Tumorpromovierende Diterpen-Fettsäureester aus Euphorbia triangularis und Euphorbia cooperi

Tumor-Promoting Diterpenyl Fatty Acid Esters from Euphorbia triangularis and Euphorbia cooperi Three diterpenic diesters were isolated from milk-juice of Euphorbia triangularis and they were identified as 13-isobutyrate (T₁), 13-tiglate (T₂) and 13-(2-methyl-butyrate) (T₃) of the new diterpene 12-desoxyphorbol. Apart from these, a mixture of corresponding 20-acetates (T₁–T₃) could be isolated and characterized. The known crotophorbolon is obtained by alkali-treatment of 12-desoxyphorbol-13-tiglate under energetic conditions. A diterpene-diester and a diterpene-triester were isolated from milk-juice of Euphorbia cooperi and they were characterized as 13-O-isobutyroyl-16-tiglate and ?20-acetate respectively of the new diterpene 12-desoxyphorbol-16-hydroxyphorbol. All the isolated diterpene esters showed more or less pronounced irritation on mice ear. In general, the 20-esters are less effective than the corresponding esters having the free 20-hydroxyl group. Exact knowledge of the isolated esters is significant from the viewpoint of environmental protection, since some of these compounds might possess co-carcinogenic properties as well.     

Neuartige Imidazoline und ihre Derivate aus Fettsäuren und Hydroxyalkylaminen

Novel Imidazolines and Their Derivatives from Fatty Acids and Hydroxyalkylamines Epoxides, derived from terminal and internal olefins, were reacted with ethylenediamine to give N-(vic.-hydroxyalkyl)-ethylenediamines and condensed with fatty acids and aromatic as well as aliphatic mono- and dicarboxylic acids to give 2-imidazolines. Quaternation of the 2-imidazolines yields imidazolinium salts, which, according to their structure, show strong microbiocide properties; they are also of interest as textile auxiliary.     

Anionen-grenzflächenaktive Stoffe aus Aminosäuren und Glycidäthern

Anionic Interfacially Active Agents from Amino Acids and Glycid Ethers After referring to the preparation of interfacially active agents by using amino carboxylic acids, especially sarkosine, experiments on the reaction of alkylene oxides as well as glycid ethers with amino carboxylic acids are described. Saturation concentrations, critical micelle concentrations and corresponding surface tensions (dyn/cm) of the aqueous solutions (0° d. H.) at 20° C are given for the adducts from glycine or sarkosine with octylene-1,2-oxide and n-octyl- or lauryl glycid ether.     

Synthese und Eigenschaften N-acylierter Thiophosphinsäureamide

Preparation and Properties of N-acylated Thiophosphinic Amides N-Acyl-, N-thioacyl- and N-sulfonyl-substituted thiophosphinic amides are prepared by the reaction of metallated acid amides with acid chlorides. The compounds exist as imides and form intermolecular hydrogen bonds. Their pK_a-values were potentiometrically determined and show a considerable acidifying influence of the thiophosphinic residues. Methylation of the imides with diazomethan gives predominantly S-methylesters of imidothiophosphinic acids.     

Cyansäureester. 29. Benzoxazolin-thion-N-imidsäureester und ihre Folgereaktionen

Cyanic Acid Esters. 29. Benzoxazoline-thione-N-imid Esters and Their Consecutive Reactions Oxazoline-thiones-(2) and aryl cyanates react to form the corresponding isoureas 4 . These compounds are remarkably stable against electrophilic reagents. The aminolysis of 4 proceeds two pathways: a transformation of the imid ester residue to the amin and a ring opening reaction by attack of the amin to the CS-bond. The hydrazinolysis causes a ring-transformation of the oxazoline- to the 1,3,4-triazole system.     

Konformation und Rotationsbarrieren substituierter Glyoxylsäureamide

Conformation and Rotation Barriers of Substituted Glyoxylic Acid Amides Semiempirical calculations predict an orthogonal orientation of the carbonyl groups in tertiary glyoxylic acid amides, which is in good agreement with an X-ray structure analysis of 5 . Due to the influence of the α-carbonyl group, the rotation barrier in the substituted glyoxylic acid amides 2a–d, 3a, 3b , and 4–6 (ΔG^#_c = 84–92 kJ mol⁻¹) is about 10 kJ/mol higher than in simple acid amides, as was found by dynamic NMR line shape analysis.     

