Anions oxidative dimerization

Ttinitroparaffins can be prepared from 1,1-dinitroparaffins by electrolytic nitration, ie, electrolysis in aqueous caustic sodium nitrate solution (57). Secondary nitroparaffins dimerize on electrolytic oxidation (58) for example, 2-nitropropane yields 2,3-dimethyl-2,3-dinitrobutane, as well as some 2,2-dinitropropane. Addition of sodium nitrate to the anolyte favors formation of the former. The oxidation of salts of i7k-2-nitropropane with either cationic or anionic oxidants generally gives both 2,2-dinitropropane and acetone (59) with ammonium peroxysulfate, for example, these products are formed in 53 and 14% yields, respectively. Ozone oxidation of nitroso groups gives nitro compounds 2-nitroso-2-nitropropane [5275-46-7] (propylpseudonitrole), for example, yields 2,2-dinitropropane (60). 

The oxidative dimerization of the anion of methyl phenyl sulfone (from a Grignard reagent) in ethereal solution in the presence of cupric chloride in 5% yield has been reported47. Despite the reported48 poor stability of the a-sulfonyl C-centered radicals, Julia and coworkers49 provoked the dimerization (in 13 to 56% yields) of the lithiated carbanion of alkyl phenyl sulfones using cupric salts as oxidants. The best results are obtained with cupric triflates in THF-isobutyronitrile medium (56% yield for R = H). For allyl phenyl sulfones the coupling in the 3-3 mode is predominant. 

Studies into oxidative dimerization have shown that only the persulfate anion is of synthetic value in these reactions. Reaction pH is also crucial with reactions proceeding fastest when a pH of 7.2-9.4 is maintained. " The reaction medium becomes more acidic as the oxidation progresses and needs either buffering or the slow addition of alkali throughout the reaction. If the reaction medium is allowed to become acidic then the starting nitroalkane is regenerated and the Nef reaction predominates. 

Bipyridyl (20) (63AHC(2)179) is synthesized by oxidative dimerization of pyridine over hot Raney nickel, while 4,4 -bipyridyl (21) (B-79MI10705) is made by free radical coupling of the pyridine radical anion generated by sodium in liquid ammonia, followed by air oxidation (Scheme 6). Quaternization of (21) with methyl chloride gives paraquat while reaction of (20) with 1,2-dibromoethane gives diquat. 

Attempts to generate the radical anion of 11 by electron transfer resulted in fast oxidative dimerization such that 11 was not observed by ESR techniques241. 

In contrast, copper (II) triflatc effects oxidative dimerization of a-anions of n-alkyl sulfones to a-disulfones (meso- and dl- isomers). Coupling of a-anions of allylic sulfones with this catalyst occurs mainly at the /-position.2... 

In an EC2j process, the initial ET step is followed by a second-order irreversible homogeneous reaction. For example, the feedback mode of SECM was employed to study the reductive hydrodimerization of the dimethyl fumarate (DF) radical anion [22]. The experiments were carried out in solutions containing either 5.15 or 11.5 mM DF and 0.1 M tetrabutylammonium tetrafluoroborate in A,A,-dimethyl form amide (DMF). The increase in the feedback current with increasing concentration of DF indicated that the homogeneous step involved in this process is not a first-order reaction. The analysis of the data based on the EC2 theory yielded the fc2 values of 180M-1 s-1 and 160M-1 s-1 for two different concentrations. Another second order reaction studied by the TG/SC mode was oxidative dimerization of 4-nitrophenolate (ArO-) in acetonitrile [23]. In this experiment, the tip was placed at a fixed distance from the substrate. The d value was determined from the positive feedback current of benzoquinone, which did not interfere with the reaction of interest. The dimerization rate constant of (1.2 0.3) x 108 M x s-1 was obtained for different concentrations of ArO-. 

