31P NMR Study on Some Phosphorus-Containing Compounds

In view of the facts that the phenomena of aggregation are inseparably related to life processes and that phosphorus-containing compounds are one of the essential building blocks of life, we have studied the aggregation behavior of some phosphonates and phosphinates1. The application of NMR to the problems in chemistry has become rather popular. In phosphorus-containing compounds, phosphorus is a central or backbone atom in molecular structures. 31P NMR is of importance and special value in …     

NMR 77Se, 125Te, 31P and Structure of Seleno-and Telluro-Phosphorus Compounds

Spectra of a nuclear magnetic resonance of seleno- and telluro-phosphorus compounds on nuclei ⁷⁷Se, ¹²⁵Te, ³¹P are described. The dependences of spectral parameters on a structure of the substitutes at phosphorus atom in these compounds are discussed.     

洗涤剂中含磷化合物的31PNMR快速检测方法

收集了常见的31种含磷无机化合物和84种含磷有机化合物,首次建立了含磷化合物的核磁共振谱图库,并以此为依据建立了31P NMR技术快速检测洗涤剂中含磷化合物的方法.对洗衣粉、金属清洗剂和除油剂样品进行31P NMR分析,经与31P谱图库比对,可快速确定含磷化合物的结构.结果表明,10种洗衣粉中仅有1种检出含磷化合物,其...     

Structure of Low-Coordinated Phosphorus (III) Compounds Including Phosphorus-Nitrogen Multiple Bond: 13C, 15N and 31P NMR Investigation

Abstract

A wide series of low-coordinated phosphorus (III) compounds including iminophosphines 1, two- 2 or mono-coordinated 3 phosphorus-containing cations, and anion 4, where Mes? = 2,4,6-tris-(tert-butyl)phenyl, has been investigated by ¹³C, ¹⁵N and ³¹P NMR spectroscopy. The spectral parameters obtained are considered in connection with the ab initio (6–31G?) calculation data of the model compounds.     

高聚合度聚磷酸铵中特征磷的31P核磁共振分析

采用一维³¹P核磁共振(³¹P NMR)、 二维J分解谱(J-resolved)和扩散核磁(³¹P DOSY)等方法, 研究了高聚合度聚磷酸铵(APP)和多聚磷酸盐的特征磷及其偶合常数. 研究表明, 多聚磷酸盐及其中所含的二聚磷酸盐端基磷分别呈双峰和单峰特征, 多聚磷酸盐自旋偶合裂分的端基磷共振峰的偶合常数为19.4 Hz. APP中含有小分子二聚磷酸铵和正磷酸铵, 用³¹P NMR定量表征APP聚合度时需排除二聚体端基磷峰的面积. 在100 ℃水中溶解APP制备的APP水溶液中, 部分高聚合度APP发生断链, 中间磷共振峰处出现短链APP的磷共振峰.     

Steric Versus Electronic Effects in the Ligation Behavior of Trivalent Phosphorus Compounds: 59Co AND 31P NMR Spectroscopic Studies

Abstract

Using NMR techniques, the role of electronic and steric influences in phosphorus(III) ester complexes of the type CoL₆ ³⁺ and AgL_n ⁺ (where n = 1–4) are assessed.     

Phosphorus dendrimers as viewed by 31P NMR spectroscopy; synthesis and characterization

This review emphasizes the role of phosphorus for the elaboration of dendrimers and of various highly sophisticated dendritic structures, and the invaluable role played by ³¹P NMR for their characterization and to ascertain their purity. A few properties, highlighting the importance of phosphorus are reported at the end of this review.     

Identification of Toxic Organophosphorus Compounds and Products of Their Destruction Using 31P NMR Spectrometry

An analytic dependence of the chemical shift in the ³¹P NMR spectrum of toxic organophosphorus compounds and products of their destruction products on the compound structure and the conditions of spectrum measurement were found.     

One- and Two-Dimensional 31P NMR Studies of Some Phosphorus Sulfides in the Liquid and Solid State

Abstract

The phosphorus sulfides of the type P₄S_n (3 ≤ n ≤ 10) exhibit a fascinating variety of structures with different molecular symmetries and crystal structures and the simplicity of the compounds combined with the 100% natural abundance of ³¹P (undiluted spin) makes these compounds ideal for studying the behaviour of the molecules in the liquid and solid state by NMR spectroscopy.     

