CN103396438A - Phosphorous acid tri-aliphatic hydrocarbon phenol ester preparation method - Google Patents
Phosphorous acid tri-aliphatic hydrocarbon phenol ester preparation method Download PDFInfo
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- CN103396438A CN103396438A CN201310359444XA CN201310359444A CN103396438A CN 103396438 A CN103396438 A CN 103396438A CN 201310359444X A CN201310359444X A CN 201310359444XA CN 201310359444 A CN201310359444 A CN 201310359444A CN 103396438 A CN103396438 A CN 103396438A
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Abstract
The invention belongs to the field of organic synthesis, and specifically relates to a phosphorous acid tri-aliphatic hydrocarbon phenol ester preparation method, wherein phosphorus trihalide and aliphatic hydrocarbon phenol are subjected to a reaction, the by-product hydrogen halide is separated, and refinement separation is performed to produce the ester to obtain the finished product. The preparation method has characteristics of no requirement of a catalyst, mild reaction temperature, low pressure requirement, and simple process.
Description
Technical field
The invention belongs to the organic synthesis field, be specifically related to a kind of preparation method of tricresyl phosphite aliphatic group phenol ester.
Background technology
The part that phosphorous acid toluene ester can be used as metal complexes uses, and also can be used as softening agent.The domestic patents that many synthetic phosphoric acid phenol ester series products are arranged, as on October 1st, 1987 disclosed patent CN86105096, on December 8th, 2004 disclosed patent CN1552719A, on January 24th, 2007 disclosed CN1902212A, on September 6th, 2006 disclosed CN1827624A, on November 22nd, 2006 disclosed 2839281Y, on June 17th, 2009 disclosed CN101456879, on May 6th, 2009 patents such as disclosed CN101426801.Tricresyl phosphite fatty group phenol ester can be used as the uses such as softening agent, metal complex catalysts part, but rarely seen phosphorous acid and with aliphatic hydrocarbon group phenol reactant, prepare the patent of the method for ester.
Summary of the invention
The preparation method who the purpose of this invention is to provide a kind of tricresyl phosphite aliphatic group phenol ester, reaction conditions is gentle, need not catalyzer, and technique is simple.
The preparation method of tricresyl phosphite aliphatic group phenol ester of the present invention is phosphorus trihalide and aliphatic group phenol reactant, first by-product hydrogen halide is separated after reaction, and then the refining ester output of separating, obtain.
Reaction process is as follows:
Described phosphorus trihalide (PX
3) be a kind of in phosphorus trifluoride, phosphorus trichloride, phosphorus tribromide or phosphorus triiodide, due to the cost reason, preferred phosphorus trichloride; Aliphatic group phenol refers to phenyl ring with a hydroxyl and can be with the phenol of 0～5 group, and structural formula is as follows:
Wherein: R1～R5 is the identical or different aliphatic hydrocarbon group of 1-10 carbon, and there is an aliphatic group at least in R1～R5 group, as p-methyl phenol,, to xylenol, p-tert-butylphenol.
Mole proportioning of described phosphorus trihalide and aliphatic group phenol is 1:2～10, preferred 1:3～6.
Described temperature of reaction is 0～200 ℃, preferred 30～100 ℃.Can divide stage time to set temperature of reaction during operation in 0～200 ℃ of scope, as first at 20 ℃, keeping certain hour, then the temperature that raises continues reaction.
Described reaction pressure is 360～2000mmhg, also can complete reaction under normal pressure.Reaction pressure is lower, more is beneficial to the discharge of by product, but also easily causes the volatilization loss of phosphorus trihalide, reacts preferred synthesis under normal pressure.
The described reaction times is 10～360min.
Reaction can be carried out in the container of the material that meets the permission that pressure corrosion requires of various indications, as the material of the anti-hydrogen halide corrosions such as glass material, ceramic material.Reaction is the liquid phase homogeneous reaction, and is less demanding to reactor shape, and reactor can be tubular, spherical, conical, oval etc.
Reaction have or not stirring all can, but, in order to guarantee speed of response and yield, preferably have and stir or be placed on vibrations in shaking table; Stirring can be used magnetic agitation, mechanical stirring or manual stirring the, preferred magnetic agitation and mechanical stirring, more preferably magnetic agitation; Agitation condition is conventional agitation condition, fully stirs and gets final product.
Reaction have or not protection of inert gas all can, but find in research, need to reduce bringing into of moisture and air as far as possible, because water and oxygen can cause beyond thought by product to generate, reduce yield, increase the product separation difficulty.
Reaction mass can be disposable admixed together, also can slowly add.Research finds, disposablely adds fashionablely, and temperature of reaction higher than more than 35 ℃ the time, has vigorous reaction and produces gas, and is unfavorable to the control of reaction like this, so preferably slowly add.
Described hydrogen halide form with gas after reaction is discharged.
Described refining sepn process is vacuum distillation.
Described distillation temperature is 180-240 ℃.
Described distillation pressure is 1-10mmhg, and distillation time is 0.5-2h.
