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Synthesis,Characterization And Extractive Behavior Of Bis-(thiophosphoryl)imines

Posted on:2002-05-12Degree:DoctorType:Dissertation
Country:ChinaCandidate:R R TangFull Text:PDF
GTID:1101360062480350Subject:Non-ferrous metallurgy
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The use of solvent extraction techniques for hydrometallurgical recovery of metal values from metal ores has been practised commercially for a few years. Since the metals are usually found in their ores in association with other metals,it is essential that the orgnic compounds extract the desired metal selectively so as to achieve a degree of separation from other metals present. A strong extractant for extracting desired metal ion from aqueous solution with excellent selective is a key step for hydrometallurgical researchers.On the basis of the importances of extractant in hydrometallury, the aim of this dissertation is to prepare strong and selective new extractants teraalkyl dithioimidophosphates.In this paper we synthesized the O,O-dialkylphosphorochoridothionates ( I t- I 2S) by the reaction of thiophosphoryl chloride with alcohol or phenol ,then O,O-dialkylphosphoroamides( II,- II25) have been obtained from aminolysis of I ;then the reaction of I with II produce 25 new extractants--Bis-(thiophosphoryl) imines (III, 20 of them are new compounds)in the presence of alkali. In all 75 compounds were reported in this paper.A new facile method for the preparation of the key intermediates O,O-dialkylphosphorochoridothionates by phase-tranfer-catalyzed nucleophile substitution are firstly reported in this paper . The optimums reaction conditions are Obtained: tetrabutylammonium bromide is used as catalyst in preparing O,0-dialkylphosphorochoridothionates , and its quantity is 3% mole of alchol; NaOH is used as acid acceptor; the ratio of reactants (PSCl3:alcohol:NaOH) is 1:2:2.3(mole) ;the reaction time is three hours and reaction temperature is 40癈(CH2C12 as solvent). In the syntheses of O,O- diarylphosphorochoridothionates, benzyltriethylammonium chloride is the best phase-tranfer-catalyst and its quantity is 3% mole of phenol, NaOH is also used as acid acceptor; the ratio of reactants (PSQ3:phenol:NaOH) is 1:2:2.l(mole) ;the reaction time is 2.5 hours and reaction temperature is 80癈(C6H6 as solvent). There are some improvements in synthesis of other two types of compounds.The structures of new compounds have been evidenced from their element anallysis and spectral alnalysis(IR,'HNMR,31PNMR,MS).The substituent effect on the various spectral characteristics of ( I ) (II) (III) has been studied detailedly.In IR spectrum,the absorbing location of P=S is varying greatly with the variation of compounds and substituents.The peak wave number reduces in order I > II, III. The precise position of P=S is lower ffrequency in O,O- diarylphosphorochoridothionates than that in O,O- dialylphosphorochoridothionates.In 'HNMR spectra of II and III, there is a good linear relation between the 5 a H(the chemical shifts ofa-C'H)and the H number of p-C in the alklyoxy substituted compounds,where as the coupling constant of P and a-C'H (JPH) is in good linear energy relationship with the alkyl substituent constant(o').The 31P-NMR chemical shifts of compound III correlate linearly with the Hammett o'of the substituents.In the aryloxy substituted compound III, the 31P-NMR chemical shifts( 8 p) and the />ara-Hammett constand (?p) of aryl group can be depicted by following equation.6 p=l.6278 op +50.5833In the arkloxy substituted compound III, the 31P-NMR chemical shifts( ?P) and the Hammett constand (o *) of alkly group can be depicted by following equation. 8p=2.3577o*+68.1342In MS spectrum,the fragmentation pattern of (I ) (II) (III)and molecular ion split laws have been studied : molecular ion peaks of compound II and compound III are obvious,but that of compound I is very weak. The base peak of compound I substituted by alkyloxy are [(HO),P(S)C1]" ions those are produced through two times of H shift; The rearranges of thiono-thiolo rearrangement take place easyly in the three types of compounds under conditins of mass spectra tested. At the same time the bind of P-O and the bind P-S decompose easyly ,it produces [M-SR]+ or [M-OAr]+ ; fragmentation ions are often producesed at lose of neutral fractio...
Keywords/Search Tags:O, O-dialkylphosphorochoridothionates, synthesis, spectral, extraction Bis-(thiophosphoryl) imines, phase-tranfer-catalyzed
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