Facile one-pot synthesis of functionalized organophosphonate esters via ketone insertion into bulky arylphosphites

The reaction of phosphorus trichloride with 2,6-diisopropyl phenol in the presence of LiCl under reflux conditions for 24 h produces a mixture of (ArO)PCl₂ and (ArO)₂PCl (Ar = 2,6-iPr₂C₆H₃). The hydrolysis of the aryloxy compounds in acetone/H₂O results in the formation of two novel phosphonate ester derivatives [(ArO)P(O)(OH)(CMe₂OH)] (1) and [(ArO)₂P(O)(CMe₂OH)] (2), respectively in a moderate yield. The title compounds have presumably formed via acetone insertion to the P-H bonds of (ArO)P(O)(H)(OH) and (ArO)₂P(O)(H), respectively, in the presence of HCl produced during the hydrolysis. Compounds 1 and 2 have been characterized by elemental analysis, and ESI-mass, Infrared and NMR spectroscopic techniques. Further, solid state structures of 1 and 2 have been established by single crystals X-ray diffraction studies.     

以镁铝水滑石为前驱体制备复合氧化物催化丙酮气相缩合反应

采用共沉淀-恒温晶化法制备了系列镁铝水滑石(Mg-Al-LDH)样品,对镁铝水滑石在500 ℃焙烧得到镁铝复合氧化物(Mg-Al-LDO),采用IR、XRD、CO₂-TPD、SEM及N₂吸附-脱附等方法对Mg-Al-LDH和Mg-Al-LDO进行了表征。在温度250 ℃、液时空速1 h^-1条件下,采用固定床对镁铝复合氧化物催化剂对丙酮缩合反应的性能进行微反活性评价。研究结果表明,晶化时间与镁铝复合氧化物的弱碱性位和强碱性位的密度相关。丙酮缩聚反应的主要产物为异佛尔酮(IP)和异丙叉丙酮(MO),以及少量的异丙烯基丙酮、双丙酮醇,均三甲苯等。丙酮缩聚制备异佛尔酮的反应需要催化剂表面弱碱性位(S_w)与强碱性位(S_s)的协同作用,S_w与S_s需要匹配。晶化12 h得到的镁铝复合氧化物催化剂(LDO-12)的S_w/S_s=1.3,异佛尔酮(IP)选择性为65.3%,单程有效收率(IP+MO)为14.8%。     

Use of A Novel Acetone-H2O2−C10− Chemiluminescence System for the Determination of Iodide Ion

Abstract

The present paper reports a new chemiluminescence system, i.e, acetone-H₂O₂?C10^?, which can be catalyzed by iodide ion (I^?). Based on this catalysis, a new chemiluminescence method for the determination of trace iodide ion is proposed. the optimum conditions are reported in this note. the detection limit is 2 × 10^?11 g/ml I^?, the linear dynamic range is 4 × 10^?10 g/ml to 3 × 10^?7 g/ml I^?, and the variation coefficient at an iodide concentration of 5 × 10^?9 g/ml I^? (n=10) is 4.6%. the method has been satisfactorily applied to the determination of trace iodide ion in water.     

The Analysis of Air for Acetone Cyanohydrin Using Solid Sorbent Sampling and Gas Chromatography

Abstract

A method for sampling and analysis of airborne acetone cyanohydrin is described. The analyte is collected on Porapak QS, a silylated styrene-divinylbenzene porous polymer. Samples are desorbed with ethyl acetate and analyzed by gas chromatography using a nitrogen-specific detector and a teflon column packed with 5% OV-17 on Chromosorb T. The detection limit is estimated to be 0.1 μg/mL acetone cyanohydrin in ethyl acetate. The method was tested by evaporating from 1.0 to 50 μg of the analyte onto sorbent beds of Porapak QS and exposing the samples to a humidified airstream for 15 min. Quantitative recovery was obtained for samples stored for one day at ambient temperature or for seven days if the samples were refrigerated immediately after collection.     

