CN103073582A - Synthesis method of monoalkyl hydrocarbyl phosphonate - Google Patents
Synthesis method of monoalkyl hydrocarbyl phosphonate Download PDFInfo
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Abstract
The invention provides a synthesis method of monoalkyl hydrocarbyl phosphonate. Particularly, the invention provides a compound shown as a formula I and a preparation method thereof. In the formula, definitions of R1, R2 and M are defined as the specification. The invention further discloses an application of taking the compound shown as the formula I as an extracting agent, and an extracting agent component prepared from the compound shown as the formula I.
Description
Technical field
What the present invention relates to is a kind of novel method of synthetic alkyl single alkyl phosphonic acid esters extractant and the application of synthetic compound thereof.
Background technology
Hydrocarbon radical phosphorate mono-alkyl ester is that a class is applicable to rare earth, nickel cobalt or other metal separation, have high extraction ability and separating factor the extraction agent type, the extraction agent P507 that is most widely used at present also belongs to a kind of in this kind of extractants.
The synthetic method of traditional P507 mainly contains following two kinds: 1. the reaction of phosphonous acid three isooctyl acrylate and halo octane-iso obtains the alkyl phosphonic acid diester, and then hydrolysis obtains product; 2. phosphonous acid diisooctyl ester and halo octane-iso react under the effect of sodium ethylate or sodium and generate the alkyl phosphonic acid diester, and hydrolysis obtains iso-octyl phosphonic acids list isooctyl acrylate again.Wherein, method one is P507 for Japanese PC88() synthetic method, but it is lower to use the product yield that this method obtains, and usually affects extraction ability with the by product such as other acidic impurities such as diprotic acid; Method two is existing domestic general synthetic method, but reaction conditions is harsh, and reaction yield is not very high, and raw material phosphorous acid diester usually can not react completely, remain in the reaction intermediate, participate in next step reaction, thereby have influence on total yield and the purity of whole product.
In sum, this area is high in the urgent need to a kind of transformation efficiency, the reaction times is short, side reaction is few, the method for the two alkyl Hypophosporous Acid, 50 of the preparation of mild condition.
Summary of the invention
Purpose of the present invention is intended to solve problems of the prior art, and a kind of synthetic method of simple and feasible suitability for industrialized production hydrocarbon radical phosphorate mono-alkyl ester is provided.
A first aspect of the present invention provides the preparation method of the compound shown in a kind of formula I,
In the formula,
R
1Be selected from lower group: H, replacement or unsubstituted C1～C18 alkyl, replacement or unsubstituted C3-C18 cycloalkyl, replacement or unsubstituted aryl (such as phenyl), replacement or unsubstituted C1-C3 alkylidene aryl (such as benzyl); Or R
1With adjacent replacement or unsubstituted-CH
2CH
2Replace or unsubstituted C3-C20 cycloalkyl-the common composition;
R
2Be selected from lower group: replace or unsubstituted C1～C20 alkyl, replacement or unsubstituted C3-C20 cycloalkyl, replacement or unsubstituted aryl (such as phenyl), replacement or unsubstituted C1-C3 alkylidene aryl (such as benzyl);
M is H or basic metal;
Wherein, described replacement refers to that the one or more hydrogen atoms on the group are selected from lower group substituting group replacement: C1～C4 alkyl, C1～C4 haloalkyl, C3～C10 cycloalkyl, C3～C10 halogenated cycloalkyl, halogen, hydroxyl, carboxyl, aldehyde radical, acyl group, amino, phenyl; Described phenyl comprises unsubstituted phenyl or has the substituent substituted-phenyl of 1-5 (preferably 1-3), and described substituting group is selected from: C1～C4 alkyl, halogen, hydroxyl, carboxyl, aldehyde radical, acyl group, amino, nitro, phenyl ring;
It is characterized in that, said method comprising the steps of (a) and (b):
(a) in inert solvent, formula Ia alkene and formula Ib phosphonous acid diester are reacted, obtain the alkyl phosphonic acid diester shown in the formula Ic;
Above-mentioned various in, R
1For replacing or unsubstituted C1-C18 alkyl, replacement or unsubstituted C3-C18 cycloalkyl, replacement or unsubstituted aryl, replacement or unsubstituted C1-C3 alkylidene aryl; Or R in the formula (Ia)
1With adjacent replacement or unsubstituted-CH=CH
2Replace or unsubstituted C3-C20 cycloolefin common the composition; M and R
2Described as defined above;
(b) in inert solvent, under the reflux condition, with described formula Ic alkyl phosphonic acid diester and alkali reaction, obtain formula I compound;
Above-mentioned various in, M, R
1And R
2Described as defined above.
In another preference, described cycloolefin comprises the cycloolefin that does not replace and replace, and wherein the definition of " replacement " is the same.
In another preference, described step (a) is 60～200 ℃ of lower reactions, preferably 80～150 ℃ of lower reactions.