When product rectifying, when at the bottom of tower, liquid temp is higher than 250 ℃, solution becomes yellow, and temperature becomes muddy garnet while reaching 280 ℃, cause the reduction of actual recovery.Because phosphorous acid phenol ester class boiling point is all higher, so adopted vacuum distillation.First isolate most unreacted raw material during distillation, then collect gas phase 193-240 ℃, the cut of pressure 1-5mmHg, obtain; Also can only distill out the unreacted raw material of the overwhelming majority, collect kettle base solution as product, just purity is slightly low.
The product that the present invention makes can be used as makes a metal-organic complex raw material, and a metal-organic complex can be used as the catalyzer of unsaturated hydrocarbons, the addition reaction of alkene nitrile.
The present invention compared with prior art, has following beneficial effect:
Reaction of the present invention need not catalyzer, and temperature of reaction is gentle, the pressure requirement is low, and technique is simple.
Embodiment
Below in conjunction with embodiment, the present invention is described further.
Raw material in example is phenol, needs first with 4A molecular sieve or distillating method, to dewater.
The 4A water-eliminating method is to get dry anhydrous 4A molecular sieve to put in phenol in container and seal, and the consumption of molecular sieve is determined according to water content.Add the 100g molecular sieve in 400g phenol as moisture 1000ppm, room temperature was placed 24 hours.
The method that distillation dewaters is that phenol is placed in matrass, and the distillation phlegma is collected in heating and sealing saves backup.Not only removed most of moisture in still-process, and removed the impurity of trace, because the color before and after distillation has been become colourless by light red.
Reaction in embodiment is to carry out in three mouthfuls of glass reaction bottles of ball-type of one 1 liter.A mouth is used for dripping phosphorus trihalide, an installation thermometer, and one is used for installing additional condenser west tube, prolong upper end connecting hose; The other end of flexible pipe connects the tail gas absorption liquid of alkalescence.Cut adopts Shimadzu GC-2014C gas chromatographic analysis.
Embodiment 1
Reaction flask is put into oil bath pan, fixes.Take 216.28 gram p-cresol and add in reaction flask, then take 137.33 gram phosphorus trichlorides and join in constant pressure funnel, then cover immediately plug and seal up the suitable for reading of constant pressure funnel, then funnel is contained on reaction flask, fix.After prolong, thermometer install, slowly open the constant pressure funnel valve, start and stir, through 40 minutes, phosphorus trichloride dripped off, stirring at room 16h, and reaction pressure is normal pressure, temperature is raised to 80 ℃, keeps 2h, and then is warming up to 190 ℃, total reflux 4h.Vacuum distillation, distillation temperature are 240 ℃, and distillation pressure is 5mmHg, and distillation time is 1h, collects 240 ℃ of gas phases, cut 145.55 grams of pressure 5mmHg, and stratographic analysis tri-p-cresyl phosphite component accounts for chromatogram and goes out 89.11% of peak area.
Embodiment 2
Reaction flask is put into oil bath pan, fixes.Take 324.42 gram ortho-cresols, due to 30.9 ℃, ortho-cresol zero pour, be the ortho-cresol heating and melting first that liquid adds in reaction flask again, taking 137.33 gram phosphorus trichlorides joins in constant pressure funnel, then cover immediately plug and seal up the suitable for reading of constant pressure funnel, again funnel is contained on reaction flask, fixes.After prolong, thermometer install, slowly open the constant pressure funnel valve, start and stir, through 40 minutes, phosphorus trichloride dripped off, stirring at room 16h, and reaction pressure is 770mmHg, temperature is raised to 70 ℃, keeps 1h, and then is warming up to 200 ℃, total reflux 4h.Vacuum distillation, distillation temperature are 230 ℃, and distillation pressure is 1mmHg, and distillation time is 2h, collects 193 ℃ of gas phases, cut 186 grams of pressure 1mmHg, and stratographic analysis tri-p-cresyl phosphite component accounts for chromatogram and goes out 90.03% of peak area.
Embodiment 3
Reaction flask is put into oil bath pan, fixes.Take 324.42 gram cresols, be the cresols heating and melting first that liquid adds in reaction flask again, take 137.33 gram phosphorus trichlorides and join in constant pressure funnel, then cover immediately plug and seal up the suitable for reading of constant pressure funnel, again funnel is contained on reaction flask, fixes.After prolong, thermometer install, slowly open the constant pressure funnel valve, start and stir, through 40 minutes, phosphorus trichloride dripped off, stirring at room 16h, and reaction pressure is 360mmHg, temperature is raised to 80 ℃, keeps 2h, and then is warming up to 180 ℃, total reflux 3h.Vacuum distillation, distillation temperature are 220 ℃, and distillation pressure is 10mmHg, and distillation time is 0.5h, collects 200 ℃ of gas phases, cut 160.2 grams of pressure 2mmHg, and stratographic analysis tri-p-cresyl phosphite component accounts for chromatogram and goes out 95% of peak area.
