Mehrfunktionelle N-Tenside. I. Nucleophile Substitutionen an Bischlornitrosoverbindungen. 1. Reaktionen mit Aminen,Mercaptanen und Natriumazid

Polyfunctionalized N-Tensides. I. Nucleophilic Substitutions with Bischloronitrosocompounds. 1. Reactions with Amines, Mercaptans and Sodium Azide Chloronitrosation of alkenes gives bischloronitrosocompounds 1 , which react with amines to α-aminooximes ( 2 and 4 ), with mercaptans to α-alkylthiooximes 11 , and with sodium azide to α-azidooximes 8 . Reduction with LiAlH₄ gives vicinal substituted diamines ( 6 , 7 , 10 ) from α-amino-or α-azidooximes ( 2 , 4 , 8 ) and β-alkylthioamines 13 from α-alkylthiooximes 11 . The determination of E- or Z-configuration in the α-substituted oximes is discussed.     

Nucleophile Substitutionen an Bischlornitrosoverbindungen. III. Reaktionen mit Salzen und Estern der Dithiocarbazinsäure sowie der N-Phenyldithiocarbazinsäure

Nucleophilic Substitutions with Bischloronitroso Compounds. III. Reactions with Salts and Esters of the Dithiocarbazinic Acid and the N-Phenyldithiocarbazinic Acid Bischloronitroso compounds 1 react with salts of the dithiocarbazinic acid to give S-(β-oximinoalkyl)-esters of the dithiocarbazinic acid. The esters easily cyclise to the corresponding 1,3,4-thiadiazine-2-thiones. Esters of the dithiocarbazinic acid lead to 2-alkylthio-1,3,4-thiadiazines. The structure of possible tautomeres follows from i.r.-, u.v./vis- and n.m.r.-spectra.     

Nucleophile Substitutionen an Kohlensäurederivaten. XII. Kinetik und Mechanismus der Reaktion von N-Nitro-N-alkylurethanen mit primären aliphatischen Aminen

Nucleophilic Substitutions to Carbonic Acid Derivates. XII. Kinetics and Mechanism of the Reaction of N-Nitro-N-alkyl-urethanes with Primary Aliphatic Amines The aminolysis of N-alkyl-N-nitrourethanes takes place, as the kinetical studies demonstrate, by means of several consecutive steps. The nucleophilic attack of the amine (first step; reaction B), as well as the proton-transfere (second step; reaction C), are quick pre-equilibres, followed by the slow, rate-determining elimination of the nitramino-group (reaction D). During the deprotonation, an intermediate with two to the nitramino-group antiperiplanar orbitals is formed, providing the necessary mesomeric assistance of the elimination.     

Eigenschaften,Anwendungsgebiete und physiko-chemische Untersuchungen von Polyethercarbonsäuren und ihren Salzen

Properties, Fields of Application and Physicochemical Research of Polyether Carbon Acids and their Salts There is a wide scope of application for polyether carbon acids as washing agents, detergents, body shampoos, emulsifiers for naphtha and as resources in the textile, printing, paper, plastic, metal and pharmaceutic industry because of the properties of these products, such as very good solubility even in aqueous inorganic salts solutions, indifference to hardness salts and hydrolysis, nontoxicity as well as a good soil-suspending power. A comprehensive compilation report of patents and scientific literature is presented in this paper. Relationships between the structure and the effect of selected polyether carboxylates are interpreted by own physicochemical research.     

Radikalreaktionen an N-Heterocyclen. XI [1] Reaktionen von 3-Methyl-pyrazolin-5-onen mit Phenoxyl-Radikalen

Free Radical Reactions of N-Heterocyclic Compounds. XI. Reaction of 3-Methyl-pyrazolin-5-ones with Phenoxy Radicals Pyrazolin-5-ones ( 3a–i ) were oxidized with 2,4,6-trisubstituted phenoxy radicals ( 2a–d ) to the corresponding radicals ( 4a–i ), which dimerised or combined with phenoxy radical ( 2a ) depending on the R¹- and R⁴-substituents in ( 3 ). In the case of 3-methyl-1-phenyl-pyrazolin-5-one ( 3f ) the primary radical combination products were not found, but the corresponding quinone methide ( 17 ) and the o-phenol derivative ( 18 ) were isolated. Products and yields have been investigated as a function of mol ratio substrate: oxidant and solvent. The radical combination products ( 7–10 ) could de-tertbutylated in the presence of aluminium chloride or in the presence of trifluoroarcetic acid, forming heterocyclic substituted phenols ( 21 ) and ( 22 ).     

Synthesen mit 1,3-Dithietanen. XIV. Ringumwandlungen von substituierten Dihydropyrazolo[5, 1-b]thiazolcarbonsäureestern

Syntheses with 1,3-Dithietanes. XIV. Ring Transformations of Substituted Dihydropyrazolo [5,1-b]thiazolecarboxylates Dihydropyrazolo[5,1-b]thiazolecarboxylates 2 react with aliphatic amines to give dihydrothiazolo[2,3-g][1,2,4]triazepinecarboxylates 4 . Compounds 2c , d and o-phenylenediamine, o-amino-phenols or o-amino-thiophenol afford substituted ethyl benzimidazol-, benzoxazol- or benzothiazol-2-yl-acetates 6 . Hydrazine hydrate and compounds 2 yield derivatives of ethyl pyrazolidin-4-yliden-4-thiazoline-5-carboxylates 8 .     

