Reaktionen von Fluorphosphoranen mit dem N,O-Bis(trimethylsilyl)-Derivat des o-Aminophenols

Reactions of Fluorophosphoranes with the N,O-Bis(trimethylsilyl) Derivative of o-Aminophenol The reaction of the N,O-bis(trimethylsilyl) derivative of o-aminophenol, 5 , with the tetrafluorophosphoranes, RPF₄, 2a–2d , (R = F, Me, Ph, and 1-adamantyl) in a 1:1 molar ratio led to monocyclic-1,3,2λ⁵-4,5-benzoxazaphospholes, C₆H₄(O)(NH)PF₂R, 6a–6d . ¹⁹F n.m.r. spectroscopic studies suggest a trigonal-bipyramidal structure with the C₆H₄(O)(NH) grouping attached to one axial and one equatorial position at five-coordinate phosphorus for these compounds. The spirophosphoranes, [C₆H₄(O)(NH)]₂PR, 8a – 8d (R = F, Me, Ph, 1-adamantyl) were obtained from the reaction of the appropriate tetrafluorophosphorane, RPF₄, 2a – 2d with 5 in a 1:2 molar ratio. The compounds 8a – 8d also result from a spontaneous scrambling reaction of 6a – 6d , with the corresponding tetrafluorophosphoranes, RPF₄ ( 2a – 2d ) as the other product. Reaction of the difluorophosphorane, Bu₃ⁿPF₂ with 5 and with N,N′-dimethyl-N,N′-bis(trimethylsilyl)urea furnished the cyclic, fluorine-free phosphoranes, 9 and 10 , respectively. The phosphonium bromide, Bu₃ⁿPFBr, reacted with 5 in a 1:1 and a 2:1 molar ratio to produce the ionic compounds, [C₆H₄(OSiMe₃)(NHPBu₃ⁿ)]⁺Br^?, 11 , and [C₆H₄(OPBu₃ⁿ)HNPBu₃ⁿ]²⁺ 2 Br^?, 12 , respectively.     

Preparation and properties of some cationic binuclear platinum(I) complexes

Reaction of [Pt₂Cl₂(μ-dppm)₂] with ligands, L, in the presence of [PF₆^- gave stable cationic diplatinum(I) complexes [Pt₂L₂(μ-dppm)₂][PF₆]₂ where L = PMe₂Ph, PMePh₂, PPh₃, NH₃, C₅H₅N. Reaction of [Pt₂(NH₃)₂(μ-dppm)₂][PF₆]₂ with CO gave [Pt₂(CO)₂(μ-dppm)₂][PF₆]₂ and an unsymmetrical complex [Pt₂(CO)(C₅H₅N)(μ-dppm)₂][PF₆]₂ was also prepared. The compounds were characterized by vibrational and ¹H and ³¹P NMR spectroscopy and the presence of direct platinumplatinum bonds is indicated.     

Reactions of phosphorus fluorides and ortho-carborane ditertiary aminophosphines

Fluorophosphine bidentate ligands containing o-carborane as backbone can be prepared by the reaction of the lithium-o-carboranes and PF₂X derivatives to give only two species: the unsymmetrical (C₆H₅)₂P[B₁₀H₁₀C₂]PF₂ and the cyclic FP[B₁₀H₁₀C₂]₂PF, both in low yield. However, exchange of F and NMe₂ groups by use of PF₅ or PF₃ provides a facile way to produce several new fluorophosphines.Phosphorus pentafluoride forms solid adducts with the o-phosphino derivatives (C₆H₅)₂P[B₁₀H₁₀C₂]P(NMe₂)₂, (Me₂N)₂P[B₁₀H₁₀C₂]P(NMe₂)₂ and (C₆H₅)₂P[B₁₀H₁₀C₂]H. All the adducts contain a phosphorus-phosphorus bond as evidenced from i.r., NMR and stoichiometry. The stability of the adducts reflects the strength of the PP bond formed upon complexation. When suspensions or solutions of the adducts are heated they exchange F and NMe₂ groups and no redox occurs. The products (C₆H₅)₂P[B₁₀H₁₀C₂]P(F)NMe₂(I) and Me₂N(F)P[B₁₀H₁₀C₂]P(F)NMe₂(II) react further with PF₅ giving (C₆H₅)₂P[B₁₀H₁₀C₂]PF₂(III) and F₂P[B₁₀H₁₀C₂]PF₂(IV).The precursors also react with phosphorus trifluoride to produce only (I) and (Me₂N)₂P[B₁₀H₁₀C₂]P(F)NMe₂(V) regardless of the reaction conditions. All the products I–V have been identified by ¹H, ¹⁹F, and ³¹P NMR and i.r. spectroscopy, mass spectrometry, and elemental analysis. The NMR spectra of the novel (IV) have been analysed as X₂AA¹X¹₂ spin system.     

