Thiophosphoryl Compounds Research Articles

Analysis of P–O–C, P–S–C and P–O–P angles: a database survey completed with four new X-ray crystal structures

Four new crystal structures, P(O)(OC6H5)2(NHNHC6H5) (I), P(S)(OCH3)2(NHCH(CH3)2) (II), P(S)(OCH3)2(NH-cyclo-C5H9) (III) and [2–Cl–C6H4CH2NH3]2[(CH3S)P(O)(O)–O–P(O)(O)(SCH3)] (IV) were studied. The P–O–C angles were analyzed, considering phosphoryl compound (I) and thiophosphoryl compounds (II) and (III) and their analogous structures deposited in the Cambridge Structural Database (CSD), including 282 P(O)(O)2(N) structures (706 P–O–C angles) and 186 P(S)(O)2(N) structures (518 P–O–C angles) with at least one P–O–C angle. The maximum populations of P–O–C angles are within 120°–122° in both P(O)(O)2(N) and P(S)(O)2(N) families of structures, confirming the hybridization state close to sp 2 for the oxygen atom of P–O–C. A survey on the CSD resulted in 11 P(O)(O)2(S–C) structures (11 P–S–C angles), and the structure (IV) belonging to this family of compounds is the first diffraction study of a salt with a (S)P(O)(O)–O–P(O)(O)(S) skeleton in the anion component. For the P–S–C angles, the maximum population was found in the range of 100°–104° showing the angles within those related to unhybridized pure p orbitals (p 3) and hybridized sp 3 for the sulfur atom of P–S–C. The analysis of 187 P(O)–O–P(O) structures (with no restriction on the other two atoms attached to phosphorus) including 538 P–O–P angles yielded the maximum population of P–O–P angles within 132°–134°, showing the more pronounced “s” character of the orbital (with respect to the sp 2 and toward sp) for the oxygen atom at the P–O–P moiety.

Pyrrole-Based New Diphosphines: Pd and Ni Complexes Bearing the PNP Pincer Ligand

A new class of diphosphine PNP pincer ligand, 2,5-bis(diphenylphosphinomethyl)pyrrole 2, was synthesized by the reaction between Ph2PH and 2,5-bis(dimethylaminomethyl)pyrrole in 90% yield. The analogous reaction of Ph2PH with 1,9-bis(dimethylaminomethyl)diphenyldipyrrolylmethane readily afforded a PNNP type diphosphine ligand, 1,9-bis(diphenylphosphinomethyl)diphenyldipyrrolylmethane 5 in 92% yield. These phosphine compounds were oxidized with H2O2 and S8 to give the corresponding phosphoryl and thiophosphoryl compounds 6-9 in very good yields. The reaction of the PNP pincer ligand 2 with [PdCl2(PhCN)2] in the presence of Et3N afforded the mononuclear Pd(II) complex, [PdCl{C4H2N-2,5-(CH2PPh2)2-κ(3)PNP}] 10 in 87% yield. Conversely, treatment of 2 with [PdCl2(PhCN)2] in the absence of Et3N gave the dinuclear Pd(II) complex [Pd2Cl4{μ-C4H3N-2,5-(CH2PPh2)2-κ(2)PP}2], the structure which is proposed based on the spectroscopic data. When 2 was treated with Pd(0) precursor [Pd2(dba)3]·CHCl3 the dinuclear Pd(I) complex [Pd2{μ-C4H2N-2,5-(CH2PPh2)2-κ(2)PN,κ(1)P}2], 12, was obtained in 23% yield. The formation of complex 12 is solvent dependent, which transforms into complex 10 in CDCl3 as studied by variable temperature (1)H and (31)P NMR methods. Treatment of 2 with [Ni(OAc)2]·4H2O gave the mononuclear Ni(II) pincer complex [Ni(OAc){C4H2N-2,5-(CH2PPh2)2-κ(3)PNP}], 13, which upon treatment with an excess of LiCl or LiBr or KI afforded the respective halide ion substituted Ni(II) complexes, [NiX{C4H2N-2,5-(CH2PPh2)2-κ(3)PNP}] (X = Cl, Br, and I), 14-16, in very good yields. The structures of 5, 2,5-bis(diphenylphosphorylmethyl)pyrrole 6, 10, 12, and 14-16 were determined by the single crystal X-ray diffraction method. In the structure of 12, two short contacts between the diagonally positioned Pd and P atoms are observed. To understand these weak interactions, density functional theory (DFT) calculations were done and an interaction MO diagram is presented.

