Perfluoralkylierte Säuren des Phosphors. II. Zur Kenntnis der Trifluormethyl-benzol-phosphinsäure

Perfluoroalkylated Acids of Phosphorus. II. On Trifluoromethyl Benzene Phosphinic Acid Bis-(trifluoromethyl-benzene) phosphinic acid anhydride 1 , easily formed by CF₃COOH and C₆H₅PCl₂, yields on reaction with aqueous Na₂CO₃ solution the sodium salt of trifluoromethyl benzene phosphinic acid 2 . The acid itself is isolated by ion exchange as a hygroscopic and highly acidic substance.     

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}.     

Darstellung und chemische Eigenschaften von N-Trifluormethylthiophosphaniminen

Preparation and Chemical Properties of N-Trifluoromethylthiophosphaneimines In n-hexane (CF₃S)₃N and (C₆H₅)₃As react to CF₃SN?As(C₆H₅)₃ and CF₃SSCF₃. With (RO)₃P (CF₃S)₃N forms CF₃SSCF₃ and CF₃SN?P(OR)₃ (R = C₆H₅, CH₃, C₂H₅). While CF₃SNP-(OC₆H₅)₃ is stable up to 100°C the other Phosphaneimines rearange to (R′O)₂P(O)N(R′)SCF₃ (R′ = CH₃, C₂H₅). Hydrolysis leads to ROH and (RO)₂P(O)N(H)SCF₃. Only for R = C₆H₅ in addition (C₆H₅O)₂P(O)NH₂ is formed. Physical data and nmr spectra of the newly prepared substances are presented.     

[2+4] and [2+2] Cycloaddition Reactions of N‐Sulfinyl Carboxylic Acid Amides with (CF3)2BNMe2. Crystal Structure of cyclo‐(CF3)2B‐NMe2‐S(=O)‐N=C(p‐CH3C6H4)‐O

N‐sulfinylacylamides R‐C(=O)‐N=S=O react with (CF₃)₂BNMe₂ ( 1 ) to form, by [2+4] cycloaddition, six‐membered rings cyclo‐(CF₃)₂B‐NMe₂‐S(=O)‐N=C(R)‐O for R = Me ( 2 ), t‐Bu ( 3 ), C₆H₅ ( 4 ), and p‐CH₃C₆H₄ ( 5 ) while N‐sulfinylcarbamic acid esters R‐O‐C(=O)‐N=S=O react with 1 to yield mixtures of six‐membered (cyclo‐(CF₃)₂B‐NMe₂‐S(=O)‐N=C(OR)‐O) and four‐membered rings (cyclo‐(CF₃)₂B‐NMe₂‐S(=O)‐N(C=O)OR) for R = Me ( 6 and 9 ), Et ( 7 and 10 ), and C₆H₅ ( 8 and 11 ). The structure of 5 has been determined by X‐ray diffraction.     

Metallkomplexe der Phosphinsäuren. XVIII. Ansa- und Oligokomplexe bifunktioneller Dithiophosphinsäuren

Metal Complexes of Phosphinic Acids. XVIII. Ansa- and Oligo-Complexes of Bifunctional Dithiophosphinic Acids The influence of R′ in the bifunctionell chelate ligands ^?S(S)P(R)? R′? (R)P(S)S^? on the association of their planar Ni^II and tetrahedral Co^II complexes is investigated by vapour pressure osmometry and in the case of diamagnetic Ni^II compounds also by ³¹P-NMR spectroscopy. While insoluble coordination polymers [S₂P(R)? R′? (R)PS₂M]_x (M = Ni^II, Co^II) are formed with R′ = p-(C₂H₄)₂C₆H₄ it can be shown, that in solutions of the complexes with R′ = o-(C₂H₄)₂C₆H₄ and R′ = o-(C₃H₆)₂C₆H₄ there exists an association equilibrium comprehending oligomers with n ? x. Above all in the latter case steric conditions seem to favour intramolecular chelating and thus formation of ansa-type complexes. Synthesis of the ligands and the complexes is described.     

