Über die Umsetzung von Pertluorisobuten mit Thiazylfluorid und Thiazyltrifluorid

On the Reaction of Perfluoro Isobutene with Thiazylfluoride and Thiazyltrifluoride From thiazylfluoride (1) and perfluoro-isobutene (2) (CF₃)₃C? N?S?N? S? C(CF₃)₃ (4) isr formed in the presence of CsF. With NSF₃NSF₂C(CF₃)₃ (8) is obtained, which isomerizes above 100°C to (CF₃)₃CNSF₂ (9). In contrast to 9, with fluoro Lewis-acids 8 forms 1:1 adducts (CF₃)₃CSF₂N · MF₅ (M = As, Sb (10a), (10b)). In 50% aqueous KOH 9 hydrolyses to give the amine (CF₃)₃CNH₂.     

Über die Umsetzung von Thiazylfluorid mit mehrfunktionellen Stickstoffderivaten

Reaction of Thiazylfluoride with Multifunctional Nitrogen Derivatives From the reaction of NSF 1 with LiN(SiMe₃)R′ (R′ = CMe₃, SiMe₃), linear [e. g. (Me₃C? N?S?N? )₂S ( 11 ), Me₃C? N?S?N? CMe₃ ( 14 ), Me₃Si? N?S?N? SiMe₃ ( 17 ), (Me₃Si)₂N? S? N?S?N? SiMe₃ ( 19 )] and cyclic thiazenes (S₄N₅F ( 22 )) are isolated, (S₃N₄)_n ( 23 ) is obtained in high yield from 1 and 17 (in the ratio 2:1). Possible structures for 23 are discussed; the reaction of 23 with AsF₅ gives S₄N₄ · AsF₅ ( 24 ) in a hitherto unknown modification. Possible reactions of the terminal SN groups are discussed and the structures of 11 and 24 are reported.     

Über die Umsetzung von Cyclophosphanen mit Tetrachlorkohlenstoff und Aminen [1]

The Reaction of Cyclophosphanes with Carbon Tetrachloride and Amines The cleavage of phenylcyclophosphanes with carbon tetrachloride leads to the chloro-trichloromethyl-phosphine 2a ; tetracyclohexycyclotetraphosphine decomposes in the same manner to the diphosphane 3 . Methyl-and ethylcyclophosphanes give with carbon tetrachloride the monoquaternary salts 4c and 4d . The cleavage products 5 , 2d and 6 are also formed. The tris-(amino)-phosphonium salts 7a – j and the chloromethylphosphonium chloride 8a are obtained by reaction of amines with cyclophosphanes and carbon tetrachloride. All phosphonium chlorides are isolated and charakterized as perchlorates.     

Über die Umsetzung von Adipinsäurediamid mit Phosphorpentachlorid

Reaction of Adipic Acid Diamide with Phosphorus Pentachloride The reaction of adipamide (I) with phosphorus pentachloride in a solvent leads to (Cl₃P?NCCl₂CCl₂CH₂)₂ (II). The stages of the reaction are: 1. chlorination of the keto and methylen groups 2. formation of the ? N?PCl₃ group. This result is a supplement of the existing conception about the course of the reaction of carboxylic acid amides with phosphorus pentachloride. The reaction of (I) with PCl₅ without any solvent has been reproduced and the course of reaction has also been investigated. This reaction gives mainly NC(CH₂)₄CN. The resulting product of a careful hydrolysis of (II) is (Cl₂OPN?CClCl₂CH₂)₂. A total hydrolysis gives back (I).     

Über die Umsetzung von Phosphor (III)-fluoriden mit Phenylazid

On the Reaction of Phosphorus(III) Fluorides with Phenyl Azide The reaction of phenyl azide with phosphorus(III) fluorine compounds was found to proceed according to the principle of a Staudinger reaction producing, normally, fluorine-containing N-phenylphosphine imides. From diethylamino difluorophosphine and phenyldifluorophosphine the dimers, [(Et₂N)F₂PNPh]₂ and [PhF₂PNPh]₂, were obtained with phenyl azide. These compounds have previously been prepared by a different route. The compounds were characterized by elemental analysis, determination of the molecular weight, either cryoscopically or by mass spectrometry as well as through their n.m.r. spectra (¹H, ¹⁹F and ³¹P).     

