CN101619074A - Asymmetric dithiophosphinic acid synthesis method - Google Patents
Asymmetric dithiophosphinic acid synthesis method Download PDFInfo
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- CN101619074A CN101619074A CN200910023427A CN200910023427A CN101619074A CN 101619074 A CN101619074 A CN 101619074A CN 200910023427 A CN200910023427 A CN 200910023427A CN 200910023427 A CN200910023427 A CN 200910023427A CN 101619074 A CN101619074 A CN 101619074A
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Abstract
An asymmetric dithiophosphinic acid synthesis method comprises the following steps: adopting phosphorus trichloride as raw material to react with organic metal reagent RMX, producing asymmetric dihydroxylphosphorus chloride, then obtaining phosphinic acid by reacting the asymmetric dihydroxylphosphorus chloride, sulphur and sodium bisulfide, purifying the corresponding salt by column chromatography or recrystallization and finally obtaining asymmetric dithiophosphinic acid by converting. The method can be used in the preparation field of dithiophosphinic acid extractant compounds.
Description
Technical field
The invention belongs to the technology of preparing of dithiophosphinic acids kind of extractants compound, relate generally to the synthetic method of asymmetric dithiophosphinic acids.
Background technology
The advanced nuclear fuel cycle technology of development is the basis that ensures China's nuclear energy Sustainable development, and the high activity liquid waste isolation technique is one of core of advanced nuclear fuel cycle technology.The target of high activity liquid waste separation process is separated actinide elements in the high activity liquid waste exactly.In existing separation process,, be in same logistics because trivalent actinides is very similar to the chemical property of lanthanon.For the transmuting that realizes trivalent actinides and the non-αization of lanthanon refuse, the trivalent actinium series further need be separated from lanthanon.Because the dithiophosphinic acids kind of extractants contains soft coordination sulphur atom, the performance that trivalent actinides is had preferential slective extraction, be expected to be used for separating trivalent actinium series and lanthanon, as Cyanex301 trivalent actinium series and lanthanon are had good extracting and separating performance, but stability not too desirable.It is a lot of that symmetry two replaces the dithiophosphinic acids synthetic method, mainly synthetic by the John Higgins method such as the diaryl dithiophosphinic acids.The synthetic difference according to experience main intermediate structure of symmetry dialkyl dithio phospho acid can be divided into multiple.Having report to use recently also can be by Grignard reagent and phosphorus thiochloride P (S) Cl
3Reaction generates connection phosphorus intermediate, becomes symmetrical dialkyl dithio phospho acid through thiolysis, acidifying then, but does not have about the asymmetric dithiophosphinic acids synthetic method of substituting group.
Summary of the invention
In order to overcome the shortcoming of above-mentioned prior art, the object of the present invention is to provide the synthetic method of asymmetric dithiophosphinic acids, have the characteristics of the preparation that can realize asymmetric dithiophosphinic acids.
In order to achieve the above object, the technical scheme taked of the present invention is:
The synthetic method of asymmetric dithiophosphinic acids, with the phosphorus trichloride is raw material, generate asymmetric dialkyl phosphorus chloride with organometallic reagent RMX reaction, and then generate phospho acid with elemental sulfur, Sodium sulfhydrate reaction successively, by column chromatography or the corresponding salt of recrystallization method purifying, change into acid again and obtain asymmetric dithiophosphinic acids; Wherein M represents atoms metal, comprises lithium, sodium, beryllium, magnesium, aluminium, gallium, indium, thallium, tin, lead, bismuth, copper, zinc, cadmium or mercury, and R represents organic group, and X represents halogen.
The synthetic method of asymmetric dithiophosphinic acids, the molecular formula of synthetic route is expressed as follows:
Wherein: M
1, M
2Represent atoms metal; Comprise lithium, sodium, beryllium, magnesium, aluminium, gallium, indium, thallium, tin, lead, bismuth, copper, zinc, cadmium or mercury respectively.
The synthetic method of asymmetric dithiophosphinic acids specifically may further comprise the steps:
The first step, organometallic reagent is R 1.
1M
1The preparation of X
With metal M
1Direct and halohydrocarbons reaction obtains; Perhaps obtain by the exchange substitution reaction between metal-metal; Wherein: M
1Represent atoms metal; Comprise lithium, sodium, beryllium, magnesium, aluminium, gallium, indium, thallium, tin, lead, bismuth, copper, zinc, cadmium or mercury respectively, R
1Represent organic group, X represents halogen;
Second step, alkyl phosphorus dichloride R
1PCl
2Synthetic
Under the argon Ar protection, with phosphorus trichloride PCl
3Be added in the there-necked flask phosphorus trichloride PCl with anhydrous diethyl ether
3With the volume ratio scope of anhydrous diethyl ether be 1: (2～10); Under constantly stirring, 1. 0.5～3 normal organometallic reagent be added drop-wise in the ebullient phosphorus trichloride diethyl ether solution react, generate white solidliquid mixture; After 1. organometallic reagent dropwises, continue heating and keep more than the backflow 1h; Stop heating, suction filtration steams the solvent that removes in the filtrate, obtains alkyl phosphorus dichloride R
1PCl
2
The 3rd step, organometallic reagent preparation 2.
