1) solutions of naphthalene derivatives, the complex equilibrium constants are found to increase in the order naphthalene < 1-methylnaphthalene < naphthalene-1-sulfonic acid < 1-naphthylmethanesulfonic acid. The sequence reflects the combined effects of the electron donor properties of these compounds and the Coulomb attraction between the diazonium cation and the sulfonate anions (where present). Arenediazonium salt solutions are also stabilized by crown ethers (see Sec. 11.2). [Pg.26]

Packer and Richardson (1975) and Packer et al. (1980) made use of the fact that electrons can be generated in water by y-radiation from a 60Co source (Scheme 8-29) to induce a free radical chain reaction between diazonium ions and alcohols, aldehydes, or formate ion. It has to be emphasized that the radiolytically formed solvated electron in Scheme 8-29 is only a part of the initiation steps (Scheme 8-30) by which an aryl radical is formed. The aryl radical initiates the propagation steps shown in Scheme 8-31. Here the alcohol, aldehyde, or formate ion (RH2) is the reducing agent (i.e., the electron donor) for the main reaction. The process is a hydro-de-diazoniation. [Pg.190]

In conclusion, it is very likely that the influence of solvents on the change from the heterolytic mechanism of dissociation of the C —N bond in aromatic diazonium ions to homolytic dissociation can be accounted for by a mechanism in which a solvent molecule acts as a nucleophile or an electron donor to the P-nitrogen atom. This process is followed by a one- or a two-step homolytic dissociation to an aryl radical, a solvent radical, and a nitrogen molecule. In this way the unfavorable formation of a dinitrogen radical cation 8.3 as mentioned in Section 8.2, is eliminated. [Pg.200]

The observations that addition of pyridine increases the rate of decomposition, shifts the order of reaction from unity to zero, and considerably diminishes formation of 4-nitrophenol also warrants attention. This is compatible with the superior electron-donor properties of pyridine as compared to DMSO (Gutmann, 1976, 1977) generation of the corresponding diazopyridinium cation in one or several of the forms corresponding to 8.59 and 8.60 competes with formation of 8.58. [Pg.206]

A large number of other sensitizers has been investigated for use in photolytic de-diazoniation. The excited states of these compounds (S ) react either by direct electron transfer (Scheme 10-97), as for pyrene, or by reaction with an electron donor with formation of a sensitizer anion radical which then attacks the diazonium ion (Scheme 10-98). An example of the second mechanism is the sensitization of arenedi-azonium ions by semiquinone, formed photolytically from 1,4-benzoquinone (Jir-kovsky et al., 1981). [Pg.280]


See other pages where Formate, electron donor is mentioned: [Pg.79]    [Pg.34]    [Pg.79]    [Pg.34]    [Pg.142]    [Pg.97]    [Pg.197]    [Pg.308]    [Pg.360]    [Pg.410]    [Pg.518]    [Pg.361]    [Pg.46]    [Pg.124]    [Pg.186]    [Pg.234]    [Pg.394]    [Pg.557]    [Pg.643]    [Pg.279]    [Pg.219]    [Pg.158]    [Pg.127]    [Pg.148]    [Pg.236]    [Pg.196]    [Pg.396]    [Pg.339]    [Pg.138]    [Pg.25]    [Pg.395]    [Pg.125]    [Pg.711]    [Pg.422]    [Pg.251]    [Pg.552]   
See also in sourсe #XX -- [ Pg.66 ]




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