Bis(fluorbenzoyloxy)methylphosphanoxide

Bis(fluorbenzoyloxy)methyl phosphane oxides CH₃P(O)[OC(O)R]₂ [R = C₆H₄2F (1), C₆H₄3F (2), C₆H₄4F (3), C₆H₃2,6F₂ (4), C₆H2,3,5,6F₄ (5)] were prepared by treating silver salts of carboxylic acids AgOC(O)R with CH₃P(O)C?₂ (IR-, ¹H-, ¹⁹?F-and ³¹P{¹H}-NMR-data). The mixed anhydrides 1–5 show unusual thermal stability at room temperature. Stability against hydrolysis decreases with increasing number of fluorine-atoms. The reaction of R′P(O)C?₂ [R′ = CH₃, C₆H₅, (CH₃)₃C] with M^IOC(O)R_F [R_F = CF₃, C₂F₅, C₆F₅; M^I = Ag^I, Na^I T?^I] was investigated.     

The reaction of perfluoro-2,4-dialkyloxolanes with anhydrous aluminum chloride

Several kinds of perfluoro-2,4-dialkyloxolanes (A), having such alkyl groups as R_fR′_fCF₃ (2a); R_fC₂F₅, R′_fCF₃ (3a); R_fCF₃, R′_fC₂F₅ (4a); R_fR′_fC₂F₅ (5a); R_fCF₃, R′_fnC₃F₇ (6a) on the 2 and 4 positions of the oxolane ring, respectively, were treated with AlCl₃ in a heterogeneous reaction to give the corresponding perfluoro-2,5,5-trichloro-2,4-dialkyloxolanes (B). For purposes of comparison, the respective reactions of perfluoro-2-methyl-oxolane (la), perfluoro-2-n-butyloxolane (7a), and perfluoro-2, 5-dimethyloxolane (8a) with AlCl₃ were also conducted. An increasingly higher reaction temperature was needed for the reaction of A with AlCl₃ to give B as the carbon number of A increased. Cis- and trans-perfluoro-4-chloro-2,4-dimethyl-γ-butyrolactones (2c) were obtained from the hydrolytic reactions of cis- and trans-perfluoro-2,5,5-trichloro-2,4-dimethyloxolanes (2b), respectively, with fuming H₂SO₄. Physical properties and ¹⁹F nmr data are given for these new compounds.     

Some novel triorganotin(IV) derivatives of β, δ-triketones

Thirty triorganotin(IV) derivatives of the type R₃Sn(R′COCHCOCH₂COR″) and [R₃Sn]₂ (R′COCHCOCHCOR″) (where R = CH₃, C₂H₅, nC₃H₇, nC₄H₉ and C₆H₅ and R′ = R″ = CH₃, C₆H₅ or R′ = C₆H₅, R″ = CH₃) have been synthesised by the interaction of R₃SnCl with mono- or disodium salt of 2, 4, 6-heptanetrione, 1-phenyl-1, 3, 5-hexanetrione and 1, 5-diphenyl-1, 3, 5-pentanetrione in 1:1 and 2:1 molar ratios, respectively. The complexes have been examined by their molecular weight, IR, PMR and elemental analyses and their tentative structures assigned. Both “Z” and “E” forms have been identified in the 1:1 complexes in equilibrium with the enol form containing five coordinate tin. The 2:1 derivatives contain one five- and other four coordinated tin(IV) except the phenyl analogue where both the tins are five coordinated.     

Organische Phosphorverbindungen XXXI. Ein einfaches Verfahren zur Herstellung von Alkylen- bzw. Arylen- bzw. diphosphiniten und von Bis-(dialkyl- und diaryl-phosphinyl)-alkanen

The reactions of dialkylamino-dialkyl- or diaryl-phosphines, R₂PNR′₂ (R = C₆H₅ C₄H₉, C₂H₅; R′ = CH₃, C₂H₅) with unsaturated alcohols, functional alcohols, α, ω-alkane-diols and α, ω-alkane-dithiols have been studied. The preparation of a large number of alkylene (or arylene) bis-phosphinites and of bis-phosphinyl-alkanes is reported and their physical properties listed.     

