Darstellung,Kristall- und Molekülstruktur von Triphenylphosphinoxidhydrochlorid (C6H5)3PO · HCl

On Phosphazo Compounds from Nitriles. IV. The Reaction of Tri, Di, and Monochloroacetonitrile with [Cl₃P?N? PCl₃]Cl. Improved Preparation of [Cl₃P?N? PCl₃]Cl Trichloroacetonitrile reacts with P₂NCl₇ to give Cl₃C? CCl₂? N?PCl₂? N?PCl₃ I , dichloroacetonitrile to give Cl₂C?CCl? N?PCl₂? N?PCl₃ II , and chloroacetonitrile to give the ring compound III . Preparation, n.m.r. and mass spectra of the new compounds are described. The mechanism of formation is discussed. An improved procedure for the preparation of P₂NCl₇ is given.     

Untersuchungen über das Reaktionsverhalten von Antimonpentachlorid. III [1]. Zur Reaktion von Antimon (V)-chlorid mit Methylisocyanat

Studies on the Reactivity of Antimony Pentachloride. III. The Reaction of Antimony(V) Chloride and Methylisocyanate Methylisocyanate CH₃NCO reacts with SbCl₅ in boiling CCl₄ by an insertion-reaction to a product of the formula C₅H₆Cl₉N₂O₂Sb I, which has the chlorformamidinium-structure (Cl? C(O)? N(CH₃)? CCl? N(CH₃)? C(O)? Cl)⊕SbCl₆?. Hydrolysis of I yields the heterocycle C₅H₆N₂O₄ II. The reaction with methanol gives (CH₃? NH? CCl? NH? CH₃)⊕SbCl₆? III and (CH₃? NH? CCl? N(CH₃)? C(O)? OCH₃)⊕SbCl₆? IV. The i.r. and Raman spectra of the compounds I, III and IV are discussed.     

Zur Kenntnis der Chemie der Silazane. IV. Über ein Sulfurylphosphazo-silazan

Trichlorophosphazo-sulphurylchloride. Cl₃P?N? SO₂Cl, reacts with heptamethyldisilazane to yield the Si? N? P compound (I) formulated in ?Inhaltsübersicht”?. (I) reacts with PCl₅ or C₆H₅? PCl₄ forming the known 2,2,2,4,4,4-hexachloro-1,3-di-methylcyclo-diphosphazane(II), accompanied by the compound Cl₃P?N? SO₂Cl and C₆H₅? PCl₂?N? SO₂Cl, respectively, which were detected by means of ³¹P-NMR spectroscopy.     

Bildung siliciumorganischer Verbindungen. 98. Umsetzung silylierter Phosphorylide mit PCl3

Formation of Organosilicon Compounds. 98. Reaction of Silylated Phosphorus Ylides with PCl₃ The reaction of Si-substituted phosphorus ylides as Me₂Si(CH₂? SiMe₂)₂C?PMe₃Br 1 , Cl₂Si(CH₂? SiCl₂)₂C?PMe₂Cl 2 , and (Cl₃Si)₂C?PMe₂Cl 3 with PCl₃ yields (Cl₂P)₂C?PMe₂Cl 5 by chlorinating cleavage of the Si-ylid-C bond. Besides 5 also (ClMe₂SiCH₂)₂SiMe₂, (Cl₃SiCH₂)₂SiCl₂, resp. SiCl₄ result from the reaction of 1, 2 and 3 with PCl₃. (Cl₂P)₂C?PMe₂Cl forms colourless crystals, mp. 84°C.     

