Asymmetric Hydrogenation of Activated Ketones on Platinum: Relevant and Spectator Species

The heterogeneous enantioselective hydrogenation of activated ketones over chirally modified platinum is reviewed with emphasis on identifying the role of the various species observed in this catalytic system. The past years have witnessed a continuous broadening of the scope of this catalytic system including new reactants and modifiers affording over 97% ee. New reaction pathways have been uncovered and the kinetic and mechanistic studies have been faced with a number of complicating factors caused by spectator species and interactions in solution and on the Pt surface. The previously proposed mechanistic models are critically assessed in the light of these new findings.     

Effects and properties of poly(arylene ether benzonitrile)s of various molecular weights blended with sulfonated poly(ether ether ketone)

Poly(arylene ether benzonitrile) (PAEBN) was synthesized with 2,6‐dichlorobenzonitrile and biphenol. PAEBNs with various molecular weights (MWs), 1,640,000 and 185,000 g/mol, were synthesized by control of the stoichiometry of the monomers and were blended with sulfonated poly(ether ether ketone) (SPEEK). The effects of MW on the water uptake, swelling, methanol permeability, and proton conductivity of the SPEEK/PAEBN blend membranes were investigated. The molecular mobility of the SPEEK/PAEBN blends was also examined in this study. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Biosynthesis and identification of volatiles released by the myxobacterium Stigmatella aurantiaca

The volatiles released by agar plate cultures of two strains of the myxobacterium Stigmatella aurantiaca (strains Sg a15 and DW4/3-1) were collected in a closed-loop stripping apparatus (CLSA) and analyzed by GC-MS. Large numbers of substances from different compound classes (ketones, esters, lactones, terpenes, and sulfur and nitrogen compounds) were identified; several of them are reported from natural sources for the first time. The volatiles 2-methyltridecan-4-one (17), its isomer 3-methyltridecan-4-one (20), and the higher homologue 2-methyltetradecan-4-one (18) were identified in the extracts of both strains and were synthesized. In addition, strain Sg a15 produced 2,12-dimethyltridecan-4-one (19), 2-methyltridec-2-en-4-one (23), and a series of phenyl ketones, among them 1-phenyldecan-1-one (14) and 9-methyl-1-phenyldecan-1-one (16), whereas strain DW4/3-1 emitted traces of 10-methylundecan-2-one (21). The biosynthesis of 14 and 16 was examined in feeding experiments with deuterated precursors carried out on agar plate cultures. The leucine-derived starter unit isovalerate was shown to be incorporated into 16, as was phenylalanine-derived benzoic acid into both 14 and 16. The results point to formation both of the phenyl ketones and of the structurally related aliphatic ketones through an unusual head-to-head coupling between a starter unit such as benzoyl-CoA and a fatty acyl-CoA, followed by decarboxylation.     

双－（p－N，N－二甲氨基苄叉）酮／二苯基碘鎓盐复合体系的电子转移光显色

不同的双－（ｐ－Ｎ，Ｎ－二甲氨基苄叉）酮ＤＭＢＫ和二苯基碘盐（ＤＰＩＯＦ）复合，组成一种新型的电子转移光显色体系，ＤＭＢＫ／ＤＰＩＯＦ复合体系在暗处有良好的热稳定性。在光作用下很快发生从激发态ＤＭＢＫ至ＤＰＩＯＦ的电子转移，并伴随ＤＭＢＫ染料的褪色，测得ＤＭＢＫ光褪色速度的次序为：ＤＭＢＡ＞ＤＭＢＰ＞ＤＭＢＨ。与此同时，电子转移又引起新的光显色反应，对ＤＭＢＡ化合物，在７００ｎｍ处出现新吸收峰。其光密度随光照时间而增长，然而，ＤＭＢＰ和ＤＭＢＨ体系这种光显色现象并未观察到，这可能由于它们的中间产物不能共平面的缘故，ＤＭＢＡ的光显色速度和最大密度明显取决于浓度和溶剂性质。本文对这种短波区光褪色和长波区光显色的光化学反应过程作了讨论。     

Mechanical properties of a cryogenically mechanically alloyed polycarbonate–poly(aryl ether ether ketone) system

