CN101429214B - Process for producing alkyl phosphonic acid - Google Patents
Process for producing alkyl phosphonic acid Download PDFInfo
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- CN101429214B CN101429214B CN2008102251808A CN200810225180A CN101429214B CN 101429214 B CN101429214 B CN 101429214B CN 2008102251808 A CN2008102251808 A CN 2008102251808A CN 200810225180 A CN200810225180 A CN 200810225180A CN 101429214 B CN101429214 B CN 101429214B
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Abstract
The invention relates to a method for preparing alkyl phosphonic acid, which comprises the following steps: (1) an alkali metal reacts with phosphite ester to obtain phosphite ester; (2) the phosphate ester reacts with halogenated alkane to obtain alkyl phosphonate ester; and (3) the alkyl phosphonate ester is hydrolyzed to obtain the alkyl phosphonic acid. The method has the advantages of reasonable reaction steps which are carried out at normal pressure, mild and smooth process condition, simple process flow, higher purity of obtained products, comparatively stable yield, and better industrialized prospect, and can be used for preparing various alkyl phosphonic acids, such as methylphosphoric acid, ethylphosphonic acid, propylphosphonic acid and the like.
Description
Technical field
The present invention relates to a kind of method for preparing alkyl phosphonic acid.
Background technology
Alkyl phosphonic acid is a kind of important organic acid, itself or its salt, ester, acid anhydride class existence form are used very extensive, also very fast as the development abroad of irreversible dewatering agent recently in water softening, floating separation, fire-retardant material, agrochemical field.
Griffin (J.0rg.Chem., 24,2049,1959) reported a kind of alkyl phosphonic acid synthetic method, this method is raw material, is that solvent prepares alkyl phosphoric acid with Glacial acetic acid or dioxane with phosphorous acid and alkene, because what adopt is free radical reaction, the by product of this method is many, and yield is between 18-28%.Patent (US6420598) has been reported the propyl group phosphoric acid synthetic method under a kind of high pressure, this method is a raw material with phosphorous acid and propylene gas, synthetic propyl group phosphoric acid under the 4Mpa pressure, in the reaction process since the alkene addition occur easily resetting, therefore by product is more, product purity is not high, and main content is about 80%, and the separation and purification difficulty.
Summary of the invention
For overcoming the above-mentioned defective of prior art, the invention provides a kind of process for producing alkyl phosphonic acid, this method is the prepared in reaction alkyl phosphonic acid under normal pressure, with gentle relatively condition obtain that purity is higher, yield stable product comparatively.
The technical scheme that the present invention solves the problems of the technologies described above is: a kind of process for producing alkyl phosphonic acid comprises the following steps:
(1) basic metal and phosphite reactions obtain phosphorous acid ester salt;
(2) phosphorous acid ester salt and halogenated alkane reaction obtains the alkyl phosphonic acid ester;
(3) hydrolysis of alkyl phosphonic acid ester obtains alkyl phosphonic acid.
The process of described step (1) can be first with the fusion in solvent of described basic metal, adopts modes such as dropping or stream add to join reaction system described phosphorous acid ester again and reacts.
Basic metal added generally should reflux behind the solvent beat huskyly, generally should adopt the back flow reaction mode after phosphorous acid ester added reaction system.
The reaction of described basic metal and phosphorous acid ester can be carried out under gas-protection-free, and the preferred 60-150 of its temperature of reaction ℃, further preferred 80～120 ℃.
Described basic metal can be lithium, sodium, potassium etc., described phosphorous acid ester can be dibutyl phosphite, phosphorous acid dipropyl, diethyl phosphite, dimethylphosphite, phosphorous acid methyl ethyl ester, phosphorous acid third butyl ester, phosphorous acid first butyl ester, phosphorous acid first propyl ester or phosphorous acid second propyl ester etc., and described solvent can be toluene, dioxane, dimethylbenzene, chlorobenzene or dichlorobenzene etc.
The process of described step (2) can be to adopt modes such as gas feeding or liquid dropping that described halogenated alkane is added reaction system, carry out back flow reaction at normal temperatures, filter after the reaction, reclaim residual basic metal, the filtrate elder generation normal pressure that obtains is reclaimed solvent down, and normal pressure or underpressure distillation obtain described alkyl phosphonic acid ester again.
Described halogenated alkane can be chloroparaffin or bromo alkane etc., for example monochloroethane, monobromethane, n-propyl chloride, 1-N-PROPYLE BROMIDE, 2 cbloropropane isopropyl chloride, 2-N-PROPYLE BROMIDE, 1-chlorobutane, 1-n-butyl bromide, Sec-Butyl Chloride, 2-n-butyl bromide.