Bildung siliciumorganischer Verbindungen. XXXIX. Teilchlorierte Carbosilane

1. Photochlorination in CCl₄ of the Si-chlorinated carbosilanes (Cl₃Si? CH₂)₂SiCl₂ and (Cl₂Si? CH₂)₃ leads to totally chlorinated compounds, e. g. (Cl₃Si? CCl₂)₂SiCl₂. After chlorination has started at one CH₂ group, formation of a CCl₂ group is preferred before another CH₂ group is involved into the reaction. Thus preparation of compounds a, b, c is possible. Cl₃Si? CCl₂? SiCl₂? CH₂? SiCl₃ (a) for (b) and (c) (see “Inhaltsübersicht”). SO₂Cl₂ (benzoyl peroxide) as chlorinating agent reacts more slowly, and opens an access to carbosilanes containing CHCl groups such as (d), Cl₃Si-CHCl? SiCl₂? CH₂? SiCl₃ (e). Reactions of compounds (a) to (d) with LiAlH₄ yields carbosilanes with SiH groups, and partially chlorinated C atoms. 2. By the high reactivity of Si? CCl₂? Si groups an exchange of Cl atoms of CCl groups in perchlorinated carbosilanes is possible for H atoms of Si? H groups in perhydrogenated carbosilanes, thus allowing the preparation of compounds containing CHCl and SiHCl groups, e. g. according to Gl.(1) (Inhaltsübersicht). Further reactions, formulated as the last equations in Inhaltsübersicht, are reported as well as the rearrangement of H₃Si? CHCl? SiH₃.     

Über Phosphorstickstoffverbindungen,XXXII. Über Vier- und fünfgliedrige Heterocyclen mit Phosphor,Stickstoff und Kohlenstoff im Ring

On reacting of oxamide with PCl₅ the syntheses of the new N-, C- and pentavalent phosphorus containing heterocycles I and II (see “Inhaltsübersicht”), built up from interconnected four- and fivemembered ring systems, have been achieved. Reaction of N, N′- dimethyloxamide with PCl₃ yields the compound III which may be chlorinated to IV. An intermolecular reaction between the PCl₃- and carbonyl groups of IV gives V. The fivemembered ring systems III and V may each be linked together via N? CH₃ bridges, i. e. via P? N(CH₃)? P and P(O)? N(CH₃)? P(O) units, respectively. N, N′- dimethyloxamide reacts with PCl₅ to form a mixture of fivemembered heterocycles containing trivalent phosphorus (as a PCl group) and chlorinated carbon.     

Bildung siliciumorganischer Verbindungen. 74. Synthese und NMR-Spektren von Si-methylierten und -chlorierten 2,2-Dichloro-1,3-disilapropanen und 2-Methyl-2-chloro-1,3-disilapropanen

Formation of Organosilicon Compounds. 74. Synthesis and NMR-Spectra of Si-methylated and -chlorinated 2,2-Dichloro-1,3-disilapropanes and 2-Methyl-2-chloro-1,3-disilapropanes The compounds me₃Si? CCl₂? Sime_nCl_3?n (n = 1–3; me = CH₃) are synthesized by reaction of me₃Si? CCl₂Li (formed from me₃Si? CCl₂H with n-buLi, bu = butyl) with the appropriate methylchlorosilanes. The compounds Clme₂Si? CCl₂? Sime_nCl_3?n are obtained by analogous reactions of (C₆H₅)me₂Si? CCl₂Li, cleavage of the Si-phenyl group with bromine and conversion of the Si? Br to the Si? Cl group with HCl in PCl₃. The 2-methyl-2-chloro-1,3-disilapropanes are synthesized by lithination of the CCl₂ group of 2,2-dichloro-1,3-disilapropanes, followed by reaction with meI. (Clme₂Si)₂CmeCl is obtained from (C₆H₅me₂Si)₂CCl₂ by reaction with n-buLi to (C₆H₅me₂Si)₂ CClLi, which forms (C₆H₅me₂Si)CClme with meI. Cleavage with bromine to (Brme₂Si)₂CClme and reaction with HCl/PCl₃ leads to the expected compound. The influence of the substitution on the ¹H, ¹³C and ²⁹Si NMR spectra is investigated.     

Carbon-13 NMR spectra of some polychloro hydrocarbons and related compounds

Data derived from the carbon-13 NMR spectra of 37 organic polychloro compounds allow one to identify readily the ? CHCl₂, ? CCl₂? and ? CH₂Cl groups, the ¹³C signals of which are registered in the shift ranges of 67 to 78 (80), 85 to 96 and 38 to 55 (59) ppm (from TMS), respectively, and have the distinctive one bond spin-spin coupling constants ¹J(C? H) 170 to 184 Hz (for the ? CHCl₂ groups) and 147 to 158 Hz (for the ? CH₂Cl groups). The ? CCl₂CH₂CH₂Cl fragment features characteristic diamagnetic shieldings of the ? CCl₂? and ? CH₂Cl that may be related to increased electron density on both of these groups.     

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).     