With metal M
2Direct and halohydrocarbons reaction obtains; Perhaps obtain by the exchange substitution reaction between metal-metal; Wherein: M
2Represent atoms metal; Comprise lithium, sodium, beryllium, magnesium, aluminium, gallium, indium, thallium, tin, lead, bismuth, copper, zinc, cadmium or mercury respectively, R
2Represent organic group, X represents halogen; Require organometallic reagent activity 2. to be higher than or to be equal to machine metal reagent activity 1., and R
2Be different from R
1
The 4th step, asymmetric dialkyl phosphorus chloride R
1R
2The preparation of PCl
Under-78 ℃, argon Ar protection, 2. made organometallic reagent in the 3rd step is dropped to alkyl phosphorus dichloride R
1PCl
2In the anhydrous ether solution, dropwise the back and continue to stir, rise to room temperature naturally until reaction mixture, gained solidliquid mixture suction filtration gets clear filtrate;
The 5th step, vulcanization reaction
Under the argon Ar protection, gained clear filtrate in the 4th step is mixed with 1～2 normal sulphur powder S, stir more than 12 hours under the room temperature, suction filtration can obtain clarified liq;
The 6th step, asymmetric dialkyl dithiophosphinic acids R
1R
2The preparation of P (S) SH
Under the argon Ar protection, gained clarified liq in the 5th step to be mixed with 1～8 normal Sodium sulfhydrate NaHS, stirring reaction is more than 1 hour under the room temperature, and suction filtration obtains clarified liq; Then with 1～2mol/L hydrochloric acid thorough mixing, with saturated nacl aqueous solution washing 2 times, anhydrous sodium sulfate drying filters again for separatory, gained diethyl ether solution, remove desolvate dithiophosphinic acids;
The 7th step, the purifying of asymmetric dialkyl dithiophosphinic acids
Gained dithiophosphinic acids crude product in the 6th step is changed into corresponding salt earlier, utilize column chromatography or recrystallization method purification of salts then, become acid to get final product with hcl acidifying more at last.
Organometallic reagent of the present invention 1. or organometallic reagent 2. comprise following organometallic reagent:
(1) organolithium reagent: method commonly used is metallic lithium and halohydrocarbons reaction, under the protection of the drying nitrogen of deoxygenation, with lithium silk and anhydrous diethyl ether according to 1: the weightmeasurement ratio of (20～30) joins in the there-necked flask, stirs, and drips alkyl bromine R down at-10 ℃
1In Br diethyl ether solution to the three mouthful reaction flask, the volume ratio of alkyl bromine and anhydrous diethyl ether is 1: (1～4); After treating that alkyl bromine diethyl ether solution drips, be warming up to 0～10 ℃ and continue to stir 1～3 hour, make the diethyl ether solution of hydrocarbyl lithium.
(2) organomagnesium reagent is a Grignard reagent: under argon Ar protection, with magnesium rod Mg and anhydrous diethyl ether according to 1: the weightmeasurement ratio of (2～4) joins in the there-necked flask, adds iodine grain 0.05～0.1g again, drips 2～3mL alkyl bromine R
1Initiation reaction in Br diethyl ether solution to the three mouthful reaction flask, alkyl bromine R
1The volume ratio of Br and anhydrous diethyl ether is 1: (1～4); Drip alkyl bromine R while stirring
1The Br diethyl ether solution after waiting to drip, continues to be heated to 30～40 ℃ and is back to the magnesium rod disappearance.
(3) organic zinc reagent: available Grignard reagent and Zinc Chloride Anhydrous effect prepare alkyl zinc; With 1 normal Zinc Chloride Anhydrous ZnCl
2Diethyl ether solution drops in the Manufactured Grignard reagent, and stirring at room is 0.5～1.5 hour then; The suction filtration reaction mixture obtains the grey clarified liq, is zincon.
(4) organic sodium reagent: direct and halohydrocarbons reaction with sodium Metal 99.5, perhaps and the exchange substitution reaction between the metal hydrocarbon based compound generation metal-metal of another activity difference prepare alkyl sodium, in addition sodium Metal 99.5 can be directly with hydro carbons or directly and acid stronger hydrocarbon replace wherein hydrogen, the exchange substitution reaction that metalloid-hydrogen takes place prepares alkyl sodium.