The processing–property relationship of a model cryogenically mechanically alloyed polymer–polymer system [polycarbonate (PC) and poly(aryl ether ether ketone) (PEEK)] was investigated. PC and PEEK powders were cryogenically mechanically alloyed for 10 h, and the resulting two‐phase powder particles were processed into testable coupons with a miniature ram‐injection molder. The bulk mechanical properties of the coupons made from the mechanically alloyed powders and nonmechanically alloyed powders were investigated as a function of mechanical alloying and injection‐molding parameters. The injection‐molded coupons were mechanically tested in the three‐point‐bending mode. The results demonstrated that no measurable improvement was achieved in the energy to break, strain at failure, or failure strength in the coupons made from the mechanically alloyed materials in comparison with those of the coupons made from the nonmechanically alloyed powders. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 88: 1196–1202, 2003     

Ketones from carboxylic acids over supported magnesium oxide and related catalysts

Silica-supported alkaline earth oxides revealed excellent activity to convert acetic acid selectively into acetone in a vapor-phase fixed-bed flow system. Acetone was obtained through the cyclic formation of alkaline earth acetate followed by decomposition. Magnesium oxide should be supported on the silica surface without formation of magnesium silicate, which was inactive for the present reaction. Attempted syntheses of benzophenone and acetophenone are also described.     

Inhibitions of cotton seedling growth by volatile ketones emitted by cover crop residues

Low-input, sustainable agriculture (LISA) systems can include soil incorporation of residues of weeds and legume cover crop species. However, both seed germination and seedling growth of crops, including cotton (Gossypium hirsutum L.), are inhibited by volatile organic compounds emitted by these residues during decomposition. A cotton seedling-growth assay was used to demonstrate that C₄ through C₉ ketones released by decomposing legume residues significantly inhibited root and shoot elongation, root and shoot fresh and dry weight gain, and cotyledon expansion. Seedling root and shoot water relationships were relatively insensitive to those components of plant residue volatile emissions. Concentration (0.0, 0.5, 1.0, 1.5, or 2.0M/cm³ sterile greenhouse soil mix) and root-zone temperature (20 or 30°C) altered the activity of the more inhibitory ketones. Molecular weight (carbon chain length), carbon chain branching, and position of the carbonyl group also influenced ketone inhibitory activity.Mention of a commercial or proprietary product does not constitute an endorsement by the U.S. Department of Agriculture.     

α-溴化芳香酮合成方法的改进

在氧化铜存在的条件下,以单质溴为溴源,芳香酮可有效地转化成相应的α-溴代酮,所有产物结构都通过了核磁共振氢谱的表征。     

First synthesis of a new fullerene oximes bis(9-[hydroxo]-1-[1′-hydroxymino-2′-oxo-2′-alkyl-ethyl])1,9-dihydro-[C60-Ih][5,6]fullerenes via reaction of C60 with ketones and NaNO2 promoted by HCl

A mixture of cis-2 and cis-3 isomers of new fullerene derivatives bis(9-[hydroxo]-1-[1′-hydroxymino-2′-oxo-2′-alkyl-ethyl])-1,9-dihydro-[C₆₀-I_h][5,6]fullerenes have been selectively synthesized with high yields at the reaction of C₆₀ fullerene with ketones Me₂CO, EtMeCO, i-PrMeCO, PhMeCO in the presence of NaNO₂ and HCl.     

An Engineered Cholesterol Oxidase Catalyses Enantioselective Oxidation of Non-steroidal Secondary Alcohols

The enantioselective oxidation of 2° alcohols to ketones is an important reaction in synthetic chemistry, especially if it can be achieved using O₂-driven alcohol oxidases under mild reaction conditions. However to date, oxidation of secondary alcohols using alcohol oxidases has focused on activated benzylic or allylic substrates, with unactivated secondary alcohols showing poor activity. Here we show that cholesterol oxidase (EC 1.1.3.6) could be engineered for activity towards a range of aliphatic, cyclic, acyclic, allylic and benzylic secondary alcohols. Additionally, since the variants demonstrated high (S)-selectivity, deracemisation reactions were performed in the presence of ammonia borane to obtain enantiopure (R)-alcohols.