The process of described step (3) can be that the alkyl phosphonic acid ester that step (2) obtains is carried out acidic hydrolysis or alkaline hydrolysis, dewater then the alkyl phosphonic acid crude product, adopt toluene etc. to carry out recrystallization to the alkyl phosphonic acid crude product again, obtain described alkyl phosphonic acid.
Used alkaline matter can be sodium hydroxide, yellow soda ash, potassium hydroxide or salt of wormwood in the described alkaline hydrolysis, and used acidic substance are hydrochloric acid, sulfuric acid, phosphoric acid or Glacial acetic acid in the described acidic hydrolysis.
The present invention can be used to prepare ethylphosphonic acid, propyl phosphonous acid, isopropyl phosphoric acid, normal-butyl phosphoric acid, isobutyl-phosphoric acid or other alkyl phosphonic acids.Because the reactions steps that the present invention adopts is reasonable, each step all can be carried out under normal pressure, and the processing condition gentleness is smooth and easy, and technical process is simple, and the product purity that obtains is higher, and yield is comparatively stable, has industrialization prospect preferably.According to applicant's experiment, adopt product content 〉=95% of the present invention's preparation, total recovery 〉=65%.
Description of drawings
Fig. 1 is a process flow diagram of the present invention.
Embodiment
Referring to Fig. 1, the main process that the present invention prepares alkyl phosphonic acid normally joins metal in the The suitable solvent under condition of normal pressure, make alkali metal fusion at 80～120 ℃, dropping or stream add phosphorous acid ester again, the halogenated alkane of back dropping liquid or the halogenated alkane of feeding gas react completely, continue to lower the temperature after reaction is finished, obtain alkyl phosphonic acid through hydrolysis, the mode that described hydrolysis can adopt prior art to pass through acidic hydrolysis or alkaline hydrolysis realizes, used alkaline matter can be a sodium hydroxide in the wherein said alkaline hydrolysis, yellow soda ash, potassium hydroxide or salt of wormwood, used acidic substance are hydrochloric acid in the described acidic hydrolysis, sulfuric acid, phosphoric acid or Glacial acetic acid repeat no more in the following example these prior aries.
Provide several embodiments of the invention below:
Embodiment 1: lithium 175g (25mol) is joined in 110 ℃ the 30L toluene, refluxing, it is husky to beat, drip phosphorous acid first propyl ester 3.46kg (25mol), continued stirring and refluxing 6 hours, drip monochloroethane 1.94kg (30mol), back flow reaction 18 hours, cooling, a little lithium that filtered and recycled is residual, filtrate elder generation normal pressure reclaims toluene, and underpressure distillation gets ethylphosphonic acid first propyl ester then, adds Glacial acetic acid in ethylphosphonic acid first propyl ester, be hydrolyzed into and react completely, dewater crude product, use the toluene recrystallization, white plates solid ethylphosphonic acid 1782g, yield 64.8%, purity 96.3%.
Embodiment 2: sodium 575g (25mol) is joined in 145 ℃ the 32L dimethylbenzene, refluxing, it is husky to beat, drip dimethylphosphite 2.76kg (25mol), continued stirring and refluxing 12 hours, dripping bromine ethane 3.27kg (30mol), back flow reaction 18 hours, cooling, a little sodium that filtered and recycled is residual, filtrate elder generation normal pressure reclaims dimethylbenzene, and underpressure distillation gets the ethylphosphonic acid dimethyl ester then, adds sodium hydroxide in the ethylphosphonic acid dimethyl ester, be hydrolyzed into and react completely, dewater crude product, use the toluene recrystallization, white plates solid ethylphosphonic acid 1869g, yield 67.9%, purity 95.6%.
Embodiment 3: potassium 978g (25mol) is joined in 130 ℃ the 30L toluene, refluxing, it is husky to beat, drip phosphorous acid first propyl ester 3.46kg (25mol), continued stirring and refluxing 6 hours, drip n-propyl chloride 2.36kg (30mol), back flow reaction 18 hours, cooling, a little lithium that filtered and recycled is residual, filtrate elder generation normal pressure reclaims toluene, and underpressure distillation gets ethylphosphonic acid first propyl ester then, adds Glacial acetic acid in ethylphosphonic acid first propyl ester, be hydrolyzed into and react completely, dewater crude product, use the toluene recrystallization, white plates solid propyl phosphonous acid 2010g, yield 64.8%, purity 96.3%.
