A new class of phosphorus macrocycles were synthesized from 2‐[(E)‐2‐2 [(hydroxymethyl) phenyl] imino ethylidene) amino] phenyl methanol 1 with various phenylphosphorodichloridates, phenyldichlorophosphine, and ethyldichlorophosphite in the presence of triethylamine at 0–10°C under N2 atmosphere in THF. All the title compounds were confirmed by analytical and spectral data (IR, 1H‐, 13C‐, 31P‐NMR, and mass). The title compounds exhibited promising anti‐oxidant activity. J. Heterocyclic Chem., (2011). 相似文献
Summary: 1,3‐Bis(methacrylamido)propane‐2‐yl dihydrogen phosphate ( 1 ) was synthesised by phosphorylation of 1,3‐bis(methacrylamido)‐2‐hydroxypropane ( 2 ) with phosphorus oxychloride in tetrahydrofuran (THF) in the presence of triethylamine (TEA). The structure of the new monomer 1 was characterised by IR, 1H NMR, 13C NMR and 31P NMR spectroscopies, elemental analysis and mass spectrometry. The monomer dissolves well in water, ethanol or aqueous THF and shows an improved hydrolytic stability compared to the corresponding methacrylate‐based dihydrogen phosphates. 1 was homopolymerised in ethanol with 2,2′‐azoisobutyronitrile (AIBN) as the initiator at 55–75 °C under the formation of an insoluble, cross‐linked product. Aqueous solutions of 1 are strongly acidic and enable to etch enamel and dentin. Nevertheless, 1 did not show any cytotoxic effect. Furthermore, the adhesive properties of 1 were measured.
Abstract We have synthesized and characterized a series of alkyl and aryl‐(4‐methyl‐6‐nitro‐quinolin‐2‐yl)amines through a high‐yield, three‐step procedure starting from 4‐methylquinolin‐2‐ol. Nitration using concentrated nitric/sulfuric acids, followed by chlorination in phosphorus oxychloride, yielded 2‐chloro‐4‐methyl‐6‐nitro‐quinoline. All of the intermediates and aminated products have been characterized by multinuclear (1H and 13C) NMR spectroscopy, elemental analysis, and, in the case of the two title compounds (ethyl and cyclohexyl‐(4‐methyl‐6‐nitro‐quinolin‐2‐yl)amine), a single crystal X‐ray structure was obtained to verify the nature of the new materials. 相似文献
A few new seven-membered phosphorus heterocyclic compounds and bis-phosphonates (5a—5g, 5f’, 5g’, 9 and 10) were prepared by the reaction of 4-bromo dioxaphosphepin (2) with various Grignard reagents followed by their oxidation with H2O2. All the compounds were thoroughly characterized by elemental analysis, IR, 1H, 13C, 31P NMR and mass spectral data. Their antimicrobial activity was evaluated and some of them possess significant activity. 相似文献
The reaction of the bis‐chlorophosphines 1 a – 1 d with bis(2‐chloroethyl)amine hydrochloride in the presence of triethylamine and with various trimethylsilylamines led to a new class of bis‐phosphorus ligands 2 a – 2 c and 3 a – 3 g . 31P‐NMR studies suggested that the bis‐phosphorus ligands undergo rotation reactions about the alkyl bridge in polar solvents. Compounds 2 a – 2 c showed initially only one sharp singlet each in their 31P‐NMR spectra. After a few days at room temperature, two signals were observed. Similar results were observed for 3 a – 3 g . In the solid state, the two phosphorus atoms in 2 c are not equivalent, as was confirmed by the observation of two signals in the solid state 31P‐NMR spectrum. Oxidation reactions of 2 a – 2 c by the hydrogen peroxide‐urea 1 : 1 adduct (NH2)2C(:O) · H2O2 led to the formation of the corresponding phosphoryl compounds 4 a – 4 c . Reaction of 2 a and 3 a with Pt[COD]Cl2 (COD = 1.5‐Cyclooctadiene) furnished the complexes 5 and 6 . The NMR spectra suggested that the two chlorine atoms are in cis position. X‐ray structure analyses were conducted for 2 a , which exhibits twofold symmetry; 2 c , which is linked into dimers by hydrogen bonds C–H…O; and 6 , confirming the cis configuration. 相似文献
