80-57-9Relevant academic research and scientific papers
Synthesis and biological activity of novel (Z)- and (E)-verbenone oxime esters
Hu, Qiong,Lin, Gui-Shan,Duan, Wen-Gui,Huang, Min,Lei, Fu-Hou
, (2017)
Twenty-seven (Z)- and (E)-verbenone derivatives bearing an oxime ester moiety were designed and synthesized in search of novel bioactive molecules. Their structures were confirmed by UV-Vis, FTIR, NMR, ESI-MS, and elemental analysis. The antifungal and herbicidal activities of the target compounds were preliminarily evaluated. As a result, compound (E)-4n (R = b-pyridyl) exhibited excellent antifungal activity with growth inhibition percentages of 92.2%, 80.0% and 76.3% against Alternaria solani, Physalospora piricola, and Cercospora arachidicola at 50 g/mL, showing comparable or better antifungal activity than the commercial fungicide chlorothalonil with growth inhibition of 96.1%, 75.0% and 73.3%, respectively, and 1.7 5.5-fold more growth inhibition than its stereoisomer (Z)-4n (R = b-pyridyl) with inhibition rates of 22.6%, 28.6% and 43.7%, respectively. In addition, seven compounds displayed significant growth inhibition activity of over 90% against the root of rape (Brassica campestris) at 100 g/mL, exhibiting much better herbicidal activity than the commercial herbicide flumioxazin with a 63.0% growth inhibition. Among these seven compounds, compound (E)-4n (R = b-pyridyl) inhibited growth by 92.1%, which was 1.7-fold more than its stereoisomer (Z)-4n (R = b-pyridyl) which inhibited growth by 54.0%.
Synthesis of (-)-3-carene-2,5-dione via allylic oxidation of (+)-3-carene
Sun, Xiaoling,Zhao, Xiaoyan,Jiang, Ying,Xu, Bochun
, p. 103 - 107 (2013)
Activated carbon-supported CuCl2 (CuCl2/AC) is a heterogeneous catalyst for the liquid-phase selective allylic oxidation of (+)-3-carene with tert-butyl hydroperoxide (TBHP) and O2 to produce (-)-3-carene-2,5-dione. The possible reaction mechanism and the effects of different factors on the allylic oxidation were investigated. The optimal conditions are as follows: reaction temperature, 45 °C; molar ratio of CuCl2 to (+)-3-carene, 1%; volume ratio of (+)-3-carene to TBHP, 1:3; and reaction time, 12 h. Under the optimal conditions, the conversion of (+)-3-carene reached 100%, whereas the selectivity for (-)-3-carene-2,5-dione reached 78%. The CuCl2/AC catalyst was characterized via X-ray diffraction, and the chemical structure of the target compound was identified via infrared spectroscopy, proton nuclear magnetic resonance spectroscopy, mass spectrometry, and optical analysis.
Individual stereoisomers of verbenol and verbenone express bioactive features
Ivanov, Marija,Kovalenko, Vitaly,Svirid, Anastasia,Kosti?, Marina,Petrovi?, Jovana,Stojkovi?, Dejan
, (2021/12/13)
Naturally occurring terpene core compounds have been used extensively in both pharmaceutical and cosmetic industry. However, since chirality of these compounds has profound influence on the level of their bioactivity, the aim of the present study was to a
Cubic CuxZrO100-x as an efficient and selective catalyst for the oxidation of aromatics active methyl, alcohol, and amine groups
Bankar, Balasaheb D.,Advani, Jacky H.,Biradar, Ankush V.
