Organische Phosphorverbindungen XXXVII. Darstellung und Eigenschaften von Bis-(dialkoxyphosphonyl-methyl)-, Bis-(alkoxyphosphinyl-methyl)-und Bis-(oxophosphoranyl-methyl)-phosphinsäureestern sowie der entsprechenden Säuren [1]

Bis-chloromethyl-alkyl-and - aryl-phosphine oxides, (CICH₂₎₂P(O)R, which are obtained by reaction of (CICH₂₎₂P(O)Cl with GRIGNARD reagents, undergo a MICHAELIS -ARBUSOV reaction when heated for several hours with trivalent phosphorus esters (phosphites, phosphonites, or phosphinites) at 170–180°C. The reaction affords bis-(dialkyloxyphosphonyl-methyl)-, bis (alkyloxyphosphinyl-methyl)-, and bis-(oxophosphoranyl-methyl)-, -alkyl- or -aryl-phosphine oxides, R(O)P[CH₂P(O)R′R″]₂ R = CH₃, C₂H₅, n-C₈H₁₇, n-C₁₂H₂₅, C₆H₅; R′ and R″ = C₂H₅O, C₄H₉O, C₆H₅, CH₃ in good yields. Conversion of the compounds containing alkyloxy groups to the free acids is achieved by refluxing with conc. HCl. Bis-(dihydroxyphosphonyl-methyl)-dodecylphosphine oxide, n-C₁₂H₂₅(O)P[CH₂P(O) (OH)_2]2, obtained by hydrolysis of the all-ethyl ester, titrates in aqueous solution as a tetrabasic acid with breaks at pH = 4 (two equivalents), pH = 6,9 (one equivalent) and pH = 9,6 (one equivalent). This acid, its disodium salt (m. p. 405–410°) and its tetrasodium salt (m.p. > 460°) are surface active and are excellent chelating agents. The ¹H- and ³¹P-NMR. spectra of all the compounds prepared are discussed.     

Organische Phosphorverbindungen XXXVI. Darstellung und Eigenschaften von Bis-(dialkoxyphosphonyl-methyl)-, Bis-(alkoxyphosphinyl-methyl)-und Bis-(oxophosphoranyl-methyl)-phosphinsäureestern sowie der entsprechenden Säuren [1]

High yields of bis-(dialkoxyphosphonyl-methyl)- phosphinic esters, (RO)₂ (O)-PCH₂P(O)OR, bis-(aloxyphosphinyl-methyl)-phosphinic esters, [R(RO)(O)PCH_2]2P(O)OR, are obtained by heating bis-chloromethyl-phosphinic esters, (CICH₂₎₂P(O)OR, with alkylphoshites, phosphonites and phosphinites, repectively, at 170 to 180°C for several hours. Hydrolysis of these esters in achieved by refluxing with conc. HCl for extended periods. Bis-(dihydroxyphosphonyl-methyl)-phosphinic acid, HO(O)P[CH₂P(O) (OH)₂]₂, obtained by hydrolysis of the all-ethyl ester, titrates in aqueous solution as a tetrabasic acid with breaks at pH = 5,2 (three equivalents) and at pH = 8,8 (one equivalent). The fifth proton can be titrated only after addition of NaCl. This acid is an excellent chelating agent for metal ions. The ¹H- and ³¹P-NMR. spectra of all the compounds prepared are discussed.     