(5) organic beryllon: the preparation method according to Grignard reagent makes corresponding Grignard reagent earlier, and then handles with excessive dichloride beryllium diethyl ether solution, and product separates with benzene extraction or distillation method, obtains the dialkyl beryllium.
(6) organoaluminum reagent: metallic aluminium and halohydrocarbon direct reaction, perhaps aluminum halide and Grignard reagent react in ether and all can be used for preparing alkyl aluminium.
(7) organic gallium, indium reagent: gallium or indium and the heating of alkyl mercury can prepare alkyl gallium or alkyl indium.
(8) organic thallium reagent: because alkyl thallium (R
2Tl) character instability is difficult for preparation, but uses TlX
3With the Grignard reagent effect, can form stable dialkyl halogenation thallium R
2TlX.
(9) organotin reagent: available Grignard reagent and anhydrous stannic chloride prepared in reaction alkyl tin.
(10) organic dithizone: available Grignard reagent and lead chloride prepared in reaction plumbane.
(11) organo-bismuth reagent: the halide reaction of using Grignard reagent or hydrocarbyl lithium and bismuth can prepare the alkyl bismuth.
(12) organic copper reagent: prepared in reaction alkyl copper under available hydrocarbyl lithium and the cuprous iodide low temperature.
(13) organic cadion: can prepare an alkyl halogenation cadmium or dialkyl cadmium with Grignard reagent and exsiccant anhydrous chlorides of rase cadmium reaction.
(14) organic mercury reagent: available Grignard reagent in anhydrous diethyl ether with mercuric bromide prepared in reaction alkyl mercury.
Utilize synthetic route of the present invention can synthesize the dithiophosphinic acids compound of following three class unsymmetrical structures: i) R
1, R
2Be alkyl, ii) R
1, R
2Be aromatic base, iii) R
1, R
2Wherein one is alkyl, and another is an aromatic base; Its structural formula is as follows:
R
1, R
2Alkyl groups such as ethyl, propyl group, butyl, amyl group, hexyl, octyl group, cyclohexyl and benzyl, phenyl, trifluoromethyl etc. be can be respectively and the aromatic group of phenyl ring and R contained
1≠ R
2
Because it is raw material that the present invention has adopted with the phosphorus trichloride, generate asymmetric dialkyl phosphorus chloride with the organometallic reagent reaction, and then be reacted into phospho acid with elemental sulfur, Sodium sulfhydrate, take the corresponding salt of purifying by column chromatography or recrystallization method, change into acid again and obtain asymmetric dithiophosphinic acids, so have the characteristics of the preparation that realizes asymmetric dithiophosphinic acids.
Embodiment
The present invention is described in further detail below in conjunction with specific embodiment.
Synthesizing of embodiment 1 neighbour-trifluoromethyl (octyl group) dithiophosphinic acids
The preparation 1. of the first step, organometallic reagent
1. organometallic reagent uses organic zinc reagent in this example;
(1), preparation Grignard reagent octyl group magnesium bromide
Under argon Ar protection, 0.525mol magnesium rod Mg12.778g and anhydrous diethyl ether 25mL are joined in the there-necked flask according to 1: 1.95 weightmeasurement ratio, add iodine grain 0.05g again; Drip 2～3mL n-octane bromide C
8H
17Br (87.0mL, 0.5mol) initiation reaction in ether (275mL) solution to the three mouthful reaction flask, n-octane bromide C
8H
17The volume ratio of Br and anhydrous diethyl ether is 1: 3.16; Drip n-octane bromide C while stirring
8H
17The Br diethyl ether solution after waiting to dropwise, continues to be heated to 30～40 ℃ and is back to the magnesium rod disappearance;
(2), gained brownish black clarified liq is that Grignard reagent is cooled to 0 ℃ with ice-water bath, and drips Zinc Chloride Anhydrous ZnCl
2(0.5mol) diethyl ether solution stirs 75min under the room temperature to above-mentioned obtained Grignard reagent;
(3), the suction filtration reaction mixture, gained filtrate is the grey clarified liq, is zincon.
Second step, octyl group phosphorus dichloride C
8H
17PCl
2Synthetic
Under the argon Ar protection, with 52.3mL (0.6mol) phosphorus trichloride PCl
3Be added in the there-necked flask phosphorus trichloride PCl with the 200mL anhydrous diethyl ether
3With the volume ratio of anhydrous diethyl ether be 1: 3.82; Under constantly stirring, 0.5 equivalent zincon dropped in the ebullient phosphorus trichloride diethyl ether solution react, generate white solidliquid mixture; After zincon dropwises, continue 30～40 ℃ of backflow 2h of heating; Stop heating, suction filtration steams the solvent that removes in the filtrate, obtains alkyl phosphorus dichloride R
1PCl
2The oil pump underpressure distillation obtains 80 ℃～96 ℃ water white transparency cut 19.421g, with n-octane bromide C
8H
17The calculated yield that feeds intake of Br is 18.1%.
