Zur Molekülverknüpfung mit Schwefelchloriden. V. Die Reaktion von Dichlorsulfan mit Allyl-phenyl-äthern. Eine Synthese für 3-Chlormethyl-2,3-dihydro-1,4-benzoxathiine durch intramolekulare Sulfenylierung

Molecule Linkage by Sulfur Chlorides. V. The Addition Reaction of Dichlorosulfane with Allyl-phenyl-ethers. A Synthesis for 3-Chloromethyl-2,3-dihydro-benz-1,4-oxathiines via Intramolecular Sulfenylation Intermediates in the reaction of dichlorosulfane (sulfur dichloride) with allylphenyl-ethers are sulfenyl chlorides (1:1 adducts). The sulfenyl chlorides with anti-Markovnikov-structure cyclize at the activated aromatic nucleus via intramolecular sulfenylation to 3-chloromethyl-2,3-dihydro-benz-1,4-oxathiines.     

Zur Molekülverknüpfung mit Schwefelchloriden. VI. Die Reaktion von Dichlorsulfan mit Thiocarbamidsäureestern

Molecule Linkage by Sulfur Chlorides. VI. The Reaction of Sulfur Dichloride with Thiocarbamic Acid Esters Sulfur dichloride reacts with thiocarbamic acid esters to form aminoacyl trisulfides. The reaction of sulfur dichloride with unsaturated thiocarbamic acid esters yields heterocycles of the 2-thiazolidinon and 3-dithiazinon type.     

Zur Molekülverknüpfung mit Schwefelchloriden. X. Bis(arylamino-chloralkyl)-sulfane aus N-β-Methallyl-N-tosyl-anilinen und Schwefeldichlorid

Molecule Linkage by Sulfur Chlorides. X. Bis(arylamino-chloroalkyl)-sulfanes from N-β-Methallyl-N-tosyl-anilines and Sulfur Dichloride Reactions of differently substituted N-β-methallyl-N-tosyl-anilines 1 with sulfur dichloride yield bis(arylamino-chloroalkyl)-sulfanes 2 and 3 and dihydrobenzo-1,4-thiazines 4 . The structural assignment of the products 2 and 3 was carried out by mass spectroscopy and ¹H-n.m.r.-spectroscopy.     

Zur Molekülverknüpfung mit Schwefelchloriden. IV. Die Addition von Dichlorsulfan an Allyl-phenyl-äther. Anti-Markovnikov-Struktur der 1:2-Addukte

Molecule Linkage by Sulfur Chlorides. IV. The Addition Reaction of Dichlorosulfane with Allyl-phenyl-ethers. Anti-Markovnikov-Structure of the 1:2 - Adducts Allyl-phenyl-ethers react with dichlorosulfane (sulfur dichloride) to anti-Markovnikov-adducts. This was demonstrated by the ¹H-n.m.r. spectra and dehydrohalogenation of the isolated bis-(β-chloroalkyl)-thio ethers.     

Zur Synthese von Octahydrochinazolinonen und deren Reaktion mit Persäure

The Synthesis of Octahydroquinazolinones and their Reaction with Peracid By reaction of cyclohexanone-2-carboxamide with ammonia and aldehydes, octahydroquinazolinones 2a–f , and with Schiff bases octahydroquinazolinones 3a–c are formed. 2-Hydroxycyclohexanone-2-carboxamide forms with ammonia and butyraldehyde the hydroxyocta-hydroquinazolinone 4 . Compound 2e reacts with monoperoxiphthalic acid to the hydroxyoxaziridine 5e which reacts with alkali hydroxide to compound 6. 8 yields with peroxy acid the hydroperoxy epoxide 9 .     

Elektrokatalytische Cyanomethylierung von Azomethinen: Eine neue Synthese für β-Aminonitrile

Electrocatalyzed Cyanomethylation of Azomethines: A New Synthesis for β-Aminonitriles Certain Schiff-bases ( 2–7 ) react in acetonitrile ( 1 ) at a Hg-cathode in a new electrocatalyzed cyanomethylation method in good yields without side-products to β-aminonitriles ( 2a–7a ). The synthesis is initiated by an electrochemical deprotonation of 1 by azomethine-radical anions in catalytical amount to acetonitril anions (B⁻). During nucleophilic reaction of B⁻ with 2–7 up to its complete consumption, the cyanomethylation synthon B− is regenerated in a cyclic, self-reproducing process. Quantum chemical calculation in context with cyanomethylation product analysis permit mechanistical insights and exact prediction of suitable azomethines and coupling position for B⁻.     

Synthese von Heterocyclen mit Hydroxymethylenketonen. XIV [1]. Zur Regioselektivität der Reaktion von Acetylacetaldehyd mit Tryptamin

Synthesis of Heterocyclic Compounds with Hydroxymethylene Ketones. XIV. Contribution to the Regioselectivity of the Reaction of Acetoacetaldehyde with Tryptamine The range of substitution products of tryptamine with acetoacetaldehyde as substituent at the basic or the indole nitrogen ( 2, 3 ) is completed by a product containing the substituent in the indole α-position ( 5 ). It is formed by ring opening of the tetrahydro-β-carboline 4 . The reaction conditions are commented and the ¹H-NMR spectra comparatively discussed. The synthesis of the azocino-indole 7 is described.     