The thermochemical cycle in Scheme 3 was used for this purpose for the Mn, Mo, and Fe dimers. The formal potentials E° (M2/2M ) were derived from equilibrium constant measurements of the redox equilibria, Eqs 26 and 27, by use of suitable reducing agents. When these formal potentials were combined with the anion oxidation potentials, the M-M BDEq could be calculated from Eq. 28 as 117 kJ moE for Mn2(CO)io, 92 kJ mol for Cp2Mo2(CO)e, and 105 kJ moE for Cp2Fe2(CO)4. For the Mn dimer, estimates for the entropy change were available and eventually led to an estimated Mn-Mn BDE of ca 159 kJ moE in enthalpy terms. 

Treatment of 2,2,4,4-tetramethyl-3-thietanone with diiron nonacarbonyl gives the binuclear iron complex 381. 2,2-Dimethyl-3-thietanone undergoes oxidative dimerization to 382 on treatment with potassium ferricyanide. Methylene-3-thietanones such as 359 add chlorine from thionyl chloride to the carbon-carbon double bond. 2,2,4,4-tetramethyl-3-thietanone is converted to the 3-thione in 14% yield by treatment with hydrogen sulfide-hydrogen chloride. Electrochemical reduction of the thione produces radical anions. 

Reduction of 9-substituted anthracenes, (91), leads to radical anions, which, because of the electron-withdrawing substituents, are quite stable with respect to protonation and cleavage in aprotic solvents. In polar aprotic solvents the radical anions exclusively dimerize, and the reaction has been the subject of a number of studies [247-258]. The products are the tail-to-tail dimeric dianions as in Eq. (57), which are fairly stable. In CV the dimer dianions can be detected as a new oxidation peak on the reverse scan at a potential several hundred millivolts anodic relative to the potential of radical anion formation. On preparative or semipreparative scales the dimer dianion has in a single case been detected by H-NMR [249], and oxidative electrolysis of the dimer dianions in most cases restores the starting material. 

Another one is to prepare vicinal, tertiary nitro compounds (XXI) by oxidative dimerization of the mononitro anion, followed by treatment of XXI with calcium amalgam in hexamethylphosphoramide [77] at room temperature. 

Matsumura and his coworkers [38] have employed the 2-pyrrolidone anion, in DMF solution, to deprotonate arylacetic acid esters with subsequent oxidative dimerization of the corresponding carbanions. This study includes a useful comparison between the electrochemical and chemical generation of the 2-pyrrolidone anion (by fluoride anion displacement in A-trimethylsilyl-2-pyrrolidone). The advantage lies with the electrochemical route, which gave yields of final product of 80%, compared with the 30% obtained with the chemically generated base (Scheme 10). The overall process, formation of dimethyl 2,3-diphenylsuccinates, is not only efficient and convenient but also operates with high diastereoselectivity when under the control of an oxazolidinone chiral auxiliary (Scheme 10). 

The anions of nitroalkanes (nitronates) can be used as precursors in a connective and regiospecific synthesis of tetrasubstituted alkenes. They are easily formed on reaction with LiOMe and undergo oxidative dimerization in the presence of bromine. The resultant 1,2-dinitroalkanes (Scheme 37) participate in a reductive elimination involving an rc1 radical chain mechanism when irradiated in the presence of Na2S, PhSNa or the lithium nitronate derived from 2-nitropropane. 

Many other examples of transition metal catalyzed reactions such as oxidation, dimerization or telomerization of conjugated diene have been performed in these borderline anions-based ionic liquids and are described in recent reviews [4]. 

Substitution reactions occurring by reaction 5 are of considerable value in organic chemistry, particularly in view of the tolerance of this reaction to appreciable steric repulsion (e.g., tertiary radicals will add to tertiary carb-anions). The scope of the reaction is limited by the fact that highly nucleophilic radicals will add only to anions of low basicity irrespective of the overall exoergicity of reaction 5. However, with electrophilic radicals, the rate of reaction 5 increases with the basicity of the carbanion and with the exoergicity of the reaction, but now oxidative dimerization can become an important competing reaction. 

Although [Co(CO)4] is undetectable during the oxidative dimerization of [Co(CO)4]-, there is some evidence for its formation when the anion... 

Reduction with Na in aprotic medium leads to oxidative dimerization giving rise to 4,4 -bipyridyl 133, since the pyridyl radical anion 132 undergoes dimerization via 4-position followed by dehydrogenation ... 

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