2J(P,C) and 3J(P,C) Coupling Constants in Some New Phosphoramidates. Crystal Structures of CF3C(O)N(H)P(O)[N(CH3)(CH2C6H5)]2 and 4‐NO2‐C6H4N(H)P(O)[4‐CH3‐NC5H9]2

Some new phosphoramidates were synthesized and characterized by ¹H, ¹³C, ³¹P NMR, IR spectroscopy and elemental analysis. The structures of CF₃C(O)N(H)P(O)[N(CH₃)(CH₂C₆H₅)]₂ ( 1 ) and 4‐NO₂‐C₆H₄N(H)P(O)[4‐CH₃‐NC₅H₉]₂ ( 6 ) were confirmed by X‐ray single crystal determination. Compound 1 forms a centrosymmetric dimer and compound 6 forms a polymeric zigzag chain, both via ‐N‐H…O=P‐ intermolecular hydrogen bonds. Also, weak C‐H…F and C‐H…O hydrogen bonds were observed in compounds 1 and 6 , respectively. ¹³C NMR spectra were used for study of ²J(P,C) and ³J(P,C) coupling constants that were showed in the molecules containing N(C₂H₅)₂ and N(C₂H₅)(CH₂C₆H₅) moieties, ²J(P,C)>³J(P,C). A contrast result was obtained for the compounds involving a five‐membered ring aliphatic amine group, NC₄H₈. ²J(P,C) for N(C₂H₅)₂ moiety and in NC₄H₈ are nearly the same, but ³J(P, C) values are larger than those in molecules with a pyrrolidinyl ring. This comparison was done for compounds with six and seven‐membered ring amine groups. In compounds with formula XP(O)[N(CH₂R)(CH₂C₆H₅)]₂, ²J(P,CH₂)_benzylic>²J(P,CH₂)_aliphatic, in an agreement with our previous study.     

Die Reaktionen von Benzoylierungsmitteln mit Phosphoriger Säure

Reactions of Benzoylating Agents with Phosphorous Acid H₃PO₃ reacts with (C₆H₅CO)₂O to yield C₆H₅C(OH)(PO₃H₂)₂ 1 . In contrast, the reaction with C₆H₅COCl proceeds with the formation of C₆H₅CCl(PO₃H₂)₂ 2 and p-ClC₆H₄CH(PO₃H₂)₂ 3 . The best yields of 2 and 3 are obtained, if the reaction are carried out under pressure. 2 is rapidly hydrolysed in alkaline solution at elevated temperatures to 1 .     

Untersuchungen an Selen-Verbindungen. LXIV. Darstellung und Eigenschaften von Säurederivaten von Phenylselen(IV) -Verbindungen (C6Hs) 2SeX2, (C6H5) 3SeX

Studies on Selenium Compounds. LXIV. Preparation and Properties of Acid Derivatives of Phenylselenium(IV) Compounds (C₆H₅) ₂SeX₂ and (C₆H₅) ₃SeX. Reactions of (C₆H₅) ₂SeBr₂ and (C₆H₅) ₃SeCl with silver salts of acids are investigated. From (C₆H₅) ₂SeBr₃ and AgY (Y = N0₃, CH₃CO₃, CF₃CO₂, 1/2 SO₄, CH₃SO₃, NCO) the compounds (C₆H₅) ₂Se(NO₃) ₂ (C₆H₅) ₂Se(CH₃CO₂) ₂, (C₆H_s) ₂Se(CF₃CO₂) ₂, (C₆H₅) ₂SeSO₄, (C₆H₅) ₂Se(CH₃SO₃) ₂ and (C₆H₅) ₂Se(NCO) ₂ are prepared. They are characterized by solubility, molecular weight and conductivity. Reaction of (C₆H₅) ₃SeCl and AgX (X = NO₃, CH₃CO₂) yields (C₆H₅) ₃SeNO₃ and (C₆H₅) ₃SeCH₃CO₂.     

l-Hydroxo/Alkoxo-l-oxo-l-sulfonato-jO:jO'-bis[trichloroantimon(V)]Verbindungen. Zweikernige Antimon(V)-Komplexe mit Sulfonatgruppen als überbrückenden Liganden