New Synthetic Route and Characterisation of Phosphorus and Arsenic Heterocyclic Compounds

Herein we report synthetic routes for the preparation of 2-chloro-1,3,2-dioxarsenane 1 , O,O'-bis(5,5-dimethyl-1,3,2-dioxarsenane)-2,2-dimethyl-1,3-propanediol 3 , 2-chloro-1,3,2-dioxaphosphorinane 4 , and 2-fluoro-1,3,2-dioxaphosphorinane 5 . The new synthetic routes described here have the advantage to be simple, very clean and to lead to the desired compounds in very good yields. Compound 2-fluoro-1,3,2-dioxarsenane 2 also was prepared in good yield and is described here for the first time. Compounds 1-5 were fully characterized on the basis of NMR spectroscopic studies. Semi-empirical structural studies have been carried out and the results show that 1 and 2 exist as a mixture of two conformers, whereas only one conformer for 4 and 5 have been found. Variable temperature 1 H NMR studies reveal a fluxional behaviour for 1 and a mechanism for the inter-conversion between its two conformers is proposed.     

Menthyl Substituted Phosphorus Compounds: Synthesis,Structures and NMR Studies

Abstract

Menthyl-substituted phosphorus compounds were synthesized:

(R=CH₃, C₂H₅, i-C₃H₇, t-C₄H₉, C₆H₅, L-Men, D-Men; Men=Menthyl) H-1- and C-13-NMR-spectra were treated by one- and two-dimensional methods to obtain stereospecific shift- and coupling-parameters. Problems of chiral, pseudo-chiral, pro-chiral and pseudo-pro-chiral compounds are discussed. Aromatic-ring-current-effects were calculated based on theories of Johnson/Bovey and Haigh/Mallion. Novel computer programs JOBO and HAMA were designed for convenient evaluation of ring-current-effects. The methods are demonstrated comparing Mosher's menthyl- und neo-menthylphosphineoxides L-Men(C₆H₅)(CH₃)PO and neo-Men(C₆H₅)(CH₃)PO R_(p) and S_(p) configurations. The programs may be obtained from the authors on request.     

The Reaction Activity of Aromatic Carbonyl Compounds with Diphenylphosphine Oxide Studied by 31P NMR

Abstract

A series of α-hydroxyphosphine oxides were prepared by the reactions of diphenylphosphine oxide and aromatic carbonyl compounds and characterized by ¹H NMR, ¹³C NMR, ³¹P NMR, FT-IR, ESI-MS, and HR-MS spectra. The reaction rates and experimental conditions of aromatic aldehydes and aromatic ketones were obviously different due to the activity of their carbonyls. The different substituents of the aromatic aldehydes affected the reaction rate too, and the quantitative reactivity of their substituent conformed to the Hammett equation. The results were confirmed by ³¹P NMR spectroscopy.     

Long-Range 31P-31P Spin Coupling Constants in the 31P NMR Spectra of Phosphite Triesters

Abstract

Data are presented on the magnitudes of ⁵ J _pp and ⁶ J _PP spin-spin coupling constants in the ³¹P NMR spectra of a variety of novel polyphosphite triesters.     

A 31P NMR Study of the Stability of Carboxyifosfamide and Carboxycyclophosphamide,Two Metabolites of Ifosfamide and Cyclophosphamide

Abstract

Ifosfamide (IF) and cyclophosphamide (CP) are two phosphorated anticancer agents used in the treatment of solid tumours. Several phosphorated metabolites, among them carboxyifosfamide (CXIF) and carboxycyclophosphamide (CXCP), were detected and quantified by ³¹P NMR in urine from patients treated with IF or CP. In agreement with other authors [1], we observed a great inter-patient variability in the urinary excretion of CXIF in patients treated with IF [2]. This variability was attributed to a genetic polymorphism of aldehyde dehydrogenase, the enzyme responsible for the formation of CXCP or CXIF [1,3]. Since CXCP and CXIF are unstable, we thought that the inter-individual variability could also be due to a degradation during the storage of urine samples. A ³¹P NMR study of the stability of CXIF and CXCP in urine as a function of time, pH (7 and 5.5) and storage temperature (25°C, 8°C, ?20°C, ?80°C) demonstrated that (i) CXCP and CXIF are more stable at pH 7 than at pH 5.5, (ii) CXCP is more stable than CXIF at both pH, (iii) the degradation decreases with temperature but still occurs at ?20°C and even ?80°C. For an accurate quantification of these compounds, the storage of urine samples must be done at ?80°C immediately after collection and not exceed 1 month at pH 7 whereas, at pH 5.5, the assay must be carried out in the few days following the sampling. To identify the degradation products of CXCP and CXIF, the time course of hydrolysis (between pH 2 and 7) of these compounds was monitored by ³¹P NMR. The structure of each compound formed was determined by mass spectrometry and ¹H and ¹³C NMR after their isolation (except compound A too unstable to be isolated). The results are reported in the following schemes.     