Organische Phosphorverbindungen 44 Darstellung und Eigenschaften von Bis-(ß-chloräthyl)-phosphinsäure-Derivaten [1]

Reaction of ClCH₂CH₂PCl₂ with ethylene oxide gives the phosphonous acid ester ClCH₂CH₂P (OCH₂CH₂Cl)₂ which on heating to 120° rearranges to the phosphinic acid ester (ClCH₂CH₂)₂P(O)OCH₂CH₂Cl ( 3 ). Chlorination of 3 with PCl₅ in CCl₄-solution yields the phosphinic chloride (ClCH₂CH₂)P(O)Cl ( 4 ), which on treatment with P₂S₅ at 170° produces the thioderivative, (ClCH₂CH₂)₂P(S)Cl, (₅). Treatment of 4 and 5 with alcohols, mercaptanes, or amines in the presence of an acid binding agent leads to the corresponding phosphinic and thiophosphinic acid derivatives, (ClCH₂CH₂) P (X)Y, (X = O, S; Y = OR, SR, NR₂) ( 6 ). Reaction of 6 with excess base yields the corresponding divinylphosphinic and divinylthiophosphinic acid derivatives (CH₂ = CH)₂P (X) Y (X = O, S; Y = OR, SR, NR₂) ( 7 ). Bis-(ß-chloroethyl)-phosphinates, e. g. (ClCH₂CH₂)₂P (O) OEt, undergo a Michaelis-Arbuzov reaction when heated with phosphites to 160–170° to give bis-(phosphonylethyl)-phosphinates, e.g. (EtO) (O)P[CH₂CH₂CH₂P(O)(OEt)₂]₂ ( 8 ), which on hydrolysis with conc. HCl under reflux yield the corresponding acid HO₂P(CH₂CH₂PO₃H₂)₂.     

Organische Phosphorverbindungen 42. Einige Reaktionen von Bis-(dialkoxyphosphonyl-methyl)-O-alkylphosphinaten und Tris-(dialkoxyphosphonyl-methyl)-phosphinoxiden [1]

The metallation of alkyl bis-(dialkyloxyphosphonyl-methyl)-phosphinates (I) and tris-(dialkyloxyphosphonyl-methyl)-phosphine oxides (II) proceeds quantitatively with Na, K, or NaH in inert organic solvents. Alkylation of these metallated derivatives is effected with alkyl halides. In addition to the mono-alkylated products, the di-alkylated and the non-alkylated products are formed also. The ester groups of II can be replaced by aryl groups by reaction with Grignard reagents to produce the corresponding tetratertiary phosphine oxides. Reduction of II with LiAlH₄ results in complete rupture of the molecule and produces only the cleavage products PH₃ and CH₃PH₂. Chlorination of the ester groups of I and II does not lead to uniform products. Concomitant with the chlorination of the ester groups, a cleavage reaction has been observed which produces as the main product Cl₂CHP(O)Cl₂. The anhydride of the hexa-acid of II is readily obtained either by reaction of this acid with (CH₃CO)₂O or by reaction of II with (PhCO)₂O. The titration behaviour and the high m. p. indicate an adamantane-like structure for the anhydride. Halogenation of the bridging PCH₂P groups of I and II is achieved by reaction with aqueous alkaline hypohalite at ambient temperature. This halogenation is accompanied by partial cleavage, and analytically pure samples could not be isolated.     

Organische Phosphorverbindungen 41. Synthese und Eigenschaften von Polyphosphinaten und Polyphosphinsäuren [1]

A process for the preparation of alkyl chloromethylphosphonites, ClCH₂P(OR)₂ (R = Et, Bu), diethyl β-chloroethylphosphonite, ClCH₂CH₂P(OEt)₂, and their conversion to polyphosphinates with the back-bone structures ? [? CH₂PO₂R? ]? _x and ? [? CH₂CH₂P(O₂R)? ]? _x, respectively, by an Arbuzov type reaction is described. Hydrolysis to the corresponding polyphosphinic acids is effected by refluxing the esters with conc. HCl for extended periods. The polyphosphinic acid with structure V is an excellent chelating agent for Ca ions.     

