16812-40-1

Upstream product

• 177698-19-0 Beta-pinene 
• 80-56-8 Pinene 
• 58434-29-0 myrtenyl hydroperoxide 
• 22321-84-2 pinocarveyl hydroperoxide 
• 18680-29-0 C₁₀H₁₆O₂ 
• 22321-84-2 trans-pinocarveyl hydroperoxide 
• 18172-67-3 beta-pinene 
• 7785-26-4 (-)-α-pinene 
• 1674-08-4 3-hydroxy-β-pinene 

Downstream Products

• 1674-08-4 3-hydroxy-β-pinene 
• 21725-97-3 6,6-dimethyl-3'-phenyl-4'H-spiro[bicyclo[3.1.1.]heptane-2,5'-isoxazol]-3-one 

Relevant academic research and scientific papers

Spectroscopic and biocatalytic properties of a chlorophyll-containing extract in silica gel

UV-Vis absorption and fluorescence spectra of chlorophyll a (in the form of spinach extract) in acetone solution and in silica gel showed a predominance of pigment dimers in its overall concentration and an evident transformation of chlorophyll a to pheophytin with time. The dimerization constant of chlorophyll a in acetone was log Kdim = 2.14, whereas the constants for chlorophyll a and pheophytin a in alcogel were log Kdim = 4.70 and log Kdim = 5.22, respectively. Biocatalytic experiments indicated the possibility of using the pigment embedded in silica gel, i.e. mainly its dimeric form, for biotransformation of α-pinene to pinocarveyl hydroperoxide, trans-pinocarveol, pinocarvone and myrtenal. The advantage of a heterogeneous biocatalytic system (composed of a solvent and silica gel) over a homogeneous system (single phase of chloroform) is the possibility of reusing the biocatalyst with about 10% preservation of its activity.

The spectral and catalytic studies of chlorophylls and pheophytins in mimetic biotransformation of α-pinene

Natural porphyrin pigments isolated from spinach in the form of a crude extract, chlorophyll a, chlorophyll b, pheophytin a and pheophytin b were studied as potential catalysts for the biomimetic transformation of α-pinene to trans-pinocarveol, pinocarvone and myrtenal. The reaction of monoterpene oxidation was performed in an organic solution under visible light irradiation. Significant changes in the distribution of the products were achieved using β-pinene as the substrate. The pheophytins showed the highest catalytic efficiency among the photocatalysts examined. The photographic visualization of α-pinene oxidation course at the beginning of the reaction, after 4 and 24 h exposure to light showed a distinct shift in the colour excited catalysts. This may indicate a change in their structure leading to their degradation. The absorbance and fluorescence spectra revealed that pheophytins are significantly stable photocatalysts in comparison to both chlorophylls. Pheophytin b displayed the highest stability in the biotransformation, whereas the highest rate of photodecomposition was proved for chlorophyll b under the reaction condition. Differences were noticed in the behaviour of the chlorophylls in the photodegradation process. From the changes in the intensity of the singlet oxygen band on infrared fluorescence spectra of pigments upon pinene addition, and from the reactivity experiments with radicals scavengers, it can be deduced that the biotransformation of pinene by chlorophylls and pheophytins proceeds by common oxygenation mechanism involving singlet oxygen and free radicals.

Selective Allylic Oxidation of Terpenic Olefins Using Co-Ag Supported on SiO2 as a Novel, Efficient, and Recyclable Catalyst

Co-Ag supported on the SiO2 catalyst was synthesized by the sol-gel method and characterized using XRD, FT-IR, TG-DTG, BET, CV, and SEM/EDX analysis. The catalytic performance of the resulting catalyst was examined by the oxidation of mono and sesquiterpenic olefins using hydrogen peroxide and tert-butyl peroxide as oxidant agents. Various parameters such as catalyst amount, temperature, and solvents have been studied. The Co-Ag supported on the SiO2 catalyst showed a high activity, selectivity, and recyclability for the selected oxidation reaction.

PINENE-DERIVED DIISOCYANATES

A pinene-derived diisocyanate compound, a process for forming a pinene-derived diisocyanate compound, and an article of manufacture containing a polyurethane polymer are disclosed. The process for forming the pinene-derived diisocyanate compound includes oxidizing the pinene to form a pinene-derived ketone compound, converting the pinene-derived ketone compound to a diamine compound in subsequent reaction steps, and reacting the diamine compound with phosgene to form the pinene-derived diisocyanate compound. The polyurethane polymer is synthesized in a reaction between a pinene-derived diisocyanate compound and a polyol.