The 3rd step, organometallic reagent preparation 2.
2. organometallic reagent uses Grignard reagent in this example;
Preparation Grignard reagent neighbour-trifluoromethyl magnesium bromide
Under argon Ar protection, 0.115mol magnesium rod Mg2.802g and anhydrous diethyl ether 8mL are joined in the there-necked flask according to 1: 2.86 weightmeasurement ratio,, add iodine 0.05g again, drip 13.5mL (0.1mol) neighbour-methyl bromobenzene trifluoride o-C of 2～3mL
7H
4F
3Initiation reaction in Br and 95mL anhydrous diethyl ether to the three mouthful reaction flask, neighbour-methyl bromobenzene trifluoride o-C
7H
4F
3The volume ratio of Br and anhydrous diethyl ether is 1: 7.04; Drip neighbour-methyl bromobenzene trifluoride o-C while stirring
7H
4F
3The Br diethyl ether solution after waiting to drip, continues to be heated to 30～40 ℃ and is back to the magnesium rod disappearance;
The 4th step, neighbour-trifluoromethyl (octyl group) phosphorus chloride synthetic
Under-78 ℃, argon Ar protection, the neighbour-trifluoromethyl magnesium bromide diethyl ether solution of system in the 3rd step is dropped to 19.421g octyl group phosphorus dichloride C
8H
17PCl
2In the 190mL anhydrous diethyl ether, dropwise the back and continue to stir, rise to room temperature until reaction mixture, gained solidliquid mixture suction filtration gets the red-brown clear filtrate.
The 5th step, vulcanization reaction
Under the argon Ar protection, gained red-brown clear filtrate in the 4th step is mixed with sulphur powder S 2.904 grams of 0.1mol, stir 12h under the room temperature; Suction filtration gets the red-brown clear filtrate, and the productive rate that calculates this step with the sulphur powder is 48.9%.
The 6th step, the preparation of neighbour-trifluoromethyl (octyl group) dithiophosphinic acids
Under the argon Ar protection, gained red-brown clear filtrate in the 5th step to be mixed with the Sodium sulfhydrate NaHS of 31.1 grams, stirring reaction is 23 hours under the room temperature, and suction filtration obtains dark red liquid; Then with 2mol/L hydrochloric acid 200mL thorough mixing, with saturated nacl aqueous solution 200mL washing 2 times, anhydrous sodium sulfate drying filters again for separatory, gained diethyl ether solution, remove desolvate dithiophosphinic acids.Vacuum rotary steam obtains phospho acid crude product 32.6g, brown liquid.
The 7th step, the purifying of neighbour-trifluoromethyl (octyl group) dithiophosphinic acids
Gained dithiophosphinic acids crude product 32.6g in the 6th step is changed into corresponding salt earlier, utilize column chromatography or recrystallization method purification of salts then, become acid to get final product with hcl acidifying more at last.So far, the synthetic of asymmetric dithiophosphinic acids finished.
Synthesizing of embodiment 2 butyl octyl dithiophosphinic acidss
The preparation 1. of the first step, organometallic reagent
1. organometallic reagent uses organic zinc reagent in this example;
(1), preparation Grignard reagent octyl group magnesium bromide
Under argon Ar protection, 0.42mol magnesium rod Mg10.0g and anhydrous diethyl ether 10mL are joined in the there-necked flask according to 1: 1 weightmeasurement ratio, add iodine grain 0.05g again; Drip 2～3mL n-octane bromide C
8H
17Br (69.4mL, 0.4mol) ether (210mL) solution initiation reaction to the there-necked flask, n-octane bromide C
8H
17The volume ratio of Br and anhydrous diethyl ether is 1: 3.04; Drip n-octane bromide C while stirring
8H
17The Br diethyl ether solution after waiting to dropwise, continues to be heated to 30～40 ℃ and is back to the magnesium rod disappearance;
(2), gained brownish black clarified liq is that Grignard reagent is cooled to 0 ℃ with ice-water bath, and drips Zinc Chloride Anhydrous ZnCl
2(0.4mol) diethyl ether solution stirs 75min under the room temperature to above-mentioned obtained Grignard reagent;
(3), the suction filtration reaction mixture, gained filtrate is the grey clarified liq, is zincon.