Embodiment 4: lithium 175g (25mol) is joined in 115 ℃ the 25L toluene, refluxing, it is husky to beat, drip dibutyl phosphite 4.86kg (25mol), continued stirring and refluxing 6 hours, drip 1-N-PROPYLE BROMIDE 3.69kg (30mol), back flow reaction 18 hours, cooling, a little sodium that filtered and recycled is residual, filtrate elder generation normal pressure reclaims toluene, and underpressure distillation gets the propyl phosphonous acid dibutylester then, adds hydrochloric acid in the propyl phosphonous acid dibutylester, be hydrolyzed into and react completely, dewater crude product, use the toluene recrystallization, white plates solid propyl phosphonous acid 2025g, yield 65.3%, purity 97.8%.
Embodiment 5: sodium 575g (25mol) is joined in 100 ℃ the 25L toluene, refluxing, it is husky to beat, drip diethyl phosphite 3.46kg (25mol), continue stirring and refluxing 6 hours, and dripped 2 cbloropropane isopropyl chloride 2.36kg (30mol), back flow reaction 18 hours, cooling, filter, a little potassium that filtered and recycled is residual, filtrate elder generation normal pressure reclaims toluene, underpressure distillation gets the propyl phosphonous acid diethyl ester then, add sulfuric acid in the propyl phosphonous acid diethyl ester, be hydrolyzed into and react completely, dewater crude product, use the toluene recrystallization, get white plates solid sec.-propyl phosphonic acids 2045g, yield 65.9%, purity 96.9%.
Embodiment 6: potassium 978g (25mol) is joined in 110 ℃ the 30L toluene, refluxing, it is husky to beat, drip phosphorous acid second propyl ester 3.81kg (25mol), continued stirring and refluxing 6 hours, drip 2-N-PROPYLE BROMIDE 3.69kg (30mol), back flow reaction 18 hours, cooling, a little lithium that filtered and recycled is residual, filtrate elder generation normal pressure reclaims toluene, and underpressure distillation gets ethylphosphonic acid first propyl ester then, adds Glacial acetic acid in ethylphosphonic acid first propyl ester, be hydrolyzed into and react completely, dewater crude product, use the toluene recrystallization, white plates solid sec.-propyl phosphonic acids 2010g, yield 64.8%, purity 96.3%.
Embodiment 7: potassium 978g (25mol) is joined in 125 ℃ the 35L dimethylbenzene, refluxing, it is husky to beat, drip phosphorous acid first butyl ester 3.81kg (25mol), continued stirring and refluxing 10 hours, drip 1-chlorobutane 2.78kg (30mol), back flow reaction 18 hours, cooling, a little potassium that filtered and recycled is residual, filtrate elder generation normal pressure reclaims dimethylbenzene, and underpressure distillation gets butyl phosphonic acids first butyl ester then, adds phosphoric acid in butyl phosphonic acids first butyl ester, be hydrolyzed into and react completely, dewater crude product, use the dimethylbenzene recrystallization, white plates solid normal-butyl phosphonic acids 2320g, yield 67.2%, purity 95.7%.
Embodiment 8: sodium 575g (25mol) is joined in 180 ℃ the 33L dichlorobenzene, refluxing, it is husky to beat, drip the phosphorous acid third butyl ester 4.51kg (25mol), continued stirring and refluxing 8 hours, drip 1-n-butyl bromide 4.12kg (30mol), back flow reaction 18 hours, cooling, a little sodium that filtered and recycled is residual, filtrate elder generation reclaim under reduced pressure dichlorobenzene, underpressure distillation gets butyl phosphonic acids third butyl ester then, adds salt of wormwood in butyl phosphonic acids third butyl ester, be hydrolyzed into and react completely, dewater crude product, use the toluene recrystallization, white plates solid normal-butyl phosphonic acids 2371g, yield 68.7%, purity 94.7%.
Embodiment 9: potassium 978g (25mol) is joined in 102 ℃ the 33L dioxane, refluxing, it is husky to beat, drip phosphorous acid methyl ethyl ester 3.10kg (25mol), continued stirring and refluxing 10 hours, drip Sec-Butyl Chloride 2.78kg (30mol), back flow reaction 18 hours, cooling, a little potassium that filtered and recycled is residual, filtrate elder generation normal pressure reclaims dioxane, and underpressure distillation gets isobutyl-phosphonic acids methyl ethyl ester then, adds yellow soda ash in isobutyl-phosphonic acids methyl ethyl ester, be hydrolyzed into and react completely, dewater crude product, use the toluene recrystallization, white plates solid isobutyl-phosphonic acids 2386g, yield 69.1%, purity 95.3%.