Abstract Nucleophilic substitution at tetracoordinated phosphorus centers has been extensively investigated.1 Transesterification of acyclic phosphinates proceeds with inversion of configuration,2 whereas four-membered phosphinates react with retention.3 In previous work4 we suggested that transesterification in six-membered phosphinates occurs via an SN2 mechanism. The title compound was synthesized as a model structure to study the stereochemical and mechanistic aspects of nucleophlic substitution at phosphorus in a six-membered ring. A mixture of diastereomers was produced and separated by column chromatography. Both the mixture and separate isomers were used for an investigation of substitution with methanol, methoxide ions, and phenoxide ions; the reactions proceeded with inversion. Transesterification reactions of the resulting thiophosphinates were studied and found to proceed with inversion. Reactions of these with phenyllithium, benzyllithium, lithium phenylacetylide, and the corresponding organomagnesium halides were also carried out. The stereochemical assignments for the title compound (cis and trans) and two derivatives have been firmly anchored by X-ray studies;5 assignments for others are tentative and based on spectroscopic measurements, including 1H, 13C, and 31P NMR data. 相似文献
Phosphole‐substituted phosphaalkenes (PPAs) of the general formula Mes*P?C(CH3)?(C4H2P(Ph))?R 5 a – c (Mes*=2,4,6‐tBu3Ph; R=2‐pyridyl ( a ), 2‐thienyl ( b ), phenyl ( c )) have been prepared from octa‐1,7‐diyne‐substituted phosphaalkenes by utilizing the Fagan–Nugent route. The presence of two differently hybridized phosphorus centers (σ2,λ3 and σ3,λ3) in 5 offers the possibility to selectively tune the HOMO–LUMO gap of the compounds by utilizing the different reactivity of the two phosphorus heteroatoms. Oxidation of 5 a – c by sulfur proceeds exclusively at the σ3,λ3‐phosphorus atom, thus giving rise to the corresponding thioxophospholes 6 a – c . Similarly, 5 a is selectively coordinated by AuCl at the σ3,λ3‐phosphorus atom. Subsequent second AuCl coordination at the σ2,λ3‐phosphorus heteroatom results in a dimetallic species that is characterized by a gold–gold interaction that provokes a change in π conjugation. Spectroscopic, electrochemical, and theoretical investigations show that the phosphaalkene and the phosphole both have a sizable impact on the electronic properties of the compounds. The presence of the phosphaalkene unit induces a decrease of the HOMO–LUMO gap relative to reference phosphole‐containing π systems that lack a P?C substituent. 相似文献
The development of novel Brønsted acids featuring the hexacoordinate phosphorus(V) anion [TRISPHAT]? {[ 1 ]?=[P(1,2‐O2C6Cl4)3]?} are reported. The title compound, H(OEt2)2[ 1 ], was synthesized from 1,2‐(HO)2C6Cl4 (3 equiv) and PCl5 in the presence of diethyl ether. This compound was fully characterized by 1H, 31P and 13C NMR spectroscopy, X‐ray crystallography and elemental microanalysis. Dissolution of H(OEt2)2[ 1 ] in acetonitrile results in the slow precipitation of crystalline H(OEt2)(NCMe)[ 1 ], which was characterized by X‐ray diffraction; however, in CD2Cl2 solution the [TRISPHAT]? anion protonated and ring‐opened. The weighable, solid H(OEt2)2 [ 1 ] was found to be a competent initiator for the polymerization of n‐butyl vinyl ether, α‐methylstyrene, styrene and isoprene at a variety of temperatures and monomer‐to‐initiator ratios. At low temperatures, polymers with Mn>105 were obtained for n‐butyl vinyl ether and α‐methylstyrene whereas slightly lower molecular weights were obtained with styrene and isoprene (104<Mn<105). The poly(α‐methylstyrene) synthesized at ?78 °C is syndiotactic‐rich (ca. 87 % rr) whereas the polystyrene obtained at ?50 °C is atactic. The polyisoprene obtained possessed all possible modes of enchainment as well as branched and/or cyclic structures that are often observed in polyisoprene. 相似文献
