共查询到20条相似文献,搜索用时 46 毫秒
1.
Jipeng Chen Yunxia Yang Mengsheng Xu Jinhua Xie Pan Liu 《Phosphorus, sulfur, and silicon and the related elements》2021,196(1):79-85
Abstract Selected 4-oxybenzaldehyde and 2,2-dioxybiphenyl cyclotriphosphazene derivatives were synthesized via substitution reactions through tailored control. The reactions of cyclotriphosphazene with 4-oxybenzaldehyde and 2,2-dioxybiphenyl gave the following synthesized derivatives: one mono-substituted open-chain compound, N3P3Cl5(O2C7H5) (1, 69%); mono spiro, N3P3Cl4(O2C12H8) (2, 91.1%); non-gem tri-substituted, N3P3Cl3 (O6C21H15) (3, 17%); dispiro, N3P3Cl2(O4C24H16) (4, 92.3%); penta-substituted, N3P3Cl(O10C35H25) (5, 92%);hexa-substituted, N3P3(O12C42H30). Most of these derivatives (1–6) are obtained with good yield (up to 97%), This work provides a simple and available approach to obtain versatile cyclotriphosphazene derivatives, which is expected to further promote the use of HCCP as phosphorus platform for the construction of multi-functional materials. 相似文献
2.
3.
Meriem Bennis Khaled Alouani 《Phosphorus, sulfur, and silicon and the related elements》2013,188(12):1490-1497
Abstract Five new complexes ZnL2(ClO4)2 (1), CdL2(ClO4)2 (2), CdL2(BF4)2 (3), CdLCl2 (4), and CdL(NO3)2 (5) [L = ((Me2N)2PSe)2NMe] have been synthesized and characterized by elemental analysis, infrared (IR) and multinuclear (31P, 77Se, and 113Cd), and nuclear magnetic resonance (NMR) spectroscopy. The 31P and 77Se NMR data showed that the title ligand is coordinated in a bidentate fashion to the metal center via its both P=Se groups. The solution structure of the cadmium complexes was further confirmed by its 113Cd NMR spectra, which displayed a quintuplet for the perchlorate complex and a triplet for each of the nitrate and chloride complexes, respectively due to coupling with four (two ligands) and two (one ligand) equivalent phosphorus nuclei, consistent with a four-coordinate tetrahedral geometry for the cadmium center. The results are discussed and compared with the corresponding oxo and thio analogues. 相似文献
4.
Soufiane Touil Hedi Zantour 《Phosphorus, sulfur, and silicon and the related elements》2013,188(1):183-192
Abstract The reaction of imines 1 with monochlorophosphines leads to β-phosphorylketones obtained in the ketonic 2 or enolic forms 2′. The structure of all obtained products is confirmed by NMR and IR spectroscopy. 相似文献
5.
《Analytical letters》2012,45(8):1303-1314
Abstract Phosphoramide mustard (PM), a key active metabolite of the widely used anticancer drug cyclophosphamide (CP), can exist in several closely-related ionized, cyclized and substituted forms. We have developed a high pressure liquid chromatographic (HPLC) method for analysing serum concentrations of PM in order to relate these serum concentrations to toxicity and efficacy of treatment of CP. 31p NMR spectroscopy is used to verify the HPLC peak homology of the proposed PM peak. 相似文献
6.
Med Abderrahmane Sanhoury Med Taieb Ben Dhia Med Rachid Khaddar 《Journal of fluorine chemistry》2011,132(11):865-869
The preparation and characterization of a series of octahedral complexes [SnF4L2] (L = (Me2N)3PO (1), L = (R2N)2P(O)F; R = Me (2); Et (3) or L = R2NP(O)F2; R = Me (4); Et (5)) are described. These new adducts have been characterised by multinuclear (19F, 31P and 119Sn) NMR, IR spectroscopy and elemental analysis. The NMR data particularly the 19F NMR spectra showed that the complexes exist in solution as mixtures of cis and trans isomers. The solution behaviour of the complexes studied by variable temperature NMR in the presence of excess ligand indicated that, unlike in the SnCl4 analogues, the ligand exchange at room temperature is slow for 1–3 and fast only for 4 and 5. The metal–ligand exchange barriers in [SnF4L2] and [SnCl4L2] systems were estimated and compared. The results indicate that in addition to the difference in the Lewis acidity between SnF4 and SnCl4 the nature of the substituents (fluorine atoms) on the phosphorus atom of the ligand can contribute considerably to the lability of the complex obtained. 相似文献
7.