Allylic oxidation of cyclic alkenes with molecular oxygen and tert-butyl hydroperoxide over copper-manganese oxides

Abstract: An efficient and mild method for the allylic oxidation of cyclic alkenes employing molecular oxygen and tert-butyl hydroperoxide as the oxidant, copper-manganese oxides as heterogeneous catalyst under ambient temperature is proposed. The catalyst, which was prepared by co-precipitation and characterized, was evaluated oxidation of isolongifolene as a typical mode substrate. The catalyst showed a good catalytic activity and remained nearly the same after four cycles. The scope of the reaction was investigated with a variety of cyclic alkenes compounds. Graphical abstract: [Figure not available: see fulltext.]

Solvent and additive-free selective aerobic allylic hydroxylation of β-pinene catalyzed by metalloporphyrins

Metallodeuteroporphyrins (MDPs) were employed as the catalysts for aerobic oxidation of β-pinene in absence of solvents and additives. Allylic hydroxylation products were found to be the main products from this protocol. The catalytic activity of MDPs with different metal nuclei and the influences of technological conditions on this reaction were investigated. This catalytic system has bright application prospect since only eco-friendly and readily available dioxygen were needed.

Biologically Inspired and Magnetically Recoverable Copper Porphyrinic Catalysts: A Greener Approach for Oxidation of Hydrocarbons with Molecular Oxygen

An efficient synthetic method for magnetically recoverable hybrid copper porphyrinic nanomaterials is reported. These functionalized magnetic materials prove to be efficient bioinspired oxidation catalysts of olefins and thiols, using molecular oxygen as oxidant, in total absence of reductants and solvents, with the highest TON (turnover number) yet achieved for this reaction (≈200 000). A comparative study between homogeneous and heterogeneous oxidation of cyclohexene is discussed, revealing the heterogeneous system to be the most promising concerning stability and reusability of the catalysts. The full characterization of the magnetic hybrid porphyrinic nanomaterials, by transmission electron microscopy, flame atomic absorption spectrometry, thermogravimetry, N2 sorption, and infrared spectroscopy, is also described.

Homo- and heterogeneous α-pinene photooxidation using a protoporphyrin-derived amide

6,7-Bis[3-(NIμ-tert-butyloxycarbonyllysine methyl ester)]-1,3,5,8-tetramethyl-2,4-divinylporphyrin (3) was synthesized and successfully immobilized in a silica matrix by a sol-gel method. Protoporphyrin (PP)-derived amide 3 showed much higher photostability than its parent PP-IX. Its UV/Vis absorption, excitation, and fluorescence spectra as well as its ability to generate 1O2 were measured both in solution and in the matrix. Subsequently, free and immobilized porphyrins 3 were used as sensitizers in the photooxidation of α-pinene, and their photocatalytic properties were compared. Newly synthesized protoporphyrin (PP)-derived amide 3 is more photostable than PP-IX. Because it is able to generate 1O2, it could be used as a biomimetic catalyst for the oxidation of α-pinene under visible light. After successful immobilization in a silica matrix, a transparent organic-inorganic hybrid was obtained that shows intensive luminescence. Copyright

β-pinene oxidation by hydrogen peroxide catalyzed by modified niobium-MCM

Although solid niobium has a high surface area, its high Lewis and Br?nsted acidity is a drawback that always compromises its catalytic performance in oxidation reactions. In this work, treating the niobium catalyst with hydrogen peroxide circumvents this disadvantage and results in a significant increase in the selectivity of the oxidation of β-pinene. In addition, the efficiency of the niobium catalysts supported on MCM was investigated. Nb-MCM//H2O2 and Nb-MCM were the most active catalysts. Good selectivity of up to 85% at a 93-97% substrate conversion has been achieved. The catalyst can easily be recovered and reused several times without loss in activity.

Solvent-free chromium catalyzed aerobic oxidation of biomass-based alkenes as a route to valuable fragrance compounds

Chromium containing mesoporous molecular sieves MCM-41 were shown to be an efficient heterogeneous catalyst for the liquid-phase aerobic oxidation of various monoterpenic alkenes under mild solvent-free conditions. The material was prepared through a direct hydrothermal method and characterized by ICP-AES, N2 adsorption-desorption, TEM, XRD, SAXS, and H2-TPR techniques. Characterizations suggest that chromium introduced in MCM-41 is essentially incorporated in the silica framework, with no extraframework chromium oxides being detected. Various oxygenated monoterpenoids important for the flavor and fragrance industry were obtained with high combined selectivities (75-92%) at 30-40% substrate conversions. The oxidation of β-pinene led almost exclusively to allylic mono-oxygenated derivatives, whereas limonene and α-pinene gave both epoxides and allylic oxidation products. The catalyst undergoes no metal leaching and can be easily recovered and re-used. A silica-included chromium catalyst prepared through a conventional sol-gel method showed activity comparable with that of Cr-MCM-41; however, selectivity was much lower.