l-Hydroxo/alkoxo-l-oxo-l-sulfonato-jO:jO'-bis[trichloroantimony(V)] Compounds. Binuclear Antimony(V) Complexes with Sulfonate Groups as bridging Ligands Sulfonic acids react with antimony(V) chloride and water and water/alcohol resp. dependent of the molar ratios yielding Cl₃SbO(OH)(O₂S(O)CH₃)SbCl₃ ( 1 ), Cl₃SbO(OH)· (O₂S(O)CF₃)SbCl₃ ( 3 ) the monohydrate Cl₃SbO(OH)· (O₂S(O)CH₃)SbCl₃·H₂O ( 2 ) and the compounds Cl₃SbO(OR')(O₂S(O)CF₃)SbCl₃ ( 4 : R'=CH₃; 5 : R'=C₂H₅) and Cl₃SbO(OCH₃)(O₂S(O)C₂H₅)SbCl₃ ( 6 ) resp. The crystal and molecular structures of 1 to 3 , 5 and 6 are determined. 1 and 3 are associated by hydrogen bonds to dimers and crystallize monoclinic ( 1 : P2₁/c; 3 : P2₁/n). 2 is a hydroxonium salt H₃O⁺[Cl₃SbO₂(O₂S(O)CH₃)SbCl₃]^– with strong hydrogen bonds between cations and anions and crystallizes triclinic (P1). 5 and 6 crystallize monoclinic ( 5 : P2₁/m; 6 : P2₁/c). In 1 and 3 to 6 there is an intramolecular reorientation or an intermolecular exchange of protons and R' groups in solution. The NMR spectra are discussed.     

Methyl group replacement on pentamethylantimony with organophosphorus substituents

Phosphinic and phosphonic acids were treated with pentamethylantimony to replace one of its methyl groups (with formation of methane) to give the following new compounds: (CH₃SbOP(O)(C₆H₅)₂, (CH₃)₄SbOP(O)(OH)CH₃, and (CH₃)₄SbOP(O)(OH)C₆H₅). The latter two compounds are associated, presumably through hydrogen bonding.     

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

Tris-chloromethyl-phosphine oxide, (ClCH₂₎₃ P?O(I), is obtained by chlorination of (HOCH₂₎₃P?O with PCl₅ or (C₆H₅₎₃PCl₂, and also by oxidation of (CICH₂₎₃P?O and (ClCh₂₎₂(CH₃)P?O. High yields of tris-(dialkyloxyphosphonly-methyl)-phosphine oxides, [RO₂(O)PCH_2]2P?O (II) (R?CH₃, C₂H₅, iso-C₃H₇, n-C₄H₉, 2- ethyl-hexyl), tris (alkyloxyphosphinyl-methyl)-phosphine oxides, [R₂(O)PCH_2]3P?O(R = C₆H₅, CH₃) are obtained by heating tris-chloromethyl-phosphine oxides, [(RO) (R′) (O)PCH_2]3P?O (R = C₄H₉, R′? C₆H₅) and tris-(oxophosphoranyl-phosphine oxides with phosphites, phosphonites and phosphinites, respectively, at 170–180°C for several hours. Compounds II possess an extraordinarily high absorption capacity. Thus a warm. 2% solution of II (R = C₂H₅) in benzene solidifies completely on cooling so that no benzene can be poured off. Tris-dihydroxyphosphonyl-methyl)-phosphine oxide, [(HO)₂(O)PCH_2]3P?O, obtained by hydrolysis of II (R ? C₂H₅) with refluxing conc. HCl or by thermal decomposition of II (R ? iso-C₃H₇) at 190°, titrates in aqueous solution as a hexabasic acid with breaks at pH = 4,4 (three equivalents) and pH = 10,7 (three equivalents). It forms crystalline salts with amines, alkali and alkaline earth metals, and is an excellent chelating agent. The ¹H- and ^31?P-NMR. spectra of all the compounds prepared are discussed.     

Trifluormethylselenyl-Verbindungen des N,P und As

Trifluoromethylselenyl Compounds of N, P, and As The reaction of CF₃SeBr with NH₃ leads, depending on conditions, to (CF₃Se)_nNH_3?n, where n = 1, 2 or 3. CF₃SNCO reacts with CF₃SeNH₂ to give CF₃SNHCONHSeCF₃, and (CF₃Se)₃N with P(C₆H₅)₃ provides CF₃SeN ?P(C₆H₅)₃. (CF₃Se)₃E (where E = P, As) is formed by the reaction of Hg(SeCF₃)₂ with EBr₃ in CS₂. Analogously, from Hg(SeCF₃)₂ and P₂J₄ in CS₂ (CF₃Se)₂PP(SeCF₃)₂ is obtained that contains (CF₃Se)₃P as a contamination. While reacting C₆H₅PJ₂ or C₆H₅P(J)(J)C₆H₅ with Hg(seCF₃)₂ respectiverly C₆H₅P(SeCF₃)₂ is formed. The latter can be also obtained from (C₆H₅P)₅ and CF₃SeSeCF₃. IR, ¹⁹F, ³¹P, ⁷⁷Se NMR, and MS data are given.     