In another preference, described step (a) reaction times is 1～8 hour, preferably is 2～4 hours.
In another preference, described step (a) is reacted in the presence of initiator.
In another preference, the mol ratio of described alkene and phosphonous acid diester 〉=1, preferably, alkene: phosphonous acid diester=2～4.
In another preference, described phosphonous acid diester prepares by the following method:
In inert solvent, with R
2OH and phosphorus trichloride reaction obtain the phosphorous acid diester.
In another preference, the product of step (a) gained carried out conventional aftertreatment after, be used for the reaction of step (b).
In another preference, described conventional aftertreatment comprises one or more processing that are selected from lower group:
The crude product Ic of washing gained;
The saturated common salt washing;
The extracted with diethyl ether water merges organic phase;
Dry filter;
The decompression desolventizing.
In another preference, described alkali is selected from lower group: sodium hydroxide solution, potassium hydroxide solution, ethanolamine solutions, or its combination.
In another preference, described step (a) and step (b) are carried out under microwave condition, and described microwave power is 5～1500W/100ml liquid reaction system, preferably are 100～400W/100ml liquid reaction system.
In another preference, described reaction is carried out in the microwave synthesis reaction vessel.
In another preference, described solvent is selected from lower group: C4～C20 alkane, C4～C20 naphthenic hydrocarbon, C4～C20 ester, C4～C20 acid, C4～C20 ether, C4～C20 alcohol, DMF, or its combination.
In another preference, described initiator is selected from lower group: di-t-butyl peroxide, benzoyl peroxide, hydrogen peroxide, ammonium peroxydisulfate, Potassium Persulfate, peracetic acid, Diisopropyl azodicarboxylate, or its combination.
In another preference, between the reaction period, add initiator in step (a).
In another preference, after step (a) is carried out 2 hours, add initiator.
A second aspect of the present invention provides a kind of suc as formula the compound shown in the I:
In the formula,
M is selected from lower group: H, basic metal;
R
1Be selected from lower group: H, replacement or unsubstituted C1～C18 alkyl, replacement or unsubstituted C3～C18 cycloalkyl, replacement or unsubstituted aryl (such as phenyl), replacement or unsubstituted C1-C3 alkylidene aryl; Or R
1With-CH
2CH
2Replace or unsubstituted C3-C20 cycloalkyl-the common composition;
R
2Be selected from lower group: replace or unsubstituted C1～C20 alkyl, replacement or unsubstituted C3-C20 cycloalkyl, replacement or unsubstituted aryl (such as phenyl), replacement or unsubstituted C1-C3 alkylidene aryl;
And, work as R
2During for iso-octyl, replace or unsubstituted R
1CH
2CH
2-be not 1-octyl group or 2-ethyl-1-hexyl;
Wherein, described replacement refers to that the one or more hydrogen atoms on the group are selected from lower group substituting group replacement: C1～C4 alkyl, C1～C4 haloalkyl, C3～C10 cycloalkyl, C3～C10 halogenated cycloalkyl, halogen, hydroxyl, carboxyl, aldehyde radical, acyl group, amino, phenyl.
In another preference, described R
2For replacing or unsubstituted C1～C12 alkyl, preferably for replacing or unsubstituted C5～C8 alkyl, for replacing or unsubstituted C8 alkyl, be iso-octyl best more preferably.
In another preference, described R
1For replacing or unsubstituted C1～C12 alkyl or replacement or unsubstituted C1～C12 cycloalkyl, preferably for replacing or unsubstituted C2～C8 alkyl or replacement or unsubstituted C3～C8 cycloalkyl.
A third aspect of the present invention provides a kind of purposes such as the described compound of second aspect present invention, it is characterized in that, for separating of or extracting metals; Or as the extraction agent of separating metal from metallic mixture.
In another preference, described metal comprises rare earth metal or nickel cobalt metal, preferably comprises lanthanum, cerium, praseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, lutetium, yttrium, nickel, Cobalt.
A fourth aspect of the present invention provides a kind of extractant composition, and described composition contains the compound of the usefulness that extracts significant quantity such as the described method preparation of first aspect present invention, or such as the described compound of second aspect present invention.
In another preference, described extractant composition is used for the extracting and separating metal mixture.
A fifth aspect of the present invention, a kind of extracting process is provided, described method with metallic mixture as extraction feed, with such as the described compound of second aspect present invention as extraction agent or with such as the described extractant composition of fourth aspect present invention, carry out extracting and separating, thereby from described mixture, extract described metal.
In another preference, described extracting process comprises step: mix with the mixture that contains metal to be separated (extraction feed) with the described compound of second aspect present invention or such as the described extractant composition of fourth aspect present invention, form the extraction phase that contains metal to be separated; And
From described extraction phase, isolate described metal to be separated.
In should be understood that within the scope of the present invention, above-mentioned each technical characterictic of the present invention and can making up mutually between specifically described each technical characterictic in below (eg embodiment), thus consist of new or preferred technical scheme.As space is limited, this tired stating no longer one by one.