Embodiment 10: lithium 175g (25mol) is joined in 132 ℃ the 33L chlorobenzene, refluxing, it is husky to beat, drip phosphorous acid dipropyl 4.16kg (25mol), continued stirring and refluxing 7 hours, drip 2-n-butyl bromide 4.12kg (30mol), back flow reaction 18 hours, cooling, a little lithium that filtered and recycled is residual, filtrate elder generation normal pressure reclaims chlorobenzene, and underpressure distillation gets the propyl phosphonous acid dipropyl then, adds potassium hydroxide in the propyl phosphonous acid dipropyl, be hydrolyzed into and react completely, dewater crude product, use the toluene recrystallization, white plates solid isobutyl-phosphonic acids 2278g, yield 66.0%, purity 96.5%.
Claims (6)
1. a process for producing alkyl phosphonic acid is characterized in that comprising the following steps:
(1) basic metal and phosphite reactions obtain phosphorous acid ester salt;
(2) phosphorous acid ester salt and halogenated alkane reaction obtains the alkyl phosphonic acid ester, and described halogenated alkane is chloroparaffin or bromo alkane;
(3) hydrolysis of alkyl phosphonic acid ester obtains alkyl phosphonic acid;
The process of described step (1) is earlier with the fusion in solvent of described basic metal, more described phosphorous acid ester is dripped or stream is added to reaction system and reacts;
Basic metal added to reflux behind the solvent beat huskyly, adopt the back flow reaction mode after phosphorous acid ester added reaction system.
2. process for producing alkyl phosphonic acid as claimed in claim 1 is characterized in that being reflected under the gas-protection-free of described basic metal and phosphorous acid ester carry out, and its temperature of reaction is 60～150 ℃.
3. process for producing alkyl phosphonic acid as claimed in claim 1 or 2, the temperature of reaction that it is characterized in that described basic metal and phosphite reactions is 80～120 ℃, described basic metal is lithium, sodium, potassium, described phosphorous acid ester is dibutyl phosphite, phosphorous acid dipropyl, diethyl phosphite, dimethylphosphite, phosphorous acid methyl ethyl ester, phosphorous acid third butyl ester, phosphorous acid first butyl ester, phosphorous acid first propyl ester or phosphorous acid second propyl ester, and described solvent is toluene, dioxane, dimethylbenzene, chlorobenzene or dichlorobenzene.
4. process for producing alkyl phosphonic acid as claimed in claim 1 is characterized in that described halogenated alkane is monochloroethane, monobromethane, n-propyl chloride, 1-N-PROPYLE BROMIDE, 2 cbloropropane isopropyl chloride, 2-N-PROPYLE BROMIDE, 1-chlorobutane, 1-n-butyl bromide, Sec-Butyl Chloride, 2-n-butyl bromide.
5. process for producing alkyl phosphonic acid as claimed in claim 1 or 2, the process that it is characterized in that described step (3) is that the alkyl phosphonic acid ester that step (2) obtains is carried out acidic hydrolysis or alkaline hydrolysis, dewater then the alkyl phosphonic acid crude product, adopt toluene to carry out recrystallization to the alkyl phosphonic acid crude product again, obtain described alkyl phosphonic acid.
6. process for producing alkyl phosphonic acid as claimed in claim 5, it is characterized in that alkaline matter used in the described alkaline hydrolysis is sodium hydroxide, yellow soda ash, potassium hydroxide or salt of wormwood, used acidic substance are hydrochloric acid, sulfuric acid, phosphoric acid or Glacial acetic acid in the described acidic hydrolysis.
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| CN104402925B (en) * | 2014-11-28 | 2016-06-08 | 苏州昊帆生物科技有限公司 | The synthetic method of n-pro-pyl phosphoric acid |
| CN105503944A (en) * | 2015-12-22 | 2016-04-20 | 三门峡奥科化工有限公司 | Method for preparing n-octylphosphonic acid |
| CN116063345A (en) * | 2021-10-30 | 2023-05-05 | 中国石油化工股份有限公司 | Phosphonic acid group monomer and preparation method thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6420598B1 (en) * | 1999-06-18 | 2002-07-16 | Clariant Gmbh | Process for preparing alkylphosphonic acids |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6420598B1 (en) * | 1999-06-18 | 2002-07-16 | Clariant Gmbh | Process for preparing alkylphosphonic acids |
Non-Patent Citations (2)
| Title |
|---|
| Stephen C. Fields.Synthesis of Natural Products Containing a C-P Bond.《Tetrahedron》.1999,第55卷12237-12273. * |
| 叶伟贞等.有机磷化合物的研究XIX.亚磷酸二烷基酯钠的相转移催化P-烷基化反应.《化学学报》.1987,第45卷622-624. * |
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