Untersuchungen über Poly(arylenvinylen)e. XVII [1]. Poly(1,4-phenylen-1,2-diphenylvinylen)

Investigations on Poly (arylenevinylene)s. XVII. Poly(1,4-phenylene-1,2-diphenylvinylene) Soluble poly(1,4-phenylene-1,2-diphenylvinylene) of high molecular mass is synthesized by dehalogenation-polycondensation reaction of 1,4-bis(phenyldichloromethyl)benzene with water-free chromous acetate in a mixture of benzene/dimethylformamide. The absorption and photoconductivity spectra as well as a number of thermal (TGA, Tg) and electrical properties are described. Both the similarity of model reactions as the dehalogenation of diphenyldichloromethane to tetraphenylethylene and the dependence of the molecular mass on the quantity of the reducing agent lead to the conclusion that the above-mentioned polycondensation reaction takes place as a step-growth mechanism.     

Folgeprodukte halogenierter Aldehyde. XVI [1]. Untersuchungen über Chloralammoniak

Derivatives of Halogenated Aldehydes. XVI. Investigations of Chloralammonia N-(1,2,2,2-Tetrachloroethyl)trichloroacetaldimine 8 is formed by heating of chloral-ammonia 2 with thionyl chloride. The reaction of 2 with phosphorus pentachloride in ether leads to a mixture of aldimine 8 , 1,2,2,2-tetrachloroethyl-phosphorodichloridate 5 , N-(1,2,2,2-tetrachloroethyl)-phosphorimidic acid trichloride 6 and N-(1,2,2,2-tetrachloroethyl)-phosphoramidic acid dichloride 7 . From compound 7 , the phosphoramidic acid ester 9 , the substituted phosphoric acid triamide 10 and the N-dichlorophosphoryl trichloroacetaldimine 11 are obtained on treatment with methanol, isopropyl amine or triethyl amine, respectively. Compound 9 is also formed from 6 by reaction with methanol. The data of i. r. spectra are concordant with the assigned structures of the compounds 6–11 .     

Untersuchungen über wirkungsmechanismen von lichtschutzmitteln. 1. mitteilung

From mechanistic considerations upon the probability of quenching-processes in the polymer matrix, it was concluded that there exists the possibility of a singlet oxygen mechanism occuring in the photodegradation of polypropylene. Using the sensitized photooxidation of rubrene, it was shown that compounds known to be light stabilizers are able to deactivate, to a greater or lesser extent, singlet oxygen. It is, therefore, not to be excluded that singlet oxygen plays also a role in the photooxidation of polymers. On the other hand, further experiments have shown that these same compounds can also act as radical scavengers or as hydroperoxide-deactivators.     

Photochemie von Aminoketonen. IV [1]. Synthese von 3-Aryl-pyrrolidinolen-(3) durch Photocyclisierung von β-Amino-propiophenonen

Photochemistry of Aminoketones. IV. Synthesis of 3-Aryl-pyrrolidinols-(3) via Photocyclization of β-Amino-propiophenones Photolysis (λ_irr ≥ 300 nm) of N-benzyl-N-benzoyl-β-aminopropiophenones 6–9 in abs. ether affords a 47–50% yield of N-benzoyl-pyrrolidinols 12–18 . The relative configurations of the diastereomeric 12–18 are determined by ¹H-n.m.r. spectroscopy. The different behaviour of the N-acylated 6–9 in contrast to N,N-dialkyl-β-aminopropiophenones is explained by assumption of a dipol-dipol interaction between the keto and the amido carbonylgroups in the n,π*-excited state.     

Untersuchungen über die Autoxydation von Margarine

Investigations on the Autoxidation of Margarine The authors investigated the influence of storage temperature, packing and of the quality of dispersion on the oxidative stability of margarine. The oxidative stability of margarine is improved with increasing fineness of the dispersion. The autoxidation can be prevented to a great extent by employing low storage temperature and suitable packing material. Packing materials containing traces of heavy metals promote the autoxidation in the upper layer of margarine.     