Description of drawings
Fig. 1 is the potentiometric titration figure of 1 synthetic compound of the embodiment of the invention.
Embodiment
The inventor is through long-term and deep research, be surprised to find that, with alkene and phosphonous acid diester under normal pressure and/or normal pressure microwave condition, carry out Radical Addition through radical initiator, through one-step hydrolysis reaction, can prepare easily symmetrical and asymmetrical hydrocarbon radical phosphorate mono-alkyl ester again.Based on above-mentioned discovery, the contriver has finished the present invention.
Term
As used herein, term " replacement " refers to replace the substituting group replacement that the one or more hydrogen atoms that refer on the group are selected from lower group: C1～C4 alkyl, C1～C4 haloalkyl, C3～C10 cycloalkyl, C3～C10 halogenated cycloalkyl, halogen, hydroxyl, carboxyl, aldehyde radical, acyl group, amino, phenyl, nitro.Wherein, described phenyl comprises unsubstituted phenyl or has 1-3 substituent substituted-phenyl, and described substituting group is selected from: C1～C4 alkyl, halogen, hydroxyl, carboxyl, aldehyde radical, acyl group, amino, nitro, phenyl ring.
Term " C1～C18 alkyl " refers to have the straight or branched alkyl of 1-18 carbon atom, for example methyl, ethyl, propyl group, sec.-propyl, butyl, isobutyl-, sec-butyl, the tertiary butyl or similar group.
Term " C3～C18 cycloalkyl " refers to have the straight or branched alkyl of 1-18 carbon atom, for example cyclopropyl, cyclobutyl, methyl cyclopropyl, cyclopentyl, or similar group.
Term " C3～C20 cycloalkyl " refers to have the straight or branched alkyl of 1-20 carbon atom, for example cyclopropyl, cyclobutyl, methyl cyclopropyl, cyclopentyl, or similar group.
Term " aryl " refers to the aryl radical of monocycle or condensed ring, the aryl radical of preferred monocycle to three ring, for example phenyl, naphthyl, anthryl, phenanthryl or similar group.Preferably, described aryl is C6～C12 aryl: have the aryl of 6～12 carbon atoms, for example phenyl, naphthyl.
Term " C4～C20 alkane " refers to have the straight or branched alkane of 4-20 carbon atom, for example butane, Trimethylmethane, hexane, heptane, or similar alkane.
Term " C4～C20 naphthenic hydrocarbon " refers to have the straight or branched alkane of 4-20 carbon atom, for example hexanaphthene, suberane, cyclooctane, or similar alkane.
Term " C4～C20 ester " refers to have the ester class of 4-20 carbon atom, such as ethyl acetate, butylacetate, tetrahydrofuran (THF), jasmal, or similar ester.
Term " C4～C20 acid " refers to have the acid of 4-20 carbon atom, such as butyric acid, valeric acid, oleic acid, or the class acidoid.
Term " C4～C20 ether " refers to have the ether of 4-20 carbon atom, such as ethyl n-butyl ether, di-n-butyl ether, diamyl ether, tetrahydrofuran (THF), oxyethane, propylene oxide, 1, and 3-dioxolane or similar ether.
Term " C4～C20 alcohol " refers to have the alcohol of 4-20 carbon atom, such as propyl carbinol, 2-butanols, the trimethyl carbinol, Pentyl alcohol, hexalin, or similar alcohol.
Term " C1～C3 alkylidene aryl " refers to have the straight or branched alkyl with 1-3 carbon atom of one or more replacements or unsubstituted aryl substituent, such as benzyl.
Term " phenyl " comprises unsubstituted phenyl or has the substituent substituted-phenyl of 1-5 (preferably 1-3), and wherein said substituting group comprises (but being not limited to): halogen, C1-C4 alkyl, OH, nitro;
Synthesizing of hydrocarbon radical phosphorate mono-alkyl ester
The synthetic method of the hydrocarbon radical phosphorate mono-alkyl ester that the present invention proposes, wherein said hydrocarbon radical phosphorate mono-alkyl ester has following structure:
Wherein, R
1Be selected from lower group: H, replacement or unsubstituted C1～C18 alkyl, replacement or unsubstituted C1～C18 cycloalkyl, replacement or unsubstituted aryl (such as phenyl), replacement or unsubstituted C1-C3 alkylidene aryl (such as benzyl); Or R
1With-CH
2CH
2Replace or unsubstituted C3-C20 cycloalkyl-the common composition;
R
2Be selected from lower group: replace or unsubstituted C1～C20 alkyl, replacement or unsubstituted C3-C20 cycloalkyl, replacement or unsubstituted aryl (such as phenyl), replacement or unsubstituted C1-C3 alkylidene aryl;
M is H or basic metal;
Wherein, described replacement refers to that the one or more hydrogen atoms on the group are selected from lower group substituting group replacement: C1～C4 alkyl, C1～C4 haloalkyl, C3～C10 cycloalkyl, C3～C10 halogenated cycloalkyl, halogen, hydroxyl, carboxyl, aldehyde radical, acyl group, amino, phenyl; Described phenyl comprises unsubstituted phenyl or has the substituent substituted-phenyl of 1-5 (preferably being 1-3), and described substituting group is selected from: C1～C4 alkyl, halogen, hydroxyl, carboxyl, aldehyde radical, acyl group, amino, nitro, phenyl ring.
