Dipyrrolophosphinanes

The reaction of trivalent phosphorus halides with dipyrrolylmethane derivatives provides an entry to a new phosphorus‐containing heterocyclic system. Properties of the newly obtained phosphorus‐containing heterocycles have been studied. © 2000 John Wiley & Sons, Inc. Heteroatom Chem 11:107–114, 2000     

Heterocondensed 1,4‐diphosphinines

A reaction of phosphorus tribromide with a compound containing two 2,5‐dimethyl‐1‐arylpyrrolyl‐3 residues bound through a phosphorus atom gave rise to a new phosphorus‐containing heterocyclic system, 1,4‐diphosphinine. The new products thus obtained have been characterized and described. © 2002 John Wiley & Sons, Inc. Heteroatom Chem 13:46–52, 2002; DOI 10.1002/hc.1105     

C‐phosphorylation of 5,10‐dimethyl‐5,10‐dihydrophenazine and its carbo‐ and heteroanalogs

This study covers phosphorylation of heterocyclic analogues of N‐methyldiphenylamine with phosphorus tribromide in pyridine solution. The reaction is found to proceed regioselectively in accordance with the orienting effect of the amino group. Mono and bis‐phosphorylated derivatives of the heterocycles have been isolated and characterized. It is pointed out that the heterocyclic systems under study exhibit reduced reactivity in electrophilic phosphorylation as compared to N‐methyldiphenylamine. The results of calculations by the PM3 method are reported for the starting molecules and their σ‐complexes. © 2001 John Wiley & Sons, Inc. Heteroatom Chem 12:652–657, 2001     

Synthesis of 4,5‐dihydroimidazo[5,1‐c][1,4,2]benzodiazaphosphinines

Derivatives of a novel phosphorus‐containing heterocyclic system, 4,5‐dihydroimidazo [5,1‐c][1,4,2]benzodiazaphosphinine, have been prepared by the direct phosphorylation of 1‐(2‐(aroyl/alkyl)aminophenyl)‐2‐methylthioimidazole with dibromophenylphosphine in a basic medium. © 2010 Wiley Periodicals, Inc. Heteroatom Chem 22:91–95, 2011; View this article online at wileyonlinelibrary.com . DOI 10.1002/hc.20658     

C‐phosphorylation of N‐arylpyrroles

Phosphorylation of N‐arylpyrroles with phosphorus tribromide proceeds regioselectively at the position 2 of the heterocyclic system. A 2‐to‐3 migration of the dibromophosphino group has been discovered, with its ease depending on the electronic nature of a substituent on the phenyl ring, solvent polarity, and the presence of pyridine hydrobromide in the reaction mixture. Further phosphorylation of 2‐ and 3‐monophosphorylated N‐arylpyrroles regioselectively involves the respective positions 4 and 5 of the heterocycle and is governed by the electron‐acceptor effect of the phosphorus‐containing substituent. © 2002 Wiley Periodicals, Inc. Heteroatom Chem 13:223–228, 2002; Published online in Wiley Interscience (www.interscience.wiley.com). DOI 10.1002/hc.10012     

Effect of the organophosphate structure on the physical and flame‐retardant properties of an epoxy resin

2‐(6‐Oxido‐6H‐dibenzo〈c,e〉〈1,2〉oxa‐phosphorin‐6‐yl)1,4‐benzenediol (ODOPB) and bis(3‐dihydroxyphenyl) phenyl phosphate (BHPP) were successfully synthesized and used as reactive flame retardants in o‐cresol formaldehyde novolac epoxy resin. Because of the rigid, cyclic, side‐chain structure of ODOPB, the resultant phosphorus‐containing epoxy resin exhibited a higher glass‐transition temperature, better flame retardancy, higher modulus, and greater thermal stability than the regular bromine‐containing tetrabromobisphenol A epoxy resin and the linear, main‐chain, phosphorus‐containing BHPP epoxy resin. A UL‐94VO rating was achieved with a phosphorus content as low as 1.1% with ODOPB (comparable to a bromine content of 12% and a phosphorus content of 2.2% with BHPP) in the cured resins, and no fumes or toxic gas emissions were observed. © 2001 John Wiley & Sons, Inc. J Polym Sci Part A: Polym Chem 40: 369–378, 2002     