Über die Reaktion von Schwefel mit Aminen und Formaldehyd. Eine neue Methode zur Herstellung von Thioformamiden und Dithiocarbamaten

The reaction of sulfur with primary or secondary amines and formaldehyde has been studied. A simple one step process for the preparation of thioformamides (RR′NCHS; R ? H, R′ ? CH₃, C₂H₅; R ? R′ ? CH₃, C₂H₅; R+R′ ? ? (CH₂), ? (CH₂), ? C₂H₄OC₂H) and the amine salts of N, N-dialkyl-dithiocarbamic acids (R₂NCS₂ · H₂NR₂, R ? CH₃, C₂H₅, C₄H₉; R₂ ? ? (CH₂), ? (CH₂), ? C₂H₄OC₂H) is reported. In addition, the isolation of diethylamidosulfoxylic acid, (C₂H₅)₂NSOH · 1/2 H₂O, the first derivative of a new class of compounds, is described. The physical properties and the ¹H-NMR. spectra of the above mentioned compounds are given.     

Über Chalkogenolate. 113 Umsetzung von Chloramin mit Kohlenstoffdisulfid und mit Methylestern von Dithiocarbamidsäuren

On Chalcogenolates. 113. Reactions of Chloramine with Carbon Disulfide and with Methylesters of Dithiocarbamic Acids The reactions of chloramine with CS₂ and with H₂N? CS? SCH₃, CH₃? NH? CS? SCH₃, and (CH₃)₂N? CS? SCH₃ have been studied. The reaction with the methylester of dithiocarbamic acid gives the known dimethyl perthiocyanate and the reaction with the methylester of N-methyldithiocarbamic acid leads to CH₃S? CS? N(CH₃)? C(?NCH₃)? SCH₃. The latter compound has been characterized by means of electron absorption spectra, infrared spectra, nuclear magnetic resonance spectra (¹H and ¹³C), and mass spectra.     

Über das Auftreten von Monoselenan- und Monotelluran-disulfandiphosphonat bei der Umsetzung von SPO mit Seleno- und Telluropolythionaten

On the Formation of Monoselenane and Monotellurane Disulphane-diphosphonate by the Reaction of SPO with Seleno and Telluropolythionates In the reaction of seleno- and telluropolythionates with SPO, SeS₂P₂O and TeS₂P₂O are formed and are described for the first time. Polysulfphane-diphosphonates, -disulphonates and -phosphonsulphonates occur as side and consecutive products. By evaluation of radiochemical double labelling with the nuclide pairs ³⁵S? ³²P and ³⁵S? ⁷⁵Se, it is possible to identify the products formed and obtain information about the reaction mechanism.     

Über die Umsetzung von Mangan(III) mit Acetylchlorid und die Fällung von Chloromanganaten in Essigsäure

In accordance with spectrophotometric measurements, manganese(III) acetate dihydrate reacts with dilute solutions of acetyl chloride in acetic acid through a 1:1 complex to a red-violet 1:4 compound which is unstable due to the oxidation potential of Mn^III ions. The action of potassium acetate on solutions of Mn^III in acetic acid in presence of a large excess of acetyl chloride leads to a dismutation of managanese(III) and initial precipitation of potassium chloromanganate(IV), K₂MnCl₆. During the reaction of potassium acetate with solutions of manganese(II)/acetic acid/acetyl chloride, under particular conditions, first nonsolvated potassium trichloromanganate(II), KMnCl₃, is formed, which transforms during further addition of potassium ions to tetrapotassium hexachloromanganate(II), K₄MnCl₆.     

Über die Reaktion von Alkalihexafluorosilicaten mit Aluminiumoxid

On Reactions of Alkali Hexafluorosilicates with Aluminum Oxides The reaction of Na- and K-hexafluorosilicates and α- or γ-Al₂O₃ has been investigated. Final reaction products are fluoroaluminates and alumosilicates. The reaction mechanism has been discussed. Influence of reaction parameters like time, temperature, layer thickness, and the effect of admixtures (fluorides, SiO₂) have been regarded. Tablet-reactions show the introduction of reaction by Si? F species.     

