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

Brønsted acidity in metal-organic frameworks.

Superacids, defined as acids with a Hammett acidity function H0 ≤ −12, are useful materials, but a need exists for new, designable solid state systems. Here, we report superacidity in a sulfated metal–organic framework (MOF) obtained by treating the microcrystalline form of MOF-808 [MOF-808-P: Zr6O5(OH)3(BTC)2(HCOO)5(H2O)2, BTC = 1,3,5-benzenetricarboxylate] with aqueous sulfuric acid to generate its sulfated analogue, MOF-808-2.5SO4 [Zr6O5(OH)3(BTC)2(SO4)2.5(H2O)2.5]. This material has a Hammett acidity function H0 ≤ −14.5 and is thus identified as a superacid, providing the first evidence for superacidity in MOFs. The superacidity is attributed to the presence of zirconium-bound sulfate groups structurally characterized using single-crystal X-ray diffraction analysis.

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Superacidity in sulfated metal-organic framework-808.

Synthesis of fine and specialty chemicals involving heterogeneous catalysts is discussed according to the type of reactions (e.g., hydrogenation, oxidation, isomerization, etc.) for various biomass derived feedstocks (carbohydrates, lignans, phenols, flavonoids, tannins, and stilbenes, tall oil, and fatty acids).

Recent Progress in Synthesis of Fine and Specialty Chemicals from Wood and Other Biomass by Heterogeneous Catalytic Processes

Generation and reactions of organic radical cations in zeolites.

The catalytic potential of zeolite H-beta in the hydration and isomerization of α-pinene was investigated. In the presence of water the main product is the monocyclic alcohol α-terpineol (48%) though selectivity towards bicyclic terpenes is higher than observed for sulphuric acid (26% vs. 5.5%). When the isomerization is performed in pure acetone, a new compound forms by a novel C C coupling reaction between α-pinene and acetone. The product is identified as α-terpinyl acetone. This coupling seems to be a general reaction between α-pinene and ketones and is catalyzed exclusively by zeolite beta.

Joachim M. Vital

Papers

The hydration and isomerization of α-pinene over zeolite beta. A new coupling reaction between α-pinene and ketones