[en] Full text: The representatives of many classes of organic compounds are tested as analytical reactants, in particular, extractants of different metal ions. But majority of investigated substances does not have selectivity in relation to given metal ions. Therefore with the purpose of discovering selective extractants for noble metals, alkyl derivatives of xanthogenic acid are synthesized: RX + K - S - C (S) OC₂H₅ → R - S - C (S) OC₂H₅ + KX. R = C₃H₇ - C₇H₁₅, i-C₄H₉; X = Cl, Br. In an IR - spectrum of xanthogenic acid derivatives there are absorption bands of following functional groups (ν, cm^-1): (-CH₂, CH₃) 2850-2950, (C-S) 650, (C-O-C) 1030 and 1210. In a H¹ NMR spectrum of S-butylxantogenate, a quartet of OCH²- group, with a constant of a spin-spin interaction J = 6,6 Hz, is observed at 4,56 p.m., whereas a triplet of S-CH₂ - group (J = 6,5 Hz) is at 3,07 p.m. The protons C-CH₂ of groups (4H) are observed as a multiplet at 1,6-1,7 p.m., and the multiplet signals of CH₃ - group are located at 1,35 p.m. A triplet signal at 0,95 p.m. belong to the three protons of CH₃ - group. Solving the mass spectrum of S-amylxantogenate has shown that the decay of a molecular ion takes place in different directions and the destruction of C-S - bond causes formation in the spectrum of the most intensive ion with m/z 122 (100 %). The ion [M + H] has lower intensity (m/z 193, 26,85 %). Upon decay of an ion m/z 122 the intensive ions with m/z 77 (18,52 %), 89 (74,07 %) and 61 (96,3 %) are formed. At a mass spectrum of this substance there is also a signal of [M-H] + ion (16,1 %). The destruction of C-S -bond causes the formation of the most intensive ion with m/e 122 (100 %). Upon destruction of C-C bond of alkyl chain the ions with m/z 177 (0,5 %) are formed. During fragmentation of a molecular ion the ions with 77 (18,52 %) are formed, and also ions with m/z 89 (44,44 %) and 61 (96,3 %), whose signals are distinguished by high intensity. As the obtained data show, the efficiency of metal extraction influences the structure of reactant, the concentration and the nature an acid. The derivatives of xanthogenic acid have shown to be weak extractants of noble metals from acid mediums. The most effective extractants were: S-heptyl - (3,0 M, Au, 64 %) and S-amyl-(1,0 M, Ag, 81,8 %; 3,0 M, Os, 66,7 %) from sulfuric acid medium; and S-amylxanthogenate (6,0 M, Ag, 65,5 %) from hydrochloric medium. Branching of alkyl chain (i-C₄H₉) results in some increase of efficiency of extraction of Au and Ag from acid mediums. Thus, alkyl derivatives of xanthogenic acid are synthesized and the structure of the obtained substances are confirmed by IR, H¹ NMR, and mass spectrometry data have been studied their complex formation properties in relation to noble metals

