3.2.3. Hydroformylation 2467 3.2.4. Dimerization 2468 3.2.5. Oxidative Cleavage and Ozonolysis 2469 3.2.6. Metathesis 2470 4. Terpenes 2472 4.1. Pinene 2472 4.1.1. Isomerization: R-Pinene 2472 4.1.2. Epoxidation of R-Pinene 2475 4.1.3. Isomerization of R-Pinene Oxide 2477 4.1.4. Hydration of R-Pinene: R-Terpineol 2478 4.1.5. Dehydroisomerization 2479 4.2. Limonene 2480 4.2.1. Isomerization 2480 4.2.2. Epoxidation: Limonene Oxide 2480 4.2.3. Isomerization of Limonene Oxide 2481 4.2.4. Dehydroisomerization of Limonene and Terpenes To Produce Cymene 2481

Chemical Routes for the Transformation of Biomass into Chemicals

The need to reduce the accumulation of CO2 into the atmosphere requires new technologies able to reduce the CO2 emission. The utilization of CO2 as a building block may represent an interesting approach to synthetic methodologies less intensive in carbon and energy. In this paper the general properties of carbon dioxide and its interaction with metal centres is first considered. The potential of carbon dioxide as a raw material in the synthesis of chemicals such as carboxylates, carbonates, carbamates is then discussed. The utilization of CO2 as source of carbon for the synthesis of fuels or other C1 molecules such as formic acid and methanol is also described and the conditions for its implementation are outlined. A comparison of chemical and biotechnological conversion routes of CO2 is made and the barriers to their exploitation are highlighted.

Utilisation of CO2 as a chemical feedstock: opportunities and challenges

3. Soluble Metal Oxides 2459 3.1. Polyoxometalates 2459 3.2. Peroxotungstates 2459 3.3. Peroxomolybdates 2460 3.4. Methyltrioxorhenium 2461 3.5. Other Metal Oxides 2461 4. Metal Oxides Generated in Situ 2461 4.1. Selenium and Arsenic Compounds 2461 4.2. Simple Metal Salts 2462 5. Coordination Complexes 2463 5.1. Manganese Porphyrins 2463 5.2. Iron Porphyrins 2464 5.3. Manganese Salen Complexes 2466 5.4. 1,4,7-Triazacyclononane (TACN) Complexes 2466 5.5. Iron and Manganese Pyridyl-Amine Complexes 2468

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Metal-Catalyzed Epoxidations of Alkenes with Hydrogen Peroxide

Heterogeneous gold-based catalysis for green chemistry: low-temperature CO oxidation and propene oxidation.

Epoxidation of olefins with hydrogen peroxide catalyzed by polyoxometalates

Synthesis of propylene oxide from propylene and hydrogen peroxide catalyzed by titanium silicalite

The epoxidation of propylene with hydrogen peroxide in the liquid phase, in the presence of titanium silicalite catalyst (TS-1), is described. The best solvents are methanol and methanol/ water mixtures. The temperature is normally between room temperature and 60°C. Under these conditions, reaction rates are fast, yields on H2O2 are quantitative, and selectivity to propylene oxide is very high. Propylene glycol and its monomethyl ethers and trace amounts of formaldehyde are the only by-products formed. Selectivity is further improved and the hydrolysis of the epoxide is almost suppressed when the residual acidity of the catalyst is completely neutralized. The activity of spent catalyst is recovered by calcining at 550°C or, more simply, by washing with solvents. Complete activity recovery shows that Ti is not removed from the crystalline framework during the epoxidation reactions.

U. Romano

Papers

Synthesis of propylene oxide from propylene and hydrogen peroxide catalyzed by titanium silicalite

Synthesis of Propylene Oxide from Propylene and Hydrogen Peroxide Catalyzed by Titanium Silicalite.