Zur Kenntnis des Aluminiumchlorids. Die Umsetzung von AlCl3 mit PCl5 und Methylamin

Aluminium trichloride forms the adducts AlCl₃ · NH₂CH₃, AlCl₃ · 2NH₂CH₃, AlCl₃ · 4NH₂CH₃; AlCl₃ · NH₃CH₃Cl, AlCl₃ · 2NH₃CH₃Cl. The interaction between AlCl₃, PCl₅ and NH₃CH₃Cl in the molar ratio 1:3:2 proceeds according to the reaction equation in “Inhaltsübersicht”. On applying other stoichiometric amounts, [Cl₂(NHCH₃)P? N(CH₃)? AlCl₃] · HCl and [Cl₃P? N(CH₃)? AlCl₃] · HCl are obtained; the latter reacts as [Cl₃P? NHCH₃][AlCl₄]. At the molar ratio AlCl₃:PCl₅:NH₃CH₃Cl = 1:2:4 a compound is formed being presumably the six-membered heterocycle formulated in “Inhaltsübersicht”. With [Cl₃P?N? PCl₃] and aluminium chloride [Cl₃P?N? PCl₃][AlCl₄] is formed.     

Bildung siliciumorganischer Verbindungen. XXXVIII. Umsetzung perchlorierter Carbosilane mit LiAlH4

By LiAlH₄ (Cl₃Si)₂CH₂, (Cl₂Si? CH₂)₂SiCl₂ are reduced to (H₃Si)₂CH₂ (a), (H₃Si? CH₂)₂SiH₂ (b) and (H₂Si? CH₂)₃(c). However with the compounds (Cl₃Si)₂CCl₂, (Cl₃Si? CCl₂0₂SiCl₂ and (Cl₂Si? CCl₂)₃ cleavages of the Si? C-bond and reduction of the CCl-groups occur apart from the normal reduction of the Si-Cl-groups to (H₃Si)₂CCl₂ (d), (H₃SiCCl₂)₂SiH₂ (e) and (H₂Si? CCl₂)₃. Excess LiAlH₄ favours this cleavage, the exact amount of a quarter of a mole LiAlH₄ per SiCl-group allows the formation of (d), (e), (f). The cleavage of (e) is in accordance with: (1), (2),(3). Therefore SiH₃₄ and (H₃Si)₂CCl₂ are the main-reaction-products and CH₃SiH₃ is formed acc. to equ. (3). Because of the cleavage of (H₂Si? CCl₂)₃ with LiAlH₄ H₃Si? CCl₂? SiH₂? CH₃and H₃Si? CH₂? SiH₂? CH₂? SiH₂? CH₃ are preferentially formed after the hydrolysis. The CH₂-containing compounds (a), (b), (c) cannot be cleaved in an analogous reaction.     

Bildung siliciumorganischer Verbindungen. 85 [1]. Bildung,Reaktionen und Struktur des 1,1,3,3-Tetramethyl-2,4-bis(trimethylsilyl)-1,3-disilabicyclo[1, 1, 0]butans

me₃Si? CCl₂?Sime₂Cl (me ? CH₃) läßt sich mit n-buLi (bu ? C₄H₉) bei–100°C (Lösungsmittel THF/Äther) in me₃Si? CCl(Li)? Sime₂Cl a überführen. das mit meJ me₃Si? CClme? Sime₂Cl bildet. Wird a in Abwesenheit eines Abfangreagenzes langsam erwärmt, so bildet sich unter Abspaltung von LiCl (Cl aus der SiCl-Gruppe) über eine reaktive Zwischenstufe des Bicyclobutans b . Die Struktur von b ist durch NMR-Untersuchung, Röntgenstrukturanalyse und Abbaureaktionen gesichert. Mit HBr bzw. CH₃OH werden die Si? C-Bindungen der Dreiringe in b gespalten, so daß sich me₃Si? CH₂? C(Sime₂X)₂Sime₃ (X ? Br, OCH₃) bildet. Formation of Organosilicon Compounds. 85. Formation, Reactions, and Structure of 1,1,3,3-Tetramethyl-2,4-bis(trimethylsilyl)-1,3-disilabicyclo[1, 1, 0]butane me₃Si? CCl₂? Sime₂Cl (me ? CH₃) with n-buLi (bu ? C₄H₉) at –100°C (solvent: THF/ether) yields me₃Si? CCl(Li)? Sime₂Cl a , which forms me₃Si? CClme? Sime₂Cl with meI. By warming a slowly in absence of any trapping reagent the bicyclobutane b is obtained via a reactive intermediate under elimination of LiCl (Cl from the SiCl group). The structure of b is established by nmr investigations, X-ray structure determination and chemical derivatisation.     

