Unsaturated Aliphatic Compounds Research Articles

An oxidation kinetic model of unsaturated chlorinated aliphatic compounds by Fenton's reagent

Abstract An oxidation kinetic model of trichloroethylene (TCE) by Fenton's reagent is developed based upon transition state theory. Hydroxylated active complexes are assumed to be the transition state after hydroxyl radicals have attacked the organic compound. The complex can either disproportionate into Cl‐ and the other products, or return to their original reactants. Because both hydroxyl radicals and the active complexes have extremely high reactivity, their steady‐state concentrations are assumed constant in developing the kinetic model. The model indicates that Fenton oxidation is first order with respect to the organic concentration. The degree of oxidation is dependent upon the dosage of H2O2 and Fe2+. Because H2O2 and Fe2+ can also react with hydroxyl radicals, neither of them should be overdosed if maximal reaction rate is to be achieved. Experiments have been conducted to obtain rate constants for three different chloroethylenes and chloroethane. It is found that the model is valid only for uns...

Thermal degradation of p-nonylphenol formaldehyde epoxy resins

Epoxy resins synthesized from p-nonylphenol formaldehyde novolac resins in reaction with epichlorohydrin have been studied by thermogravimetry, differential thermal analysis and pyrolysis in combination with gas chromatography. The epoxy resins investigated in the range of temperatures between 200 and 600° show a complex degradation mechanism. The complexity of the reaction increases passing from the liquid resins to the solid resins, when the apparent thermal stability increases too. The organic decomposition products analysed include gases and liquids. They consist of C 1-C 4 saturated and unsaturated aliphatic hydrocarbons, carbonylic compounds, ethers, aromatic hydrocarbons, phenol, cresols and higher phenols, respectively. Phenol and cresols are the main decomposition products evolved at temperatures below 350°, while content of aromatic hydrocarbons becomes importantly at temperatures between 400 and 600°.

Synthesis of 1,4-Diketones by Reaction of Bicyclic Lactams Derived from 4-Oxoalkanoic Acids with Organolithium Compounds

Bicyclic lactams obtained from ethyl 4-oxoalkanoates and 2-aminoethanol add saturated and unsaturated aliphatic lithium compounds forming the corresponding 1,4-diketones in 41-61% yield after acidic hydrolysis.

Thermal decomposition of polystyrene: Volatile compounds from large-scale pyrolysis

In order to document volatile compounds, some of which are potentially toxic, generated during large-scale commercial processes or fires, 210 mg of a polystyrene (PS) sample were degraded in a Pyrex® pyrolysis unit at 300 °C in air or nitrogen. The volatiles were desorbed with hexane from an enriched glass cold trap, following cooling in liquid nitrogen, and analysed by GC and GC/MS on a 25 m SE-54 column using splitless-mode injection. Temperature-programmed retention indices using C 7C 36 n-alkane standards were calculated and used to identify compounds common to decomposition in air and nitrogen. Varying proportions of chiefly phenyl-substituted saturated or unsaturated aliphatic compounds of up to 12 carbon atoms in chain length and molecular weight in the range 92–430 were found. The compounds also included a number of oxygen-containing compounds in the form of alcohols, aldehydes and ketones. Taken together, air and nitrogen decomposition produced at least 190 compounds, with at least 45 of these common to decomposition in both atmospheres. Most of the compounds occurred in small relative yields.

ChemInform Abstract: ESR Studies on Nitrogen‐Centered Free Radicals. Part 34. Addition of a Sulfonamidyl Radical to Unsaturated Aromatic and Aliphatic Hydrocarbons.

AbstractThe reaction of the title radical (II), generated by thermal dissociation of (I), with the unsaturated aromatic hydrocarbons (IV), (VIII), styrene and acenaphthylene, as well as with the unsaturated aliphatic compounds (XI), cyclohexene and 1‐butene are studied and compared with analogous reactions of the more stabilized radical (III) described previously.

Structure and Sensory Analyses of Tainting Substances in Finnish Freshwater Environments

GC/MS/SNIFF/TASTE methods have been used in Finland to identify the causes of three tainting problems in water and one in fish nets. Structure determination was often verified by comparison with authentic compounds. Algal growth was implicated to be the source of geosmin and MIB in river water in Northern Finland and was associated with the appearance of tainting problems in raw water and reservoir water in Åland county. Terpenoids (e.g. camphor), degradation products of natural lipids (e.g. aldehydes, ketones and unsaturated aliphatic compounds) and volatile organohalogen compounds were frequently found in contaminated water but showed minor tainting effects compared to geosmin and MIB. Di-tert.-butyl-p-cresol and chlorobenzene also produced only minor tainting effects.