Untersuchungen über den Einsatz von Rapsextraktionsschrot (Erglu) bei Schweinen

Studies on the Use of Extracted Rapeseed Meal (Erglu) in Feeding Pigs Extracted rapeseed meal of the Erglu variety (low in erucic acid and glucosinolate content) was evaluated as protein feedstuff in growing pigs. In a starting ration (step 0) containing soybean (18%) and barley (72%) the extracted soybean meal was successively exchanged by an equivalent amount of protein from extracted rapeseed meal up to a level of rapeseed meal (24.6%) and barley (65.4%) (step 6). Growth was similar in all experimental groups. However, feed consumption and feed requirement increased with increasing proportions of rapeseed owing to lower content of utilizable energy in extracted rapeseed meal. No effect due to feeding was found with regard to quality of the slaughtered meat, whereas a linear increase in the size of liver and thyroid was found with increasing proportions of rapeseed in the ration.     

Derivate des Phosphorsäure-o-phenylenesters. XV [1]. Synthese von Tris-(o-phenylendioxy)-phosphorat(V)

Derivatives of o-Phenylenephosphate. XV. Synthesis of Tris-(o-phenylenedioxy)-phosphorate(V) The structure of an orthophosphate which had been supposed earlier to represent type 1 , has been proven to be a compound having only one P-nucleus in the molecule, with a penta( 4 ) resp. hexacoordinated ( 5 ) structure depending on the solvent. The triethyl-ammonium salt 8 of this first example of a hexacoordinated phosphoric acid with 6 P O-bonds ( 5 ) is formed simply from tri- als well as from tetra- and pentacoordinated derivatives of phosphorous resp. phosphoric or thiophosphoric acid.     

DIELS-ALDER-Reaktionen. IV. Untersuchungen über die Mischdimerisierung von Cyclopentadien mit Butadien-(1,3)

Diels-Alder Reactions. IV. Studies on the Codimerization of Cyclopentadiene with Butadiene The reaction of cyclopentadiene with butadiene between 120°C and 170°C yields only about 35% exo/endo-2-vinylbicyclo[2,2,1]heptane-(5); 4,7,8,9-tetrahydroindene, dicyclopentadiene and the homodimers of butadiene are formed as inevitable by-products. The parallel and consecutive reactions which take place in the system cyclopentadiene/butadiene were separately studied as far as possible, and the activation parameters were determined. Surprisingly, in the homodimerization of butadiene the activation parameters for the symmetry-allowed formation of 4-vinylcyclohexene and the symmetry-forbidden formation of trans-1,2-divinylcyclobutane and of cyclooctadiene-(1,5) show very similar values.     

Kinetische Untersuchungen über die Autoxidation von Olefinen

Kinetic Studies on the Autoxidation of Olefins The oxidabilities \documentclass{article}\pagestyle{empty}\begin{document}$ {{{\rm k}_{\rm p} } \mathord{\left/ {\vphantom {{{\rm k}_{\rm p} } {\sqrt {2{\rm k}_{\rm t} } }}} \right.\kern-\nulldelimiterspace} {\sqrt {2{\rm k}_{\rm t} } }} $\end{document} at 50°C were determined for 37 olefins, using chlorobenzene as the solvent and azodiisobutyronitril as the initiator. In the group of acyclic aliphatic olefins the oxidability rises with increasing number of alkyl groups bound to the double bond. This is also true for cyclic olefins, but in this case the ring size has also a great influence on the oxidability. So the oxidability decreases from five-ring to eight-ring cycloolefins. Particularly high oxidabilities are found in the case of olefins in which a phenyl group is attached directly to the C C-double bond.     

Untersuchungen zur Sulfochlorierung von Paraffinen. VII. Untersuchungen über die Chlorierung von definierten Alkansulfochloriden

Studies on Sulphochlorination of Paraffins. VII. Studies on the Chlorination of Individual Alkane Sulphochlorides The products of the chlorination of individual C₂–C₆ alkane sulphochlorides were studied by means of ¹³C-n.m.r. spectroscopy. In no case a geminal chloro sulphochloride could be found, and only in very few cases chlorination at vicinal C H-bonds took place. As in the sulphochlorination of alkane sulphochlorides the C H-bonds geminal and vicinal to the sulphochloride group are strongly descativated. The results of ¹³C-n.m.r. analyses were confirmed by the results of gaschromatography of the sulphonic acid dimethyl amides, formed by the reaction of the chlorination mixtures with dimethyl amine.     