Reaktionen an Isocyanidverbindungen

By the reaction of FSO₂N?PCl₃ with perfluorpropionic acid FSO₂NHC(O)C₂F₅ is formed, which yields FSO₂N?C(Cl)? C₂F₅ (I) with PCl₅. The chlorine atom in (I) could be replaced by the substituents NH₂ (II) and N(C₂H₅)₂ (III). FSO₂N?C(Cl)? CF₃ reacts with AgOCN, AgSCN, unhydrous HF and 2,3-dimethylbutadiene. FSO₂N(CH₃)? C(O)F reacts with elemental fluorine under exchange of a proton against a fluorine atom to give FSO₂N(CH₂F)? C(O)F, which liberates at room temperature COF₂ and trimerises to form 1,3,5-Tris-fluorosulfonyl-s-triazine (VIII). The amides FSO₂N?C(CH₃)NH₂ and FSO₂N?C(CF₃)NH₂ react with SF₄ in the presence of NaF to yield the iminosulfur difluorides FSO₂N?C(CH₃)? NSF₂ (IX) and FSO₂N?C(CF₃)? NSF₂ (X)     

Phosphor–Kohlenstoff–Halogen-Verbindungen. XXV [1]. α-Trimethylsilyl-substituierte Methylphosphane: Darstellung und CCl4-Oxydation zu P-Chlor-methylenphosphoranen

Zwei Verfahren zur Darstellung α-trimethylsubstituierter Methylphosphane von genereller Anwendungsbreite werden vorgestellt. Phenylierte Vertreter PhPR? CH₂? Tms ( 2a— ) lassen sich durch Na-Spaltung in NH₃ und nachfolgende Kondensation mit Cl? CH₂? Tms gewinnen. Metallierung mit n-BuLi und TmsCl? Einwirkung führt zur Zweitsilylierung in αPosition ( 3a—d, f . Diorganylamino-funktionelle Derivate 5a—e und 6 sind vorteilhaft über eine Primäraktivierung (Grignardierung oder Lithiierung) der Silylmethan-Komponenten zu erhalten. Die oxidative Ylidierung mit CCl₄ ergibt nach Gl. (7) in allen Fällen P-Chlor-methylphosphorane. Außer durch Elementaranalyse wird die Konstitution sämtlicher Verbindungen durch die ³¹P{¹H}- und komplementären ¹³C{¹H}-Daten gesichert. Phosphorus-Carbon-Halogen Compounds. XXV. α-Trimethylsilyl-substituted Methylphosphanes: Synthesis and CCl₄? Oxidation to P-Chlor-methylene-phosphoranes Two procedures of general applicability for the synthesis of αxyltrimethylsilyl-substituted methylphosphanes are reported. Phenylated species PhPR? CH₂? Tms ( 2a—e ) can be obtained by Na cleavage in NH₃ and subsequent condensation with Cl? CH₂? Tms. Metallation with n-BuLi and treatment with TmsCl causes two-fold silylation in α-position ( 3a—d, f ). Diorganylamino-functionalized derivatives 5a—e and 6 are preferrably prepared by initial activation (grignardation or lithiation) of the silylmethane component. Oxidative ylidation with CCl₄ yields in all cases P-chloro-methylenephosphoranes according to eq. (7). The constitution of all compounds has been confirmed by ³¹P{¹H} and complementary ¹³C{¹H} data in addition to elemental analyses.     

Über Trichlorphosphazo-Verbindungen aus Nitrilen. I

The compound [HCCl=C(NPCl₃)(PCl₃)[PCl₆], VI, is formed in the reaction between acetonitrile and PCl₅. Reaction of H₂S with VI results in the formation of the chloride and by further reactions of this chloride with BCl₃ and SbCl₅ the tetrachloroborate and hexachloroantimonate salts respectively, are obtained. Chloroacetonitrile can be made to react with PCl₅ to give HCCl?C(NPCl₃)Cl, II, by use of suitable conditions. There is no indication that mixtures of cis/trans isomers of VI or II exist as has been previously postulated. The ¹H and ³¹P NMR spectra of the above-mentioned compounds and numerous further products from the reactions of CH₃CN, ClCH₂CN and Cl₂CHCN with PCl₅ are discussed in detail. II occurs in a cisoid and a transoid conformation.     