M. A. M. Khouna M. T. Ben Dhia M. R. Khaddar 《Phosphorus, sulfur, and silicon and the related elements》2013,188(7):1673-1682
The two octahedral complexes SnCl4·2(O)PF(NR2)2 (R = Me or Et) were prepared from reaction of SnCl4 with the ligand (R2N)2P(O)F in anhydrous CHCl3. The new adducts have been characterized by elemental analysis, IR, and multinuclear (119Sn, 31P, 19F, and 1H) NMR spectroscopy. The NMR data show that the adducts exist in solution as a mixture of cis and trans isomers with markedly different proportions. When compared with previously described hexamethylphosphoramide (HMPA) and trimethylphosphate (TMPA) analogues, our results indicate that the cis isomer is the predominant species in solution. Low temperature 31P and 119Sn NMR spectra show that the compounds partially dissociate in dichloromethane. 相似文献
8.
Helmut Duddeck Shahid Malik S. Moeller Tamás Gáti Gábor Tóth Zbigniew Rozwadowski 《Phosphorus, sulfur, and silicon and the related elements》2013,188(3-4):993-1000
Abstract Diastereomeric adducts of chiral soft-base selenium ligands with the enantiopure dirhodium complex Rh* allows stereodifferentiation by NMR spectroscopy of various nuclei (dirhodium method). The individual adduct species can be identified by low-temperature NMR spectroscopy. 相似文献
9.
T. Meier M. Braun W. Frank 《Phosphorus, sulfur, and silicon and the related elements》2013,188(10):2536-2544
The reaction of (S)-1,1,2-triphenylethanediol (3) with phosphorus trichloride leads to the diastereoselective formation of (S C,R P)-2-chloro-1,3,2-dioxaphospholane (2). Its configuration has been determined by single crystal X-ray diffraction. When reacted with racemic secondary alcohols, diastereomeric phosphites are obtained, which display substantial shift differences in the 31P NMR spectra. Thus, chlorodioxaphospholane 2 can serve as derivatizing reagent for chiral secondary alcohols permitting to determine their enantiomeric excess. 相似文献
10.
《Journal of Coordination Chemistry》2012,65(12):2074-2086
Mercury cyanide complexes of alkyldiamines (1–6), [Hg(L)(CN)2] (where L?=?en (1,2-diaminoethane), pn (1,3-diaminopropane), N-Me-en, N, N′-Me2-en, N, N′-Et2-en, and N, N′-ipr2-en), have been synthesized and characterized by elemental analysis, IR, 13C, and 15N solution NMR in DMSO-d6, as well as 13C, 15N, and 199Hg solid-state NMR spectroscopy. Complexes 1 and 2 have been studied computationally, built and optimized by GAUSSIAN03 using DFT at B3LYP level with LanL2DZ basis set. Binding modes of en and bn (where bn?=?1,4-diaminobutane) toward Hg(CN)2 are completely different. Complexes with en and pn show chelating binding to Hg(II), while bn behaves as a bridging ligand to form a polymeric structure, [Hg(CN)2-bn]∞ [B.A. Al-Maythalony, M. Fettouhi, M.I.M. Wazeer, A.A. Isab. Inorg. Chem. Commun., 12, 540 (2009).]. The solution 13C NMR of the complexes demonstrates a slight shift of the ?C≡N (0.9 to 2?ppm) and ?C–NH2 (0.25 to 6?ppm) carbon resonances, while the other resonances are relatively unaffected. 15N labeling studies have shown involvement of alkyldiamine ligands in coordination to the metal. The principal components of the 13C, 15N, and 199Hg shielding tensors have been determined from solid-state NMR data. Antimicrobial activity studies show that the complexes exhibit higher antibacterial activities toward various microorganisms than Hg(CN)2. 相似文献
11.
R. Ahmad M. Zia-ul-Haq H. Duddeck L. Stefaniak J. Sitkowski 《Monatshefte für Chemie / Chemical Monthly》1997,128(6-7):633-640
Summary Variable temperature1H NMR experiments of 2-(2-hydroxyphenyl)-4-phenyl-3H-1,5-benzodiazepine (5a) and its derivatives5d and5e were carried out in order to investigate the conformational behaviour of these compounds. The G* values for the ring inversion barriers of5a and5d areca. 52 kJ/mol,i.e. they do not differ significantly as compared to analogous compounds without phenolic OH group(s). This indicates that the hydrogen bond has not to be opened during the inversion process. In5e the barrier is about 2–3 kJ/mol higher which can be explained by steric interference between the additional methoxy group and the H-3 atoms during ring inversion.15N NMR data which can be discussed in terms of hydrogen bond strength support this interpretation.
