Cyclopentanone Compounds Research Articles

Hydrogenative Ring-Rearrangement of Biobased Furanic Aldehydes to Cyclopentanone Compounds over Pd/Pyrochlore by Introducing Oxygen Vacancies

Upgrading furanic aldehydes (such as furfural or 5-hydroxymethyl furfural) to cyclopentanone compounds (such as cyclopentanone or 3-hydroxymethyl cyclopentanone) is of great significance for the sy...

Double-metal cyanide-supported Pd catalysts for highly efficient hydrogenative ring-rearrangement of biomass-derived furanic aldehydes to cyclopentanone compounds

The hydrogenative ring-rearrangement of biomass-derived furanic aldehydes (furfural or 5-hydroxymethyl furfural) to cyclopentanone compounds (cyclopentanone or 3-hydroxymethyl cyclopentanone) is of great significance for high-value chemicals. The Brønsted acid in metal-support bifunctional catalysts causes a serious carbon loss, and the weak Lewis acid is difficult to induce hydrolysis reaction steps. Here, a double-metal cyanide (DMC) catalyst with pure moderate Lewis acid sites was investigated for solving the above problems. The crystal structure and the Lewis acidity of the catalyst are controlled by different kinds of metals, and the surface properties are changed by a complexing effect. Pd clusters of 8 nm are uniformly dispersed on the surface after impregnation on the double-metal cyanide. For the reaction of furanic aldehydes, the Pd/FeZn-DMC catalyst with a moderate Lewis acidity shows a high efficiency for the synthesis of cyclopentanone compounds, whereas the Pd/FeNi-DMC and Pd/FeCo-DMC catalysts with a weak Lewis acidity result in a yield above 90.2% of furanic alcohols (furfuryl alcohol or 2,5-bis(hydroxymethyl)furan). The catalytic activity of Pd/FeZn-DMC is controlled by the surface area based on the accessibility of the Lewis acid sites, and the highest yields of 96.6% and 87.5% are obtained for cyclopentanone and 3-hydroxymethyl cyclopentanone, respectively. Furthermore, the catalyst is resistant to leaching and performs stably after 6 runs. This study not only provides a promising route for efficient production of cyclopentanone compounds but also shows the excellent advantage of DMC-based bifunctional catalysis in biomass conversion reactions.

Pd/Cu-MOF as a highly efficient catalyst for synthesis of cyclopentanone compounds from biomass-derived furanic aldehydes

Herein, a series of Pd nanoparticles supported on Cu-MOFs (Cu3(BTC)2, FeCu-DMC) with pure Lewis acidity are synthesized for hydrogenative ring-rearrangement reaction of furanic aldehydes (furfural, 5-hydroxymethyl furfural) to cyclopentanone compounds (cyclopentanone, 3-hydroxymethyl cyclopentanone). For both furfural and 5-hydroxymethyl furfural, the hydrogenation rate catalyzed by the Pd/Cu-BTC is six times faster than Pd/FeCu-DMC, due to the higher dispersion of Pd nanoparticles. Meanwhile, Pd/Cu-BTC with strong acidity for the selectivity of cyclopentanone compounds is more than 90%, while as for Pd/FeCu-DMC, furanic alcohols (furfuryl alcohol, 2,5-bis(hydroxymethyl)furan) are only actually be obtained because weak acidity cannot incur subsequent hydrolysis reaction.

Highly efficient hydrogenative ring-rearrangement of furanic aldehydes to cyclopentanone compounds catalyzed by noble metals/MIL-MOFs

Hydrogenative ring-rearrangement reaction of biomass-derived furanic aldehydes to cyclopentanone compounds catalyzed by metal/support bifunctional catalysts suffers a low selectivity of target product and serious carbon loss because of the Brønsted acid catalysis. Herein, a series of pure Lewis acid sites MIL-MOFs (Fe-MIL-100, Fe-MIL-101 and Cr-MIL-101) with different crystal topology structures and metals are synthesized. Then the nanoparticles of Ru, Pt, Pd and Au are uniformly dispersed on the internal surface of the MOF support. The hydrogenation rate catalyzed by the noble metals/Fe-MIL-100 is three times faster than those obtained with Fe-MIL-101 and Cr-MIL-101-based catalysts due to the higher dispersion of nanoparticles on the former to make it more accessible to reactants. Meanwhile, both of the noble metals on Fe-MIL-100 and Fe-MIL-101 have a higher selectivity of cyclopentanone compounds than that on Cr-MIL-101, since the Fe ions in the MOF host with a higher oxophilicity will promote the adsorption and hydrolysis of the intermediate furanic alcohols (furfural alcohol or 2,5-bis(hydroxymethyl)furan). Furthermore, the noble metals/MIL-MOFs catalyst can maintain a good activity and stability after recycling for five runs. The current work will present an efficient catalytic reaction system for the hydrogenative ring-rearrangement of furfural and 5-hydroxymethyl furfural to synthesize cyclopentanone compounds.