Synthesis and Characterization of 1,3,2‐Bis (arylamino) phospholidine, 2‐oxide Derivatives: Crystal Structures of $\rm Cl(O)\overline{PN(p-Me-C_{6}H_{4})CH_{2}CH_{2}N}(p-Me-C_{6}H_{4})$ and $\rm ((CH_{2}C_{6}H_{5})(O)\overline{PN(p-Me-C_{6}H_{4})CH_{2}CH_{2}N}(p-Me-C_{6}H_{4})$

Using phosphoryl chloride as a substrate, a family of 1,3,2‐bis(arylamino) phospholidine, 2‐oxide of the general formula ; (X=Cl, 6a ; X=NMe₂, 1b ; X=N(CH₂C₆H₅)(CH₃), 2b ; X=NHC(O)C₆H₅, 3b ; X=4Me‐C₆H₄O, 4b ; X=C₆H₅O, 5b ; X=NHC₆H₁₁, 6b ; X=OC₄H₈N, 7b ; X=C₅H₁₀N, 8b ; X=NH₂, 9b ; X=F, 10b and Ar=4Me‐C₆H₄) was prepared and characterized by ¹H, ¹⁹F, ³¹P and ¹³C NMR and IR spectroscopy, and elemental analysis. A general and practical method for the synthesis of these compounds was selected. The structures of 6a and 2b were determined by single‐crystal X‐ray diffraction techniques. The low temperature NMR spectra of 2b revealed the restricted rotation of P‐N bond according to two independent molecules in crystalline lattice.     

Conversion of iminoacyl quinolinylpalladium (II) complexes into novel oxo‐pyrrolo[3,4‐b] quinolines via depalladation reactions

Oxidative addition reactions of quinolines 1a , b with Pd(dba)₂ in the presence of PPh₃ (1:2) in acetone gave dinuclear palladium complexes [Pd(C,N‐2‐C₉ H₄N‐CHO‐3‐R‐6)Cl(PPh₃)]₂ [(R = H ( 2a ), R = OMe ( 2b ), which were reacted with isocyanide XyNC (Xy = 2,6‐Me₂C₆H₃) to give novel iminoacyl quinolinylpalladium complexes 3a , b in good yields (81 and 77%). Cyclopalladated complexes 3a , b were also obtained in low yields (39 and 33.5%) via one‐pot reaction of 1a , b with isonitrile XyNC:Pd(dba)₂ (4:1). The reaction of 3a , b with Tl(TfO) (TfO = triflate, CF₃SO₃) in the presence of H₂O or EtOH causes depalladation reactions of complexes to provide the corresponding organic compounds 4a , b , 5a , b and 6a , b in yields of 41, 27 and 18 ? 19%, respectively. The products were characterized by satisfactory elemental analyses and spectral studies (IR, ¹H, ¹³C and ³¹P NMR). The crystal structures 2a , 3a and 3b were determined by X‐ray diffraction studies. Copyright © 2008 John Wiley & Sons, Ltd.     

A 19F NMR STUDY OF THE HYDROLYSIS OF ORGANOPHOSPHORUS FLUORIDATES IN AQUEOUS SOLUTION Doubling of the 19F nmr in Diastereoisomeric Mixtures

Abstract

¹H and ¹⁹F nmr spectra of two series of organophosphorus esters containing a P–F bond were studied. 2-Fluoro-4-methyl 1,3,2-dioxaphosphorinane 2-oxide (2) was found to be a mixture of two diastereoisomers in the ratio of trans/cis = 4.

