Beyond Oil and Gas: The Methanol Economy

Starting with coal, followed by petroleum oil and natural gas, the utilization of fossil fuels has allowed the fast and unprecedented development of human society. However, the burning of these resources in ever increasing pace is accompanied by large amounts of anthropogenic CO2 emissions, which are outpacing the natural carbon cycle, causing adverse global environmental changes, the full extent of which is still unclear. Even through fossil fuels are still abundant, they are nevertheless limited and will, in time, be depleted. Chemical recycling of CO2 to renewable fuels and materials, primarily methanol, offers a powerful alternative to tackle both issues, that is, global climate change and fossil fuel depletion. The energy needed for the reduction of CO2 can come from any renewable energy source such as solar and wind. Methanol, the simplest C1 liquid product that can be easily obtained from any carbon source, including biomass and CO2, has been proposed as a key component of such an anthropogenic carbon cycle in the framework of a “Methanol Economy”. Methanol itself is an excellent fuel for internal combustion engines, fuel cells, stoves, etc. It's dehydration product, dimethyl ether, is a diesel fuel and liquefied petroleum gas (LPG) substitute. Furthermore, methanol can be transformed to ethylene, propylene and most of the petrochemical products currently obtained from fossil fuels. The conversion of CO2 to methanol is discussed in detail in this review.

Recycling of carbon dioxide to methanol and derived products – closing the loop

Chemistry and technology of explosives

The present Review highlights the challenges and opportunities when using the combination CO2 /H2 as a C1 synthon in catalytic reactions and processes. The transformations are classified according to the reduction level and the bond-forming processes, covering the value chain from high volume basic chemicals to complex molecules, including biologically active substances. Whereas some of these concepts can facilitate the transition of the energy system by harvesting renewable energy into chemical products, others provide options to reduce the environmental impact of chemical production already in today's petrochemical-based industry. Interdisciplinary fundamental research from chemists and chemical engineers can make important contributions to sustainable development at the interface of the energetic and chemical value chain. The present Review invites the reader to enjoy this exciting area of "catalytic chess" and maybe even to start playing some games in her or his laboratory.

Selective Catalytic Synthesis Using the Combination of Carbon Dioxide and Hydrogen: Catalytic Chess at the Interface of Energy and Chemistry

The reactions of iodobenzene with azole compounds, 1,2-disubstituted imidazoles and 2-substituted oxazoles and thiazoles, were examined in the presence of catalytic amounts of Pd(OAc)2 and PPh3 in DMF using alkali metal carbonates as bases. It was found that the coupling products, 5-arylazoles, could be selectively produced in good yields by using Cs2CO3. In the case that their 2-position is unsubstituted, the site could also be arylated. In reactions using bromobenzene in place of iodobenzene, K2CO3 was also as effective as Cs2CO3. The addition of a stoichiometric amount of CuI appeared to specifically promote the reactions of thiazoles as well as those of thiophene derivatives. The reactions of 2-unsubstituted azole compounds with aryl iodides could be mediated by CuI to some extent without using the palladium species to give 2-arylazoles.

Palladium-Catalyzed Arylation of Azole Compounds with Aryl Halides in the Presence of Alkali Metal Carbonates and the Use of Copper Iodide in the Reaction

Die fossilen Brennstoffe Kohle, Mineralol und Erdgas sind gleichzeitig Ausgangsmaterialien fur die chemische Industrie.

Methanol — Chemie und Energierohstoff

Mono-olefins;: Chemistry and technology,

Über die gemeinsame Einwirkung von elementarem Schwefel und gasförmigem Ammoniak auf Ketone, LII1). Darstellung von α-Oxothionamiden und substituierten Imidazolin-Δ3-thionen-(5)2)

Die durch Titan (IV)-Verbindungen katalysierte Stellungsisomerisierung einer sekundaren Alkyl-Grignard-Verbindung zum primaren Isomeren ist nicht, wie in der Literatur angegeben, auf 1-methylverzweigte Alkylmagnesiumchloride beschrankt. Bei Einhaltung geeigneter Reaktionsbedingungen konnen auch Alkylmagnesiumchloride mit weiter im Inneren der Molekulkette angeordneter funktioneller Gruppe, wie sie z. B. Aus dem durch Chlorierung eines Alkans erhaltenen Alkylchlorid-Isomerengemisch darstellbar sind, in die primare Grignard-Verbindung umgelagert werden. Wesentlich fur diese Reaktion ist die Verwendung von Tetrahydrofuran als Losungsmittel und die kontinuierliche Zugabe des Katalysators uber die gesamte Reaktionszeit hinweg.



Isomerization of Secondary Alkylmagnesium Chlorides



The isomerization of secondary alkylmagnesium chlorides to the primary isomers, catalyzed by titan(IV) compounds, is not restricted to α-methyl branched alkylmagnesium chlorides as reported in the literature. Under proper conditions secondary alkylmagnesium chlorides with the functional group in a more internal position, prepared for example form the monochlorinated alkane, can also be isomerized to the primary Grignard compound. Tetrahydrofuran as solvent and a continuous addition of the catalyst during the whole reaction time are essential for this isomerization reaction.

Friedrich Asinger

Papers

Methanol — Chemie und Energierohstoff

Mono-olefins;: Chemistry and technology,

Über die gemeinsame Einwirkung von elementarem Schwefel und gasförmigem Ammoniak auf Ketone, LII1). Darstellung von α-Oxothionamiden und substituierten Imidazolin-Δ3-thionen-(5)2)

Stellungsisomerisierung sekundärer Alkylmagnesiumchloride

Über die gemeinsame Einwirkung von elementarem Schwefel und gasförmigem Ammoniak auf Ketone, LXXXVII1) Reaktionen von α‐Mercaptoketonen