Structural and photophysical properties of alkylamino substituted 2-arylidene and 2,5-diarylidene cyclopentanone dyes

A series of alkylamino substituted 2-arylidene and 2,5-diarylidene cyclopentanone compounds were synthesized. Spectroscopic and photophysical properties of these compounds have been measured in a variety of solvents. Absorption and fluorescence maxima have been correlated with the Empirical Scale of Solvent Polarity (ET(30)). Theoretical TD-DFT spectral calculations and Lippert–Mataga analysis support the internal charge transfer (ICT) nature of the S0 → S1 excitation for these compounds, with higher degrees of ICT depicted for the alkylamino substituted 2,5-diarylidene cyclopentanones. Photophysical properties consisted of measuring the fluorescence quantum yields (Φf) and lifetimes (τf) in a variety of solvents. Radiative and nonradiative decay constants have been determined from the Φf and τf data. Variation with solvent in the nonradiative rate of decay is interpreted in terms of a competition between internal conversion and intersystem crossing. Lastly, two compounds presented have been shown to undergo excited state protonation in glacial acetic acid.

ChemInform Abstract: A Review (Research and Patents) on Jasmonic Acid and Its Derivatives

AbstractReview: 128 refs.

A Review (Research and Patents) on Jasmonic Acid and Its Derivatives

In medicinal chemistry there is a growing interest in using small molecules, including plant stress hormones. Jasmonic acid (JA) and its volatile methyl ester (MJ), collectively termed jasmonates, are lipid-derived cyclopentanone compounds that occur ubiquitously and exclusively in the plant kingdom. This review covers the synthesis, usage, and biological activities of JA and its derivatives. A brief overview of the available information on JA and its features is given, followed by a detailed review of JA and its derivatives as drugs and prodrugs; the properties in plants and the synthesis in recent patents are described. This review shows the direction of long-term drug/nutraceutical safety trials and provides insights for future research in this area. Research on JA continues to be of major interest. Recent innovations offer hope for the development of new therapeutics in related fields. It is anticipated that several analogs can be advanced to preclinical and clinical studies.

Synthesis of 2,5-bis-(4’-hydroxybenzylidene) cyclopentanone and 2,5-bis-(4’-chlorobenzylidene) cyclopentanone compounds and antiproliferative tests to HeLa cells

2,5- bis - ( 4’-hydroxy-3’- methoxybenzylidene ) cyclopentanone com- pound was know have cytotoxic activity to Mieloma , Raji and HeLa cells better than curcumin. In effort to discovered new compound which have cytotoxic activity, it necessery to modify this compound by changing some group on it with lossing methoxy group, so was yielded two compounds, there were 2,5- bis - ( 4’-hydroxy benzylidene) cyclopentanone and 2,5-bis – ( 4-chlorobenzylidene ) cyclopentanone. The synthesis was done by reaction between 4-hydroxyand 4-chlorobenzaldehydes and cyclopentanone through Claisen-Schmidt condensation reaction catalyzed by sulfuric acid with methanol and 2-butanol as solven. The structure of product was characterized by spectra of Infrared and Massspectroscopy, then anti proliferation activity to HeLa cells counted base on IC50 values The results showed that 2,5- bis -(4’-hydroxy benzylidene) cyclopentanone (IC50 value : 0.656 mM) have higher toxicity than 2,5- bis -(4’-chlorobenzylidene) cyclopentanone (IC50value : 5.376 mM). Key words : Claisen-Schmidt condensation; 2,5- bis -(4’-hydroxy benzylidene) cyclopentanone; 2,5- bis -(4’-chloro-benzylidene) cyclopentanone; anti proliferative; HeLa cell.