Untersuchung des Konformationsgleichgewichtes einiger 2-(2-Hydroxyphenyl)-4-aryl-3H-1,5-benzodiazepine mit Hilfe der1H- und15N-NMR-Spektroskopie
Zusammenfassung Es wurden1H-NMR-Experimente mit 2-(2-Hydroxyphenyl)-4-aryl-3H-1,5-benzodiazepin (5a) und seinen Derivaten5d und5e bei unterschiedlichen Temperaturen durchgeführt. Die G*-Werte für die Ring-Inversion von5a und5d betragenca. 52 kJ/mol, d.h. sie sind gegenüber Verbindungen ohne eine phenolische OH-Gruppe kaum verändert. Das zeigt an, daß die Wasserstoffbrückenbindung während der Inversion nicht geöffnet werden muß. In5e ist die Barriere um ungefähr 2–3 kJ/mol höher, was durch eine sterische Wechselwirkung zwischen der zusätzlichen Methoxygruppe und den H-3-Atomen während der Inversion erklärt werden kann.15N-NMR-Daten können als Hinweise auf die Stärke der Wasserstoffbrückenbindung interpretiert werden.相似文献
12.
Lothar Riesel Jürgen Haenel 《Phosphorus, sulfur, and silicon and the related elements》2013,188(1-4):215-218
Abstract A new method for producing fluoro(organyl) phosphanes is presented. They are prepared by Cl/F-exchange from the corresponding chloro compounds using Et3N.nHF as a fluorinating agent. Phosphanyl fluorophospharanes, R2P-PR2F2, are found to be intermediates of the disproportionation of Fluoro (diorganyl) phosphanes. R2PF react with aldehydes to form phosphinito phosphoranes, R2PF2-CHR'-OPR2. Oxaphospholenes are formed in their reaction with α, β- unsaturated aldehydes. Furthermore, the reactions with 1.2-diketones, carboxylic acid derivatives, and covalent azides are described. 相似文献
13.
Santiago García-Granda Baudilio Tejerina Alain Fruchier Nadine Jagerovic José Elguero 《Structural chemistry》1996,7(4):245-251
New phosphines1–3 have been synthetized by reaction of pyrazolate anion with tris(pentafluorophenyl)phosphine and characterized by1H,31P, and19F NMR studies.19F NMR spectral data contribute to the evidence for apara-substitution of tetrafluorophenyl rings. The crystal structure of tris(4-pyrazol-1-yl-2,3,5,6-tetrafluorophenyl)phosphine 1 has been determined, proving that the assignment based on spectroscopic data was correct: C27H9F12N6P,M
r
= 676.37, monoclinic, space group P2l/c,a=10.754(2) å,b=10.316(2) å,c = 23.598(5) å,=95.36(3),V=2607(1), å3,Z=4,R
1=0.042, andwR
2=0.122. 相似文献
14.
Thomas M. Klapötke Stefan M. Sproll 《Phosphorus, sulfur, and silicon and the related elements》2013,188(8):1803-1813
Methyl 1,2,3,4-thiatriazol-5-ylcarbamate (2a), ethyl 1,2,3,4-thiatriazol-5-ylcarbamate (2b), 2-butyl 1,2,3,4-thiatriazol-5-ylcarbamate (2c), allyl 1,2,3,4-thiatriazol-5-ylcarbamate (2d), and 3-(1,2,3,4-thiatriazol-5-yl)oxazolidin-2-one (2e) were synthesized with high yields by the reaction of the corresponding carbon(isothiocyanatidic) acid, alkyl esters, and sodium azide in aqueous solution. The compounds were characterized by 1H, 13C, and 15N NMR, vibrational spectroscopy (IR), and single crystal X-ray diffraction. The thermal stability was investigated by differential scanning calorimetry. 相似文献
15.
16.