Second step, octyl group phosphorus dichloride C
8H
17PCl
2Synthetic
Under the argon Ar protection, with 31.8mL (0.48mol) phosphorus trichloride PCl
3Be added in the there-necked flask phosphorus trichloride PCl with the 200mL anhydrous diethyl ether
3With the volume ratio of anhydrous diethyl ether be 1: 6.29; Under constantly stirring, 3 equivalent zincons are dropped in the ebullient phosphorus trichloride diethyl ether solution react, generate white solidliquid mixture; After zincon dropwises, continue 30～40 ℃ of backflow 2h of heating; Stop heating, suction filtration steams the solvent that removes in the filtrate, obtains alkyl phosphorus dichloride R
1PCl
2The oil pump underpressure distillation obtains 76 ℃～82 ℃ water white transparency cut 17.482g, with n-octane bromide C
8H
17The calculated yield that feeds intake of Br is 20.3%.
The 3rd step, organometallic reagent preparation 2.
2. organometallic reagent uses Grignard reagent in this example;
Preparation Grignard reagent butyl magnesium bromide
Under argon Ar protection, 0.095mol magnesium rod Mg2.3g and anhydrous diethyl ether 5mL are joined in the there-necked flask according to 1: 2.17 weightmeasurement ratio, add iodine 0.05g again, drip 9.7mL (0.082mol) the butyl bromide C of 2～3mL
4H
9Initiation reaction in Br and 30mL anhydrous diethyl ether to the three mouthful reaction flask, butyl bromide C
4H
9The volume ratio of Br and anhydrous diethyl ether is 1: 3.09; Drip butyl bromide C while stirring
4H
9The Br diethyl ether solution after waiting to drip, continues to be heated to 30～40 ℃ and is back to the magnesium rod disappearance;
The 4th step, butyl octyl phosphorus chloride synthetic
Under-78 ℃, argon Ar protection, the butyl magnesium bromide diethyl ether solution of system in the 3rd step is dropped to 17.482g octyl group phosphorus dichloride C
8H
17PCl
2In the 170mL anhydrous diethyl ether, dropwise the back and continue to stir, rise to room temperature until reaction mixture, gained solidliquid mixture suction filtration gets achromaticity and clarification filtrate.
The 5th step, vulcanization reaction
Under the argon Ar protection, gained achromaticity and clarification filtrate in the 4th step is mixed stirring at room 12h with sulphur powder S 4.013 grams of 0.123mol; Filter yellow clear filtrate, the productive rate that calculates this step with the sulphur powder is 58.4%.
The 6th step, the preparation of butyl octyl dithiophosphinic acids
Under the argon Ar protection, the yellow clear filtrate of gained in the 5th step is mixed with the Sodium sulfhydrate NaHS of 27.0 grams, stirred 15 hours under the room temperature, suction filtration obtains yellow liquid; Then with 2mol/L hydrochloric acid 200mL thorough mixing, with saturated nacl aqueous solution 200mL washing 2 times, anhydrous sodium sulfate drying filters again for separatory, gained diethyl ether solution, remove desolvate dithiophosphinic acids.Vacuum rotary steam obtains phospho acid crude product 18.529g, yellow liquid.
The 7th step, the purifying of butyl octyl dithiophosphinic acids
Gained dithiophosphinic acids crude product 18.529g in the 6th step is changed into corresponding salt earlier, utilize column chromatography or recrystallization method purification of salts then, become acid to get final product with hcl acidifying more at last.So far, the synthetic of asymmetric dithiophosphinic acids finished.
Synthesizing of embodiment 3 neighbours-trifluoromethyl (phenyl) dithiophosphinic acids
The first step, 1. organometallic reagent prepares
1. organometallic reagent uses Grignard reagent in this example;
Preparation Grignard reagent phenyl-magnesium-bromide
Under argon Ar protection, 0.105mol magnesium rod Mg2.553g and anhydrous diethyl ether 5mL are joined in the there-necked flask according to 1: 1.99 weightmeasurement ratio, add iodine grain 0.05g again; Drip 2～3mL bromobenzene C
6H
5Br (10.5mL, 0.1mol) ether (35mL) solution initiation reaction to the there-necked flask, bromobenzene C
6H
5The volume ratio of Br and anhydrous diethyl ether is 1: 3.33; Drip bromobenzene C while stirring
6H
5The Br diethyl ether solution after waiting to dropwise, continues to be heated to 30～40 ℃ and is back to the magnesium rod disappearance;
Second step, phenyl phosphorus dichloride C
6H
5PCl
2Synthetic
Under the argon Ar protection, with 10.5mL (0.12mol) phosphorus trichloride PCl
3Be added in the there-necked flask phosphorus trichloride PCl with the 80mL anhydrous diethyl ether
3With the volume ratio of anhydrous diethyl ether be 1: 7.62; Under constantly stirring, 2.5 equivalent Grignard reagents are dropped in the ebullient phosphorus trichloride diethyl ether solution react, generate white solidliquid mixture; After Grignard reagent dropwises, stirring at room 3-12 hour, stop heating, suction filtration steams the solvent that removes in the filtrate, obtains alkyl phosphorus dichloride R
1PCl
2The oil pump underpressure distillation obtains 62～70 ℃ water white transparency cut.