Organische Phosphorverbindungen XXV Darstellung und Eigenschaften von sekundären und tertiären Phosphinsulfiden

Two new processes for the preparation of sec. phosphine sulfides which involve reaction of dialkylamino-dialkyl or diaryl phosphines with hydrogen sulfide, and of dialkylthionophosphonates, (RO)₂P(S)H, with GRIGNARD or organolithium reagents, respectively, are described. The addition of sec. phosphine sulfides to olefins and the condensation of sec. phosphine sulfides with N-hydroxymethyldialkylamines are reported. The conversion of tert. Phosphine sulfides to the corresponding tert. phosphine oxides is readily achieved with hydrogen peroxyde. The physical properties of several new unsymmetrical tert. phosphine sulfide and oxides are listed.     

Darstellung und Eigenschaften von Chlorozinksäuren

Contributions to the Chemistry of Hydrazine and its Derivatives. 53. Synthesis of P-, As-, and Sb-substituted Hydrazines by Addition of P? H, As? H, and Sb? H Groups to N?N Double Bonds Addition of diphenylphosphinous acid, diphenylthiophosphinous acid, methyl hydrogen phenylphosphonite, diethyl hydrogen phosphite, diphenylphosphane, dibutylphosphane, diphenylarsane, diethylarsane, and diphenylstibane to the N?N double bond of diethyl azodicarboxylate, dimethyl azodicarboxylate, ethyl phenylazocarboxylate, and azobenzene yields the P-, As-, and Sb- substituted hydrazines 1–23 . The spectroscopic data agree with the structural formulae. The course of the reactions suggests a polar reaction mechanism except in the case of the synthesis of 15 , which probably proceeds via radical intermediates. The azo systems employed show a distinct graduation in their ability to add to the element-hydrogen groups used.     

Organische Phosphorverbindungen XXX. Herstellung und Eigenschaften aromatisch substituierter Cyclopolyphosphine [1]

The interaction of ClC₆H₄PCl₂ or o-CH₃C₆H₄PCl₂ with the corresponding primary phosphines has been studied under a variety of conditions.     

Salze von Halogennophosphorsäuren. VII Darstellung und Eigenschaften von Siliciumdichlorphosphaten

Salts of Halogenophosphoric Acids. VII. Preparation and Properties of Silicon Dichlorophosphates By reaction of SiCl₄ or SiHCl₃ with dichlorophosphoric acid the compounds H[Si(PO₂Cl₂)₅] · C₂H₅OC₂H₅, H[Si(PO₂Cl₂)₅] or Si(PO₂Cl₂)₄ have been prepared, the composition of which depends on the solvents used. Some properties of these compounds are described and possible Constitutions are discussed.     

Darstellung und einige Eigenschaften von Silylderivaten der hyposalpetrigen Säure und ihrer Amide

Preparation and Some Properties of Silyl Derivatives of Hyponitrous Acid and of its Amides Bis(trimethylsilyl)hyponitrite Me₃SiO? N?N? OSiMe₃ ( 1 ) is formed by reaction of Ag₂N₂O₂ with Me₃SiCl and of (Me₃Si)₂NOLi with SO₂Cl₂. Tris(trimethylsilyl)-1-hydroxytriazen ( 2 ) is formed by reaction of (Me₃Si)₃N₂Li and i-amyl nitrite. The thermolysis of 1 leads to nitrogen, trimethylsilanol, and hexamethyldisiloxane, the thermolysis of 2 leads to hexamethyldisiloxane and trimethylsilylazide. HO? N?N? NH₂ could not be isolated as a product of protolysis of 2. 2 is converted into LiO? N?N? N(SiMe₃)₂ ( 4 ) by LiNR₂ (R = Me, SiMe₃), 4 is converted into MeO? N?N? N(SiMe₃)₂ ( 5 ) by Me₂SO₄. The thermolysis of 4 leads to LiN₃ and (Me₃Si)₂O, the thermolysis of 5 leads to Me₃SiN₃ and Me₃SiOMe.     