Stereospecific catalysis of phosphate and maleate anions in the hydrolysis of 2 was observed, leading to enrichment of the non-hydrolysed fluoridates with the trans isomer.

The ¹⁹F nmr spectra of O-2-butyl methylphosphonofluoridate (7) and O-pinacolyl methylphosphonofluoridate (8), showed doubling of the ¹⁹F nmr spectra, giving rise to two sets of double quartets of equal intensity. 1:1 mixtures of diastereoisomers account for the doubling of the resonance rather than sterically hindered rotation. The applicability of nmr spectroscopy to the study of stereospecific displacement reactions at tetrahedral phosphorus is discussed.     

H3N·PF5 and H2NPF5−, new compounds in the system H3N/PF5

Phosphorus pentafluoride was reported long ago to give adducts 2 PF₅ ·5 NH₃ (1) and nNH₃·PF₅ (n= 1 ? 4) (2). None of the compounds was characterised in detail. Repeating the reaction of PF₅ and NH₃ we found the adduct H₃N·PF₅, $\text{1}$, in 8% yield besides (H₂N) ₂PF₃ (3) and NH₄PF₆. However, HF and (F₂P=N)₃ gave $\text{1}$ in 41% yield. The ¹H, ¹⁹F, and ³¹P n.m.r. spectra of $\text{1}$ exhibit ¹⁴NH, ¹⁴NPF(cis), and ¹⁴NP coupling. The x-ray structure determination shows almost perfect octahedral geometry at phosphorus with a PN bond length of 1.842 ā. Compound $\text{1}$ is soluble in water without decomposition. Treatment with NH₃ leads to the anion H₂NPF₅^?. Upon heating $\text{1}$ forms in good yield H₂NPF₄ and NH₄PF₆. Without a solvent $\text{1}$ and NH₃ react to give (H₂N) ₂PF₃. A mechanism for the ammonolysis of PF₅ is proposed.     

Zur Darstellung von N,N′-Dimethyldiaza-bis-fluorodichlorophosphetidin Stereoselektive Fluorierung von Phosphor(V)-Verbindungen mittels Bortrifluorid 19F- und 31-NMR-spektroskopischer Nachweis von Brenzcatechylphosphordifluoridchlorid und Brenzcatechylphosphortrifluorid

The reaction between BF₃ and (CH₃NPCl₃)₂ proceeds in benzene solution under substitution of two chlorine atoms by fluorine to give the compound (CH₃NPFCl₂)₂. The two fluorine atoms are located at the axial positions of the two trigonal bipyramidal phosphorus atom environments. The reaction between C₆H₄O₂PCl₃ and BF₃ in benzene solution results in the formation of the known products C₆H₄O₂PFCl₂ and (C₆H₄O₂)₂PCl, and the new compounds C₆H₄O₂PF₂Cl and C₆H₄O₂PF₃. ³¹P and ¹⁹F n.m.r. spectra are discussed.     

A facile synthesis and spectral (ir, 1H, 13C, 31P nmr) studies of 2,10-dichloro-6-aryloxy-12H-dibenzo[d,g][1,3,2]dioxaphosphocin 6-sulfides

The synthesis of new 2,10-dichloro-6-aryloxy-12H-dibenzo[d,g][1,3,2]dioxaphosphocin 6-sulfides 4 was achieved in two steps with high yields from the simple materials 5,5′-dichloro-2,2′-dihydroxydiphenyl-methane (1) and thiophosphoryl chloride (2) which produced the key intermediate 2,6,10-trichloro-12H-dibenzo[d,g][1,3,2]dioxaphosphocin 6-sulfide (3) . Treatment of 3 with substituted phenols under phase transfer catalytic (PTC) conditions led to members of 4 . Long range coupling [⁵J_(P,H) = 3.6 Hz] was observed between phosphorus and one of the bridged methylene protons in 4 . A ¹³C nmr analysis revealed ²J_(P,O,C), ³J_(P,O,C) ⁴J(P,O,C) and ⁵J(P,O,C) couplings. All ³¹P nmr chemical shifts for thirteen members of these new heterocycles are reported for the first time. The nmr data are not totally definitive to confirm a boat-chair as the major conformer for the central eight-membered dioxaphosphocin ring, but such a conformer is tentatively suggested as favored.     