The 3rd step, organometallic reagent preparation 2.
2. organometallic reagent uses Grignard reagent in this example;
Preparation Grignard reagent neighbour-trifluoromethyl magnesium bromide
Under argon Ar protection, 0.063mol magnesium rod Mg1.512g and anhydrous tetrahydro furan 2mL are joined in the there-necked flask according to 1: 1.32 weightmeasurement ratio; Add iodine 0.05g again, drip 0.060mol neighbour-methyl bromobenzene trifluoride o-C of 2～3mL
7H
4F
3The initiation reaction to the there-necked flask of Br8.2mL and anhydrous tetrahydro furan 80ml solution, neighbour-methyl bromobenzene trifluoride o-C
7H
4F
3It is 1: 9.76 that Br and anhydrous tetrahydro furan get volume ratio; Drip neighbour-methyl bromobenzene trifluoride o-C while stirring
7H
4F
3Br and anhydrous tetrahydrofuran solution after waiting to dropwise, continue to be heated to 30～40 ℃ and are back to the magnesium rod disappearance;
The 4th step, phenyl (neighbour-trifluoromethyl) phosphorus chloride synthetic
Under-78 ℃, argon Ar protection, made neighbour-trifluoromethyl magnesium bromide tetrahydrofuran solution in the 3rd step is dropped to 6.8mL (0.05mol) phenyl phosphorus dichloride C
6H
5PCl
2In the 70mL anhydrous tetrahydro furan, dropwise the back and continue to stir, rise to room temperature until reaction mixture, gained solidliquid mixture suction filtration gets the garnet clear filtrate.
The 5th step, vulcanization reaction
Under the argon Ar protection, gained garnet clear filtrate in the 4th step is mixed stirring at room 12h with sulphur powder S 2.405 grams of 0.075mol; Filter the garnet clear filtrate.
The 6th step, the preparation of phenyl (neighbour-trifluoromethyl) dithiophosphinic acids
Under the argon Ar protection, gained garnet clear filtrate in the 5th step is mixed with the Sodium sulfhydrate NaHS of 16.5 grams, stirred 20 hours under the room temperature, suction filtration obtains yellow little red solid; This solid 100mL ether dissolution, then with the hydrochloric acid 100mL thorough mixing of 1mol/L, with saturated NaCl solution 100mL washing 2 times, anhydrous sodium sulfate drying filters again for separatory, gained diethyl ether solution, remove desolvate dithiophosphinic acids.Vacuum rotary steam gets phospho acid crude product 8.80g, red dark-brown oily matter.
The 7th step, the purifying of phenyl (neighbour-trifluoromethyl) dithiophosphinic acids
Gained dithiophosphinic acids crude product 8.80g in the 6th step is changed into corresponding salt earlier, utilize column chromatography or recrystallization method purification of salts then, become acid to get final product with hcl acidifying more at last.So far, the synthetic of asymmetric dithiophosphinic acids finished.
In sum, the synthetic method of asymmetric dithiophosphinic acids can realize the preparation of asymmetric dithiophosphinic acids, can be applied to the preparation field of dithiophosphinic acids kind of extractants compound.
Claims (4)
1, the synthetic method of asymmetric dithiophosphinic acids, it is characterized in that: be raw material with the phosphorus trichloride, generate asymmetric dialkyl phosphorus chloride with organometallic reagent RMX reaction, and then be reacted into phospho acid with elemental sulfur, Sodium sulfhydrate, by column chromatography or the corresponding salt of recrystallization method purifying, change into acid again and obtain asymmetric dithiophosphinic acids; Wherein M represents atoms metal, comprises lithium, sodium, beryllium, magnesium, aluminium, gallium, indium, thallium, tin, lead, bismuth, copper, zinc, cadmium or mercury, and R represents organic group, and X represents halogen.
2, the synthetic method of asymmetric dithiophosphinic acids according to claim 1 is characterized in that: may further comprise the steps:
The first step, organometallic reagent is R 1.