Fasern und folien aus poly-α-aminosäuren

Poly-α-aminoacid-fibers are protein like. Therefore their behaviour is like the naturally protein fibers silk and wool in some respect. Poly-α-aminoacids are made by thermic or ion-initiated polymerization of the corres- ponding Leuchs anhydrides (N-carboxyanhydrides). Fibers from the polymers are made by wet spinning. In general only from the pure D- or L-form of the aminoacids fiber forming polymers are obtained. Spinnability and the behaviour of the fibers are determined by the conformation of the polymer molecules. For instance the silk like character of Poly-L-alanine is attributed to the/?-pleated sheet conformation, the wool like behaviour of Poly-L-leucine is connected with the α-helical conformation of the Poly-L-leucine molecules. Because of the fact that film-forming ability is essential for spinnability not only fibers but also films are obtained from all these polymers. Moreover, Poly-α-aminoacids with no spannability due to long side-chains with strong interactions may have film forming ability. Besides the interest in producing fibers for textile use, they are also valuable as model substances for physico-chemical investigations on the stabilisation of the conformation by intermolecular forces and steric factors. In the case of Poly-L-alanine the tenacity is somewhat higher and the elongation lower as in the case of bombyx mori silk due to the lack of bulky side-chains being responsible for non-periodic conformations. On the contrary to silk Poty-L-alanine fibers undergo no contraction in LiBr-solutions between 5,4–7.2 mole/l and are absolutely insoluble at higher concentrations up to the boiling point. According to DTA-measurements the temperature of decomposition of Poly-L-alanine is remarkable higher (350°C) than that of silk (280°C). The important role of conformation and side chains for physical and textile behaviour results from the fact that the elongation of the wooly, α-helical Poly-L-leucine is about six times higher than that of Poly-L-alanine in the pleated-sheet conformation. Ionic side-chains like carboxylic groups in Poly-L-glutamic acid influence the physico- chemical behaviour of the fibers drastically. They are pretty soluble in moderate concen- trated electrolyte solutions and show supercontraction like behaviour in neutral and week alkaline solutions of cationactive detergents. As postulated sometimes ago ionic interaction between detergent-ions and ionic sidechains are necessary for this phenomenon. Furthermore the heat stability of Poly-L-glutamic acid fibers are comparable low in respect to Poly-L-alanine and Poly-L-leucinc fibers. As a consequence of the protein-like character of Poly-L-amino acid fibers and films they underlie biological degradation by proteolytic enzymes. For instance copolymers of L-alanine and L-lysine could be degradated by tryptic digestion.     

Cyclische oligomere in polyestern aus diolen und aromatischen dicarbonsäuren

Cyclic oligomers have been separated and determined quantitatively by high pressure liquid chromatography on a number of polyesters of the diol-aromatic dicarbonic acid-type. Percentage of cyclic oligomers is related to the chemical structure of the polyesters as well as to the technology of polycondensations. Main component proved to be the cyclic dimer except in case of poly(ethyleneterephthalate), poly(1,4-dimethylenecyclohexaneterephthalate) and poly(1,4-dimethylenebenzeneterephthalate). Here — due to reasons of ring tension — cyclic trimers are predominant. Separation of stereoisomer cyclic oligomers, resulting from use of a trans/cis-1,4-cyclohexanedimethanol blend, could be achieved. Cyclic oligomers of copolyesters with diolethers, if modified to a low degree, only have one diolether group.     

Isolierung und Strukturaufklärung polyverzweigter Fettsäuren aus Fischöl

Isolation and Structure Determination of the Polybranched Fatty Acids from Fish Oil From a sample of sea fish oil, three saturated polymethyl branched fatty acids could be separated in pure state as methyl esters by using urea adduct, column chromatography and distillation methods. These could be identified as 4,8,12-trimethyl-tridecanoic acid, 2,6,10,14-tetramethyl-pentadecanoic acid and 3,7,11,15-tetramethyl-hexadecanoic acid, with the help of molecular weight determination, ultimate analysis, IR-, NMR- and mass-spectroscopy. The structures could be proved by synthesis. Many other branched chain fatty acids were synthesised for comparison. The synthesis and the infrared spectrums of these compounds are given in details.     