Ladder‐Type π‐Conjugated 4‐Hetero‐1,4‐dihydrophosphinines: A Structure–Property Study

π‐Conjugated six‐membered 1,4‐dihydrophosphinines containing a heteroatom (Si, P, S) at the 4 position were synthesized and systematically studied. X‐ray crystallographic analyses showed that the central six‐membered heterocyclic rings are almost planar. The sum of the angles around the phosphorus atom increases by 23° from the trivalent phosphorus to the phosphonium atom in the thiaphosphinine system, which is consistent with the NMR spectroscopic studies. UV/Vis spectroscopy and theoretical calculations revealed that the communication between the phosphorus center and the benzothiophene moiety is enhanced by the incorporation of a sulfur atom into the molecular scaffold. The increased conjugation endows the thiaphosphinines with interesting emission properties. Theoretical calculations supported the postulation that the orbital coupling between the π system and a σ* orbital could be enhanced in the thiaphosphinine system, especially through a phosphonium center. Cyclic voltammetry studies revealed that the thiaphosphinine oxide, thiaphosphonium, and cis‐diphosphinine oxide exhibit quasi‐reversible reduction processes, which demonstrate that simple changes in the bridge heteroatoms help to efficiently tune the redox properties of the ladder‐type 4‐hetero‐1,4‐dihydrophosphinines.     

Hydrolysis of the reaction products of hexaethyltriamidophosphite and 2-diethylaminomethyl-6-methylphenol

Conclusions The authors study the hydrolysis of some pentavalent compounds of phosphorus containing phosphaindan heterocyclic groups and a P-N bond. Hydrolysis leads to rupture or retention of the phosphaindan heterocyclic group, depending on the structure.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 1, pp. 154–156, January, 1969.     

Montmorillonite‐based nanocomposites of polybenzoxazole: Synthesis and characterization (I)

Poly(amic acid) was synthesized by means of low‐temperature‐solution polymerization of 3,3′‐dihydroxybenzidine and pyromellitic dianhydride in N,N‐dimethylacetamide. The precursor polymer was heat‐treated at different temperatures to create a polybenzoxazole (PBO) through a polyimide (PI). PI containing the hydroxyl group was rearranged by decarboxylation with heat treatment, resulting in a fully aromatic PBO. Hexadecylamine was used as an organophilic alkylamine in organo‐clay. We have tried to clarify the intercalation of heterocyclic polymer chains to hexadecylamine–montmorillonite (C₁₆‐MMT) and improve tensile properties. It was found that the addition of only a small amount of organo‐clay was enough to improve the mechanical properties of PBO. Maximum enhancement in the ultimate tensile strength for PBO hybrids was observed for the blends containing 4% C₁₆‐MMT. The initial modulus monotonically increased with further increases in the C₁₆‐MMT content. © 2001 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 39: 471–476, 2001     

Study of the Air‐Tolerant 1,3‐Diphosphacyclobutane‐2,4‐diyl through the Direct Arylation

Installing π‐functional substituents on the skeletal phosphorus atoms of the air‐tolerant 1,3‐diphosphacyclobutane‐2,4‐diyl unit are promising for tuning the open‐shell singlet P‐heterocyclic chromophore. The sterically encumbered 1,3‐diphosphaCycloButen‐4‐yl Anion ( CBA ), generated from the phosphorus‐carbon triple bond, was available for the regioselective arylation via nucleophilic aromatic substitution (S_NAr) reaction, addition to arynes, and single‐electron transfer (SET) process affording the corresponding P‐arylated 1,3‐diphosphacyclobutane‐2,4‐diyls. The photo‐absorption and redox properties correlated with the effects of the aryl substituents on the 1,3‐diphosphacyclobutane‐2,4‐diyl unit. The X‐ray analyses enabled not only to discuss the metric parameters but also to visualize the radicalic electrons via the electron‐density distribution analysis. The electron‐donating character of the P‐heterocyclic chromophores induced the p‐type semiconductor behavior. Detection of hydrogen fluoride via formation of the 1λ⁵,3λ⁵‐diphosphete derivative was also developed.     

