Physico-chemical aspects of polyethylene processing in an open mixer. Part 26: Formal kinetics of aldehyde and carboxylic acid formation at a constant rate

Formation of carboxylic acids at a constant rate can be easily explained. It seems to result from the formation and decomposition of α,γ-keto-hydroperoxides. Formal kinetics based on formation and decomposition of these structural units is in agreement with the experimental findings. The activation energy deduced from the calculations is negligible, in agreement with the experimental data showing the constant rate to be practically temperature independent. Comparison of the acids with the hydroperoxides and ketones formed initially shows that the rate of oxygen addition to alkyl radicals is significantly smaller than in low molecular mass liquids. The same conclusion is reached on comparing directly the acids formed on decomposition of α,γ-keto-hydroperoxides in polyethylene melt and in hexadecane. The rate of oxygen addition in polyethylene melt is closer to 2 × 10⁵ than to 6 × 10⁵ (s⁻¹) that is valid in hexadecane.It is possible to attribute the relatively small amount of aldehydes that might be formed at a constant rate to different reactions of alkoxy radicals that are not in a cage with other radicals. These alkoxy radicals result from the addition of peroxy radicals to unsaturated bonds. This addition is followed mainly by epoxide formation and simultaneous release of an alkoxy radical.     

Catalytic air oxidation of ambient temperature hydrocarbons

Catalytic air oxidation of the aliphatic hydrocarbons n-decane, hexanes, gasoline and diesel fuel was conducted at ambient temperature with novel iron catalysts. The concentration of n-decane in water was reduced from 1.42 g in 100 ml to 0.07 g in 100 ml in 5 h at room temperature forming carbon monoxide and water by means of intermediate aldehydes. Results of FT–IR and GC–MS analyses demonstrated formation of aldehydes and unsaturated alcohols. Carbon monoxide was detected on catalyst residues and in the vapor phase. The indicated catalytic reaction mechanisms are discussed.     

Enantiospecific synthesis of isomers of AES, a new environmentally friendly chelating agent

Three four-step enantiospecific syntheses of different diastereomers of AES, a new biodegradable chelating agent, are described. The stereocenters in each of the isomers are accessible from l- and d-malic and aspartic acids.     

Direct, organocatalytic α-sulfenylation of aldehydes and ketones

A method for direct sulfenylation of aldehydes and ketones, catalyzed by a novel pyrrolidine trifluoromethanesulfonamide organocatalyst, has been developed. This process serves as an efficient and mild approach to the preparation of α-phenylthio-ketones and -aldehydes.     

A versatile and practical synthesis of bis(indolyl)methanes/bis(indolyl)glycoconjugates catalyzed by trichloro-1,3,5-triazine

A practical and efficient electrophilic substitution reaction of indoles with a variety of aldehydes was carried out using catalytic trichloro-1,3,5-triazine (10 mol %) in acetonitrile to furnish the corresponding bis(indolyl)methanes in excellent yields. Similarly, sugar derived aldehydes gave hitherto unknown bis(indolyl)glycoconjugates in very good yields.     

Physico-chemical aspects of polyethylene processing in an open mixer. Part 24: Experimental kinetics of aldehyde and carboxylic acid formation

The experimental kinetics for carboxylic acids shows more complexity than that for ketones. The fitting of the experimental results for the initial stages to the equation consisting of a linear and a quadratic term in processing time accounts well for the ketone data but not for the acid data. Instead of that, the data for the acids show fair fit to an equation containing a linear term and another term that is cubic in processing time. In the temperature range of the experiments the linear term is practically constant. The cubic term increases strongly with temperature. The combination of a linear and a quadratic term can account for the advanced stages of processing. The corresponding quadratic term shows strong increase if the processing temperature passes from 150 to 160 °C. However, for higher processing temperatures it remains constant within experimental error. The difference carbonyl absorbance measured after treatment of the polyethylene films with ammonia corresponds to the sum of the acids and aldehydes. It shows similarly complex kinetics. Some of the difficulties encountered with the experimental kinetics cannot be resolved with the data available. It is only the comparison with the formal kinetics based on potential mechanisms of product formation that allows for better understanding of the experimental results.     

Pentamethylcyclopentadienide in organic synthesis: nucleophilic addition of lithium pentamethylcyclopentadienide to aromatic aldehydes and carbon-carbon bond cleavage of the adducts affording the parent aldehydes

Treatment of aromatic aldehyde with lithium pentamethylcyclopentadienide provided the corresponding carbinol in excellent yield. The carbinol returns to the parent aldehyde and pentamethylcyclopentadiene upon exposure to an acid or due to heating. The combination of the two reactions can represent a protection of aromatic aldehyde.     

Physico-chemical aspects of polyethylene processing in an open mixer. Part 21: Improved product yields on true bimolecular hydroperoxide decomposition

The product yields from the reaction between two hydroperoxide groups have been re-calculated. This is a consequence of the fact that β-scission of secondary alkoxy radicals cannot be neglected in the high temperature range of the polyethylene processing experiments (170-200 °C). It must be taken into account in addition to disproportionation/combination and hydrogen abstraction by alkoxy radicals. The increased complexity caused by the additional reaction results mainly from the larger number of caged radical pairs involved in the reactions and also in the calculations. Among other products it becomes possible to calculate the yields of aldehyde and vinyl groups that would not result from hydroperoxide decomposition in the absence of β-scission. The yields of the main oxidation products such as alcohols, ketones and trans-vinylene groups are reduced to some extent in comparison with the values calculated if β-scission is neglected. The vinyl group yield corresponds to slightly more than 10% of the yield of trans-vinylene groups in the temperature range of the experiments. The aldehyde yield is significantly larger than the vinyl group yield and is important in the whole temperature range examined. Main-chain scissions are important at the temperatures of the experiments. They become more important than the sum of the different combination reactions from a temperature of 200 °C on.     

Synthesis and catalytic activity of a fluorous-tagged TEMPO radical

A fluorous-tagged TEMPO radical has been prepared and its catalytic activity in the chemoselective oxidation of alcohols to carbonyl compounds has been investigated. The new fluorous radical proved to be an efficient, selective and easily recoverable catalyst, which can be conveniently used in standard organic solvents and then isolated and recycled by fluorous liquid-liquid extraction.     

Gallium metal mediated allylation of carbonyl compounds and imines under solvent-free conditions

Gallium metal is effective in mediating the allylation of various carbonyl compounds and imines under solvent-free conditions, with the application of sonic energy, affording the corresponding homoallylic alcohols and amines. The imines themselves were also prepared under solventless conditions in high yield, thereby establishing a two-step solvent-free synthesis of homoallylic amines. In comparison, indium metal produced a mixture of the desired homoallylic secondary amine and the bis-allylated species via an iminium ion intermediate.