The reaction formula of synthetic method of the present invention is as follows:
Synthetic method comprises one or more the following steps:
(a) in inert solvent, phosphonous acid diester and alkene are reacted, obtain the alkyl phosphonic acid diester; And/or
(b) in inert solvent, under the reflux condition, alkyl phosphonic acid diester and alkaline solution reaction with step (a) obtains obtain formula I compound;
Above-mentioned various in, M and R
2Described as defined above;
R
1For replacing or unsubstituted C1-C18 alkyl, replacement or unsubstituted C3-C18 cycloalkyl, replacement or unsubstituted aryl, replacement or unsubstituted C1-C3 alkylidene aryl;
Or R
1With replacement or unsubstituted-CH=CH
2The common C3-C20 of composition replaces and unsubstituted cycloolefin;
Or R
1With replacement or unsubstituted-CH
2CH
2-jointly form C3-C20 to replace or unsubstituted naphthenic hydrocarbon;
Wherein, the definition of replacement is the same.
Described step (a) is for example reacted under 60～200 ℃ under heating condition, preferably reacts under 80～150 ℃.
Described step (a) reaction times is not particularly limited, and reacts completely but nuclear-magnetism P spectrum is followed the tracks of, and is preferably 1～8 hour, more preferably is 2～4 hours.
Between the reaction period, optionally in reaction system, add initiator in step (a).Preferably, after step (a) is carried out 2 hours, add initiator.
Preferably, the mol ratio of described reaction raw materials 〉=1, preferably, alkene: phosphonous acid diester=2～4.
Above-mentioned reaction can be carried out under microwave condition, and described microwave power preferably can be 5～1500W/100ml liquid reaction system, is preferably 100～400W/100ml liquid reaction system.
The raw material that reacts used can obtain by commercially available approach, also can prepare by ordinary method.In another preference, described phosphonous acid diester prepares by the following method:
In inert solvent, with R
2OH and phosphorus trichloride reaction obtain the phosphorous acid diester.
The product of step (a) gained can be directly used in the reaction of step (b), also can carry out first being used further to after the conventional aftertreatment reaction of step (b).In another preference, described conventional aftertreatment comprises and is selected from one or more steps of lower group:
The crude product of washing gained;
The saturated common salt washing;
The extracted with diethyl ether water merges organic phase;
Dry filter;
The decompression desolventizing.
In a preference of the present invention, described reactions steps is as follows:
Phosphonous acid diester, alkene, initiator and solvent are placed in proportion the there-necked flask of microwave synthesizer reactor or synthesis under normal pressure, in 60～200 ℃ of reactions 1～8 hour, preferred 80～150 ℃ of lower reactions 2～4 hours, during add initiator; The mol ratio of alkene and phosphonous acid diester 〉=1 wherein, preferred 2～4, the mol ratio of acid and inferior sodium phosphate＞1, preferred 1.3～2.
With alkyl phosphonic acid diester washing twice obtained above, the saturated common salt washing, the extracted with diethyl ether water merges organic phase, is washed to neutrality, and behind the dry filter, the decompression desolventizing obtains product.
With phosphonate ester obtained above and alkaline solution reflux, unnecessary raw material and solvent are removed in continuous rear underpressure distillation, and residue is dissolved in sherwood oil, uses 3M sulfuric acid or 6M hcl acidifying 2 times, is washed to neutrality, dry filter, and desolventizing gets product.
In the above-mentioned reaction, described initiator is selected from lower group: di-t-butyl peroxide, benzoyl peroxide, hydrogen peroxide, ammonium peroxydisulfate, Potassium Persulfate, peracetic acid, Diisopropyl azodicarboxylate, or its combination.
Described solvent is selected from lower group: C4～C20 alkane, C4～C20 naphthenic hydrocarbon, C4～C20 ester, C4～C20 acid, C4～C20 ether, C4～C20 alcohol, DMF, or its combination.
Representational alkaline solution comprises (but being not limited to): sodium hydroxide solution, potassium hydroxide solution, ethanolamine solutions, or its combination.
Extraction agent and application
The hydrocarbon radical phosphorate mono-alkyl ester that the present invention synthesizes can be used as extraction agent, both can be used for the extracting and separating of rare earth element, also can be used for the separating-purifying of nickel cobalt element or the separating-purifying of other metallic elements.The extraction agent that the present invention synthesizes both can be used as single extraction agent and had used, and also can cooperate by a certain percentage as extraction agent with other extraction agents (such as two alkyl phosphonic acids) and use.