Facile synthesis of magnetic zinc metal‐organic framework for extraction of nitrogen‐containing heterocyclic fungicides from lettuce vegetable samples

We present a simple method for the fabrication of a magnetic amino‐functionalized zinc metal‐organic framework based on a magnetic graphene oxide composite. The resultant framework exhibited a porous 3D structure, high surface area and good adsorption properties for nitrogen‐containing heterocyclic fungicides. The adsorption process and capacity indicated that the primary adsorption mechanism might be hydrogen bonding and π‐π conjugation. In addition, an optimized protocol for magnetic solid phase extraction was developed (such as adsorbent content, pH, and desorption solvent), and utilized for the extraction of nitrogen‐containing heterocyclic fungicides from vegetable samples. Quantitation by high performance liquid chromatography coupled with tandem mass spectrometry offered a detection limit of 0.21–1.0 μg/L (S/N = 3) with correlation coefficients larger than 0.9975. These results demonstrate that magnetic amino‐functionalized zinc metal‐organic framewor is a promising adsorbent for the extraction and quantitation of nitrogen‐containing heterocyclic fungicides.     

Synthesis of pyridazinedione derivatives starting from anhydrides of 2,3-pyridine- and 2,3-quinolinedicarboxylic acids

A method was developed of preparation of heterocyclic compounds with pyridopyridazinoisoquinalinedione and isoquinopyridazinoquinalinedione structures formed regioselectively by intramolecular cyclization of phosphorus ylides containing pyridopyridazinedione and pyridazinoquinolinedione fragments.     

Flame‐retardant epoxy resins: An approach from organic–inorganic hybrid nanocomposites

Phosphorus‐containing epoxy‐based epoxy–silica hybrid materials with a nanostructure were obtained from bis(3‐glycidyloxy)phenylphosphine oxide, diaminodiphenylmethane, and tetraethoxysilane in the presence of the catalyst p‐toluenesulfonic acid via an in situ sol–gel process. The silica formed on a nanometer scale in the epoxy resin was characterized with Fourier transform infrared, NMR, and scanning electron microscopy. The glass‐transition temperatures of the hybrid epoxy resins increased with the silica content. The nanometer‐scale silica showed an enhancement effect of improving the flame‐retardant properties of the epoxy resins. The phosphorus–silica synergistic effect on the limited oxygen index (LOI) enhancement was also observed with a high LOI value of 44.5. © 2001 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 39: 986–996, 2001     

Phosphorylation of imidazo[2,1‐b]thiazoles with phosphorus(III) halides in the presence of bases

The reaction of phosphorus(III) halides with 6‐substituted imidazo[2,1‐b]thiazoles in the presence of bases proceeds regioselectively and affords 5‐phosphinoimidazo[2,1‐b]thiazoles, useful synthons for the preparation of various P(III) and P(V) derivatives. 5‐Phosphinoimidazo[2,1‐b]thiazoles are selectively alkylated at the phosphorus or heterocyclic nitrogen atom, depending on the alkylating agent. © 2005 Wiley Periodicals, Inc. Heteroatom Chem 16:648–655, 2005; Published online in Wiley InterScience ( www.interscience.wiley.com ). DOI 10.1002/hc.20166     

Bulky Phosphinines: From a Molecular Design to an Application in Homogeneous Catalysis

The design and preparation of an asymmetrically substituted and bulky phosphinine was achieved by introducing sterically demanding substituents into specific positions of a rigid phosphorus‐heterocyclic framework. Compound 5 shows, at the same time, axial chirality and a sufficiently high energy barrier for internal rotation to prevent enantiomerization. Both enantiomers of 5 were isolated by means of chiral analytical HPLC, and their absolute configurations could be assigned by combining experimental data and DFT calculations. Despite its substitution pattern, 5 can still coordinate to transition‐metal centers through the lone pair of electrons on the phosphorus atom. Rapid C? H activation on the adjacent aryl substituent at the 2‐position of the phosphorus heterocycle was achieved by using [{Cp*IrCl₂}₂] (Cp*=1,2,3,4,5‐pentamethylcyclopentadienyl) as a metal precursor. A racemic mixture of 5 was applied as a π‐accepting low‐coordinate phosphorus ligand in the Rh‐catalyzed hydroformylation of trans‐2‐octene, which showed a clear preference for the formation of 2‐methyloctanal.     