Metallkomplexe mit biologisch wichtigen Liganden. CLVII [1] Halbsandwich‐Komplexe mit Isocyanoacetylaminosäureestern und Isocyanoacetyldi‐ und tripeptidestern („Isocyano‐Peptide”︁)

Metal Complexes of Biologically Important Ligands, CLVII [1] Halfsandwich Complexes of Isocyanoacetylamino acid esters and of Isocyanoacetyldi‐ and tripeptide esters (?Isocyanopeptides”?) N‐Isocyanoacetyl‐amino acid esters CNCH₂C(O) NHCH(R)CO₂CH₃ (R = CH₃, CH(CH₃)₂, CH₂CH(CH₃)₂, CH₂C₆H₅) and N‐isocyanoacetyl‐di‐ and tripeptide esters CNCH₂C(O)NHCH(R¹)C(O)NHCH(R²)CO₂C₂H₅ and CNCH₂C(O)NHCH(R¹)C(O)NHCH (R²)C(O)NHCH(R³)CO₂CH₃ (R¹ = R² = R³ = CH₂C₆H₅, R² = H, CH₂C₆H₅) are available by condensation of potassium isocyanoacetate with amino acid esters or peptide esters. These isocyanides form with chloro‐bridged complexes [(arene)M(Cl)(μ‐Cl)]₂ (arene = Cp*, p‐cymene, M = Ir, Rh, Ru) in the presence of Ag[BF₄] or Ag[CF₃SO₃] the cationic halfsandwich complexes [(arene)M(isocyanide)₃]⁺X^? (X = BF₄, CF₃SO₃).     

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.     

Synthese und Eigenschaften von Diethyldithiocarbaminsäureperfluororganylestern, (C2H5)2NC(S)SRf (Rf = CF3, C2F5, i‐C3F7, n‐C4F9, C6F5)

Syntheses and Properties of Perfluoroorgano Esters of the Diethyldithiocarbamic Acid, (C₂H₅)₂NC(S)SR_f (R_f = CF₃, C₂F₅, i‐C₃F₇, n‐C₄F₉, C₆F₅) Tetraethylthiuram disulfide reacts under different conditions with perfluoroorgano silver(I), AgR_f, and perfluoroorgano cadmium compounds, Cd(R_f)₂, to give the corresponding perfluoroorgano esters of diethyldithiocarbamic acid, (C₂H₅)₂NC(S)SR_f (R_f = CF₃, C₂F₅, i‐C₃F₇, n‐C₄F₉, C₆F₅), and metal diethyldithiocarbamates, AgSC(S)N(C₂H₅)₂ and Cd[SC(S)N(C₂H₅)₂]₂. The mechanisms of the reactions with AgR_f and Cd(R_f)₂ are discussed.     

Diphenyl(pentafluorbenzoyloxy)phosphanoxid und -sulfid

Diphenyl(pentafluorobenzoyloxy)phosphane chalcogenides (C₆H₅)₂P(E)(OC(O)C₆F₅) [E = 0 (2a); E = S (1b)] were prepared by treating AgOC(O)C₆F₅ with (C₆H₅)₂P(E)Cl [E = O (1a); E = S (1b)] (¹H-, ¹⁹F-; and ³¹P{¹H}-NMR- and IR- data). Phosphino-thiono- or phosphino-thiolo-rearrangements are not observed under conditions of synthesis.     

Über Chalkogenolate. 81. Untersuchungen über N-Hydroxydithiocarbamidsäure 3. Ester der N-Hydroxydithiocarbimidsäure und -carbamidsäure

On Chalcogenolates. 81. Studies on N-Hydroxy Dithiocarbamic Acid. 3- Esters of N-Hydroxy Dithiocarbimic Acid and Dithiocarbamic Acid The reaction between hydroxylamine, carbon disulfide, and alkyl halide leads to the corresponding ester of N-hydroxy dithiocarbimic acid HO? N?C(SR)₂ with R = CH₃, C₂H₅; R₂ = ? CH₂? CH₂? . The phenyl ester of N-hydroxy dithiocarbamic acid HO? NH? CS(SC₆H₅) has been prepared by reaction of hydroxylammonium chloride with the phenyl ester of chlorodithioformic acid. N-Methyl hydroxylammonium chloride reacts with carbon disulfide and alkyl iodide to form the corresponding ester of the dithiocarbamic acid HO? N(CH₃)? CS(SR) with R = CH₃, C₂H₅. The unstable compounds have been characterized by different methods.     