ChemInform Abstract: Sigmatropic Rearrangements in Phosphorylated 2-Azaallyl Systems. Part 8. Reaction of N-Benzyltrifluoroacetimidoyl Chloride with Thiophosphoryl Compounds.

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Biocatalytic oxidation of thiophosphoryl compounds: a new chemo-enzymatic approach to enantiomeric insecticidal thionophosphates and their oxons

The biocatalytic oxidation of racemic O- S-dimethyl O- p-nitrophenyl phosphorodithioate 5 catalyzed by chloroperoxidase from Caldariomyces fumago resulted in the formation of the (−)-( S)-enantiomer of the corresponding oxon 4 and unoxidized substrate 5 with a (+)-( R)-configuration. Both compounds were obtained with very high enantiomeric excesses, 99.6% and 97%, respectively. The thionation reaction of the resulting (−)-( S)-oxon 4 with Lawesson’s reagent gave (−)-( S) -phosphorodithioate 5 with full stereoselectivity, while the oxidation of unreacted substrate (+)-( R)- 5 with iodoxybenzene afforded oxon (+)-( R)- 4 with 94.9% ee.

Thiophosphoryl disulfides as crosslinking agents for chloroprene rubber

AbstractThe objective of this investigation was the determination of a suitable substitute for ethylene thiourea (ETU), a well‐known vulcanizing agent for polychloroprene rubber (CR). Unfortunately, ETU is a potent carcinogenic compound, and so its replacement is needed. The efficacy of several thiophosphoryl disulfides as crosslinking agents for CR, either alone or in combination with other compounds, was examined. It was shown that bis(diisopropyl)thiophosphoryl disulfide (DIPDIS) and bis(dicyclohexyl)thiophosphoryl disulfide (DCHDIS), being ecofriendly, could be replacements. Additionally, these thiophosphoryl compounds were shown to provide significant antioxidant protection. CR vulcanizates containing DIPDIS or DCHDIS exhibited higher tensile strengths than those containing ETU. Bis(3‐ethoxysilylpropyl) tetrasulfide imparted to CR vulcanizates a notable modulus, which was comparable to that obtained with ETU‐cured products. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 91: 1913–1919, 2004

A DFT and MP2 Study on the Molecular Structure and Vibrational Spectra of Halogenosubstituted Phosphoryl and Thiophosphoryl Compounds

The molecular geometrical parameters, rotational constants, dipole moments and vibrational infrared properties of a series of phosphoryl compounds (OPX i Y j Z k , X, Y, Z = F, Cl, Br; i+ j + k = 3) and their thio analogs are predicted by density functional and MP2 calculations using the 6-311G(2d,2p) basis set. Both methods yielded similar results. The predicted molecular parameters and the vibrational Raman and infrared spectra agree well with the available experimental data. The Raman Scattering Activities (RSA) and depolarization ratios (Dep) of the molecules are obtained by DFT calculations. Considering the different substitution modes of various halogen atoms, the resultant changes in the geometrical and vibrational properties are discussed. Such studies permit detailed information to be obtained concerning unknown molecules and can define the guidelines for synthesizing molecules of particular characteristics.

Effect of thiophosphoryl compounds as accelerators and coupling agents on the vulcanization of NR‐XNBR blend

AbstractThe effect of a number of thiophosphoryl compounds [viz., bis(isobutyl) thiophosphoryl di‐, tri‐, and tetrasulfides and bis(dicyclohexyl) thiophopsphoryl di‐, tri‐, and tetrasulfides] on natural rubber (NR)‐carboxylated nitrile rubber (XNBR) blend was studied. All these thiophosphoryl compounds are capable of forming interrubber links leading to covulcanized blends which exhibit a fair degree of synergism with respect to physical properties, the maximum being obtained at the 25% NR and 75% XNBR blend composition. This is an obvious claim that the blend under investigation is technologically compatible, having some degree of interrubber interaction which is enhanced in case of two‐stage vulcanization. The existence of interrubber interaction is judged by the swelling experiment. The blend morphology assessed by SEM micrographs corroborates the foregoing observations and accounts for the significant improvement in physical properties of the blend vulcanizates, particularly in two‐stage vulcanization. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 3286‐3299, 2002