Investigation the chemical reactivity of positions N‐3, C‐5 and C6‐methyl group in biginelli type compounds and synthesis of new dihydropyrimidine derivatives

The compounds 5‐ethoxycarbonyl‐1,6‐dimethyl‐4‐(3‐nitrophenyl)‐3,4‐dihydropyrimidin‐2(lH)‐one (5) and 5‐ethoxycarbonyl‐1‐phenyl‐6‐methyl‐4‐(3‐nitrophenyl)‐3,4‐dihydropyrimidin‐2(lH)‐one (1) were prepared by the Biginelli condensation method and they converted to eight N‐3 substituted dihydropyrimidines using NaH and various electrophiles (ClCO₂Et, TsCl, Ac₂O, AcCl and PhCOCl). Compound (1) was mono‐brominated at the C₆‐methyl group using bromine solution. Reaction of the bromo derivative with amino nucleophiles such as methyl amine and cyclohexyl amine produced two pyrrolo‐pyrimidine derivatives. All the compounds except 5‐ethoxycarbonyl‐1‐phenyl‐6‐methyl‐4‐(3‐nitrophenyl)‐3,4‐dihydropyrimidin‐2(l_H)‐one ( 4 ) were purified by recrystallization methods. The structure of all the new compounds was confirmed using FT‐ir,¹H nmr, ¹³C nmr spectral and elemental analyses methods.     

Derivatives of M(η5-C5H5)2 (M = Mo,W) with alkenylpyridines and related ligands

Reactions of ligands 2-vinylpyridine 1, 4-vinylpyridine 2, 2-allylpyridine 3, 1-allylpyrazole 4, acrylonitrile 5 and allylcyanide 6 with the metallocene derivatives [Mo(η⁵-C₅H₅)₂H₃][PF₆] 7, [Mo(η⁵-C₅H₅)₂HI] 8, [W(η⁵-C₅H₅)₂H₃] [PF₆] 9, [Mo(η⁵-C₅H₅)₂H₂] 10, [M(η⁵-C₅H₅)₂Br₂], M = Mo 11, M = W 12 are described. Reaction of 7 with 1, 8 with 1, 3 with 8 and 4 with 8 gave mixtures of metallocyle isomers resulting from coordination of the nitrogen atom to molybdenum followed by internal hydrometallation; reaction of 11 with 1 gave an olefinic π complex; reaction of either 9 or 11 with 1 gave intractable oils; reactions of 8 with 2, 11 with 5, 12 with 5, 11 with 6 and 12 with 6 yielded monosubstituted products in which the ligand is N-coordinated.     

Synthesis of some novel 5-substituted benzamido-6-arylamino-pyrazolo[3,4-D]pyrimidin-4-one derivatives for herbicidal activity

Abstract

Sixteen novel 3-methylthio-5-substituted benzamido-6-arylamino-1-phenyl-1H-pyrazolo[3,4-d]pyrimidin-4 (5H)-one derivatives (4a–p) were successfully synthesized from iminophosphoranes, aryl isocyanate, and substituted benzoylhydrazine. The structures of the title compounds were elucidated by FT-IR, ¹H NMR, ¹³C NMR, and HRMS. Herbicidal activity of the compounds 4a–p against Brassica napus (rape), Echinochloa crusgalli (barnyard grass), Cucumis sativus (cucumber), and Triticum aestivum (wheat) were determined. The results showed that 5-(2-chlorobenzamido)-6-phenylamino-3-methylthio-1-phenyl-1H-pyrazolo[3,4-d]pyrimidin-4 (5H)-one (4c) displayed remarkable inhibition activity against the stalk and root of rape with 100% inhibition rate at the dosages of 10?mg/L and 100?mg/L, and 5-(4-nitrobenzamido)-6-phenylamino-3-methylthio-1-phenyl-1H-pyrazolo[3,4-d]pyrimidin-4 (5H) -one (4d) exhibited excellent activity against the stalk and root of barnyard grass with 100% inhibition rate at the same dosages.     