, (2021/03/14)
The local structure of a supported active metal plays a vital role in determining the desired product's selectivity in heterogeneous catalysis. Herein, we have developed a simple protocol for the synthesis of Cu doped on cubic ZrO2 mixed metal oxide catalysts and used it for the selective oxidation of various functional groups. The catalyst was synthesized by varying the wt.% of Cu (1–20%) on ZrO2 by co-precipitation, followed by hydrothermal treatment. The X-ray diffraction pattern of the catalysts confirmed the formation of the cubic phase of ZrO2, and the growth of CuO occurred along the (1 1 1) plane. The microscopy analysis revealed the uniform distribution of Cu on the ZrO2 surface, while XPS analysis confirmed the presence of copper in the +2 oxidation state. The synthesized catalyst with 2 wt% loading of Cu on ZrO2 showed excellent liquid-phase oxidation properties and gave good to best conversion of active methyl groups, alcohols, and amines with high selectivities to corresponding ketones, aldehydes, and amides, respectively, under milder reaction conditions. Furthermore, the synthesized catalyst showed a broader substrate scope for the various substituted active methyl groups, alcohols, and amines with good conversion and selectivity.
Development of rapid and selective epoxidation of α-pinene using single-step addition of H2O2in an organic solvent-free process
Eze, Valentine C.,Harvey, Adam P.,López Fernández, Ana María,Mukhtar Gunam Resul, Mohamad Faiz,Rehman, Abdul
, p. 33027 - 33035 (2021/12/07)
This study reports substantial improvement in the process for oxidising α-pinene, using environmentally friendly H2O2 at high atom economy (～93%) and selectivity to α-pinene oxide (100%). The epoxidation of α-pinene with H2O2 was catalysed by tungsten-based polyoxometalates without any solvent. The variables in the screening parameters were temperatures (30-70 °C), oxidant amount (100-200 mol%), acid concentrations (0.02-0.09 M) and solvent types (i.e., 1,2-dichloroethane, toluene, p-cymene and acetonitrile). Screening the process parameters revealed that almost 100% selective epoxidation of α-pinene to α-pinene oxide was possible with negligible side product formation within a short reaction time (～20 min), using process conditions of a 50 °C temperature in the absence of solvent and α-pinene/H2O2/catalyst molar ratio of 5?:?1?:?0.01. A kinetic investigation showed that the reaction was first-order for α-pinene and catalyst concentration, and a fractional order (～0.5) for H2O2 concentration. The activation energy (Ea) for the epoxidation of α-pinene was ～35 kJ mol-1. The advantages of the epoxidation reported here are that the reaction could be performed isothermally in an organic solvent-free environment to enhance the reaction rate, achieving nearly 100% selectivity to α-pinene oxide.
Selective Allylic Oxidation of Terpenic Olefins Using Co-Ag Supported on SiO2 as a Novel, Efficient, and Recyclable Catalyst
Aberkouks, Abderrazak,Mekkaoui, Ayoub Abdelkader,Ait Ali, Mustapha,El Firdoussi, Larbi,El Houssame, Soufiane
, (2020/02/15)
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.
Stereospecific synthesis of S-(?)-trans-verbenol and its antipode by inversion of sterically hindered alcohols
Fang, Jia-Xing,Kong, Xiang-Bo,Liu, Fu,Zhang, Su-Fang,Zhang, Zhen
, (2020/12/15)
S-(?)-trans-Verbenol (1) and its antipode, R-(+)-trans-verbenol (1′) have been confirmed as the critical pheromone components of bark beetles. Synthesis of these two active secondary alcohols (1 and 1′) from commercially available starting materials S-α-pinene and R-α-pinene was reported. The key steps were mainly depended on the effective SN2 stereo-inversion of the hydroxy group of sterically hindered alcohols (3 and 3′), using Mitsunobu reaction or hydrolysis of mesylate ester, alternatively. Our results provide a new and stereo-selectivity way to obtain optically active insect pheromones.
A Simple, Mild and General Oxidation of Alcohols to Aldehydes or Ketones by SO2F2/K2CO3 Using DMSO as Solvent and Oxidant
Zha, Gao-Feng,Fang, Wan-Yin,Leng, Jing,Qin, Hua-Li
supporting information, p. 2262 - 2267 (2019/04/17)
A practical, general and mild oxidation of primary and secondary alcohols to carbonyl compounds proceeds in yields of up to 99% using SO2F2 as electrophile in DMSO as both the oxidant and the solvent at ambient temperature. No moisture- and oxygen-free conditions are required. Stoichiometric amount of inexpensive K2CO3, which generates easy to separate by-products, is used as the base. Thus, 5-gram scale runs proceeded in nearly quantitative yields by a simple filtration as the work-up. The use of a polar solvent such as DMSO, which usually promotes competing Pummerer rearrangement, is also noteworthy. This protocol is compatible with a variety of common N-, O-, and S-functional groups on (hetero)arene, alkene and alkyne substrates (68 examples). The protocol was applied (99% yield) to a formal synthesis of the important cholesterol-lowering drug Rosuvastatin. (Figure presented.).