New Phosphorus-Containing Polycylic Large-Ring Systems Involving Heteroatoms

The [1+1] cyclocondensation of the bis-PCl species 1,2-bis(benzo-1-methyl-2-chloro- 1,3,2-diazaphosphorin-4-on-3-yl)ethane 1 and 1,3-bis(benzo-1-methyl-2-chloro-1,3,2-diazaphosphorin- 4-on-3-yl)propane 2 with the 1,2-benzenediol bis(trimethylsilyl) ether 3a and 2,3- naphthalenediol bis(trimethylsilyl) ether 3b gave the symmetrical phosphorus-containing largering systems 4 - 7 in moderate yield. The phosphoryl compounds 8 - 11 were obtained by the oxidation of 4 - 7 with (H2N)2C(:O) H2O2. Oxidation of 6 and 7 with elemental sulfur furnished the thiophosphoryl compounds (12 and 13). All new compounds formed in the reactions were characterized unambiguously by NMR spectroscopy, mass spectrometry, and elemental analysis. For compounds 6, 9, 10, 11 and 12, X-ray crystal structure determinations were conducted. The compounds with ten-membered rings show approximate (6, 12) or exact (10) twofold symmetry. In each of the compounds 9 and 11 the two six-membered heterocycles are appreciably different; one is approximately planar, whereas in the other, phosphorus lies outside the plane of the other five atoms

Kinetic resolution of P-chiral tertiary phosphines and chlorophosphines: a new approach to optically active phosphoryl and thiophosphoryl compounds

Treatment of racemic P-stereogenic tertiary phosphines with enantiomerically pure bis-phosphoryl and bis-thiophosphoryl disulfides under kinetic resolution conditions (2:1 ratio) afforded enantiomerically enriched tertiary phosphine oxides or phosphine sulfides with ee values up to 39%. In a similar way from racemic tert-butylphenylchlorophosphine, optically active tert-butylphenylphosphinoyl chloride with 50% ee was obtained. The same reaction performed under dynamic kinetic resolution conditions (1:1 ratio of reagents) in the presence of chloride ions gave phosphinoyl chloride with 70% ee.

Chemo-, regio- and stereoselective conversion of P-chirogenic phosphorus borane complexes into their PO or PS derivatives

Chiral and achiral organophosphorus borane complexes are readily transformed into their corresponding phosphoryl or thiophosphoryl compounds in high yields using one-pot procedures with stereoselectivities reaching 100% in many cases. Both oxidation and sulfuration were performed under neutral or mild conditions and were applied to various organophosphorus borane complexes (phosphines, phosphinates, chlorophosphines, aminophosphines, etc.). In the case of the dissymmetric diphosphine or aminophosphine phosphinite ligands, the reaction of their diborane complexes proceeds regiospecifically to a single phosphorus group, affording the corresponding hybrid derivatives.

Synthesis and Some Transformations of 1,2-Heterophosphacyclanes

The general pathway to 1,2-monoheterophosphacyclanes via intramolecular S-and N-alkylation of ω-halogenoalkylsubstituted thiophosphoryl and iminophosphoryl compounds has been developed. Intramolecular alkylation of 3-and 4-halogenoalkyldiphenylphosphine sulfides results in 1,2λ4-thiaphospholanium and thiaphosphorinanium halogenides. In solution of these compounds the rare ring-chain halogenotropic tautomerism has been observed and investigated in detail. Intramolecular Pishchimuka rearrangement of the esters of ω-halogenoalkylsubstituted thiophosphorus acids was found to be a synthetic route to 2-oxo-1,2λ5-thiaphospholanes and thiaphosphorinanes.