1M
1The preparation of X: method commonly used is a metal M
1Directly with halohydrocarbons reaction or by the exchange substitution reaction between the generation metal-metal;
Second step, alkyl phosphorus dichloride R
1PCl
2Synthetic
Under the argon Ar protection, with phosphorus trichloride PCl
3Be added in the there-necked flask phosphorus trichloride PCl with the anhydrous diethyl ether of respective volume
3With the volume ratio scope of anhydrous diethyl ether be 1: (2～10); Under constantly stirring, 1. 0.5～3 normal organometallic reagent be added drop-wise in the ebullient phosphorus trichloride diethyl ether solution react, generate white solidliquid mixture; After 1. organometallic reagent dropwises, continue heating and keep more than the backflow 1h; Stop heating, suction filtration steams the solvent that removes in the filtrate, obtains alkyl phosphorus dichloride R
1PCl
2
The 3rd step, organometallic reagent preparation 2.
Preparation method and the first step organometallic reagent 1. the preparation method is identical, but organometallic reagent activity 2. is higher than or is equal to machine metal reagent activity 1., and R
2Be different from R
1
The 4th step, asymmetric dialkyl phosphorus chloride R
1R
2The preparation of PCl
Under-78 ℃, argon Ar protection, 2. made organometallic reagent in the 3rd step is dropped to alkyl phosphorus dichloride R
1PCl
2In the anhydrous ether solution, dropwise the back and continue to stir, rise to room temperature naturally until reaction mixture, gained solidliquid mixture suction filtration gets clear filtrate;
The 5th step, vulcanization reaction
Under the argon Ar protection, gained clear filtrate in the 4th step is mixed with 1～2 normal sulphur powder S, stir more than 12 hours under the room temperature, suction filtration can obtain clarified liq;
The 6th step, asymmetric dialkyl dithiophosphinic acids R
1R
2The preparation of P (S) SH
Under the argon Ar protection, gained clarified liq in the 5th step to be mixed with 1～8 normal Sodium sulfhydrate NaHS, stirring reaction is more than 1 hour under the room temperature, and suction filtration obtains clarified liq; Then with 1～2mol/L hydrochloric acid thorough mixing, with saturated nacl aqueous solution washing 2 times, anhydrous sodium sulfate drying filters again for separatory, gained diethyl ether solution, remove desolvate dithiophosphinic acids;
The 7th step, the purifying of asymmetric dialkyl dithiophosphinic acids
Gained dithiophosphinic acids crude product in the 6th step is changed into corresponding salt earlier, utilize column chromatography or recrystallization method purification of salts then, become acid with hcl acidifying more at last.So far, the synthetic of asymmetric dithiophosphinic acids finished.
3, the synthetic method of asymmetric dithiophosphinic acids according to claim 1 and 2 is characterized in that: 1. the described organometallic reagent of present method the first step comprises following organometallic reagent:
(1) organolithium reagent: method commonly used is metallic lithium and halohydrocarbons reaction, under the protection of the drying nitrogen of deoxygenation, with lithium silk and anhydrous diethyl ether according to 1: the weightmeasurement ratio of (20～30) joins in the there-necked flask, stirs, and drips alkyl bromine R down at-10 ℃
1In Br diethyl ether solution to the three mouthful reaction flask, the volume ratio of alkyl bromine and anhydrous diethyl ether is 1: (1～4); After treating that alkyl bromine diethyl ether solution drips, be warming up to 0～10 ℃ and continue to stir 1～3 hour, make the diethyl ether solution of hydrocarbyl lithium.
(2) organomagnesium reagent is a Grignard reagent: under argon Ar protection, with magnesium rod Mg and anhydrous diethyl ether according to 1: the weightmeasurement ratio of (2～4) joins in the there-necked flask, adds iodine grain 0.05～0.1g again, drips 2～3mL alkyl bromine R
1Initiation reaction in Br diethyl ether solution to the three mouthful reaction flask, alkyl bromine R
1The volume ratio of Br and anhydrous diethyl ether is 1: (1～4); Drip alkyl bromine R while stirring
1The Br diethyl ether solution after waiting to drip, continues to be heated to 30～40 ℃ and is back to the magnesium rod disappearance.
(3) organic zinc reagent: use Grignard reagent or organolithium reagent and Zinc Chloride Anhydrous effect and can prepare alkyl zinc; With 1 normal Zinc Chloride Anhydrous ZnCl
2Diethyl ether solution drops in the Manufactured Grignard reagent, and stirring at room is 0.5～1.5 hour then; The suction filtration reaction mixture obtains the grey clarified liq, is zincon.
(4) organic sodium reagent: sodium Metal 99.5 can be directly and halohydrocarbons reaction, perhaps and the exchange substitution reaction between the metal hydrocarbon based compound generation metal-metal of another activity difference prepare alkyl sodium, in addition sodium Metal 99.5 can be directly with hydro carbons or directly and acid stronger hydrocarbon replace wherein hydrogen, the exchange substitution reaction that metalloid-hydrogen takes place prepares alkyl sodium.