Synthesen auf der Basis von 2-Oxoglutarsäure. III [1] Synthese und Reaktionen von (E)-2-Oxoglutaconsäuredimethylester

Organic Syntheses Based on 2-Oxoglutaric Acid. III. Synthesis and Reactions of Dimethyl (E)-2-oxoglutaconate Dimethyl (E)-2-oxoglutaconate 1 obtained by dehydrobromination of dimethyl 3-bromo-2-oxoglutarate reacts with o-phenylendiamine to form the quinoxalin-2(1H)-one 2 , and with phenylhydrazine to yield the 4,5-dihydropyrazole 3 . Furthermore, a Doebner-von Miller-type reaction affords the 8-carboxy quinoline derivative 4 . Finally, addition of bromine leads diastereoselectively to the racemate of dimethyl 3S,4R- and 3R,4S-dibromo-2-oxoglutarate 5 .     

NMR- und IR-spektroskopische Bestimmung des Zahlenverhältnisses von Methyl- und Methylengruppen in Kohlenwasserstoffen,Alkoholen, Carbonsäuren und deren Estern. Besonderheiten bei verzweigten Carbonsäuren,Olefinen und cyclischen Verbindungen

NMR- and IR-Spectroscopic Determination of the Ratio Between Methyl and Methylene Groups in Hydrocarbons, Alcohols, Carboxylic Acids and Their Esters. Special Characteristics of Branched Carboxylic Acids, Olefins and Cyclic Compounds A series of typical examples of compounds from various important classes have been studied in order to compare the ratio of methyl to methylene groups (degree of branching) as determined by NMR- and IR-spectroscopy with the theoretical values. Considerable agreement was found in most of the cases, however, deviations were observed with olefins containing internal double bonds, alcohols, α-methyl branched carboxylic acids and aromatic compounds. The main reasons for such deviations were found out by comparative application of the various methods. The advantage of combined application of both the methods is demonstrated in the analysis of technical products.     

Kristallstrukturuntersuchungen an Fettalkoholen und Fettsäuren mit Elektronen- und Röntgenbeugung I

Studies on Crystal Structures of Fatty Alcohols and Fatty Acids Using Electron and X-Ray Diffraction I For the homologous series of even numbered saturated fatty alcohols from dodecanol (C₁₂H₂₅OH) up to hexacosanol (C₂₆H₅₃OH) the almost orthorhombic unit cells of the β₀₁-modifications could be shown by using electron and X-ray diffraction. Fouriersynthesis based on hkO-reflexes showed the presence of a β₀₂-form which has half the edge length c compared to the β₀₁-modification. Moreover, the eight γ₃- to γ₁₀-modifications of the various alcohols were detected. Unit cell parameters and the chain tilt were determined for all crystal structures. By X-ray diffraction, stearic acid was shown to exhibit five β_n-(n = 2, 4, 5, 8) and seven γ₂- to γ₈-forms. The β_n-forms consist of molecules tilted over the short subcell a_s-axis, whereas in γ_n-forms the molecular chains are tilted over the b_s-axis. All the modifications of alcohols and fatty acids studied have an orthorhombic subcell, while the neighbouring molecules in monomolecular layers are turned to each other at an angle of about 90°.     

Synthese und charakterisierung von stationären phasen auf der basis von mit epoxidiertem polybutadien (PBDE) modifizierten polykieselsäuren. I. Untersuchungen zur oberflächenmodifizierung von polykieselsäuren mit epoxidierten polybutadienen

The surface modification of silicas with epoxidized polybutadienes succeeds completely under optimal conditions of the synthesis with combination of properties of the polymer (functionality, pH-stability) and of the inorganic support (pressure stability, special surface properties). The best results are obtained using epoxidized zeigten unsere Untersuchungen, daß die Reaktionskomposite aus anorganischen Tragermaterialien auf Basis von SiO₂ eine erhohte pH-Stabilitat aufweisen²³. In Fortfuhrung der hier dargestellten Ergebnisse konnten wir zeigen, daß die erhaltenen Reaktionskomposite aufgrund von an der Oberflache vorhandenen und spektroskopisch nachweisbaren Epoxidfunktionen ein hohes Synthesepotential bezuglich ihrer weiteren Modifizierung zu speziellen Anwendungszwecken besitzen. Diese Modifizierungsmoglichkeiten sowie die Ergebnisse der Testung der Materialien in der HPLC bzw. anderen Gebieten des Einsatzes funktionalisierter stationarer Phasen sind Gegenstand weiterer Veroffentlichungen.     

Heterocyclen aus o-Aminoketonen. XXIII [1]. Umsetzung von o-Aminoketonen mit Dicarbonsäuren

Heterocyclic Compounds from 2-Aminoketones. XXIII. Reaction of o-Aminoketones with Dicarboxylic Acids Saturated aliphatic dicarboxylic acids (C₄ C₇ and C₁₀) react with 2-aminobenzophenones in polyphosphoric acid (PPA) to form substituted derivatives of partial hydrogenated benzo[b][1,8]naphthyridines 2a–d and 2-anilino-quinoline-3-alkanoic-acids 5a–h . The heterologous derivatives of glutaric acid — containing S or N instead of β-CH₂ — with aminoketon undergo ring closure to give thiazino- and oxazino[3,2-b]quinolines 2e–h . Aromatic o-dicarboxylic acids with a –CH₂ CO- group react with aminoketones to yield anilinosubstituted 5i or pyrano[b]-condensed quinolines 6 . N,N′-Di-(2-benzoylphenyl)-dicarboxylicacid-diamides 3 with ammonia undergo cyclisation to α,ω-di-(4′phenyl-quinazolinyl-(2′))-alkanes 4 .