Alkylendiamide und Alkylendiisoimide von Äthyleniminocarbonsäuren und -dicarbonsäuren

Alkylenediamides and Alkylenediisoimides from Ethyleneimino Carboxylic Acids and Ethyleneimino Dicarboxylic Acids Preparation and properties of some alkylenediamides from β-ethyleneiminopropionic acid and ethyleneiminosuccinic acid as well as of two alkylenediisoimides of ethyleneiminosuccinic acid are described.     

Cyansäureester, 27 [1]. Triazino-benzimidazole aus 2-Amino-benzimidazol-1-imidsäureestern und carbonylanalogen Verbindungen

Cyanic Acid Esters. 27. Triazino-benzimidazoles from 2-Amino-benzimidazole-1-imid-esters and Carbonyl Analogic Compounds The Cyclocondensation of 2-amino-benzimidazole-1-imid-esters with aldehydes, carbonic acid anhydrides and isocyanates has been investigated. With aldehydes in the presence of piperidine 4-aryloxy-1,2-dihydro-1,3,5-triazino[1,2-a]benzimidazoles 3 and with carbonic acid anhydrides 4-aryloxy-1,3,5-triazino[1,2-a]benzimidazoles 5 are formed. Isocyanates react with the imid esters to the corresponding 3-substituted ureas 8 which on heating undergo acyl migration of the carbamoyl group followed by cyclocondensation to 4-imino-2-oxo-1,2,3,4-tetrahydro-1,3,5-triazino[1,2-a]benzimidazoles 12 .     

Massenspektrometrische Identifizierung von verzweigtkettigen Fettsäuren und Alkoholen aus Bürzellipiden

Mass Spectrometric Identification of Branched Chain Fatty Acids and Alcohols from Preen Gland Lipids The preen gland lipids of some birds were isolated, the waxes separated and resolved into fatty acid and alcohol fractions. The alcohols were oxidised with chromic acid to form the corresponding fatty acids. After methylation with methanolic HCl, the fatty acid methyl esters were investigated by capillary gas chromatography-mass spectrometry. The fatty acids possess mainly mono-, di- and trimethyl branched structures, the branching positions being located preferentially on C–2/–3/–4/–6, C–2,4/–2,6/–2,8/–3,7 C–2,4,6/–2,6,10 and C–6/C–10 or C–14. The mass spectrometric fragmentations which are significant for the structure elucidation of these fatty acid methyl esters are discussed in detail. The investigations indicate a correlation between the composition of the birds to defined orders of the natural system (chemotaxonomy).     

Diesterwachse und ungewöhnliche Fettsäuren aus Bürzeldrüsenlipiden

Diester Waxes and Unusual Fatty Acids in Lipids of Sebaceous Gland Systematic investigations of lipids of sebaceous gland of birds have shown close relationship between the structure of these lipids and the individual species in the natural system of birds. In almost all the species studied so far the lipids of sebaceous gland consist of wax esters which are made up of unusual fatty acids and alcohols. Thus in the group of passeriformes (sparrows) 3-methyl substituted fatty acids, in the group of strigiformes (owls) 2-propyl and 2-butyl substituted fatty acids, and in the group of columbiformes (pigeons) 3-hydroxy fatty acids are found as constituents of the wax esters. Diester waxes are found in galliformes (hens), columbiformes, limicolae (snipes) and in some members of passeriformes. Unusual constituents of these waxes are alkanediols, 3-hydroxy fatty acids, and alkylhydroxymalonic acids. The structures were elucidated by a combination of GLC and mass spectrometry. Some of the mass spectra are discussed.     

Oxidatives Verfahren zur Herstellung kurzkettiger Carbonsäuren aus ungesättigten Fettsäuren

Oxidative Procedure for Production of Short-Chain Carbon Acids from Unsaturated Fatty Acids For decades, the oxidation of oleic acid to acelaic and pelargonic acid has been carried out in industrial scale by ozone. The high costs of ozone production are a problematical point in this procedure. Thanks to the high selectivity the procedure is today still economic. Efforts to replace the ozone oxidation by an oxygen one haven't yet led to a procedure which can be applied in industry. In this work the oxygen oxidation of oleic acid with aldehyds as intermediary carrier of oxygen is reported.