Peptide. XXV. Synthese von Bradykinin-Analoga und Partialsequenzen mit Tyrosin für Elektronenspinresonanz-und Fluoreszenzuntersuchungen

Peptides. XXV. Synthesis of Bradykinin Analogues and Partial Sequences with Tyrosine for Electron Spin Resonance and Fluorescence Studies The syntheses of [5-tyrosine, 6-glycine]-, [8-tyrosine, 6-glycine]-, [5,8-Di-tyrosine, 6-glycine]-bradykinin, and the C-terminal partial sequences are described. The analogues have been labelled with the dansyl group or an aminoxyl radical, respectively.     

Verwendung von 2-Furaldehyd für die Synthese von selbstlöschenden Polyurethanwerkstoffen

New Utilization Possibility of Furfural for the Synthesis of Self-Extinguishing Polyurethane Resins A new method for the conversion of furfural into heptane-1, 4-diol, 3, 5-dichloroheptane-1, 4-diol as well as 3, 5-dibromoheptane-1, 4-diol is presented, and the possibilities of applying of two last alcohols for the syntheses of self-extinguishing polyurethane resins are discussed. In addition, a method for the preparation of ethyl 3, 5-dichloro-4-keto- and 3, 5-dibromo-4-ketoheptanoate is described.     

Cyclofunktionalisierung von 2-Allyl-phenolen mit Schwefelchloriden. 2-Arylthiomethyl-2,3-dihydrobenzofurane aus 2-Allyl- und 2-Methallyl-phenolen und Arylsulfenylchloriden

Cyclofunctionalization of 2-Allyl-phenols with Sulfur Chlorides: Synthesis of 2-Arylthiomethyl-2,3-dihydrobenzofurans by Reaction of 2-Allyl- and 2-Methallyl-phenols, Respectively, and Arylsulfenyl Chlorides Reactions of acetylamino substituted 2-allyl-phenols ( 1 and 2 ), and 2-methallyl-phenol ( 6 ), respectively, with different arylsulfenyl chlorides ( 3a—d ) yield the products of a cyclofunctionalization 5- or 7-acetylamino-2-arylthiomethyl-2,3-dihydrobenzofurans ( 4a–d ) or ( 5a–d ) and 7-acetylamino-2-arylthiomethyl-2-methyl-2,3-dihydrobenzofurans ( 7a–d ). The compounds 7 are the first examples of cyclofunctionalization of 2-methallylphenols by means of sulfur chlorides. The identification of the products was carried out by mass spectrometry, ¹H-n.m.r. spectroscopy and elemental analysis.     

Synthese von Cyclobutan durch Dehalogenierung von 1,4-Dihalogenbutanen mit Alkalimetalldämpfen. Zur Relation von radikalischen und metallorganischen Reaktionskanälen

Synthesis of Cyclobutane by Dehalogenation of 1,4-Dihalogenbutane in Alkali-Metall-Bathway. The Relation of Radical and Metallorganic Reaction-channels. Gasphase dehalogenation of 1,4-dichloro-, 1-chlor-4-bromo, 1,4-dibrombutanes and 1,4-dibrompentane by Na/K vapors produces cyclobutane resp. methylcyclobutane with selectivities of resp. 55.5, 46.7, 32.0 and 17 moles/100 moles. Side products of the reaction are ethylene and hydrogen, yields of which increase with increasing temperature and rising degree of substitution of chlorine by bromine. A mechanism is discussed in which the initiation step is the generation of halobutyl radicals of the type H₂Ċ (CH₂)₂ CH₂X (X = Cl, Br) which are reacting further in two ways – by formation of tetramethylenediradical, splitting off the second halogen atom, or by the formation of the metallorganic compound 1-kalium-4-halogenbutane, which further cyclisize to cyclobutane splitting off KX. Using some methods of theoretical chemistry such as quantumchemical calculations based on ab initio (STO-3G) and semiempirical (AM1) structures, on the relative energies of conformeres of halogenbutylradicals and on models of the metallorganic intermediates, but also by conformation calculations of the content of rotation isomers of the intermediate formed, the correlation between the two reaction channels in dependence of the type of halogen was estimated. The calculations showed, that only about 20% of cyclobutane are generated by the radical pathway. The high predominance of the metallorganic channel in the case of 1,4-dichlorbutaneis caused by the high lifetime of chlorobutyl radicals in comparison with his bromoanalogues.     

Darstellung und Reaktionen von β-Oxosulfenylchloriden. II. Direkte Chlorsulfanylierung von disubstituierten Acetaldehyden mit Schwefeldichlorid

Preparation and Reactions of β-Oxosulfenyl Chlorides. II. Direct Chlorosulfenylation of Disubstituted Acetaldehydes by Sulfur Dichloride The reaction of dialkylacetaldehydes ( 1a , b ) with sulfur dichloride yields the corresponding β-oxosulfenylchlorides ( 2a , b ). Examples for addition- and substitution-reactions of 2a , b are described.     

Oligosiloxane mit funktionellen Gruppen. II Reaktion von 1,4-Bis(trimethylsiloxy)-but-2-en mit H-Silanen in Gegenwart von Hexachloroplatin-säure

Oligosiloxanes with Functional Groups. II. Reaction of 1.4-Bis(trimethylsiloxy)-but-2-ene with H-Silanes in the Presence of Hexachloroplatinic Acid The synthesis of silicon-modified butane-1.4-diol derivatives by the hydrosilylation of 1.4-bis (trimethylsiloxy) but-2-ene (1) is described. Under the conditions of the hydrosilylation 1 is isomerized with high selectivity. At a temperature above 150°C hydrosilylation and isomerization take place simultaneously.