7299-40-3

We report the use of five alpha-hydroxy acids (citric, tartaric, mandelic, lactic and glycolic acids) as catalysts in the synthesis of terpineol from alpha-pinene. The study found that the hydration rate of pinene was slow when only catalyzed by alpha-hydroxyl acids. Ternary composite catalysts, composed of AHAs, phosphoric acid, and acetic acid, had a good catalytic performance. The reaction step was hydrolysis of the intermediate terpinyl acetate, which yielded terpineol. The optimal reaction conditions were as follows: alpha-pinene, acetic acid, water, citric acid, and phosphoric acid, at a mass ratio of 1:2.5:1:(0.1–0.05):0.05, a reaction temperature of 70? C, and a reaction time of 12–15 h. The conversion of alpha-pinene was 96%, the content of alpha-terpineol was 46.9%, and the selectivity of alpha-terpineol was 48.1%. In addition, the catalytic performance of monolayer graphene oxide and its composite catalyst with citric acid was studied, with acetic acid used as an additive.

[Mn(LH)(H2O)]n {1, where LH2- is the dianion of N-(4-carboxybenzyl)iminodiacetic acid} has been synthesized and its crystal structure has been determined. The crystal of 1 is built from 1D polymeric ladder-shaped chains that extend to a 3D supramolecular architecture through H-bonds. The compound was characterized with spectroscopic and physicochemical techniques. Variable-temperature magnetic data suggest that there are weak antiferromagnetic interactions. Compound 1 has been evaluated as a heterogeneous oxidation catalyst. It catalyzes alkene epoxidation selectively in relatively high yields.

The organometallic fragment [MoI2(CO)3] was coordinated to magnetic iron oxide nanoparticles of different sizes (average size of 11 and 30 nm) which have been previously coated with a silica shell and grafted with a pyridine derivative ligand. The Mo loading was found to be approximately 0.37 wt-% Mo and 0.57 wt-% Mo, corresponding to 0.150 mmol Mo g-1 and 0.230 mmolMo g-1 for materials MNP30-Si-inic-Mo and MNP11-Si-inic-Mo, respectively. Preparation of these organometallic decorated magnetic nanoparticles was further confirmed by evidence obtained from extensive characterization by powder XRD, SEM/TEM analysis, as well as from data of 57Fe M?ssbauer and FTIR spectroscopy. Olefin epoxidation of a variety of substrates promoted by these organometallic nano-hybrid materials using tbhp as oxidant, was performed with very good results. The catalytic studies show that the catalysts yield selectively the desired epoxides of a series of olefins. In addition, these catalysts are found to work under a wide temperature range and over several catalytic cycles without notorious performance loss in most cases.

Linalool is an important intermediate for syntheses of isoprenoid fragrance compounds and vitamins A and E. One process option for its production is the thermal gas-phase isomerization of cis- and trans-pinan-2-ol. Investigations of this reaction were performed in a flow-type apparatus in a temperature range from 350-600 °C and a residence time range of 0.6-0.8 s. Rearrangement of the bicyclic alcohol led to linalool, plinols arising from consecutive reactions of linalool and other side products. Effects of residence time, temperature, surface-to-volume-ratio, carrier gas, and the presence of additives on yield and selectivity were studied. Furthermore, the effects of such parameters on ene-cyclization of linalool affording plinols were investigated. Results indicate that manipulation of the reaction in order to affect selectivity is difficult due to the large free path length to other molecules in the gas phase. However, conditions have been identified allowing one to increase the selectivity and the yield of linalool throughout pyrolysis of pinan-2-ol.

Four monoterpene hydroperoxides were isolated from aerial parts of Chenopodium ambrosioides along with ascaridole (1), the anthelmintic principle of this plant, as anti-trypanosomal compounds. The structures of these monoterpenes were determined to be (-)

Some representative monoterpenes have been isomerised under the influence of Schlosser's lithium-potassium mixed superbases, promoting β-elimination reactions. The results are compared with those obtained with butyllithium and LDA. Different selectivities and different reaction yields are achieved as a function of the base employed. These results confirm the particular reactivity of bimetallic reagents. In this paper it is proposed that the observed selectivities might depend on the conformational features of the substrate, on the strength of the organometallic reagent, as well as on steric requirements of the elimination reaction.

1,8-Cineoles can be synthesized by ring closure of p-menthane precursors carrying the potential ether oxygen atom on either C1 or C8. Comparisons are made between these two routes.

Bifunctional aluminosilicate catalysts containing framework Ti are prepared, with two different topologies and pore sizes; these samples contain both acid and oxidizing catalytic sites and are highly selective for carrying out multistep reactions with selectivities close to those obtained with epoxidases, this is shown to occur for the oxidation of linalool to cyclic hydroxy ethers.

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Reaction of oxiranes with alkali metals in aprotic solvents yields a variety of products depending on the nature of the metal and the structure of the oxirane.Deoxygenation to olefins is the major reaction in case of lithium.Rearrangement to carbonyl compounds, reduction to alcohols and formation of dimeric products occur when oxiranes are treated with sodium.All the reactions could be rationalised by a mechanism involving an initial single electron transfer leading to the formation of radical-anion intermediate.

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