Iodine–azide reagent for the detection of biologically oriented thiophosphoryl compounds in thin-layer chromatography systems

The correlation between induction factors ( F i) of phosphorothioates in the iodine–azide reaction and their detection limits (DLs) using the iodine–azide reagent has been established. The iodine–azide reagent has been used for the selective thin-layer chromatographic detection of several sugar phosphorothioates and related compounds. In several cases, hydrolytic treatment of phosphorothioates, prior to their detection on thin-layer chromatography (TLC) plates with the iodine–azide reagent, was accompanied by a dramatic increase in the detectability of the starting compounds. Comparison of TLC detection systems for phosphorothioates using iodine–azide procedures and other representative procedures are presented. The application of the iodine–azide procedure combined with the molybdate procedure for selective TLC detection of phosphates and phosphorothioates is illustrated.

Complexes Of Thiophosphoryl Compounds with AgNO3

Abstract Under conditions of interphase catalysis complexiDg agenta L1, L2 and L3 have been synthesizedl. Using spectral and X-ray methods complex fomation of thises ligands with AgNO3 has been studied

Synthesis, Conformational Studies, X-ray Structures, and Complexation Properties of Semirigid Macrocyclic Phosphonamides.

The semirigid phosphonamide ligands 1-5 have been synthesized from the macrocyclic precursors 6-9 by reaction with 1,3-propanediol ditosylate or 1,2-dichloroethane. For the thiophosphoryl compounds 1 and 2, and the phosphoryl derivative 5, the reactions were carried out in biphasic aqueous NaOH solutions. The phosphoryl derivatives 3 and 4 were better obtained from NaH in anhydrous tetrahydrofuran. The conformations of the hosts in solution were deduced from low-temperature NMR and NOE difference experiments. Conformational equilibria between exo and endo forms are observed for the 18-membered macrocycles 1 and 3. The exo conformer predominates in solution for the 21-membered macrocycle 2, whereas 4 exists as rapidly exchanging conformers. The X-ray crystal structures of macrocycles 1, 2, and 5 have been determined as well as the complexes 1.Hg(SCN)(2) and 5.LiNO(3). In the Hg(2+) complex the metal ion is located out of the macrocyclic cavity and is coordinated to the thiophosphoryl unit. In 5.LiNO(3)()()the Li(+) cation is located inside the macrocyclic cavity and is coordinated to a tetrahedral array of oxygen donors. Free energies of complexation (DeltaG degrees ) of the phosphorylated ligands 3-5 with alkali metal and ammonium cations were determined in CHCl(3) saturated with H(2)O by picrate extraction experiments. The -DeltaG degrees values are greatest for 4 complexing K(+) and NH(4)(+) (7.3 and 8.0 kcal/mol, respectively). The relationships between structure and binding are discussed.

α-HYDROXYPHOSPHINOXIDE UND -SULFIDE DURCH ADDITION VON DIMETHYLPHOSPHINOXID BZW. -SULFID AN ALDEHYDE UND KETONE

Abstract Me2P(:O)H and Me3P(:S)H reacted with several aldehydes with formation of the corresponding tertiary phosphine oxides and sulfides 1-5. While the phosphoryl compounds 1 and 3 show intramolecular hydrogen bridges of the type P[dbnd]O … H—O (IR spectroscopy), no analogous bridges were observed in the case of the thiophosphoryl compounds 2,4 and 5. Me2P(:O)H also reacted with diacetylmonoxime to give the mono-adduct 6 and with 1,1′-diacetylferrocene to give the di-adduct 7. In both cases the addition took place only in the presence of KO'Bu (6: excess KO'Bu, 7: catalytic amounts).

Ab initio IGLO calculations of 31P NMR shielding tensors of thiophosphoryl compounds. I—dithiadiphosphetanes and dithioxophosphoranes

AbstractBy means of the IGLO method the 31P NMR chemical shift, δiso, the principal values, σii, and the orientation of the principal axes of the shielding tensor were calculated for a number of dithiadiphosphetanes [RP(S)S]2 and of dithioxophosphoranes RPS2 with RH, CH3 or C6H5. The calculated compare well to the available experimental data from solid‐state NMR and can be taken as predictions where no experimental data are available. The dependence of the principal values σii on geometry changes and the substitution was studied. The shielding tensors were calculated as sums of contributions of localized molecular orbitals. These contributions were used to discuss the effects observed. They provide valuable insights into relationships between geometrical structure and the principal values of σ.