Major advantage of the present invention
The present invention is to provide a kind ofly from alkene and phosphonous acid diester reaction preparation alkyl phosphonic acid diester, hydrolysis obtains the novel method of hydrocarbon radical phosphorate mono-alkyl ester.This method synthesis material carries out Radical Addition for Industrial products alkene and the phosphorous acid diester that comparatively is easy to get, and reaction conditions is easy, and reaction is clean, substantially generates without other side reactions and by product, and yield is high, and aftertreatment is easy, and product purity is also higher.
Compared to the synthetic alkyl phosphonic acid diester under basic metal or an alkali metal salt catalytic condition with halogenated alkane and phosphorous acid diester, hydrolysis prepares the method for alkyl phosphate again, uses olefine reaction, raw material is simple and easy to, react completely, rare by product generates, and yield and purity can both obtain higher value.The present invention is particularly useful for long carbochain or with the preparation of the alkyl phosphonate monoester of branched-chain alkyl.
Below in conjunction with specific embodiment, further set forth the present invention.Should be understood that these embodiment only to be used for explanation the present invention and be not used in and limit the scope of the invention.The experimental technique of unreceipted actual conditions in the following example, usually according to normal condition, or the condition of advising according to manufacturer.Unless otherwise indicated, otherwise per-cent and umber calculate by weight.
Embodiment 1:1-octyl phosphonic acid list iso-octyl ester synthesis
With a hydration phospho acid sodium 10.6g, Glacial acetic acid 80mL, 1-octene 11.2g, peroxidized t-butyl perbenzoate 4mL joins in the there-necked flask successively, normal heating to 130 degree, back flow reaction 2 hours.After adding initiator peroxidized t-butyl perbenzoate 4mL, continued back flow reaction 2 hours.Wash 2 times, extracted with diethyl ether 2 times are used in saturated common salt washing 1 time, merge organic phase, after washing with water, and anhydrous sodium sulfate drying, suction filtration, the decompression desolventizing gets product 30.6g, yield 73.2%.Add thanomin 52ml, heating reflux reaction 30 hours, the thanomin that reclaim under reduced pressure is excessive is dissolved in sherwood oil with resistates, uses 3M sulfuric acid acidation 2 times, is washed to neutrality, desolventizing, drying gets product 18.9g, yield 84.4%.
31P NMR:1-octyl phosphonic acid list isooctyl acrylate: δ: 35.281ppm94.7% (purity is pressed peak meter)
Neutralization equivalent: the 92.6%(0.1657g sample consumes 6.8278mLNaOH (0.07344mol/L) solution meter)
Take by weighing an amount of extractant complex, be dissolved in 75% ethanolic soln, drip the sodium hydroxide solution of concentration known to titration end point, the result only has the terminal point of a potential break as shown in Figure 1, and illustrating does not have other acidic impurities to exist.
Embodiment 2:1,2-dimethyl-1-propyl phosphonous acid list iso-octyl ester synthesis
With a hydration phospho acid sodium 10.6g, DMF80mL, isopentene 7.0g, benzoyl peroxide 4.8g joins in the there-necked flask successively, normal heating to 110 degree, back flow reaction 2 hours.After adding initiator benzoyl peroxide 4.8g, continued back flow reaction 2 hours.After adding again initiator benzoyl peroxide 4.8g, continued back flow reaction 2 hours.Wash 2 times, extracted with diethyl ether 2 times are used in saturated common salt washing 1 time, merge organic phase, after washing with water, and anhydrous sodium sulfate drying, suction filtration, the decompression desolventizing gets product 29.4g, yield 78.2%.Add thanomin 55ml, heating reflux reaction 30 hours, the thanomin that reclaim under reduced pressure is excessive is dissolved in sherwood oil with resistates, uses 3M sulfuric acid acidation 2 times, is washed to neutrality, desolventizing, drying gets product 21.7g, yield 82.2%.
31P NMR:1,2-dimethyl-1-propyl phosphonous acid list isooctyl acrylate: δ: 37.396ppm95.3% (purity is pressed peak meter)
Neutralization equivalent: the 93.9%(0.1704g sample consumes 8.2578mLNaOH (0.07344mol/L) solution meter)
Embodiment 3:2,3-dimethyl-1-butyl phosphine monooctyl acid octyl group ester synthesis
With a hydration phospho acid sodium 10.6g, Glacial acetic acid 80mL, 2,3-dimethyl-1-butylene 8.4g, Diisopropyl azodicarboxylate 3.4g joins in the there-necked flask successively, normal heating to 110 degree, back flow reaction 2 hours.After adding initiator Diisopropyl azodicarboxylate 3.3g, continued back flow reaction 2 hours.After adding again initiator Diisopropyl azodicarboxylate 3.3g, continued back flow reaction 2 hours.Wash 2 times, extracted with diethyl ether 2 times are used in saturated common salt washing 1 time, merge organic phase, after washing with water, and anhydrous sodium sulfate drying, suction filtration, the decompression desolventizing gets product 31.2g, yield 80.0%.Add thanomin 52ml, heating reflux reaction 30 hours, the thanomin that reclaim under reduced pressure is excessive is dissolved in sherwood oil with resistates, uses 3M sulfuric acid acidation 2 times, is washed to neutrality, desolventizing, drying gets product 18.5g, yield 83.2%.