Reaktionsprodukte aus Chlormethoxiphosphinen und Antimon(V)-chlorid. Schwingungsspektren der 1:1 Addukte aus Methoxiphosphorylverbindungen und Antimon(V)-chlorid

Reaction Products of Chloromethoxiphosphines and Antimony (V) Chloride. Vibrational Spectra of the 1:1-adducts of Methoxiphosphoryl Compounds and Antimony (V) Chloride Chloromethoxiphosphines react with antimony(V) chloride in a redox process to yield the chloromethoxiphospllonium hexachloroantimonates(V) (CH₃O)₃PCl₂⁺SbCl₆^? (II) and CH₃OPCl₃⁺SbCl₆^? (III). II, III, (CH₃O)₃PCl⁺SbCl₆^?(1) and (CH₃O)₄P⁺SbCl₆^? eliminate easily methyl chloride and give the addition compounds OP(OCH₃)₃·SbCl₅(IV), OPCl(OCH₃)₂ · SbCl₅ (V), OPCl₂(OCH₃)·SbCl₅ (VI) and OPCl₃·SbCl₅ (VII). The vibrational spectra of IV, V nnd VI are discussed.     

Über Polystannane. III. 1,2-Dichlortetramethyldistannan,eine Sn?Sn-verknüpfte helicale Bandstruktur [(…︁SnMe2?Cl…︁SnMe2?Cl…︁)∞]2

On Polystannanes. III. 1,2-Dichloro-tetramethyl-distannane. Forming a Sn? Sn-connected Helical Double Chain Structure [(…?SnMe₂Cl…?SnMe₂? Cl…?)_∞]₂ The crystal structure of the title compound has been determined at ?160°C and refined to R = 0.071 (bond lengths Sn? Sn 277.0(2), Sn? Cl 244.2(3) and 244.8(3), Sn? C 214(2) pm). Intermolecular Sn…?Cl connection (324.0(3) and 329.2(3) pm) results in a double chain structure. ¹¹⁹Sn-NMR spectra in CH₂Cl₂ and acetone exhibit a movable temperature dependent coordination of acetone at the distannane (¹J(¹¹⁹Sn? ¹¹⁹Sn) 8000 to 9000 Hz; appr. 5000 Hz in CH₂Cl₂).     

Phenylphosphonsäure-bis(methylamid) und seine Reaktionen mit Phosphor(III)-Halogeniden

Phenyl Phosphonic Bis(methylamide) and its Reactions with Phosphorus (III) Halides Preparation of phenyl phosphonic bis(methylamide), I , from phenyl phosphonic dichloride and methylamine is described. I is characterized by its nmr, mass, and vibration spectra and by its reactions with PCl₃, CH₃PCl₂, and C₆H₅PCl₂. The two reactions mentioned last yield C₆H₅P(O)[N(CH₃)P(CH₃)Cl]₂ ( IIIa ) and C₆H₅P(O)[N(CH₃)P(C₆H₅)Cl]₂ ( IIIb ), respectively.     

Ein neuer Beitrag zur Phosphazoreaktion

A New Contribution to the Phosphazo Reaction The reaction of acrylonitrile with phosphorus pentachloride gives ClCH₂CCl₂CCl₂NPCl₃ (I) and a hexachlorophosphate with the composition C₃H₂Cl₁₄NP₃ (II). For the first time the structure of (II) has been exactly determined by using ¹H- and ³¹P-NMR-spectra. The course of reaction was studied in detail. 3-chloropropionitrile has been found as the product of a secondary reaction. The reaction of butyramide with PCl₅ has also been investigated, and was found to be analogous.     

Synthese und Eigenschaften linearer Phosphorylchlorphosphazene

Synthesis and Properties of Lineary Phosphorylchlorphosphazenes The phosphorylchlorphosphazenes, Cl₂(O)P—[N?PCl₂]_n—Cl, (n = 1, 2, 3) react like POCl₃ with hexamethyldisilazan forming silylamides, Cl₂(O)P—[N ? PCl₂]_n—NHSi(CH₃)₃, (n = 0, 1, 2, 3). From these are obtained the phosphorylchlorphosphazenes by reaction with PCl₅ containing one group —N ? PCl₂ more.