Über Chalkogenolate. 134. Untersuchungen über Ester von Halogenoameisensäuren 2. Darstellung und Eigenschaften von Se-Alkylestern der Chloromonothiomonoselenoameisensäure [1]

On Chalcogenolates. 134. Studies on Esters of Haloformic Acids 2. Synthesis and Properties of Se-Alkyl Esters of Chloromonothiomonoselenoformic Acid The hitherto unknown esters RSe? CS? Cl with R ? C₂H₅ and ⁿC₃H₇ have been prepared by reaction of thiophosgene with the corresponding alkane selenol. The compounds have been characterized with electron absorption, nuclear magnetic resonance (¹H, ¹³C, and ⁷⁷Se), infrared, and mass spectra.     

Organische Phosphorverbindungen XXII. Darstellung und Eigenschaften von diprimären α,ω-Bis-phosphino-alkanen

The preparation and properties of diprimary α,ω-bis-phosphino-alkanes of the general structure H₂P(CH₂)_n PH₂ (n = 1, 2, 3, 4) are described. Their reactions with N-hydroxymethyl-dialkylamines and with olefins, which yield ditertiary α,ω-bisphosphino-alkanes, (R₂NCH₂)₂P(CH₂)_nP(CH₂NR₂)₂ and R₂P(CH₂)_nPR₂, respectively, are also reported. The physical properties of two new α,ω-bis-dialkylphosphinyl-alkanes have been determined.     

Organische Phosphorverbindungen XXVIII. Die α-Aminoalkylierung von elementarem weissem Phosphor. Eine einfache Methode zur Darstellung von tertiären Phosphinoxiden,Phosphinsäuren und Phosphonsäuren [1]

White phosphorus reacts with N-hydroxymethyl-dialkylamines to give mainly three products, i.e., tris(dialkylaminomethyl) phosphine oxides, bis(dialkylamino-methyl) phosphinic acids, and dialkylaminomethyl phosphonic acids, according to the equation: The yield of the various products depends mainly upon the ratio of the reactants, the pH, and the solvents used.     

Darstellung und Eigenschaften von Tris-(β-chloräthyl) phosphinoxid und Bis-(β-chloräthyl)-(chlormethyl)-phosphinoxid. 43. Mitteilung über organische Phosphorverbindungen [1]

The oxidative degradation of [(HOCH₂CH₂)₃PCH₂OH]⁺Cl^? ( 1 ) with Cl₂ yields, dependent on the pH used, either (HOCH₂CH₂)₃P?O ( 2 ) or (HOCH₂CH₂)₂ (HOCH₂) P?O ( 3 ). Chlorination of 2 and 3 with PCl₅ produces the corresponding chlorides (ClCH₂CH₂)₃P?O ( 4 ) and (ClCH₂CH₂)₂ (ClCH₂)P?O ( 5 ), respectively. Acetylation of 2 and 3 gives the corresponding esters (CH₃CO₂CH₂CH₂)₃P?O ( 6 ), and (CH₃CO₂CH₂CH₂)₂ (CH₃CO₂CH₂)P?O ( 7 ), respectively. Reaction of 7 with HBr results in the formation of (BrCH₂CH₂)₂ (BrCH₂)P?O. Nucleophilic substitution of the chlorine atoms in 4 and 5 with alkoxide or mercaptide gives e.g., 9 , 10 , 11 or 11a , while treatment with tertiary amines yields the vinyl compounds (CH₂?CH)₃P?O ( 12 ) and (CH₂?CH)₂ (CH₂Cl)P?O ( 13 ). 4 and 5 also undergo an Arbuzov type reaction with tertiary phosphites to give 14 and 15 , respectively, which on hydrolysis with conc. HCl give the corresponding acids 16 and 17 , respectively.     