Zur Reaktion des 1-Lithio-3-(trimethylsilyl)-2,2,4,4,6,6-hexamethylcyclotrisilazans mit Silicium-Fluor-Verbindungen

The Reaction of 1-Lithio-3-(trimethylsilyl)-2,2,4,4,6,6-hexamethylcyclotrisilazane with Silicon-Fluoro Compounds 1-lithio-3-(trimethylsilyl)-2,2,4,4,6,6-hexamethylcyclotrisilazane reacts with fluoroorganylsilanes RR′SiF₂ (R = F, CH₃, sec-C₄H₉; R′ = CH₃, sec-C₄H₉, C₆H₅) to give mono- and disubstituted trimethylsilylhexamethylcyclotrisilazanes and LiF. The mass-, ¹H- and ¹⁹F-n.m.r. spectra are reported.     

Synthesis of quinazolino-1,3-benzothiazine derivatives

The ring-closure reactions of N-(3,4-dimethoxyphenylthiomethyl)-2-nitrobenzamide derivatives 5a,b with phosphoryl chloride gave 4-(2-nitrophenyl)-2H1,3-benzothiazine derivatives 7a,b , which on reduction yielded 4-(2′-aminophenyl)-3,4-dihydro-2H-1,3-benzothiazines 8a,b. Reaction of these compounds with phosgene led to a new heterocyclic ring system, 6H,8H-quinazolino[3,4-c][1,3]benzothiazine derivatives 9a,b. The structures of the title compounds were proved via their ir and nmr (¹H, ¹³C) spectra.     

Pentafluorphenylverbindungen des Phosphors

Pentafluorophenyl Compounds of Phosphorus The preparation of compounds of the type R(C₆F₅)PX (R = CH₃, C₂H₅, t-C₄H₉ and C₆H₅: X = F, Cl, Br and N(C₂H₅)₂) is described. These derivatives are converted to trifluorophosphoranes, R(C₆F₅)PF₃, and phosphinic acid fluorides, R(C₆H₅)P(:O)F. The n.m.r. spectra are discussed.     

Structural studies of spiroarsoranes derived from 2-aminophenols

This paper describes the structural studies of 2-phenyl-9,9′-dimethyl-2,2′-spirobis(1,3,2-λ⁵-benzoxazarsoline) 5, 2-phenyl-8,8′-dimethyl-2,2′-spirobis(1,3,2-λ⁵-benzoxazarsoline) 6 by ¹H,¹³C,¹⁵N NMR in [²H₆]DMSO and CDCl₃. The solid state studies were made by X-ray experiments. Infrared spectroscopy was obtained in CDCl₃ and the vibrational signals were assigned using DFT calculations. The nature of the As–N, As–C and As–O bonds in these compounds was established by NBO studies.     

Hydroxylation of azomethine carbon: isolation of complexes of η5 and η6-cyclic hydrocarbon platinum group metals with a new Schiff-base ligand

A new Schiff base, (pyridin-2-yl)-N-(3,5-di(pyridin-2-yl)-4H-1,2,4-triazol-4-yl)methanimine, (L), was synthesized. Reaction of [(η⁶-arene)Ru(µ-Cl)Cl]₂ and [Cp*M(µ-Cl)Cl]₂ (M = Rh and Ir) with one equivalent of L in the presence of NH₄PF₆ in methanol yielded dinuclear complexes, [(η⁶-arene)₂Ru₂(L-OH)Cl](PF₆)₂ {arene = C₆H₆ (1), p-ⁱPrC₆H₄Me (p-cymene) (2) and C₆Me₆ (3)}, and [Cp*₂M₂(L-OH)Cl](PF₆)₂ [M = Rh (4) and Ir (5)], respectively, leading to the formation of five new chiral complexes with –OH on the azomethine carbon. L is a pentadentate ligand where one of the metal centers is coordinated to two nitrogen atoms in a bidentate chelating fashion while the other metal is bonded tridentate to three nitrogen atoms. Although the ligand is neutral before coordination, after complexation it is anionic (uni-negative) with negative charge on the azo nitrogen {see the structures: N(5) in 2[PF₆]₂ and N(3) for 4[PF₆]₂}. The complexes have been characterized by various spectroscopic methods including infrared and ¹H NMR and the molecular structures of the representative complexes are established by single-crystal X-ray diffraction studies.     

