Zur Umsetzung des Zweikomponentensystems Triethylphosphit/Tetrachlorkohlenstoff mit wasserstoffhaltigen Nucleophilen 1. Die Reaktion mit Säureamiden

Reaction of the Two-component System Triethylphosphite/Carbon Tetrachloride with Nucleophiles Containing Hydrogen. 1. Reaction with Acyl Amides Acyl amides react with the two-component system triethylphosphite/carbon tetrachloride yielding N-acyl phosphazenes, (EtO)₃P?N? Ac. In this way (EtO)₃P?N? P(O)(OEt)₂, (EtO)₃P?N? CN, (EtO)₃P?N? C(O)Ph, and (EtO)₃P?N? SO₂Ph were prepared. Ethyl esters of phosphoric acid and trichloromethane phosphonic acid were obtained as by-products.     

Organische Phosphorverbindungen 40. Methoden zur Herstellung von Pentamethylen-1,5-bis-(dihydroxyphosphonylmethyl-phosphinsäure) [1]

Alkyl-pentamethylene-1,5-bis-(dialkyloxyphosphonylmethyl-phosphinates) (VII) are formed in high yield by heating alkyl pentamethylene-1,5-diphosphonites, (RO)₂P(CH₂)₅P(OR)₂, with alkyl chloromethylphosphonates, ClCH₂P(O)(OR)₂, at 170° for several hours until evolution of alkyl halides ceases. Hydrolysis to the corresponding acid (VIII) is effected by refluxing with conc. HCl for 40 h. The synthesis and properties of some other 1,5-diphosphorus-substituted pentanes, i.e., H₂P(CH₂)₅PH₂, Cl₂P(CH₂)₅PCl₂, (Et₂N)₂P(CH₂)₅P(NEt₂)₂, (EtO) (HO)P(CH₂)₅P(OH)(OEt), and (HO)₂P(CH₂)₅P(OH)₂, are also reported.     

Substitutions- und Oxydationsreaktionen des N-Dichlorphosphanyl-triphenylphosphazens,Ph3PN?PCl2

Replacement and Oxidation Reactions of N-Dichlorophosphanyl Triphenylphosphazene, Ph₃P?N? PCl₂ The title compound ( 1 ) reacts with MeOH, EtOH, PhOH, EtSH, and water forming N-phosphanyl or N-phosphinoyl phosphazenes, resp., Ph₃P?N? PX₂ (X ? OPh( 8 ), SEt( 9 )) or Ph₃P?N? PH(O)X (X ? Cl( 3 ), OH( 4 ), OMe( 5 ), OEt( 7 )). The reaction of 1 with P(NEt₂)₃ yields Ph₃P?N? P(NEt₂)₂ ( 10 ). Ph₃P?N? PF₂( 11 ) and Ph₃P?N? PH(O)F ( 12 ) are obtained by chlorine-fluorine exchange. The N-phosphanyl compounds 1 , 8 , 9 and 11 are oxidized by NO₂ yielding the corresponding N-phosphoryl derivatives, Ph₃P?N? P(O)X₂ (X ? Cl( 2 ), OPh( 13 ), SEt ( 14 ), F( 15 )). The thiophosphoryl compounds, (Ph₃P?N? P(S)X₂ (X ? Cl( 16 ), OPh( 17 ), F( 18 )) are obtained by oxidizing 1 , 8 , and 11 with sulfur.     

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.     

Vergleich der Reaktivität von Triethyltrithiophosphit und Trialkylphosphit bei der Synthese von P?N-Verbindungen

Comparison of the Reactivity of Triethyl Phosphorotrithioite and Triethylphosphite by Synthesis of P? N Compounds Triethyl phosphorotrithioite, (EtS)₃P, reacts unlike triethylphosphite with carbon tetrachloride and nitrogen containing nucleophiles. No reaction occurs with diester amides of phosphoric acid. When (EtS)₃P is allowed to react with primary aliphatic amines not amides of phosphoric acid are obtained, but (EtS)₂PCCl₃ and EtSNHEt are yielded. In the reaction of (EtS)₃P with (EtO)₂P(O)H, CCl₄, and NaN₃ results the expected monophosphazene (EtO)₂P(O)? N?P(SEt)₃ only. The different nucleophilicity of phosphorus in (EtS)₂P and (EtO)₃P follows from CNDO/2-MO calculations, too.     