Organische Phosphorverbindungen XXIX. Eine neue Methode zur Darstellung von dialkylaminomethylsubstituierten Phosphonig- und Phosphinsäuren der allgemeinen Formel R2NCH2PH(O)OH und (R2NCH2)2P(O)OH [1]

A new method for the preparation of dialkylaminomethyl-phosphonous and-phosphinic acids, R₂NCH₂P(O)H(OH) and (R₂NCH₂)₂P(O)OH, is described. This involves reaction of hypophosphorous acid with hydroxymethyl-dialkyl-amines or a mixture of formaldehyde and a secondary amine. and The crystalline acids form monohydrates which are stable up to the melting points of the acids. The IR. and ³¹P-NMR. spectra are reported.     

Untersuchungen an Dialkylmetallphosphor- und -phosphinsäurederivaten der Elemente Aluminium,Gallium, Indium und Thallium. I. Darstellung,Eigenschaften und Kernresonanzspektren von Dialkylmetallphosphor- bzw. -phosphinsäurederivaten

Studies on Dialkyl Metal Phosphoric and Phosphinic Acid Derivatives of the Elements Aluminium, Gallium Indium, and Thallium. I. Preparation, Properties, and NMR Spectra of Dialkyl Metal Phosphoric and Phosphinic Acid Derivatives. The trialkyl compounds of Al, Ga, In and Tl react with equimolar quantities of phosphoric or phosphinic acids, HOOPX₂ (X = F, Cl, H), HOSP(CH₃)₂ or HSSP(CH₃)₂, to form dialkylmetal phosphoric and phosphinic acid derivatives, respectively. The properties and the degree of association of these compounds are listed. The NMR- spectra (¹H, ¹⁹F and ³¹P) show that the phosphorus containing groups act as bidentate ligands.     

Organostibonsäureester. II. Darstellung und Eigenschaften von Methanstibonsäureestern Struktur von Di-μ-methoxy-bis [dibromo-methoxy-methyl-antimon(V)]

Esters of Stibonic Acid. II. Preparation and Properties of Esters of Methanestibonic Acid; Structure of Di-μ-methoxy-bis[dibromo-methoxy-methyl-antimony(V)] Dimeric alkoxy-bridged compounds of the type [CH₃SbX₂(OR)(μ-OR)]₂ (X = Cl, Br; R = CH₃, C₂H₅) are prepared by oxidation of CH₃Sb(OR)₂ with Br₂ or SO₂Cl₂ in CH₂Cl₂ below ?60°C as light sensitive crystals. The structure of [CH₃SbBr₂(OCH₃)(μ-OCH₃)]₂ was determined by X-Ray analysis. By reaction with sodium alkoxides in the corresponding alcohol at 0°C dimeric tetraalkoxymethylstiboranes are obtained. Exchange reactions of tetramethoxymethylstiborane with ethanol give the ethoxy derivative and with diols symmetric spirocyclic esters of methanestibonic acid.     

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.     

Zur Kenntnis der Organophosphorverbindungen. XV. Darstellung und Reaktionen von Trimethylsilylestern der Phosphinsäuren

On Organophosphorus Compounds. XV. Preparation and Reactions of Trimethylsilyl Esters of Phosphinic Acids Trimethylsilylesters of Phosphinic acids R₂P(X)YSi(CH₃)₃ (R ? CH₃, C₂H₅, C₃H₇, t?C₄H₉, C₆H₅; X, Y ? O, S) were prepared by 7 different methods as in some cases easily hydrolysable but thermally remarkably stable compounds. The properties and some reactions of these substances are reported, their structures confirmed by IR? as well as ¹H- and ³¹P-NMR-spectroscopy. Dimethylsilylen-bis(phosphinic acid esters) were obtained according to \documentclass{article}\pagestyle{empty}\begin{document}$ 2{\rm R}_{2} {\rm P(\rm X)\rm ONH}_{4} + {\rm R}_{\rm 2} {\rm SiCl}_{2} \to 2{\rm E NH}_{4} {\rm Cl + R}_{2} {\rm P(X) - O - SiR}_{2} - {\rm O - P(X)R}_{2} ({\rm R = CH}_{3};{\rm X = O,S}) $\end{document}.