Nanoparticles of nine phosphazenes with general formula 4‐CH3C6H4S(O)2N=PX3 [X = Cl ( A ), NC4H8 ( 1 ), NC6H12 ( 2 ), NC4H8N–C(O)OC2H5 ( 3 ), NC4H8N–C(O)OC6H5 ( 4 ), NC4H8O ( 5 ), NHCH2–C4H7O ( 6 ), N(CH3)(C6H11) ( 7 ), NHCH2–C6H5 ( 8 ), and 2‐NH‐NC5H4 ( 9 )] were synthesized using ultrasonic method and characterized by 1H, 13C, 31P NMR, FT‐IR, fluorescence, as well as UV/Vis spectroscopy and additionally with XRD, FE‐SEM, N2 sorption, and elemental analysis. The 31P NMR spectra of compounds 1 – 9 reveal the most up field shift δ(31P) for 9 at –11.45 ppm reflecting the most electron donation of 2‐aminopyridinyl rings through resonance to the phosphorus atom. The 1H, 13C NMR spectra of 7 exhibit two sets of signals for the hydrogen and carbon atoms of its two isomers present in the solution state in 1:4 ratio. The FE‐SEM micrographs illustrate that the nanoparticles of compounds 1 – 9 have spherical morphology and a size of 27–42 nm. From the XRD patterns, the crystal sizes were estimated to about 24–86 nm. The highest bandgap was measured for 3 (3.81 eV) whereas the smallest was measured for 8 (3.50 eV). The structures of two polymorphs of compound 5 ( 5 , 5′ ) were determined by X‐ray crystallography at 120 K. Both of these polymorphs are triclinic with P1 space group but 5 has a doubled unit cell volume and two symmetrically independent molecules ( 5a and 5b ). In structures 5a and 5′ , the phosphorus and all endocyclic atoms of two morpholinyl rings display disorder, whereas the molecule 5b does not show disorder. The strong intermolecular O–H ··· O hydrogen bonds plus weak intermolecular C–H ··· O and C–H ··· N interactions create three‐dimensional polymers in the crystalline networks of 5 and 5′ . The DFT computations illustrate that molecule 5b is more stable than 5a by –1.1062 and –0.9779 kcal · mol–1 at B3LYP and B3PW91 levels, respectively. The NBO calculations presented sp3d hybridization for phosphorus and sulfur atoms and sp2, sp3 hybrids for the nitrogen and oxygen atoms. 相似文献
Some new and optically active 1,2,4‐triazolo thiadiazoles bearing N‐phthaloyl‐l ‐amino acids were synthesized by reaction of 4‐amino‐5‐(3‐ or 4‐)pyridyl‐3‐mercapto‐(4H)‐1,2,4‐triazoles with N‐phthaloyl‐l ‐amino acids in the presence of phosphorus oxychloride. All the newly synthesized compounds were confirmed by IR, 1H NMR, 13C NMR and elemental analysis. 相似文献
Pseudo‐ephedrine derived 2‐imino‐1,3‐thiazolidine 1 reacts with tris(diethylamino)phosphane by stepwise replacement of the diethylamino group to give the mono‐, bis‐ and tris(imino)phosphanes 2 , 3 and 4 , respectively, of which 4 could be isolated in pure state. The analogous reaction with diethylamino‐diphenylphosphane affords the imino‐diphenylphosphane 5 . The iminophosphanes react with sulfur or selenium to give the corresponding phosphorus(V) compounds. In contrast, the reaction of the iminophosphanes with oxygen is very slow; anhydrous trimethylamine N‐oxide reacts in the melt with the phosphanes to give the oxides 4(O) and 5(O) . The molecular structures of 4(O) (in mixture with 4 ), 4(Se) , 5(S) and 5(Se) were determined by X‐ray analysis. In all cases the ring‐sulfur and the phosphorus atoms are in cis‐positions at the C=N bonds. The analogous solution structures were determined by 1H, 13C, 15N, 31P and 77Se NMR spectroscopy. In the case of the compounds 5 , 5(O) , 5(S) and 5(Se) the isotope‐induced chemical shifts 1δ14/15N(31P) were determined, using INEPT‐HEED experiments. 相似文献
Oxophosphonium ions (R2P=O)+ are fascinating chemical intermediates related to the well‐known acylium cations (RC=O)+, and comprise a tricoordinate phosphorus(V) center with a phosphorus–oxygen double bond. Here, we report the synthesis of two oxophosphonium ions stabilized by bulky imidazolin‐2‐imine and imidazolin‐2‐olefin substituents attached to phosphorus. The novel species were characterized by NMR spectroscopy and single‐crystal X‐ray diffraction analysis, and the bonding situation was probed by DFT calculations. Determination of the acceptor number and the fluoride ion affinity revealed that the choice of the substituents has a strong influence on the electrophilicity of the phosphorus center. Additionally, the formation of Lewis base adducts with pyridine derivatives and the reactivity with isopropyl alcohol was explored. 相似文献