Die Reaktion der Zweikomponentensysteme P(OR)3 − x(NR2)x (x = 0–3)/CCl4 und P4/CCl4 mit HF-Donatoren

Reaction of the Two-component Systems P(OR)_{3 ? x}(NR₂)_x (x = 0–3)/CCl₄ and P₄/CCl₄ with HF-Donators The combination of organylammonium fluorides and carbon tetrachloride is a good agent for oxidative fluorination of trivalent phosphorus compounds. As oxidation products [(RO)PF₅]^? and (RO)₂P(O)F are obtained from P(OR)₃, (Et₂N)₂P(O)F and (Et₂N)₂(EtO)PF₂ from P(OEt)(NEt₂)₂ as well as (Et₂N)₃PF₂ and [(Et₂N)₃PF]⁺ from P(NEt₂)₃. In the system R₂NH/CCl₄/Et₃N · n HF P₄ is fast oxidized forming [HPF₅]^?, R₂NH · PF₅ and (R₂N)₂P(O)F. In the case of simultaneous addition of alcohols [(RO)PF₅]^?, (RO)₃PO and (R₂N)₂P(O)F are formed. The reactions are controlled by the nucleophilic power and the concentration of fluoride, the acidity of the system, and the temperature.     

Synthesis and characterization of modular polyphosphonate homopolymers and copolymers

Linear polyphosphonates with the generic formula –[P(Ph)(X)OR′O]_n– (X = S or Se) have been synthesized by polycondensations of P(Ph)(NEt₂)₂ and a diol (HOR′OH = 1,4-cyclohexanedimethanol, 1,4-benzenedimethanol, tetraethylene glycol, or 1,12-dodecanediol) followed by reaction with a chalcogen. Random copolymers have been synthesized by polycondensations of P(Ph)(NEt₂)₂ and mixture of two of the diols in a 2:1:1 mol ratio followed by reaction with a chalcogen. Block copolymers with the generic formula –[P(Ph)(X)OR′O]_{(x + 2)} –[P(Ph)(X)OR′O]_{(x + 3)}– (X = S or Se) have been synthesized by the polycondensations of Et₂N[P(Ph)(X)OR′O]_{(x + 2)}P(Ph)NEt₂ oligomers with HOR′O[P(Ph)(X)OR′O]_{(x + 3)}H oligomers followed by reaction with a chalcogen. The Et₂N[P(Ph)(X)OR′O]_{(x + 2)}P(Ph)NEt₂ oligomers are prepared by the reaction of an excess of P(Ph)(NEt₂)₂ with a diol while the HOR′O[P(Ph)(X)OR′O]_{(x + 3)}H oligomers are prepared by the reaction of P(Ph)(NEt₂)₂ with an excess of the diol. In each case the excess, x is the same and determines the average block sizes. All of the polymers were characterized using ¹H, ¹³C{¹H}, and ³¹P{¹H} NMR spectroscopy, TGA, DSC, and SEC. ³¹P{¹H} NMR spectroscopy demonstrates that the random and block copolymers have the expected arrangements of monomers and, in the case of block copolymers, verifies the block sizes. All polymers are thermally stable up to ~300°C, and the arrangements of monomers in the copolymers (block vs. random) affect their degradation temperatures and T_g profiles. The polymers have weight average MWs of up to 3.8 × 10⁴ Da.     

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.     

Epoxidation of alkenes with tungsten catalysts immobilised on organophosphoryl macroligands

Organophosphorus ligands when grafted onto porous polymers are able to complex with peroxotungstic acid to give immobilised catalytic species for the epoxidation of alkenes with hydrogen peroxide. The macroligands described here contain the phosphoryl (OP) subunit and are related to phosphine oxides R₃PO, phosphonic, phosphinic or phosphoric acid amides RP(O)(NRR)₂, RR>P(O)NR₂ and PO(NR₂)₃, respectively. These different ligands were introduced in hydrophobic polystyrene and hydrophilic polymethacrylate resins of gel- or macroporous type. This allowed the study of the influence induced on the reactivity and on the selectivity of the epoxidation by the nature of the ligand and by the polar environment around the catalytic sites inside the polymeric beads.     