Organothiophosphorus compounds as inductors of the iodine—azide reaction. Analytical application

Thiophosphoryl compounds were found to exhibit strong induction activity in the iodine—azide reaction. On this basis three procedures for their determination: titrimetric (0.15–1 μmol), coulometric (1–20 nmol) and spectrophotometric (0.5–5 nmol) have been developed. RSD in all applied methods (techniques) have been found at the 1–7% level. The induction coefficients were dependent on the type of compound applied and on the reaction condition and varied from 90 to 450.

Beiträge zur Chemie des 4,5-Benzo-3-methyl-1,3,2-oxazaphosphorinan- 6-on Ringsystems: Röntgenstrukturanalysen an einem Bis(2-chlorethyl)amino- und einem Acetamido-substituierten Derivat / Chemistry of the 4,5-Benzo-3-methyl-1,3,2-oxazaphosphorinan-6-one Ring System: X-Ray Crystal Structure Analysis of a Bis(2-chloroethyl)amino- and of an Acetamido-Substituted Derivative

Abstract The reaction of 4,5-benzo-2-chloro-3-methyl-1,3,2-oxazaphosphorinan-6-one 1 with 1,2-bis- (trimethylsiloxy)ethane led to the bisphosphoryl species 2a and to the isomeric bisphosphite derivative 2b. The reaction of 1 with heptamethyldisilazane furnished the expected diphos­phorus compound 3, with two λ3P(III) atoms linked by a methylamino group. Substitution of the chlorine atom of 1 by the 2-chloroethylamino and bis(2-chloroethyl)amino group led to the oxazaphosphorinanones 4 and 6. By oxidation of 4 with the hydrogen peroxide/urea 1:1-adduct, the phosphoryl compound 5 was formed. Oxidation of 4,5-benzo-2-diethyl- amino-3-methyl-1,3,2-oxazaphosphorinan-6-one 7 [1] with hydrogen peroxide, sulfur and se­lenium led to the corresponding phosphoryl, thiophosphoryl and selenophosphoryl com­pounds 8-10. Analogously, the reaction of the dimethylamino- and acetamido-substituted derivatives 11 and 13 [1] with elemental sulfur furnished the thiophosphoryl compounds 12 and 14. X-ray crystal structure determinations of 4 and 14 confirmed the molecular structures, proposed in accord with NMR spectroscopic and mass spectrometric data. The heterocyclic rings are essentially planar. In 14 a hydrogen bond N-H···O (amide) is observed.

X‐Ray determination of the effective charges on sulfur and phosphorus atoms in chemical compounds

AbstractThe dependencies of Kα line shifts of the P and S atoms on effective charges of the atoms, calculated by CNDO/S, CNDO/2, INDO, and MNDO methods in the minimal and extended basis sets, have been investigated for model compounds. Good linear relationships between Kα shifts and atomic charges have been obtained for all cases investigated except for CNDO/2 and INDO calculations in the extended basis set. It is found that the PS bond ionicity is a nearly constant value, whereas the PS bond ionicity increases linearly with an increase in the positive charge of the central P atom. It is shown that the P and S atom charge in sulfides and phosphines containing no substituents with a strong M‐effect at the central atom depend only on inductive substituent effects. Also, the positive charge on the central atom increases with the growth of the π‐donor properties of substituents in sulfides and phosphines containing substituents exerting a strong M‐effect, as well as in phosphoryl and thiophosphoryl compounds and sulfones.

Application of the iodine-azide reagent for selective detection of thiophosphoryl compounds in thin-layer chromatography

The application of the iodine-azide-induced reaction for the detection of thiophosphoryl compounds in thin-layer chromatographic systems is described. The detection limits of the derivatives tested were found to be at the nanomole level and depend on the nature of the P(S) n function, particularly on the degree of polarity of the PS bond and the number of sulphur atoms in the molecule. A comparison of the iodine-azide test reaction with other procedures used for thiophosphoryl compounds is presented. A procedure for the differentiation of thiophosphoryl compounds and sulphur compounds based on the combined molybdate procedure preceded by a preoxidation stage is demonstrated.