Artifact Formation In The Soxhlet Extraction Of Environmental Samples With Acetone

Abstract

A study was performed to confirm suspected artifactual formation of acetone derivatives during the Soxhlet extraction of soil samples with acetone. The conditions employed simulated very closely those normally employed for the extraction of soils for neutral and moderately polar organic compounds such as pesticides. A series of acidic, neutral, and basic organic-free soils were extracted with hexane/acetone solvent mixture and the extracts concentrated in a Kuderna-Danish apparatus. The extracts were analyzed by capillary column gas chromatographic mass spectrometry. In nearly all cases, simple dimeric products such as diacetonecohol and mesityl oxide were formed in varying amounts. The acidified and basic soils yielded complex mixtures of dimers, trimers, tetramers and other complex homologs. Some of the more common substances found include phorone, mesitylene and isophorone. The latter substance is listed as an EPA priority pollutant.     

Reactions in clusters of acetone and fluorinated acetones triggered by low energy electrons

Electron attachment to clusters of acetone (A), trifluoroacetone (TFA) and hexafluoroacetone (HFA) is studied in a crossed beam experiment with mass spectrometric detection of the anionic products. We find that the electron attachment properties in A change dramatically on going from isolated molecules to clusters. While single acetone is a very weak electron scavenger (via a dissociative electron attachment (DEA) resonance near 8.5 eV), clusters of A capture electrons at very low energy (close to 0 eV). The final ionic products consist of an ensemble of molecules (M) subjected to the loss of two neutral H₂ molecules ((M_n−2H₂)⁻, n ≥ 2). Their formation at low energies can only be explained by invoking new cyclic structures and polymers. In clusters of TFA, anionic complexes containing non-decomposed molecules (M_n⁻) including the monomer (M⁻) and ionic products formed by the loss of one and two HF molecules are observed. Loss of HF units is also interpreted by the formation of new cyclic structures in the anionic system. HFA is a comparatively stronger electron scavenger forming a non-decomposed anion via a narrow resonant feature near 0 eV in the gas phase. In HFA clusters, the non-decomposed parent anion is additionally observed at higher electron energies in the range 3–9 eV. The M⁻ signal carries signatures of self-scavenging processes, i.e., inelastic scattering by one molecule and capture of the completely slowed down electron by a second molecule within the same cluster. The scavenging spectrum is hence an image of the electronically excited states of the neutral molecule.     

Antioxidant and Antimicrobial Activities of Erodium arborescens Aerial Part Extracts and Characterization by LC-HESI-MS2 of Its Acetone Extract

The phytochemical analysis of antioxidant and antibacterial activities of Erodium arborescens aerial part extracts constitute the focus of this research. The chemical composition of an acetone extract was investigated using LC-HESI-MS², which revealed the presence of 70 compounds. The major identified components were tannin derivatives. Total polyphenol and total flavonoid contents were assessed in plant extracts (hexane, ethyl acetate, acetone and methanol). The results showed that the acetone extract exhibited the highest contents of polyphenols and flavonoids, 895.54 and 36.39 mg QE/g DE, respectively. Furthermore, when compared to other extracts, Erodium arborescens acetone extract was endowed with the highest antioxidant activity with 2,2-diphenyl-1-picrylhydrazyl (DPPH), ferric reducing antioxidant power (FRAP) and total antioxidant capacity (TAC) tests. In addition, the four extracts of Erodium arborescens showed variable degrees of antimicrobial activity against the tested strains, and the interesting activity was obtained with acetone and methanol extracts.     

Ultrasound assisted crystallization for the recovery of lactose in an anti‐solvent acetone

Continuous worldwide increase in high‐scale production of dairy products leads to the constant generation of vast amounts of liquid by‐product, whey. Disposal of liquid whey is costly due to its high biological oxygen demand (BOD) and water content. More than 90% of whey BOD is due to lactose. Recovery of lactose from whey solves both the problems of improving economics of whey utilization and pollution reduction as lactose recovery itself can reduce BOD of whey by more then 80%. Commercial effluent treatment techniques focus on degradation rather than recovery of useful by‐products like lactose. Also, these techniques are time consuming and hence not effective enough. Sonocrystallization is the use of power ultrasound to control the crystallization process during the nucleation phase. In the present study, the process of lactose crystallization has been studied for the recovery of lactose from reconstituted lactose solutions with the aid of ultrasound, in the presence of ‘acetone’, as an anti‐solvent. The crystallization is found to be completed with excellent yields in the range of 80 – 92% within 4 minutes of sonication. (© 2009 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)