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).     

Oligomere μ-Imidophosphorsäurechloride und -amide

Oligomeric μ-Imidophosphoric Acid Chlorides and Amides Oligomeric μ-imidophosphoric acid chlorides. Cl₂(O)P? [NH? P(O)Cl]_n? Cl, (n = 1, 2, 3) are obtained by solvolysis of the linear phosphorylchlorphosphazenes, Cl₂(O)P? [N?PCl₂]_n? Cl, with the stoichiometric amount of anhydrous formic acid. The chlorides react with ammonia forming the amides. The amides are characterized by paper and gel chromatography. Course and rate of hydrolysis of diimidotriphosphoric acid pentaamide depend on pH.     

NMR-spektroskopische Untersuchungen an 15N-markierten N-Methyl-imidodiphosphorsäure-Derivaten

NMR Spectroscopic Studies of ¹⁵N Labelled N-Methyl-imidodiphosphoric Acid Derivatives ¹⁵N labelled compounds (EtO)_mCl_2?m(O)P? NMe? P(O)(OEt)_nCl_2?n (m = 0–2, n = 0–2) were prepared as a mixture and investigated by means of ³¹P and ¹⁵N NMR spectroscopy. The chemical shift values δ_P and δ_N, and the coupling constants ¹J_PN and ²J_PP are discussed and interpreted qualitatively by semiempirical quantumchemical calculations (CNDO/2) using POPLE 'S ΔE-model.     

Phosphorsäurebis(trimethylsilyl)ester des 1,1,1,4,4,4-Hexafluor-2,3-bis(trifluormethyl)-2,3-butandiols und des 1,1,1,3,3-Pentafluor-2-propenols

Bis(trimethylsilyl)phosphates of 1,1,1,4,4,4-Hexafluoro-2,3-bis(trifluoromethyl)-2,3-butanediol and 1,1,1,3,3-Pentafluoro-2-propenol The monocyclic phosphorane (EtO)₃P[OC(CF₃)₂C(CF₃)₂O] 1 was hydrolized to give a mixture of an acyclic and a cyclic phosphate, 3 and 4 . The trihydroxyphosphorane 2 could not be obtained. Iodotrimethylsilane 6 converts 1 into the silylated derivative of 4 which was found also besides (Me₃SiO)₂P(O)OC(CF₃)₂C(CF₃)₂OSiMe₃ 8 in the reaction of 3 and 4 with Me₃SiCl/(Me₃Si)₂NH. (Me₃SiO)₃P 10 and hexafluoroacetone did not yield the tris(trimethylsiloxy)phosphorane 5 , but the phosphonate 11 which gave (Me₃SiO)₂P(O)OC(CF₃) ? CF₂ 12 upon heating with the loss of fluorotrimethylsilane.     

Radical telomerization of vinyltrimethylsilane with diethyl phosphite

Telomerization of vinyltrimethylsilane with diethyl phosphite was carried out in the presence of tert-butyl peroxide (TBP), affording a series of regular telomers (EtO)₂P(O)(CH₂CHSiMe₃)_nH (n=1–3)(T_n) and the compounds Me₃Si· (CH₂)₂CH(CH₃)OP(O)(OEt)(CH₂)₂SiMe₃(T₂). Arguments are presented which support a rearrangement with 1,5-H migration in the first propagating radical along a chain including P and O atoms. The partial chain-transfer constant C₁ (6.2) was evaluated.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 8, pp. 1883–1887, August, 1990.     

