Catalytic oxidative coupling

J.H. Lunsford., The Catalytic Oxidative Coupling of Methane, 34, Angew. Chem. Ed. Engl, 970, (1995). 

CATALYTIC OXIDATIVE COUPLING OF 7-ALKOXY-l-NAPHTHOLS BY CHIRAL VANADIUM COMPLEXES... 

Osa and coworkers [405,466] developed a graphite felt electrode modified with 2,2,6,6-tetramethylpiperidin-l-yloxyl (TEMPO) and applied it to enantioselective, electro-catalytic oxidative coupling of naphthol, naphthyl ether, and phenanthrol in the presence of (—)-sparteine as a base. The enantioselectivity of the coupling products were as high as 98%. 

Several reaction mechanisms have been proposed for the catalytic oxidative coupling of methane. This summary will focus only on the most impcxtant mechanisms, since it is believed that they give a good approximation of gas-phase and surface processes taking place during catalytic activation of methane. 

The Problems. Challenges and Opportunities Ahead In summary, though the catalytic oxidative coupling methane to form ethylene/ethane has now been amply demonstrated 1n many research laboratories worldwide, the commercial feasibility of such a process depends critically on ... 

THE PRODUCTION OF LIQUID FUELS VIA THE CATALYTIC OXIDATIVE COUPLING OF METHANE... 

The production of higher hydrocarbons directly from methane by catalytic oxidative coupling is a novel methane conversion process which warrants further study. When combined with an ethylene oligomerisation step it is a potential alternative to conventional processes, based on synthesis gas, for producing liquid fuels from methane. However, further research is necessary to provide the information required to assess the commercial prospects for this route. 

Experiment 3 was carried out to see whether application of these ideas would give a further improvement of the yield of hydrocarbons using an improved catalyst. The total concentration of products obtained is, to our knowledge, the highest reported until now for the catalytic oxidative coupling of methane. 

The catalytic oxidative coupling of two dissimilar arenes is also possible, for example, iV-acetyl indoles, or benzofurans, with benzene and other simple arenes. The mechanism involves sequential metallations in the two rings. The regioselectivity can be controlled by the choice of oxidant, Cu(OAc)2 favouring C-3 and AgOAc, C-2 substitution in 1-acetylindole. ... 

This article provides a comprehensive review of advanced processes for direct conversion of methane. These processes include (1) direct partial oxidation of methane to methanol, (2) catalytic oxidative coupling, and (3) oxyhydrochlorination. The primary goal of this review is to present an overview of the state of the art of these technologies and provide an initiative for advancing the... 

In 1955, Terent ev and Mogilyanskii reported the catalytic oxidative coupling of aniline to azobenzene with a yield of 88%, mediated by copper chloride in pyridine (which acts as both a metal ligand and solvent) in the presence of molecular oxygen [1]. This system was subsequently used for the generation of various conjugated and nonconjugated main-chain aromatic azo polymers from primary aromatic diamines [2]. In contrast, the use of CUCI-O2 with phenol produces tars [3] as a result of the inherent properties of this reactant. Indeed, while the metal salt produces iV-centered aniline radicals that dimerize to form azobenzene... 

Lunvongsa S., Takayanagi T., Oshima M. and Motomizu S. (2006) Novel catalytic oxidative coupling reaction of N,N-dimethyl-p-phenylenediamine with 1,3-phenylenediamine and its applications to the determination of copper and iron at trace levels by flow injection technique. Analytica Chimica Acta, 576,261-269. 

Scheme 2.13 Synthesis of fluorinated poly(arylene ether) containing naphthalene moiety by catalytic oxidative coupling polymerization using FeCIs. Taken from Ref [63].

Ueda et al. [63] synthesized a fluorinated PAE containing naphthalene moiety and investigated its properties. The polymer was synthesized by catalytic oxidative coupling polymerization using FeCls (Scheme 2.13). The polymer had an Mn of 32,000g/ mol with good film processability. The polymer had a Tg value of 230 °C and was recorded at 530 °C. 

Shvo Y, Blum Y, Reshef D, Menzin M (1982) Catalytic oxidative coupling of diols by Ru3(CO)j2. J Organomet Chem 226 C21-C24... 

Mleczko L, Rothaemel M, Andorf R, Baerns M. Fluidized bed reactor performance for the catalytic oxidative coupling of methane to C2+ hydrocarbons. In Potter OE, Nicklin DJ, eds. Fluidization VII, Brisbane, Australia, 1992, pp 487-494. 

The catalytic oxidative coupling of furans with acrylonitrile to yield 2-alkenenitriles proceeds in good yield. ... 

Homogeneous, catalytic, oxidative coupling of methane to acetic acid in one step. Top. CataL, 32,169 174. 

Lunsford JH (1995) The catalytic oxidative coupling of methane. Angew Chem hit Ed 34 970-980... 

Bi, Y., Zhen, K., Jiang, Y., Teng, C, and Yang, X. (1988) Catalytic Oxidative Coupling of Methane over Alkali, Alkaline Earth and Rare Earth Metal Oxides , Appl. Catal. 39,185-90. 

Sofranko, J.A., Leonard, J.J., Jones, C.A., Gaffney, A.M., and Withers, H.P. (1988b) Catalytic Oxidative Coupling of Methane Over Sodium-Promoted Mn/SiOi and Mn/MgO , Catalysis Today 3,127-35. 

These findings have been well documented in various review articles (for references see [7]). Therefore, only selected results are cited in this contribution to leave space for introducing more recent results in the area of catalytic oxidative coupling of methane. 

Figure 27. Process scheme for catalytic oxidative coupling of methane to ethylene [57].

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