31P NMR:2,3-dimethyl-1-butyl phosphine monooctyl acid octyl group ester: δ: 36.115ppm91.7% (purity is pressed peak meter)
Neutralization equivalent: the 89.4%(0.1665g sample consumes 7.2912mLNaOH (0.07344mol/L) solution meter)
Embodiment 4:3,3-dimethyl-1-butyl phosphine monooctyl acid octyl group ester synthesis
With a hydration phospho acid sodium 10.6g, hexanaphthene 80mL, 3,3-dimethyl 1-butylene 8.4g, di-t-butyl peroxide ether 4mL joins in the there-necked flask successively, normal heating to 130 degree, back flow reaction 2 hours.After adding initiator di-t-butyl peroxide ether 4mL, continued back flow reaction 2 hours.Add initiator di-t-butyl peroxide ether 4mL after continuous, continued back flow reaction 2 hours.Wash 2 times, extracted with diethyl ether 2 times are used in saturated common salt washing 1 time, merge organic phase, after washing with water, and anhydrous sodium sulfate drying, suction filtration, the decompression desolventizing gets product 28.5g, yield 73.1%.Add thanomin 52ml, heating reflux reaction 30 hours, the thanomin that reclaim under reduced pressure is excessive is dissolved in sherwood oil with resistates, uses 3M sulfuric acid acidation 2 times, is washed to neutrality, desolventizing, drying gets product 17.5g, yield 86.2%.
31P NMR:3,3-dimethyl-1-butyl phosphine monooctyl acid octyl group ester: δ: 36.539ppm90.8% (purity is pressed peak meter)
Neutralization equivalent: the 87.5%(0.1780g sample consumes 7.6324mLNaOH (0.07344mol/L) solution meter)
Embodiment 5:3-methyl isophthalic acid-butyl phosphine monooctyl acid octyl group ester synthesis
With a hydration phospho acid sodium 10.6g, Glacial acetic acid 80mL, 3-methyl-1-butene 7.0g, peroxidized t-butyl perbenzoate 4mL joins in the there-necked flask successively, normal heating to 110 degree, back flow reaction 2 hours.After adding initiator peroxidized t-butyl perbenzoate 4mL, continued back flow reaction 2 hours.Add peroxidized t-butyl perbenzoate 4mL after continuous, continued back flow reaction 2 hours.Wash 2 times, extracted with diethyl ether 2 times are used in saturated common salt washing 1 time, merge organic phase, after washing with water, and anhydrous sodium sulfate drying, suction filtration, the decompression desolventizing gets product 27.8g, yield 73.9%.Add thanomin 52ml, heating reflux reaction 30 hours, the thanomin that reclaim under reduced pressure is excessive is dissolved in sherwood oil with resistates, uses 3M sulfuric acid acidation 2 times, is washed to neutrality, desolventizing, drying gets product 17.3g, yield 88.6%.
31P NMR:3-methyl isophthalic acid-butyl phosphine monooctyl acid octyl group ester: δ: 36.569ppm95.6% (purity is pressed peak meter)
Neutralization equivalent: the 90.2%(0.1682g sample consumes 7.8214mLNaOH (0.07344mol/L) solution meter)
Embodiment 6:2-ethyl-1-hexyl phosphonic acids list iso-octyl ester synthesis
With a hydration phospho acid sodium 10.6g, Glacial acetic acid 80mL, isooctene 11.2g, di-t-butyl peroxide ether 4mL adds in the microwave synthesis reaction vessel successively, and power setting becomes 400w, lower 15 minutes programmed heating to 130 degree of condition of normal pressure, back flow reaction 2 hours.After adding initiator di-t-butyl peroxide ether 4mL, continued back flow reaction 2 hours.Add di-t-butyl peroxide ether 4mL after continuous, continued back flow reaction 2 hours.Wash 2 times, extracted with diethyl ether 2 times are used in saturated common salt washing 1 time, merge organic phase, after washing with water, and anhydrous sodium sulfate drying, suction filtration, the decompression desolventizing gets product 31.9g, yield 76.3%.Add thanomin 52ml, heating reflux reaction 30 hours, the thanomin that reclaim under reduced pressure is excessive is dissolved in sherwood oil with resistates, uses 3M sulfuric acid acidation 2 times, is washed to neutrality, desolventizing, drying gets product 18.8g, yield 80.5%.