NMR Studies of the Structures of Cyclic Phosphorus Compounds

Abstract

[RNPOCl]₃ (R = Ph, p-Tol, p-MeOC₆H₄) has been shown by ³¹P n.m.r. to consist mainly of the 2α, 4α, 6β(C₂) isomer (AB₂ spin system), along with small amounts of the symmetric (C₃) isomer (2α, 4α, 6α). The ³¹P shifts are almost independent of the nature of the group R. Confirmation of the ring structure requires the determination of J_BB which is achieved by second-order analysis of ¹³C or ¹H spectra. Similar techniques have been applied to the phosphorus-oxygen ring system [PhPO₂]₃. We have discovered a relationship between the orientation of N-phenyl substituents on cyclophosphazane ring systems and the ¹³C n.m.r. shifts of the ring carbons. In cyclodiphosphazanes the phenyl rings are coplanar with the P-N ring, whereas in cyclotriphosphazanes the phenyl rings are perpendicular to the P-N-P plane; the ¹³C shifts of the ortho and para carbons are quite different in these two situations, and we have used these shifts to obtain structural information on a number of cyclophosphazanes. Rotation of the ring about the C-N bond has also been studied by low-temperature n.m.r.     

^31P NMR Studies on the Ligand Dissociation of Trinuclear Molybde-num Cluster Compounds

A series of carboxylate-substituted trinudear molybdenum dus-ter compounds formulated as Mo3S4(DTP)3(RCO2)(L), where RffiH, CH3, C2H5, CH2Cl, CCl3, R^1C6H4(R^1 is the group on the benzene ring of aromatic carboxylate ), L=pyridine,CH3CN, DMF, have been synthesized by the ligand substitu-tion reaction. The dissociation of the loosely-coordinated ligand L from the cluster core was studied by ^31p NMR. The dissocia-tion process of L is related to the solvent, temperature, and acidity of carboxylate groups, so as to affect the solution struc-ture and reactive properties of the duster. The long-distance in-teraction between ligands RCO2 and L is transported by Mo3S4 core.     

Purity Determination of Phosphorus Compounds by Internat- Standard31 P Nmr Spectroscopy. an Experimental Study and Validation

Abstract

Due to the proportionality between the area of the NMR signal and the number of nuclei, internal standard³¹P NMR spectroscopy is in principle a rapid and simple method for determination of the purity of phosphorus compounds.nuclei, internal standard³¹P NMR spectroscopy is in principle a rapid and simple method for determination of the purity of phosphorus compounds.nuclei, internal standard³¹P NMR spectroscopy is in principle a rapid and simple method for determination of the purity of phosphorus compounds.nuclei, internal standard³¹P NMR spectroscopy is in principle a rapid and simple method for determination of the purity of phosphorus compounds.     

Crystal Structures and Antimicrobial Activity of Two Phosphorus Compounds

1 INTRODUCTION Both phosphorus and sulfur are the non-metal ele- ments rich in biological bodies. Phosphorus is the core element of nucleic acid, which is the principal ingredient of lives; and sulfur is the important ele- ment in the skeleton of nitrogen-fixing enzyme’s activity center[1]. It has been found that LR, 4-bis(4- methoxyphenyl)-1,3,2,4-dithiadiphosphe-tane-2,4- disulfide (Scheme 1), is an effective thiation reagent for ketones, carboxamides, esters, S-substituted thio- est…     

31P NMR Spectral Evidence for the Hexacoordinated Phosphorus Intermediates in the Reaction of Oxyphosphorochloridate With Amino Acids

Abstract

The nucleophilic groups on the side chain of amino acid can attack phosphoryl to form high-coordinated phosphorus intermediate. which was similar to the active sits of the CAMP-enzyme system [1, 2]