Investigations on organotin,organolead, lead(IV), and lead(II) dithiolates

Bis(triorganometal) 1,2-dithiolates (R₃M)₂S₂R′ [(HS)₂R′ = C₇H₈S₂ for toluene-dithiol-3,4 (H₂TDT); M = Sn, Pb; R = Ph; or (HS)₂R′ = C₁₀H₁₄S₂ for 1,2-dimethyl-4,5-bis(mercaptomethyl)benzene (H₂DBB); M = Sn, R = CH₃, C₆H₅; M = Pb, R = C₆H₅], diorganometal 1,2-dithiolates R₂MS₂R′ [(HS)₂R′ = C₆H₆S₂ for 1,2-dimercaptobenzene (H₂DMB); M = Pb, R = CH₃, C₂H₅, C₆H₅; or (HS)₂R′ = H₂TDT; M = Sn, R = CH₃, C₆H₅; M = Pb, R = C₆H₅; or (HS)₂R′ = H₂DBB; M = Sn, R = CH₃, C₆H₅; M = Pb, R = CH₃, C₂H₂, C₆H₅; or (HS)₂R′ = C₈H₆N₂S₂ for 2,3-dimercaptoquinoxaline (H₂QDT); M = Pb, R = C₆H₅] and some lead(IV) and lead(II) dithiolates Pb(S₂R′)_n [(HS)₂R′ = H₂DMB, n = 2; (HS)₂R′ = H₂TDT, n = 2; (HS)₂R′ = H₂DBB, n = 1 or 2] have been prepared. Vibrational, ¹H NMR, and Mössbauer spectroscopic data are consistent with pentacoordination of tin in R₂SnTDT and with tetracoordination of tin in R₂SnS₂R′ and (R₃Sn)₂S₂R′ in the solid state. The soluble compounds are monomeric in solution. Coupling constants for the methyltin compounds indicate tetracoordination in solution.     

Synthesis of organoantimony(V) and μ-oxy-bis(triarylantimony) selenocyanates using a phase-transfer catalyst

Several new, pentacoordinated, triorganoantimony bis-selenocyanates [R₃Sb(SeCN)₂ (R = Me, Ph, p-CH₃C₆H₄, p-ClC₆H₄, p-F-C₆H₄ or C₆F₅)], tetraorganostibonium selenocyanates [R₃R′Sb(SeCN) (R = R′ = Ph; R = Ph, and R′ = CH₂CHCH₂)] and μ-oxy-bis(triarylantimony) bis-selenocyanates {[Ar₃SbOSbAr₃](SeCN)₂ (Ar = Ph, p-CH₃C₆H₄, p-ClC₆H₄ or p-FC₆H₄)} have been synthesized from potassium selenocyanate and the corresponding organoantimony halide (chloride and/or bromide) in the presence of the phase-transfer catalyst 18-crown-6, and characterized. Spectroscopic evidence suggested an iso structure (Sb—NCSe). The compounds were also obtained in the absence of 18-crown-6 but in lower yields. Some of these compounds were found to exhibit a significant biological activity.     

Thermolyse des halogenures de perfluoroalcanesulfonyle

Perfluoroalkanesulfonyl chlorides [R_FSO₂Cl ; R_F  CF₃, C₂F₃, C₄F₉], decompose thermally to give the corresponding perfluoroalkyl chlorides with evolution of SO₂. The latter retards the reaction, but it is catalysed by copper which also inhibits the SO₂ effect. 2-methyl-2-nitrosopropane traps the perfluoroalkyl free radicals. In the presence of a perfluoroalkyl iodide [R′_FI ≠ R′_F≠R_F], other products, R_FI and R_FCl, are obtained. A free radical chain-mechanism is then suggested.On the other hand, perfluorobutanesulfonyl fluoride is very stable thermally.     

Synthese und reaktivität von dienylmetall-verbindungen : III. Phosphinigsäureimide als liganden in cyclopentadienylnickelkomplexen

Phosphinous imides form ionic complexes of the type [C₅H₅Ni-(R₂PNR′PR₂)]X (R = C₆H₅; R′ = CH₃, C₆H₅; X = BF₄, Cl). NaCN reacts with [C₅H₅Ni(R₂PNCH₃PR₂)]BF₄ to give the neutral complex C₅H₅Ni-(R₂PNCH₃PR₂)CN (R = C₆H₅) in which the phosphinous imide acts as a monodentate ligand.     

Synthese de polysiloxanes fluores. Partie IV. Obtention de disiloxanes fluores

New disiloxanes containing aromatic or aliphatic fluorinated groups are prepared and identified. The general formula of these compounds is: R_F-Q-CH₂-CH₂-Si(CH₃)₂-O-Si(CH₃)₂-CH₂-CH₂-Q′-R′_F · R_F and R′_F are halogenated groups such as C₆F₅-, C_nF_2n+1-, Cl(CFCl-CF₂)_n, CF₃-CFH-CF₂-, CF₃-, or CCl₃-. In most cases, Q or Q′ is an oxygen atom. Symmetrical disiloxanes are obtained by hydrolysis of corresponding fluorinated monochlorodimethylsilanes, and the asymmetrical ones are prepared in two steps by reacting the fluorinated olefins H₂C = CH-Q-R_F and H₂C = CH-Q′-R′_F with dihydrotetramethylsiloxane. The structures of these various compounds are elucidated by ¹H-, ¹³C- NMR and IR spectroscopy     