Oxy-functionalization of olefins with neat and heterogenized binuclear V(IV)O and Fe(II)complexes: Effect of steric hindrance on product selectivity and output in homogeneous and heterogeneous phase
Parmar, Digvijaysinh K.,Butani, Pinal M.,Thumar, Niraj J.,Jasani, Pinal M.,Padaliya, Ravi V.,Sandhiya, Paba R.,Nakum, Haresh D.,Khan, Md. Nasim,Makwana, Dipak
, (2019/06/05)
Neat {[VO(sal2bz)]2; [Fe(sal2bz)(H2O)2]2·2H2O} and zeolite-Y immobilized {[VO(sal2bz)]2-Y; [Fe(sal2bz)(H2O)2]2-Y} binuclear complexes have been prepared and characterized by spectroscopic techniques (IR, UV–vis), elemental analyses (CHN, ICP-OES), thermal study (TGA), scanning electron micrograph (SEM), adsorption study (BET)and X-ray diffraction (XRD)patterns. Neat (homogeneous)and immobilized (heterogeneous)complexes were employed as catalysts in the oxidation of olefins, namely, cyclohexene, limonene and α-pinene in the presence of 30% hydrogen peroxide. 100% conversion of cyclohexene and α-pinene was obtained while limonene was oxidized up to 90%. Homogeneous catalysts showed highly selective result as neat [VO(sal2bz)]2 complex has provided 87% cyclohexane-1,2-diol and neat [Fe(sal2bz)(H2O)2]2·2H2O complex has provided 79% verbenone in oxidation of cyclohexene and α-pinene, respectively. We have observed that due to steric hindrance, formation of olefinic oxidation products increases on moving from α-pinene to limonene and limonene to cyclohexene. Additionally. recovered heterogeneous catalysts showed intact results up to two consecutive runs. Probable catalytic mechanism has been proposed for oxidation of cyclohexene.
A Cu-Doped ZIF-8 metal organic framework as a heterogeneous solid catalyst for aerobic oxidation of benzylic hydrocarbons
Nagarjun, Nagarathinam,Dhakshinamoorthy, Amarajothi
, p. 18702 - 18712 (2019/12/09)
Mixed-metal metal organic frameworks have received considerable attention in recent years and it has been shown that the activity of the parent metal organic framework (MOF) is often enhanced upon doping with external metal ions within the framework. In this context, Cu2+ ions with different loadings were incorporated within the ZIF-8 framework to obtain a series of Cu-doped ZIF-8 materials and their activity was examined in the aerobic oxidation of hydrocarbons. The as-synthesized Cu-doped solids were characterized by powder X-ray diffraction (XRD), ultraviolet diffuse reflectance spectroscopy (UV-DRS), scanning electron microscopy (SEM), Fourier Transform infrared (FT-IR), electron paramagnetic resonance (EPR) and inductively coupled plasma (ICP) analysis. The experimental results revealed that the activity of Cu-doped ZIF-8 is much higher than that of the parent ZIF-8 in all the tested substrates at 120 °C. Furthermore, the activity of the Cu-doped ZIF-8 with the highest Cu loading was eight fold higher than that of the parent ZIF-8 in the aerobic oxidation of cyclooctane (1) at 120 °C with more than 80% selectivity to the corresponding cyclooctanol/cyclooctanone (ol/one) mixture. Cu-doped ZIF-8 was reused two times with no significant drop in its activity under identical conditions. Furthermore, comparison of the two times reused solid with that of the fresh solid by powder XRD and SEM analysis revealed identical structural integrity and morphology, respectively during the oxidation reactions.
