3917-59-7

Usage

Uses

Used in Organic Chemistry:
[1R-(1alpha,3alpha,5alpha)]-6,6-dimethyl-2-methylenebicyclo[3.1.1]heptan-3-ol is used as a key intermediate for the synthesis of various organic compounds due to its unique structure and reactivity.
Used in Pharmaceutical Industry:
[1R-(1alpha,3alpha,5alpha)]-6,6-dimethyl-2-methylenebicyclo[3.1.1]heptan-3-ol is used as a building block for the development of novel pharmaceuticals, potentially targeting specific biological pathways or receptors due to its distinctive chemical properties.
Used in Perfumery:
[1R-(1alpha,3alpha,5alpha)]-6,6-dimethyl-2-methylenebicyclo[3.1.1]heptan-3-ol is used as a fragrance ingredient in the perfumery industry, leveraging its unique scent profile and potential for creating complex and long-lasting fragrances.

Upstream product

• 58434-29-0 myrtenyl hydroperoxide 
• 22321-84-2 trans-pinocarveyl hydroperoxide 
• 1686-14-2 α-pinene epoxide 
• 80-56-8 Pinene 
• 177698-19-0 Beta-pinene 
• 18172-67-3 beta-pinene 
• 17004-05-6 3-amino-β-pinene 
• 7785-26-4 2,6,6-trimethylbicyclo[3.1.1]hept-2-ene 
• 22321-84-2 pinocarveyl hydroperoxide 
• 515-00-4 myrtenol 
• 50-00-0 formaldehyd 
• 34413-88-2 pinocarvone 
• 25488-94-2 5,7,7-trimethyl-3-oxa-tricyclo[4.1.1.0^2,4]octane 

Downstream Products

• 18172-67-3 (?)-β-pinene 
• 7785-26-4 2,6,6-trimethylbicyclo[3.1.1]hept-2-ene 
• 38086-92-9 (4Z)-2,7-Dimethyl-2,4,6-octatriene 
• 99-48-9 (4R,6R)-carveol 
• 28385-58-2 3,6-dimethyl-2-methylene-hept-5-enal 
• 28385-56-0 (R)-7-methyl-3-methylene-octa-1,6-dien-4-ol 

Relevant academic research and scientific papers

Synthesis and oxidative transformations of new chiral pinane-type γ-ketothiols: Stereochemical features of reactions

Chiral γ-ketothiols, thioacetates, thiobenzoate, disulfides, sulfones, thiosulfonates, and sulfonic acids were obtained from β-pinene for the first time. New compounds open up prospects for the synthesis of other polyfunctional compounds combining a biologically active pinane fragment with various pharmacophore groups. It was shown that the syntheses of sulfanyl and sulfonyl derivatives based on 2-norpinanone are characterized by high stereoselectivity in comparison with similar reactions of pinocarvone. The conditions for the preparation of diastereomerically pure thioacetyl and thiobenzoyl derivatives based on pinocarvone, as well as for the chemoselective oxidation of γ-ketothiols with chlorine dioxide to the corresponding thiolsulfonates and sulfonic acids, were selected. The effect of the VO(acac)2 catalyst on the increase in the yields of thiosulfonates was shown. A new direction of the transformation of thiosulfonates with the formation of sulfones was revealed. In the case of pinocarvone-based sulfones, the configuration is inversed at the C2 atom. An epimerization scheme is proposed.

Design of stable mixed-metal MIL-101(Cr/Fe) materials with enhanced catalytic activity for the Prins reaction

This work highlights the benefit of designing mixed-metal (Cr/Fe) MOFs for enhanced chemical stability and catalytic activity. A robust and stable mixed-metal MIL-101(Cr/Fe) was prepared through a HF-free direct hydrothermal route with Fe3+ content up to 21 wt%. The incorporation of Fe3+ cations in the crystal structure was confirmed by 57Fe M?ssbauer spectrometry. The catalytic performance of the mixed metal MIL-101(Cr/Fe) was evaluated in the Prins reaction. MIL-101(Cr/Fe) exhibited a higher catalytic activity compared to MIL-101(Cr), improved chemical stability compared to MIL-101(Fe) and a higher catalytic activity for bulky substrates compared to MIL-100(Fe). In situ infra-red spectroscopy study suggests that the incorporation of Fe3+ ions in MIL-101 structure leads to an increase in Lewis acid sites. It was thus concluded that the predominant role of Cr3+ ions was to maintain the crystal structure, while Fe3+ ions enhanced the catalytic activity.

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.

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.