(5) organic beryllon: the preparation method according to Grignard reagent makes corresponding Grignard reagent earlier, and then handles with excessive dichloride beryllium diethyl ether solution, and product separates with benzene extraction or distillation method, obtains the dialkyl beryllium.
(6) organoaluminum reagent: metallic aluminium and halohydrocarbon direct reaction, perhaps aluminum halide and Grignard reagent react all in ether and can prepare alkyl aluminium;
(7) organic gallium, indium reagent: gallium or indium and alkyl mercury long-time heating can prepare alkyl gallium or alkyl indium.
(8) organic thallium reagent: because alkyl thallium (R
2Tl) character instability is difficult for preparation, but uses TlX
3With the Grignard reagent effect, can form stable dialkyl halogenation thallium R
2TlX.
(9) organotin reagent: available Grignard reagent and anhydrous stannic chloride prepared in reaction alkyl tin.
(10) organic dithizone: available Grignard reagent and lead chloride prepared in reaction plumbane.
(11) organo-bismuth reagent: the halide reaction of using Grignard reagent or hydrocarbyl lithium and bismuth can prepare the alkyl bismuth.
(12) organic copper reagent: prepared in reaction alkyl copper under available hydrocarbyl lithium and the cuprous iodide low temperature.
(13) organic cadion: can prepare an alkyl halogenation cadmium or dialkyl cadmium with Grignard reagent and exsiccant anhydrous chlorides of rase cadmium reaction.
(14) organic mercury reagent: available Grignard reagent in anhydrous diethyl ether with mercuric bromide prepared in reaction alkyl mercury.
4, the synthetic method of asymmetric dithiophosphinic acids according to claim 1 and 2 is characterized in that: the dithiophosphinic acids compound of synthetic unsymmetrical structure comprises: i) R
1, R
2Be alkyl, ii) R
1, R
2Be aromatic base, iii) R
1, R
2Wherein one be alkyl another be aromatic base; Its structural formula is as follows:
R
1, R
2Can be respectively the alkyl group of ethyl, propyl group, butyl, amyl group, hexyl, octyl group or cyclohexyl and the aromatic group that contains phenyl ring of benzyl, phenyl or trifluoromethyl, and R
1≠ R
2
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108517406A (en) * | 2018-04-19 | 2018-09-11 | 中国人民解放军国防科技大学 | Solid phase extracting agent for selectively separating trivalent minor actinide and trivalent lanthanide, and preparation method and application thereof |
| CN109081944A (en) * | 2018-06-28 | 2018-12-25 | 浙江大学 | Dialkyl dithio hypophosphite fire retardant and its application |
| CN109824495A (en) * | 2019-02-02 | 2019-05-31 | 盐城锦明药业有限公司 | A kind of novel coupling reaction is preparing the application in carbon-carbon bond structural compounds |
| CN112573550A (en) * | 2020-11-24 | 2021-03-30 | 衢州学院 | Method for preparing magnesium-based flame retardant by utilizing Grignard wastewater |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE19502197A1 (en) * | 1995-01-25 | 1996-08-01 | Bayer Ag | Process for the preparation of thiophosphoric acid-O, O'-diesters and their salts and their use |
| CA2550557C (en) * | 2006-06-14 | 2011-03-29 | Cytec Canada, Inc. | Novel phosphinic acids and their sulfur derivatives and methods for their preparation |
| CN101343287B (en) * | 2008-08-29 | 2011-05-11 | 清华大学 | Synthesis of sicycle-ring hexyl di-thiophosphinic acid |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108517406A (en) * | 2018-04-19 | 2018-09-11 | 中国人民解放军国防科技大学 | Solid phase extracting agent for selectively separating trivalent minor actinide and trivalent lanthanide, and preparation method and application thereof |
| CN109081944A (en) * | 2018-06-28 | 2018-12-25 | 浙江大学 | Dialkyl dithio hypophosphite fire retardant and its application |
| CN109824495A (en) * | 2019-02-02 | 2019-05-31 | 盐城锦明药业有限公司 | A kind of novel coupling reaction is preparing the application in carbon-carbon bond structural compounds |
| CN109824495B (en) * | 2019-02-02 | 2022-12-09 | 盐城师范学院 | Application of novel coupling reaction in preparation of carbon-carbon bond structure compound |
| CN112573550A (en) * | 2020-11-24 | 2021-03-30 | 衢州学院 | Method for preparing magnesium-based flame retardant by utilizing Grignard wastewater |
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