Novel organosilicon monomer for preparing transparent matrices doped with lanthanide complexes

Perfluoroadipic bis(trialkoxysilylpropyl)amide was synthesized as a mixture of five compounds with the general formula (EtO) _n (MeO)_3-n Si(CH₂)₃NHC(O)(CF₂)₄C(O)NH(CH₂)₃-Si(OMe) _n (OEt)_3-n (1, n = 1, 2). Hydrolysis of this product by a specified amount of water (1: 4) gave oligomers EtO[(HO)(EtO)Si(CH₂)₃NH(O)C(CF₂)₄C(O)NH(CH₂)₃Si(OEt)₂O]_nH ( _n = 7–9). From oligomer solutions, transparent glassy thermally stable films were obtained. The film material was studied by IR spectroscopy, atomic force microscopy, transmission electron microscopy, and powder X-ray diffraction. Compound 1 and oligomers can efficiently solvate lanthanide diketonate complexes. They displace water from the metal coordination sphere, and this water is then spent for hydrolysis of trialkoxysilyl groups. The luminescence intensity of matrix films based on the oligomers depends on the concentration of lanthanide complexes and is very low at 7n_exc = 330 nm, whereas the luminescence intensity of the Eu³⁺ cation is very high.     

Trivalent-pentavalente Phosphorverbindungen/Phosphazene. IV. Darstellung und Eigenschaften neuer N-silylierter Diphosphazene

Trivalent-Pentavalent Phosphorus Compounds/Phosphazenes. IV. Preparation and Properties of New N-silylated Diphosphazenes Phosphazeno-phosphanes, R₃P = N? P(OR′) ₂ (R = CH₃, N(CH₃)₂; R′ = CH₂? CF₃) react with trimethylazido silane to give N-silylated diphosphazenes, R₃P = N? P(OR′)₂ = N? Si(CH₃)₃ compounds decompose by atmospherical air to phosphazeno-phosphonamidic acid esters, R₃ P?N? P(O)(O? CH₂? CF₃)(NH₂). Thermolysis of diphosphazene R₃P = N? P(OR′) ₂ = N? Si(CH₃)₃ (R = CH₃, R′ = CH₂? CF₃) produces phosphazenyl-phosphazenes [N?P(N?P(CH₃)₃)OR′] _n. The compounds are characterized by elementary analysis, IR-, ¹H_-, ²⁹Si-, ³¹P-n.m.r., and mass spectroscopy.     

有机磷化合物的研究XXII: 亚甲基双(膦酸二烷基酯)及其衍生物

研究了从甲基膦酸二乙酯衍生的碳阴离子的磷酰化合成亚甲基双(膦酸二烷基酯)(1)的新方法.     

Reaktion von N-Alkyl-bis(difluorophosphoryl)amiden,RN(POF2)2, mit silylierten Nukleophilen und Et2NSF3

Reaction of N-Alkyl-bis(difluorophosphoryl)amides, RN(POF₂)₂, with Silylated Nucleophiles and Et₂NSF₃ N-Alkyl-bis(difluorophosphoryl)amides, RN(POF₂)₂ (R = Me, Et), react in any case with silylated nucleophiles such as Me₃SiOMe and Me₃SiNEt₂ under cleavage of the PNP bridge forming derivatives of di- and monofluorophosphoric acid. In their reaction with Et₂NSF₃ (RNPF₃)₂ and OPF₃ or PF₅, resp., are obtained. The compounds F₂P(O)? NR? PF₄ and RN(PF₄)₂ postulated as intermediates are not stable.     

Functionalized Pentafluoroethylphosphanes

Bis(diethylamino)pentafluoroethylphosphane represents a versatile starting material for the synthesis of functionalized pentafluoroethylphosphanes. Perfluoroalkyl substituted aminophosphanes themselves already exhibit interesting coordination properties and were treated with the catalytically relevant salts PtCl₂ and PdCl₂ affording trans‐[Cl₂M{P(C₂F₅)(NEt₂)₂}₂]. The hitherto unknown (C₂F₅)PBr₂, accessible in good yields by treatment of C₂F₅P(NEt₂)₂ with HBr, was smoothly transformed into the corresponding phosphane, C₂F₅PH₂, or fluoro derivative, C₂F₅PF₂. Acidic hydrolysis of C₂F₅P(NEt₂)₂ yielded the phosphinic acid C₂F₅P(O)(OH)H, the anion of which was structurally characterized. The phosphinic acid smoothly adds to the carbonyl group of acetone under P?C bond formation. An analogous reaction with aldehydes, for example, salicyl aldehyde, offers the possibility to generate stereocenters.     