[en] Full text: The derivatives of acids of phosphorus, due to variety of properties, are a subject of numerous researches. Now it is known, that the derivatives of acids of phosphorus apart from insect, neurotoxic, antienzym and other kinds of physiological activity have also complex forming properties. As extra gents of noble metals particularly are analyzed by the derivatives of dithio phosphor of acids although organ phosphorus compounds with one nuclear of sulfur make extraction properties. Therefore, with the purpose of detection of effective extra gents of ions of argentum the phosphorylated derivatives of heterogeneous ring compounds were synthesized: Ph(RO)P(O)Cl + HOCH(CH₃)CH₂-R^'-> Ph(RO)P(O)OCH(CH₃)CH₂-R^' + HCl. R C₂H₅ - C₆H₁₃, R^' = a piperidine, morpholine, anabasine Structure of the obtained connections is confirmed by the results IR -, Pm- and mass- spectrometry. In an IR-spectrum O-hexyl-O - [piperidynoisopropyl] phenylphosphonate has lines of absorption bands of the following functional groups (ν, cm^-1): (P-O-C₅H₁₁) 990-1000, (P = 0) 1260, (P-C₆H₅)1450, (C-N in cycle) 1550. In an IR-spectrum O-pentyl-[anabasinoisopropyl] phenylphosphonate has lines of absorption bands of the following functional groups (ν, cm^-1): (P-O-C₅H₁₁) 990-1000, (P = 0) 1250, (P-C₆H₅)1450, (C-N in cycle) 1550. In a spectrum PMR about O-pentyl-[morpholyniisopropyl] phenylphosphonate in the field of a weak field (7, 18-7, 29 p.m.) the multiplet about tones of phenyl group is watched. Me tin proton resonate at 4,66 m.d.as multiplet The signals O-CH₂ of protons of morpholinic cycle appear at 3,58 m.d.. 4H) by the way of triplet. The protons N-CH₂ (6H) three methylene groups will derivate a composite multiple at 2, 10-2, 70 m.d.. The signal of metil group's protons (3H) is watched at 1,15m.d.as doublet. Final metal group resonates at 0, 87 p.m. Six of C-CH₂ of groups give a complex signal in the field of 1, 2-1, 8 m.d. The obtained connections are analyzed as extra gents of ions of argentum from salt-sulphate acid medium. Process of extraction was analyzed by a method of radioactive nuclides of metals (¹¹⁰Ag). The synthesized connections have appeared by weak extra gents of ions of argentum irrespective of the nature and density of inorganic acids. As the results of the lengthening of alkyl radicals in a molecule there is a rise of efficiency of extraction of metals. By rather more effective extra gent of metal has appeared in phosphorylated derivative of anabasine (E = 52 %)

[en] Full text:With the aim to get new effective and selective extra gents of noble and non-ferrous metals from acid solution and industrial sewage, research of the dependence of 'structure effectiveness' the various phosphor acid derivatives with logical changeable structure (thio phosphor acids, derivatives of dialkoxythiophosphor, O-alkyl-methylphosphon, alkylphenylphosphon, diphenylphosphine acids also 4 methyl-1,3,2 dioxaphosphorinane) which contain different functional groups, the remains of heterocyclic amines and alkaloids, new derivatives of some analytical reagents were synthesized. The structure of synthesized compounds is approved by the results of IR-, PMR-, mass-spectrum analyze. Researching mass-spectrum decay of synthesized phosphor acid derivatives we defined that differing from O-dihexyl-S-propargyl-benzylthio phosphat, mass spectrum decay of O-dialkyl-S-(piperdynobutin-2-il)thio phosphat is characterized by the appearing [M-H]⁺ ions and during the decay ions with high intensiveness are formed. Fragmentation of M⁺ O-alkyl-O-(aminoalkyl)phenylphosphonate proceeds in various directions and characterized with the great number of phosphor containing ions, the possession of the second phenyl radical in the molecule of diphenylphosphon acid derivatives changes the fragmentation of molecular ion of diphenylphosphon acid derivatives. The process of extraction of noble (Au, Ag, Pt, Pd, Os) metals from hydrochloric-sulphur-nitrogen acid medium was analyzed by radioactive indicator's method. It was noticed that structure, strength, conformation of compounds, the temperature, of acid medium (0,1-10 M) and the nature of acids (HCL, H₂SO₄, HNO₃) could have strong influence to the effectiveness of metal extraction. During the research of metals extraction from pure solutions we can see the followings: 1) There are such substances, which can be used as effective group reagent towards the Au, Ag and Pd. 2) Derivatives with acetylene extract ions of gold from medium of HCl better and ions of silver from medium H₂SO₄. 3) If we complicate the structure of heterocyclic amine it can have positive influence to extraction of silver as the result of transition from morpholine to salsolidyn we can achieve the rise of effectiveness the extraction 2-5 times, but the branching of O-alkyl link between phosphoric parts and remains of hetero atom leads to the reduction of extraction effectiveness 2-5 times. Analyses of metal's extraction from technological solutions show that effective phosphor organic extra gents are: a) Lengthening of O-alkyl radicals in compounds molecule leads to the rise of effective extraction so Au as Ag. b) By the method of variation the length of O-alkyl and structure of main radical of phosphor acid derivatives we can derive ions of gold from silver. c) There are such compounds, which extract ions of Pt, Os, Au, and Ag from technological solution effectively. We worked out methods of defining the contest of metals in factory sewage