Observation of a Metastable P‐Heterocyclic Radical by Muonium Addition to a 1,3‐Diphosphacyclobutane‐2,4‐diyl

A 1,3‐diphosphacyclobutane‐2,4‐diyl contains a unique unsaturated cyclic unit, and the presence of radical‐type centers have been expected as a source of functionality. This study demonstrates that the P‐heterocyclic singlet biradical captures muonium (Mu=[μ⁺e^?]), the light isotope of a hydrogen radical, to generate an observable P‐heterocyclic paramagnetic species. Investigation of a powder sample of 2,4‐bis(2,4,6‐tri‐t‐butylphenyl)‐1‐t‐butyl‐3‐benzyl‐1,3‐diphosphacyclobutane‐2,4‐diyl using muon (avoided) level‐crossing resonance (μLCR) spectroscopy revealed that muonium adds to the cyclic P₂C₂ unit. The muon hyperfine coupling constant (A_μ) indicated that the phosphorus atom bearing the t‐butyl group trapped muonium to provide a metastable P‐heterocyclic radical involving the ylidic MuP(<)=C moiety. The observed regioselective muonium addition correlates the canonical formula of 1,3‐diphosphacyclobutane‐2,4‐diyl.     

Structural and 31P NMR solution studies on some cyclic triphosphenium ions and their 2‐arsa‐analogues

Several new cyclic triphosphenium ions and their 2‐arsa‐analogues have been identified in solution by ³¹P NMR spectroscopy. The crystal and molecular structures of the cations 1a,b , as their hexachlorostannate (IV) salts have shown that the five membered heterocyclic rings are planar, whereas the cation 9b as its diphosphanedioxide‐bis[pentachlorostannate(IV)] salt is nonplanar, like its saturated phosphorus counterpart. © 2001 John Wiley & Sons, Inc. Heteroatom Chem 12:501–510, 2001     

1,2‐migration in N‐phosphano functionalized N‐heterocyclic carbenes

1,2‐Migration of the phosphano‐group to the carbene center in N‐phosphano functionalized N‐heterocyclic carbenes has been studied by density functional theory (DFT) calculations. An intramolecular mechanism with a three‐center transition state structure seems to be most plausible for the isolated carbenes, while an intermolecular pathway catalyzed by azolium salts may be preferable for a migration proceeding in the course of generating the carbenes in situ. Our calculations show that amino‐substitution at the phosphorus atom and an enhanced nucleophilicity of the heterocycle scaffold facilitate the phosphorus shift. Calculated singlet‐triplet energy gaps do not correlate with thermodynamic stability of the studied carbenes and their disposition toward the 1,2‐rearrangement. © 2014 Wiley Periodicals, Inc.     

Synthesis of some new pyrido[2,3‐d]pyrimidines and their ribofuranosides as possible antimicrobial agents

The ribofuranosides, namely, 4‐amino‐5,7‐disubstituted‐1‐[2′,3′,5′‐tri‐O‐benzoyl‐α‐d ‐ribofuranosyl]pyrido‐[2,3‐d] pyrimidine‐2(1H)‐thiones, have been synthesized by the condensation of trimethylsilyl derivatives of 5,7‐disubstituted pyrido[2,3‐d]pyrimidine‐2(1H)‐thiones with β‐d ‐ribofuranose‐1‐acetate‐2,3,5‐tribenzoate in the presence of SnCl₄. The heterocyclic bases, namely, 4‐amino‐5,7‐disubstituted pyrido[2,3‐d]pyrimidine‐2(1H)‐thiones, were synthesized by the treatment of 2‐amino‐3‐cyano‐4,6‐disubstituted pyridines with thiourea. The structures of all the synthesized ribofuranosides and their precursors have been established by elemental analysis, IR, and ¹H NMR spectral data. The ¹³C NMR data of ribofuranosides has also been presented. All the synthesized heterocyclic bases and their ribofuranosides have been screened for their antibacterial and antifungal activities. © 2001 John Wiley & Sons, Inc. Heteroatom Chem 12:52–56, 2001