Chemistry of Fischer-type rhenacyclobutadiene complexes. II. Reactions with alkynes and sulfonium ylides, and rearrangements induced by nitriles and pyridine

Further investigations into the chemistry of the rhenacyclobutadiene complexes (CO)₄Re(η²-C(R)C(CO₂Me)C(X)) (1: R=Me, X=OEt (1a), O(CH₂)₃CCH (1b), NEt₂ (1c); R=CHEt₂, X=OEt (1d); R=Ph, X=OEt (1e)) are reported. Reactions of 1 with alkynes at reflux temperature of toluene and at ambient temperature either under photochemical conditions or in the presence of PdO yield ring-substituted η⁵-cyclopentadienylrhenium tricarbonyl complexes, 2. The symmetrical alkynes R^′CCR^′ (R^′=Ph, Me, CO₂Me) afford the pentasubstituted complexes (η⁵-C₅(Me)(CO₂Me)(OEt)(Ph)(Ph))Re(CO)₃ (2d), (η⁵-C₅(Me)(CO₂Me)(OEt)(Me)(Me))Re(CO)₃ (2e), (η⁵-C₅(Me)(CO₂Me)(OEt)(CO₂Me)(CO₂Me))Re(CO)₃ (2f), and (η⁵-C₅(Me)(CO₂Me)(NEt₂)(CO₂Me)(CO₂Me))Re(CO)₃ (2i) on reaction with the appropriate 1, whereas the unsymmetrical alkynes R^′CCR″ (R^′=Ph; R″=H, Me) give either only one, (η⁵-C₅(Me)(CO₂Me)(OEt)(Ph)H)Re(CO)₃ (2a)), or both, (η⁵-C₅(Me)(CO₂Me) (OEt)(Ph)(Me))Re(CO)₃ (2b) and (η⁵-C₅(Me)(CO₂Me)(OEt)(Me)(Ph))Re(CO)₃ (2c), (η⁵-C₅(Ph)(CO₂Me)(OEt)(Ph)H)Re(CO)₃ (2g) and (η⁵-C₅(Ph)(CO₂Me)(OEt)(H)(Ph))Re(CO)₃ (2h), of the possible products of [3 + 2] cycloaddition of alkyne to η²-C(R)C(CO₂Me)C(X). Thermolysis of (CO)₄Re(η²-C(Me)C(CO₂Me)C(O(CH₂)₃CCH)) (1b) containing a pendant alkynyl group proceeds to (η⁵-C₅(Me)(CO₂Me)(O(CH₂)₃)H)Re(CO)₃ (2j), a η⁵-cyclopentadienyl-dihydropyran fused-ring product. Competition experiments showed that each of PhCCH and MeO₂CCCCO₂Me reacts faster than PhCCPh with 1a. The results with unsymmetrical alkynes are rationalized by steric properties of substituents at the CC and ReC bonds and by a preference of ReC(Me) over ReC(OEt) to undergo alkyne insertion. A mechanism is proposed that involves substitution of a trans CO by alkyne in 1, insertion of alkyne into ReC bond to give a rhenabenzene intermediate, and collapse of the latter to 2. Complexes 1a and 1d undergo rearrangement in MeCN at reflux temperature to give rhenafuran-like products, (CO)₄Re(κ²-OC(OMe)C(CHCR₂)C(OEt)) (R=H (3a) or Et (3b)). The reaction of 1d also proceeds in EtCN, PhCN, and t-BuCN at comparable temperature, but is slower (especially in t-BuCN) than in MeCN. In pyridine at reflux temperature, 1a undergoes a similar rearrangement, with CO substitution, to give (CO)₃(py)Re(κ²-OC(OMe)C(CHCEt₂)C(OEt)) (4). A mechanism is proposed for these reactions. The sulfonium ylides Me₂SCHC(O)Ph and Me₂SC(CN)₂ (Me₂SCRR^′) react with 1a in acetonitrile at reflux temperature by nucleophilic addition of the ylide to the ReC(Me) carbon, loss of Me₂S, and rearrangement to a rhenafuran-type structure to yield (CO)₄Re(κ²-OC(OMe)C(C(Me)CRR^′)C(OEt)) (R=H, R^′=C(O)Ph (5a); R=R^′CN (5b)). All new compounds were characterized by a combination of elemental analysis, mass spectrometry, and IR and NMR spectroscopy.