A stereoselective synthesis of dialkylaminomethyl substituted halobutadienes via amine induced ring-opening of thiophene-1,1-dioxides

2,5-Dimethylthiophene-1,1-dioxide and 3-chloro-2,5-dimethy1-thiophene-1, 1-dioxide react with aqueous piperidine at room temperature in a Michael addition fashion to give respectively 2,5-dimethyl-3-piperidino-trans-2, 3-dihydrothiophene-1,1-dioxide and 3-chloro-2,5-dimethyl-4-piperidino- trans -4, 5-dihydrothiophene-1,1-dioxide in good yields. The reaction of 3-chloro- and 3-bromo-2,5-dimethylthiophene-1, 1-dioxide with piperidine, pyrrolidine and morpholine at 100 °C in toluene on the other hand gave only one of the four possible isomeric dialkylaminomethyl-substituted hatobutadienes as main products and dialkylamino-substituted cis -2,3-dihydrothiophene-1,1-dioxides as by-products. Possible reaction paths are discussed. This useful preparation of dialkylaminomethyl substituted halobutadienes is another example of the synthetic strategy using thiophenes for the regio- and stereospecific syntheses of highly functionalized unsaturated aliphatic compounds. This paper is dedicated to Professor Hans Wynberg on the occasion of his sixty-fifth birthday.

Analysis of nutmeg oil using chromatographic methods

Various chromatographic methods were used for the analysis of nutmeg oil. In addition to the fourteen known monoterpene hydrocarbons, a, p-dimethylstyrene has been identified together with sixteen monoterpene alcohols, seven esters and eight sesquiterpene hydrocarbons. The occurrence of the missing trans-isomer of p-menth-2-en-1-ol and a bifunctional derivative of the same type ( trans- p-menth-2-ene-1,4-diol) are of special interest. Besides the terpenoid constituents, two unsaturated aliphatic compounds, namely, ( E)-3-methyl-4-decen-1-ol and its acetate, were detected for the first time in a natural substrate.

The pyrolysis of cellulose derivatives

AbstractThe thermal degradation in vacuo of ethyl cellulose and cellulose acetate in the form of very thin films or bulk material between 230° and 320°C has been studied. With the ethyl cellulose films, volatilization (as measured by weight loss) was a first‐order process up to about 50% reaction, with an activation energy of 208 kJ/mole. This is about the same as that associated with the initial drop in intrinsic viscosity of the solid during bulk pyrolysis, in which very high molecular weight material, probably crosslinked, was formed at a later stage. The volatile products from ethyl cellulose included H2O, CO, CO2, C2H4, C2H6, C2H5OH, CH3CHO, unsaturated aliphatic compounds, and furan derivatives. Acetic acid and acetyl derivatives of D‐glucose were produced from cellulose acetate. It is suggested that the polymers degrade by radical chain mechanisms, and a number of possible elementary steps are proposed.

Degradation of compounds containing carbon atoms by photooxidation in the presence of water.

It was shown that all compounds containing carbon atoms, tested in this study, were degraded by the coincident influence of light, oxygen (air), and water. By this photooxidation, saturated as well as unsaturated aliphatic and aromatic compounds, monomeric, polymeric and high polymeric compounds were degraded and the carbon atoms of these compounds as well as carbon itself in form of amorphous carbon or diamond, were converted to carbon dioxide, if dispersed in water or together with water as very small solid, liquid, or gaseous particles. As such conditions occur extensively in nature, it was concluded that this degradation of organic substances is of great importance in nature, in addition to microbial and enzymatic degradation. This photooxidation further represents a possibility for pollution control to prevent damage to environment by degrading organic substances which are either slightly soluble or practically insoluble in water, as well as compounds which will not be destroyed by microbial and enzymatic degradation.

ChemInform Abstract: THE CYCLOPROPANATION OF SILYL ENOL ETHERS. A POWERFUL SYNTHETIC TOOL

AbstractDer Artikel befaßt sich mit verbesserten Simmons‐Smith‐Reaktionen, der Cyclopropanierung von Silylenolaten gesättigter Aldehyde und Ketone sowie der Synthese von Hydroxybicyclo(n,1,0)alkenen.

ChemInform Abstract: INTERRELATIONS OF UNSATURATED ALIPHATIC COMPOUNDS PART 1, GENERAL CONSIDERATIONS

Chemischer InformationsdienstVolume 6, Issue 19 Preparative Organic Chemistry ChemInform Abstract: INTERRELATIONS OF UNSATURATED ALIPHATIC COMPOUNDS PART 1, GENERAL CONSIDERATIONS J. F. ARENS, J. F. ARENSSearch for more papers by this author J. F. ARENS, J. F. ARENSSearch for more papers by this author First published: May 13, 1975 https://doi.org/10.1002/chin.197519123AboutPDF ToolsRequest permissionExport citationAdd to favoritesTrack citation ShareShare Give accessShare full text accessShare full-text accessPlease review our Terms and Conditions of Use and check box below to share full-text version of article.I have read and accept the Wiley Online Library Terms and Conditions of UseShareable LinkUse the link below to share a full-text version of this article with your friends and colleagues. Learn more.Copy URL Share a linkShare onFacebookTwitterLinked InRedditWechat No abstract is available for this article. Volume6, Issue19May 13, 1975 RelatedInformation