Über das Auftreten von Polysulfan-diphosphonaten bei der Umsetzung von Monothiophosphat mit Disulfan-diphosphonat

On the Formation of Polysulphane Diphosphonates by the Reaction of Monothiophosphonate with Disulphane Diphosphonate In acid solution SPO reacts with S₂P₂O forming higher polysulphane diphosphonates. The formation of S₃P₂O and S₄P₂O is proved by evaluation of the double labelling with ³⁵S? ³²P after high paper electrophoresis.     

Über Chalkogenolate. 125. Untersuchungen über N-Cyanformamidinodithiocarbimidsäure 1. Darstellung und Eigenschaften von N-Cyanformamidinodithiocarbimaten,Umsetzung mit Säuren und elementarem Schwefel

On Chalcogenolates. 125. Studies on N-Cyanformamidino Dithiocarbimic Acid. 1. Synthesis and Properties of N-Cyanformamidino Dithiocarbimates, Reaction with Acids and with Elemental Sulfur N-Cyanguanidine reacts with carbon disulfide in the presence of the corresponding alkali metal hydroxide to form N-cyanformamidino dithiocarbimates M₂[S₂C?N? C(NH₂)?N? CN], where M = K and Rb. They react with acids to form and with elemental sulfur to yield . The potassium salt and the methyl compound were isolated. All compounds have been characterized by chemical and spectroscopic methods.     

Über die Reaktivität von Phenylgalliumdiiodid und Methylgalliumdiiodid mit Alkyl- und Arylthiolen

On the Reactivity of Phenyldiiodogallane and Methyldiiodogallane with Alkyl- and Arylthiols Phenyldiiodogallane as well as methyldiiodogallane react with alkyl- as well as arylthiols under formation of the corresponding diiodoalkylthio- and diiodoarylthiogallanes. The reactions of methyldiiodogallane primary lead to the adducts, which can be characterized by ¹H-n.m.r. and i.r. spectra; it is even possible to take hold of some of these adducts for a short time in substance. The ¹H-n.m.r. spectra of some thiogallanes are pointing out an interesting structural phenomenon. I.r. spectra and molecular weights are reported.     

Über die Umsetzung von Dibenzylidensulfamiden mit Aminen

Addition of amines to dibenzylidene sulfamide1 a yields the correspondingSchiff bases3 a, b and monobenzylidene sulfamide2. Reaction of several dibenzylidene sulfamides1 with various lithium-amides gives N¹-substituted N²-benzylsulfamoyl-benzamidines7 a-k via an intramolecular hydride transfer reaction, whereas by treatment of1 a with sodium amide 2-benzyl-3,5-diphenyl-3,4-dihydro-2H-1,2,4,6-thiatriazine-1,1-dioxide8 is obtained, which on hydrolysis yields9 and11. Alkylation products are described, the isomeric products12a/13a and12b/13b are isolated, their structures are confirmed by synthesis, IR and NMR-spectra.

     

Über die Reaktion von Thiophosphoryltrichlorid mit Hexamethyldisilazan

On the Reaction of Thiophosphoryl Chloride with Hexamethyl Disilazane On the basis of a ³¹P n.m.r. spectroscopic study of the reaction of PSCl₃ with hexamethyl disilazane a method for the preparation of Me₃SiNHP(S)Cl₂( 1 ) and the diazadiphosphetidine 2 , [Me₃SiNHP(S)?NSiMe₃]₂ has been developed. These new crystalline compounds have been characterized by i.r., Raman, ³¹P n.m.r. and mass spectroscopy, and their thermal behaviour has been studied. The formation and constitution of 2 are discussed, and its ¹H and ²⁹Si n.m.r. spectra are reported.     

Über die Reaktion von Phenolen mit N-substitutierten Maleinimiden

The Reaction of Phenols with N-substituted Maleinimides Phenoxysuccinimides are formed by the base catalysed addition of phenols to N-substituted maleinimides. In the presence of catalytic amounts of tertiary aliphatic amines yields as high as 90% are obtained. A series of adducts of mono-and di-phenols to mono- and bismaleinimides is described. Pure phenoxysuccinimides are stable compounds but the basic catalysts of their formation give rise to their decomposition into the phenolic component and oligomeric maleinimide. A nucleophilic reaction mechanism both for the formation and the decomposition is discussed. A new crosslinked addition polymer from a diphenol and a bismaleinimide with a surprisingly high heat stability is described.