Transformation products of the cationic rhodium complex [(1,5-COD)Rh(—)R,R-DIOP]+CF3SO3
– (1) (COD is cycloocta-1,5-diene and DIOP is (±)-2,3-O-isopropylidene-2,3-dihydroxy-1,4-bis(diphenylphosphino)butane), which were obtained in its reactions with molecular hydrogen, base (NEt3), and solvents in the absence of a substrate, were investigated by 1H and 31P NMR spectroscopy. The solvate complexes [(Solv)2Rh(—)R,R-DIOP]+CF3SO3
–, which were generated from complex 1 in its reaction with molecular hydrogen, underwent destruction of the diphosphine ligand with elimination of benzene and were subjected to oxidation by traces of moisture and oxygen to form the DIOP dioxide complex with RhI. In the absence of hydrogen, complex 1 in solutions produced the diphosphine dioxide rhodium(i) complex and mono- and binuclear rhodium(i) solvate complexes. The scheme of deactivation of the complex in the absence of the substrate was proposed. The catalytic activity of the solvate complexes [(ArH)Rh(—)R,R-DIOP]+CF3SO3
–, which contain benzene, p-xylene, and mesitylene in the coordination sphere, was studied in hydrogenation of Z--acetamidocinnamic acid. 相似文献
17.
Sueg-Geun Lee Wesley G. Bentrude 《Phosphorus, sulfur, and silicon and the related elements》2013,188(1-2):219-222
Abstract A surprising linear downfield effect on the 31P chemical shift of a benzylphosphonate of deuterium substitution on the benzyl carbon has been noted. Its potential usefulness in mechanistic studies is suggested. 相似文献
18.
Mitsuo Komatsu Nobuyuki Harada Hiroshi Kashiwagi Yoshiki Ohshiro Toshio Agawa 《Phosphorus, sulfur, and silicon and the related elements》2013,188(1-2):119-133
Abstract Although it was shown that the reactions of sulfur dichloride (SCl2) with the imines la-c or with the azine 14 gave rise to very unstable 1 : 1 adducts, 1-aza- and 2-azabutadienes, 5 and 10, reacted with SCl2 to afford the isothiazoles 6 and the thiazoles 11, respectively, in high yields. Addition of SCl2 to heterocumulenes was also studied and the ketenimines 16 and diphenylketene 27 gave 1 : 1 adducts which were applied to heterocyclic synthesis as bifunctional reagents. Addition of SCl2 to these compounds was investigated by monitoring the reactions by 13C nmr spectroscopy. 相似文献
19.
The reaction of mercury(II) chloride with neutral phosphine telluride ligands (R3PTe) produced new mercury(II) complexes, HgCl2(R3PTe)2 [R = Me2N (1), Et2N (2), C4H8N (3), C5H10N (4) or n-Bu (5)]. Attempts to isolate the complex of HgCl2 with the morpholinyl ligand, (OC4H8N)3PTe, were unsuccessful. Complexes 1–5 have been characterized by elemental analyses, IR, and multinuclear (31P, 125Te, and 199Hg) NMR spectroscopy. The solution behavior of the complexes was investigated using variable temperature NMR spectroscopy in the presence of excess ligand and indicated fast ligand exchange on the NMR timescale at room temperature. The metal–ligand exchange barriers in these complexes were estimated to be in the range 8–11 kcal/mol. The results suggest that a slight change in the nature of the substituents on the phosphorus of the ligand can contribute considerably to the lability of the complex obtained. The NMR data are discussed and compared with those obtained for related phosphine chalcogenide systems. 相似文献
20.
《Journal of Coordination Chemistry》2012,65(14):2357-2364
A new series of bimetallic bis(diphenylphosphino)acetylene-bridged copper(I) 1,10-phenanthroline complexes, [Cu2(dppa)2(L)2](BF4)2; L?=?1,10-phenanthroline (1); 4-methyl-1,10-phenanthroline (2); 4,7-dimethyl-1,10-phenanthroline (3); and 2,9-dimethyl-1,10-phenanthroline (4), have been prepared and characterized by spectroscopic methods. The X-ray structures of 1 and 4 were determined. The structures consist of centrosymmetric bimetallic 10-membered chair-like dimetallacycles. In 1, intermolecular C–H?π interactions result in bending of the phenanthroline ligand and sterically induced lengthening of one Cu–P bond. In 1–4, the 31P NMR downfield coordination shift, relative to the free ligand, correlates with the basic strength of the 1,10-phenanthroline ligands. 相似文献