Beta-pinene selective hydroxylation oxidation method and product thereof

The invention discloses a beta-pinene selective hydroxylation oxidation method and a product thereof. The beta-pinene selective hydroxylation oxidation method uses ordinary-pressure oxygen or oxygen-enriched air as an oxidant, uses metal porphyrin or their solid carriers as a catalyst and is performed in the absence of an additional solvent or a co-oxidation reducer, and the beta-pinene hydroxylation oxidation product is obtained by means of the method in a high-selectivity mode. Main oxidation products include pinocarveol, 2,10-epoxy pinane and myrtenol, wherein the overall selectivity of the hydroxylation oxidation products 1 and 3 is above 90%. The usage amount of the catalyst used in method is small, a reaction process is simple, the temperature is low, the initiation rate is high, the selectivity is good, homogeneous catalysis can be achieved, and heterogeneous catalysis can also be performed after immobilization.

Synthesis of bimetallic Zr(Ti)-naphthalendicarboxylate MOFs and their properties as Lewis acid catalysis

Bimetallic Zr(Ti)-NDC based metal-organic frameworks (MOFs) have been prepared by incorporation of titanium(iv) into zirconium(iv)-NDC-MOFs (UiO family). The resulting materials maintain thermal (up to 500 °C), chemical and structural stability with respect to parent Zr-MOFs as can be deduced from XRD, N2 adsorption, FTIR and thermal analysis. The materials have been studied in Lewis acid catalyzed reactions, such as, domino Meerwein-Ponndorf-Verley (MPV) reduction-etherification of p-methoxybenzaldehyde with butanol, isomerization of α-pinene oxide and cyclization of citronellal.

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.

Continuous flow photooxygenation of monoterpenes

Photooxygenation of monoterpenes was conducted in two continuous flow reactors. The first, suitable for lab-scale research, had a maximum yield of 99.9%, and the second, focused on industrial applications, showed a daily output that was 270.0-fold higher than that in batch systems. The use of sunlight instead of an LED lamp gave 68.28% conversion.

H- and Fe-modified zeolite beta catalysts for preparation of trans-carveol from α-pinene oxide

The isomerisation of a-pinene oxide has been intensively investigated for selective preparation of campholenic aldehyde, a compound used in the synthesis of fragrances. Selective preparation of another product of α-pinene oxide rearrangement, trans-carveol, still remains a challenging task. Trans-carveol is a highly valuable compound used in perfume bases, food flavour compositions and as an active pharmaceutical substance in chemoprevention of mammary carcinogenesis. In the present work zeolite beta with different SiO2/Al2O3 molar ratios was modified by iron, characterised and tested per se and in the modified form for trans-carveol preparation from a-pinene oxide. The isomerisation reaction was carried out in a polar basic solvent N, N-dimethylacetamide at 140 °C. The activities and selectivities of the catalysts were correlated with their acid properties and with the iron content.

Hydrocarbon oxidation over Fe- and Cr-containing metal-organic frameworks MIL-100 and MIL-101-a comparative study

Catalytic properties of Fe- and Cr-based metal-organic frameworks (MOFs) MIL-100 and MIL-101 have been assessed in two liquid-phase reactions: solvent-free allylic oxidation of alkenes (cyclohexene, α- and β-pinenes) with molecular oxygen and oxidation of anthracene (AN) with tert-butyl hydroperoxide (TBHP). In the oxidation of alkenes, the product selectivity strongly depends on the nature of metal (Fe or Cr) but, for the same metal, only slightly differs for the MIL-100 and MIL-101 structures. The Fe-containing MOFs afford the formation of unsaturated alcohols while Cr-based MOFs give mainly unsaturated ketones. Both Cr-MIL-100 and Cr-MIL-101 favor decomposition of cyclohexenyl hydroperoxide to produce 2-cyclohexen-1-one with 67-69% selectivity. Stability toward destruction reduced in the order Cr-MIL-101, Cr-MIL-100 > Fe-MIL-100 > Fe-MIL-101. In the oxidation of anthracene over both Cr-MOFs and Fe-MIL-101, the selectivity toward 9,10-anthraquinone (AQ) attained 100% at 92-100% AN conversion. The turnover frequency (TOF) decreased in the order Cr-MIL-101 > Fe-MIL-101 > Cr-MIL-100 > Fe-MIL-100. Cr-MIL-101 revealed superior catalytic performance in terms of AN conversion, AQ selectivity and TOF. Nearly quantitative yield of AQ was obtained after 1.5 h at 100 °C in chlorobenzene as solvent. No leaching of active metal occurred under optimal reaction conditions and the MOFs could be recycled several times without deterioration of the catalytic properties.