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 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 NN-Dihalogenperfluoralkanaminen mit Schwefel und Schwefelderivaten

Reactions of NN-Dihaloperfluoroalkaneamines with Sulfur and Sulfur Derivatives Reactions of NN-Dihaloperfluoroalkaneamines R_fNX₂ (R_f = CF₃, C₂F₅; X = Cl, Br) with S₈, S₄N₄ and A = SX₂ (A = R_fN, O) are described. The products isolated are: Sulfurdihalideimides R_fNSX₂ (R_f = CF₃, C₂F₅; X = Cl, Br), Sulfurdiimides R_fNSNR_f and Bis(sulfurdiimido)sulfides (R_fNSN)₂S(R_f = CF₃, C₂F₅). Thionylimides R_fNSO were not obtained in preparative quantities.     

Über die Reaktion von Phosphorpentachlorid mit den BF3-Addukten primärer Amine

Reaction of CH₃NH₂ · BF₃ and PCl₅ yields CH₃N(PCl₃)(BCl₃), (I), the behaviour of which to PCl₅, pyridine and H₂S is described. By using smaller amounts of PCl₅, CH₃N(PCl₃)(BCl₂F) (VI) is obtained. C₆H₅NH₂ · BF₃ reacts with PCl₅ to give C₆H₅N(PCl₃)(BCl₃) (IX). Physical data, especially the NMR spectra of the new compounds, are given and discussed.     

Über die Reaktion von Phosphorpentachlorid mit BF3 · NH3

Phosphorus pentachloride reacts with BF₃ · NH₃ to give [Cl₃P?N? PCl₃][BCl₄](Va). Mechanism of formation and chemical behaviour to SO₂ and H₂S are described, followed by a presentation and discussion of the ³¹P, ¹⁹F, and ¹¹B NMR spectra of the adducts formed by P₂NOCl₅ and BF₃, BCl₃, and PF₅, respectively.     

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 Phosphorpentachlorid mit den BF3-Addukten sekundärer und tertiärer Amine

Reaction of F₃B · NH(CH₃)₂ with PCl₅ yields [(CH₃)₂NPCl₃][BCl₄] (I), which can also be obtained by reaction of [(CH₃)₂NBCl₂]₂ with PCl₅. In BF₃ · N(CH₃)₃ the fluorine atoms are exchanged with chlorine atoms, by PCl₅, ³¹P, ¹⁹F, and ¹¹B-NMR spectra of the reactions products are described and discussed.     

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 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 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 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 die Umsetzung von 1-Phenylpyrazol mit Äthylmagnesiumbromid. 8. Mitteilung über Grignard-Reaktionen [1]

In contrast to butyllithium, ethylmagnesium-bromide reacts with 1-phenyl-pyrazole exclusively by deprotonation, at the ortho position of the phenyl-ring. With nitriles the intermediate 2-(1-pyrazolyl)-phenylmagnesiumbromide gave good to excellent yields of 1-(2-aroyl or 2-hetaroyl-phenyl)-pyrazoles (Table 1, compounds 5a – 5i ); with ketones the corresponding methanol derivatives (Table 2, compounds 6a – 6c ) were found, whilst CO₂ yielded the corresponding 1-(2-carboxyphenyl)-pyrazole ( 3 ). Surprisingly enough, 1-(o-bromo-phenyl)-pyrazole and magnesium did not yield a single product, but a mixture of 3 compounds, which on reaction with 4-benzoylpyridine gave the three alcohols 19 , 20 and 21 .     

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 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 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.