31P NMR:2-ethyl-1-hexyl phosphonic acids list isooctyl acrylate: δ: 35.917ppm93.6% (purity is pressed peak meter)
Neutralization equivalent: the 91.9%(0.1741g sample consumes 7.1233mLNaOH (0.07344mol/L) solution meter)
Embodiment 7:2,4,4-trimethylammonium-1-amyl group phosphonic acids list iso-octyl ester synthesis
With a hydration phospho acid sodium 10.6g, Glacial acetic acid 80mL, diisobutylene 11.2g, Diisopropyl azodicarboxylate 3.5g joins in the microwave synthesis reaction vessel successively, and power setting becomes 400w, lower 15 minutes programmed heating to 135 degree of condition of normal pressure, back flow reaction 2 hours.After adding initiator Diisopropyl azodicarboxylate 3.4g, continued back flow reaction 2 hours.After adding again initiator Diisopropyl azodicarboxylate 3.4g, continued back flow reaction 2 hours.Wash 2 times, extracted with diethyl ether 2 times are used in saturated common salt washing 1 time, merge organic phase, after washing with water, and anhydrous sodium sulfate drying, suction filtration, the decompression desolventizing gets product 30.3g, yield 72.5%.Add thanomin 52ml, heating reflux reaction 30 hours, the thanomin that reclaim under reduced pressure is excessive is dissolved in sherwood oil with resistates, uses 3M sulfuric acid acidation 2 times, is washed to neutrality, desolventizing, drying gets product 19.3g, yield 86.2%.
31P NMR:2,4,4-trimethylammonium-1-amyl group phosphonic acids list isooctyl acrylate: δ: 34.166ppm93.3% (purity is pressed peak meter)
Neutralization equivalent: the 91.8%(0.1553g sample consumes 6.3431mLNaOH (0.07344mol/L) solution meter)
Embodiment 8: cyclopentyl phosphonic acids list iso-octyl ester synthesis
With a hydration phospho acid sodium 10.6g, DMF80mL, cyclopentenes 7.0g, benzoyl peroxide 4.8g joins in the there-necked flask successively, normal heating to 110 degree, back flow reaction 2 hours.After adding initiator benzoyl peroxide 4.8g, continued back flow reaction 2 hours.After adding again initiator benzoyl peroxide 4.8g, continued back flow reaction 2 hours.Wash 2 times, extracted with diethyl ether 2 times are used in saturated common salt washing 1 time, merge organic phase, after washing with water, and anhydrous sodium sulfate drying, suction filtration, the decompression desolventizing gets product 28.3, yield 75.3%.Add thanomin 55ml, heating reflux reaction 30 hours, the thanomin that reclaim under reduced pressure is excessive is dissolved in sherwood oil with resistates, uses 3M sulfuric acid acidation 2 times, is washed to neutrality, desolventizing, drying gets product 16.7g, yield 84.1%.
31P NMR: cyclopentyl phosphonic acids list isooctyl acrylate: δ: 37.422ppm96.6% (purity is by peak meter) neutralization equivalent: the 89.2%(0.1815g sample consumes 8.3545mLNaOH (0.07344mol/L) solution)
The performance test of the dialkyl phosphinic acid extracting rare-earth of embodiment 9 different structures:
Organic phase: dialkyl phosphinic acid is mixed with 0.5M n-dodecane solution
Water: [Ln]=0.01M, [(H, Na) Cl]=1.0M[H
+]=0.05M
The dialkyl phosphinic acid extractant of embodiment 1～8 preparation, the performance of extracting rare-earth is as shown in the table:
Wherein, embodiment 6 is classical extraction agent P507, and the synthetic P507 of method and the PC88 (being P507) of Japanese import compare thus, and the extraction ability result is basically identical.
Compare with P507, the compound that the embodiment of the invention 2,3,4,5 prepares has not only kept suitable extracting power, and is showing better separating effect aspect the heavy rare earths separation, has higher separating factor value.
All quote in this application as a reference at all documents that the present invention mentions, just as each piece document is quoted separately as a reference.Should be understood that in addition those skilled in the art can make various changes or modifications the present invention after having read above-mentioned teachings of the present invention, these equivalent form of values fall within the application's appended claims limited range equally.