Zur Bindungsisomerisierung von Acetylen- und Allen-Kohlenwasserstoffen. II [1]. Kinetische Untersuchungen über die Isomerisierung von Propin und Allen an einem sauren Molekularsiebkatalysator in der Gasphase

About the Bond Isomerization of Acetylenic and Allenic Hydrocarbons. II. Kinetic Studies on the Isomerization of Propine and Allene with an Acidic Molecular Sieve Catalyst in the Gas Phase The gas phase isomerization of propine and allene (propadiene) was studied on a molecular sieve 13X, modified with Ni and Ca, in the temperature range of 108–173 °C with the aid of a close circulation apparatus. The bond isomerization may be considered as an example of a monomolecular, reversible, heterogeneous catalyzed reaction of the type A ⇌ B. For the studied isomerizations the rate equations of the Langmuir-Hinshelwood-type were derived by kinetic analysis of the experimentally obtained dependence of the mole fractions from the residence time. The rate and adsorption constants of the Langmuir-Hinshelwood equations were determined, their physical interpretation was possible.     

Untersuchungen über die toxikologischen Eigenschaften von Waschmittelenzymen

Investigations on the Toxicological Properties of Enzymes Used in Washing Agents Enzymes used in washing agents and enzyme-containing washing agents were tested in animal experiments for their general and local tolerance. The results of these investigations confirm that enzymes employed in washing agents are not toxic. The amounts of enzymes that are added to washing agents do not alter the local tolerance of such products. Similar observations were made in dermatological investigations on testpersons. From the results, it may be concluded that enzyme-containing washing agents do not present any hazard to the health of consumers. The same is also true for allergic reactions. Enzymes used in washing agents do have histamine-and kinin-liberating properties, however, only at such concentration-ranges that are insignificant for the practice.     

Untersuchungen zur Sulfochlorierung von Paraffinen. VI. Untersuchungen über die Sulfochlorierung von definierten Alkylchloriden

Studies on Sulphochlorination of Paraffins. VI. Studies on the Sulphochlorination of Individual Alkyl Chlorides The products of sulphochlorination of individual C₂–C₇ alkyl chlorides were studied by means of ¹H- and ¹³C-n.m.r. spectroscopy. Gaschromatographic determination of the isomers formed was possible after the reaction of the chloroalkane sulphochloride mixture with dimethyl amine in ether. In no case geminal chloroalkane sulphochlorides were formed. Vicinal chlorosulphochlorides are formed, but substitution in greater distance from the chlorine is preferred if possible. Thus higher alkyl chlorides yield only very little amounts of vicinal chloroalkane sulphochlorides. The relative rates of sulphochlorination of alkyl chlorides were determined by competitive reactions.     

Untersuchungen zur Sulfochlorierung von Paraffinen. II. Untersuchungen über die Reaktion von aliphatischen Sulfochloriden mit Nucleophilen

Studies on the Sulphochlorination of Paraffins. II. Studies on the Reaction of Aliphatic Sulphochlorides with Nucleophiles The reaction of sterically pure cis- and trans-4-methyl-cyclohexyl sulphochlorides with dimethyl amine, natrium methylate, and natrium phenolate in each case gives mixtures of the cis- and trans-isomers of the corresponding derivatives of 4-methylcyclohexyl sulphonic acid, which could be separated by gas chromatography. Reaction of cis- and trans-4-methyl-cyclohexyl sulphochlorides with potassium fluoride in DMF/H₂O gives 4-methylcyclohexyl sulphofluoride; the cis- and trans-forms of this compound could not be separated by gas chromatography. If n-propyl or isopropyl sulphochloride react with potassium fluoride in DMF/D₂O; the sulphofluorides which are formed do not contain deuterium. Evidently the reaction of primary and secondary aliphatic sulphochlorides with basic nucleophiles proceeds by an elimination-addition-mechanisms with sulphenes as short-living intermediates, but the reaction with fluoride ions proceeds by an addition-elimination-mechanism.     

Untersuchungen zur Sulfochlorierung von Paraffinen. VIII. Untersuchungen über die Verseifung von definierten Alkansulfochloriden mit Natronlauge

Studies on Sulphochlorination of Paraffins. VIII. Studies on the Hydrolysis of Individual Alkane Sulphochlorides by Sodium Hydroxide The hydrolysis of individual C₁ C₅ alkane sulphochlorides by sodium hydroxide in dioxane/water (1:1) was kinetically studied at 25°C by means of stopped-flow technique, measuring the change of electric conductivity. The rate constants were influenced by steric hindrance, but in all cases were higher than the rate constant for alkaline hydrolysis of benzene sulphochloride, which cannot react according to the elimination-addition (sulphene) mechanism. The reaction enthalpy of the alkaline hydrolysis of four individual alkane sulphochlorides was determined by a simple calorimetric apparatus; the average value amounts to δ_RH = −239 kJ mol⁻¹.