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[en] Full text: With the purpose of detection of new effective extra gents of metals from number of sulphur containing derivatives of acids of phosphorus with different functional groups, analysis of effect of the different factors on selectivity of allocation of metals, installation of optimum conditions of an extraction, the detections of effective extra gents of noble metals from industrial sewage waters, are synthesized phosphorylated derivatives of the anabasine - O-alkyl-O-(anaba-sinoisopropyl)- and O-alkyl-O-(anabasinobutyn-2-yl)phenyl phosphonates and O-(anabasinoisopropyl)- and O-(anabasinobutyn-2-yl)diphenyl phosphonates In an IR-spectrum about O-pentyl-O-[anabasinoisopropyl]phenylphosphonate There are absorption band of the following functional groups (ν, cm^-1): (P-O-C₅H₁₁) 990-1000, (P = 0) 1250, (P-C₆H₅)1450, (C-N in cycle) 1550. In a spectrum PMR O-(anabasinobutyn-2-yl)phenylphosphonate in the field of a weak field apart from signals of two phenylic radicals the signals of a b-displaced pyridine, reference for a molecule anabasine are observed: Hαa-8,46 p.m., H_α'-8,41 p.m., H_γ-7,60 p.m. And H_β-7,15 p.m. A double triplet at 4,70 p.m. And triplet at 3,05 p.m. Belong to signals OCH₂ and N-CH₂ of groups, accordingly, separated by acetylene bond. The signals of piperidine cycle of anabasine have the following chemical shifts: H_2a-3,27 p.m., H_6e-2,78 p.m., H_6a-2,45 p.m., and remaining protons (6H, m, CH₂) are in resonance in the field of 1,1-1,9 p.m. The analysis of mass-spectrometer decay of the synthesized connections has shown, that the mass-spectrometer fragmentation M^* about - O-alkyl-O- (anabasinoisopropyl) phenylphosphonates flows past in different directions and is characterized, as against about O-alkyl-O-(anabasinobutyn-2-yl)phenyl-phosphonates, large number of phosphor containing ions; the availability of the second phenylic radical in molecules anabasincontaining derivatives of a diphenyl phosphinic acid essentially changes fragmentation of a molecular ion. Usage of connections as extra gents of gold and argentum from technological solutions has shown, that some of them allow in 80 times more effective to extract ions Au, than Ag

[en] Phosphorylated derivatives of 8-mercaptoquinoline and 2,5-dimercapto-1,3,5-thiadiazole have been synthesized and studied as extractant of thallium ions. Thus is showed that among them there are effective extractants of metal. (author)

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[en] It is known that stability of composite compounds in solutions is defined by great amount of parameters characterising metal and ligand cations. As such situation makes the development of theoretical quantitative approach difficult, now one have to be satisfied with different types of qualitative classifying schemes which are based on generalization of experimental facts. There are a lot of such schemes and one of them is the Luis's principle of hard acids and bases. According to Pirson's principle the soft acid such as ions of noble metals react with soft bases because soft acids have affinity to sulphur and nitrogen. Therefore we have synthesised and studied complex forming properties of phosphorous acids and their derivatives. The obtained results on the extraction of Au, Ag, Pt, Pd and Os have shown that these compounds are chelatoforming complex forming ones. Research on the noble metals extraction from acid medium by neutron-activation analysis method shows that: Some of these compounds can be used as effective group reagent in regard to gold, silver and palladium. (0.1-1.0 M, 97-99 %); Compounds with acetylene bonds are more suitable for extracting gold and silver ions from HCl (88-90 %) and H₂SO₄ mediums (97- 83 %) respectively. In the low concentrated acids gold and silver ions can be extracted better by S - benzene-sulphonate from chloride acid medium in organic phase (Au-87 %, Ag-93 %) than from sulphuric acid (Au-24 %, Ag-69 %); Extension of O-alcil radicals in S-β ephoxipropiltio-phosphate molecules leads to little change of silver's extraction efficiency at 0.1-1.0 M H₂SO₄, while increase of HCl concentration leads to sharp reduction of this efficiency (from 86 till 5%)

No abstract available