Metallabis(phosphonate) als Chelatliganden. II. Synthese und Reaktivität ein- und zweikerniger Palladiumbis(phosphonat)-Komplexe mit OHO- und OBF2O-Brückenbindungen

Metallabisphosphonates as Chelating Ligands. II. Synthesis and Reactivity of Mono- and Binuclear Palladiumbisphosphonate Complexes Containing OHO and OBF₂O Bridges The complexes C₅H₅Pd[{P(OR)₂O}₂H] ( 1 : R = Me; 2 : R = Et) are formed either by reaction of C₅H₅Pd(2-MeC₃H₄) with dimethyl- and diethylphosphite or by reaction of [ClPd{P(OR)₂O}₂H]₂ ( 3 : R = Me; 4 : R = Et) with TlC₅H₅. With excess HP(O)(OMe)₂, the π-allyl complex (2-MeC₃H₄)Pd[{P(OMe)₂O}₂H] ( 5 ) is also formed (besides 1 ) from C₅H₅Pd(2-MeC₃H₄). The ¹H and ³¹P n.m.r. spectra indicate that in 1 – 5 the PdP₂O₂H chelate ring presumably contains a symmetrical OHO-hydrogen bond. The reaction of 3 with BF₃ etherate leads to the binuclear complex [ClPd{P(OMe)₂O}₂BF₂]₂ ( 6 ) which reacts with TlC₅H₅ to yield C₅H₅Pd[{P(OMe)₂O}₂BF₂] ( 7 ). From C₅H₅Pd[{P(OR)₂O}₂H] ( 1 , 2 ) and NH₃ the bisamminepalladium bisphosphonates(NH₃)₂Pd[P(OR)₂O]₂ ( 8 , 9 ) are formed which probably possess a trans-configuration. The reaction of 8 , 9 with CF₃COOH does not lead to a corresponding Pd[{P(OR)₂O}₂H] chelate complex but instead gives by elimination of NH₃ polymeric palladium bisphosphonates [Pd{P(OR)₂O}₂]_n ( 10 , 11 ). 1 reacts with thallium acetylacetonate to give C₅H₅Pd[P(OMe)₂O]₂Tl ( 12 ).     

Über Chalkogenolate. 136 [1]. Alkylester der Cyanoameisensäure und der Cyanomonothioameisensäure

On Chalcogenolates. 136. Alkyl Esters of Cyanoformic Acid and of Cyanomonothioformic Acid By use of the phase transfer catalyst 18-crown-6 the esters CH₃O—CO—CN, C₂H₅O—CO—CN, C₂H₅S—CO—CN, and ⁿC₃H₇S—CO—CN have been prepared by reaction of the corresponding chloro compound with potassium cyanide. The prepared compounds have been characterized by means of electron absorption, infrared, nuclear magnetic resonance (¹H and ¹³C), and mass spectra.     

Fluoroborates by Cleavage of Trimethylamine‐bis(trifluoromethyl)boranes with NEt3 × 3 HF. Structures of C6F5(CF3)2B · NMe3, K[C6H5CH2(CF3)2BF], and K[C6H5(CF3)2BF]

Trimethylamine‐bis(trifluoromethyl)boranes R(CF₃)₂B · NMe₃ (R = cis/trans‐CF₃CF=CF ( 1/2 ), HC≡C ( 3 ), H₂C=CH ( 4 ), C₂H₅ ( 5 ), C₆H₅CH₂ ( 6 ), C₆F₅ ( 7 ), C₆H₅ ( 8 )) react with NEt₃ × 3 HF depending on the nature of R at 155–200 °C under replacement of the trimethylamine ligand to form the corresponding fluoro‐bis(trifluoromethyl)borates [R(CF₃)₂BF]^– ( 1 a/2 a – 8 a ). The structures of 7 , K[C₆H₅CH₂(CF₃)₂BF] ( K‐6 a ), and K[C₆H₅(CF₃)₂BF] ( K‐8 a ) have been investigated by single‐crystal X‐ray diffraction. In 7 the CF₃ groups make short repulsive contacts with NMe₃ and C₆F₅ entities – the B–CF₃ bonds being unusually long. The B–F bond lengths of K‐6 a and K‐8 a (1.446(3) and 1.452(2) Å, respectively) are long for a fluoroborate.