Claims (10)
1. the preparation method of the compound shown in the formula I,
In the formula,
R
1Be selected from lower group: H, replacement or unsubstituted C1～C18 alkyl, replacement or unsubstituted C3-C18 cycloalkyl, replacement or unsubstituted aryl (such as phenyl), replacement or unsubstituted C1-C3 alkylidene aryl (such as benzyl); Or R
1With adjacent replacement or unsubstituted-CH
2CH
2Replace or unsubstituted C3-C20 cycloalkyl-the common composition;
R
2Be selected from lower group: replace or unsubstituted C1～C20 alkyl, replacement or unsubstituted C3-C20 cycloalkyl, replacement or unsubstituted aryl (such as phenyl), replacement or unsubstituted C1-C3 alkylidene aryl (such as benzyl);
M is H or basic metal;
Wherein, described replacement refers to that the one or more hydrogen atoms on the group are selected from lower group substituting group replacement: C1～C4 alkyl, C1～C4 haloalkyl, C3～C10 cycloalkyl, C3～C10 halogenated cycloalkyl, halogen, hydroxyl, carboxyl, aldehyde radical, acyl group, amino, phenyl; Described phenyl comprises unsubstituted phenyl or has the substituent substituted-phenyl of 1-5 (preferably 1-3), and described substituting group is selected from: C1～C4 alkyl, halogen, hydroxyl, carboxyl, aldehyde radical, acyl group, amino, nitro, phenyl ring;
It is characterized in that, said method comprising the steps of (a) and (b):
(a) in inert solvent, formula Ia alkene and formula Ib phosphonous acid diester are reacted, obtain the alkyl phosphonic acid diester shown in the formula Ic;
Above-mentioned various in, R
1For replacing or unsubstituted C1-C18 alkyl, replacement or unsubstituted C3-C18 cycloalkyl, replacement or unsubstituted aryl, replacement or unsubstituted C1-C3 alkylidene aryl; Or R in the formula (Ia)
1With adjacent replacement or unsubstituted-CH=CH
2Replace or unsubstituted C3-C20 cycloolefin common the composition; M and R
2Described as defined above;
(b) in inert solvent, under the reflux condition, with described formula Ic alkyl phosphonic acid diester and alkali reaction, obtain formula I compound;
Above-mentioned various in, M, R
1And R
2Definition such as claim 1 described in.
2. the method for claim 1 is characterized in that, described alkali is selected from lower group: sodium hydroxide solution, potassium hydroxide solution, ethanolamine solutions, or its combination.
3. the method for claim 1, it is characterized in that, described step (a) and step (b) are carried out under microwave condition, and described microwave power is 5～1500W/100ml liquid reaction system, preferably are 100～400W/100ml liquid reaction system.
4. the method for claim 1 is characterized in that, described solvent is selected from lower group: C4～C20 alkane, C4～C20 naphthenic hydrocarbon, C4～C20 ester, C4～C20 acid, C4～C20 ether, C4～C20 alcohol, DMF, or its combination.
5. the method for claim 1 is characterized in that, described initiator is selected from lower group: di-t-butyl peroxide, benzoyl peroxide, hydrogen peroxide, ammonium peroxydisulfate, Potassium Persulfate, peracetic acid, Diisopropyl azodicarboxylate, or its combination.
6. the method for claim 1 is characterized in that, between the reaction period, adds initiator in step (a).
7. one kind suc as formula the compound shown in the I:
In the formula,
M is selected from lower group: H, basic metal;
R
1Be selected from lower group: H, replacement or unsubstituted C1～C18 alkyl, replacement or unsubstituted C3～C18 cycloalkyl, replacement or unsubstituted aryl (such as phenyl), replacement or unsubstituted C1-C3 alkylidene aryl; Or R
1With-CH
2CH
2Replace or unsubstituted C3-C20 cycloalkyl-the common composition;
R
2Be selected from lower group: replace or unsubstituted C1～C20 alkyl, replacement or unsubstituted C3-C20 cycloalkyl, replacement or unsubstituted aryl (such as phenyl), replacement or unsubstituted C1-C3 alkylidene aryl;
And, work as R
2During for iso-octyl, replace or unsubstituted R
1CH
2CH
2-be not 1-octyl group or 2-ethyl-1-hexyl;
Wherein, described replacement refers to that the one or more hydrogen atoms on the group are selected from lower group substituting group replacement: C1～C4 alkyl, C1～C4 haloalkyl, C3～C10 cycloalkyl, C3～C10 halogenated cycloalkyl, halogen, hydroxyl, carboxyl, aldehyde radical, acyl group, amino, phenyl.
8. the purposes of a compound claimed in claim 7 is characterized in that, for separating of or extracting metals; Or as the extraction agent of separating metal from metallic mixture.
9. an extractant composition is characterized in that, contains the prepared compound of method of the claim 1 that extracts significant quantity, or compound as claimed in claim 7.
10. an extracting process is characterized in that, comprises step: compound claimed in claim 7 or extractant composition as claimed in claim 9 are mixed with the mixture that contains metal to be separated (extraction feed), form the extraction phase that contains metal to be separated; And
From described extraction phase, isolate described metal to be separated.
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| WO2015096071A1 (en) * | 2013-12-25 | 2015-07-02 | 苏州鹏旭医药科技有限公司 | Method for preparing aliphatic phosphate ester having protected hydroxyl with optical activity |
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| WO2015096071A1 (en) * | 2013-12-25 | 2015-07-02 | 苏州鹏旭医药科技有限公司 | Method for preparing aliphatic phosphate ester having protected hydroxyl with optical activity |
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