Synthesis of Symmetrical Bis-(2-chloro-1,3,2-benzodiazaphosphorinones) Hydrolysis and Fluorination of Selected Compounds

The series of symmetrical bis-amides 3 was formed by the reaction of N-methylisatoic anhydride ( 1 ), with the diamines 2 . Reaction of 3 with phosphorus trichloride led to the formation of the symmetrical bis-(1,3,2-benzodiazaphosphorinones) ( 4 ). 4 c , 4 d and 4 e were easily hydrolyzed in moist air, leading to the formation of 5 c , 5 d and 5 e . In the presence of triethylamine, 4 c , 4 d and 4 e were allowed to react with Et₃N · 3 HF to give the symmetrical bis-P–F derivatives 6 c , 6 d and 6 e , which could be readily oxidized by (NH₂)₂C(:O) · H₂O₂, leading to the formation of a series of P(:O)F compounds 7 c , 7 d and 7 e . All compounds were characterized unambiguously by ¹H, ¹³C, ¹⁹F, and ³¹P-NMR-spectroscopy, mass spectrometry, and elemental analysis. All the bis-amides and bis-(1,3,2-benzodiazaphosphorinones), except 4 b and 4 f , exist as single conformers in common solvents such as toluene, diethyl ether, dichloromethane or chloroform. For compound 6 c , a single crystal X-ray structure analysis was conducted. The molecule displays crystallographic inversion symmetry.     

Darstellung und spektroskopische Charakterisierung der Monofluorohydro-closo-Borate [B6H5F]2− und [B12H11F]2−

Preparation and Spectroscopic Characterization of the Monofluorohydro-closo-borates [B₆H₅F]^2? and [B₁₂H₁₁F]^2? By treatment of [B₆H₆]^2? with 1-(chloromethyl)-4-fluoro-1,4-diazabicyclo[2.2.2]octane-bis(tetrafluoroborate)in acetonitrile monofluorohydro-closo-hexaborate [B₆H₅F]^2? ( 1 ) is formed in good yields. [B₁₂H₁₂]^2? reacts with unhydrous HF yielding the monofluorododecaborate [B₁₂H₁₁F]^2? ( 2 ). These compounds are separated by ion exchange chromatography on diethylaminoethyl(DEAE) cellulose from by-products. The ¹¹B nmr spectra exhibit the characteristic patterns (1 : 4 : 1) of a monosubstituted B₆ octahedron and (1 : 5 : 5 : 1) of a monosubstituted B₁₂ icosahedron with strong downfield shifts of the ipso-B nuclei at +9.3 ppm ( 1 ) and at +9.0 ppm ( 2 ). The ¹⁹F nmr spectra reveal quartets at ?212 ppm ( 1 ) and ?209 ppm ( 2 ) proving a B? F bonding. In the i.r. spectra, for ( 1 ) in the Raman spectrum too, cage vibrations depending on the F substituent at 1195 ( 1 ) and at 1182/1154 cm^?1 ( 2 ) are observed. The Raman spectra show the B₆F stretching mode at 535 cm^?1 and the B₁₂F stretching vibration at 445 cm^?1.     

Fluorinated Mono and Spirocyclic Δ5[sgrave]5P and Δ5[sgrave]6P Derivatives of (HO)3−nHnPO (n= 0−3)

Abstract

The properties of PF₅, HPF₄, H₂PF₃, and H₃PF₂ (Δ⁵[sgrave]⁵P derivatives of (HO)₃PO, (HO)₂HPO, (HO)H₂PO, and of the hypothetic H₃PO) and the formation of the related Δ⁵[sgrave]⁶P anions PF₆ ^–, HPF₅ ^–, and trans-H₂PF₄ ^– have been studied some years ago ^1–4. The mono and spirocyclic dioxa and tetraoxa analogues, 1 and 2 available from the corresponding precursor phosphoranes by fluoride addition could be found also as products in the reaction of phosphite 3⁵ and K⁺(CF₃)₂CFO^– together with two other phosphates, 4 and 5. A ¹⁹F–¹⁹F homocorrelated 2 D NMR spectrum of 2 indicated coupling of the P–F fluorine nuclei with two CF₃ groups by a non bond mechanism.