PFC's biological carriers of gases: synthesis of F-alkylated sulfides and related compounds

New compounds (R_FC₂H₄SC₂H₄R′_F with R_F=R′_F ou RF≠R′_F), corresponding sulfoxides and sulfones, and related compounds, were prepared, purified and characterized to investigate further the relationship between chemical structure and their usefulness as components of artificial blood.The Sulfides are chemically inert; only oxidations leading to sulfoxides and sulfones under very hard conditions (concentrated H₂O₂, heating) were performed.The oxygen carrier capability was leasured by two ways: —Determination of magnetic susceptibility by NMR using two different configuration spectrometers. — Gas chromatography.Results of the two methods are in good agreement and the same as the best products used as artificial blood substitutes : O₂(40% vol., NMR and G.C.), N₂(35% vol., G.C.), CO₂(150ml/100ml G.C.). Other avantages of such products : — Synthesis quite simple, specific univocal chemical routes. -Series of homologous compounds to permit optimisation of vapor pressure and viscosity on which depends the most important parameters of emulsions - Starting materials commercially available; -Quite quantitative yields. News series of related compounds were obtained, modifying basic structure in the former step of the synthesis by chemical routes.     

Synthese et reactivite d'organomagnesiens perfluores. V.[1] Synthese et identification de nouveaux composes perfluoroalkyles du mercure a chaine longue.

The reaction of mercuric salts HgY₂ or organic mercuric compounds R_HHgX with long chain perfluorinated Grignard reagents R_FMgBr leads to a series of new perfluoroalkyl mercury derivatives with the general formula R_FHgZ (R_F=C₄F₉, C₆F₁₃, C₈F₁₇ ; Z=R_F,R_H,Y with Y = I,Br,Cl, NO₃,OCOCH₃,OCOCF₃).The synthesis of these organomercuric compounds is described, and their spectroscopic properties are reported.     

Reactions of (η5-C5H5)2Tir compounds with organic cyanides

The syntheses and properties of the titanium(III) complexes Cp₂Tir · R′CN (R = C₆H₅, o-, m-, p-CH₃C₆H₄, CH₂C₆H₅, C₆F₅, Cl; R′ = CH₃, t-C₄H₉, C₆H₅, o-CH₃C₆H₄, 2,6-(CH₃)₂C₆H₃) are described. In the complexes the nitrogen atom of the cyanide ligands is coordinated to the metal. The thermal stabilities of the complexes depend markedly on R and R′; on heating they undergo a novel reaction in which two cyanide ligands are coupled by formation of a CC bond, while the metal is oxidized to titanium(IV).     

The Reactivity of Potassium Polyfluoroaryl‐, Polyfluoroalkenyl‐, and Perfluoroalkyltrifluoroborates and their Hydrocarbon Analogues towards Acids of Different Strength: A Systematic Study of the Hydrodeboration

The hydrodeboration of the (fluoroorgano)trifluoroborates K [R_FBF₃] [R_F = C₆F₅, XCF=CF (X = F, cis‐ and trans‐Cl, C₃F₇O, cis‐C₂F₅, trans‐C₄F₉, ‐C₄H₉) and C₆F₁₃] and of the organotrifluoroborates K [RBF₃] (R = C₆H₅, cis‐ and trans‐C₄H₉CH=CH, C₄H₉ and C₈H₁₇) with CH₃CO₂H (100 %), CF₃CO₂H (100 %), aqueous HF and anhydrous HF was investigated. In the alkenyltrifluoroborates K [R'CF=CFBF₃] the formal replacement of BF₃ by a proton occurred stereospecifically under retention of the configuration. The ¹⁹F NMR spectra of K [R_FBF₃] in acids indicate strong interactions of the BF₃ group with protons or acid molecules.     

Synthese von Mono- und Bis(silyl)hydroxylaminen

Synthesis of Mono- and Bis(silyl)hydroxylamines Silylamines reacts with hydroxylaminehydrochlorid to give the monosilylhydroxylamines: R₂FSiONH₂ (R = CMe₃ 1 ), R₂R′SiONH₂ (R = CMe₃, R′ = Me 2 ), R₂(NH₂)SiONH₂ (R = CMe₃ 3 ). The reaction of 1 in the present of HCl-acceptors or the reaction of lithiated 1 with Me₃SiCl or F₂Si(CMe₃)₂ leads to the formation of bis(silyl)hydroxylamines, (Me₃C)₂FSiONHSiMe₃ 4 , and (Me₃C)₂FSiONHSiF(CMe₃)₂ 5 . The lithium derivatives of Me₃SiONH₂ and 2 react with fluorosilanes to the bis(silyl)hydroxylamines: Me₃SiONHSiFRR′ (R = R′ = CMe₃, 6 , R = CMe₃, R′ = F 7 , R = R′ = NMeSiMe₃ 8 ), (Me₃C)₂MeSiNHOSiFRR′ (R = CMe₃, R′ = F 9 , R = (Me₃C)₃C₆H₂, R′ = F 10 , R = R′ = CMe₃ 11 , R = R′ = CHMe₂ 12 ). The bis(silyl)hydroxylamines 4 and 6 are structure isomers.     