Complex formation between azacrown derivatives of dibenzylidenecyclopentanone and alkali-earth metal ions

The complex formation of 2,5-bis[4-(1,7,10,13-tetraoxa-4-azacyclopentadec-4-yl)benzylidene]cyclopentanone and several model compounds, prospective metal-sensitive fluorescent probes, with Mg2+, Ca2+, and Ba2+ ions in acetonitrile was studied. The azacrown derivatives of dibenzylidenecyclopentanone have two complex formation centers, azacrown cycle and carbonyl group. The sequence of binding to these sites is different for different ions. The efficient ejection of the Ca2+ and Ba2+ ions from their complexes with azacoronands was observed in the excited state, whereas in the case of the Mg2+ ion, this process occurred only partially.

JIPs and RIPs: the regulation of plant gene expression by jasmonates in response to environmental cues and pathogens.

After its first description as a fragrant constituent of the es? sential oil of Jasminum grandiflorum (Demole et al., 1962), (-)-jasmonic acid methyl ester (methyl c/s-2-(2-penten-1-yl)3-oxocyclopentenyl acetate, also known as methyl jasmonate [MeJA]), and related compounds were found to be widespread in the plant kingdom (Meyer et al., 1984). In addition, jas? monates occur in fungi and algae (for references, see Sembdner and Parthier, 1993). Interestingly, MeJA js also a component of female-attracting pheromones in certain moths (Baker et al., 1991). (-)-Jasmonic acid [(-)-JA] and its derivatives are cyclopentanone compounds that are synthesized from linolenic acid by a sequence of as yet poorly characterized reactions (Vick and Zimmerman, 1984). The natural biosynthetic product of this pathway in most plant species appears to be (+)-7-/so-JA, which is rapidly converted into (-)-JA by isomerization. (-)-JA has been shown to undergo various modifications, giving rise to numerous metabolites with differing structures and biologi? cal activities. Major physiologically active compounds are (-)-JA, MeJA, and the amino acid conjugates of (-)-JA with isoleucine, valine, or leucine (for review, see Sembdner and Parthier, 1993). (-)-JA and MeJA (which will be collectively referred to throughout this review as jasmonates) affect plant growth and development in a pleiotropic manner (for reviews, see Parthier, 1990,1991; Staswick, 1992; Sembdner and Parthier, 1993). Re? cently, jasmonates have been proposed to be stress-related compounds (Farmer and Ryan, 1990; Parthier, 1990, 1991; Enyedi et al., 1992; Farmer et al., 1992; Gundlach et al., 1992; Muller et al., 1993). MeJA, in particular, is a signal molecule that is released in plants in response to various stresses, such as wounding or pathogen attack (Creelman et al., 1992),

Jasmonates, New Regulators of Plant Growth and Development: Many Facts and Few Hypotheses on their Actions

AbstractJasmonates, ubiquitous cyclopentanone compounds, are reviewed as new regulators for plant growth and development. They may complement the group of well‐established “classic” phytohormones. Jasmonates influence a multiplicity of plant physiological processes by inhibition, promotion or induction. In many aspects they are similar to abscisic acid, especially in responses to stress. The review contains information on the chemical structures and metabolism of jasmonates, contributes to their biological role and describes possible mode(s) of action at the level of molecular biology and gene expression. In particular, emphasis is placed on the gene expression and accumulation of jasmonate‐induced abundant polypeptides as a stress response of the plant cells. A hypothesis is attempted in which endogenous jasmonates represent an integral part of the signal transduction chain between stress signal(s) and stress response(s).

Jasmonates: Hormonal regulators or stress factors in leaf senescence?

Specific cyclopentanone compounds such as (−)-jasmonic acid (JA) and its methyl ester (JA-Me) or (+)-7-iso-jasmonic acid are considered putative plant growth regulators for a number of reasons, including their ubiquitous occurrence in the plant kingdom, structural specificity in physiological responses, and interaction with other phytohormones in the biological activities of jasmonates. In this respect leaf senescence promotion is of particular preponderance. Recent progress in the mode of jasmonate actions in the barley leaf segment senescence model system demonstrates two effects at the level of gene expression: the induction by exogenously applied jasmonates of abundant specific proteins and their mRNAs (transcription control), and the cessation of synthesis of normal leaf proteins but not their respective mRNAs (translation control). These effects resemble cellular responses to well-known stress factors. The arguments for and against hormonal or stressor-like actions of jasmonates in leaf senescence are discussed in this review.