The cyclopropanation of silyl enol ethers. A powerful synthetic tool

Abstract

UV photoelectron spectra and sum rule consideration

Abstract He(l) photoelectron spectra are presented for various planar unsaturated aliphatic compounds such as mono- and di-methyl substituted ethylenes, alkyl aldehydes, chloro-substituted aldehydes, ketones and alkyl acids. Each photoelectron spectrum is resolved into individual bands by considering the band shape, the relative intensity and the number of p-type localized MO's (LO's). The sum rule previously proposed on vertical ionization energies by the present authors is applied to the photoelectron bands associated with out-of-plane LO's. In each compound, a partial sum P (a″) is obtained over all the out-of-plane LO's and it is shown that the calculated P (a″) value is in good agreement with the experimental one which may be obtained by an appropriate sum of vertical ionization energies with negative signs.

Interrelations of unsaturated aliphatic compounds I. General considerations

AbstractGraphs depicting the interrelations of unsaturated systems (eliminations, additions, substitutions and isomerizations) are presented.Such graphs are suitable frameworks for interrelation studies, especially for tele reactions (a large group of reactions occurring at the ends of conjugated systems and involving only a change of hybridization of the terminal atoms).

Electronic absorption spectra of ion radicals and their molecular orbital interpretation. IV. Anion radicals of aromatic and unsaturated aliphatic carbonyl compounds

Electronic absorption spectra of ion radicals and their molecular orbital interpretation. IV. Anion radicals of aromatic and unsaturated aliphatic carbonyl compounds

Chapter 16. Aliphatic compounds. Part (i) Unsaturated aliphatic compounds

The first page of this article is displayed as the abstract.

Catalytic Activity of Iron Pentacarbonyl in the Hydrogenation of Unsaturated Aliphatic Compounds

Author could prove that the catalyst species in the hydrogenation by iron pentacarbonyl is a homogeneous one by the, following experimental results that a glycerid and its methylester could be hydrogenated with same rate and selectivity and that the system which contains colloidal iron formed by thermal decomposition of iron pentacarbonyl in saturated fatty acid ester at 250°C in hydrogen atmosphere displayed no catalytic activity.In view of the fact that monoene was reduced with same initial rate as diene and also the catalyst was decomposed more rapidly in monoene, it seemes reasonable to assume that the π-diene iron tricarbonyl complex is not an essential catalyst type but a stabilized type of catalyst species. In as much as the hydrogen-uptake by diiron enneacarbonyl and triiron dodecacarbonyl began at same temperature as iron pentacarbonyl, the reduction process which proceeds through unstableπ-mono-ene iron tetracarbonyl complex is deniable.Great value in activation energy of about 60 kcal at 180-200°C suggests that the rate determining step in this hydrogenation is thermal- and partial-decomposition of stable iron pentacarbonyl.The hydrogenation is strongly obstructed by addition of pyridine or free fatty acid and only isomerzation is accelerated. In the latter case the catalyst was decomposed into iron soap. Obstruction by hydroxyl group was not so remarkable.Upon discussion of these data, it seemed reasonable to assume that the active catalyst species is a type of Fe (CO)3, which will be then thermally accelerated to takeup hydrogen from proper hydrogen sources, i.e. molecular hydrogen or active methylene group, and acts as iron corbonyl hydrid such as H2Fe (CO)3.

Studies on the Relation of Chemical Structure to Plant Growth-Regulator Activity in the Pineapple Plant IV. Hydrazine Derivatives, Compounds with an Unsaturated Aliphatic Moiety and Miscellaneous Chemicals

1. Results of tests with 39 hydrazine derivatives, 30 compounds with an unsaturated aliphatic moiety, and 117 miscellaneous compounds for induction or inhibition of flowering and toxicity to the pineapple plant are given. In addition, the split pea-stem curvature test results are listed for many of the materials. 2. Ethylhydrazine, sym-diethylhydrazine, β-hydroxyethylhydrazine, unsym-bis-(β-hydroxyethyl)hydrazine, 2-hydroxyethyl N-(2-hydroxyethyl)carbazinate, and 2-(2-hydroxyethyl)semicarbazide were the only hydrazine derivatives which forced pineapple plants to flower. The latter two compounds were not active in all tests. 3. Acetylene, ethylene, and propylene were the only unsaturated aliphatic compounds which forced. Several fairly simple modifications of these compounds eliminated their forcing property. 4. A number of compounds with the functional groups named, and several of the miscellaneous compounds, were in some measure inhibitory to flowering or toxic to the pineapple plant, but it is pointed out that a non-toxic inhibitor of flowering has not yet been developed which is sufficiently effective for commercial usage.