Synthese et reactivite des F-alkyl sulfures et sulfones actives

In this paper we report syntheses of F-alkyl compounds such as R_FC₂H₄S(O)_nCH₂Z (with n=0,2 and Z=H,Ø(C₆H₅),COØ,COOEt,COCH₃,CN). Using the carbanionic reactivity of these compounds, we would like to use them as precursors of surfactants, grafting hydrophilic functions on the carbons α or α′ to the sulfur atom. The compounds were not very reactive. Alkylation or acylation on this site could only be obtained with a ‘pseudo malonic’ CH₂ (R_FC₂H₄SO₂CH₂Z with Z=COØ, COOEt,COCH₃,CN). Only methyl iodide and acetyl chloride led to positive results.     

Reactions of diorganoytterbium compounds with ketones and aldehydes

Reactions of the diorganolanthanoids R₂Yb (R = PhCC or C₆F₅) with aldehydes (R′CHO) and ketones (R′₂CO) (R = Me or Ph) followed by hydrolysis generally gives the alcohols RR′CH(OH) or RR′₂COH, but, with benzophenone, reduction giving benzopinacol either competes (R = PhCC) or is predominant (R = C₆F₅).     

Aryl(pentafluorphenyl)iodoniumtetrafluoroborate: allgemeine Synthesemethode,typische Eigenschaften und strukturelle Gemeinsamkeiten

Pentafluorophenyliodine(III) Compounds. 4 [1] Aryl(pentafluorophenyl)iodoniumtetrafluoroborates: General Method of Synthesis, Typical Properties, and Structural Features Aryl(pentafluorophenyl)iodoniumtetrafluoroborates [Ar′Ar″I][BF₄] (Ar′ = C₆F₅, Ar″ = C₆H₅, o‐C₆H₄F, m‐C₆H₄F, p‐C₆H₄F, 2,6‐C₆H₃F₂, 3,5‐C₆H₃F₂, 2,4,6‐C₆H₂F₃, 3,4,5‐C₆H₂F₃, C₆F₅) are prepared in good yields and high purity by the reaction of C₆F₅IF₂ with Ar″BF₂ in CH₂Cl₂. This convenient method can be applied generally to many iodonium compounds. Thermal and spectroscopic properties (¹H, ¹³C, ¹⁹F NMR, IR, Raman) are reported and discussed. The solid state structures of six iodonium compounds show significant cation‐anion interactions which result in two different arrangements: a dimer with a 8‐membered ring or polymers with infinite zigzag chains. Ab initio calculations on prototypes of aryliodonium cations show relations between the kind of the aryl group (C₆H₅ vs. C₆F₅) and structural parameters as well as charges. By means of ¹⁹F NMR the σ_I‐ and σ_R‐constants of the [C₆F₅I]⁺‐substituent are determined.     

Darstellung und Eigenschaften von Diorganyl-bis(seleninato-O,O′)-Komplexen des Bleis und Zinns

Preparation and Properties of Diorganyl-bis(seleninato-O,O′) Complexes of Lead and Tin The colourless, thermically stable diorganyl-bis(seleninato-O , O ′) complexes of lead and tin R₂E(O₂SeR′)₂[E = Pb (1) , Sn (2) ] are obtained by reaction of diorganyllead- and -tindichlorides R₂ECl₂ (R = C₆H₅, CH₃, C₂H₅, n-C₄H₉) with different sodiumseleninates R′SeO₂Na (R′ = C₆H₅, CH₃, C₂H₅) at 20°C. On the basis of their i.r., Raman, and Mößbauer spectra and their slightly solubility in all organic solvents a polymeric structure is supposed in which each two R′SeO₂ - ligands are linking two lead and tin atoms respectively (c.n. = 6) intermolecular (seleninato-O , O ′). The organic residues are in trans-position.     

Triorganyltelluroniumcarboxylate

Triorganyltelluronium Carboxylates By reaction of triphenyltelluronium methoxyd or trimethyltelluronium hydroxyd with carboxylic acid, triorgayltelluronium carboxylates of the type R₃TeO₂CR′ (R ? CH₃, C₆H₅; R′ ? CH₃, CHCl₂, CCl₃, C₆H₅) are obtained. Another preparative method is the reaction of trimethyltelluronium iodide or triphenyltelluronium chloride with silver acetate.     

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.