Embodiment 4
Reaction flask is put into oil bath pan, fixes.Take 324.42 gram ortho-cresols, due to 30.9 ℃, ortho-cresol zero pour, be the ortho-cresol heating and melting first that liquid adds in reaction flask again, taking 205.99 gram phosphorus trichlorides joins in constant pressure funnel, then cover immediately plug and seal up the suitable for reading of constant pressure funnel, again funnel is contained on reaction flask, fixes.After prolong, thermometer install, slowly open the constant pressure funnel valve, start and stir, through 40 minutes, phosphorus trichloride drips off, stirring at room 16h, and reaction pressure is 2000mmHg, temperature is raised to 70 ℃, keep 2h, and then be warming up to 200 ℃, total reflux 2h.Vacuum distillation, distillation temperature are 210 ℃, and distillation pressure is 6mmHg, and distillation time is 1h, collects 210 ℃ of gas phases, cut 192 grams of pressure 3mmHg, and stratographic analysis tri-p-cresyl phosphite component accounts for chromatogram and goes out 91.05% of peak area.
Embodiment 5
Reaction flask is put into oil bath pan, fixes.Take 1081.4 gram ortho-cresols, due to 30.9 ℃, ortho-cresol zero pour, be the ortho-cresol heating and melting first that liquid adds in reaction flask again, taking 270.72 gram phosphorus tribromides joins in constant pressure funnel, then cover immediately plug and seal up the suitable for reading of constant pressure funnel, again funnel is contained on reaction flask, fixes.After prolong, thermometer install, slowly open the constant pressure funnel valve, start and stir, through 40 minutes, phosphorus tribromide dripped off, stirring at room 16h, and reaction pressure is 800mmHg, temperature is raised to 70 ℃, keeps 1h, and then is warming up to 200 ℃, total reflux 2h.Vacuum distillation, distillation temperature are 180 ℃, and distillation pressure is 8mmHg, and distillation time is 1.5h, collects 230 ℃ of gas phases, cut 540.8 grams of pressure 1mmHg, and stratographic analysis tri-p-cresyl phosphite component accounts for chromatogram and goes out 85.03% of peak area.
Embodiment 6
Reaction flask is put into oil bath pan, fixes.Take 648.84 gram p-cresol, then take 270.72 gram phosphorus tribromides and join in constant pressure funnel, then cover immediately plug and seal up the suitable for reading of constant pressure funnel, then funnel is contained on reaction flask, fix.After prolong, thermometer install, slowly open the constant pressure funnel valve, start and stir, through 40 minutes, phosphorus tribromide dripped off, stirring at room 16h, and reaction pressure is 700mmHg, temperature drops to 0 ℃ of reaction 10min.Vacuum distillation, distillation temperature are 200 ℃, and distillation pressure is 4mmHg, and distillation time is 2h, collects 200 ℃ of gas phases, cut 367.8 grams of pressure 4mmHg, and stratographic analysis tri-p-cresyl phosphite component accounts for chromatogram and goes out 89.11% of peak area.
Claims (10)
1. the preparation method of a tricresyl phosphite aliphatic group phenol ester, is characterized in that phosphorus trihalide and aliphatic group phenol reactant, first by-product hydrogen halide separated after reaction, and then the refining ester output of separating, obtain.
2. the preparation method of tricresyl phosphite aliphatic group phenol ester according to claim 1, is characterized in that described phosphorus trihalide is a kind of in phosphorus trifluoride, phosphorus trichloride, phosphorus tribromide or phosphorus triiodide; Aliphatic group phenol refers to phenyl ring with a hydroxyl and can be with the phenol of 0～5 group, and structural formula is as follows:
Wherein: R1～R5 is the identical or different aliphatic hydrocarbon group of 1-10 carbon.
3. the preparation method of tricresyl phosphite aliphatic group phenol ester according to claim 1, a mole proportioning that it is characterized in that described phosphorus trihalide and aliphatic group phenol is 1:2～10.
4. the preparation method of tricresyl phosphite aliphatic group phenol ester according to claim 1, a mole proportioning that it is characterized in that described phosphorus trihalide and aliphatic group phenol is 1:3～6.
5. the preparation method of tricresyl phosphite aliphatic group phenol ester according to claim 1, is characterized in that described temperature of reaction is 0～200 ℃.
6. the preparation method of tricresyl phosphite aliphatic group phenol ester according to claim 1, is characterized in that described reaction pressure is 360～2000mmhg.
7. the preparation method of tricresyl phosphite aliphatic group phenol ester according to claim 1, is characterized in that the described reaction times is 10～360min.
8. the preparation method of tricresyl phosphite aliphatic group phenol ester according to claim 1, is characterized in that described refining sepn process is vacuum distillation.
9. the preparation method of tricresyl phosphite aliphatic group phenol ester according to claim 8, is characterized in that described distillation temperature is 180-240 ℃.
10. the preparation method of tricresyl phosphite aliphatic group phenol ester according to claim 9, is characterized in that described distillation pressure is 1-10mmhg, and distillation time is 0.5-2h.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103724370A (en) * | 2013-12-31 | 2014-04-16 | 中国天辰工程有限公司 | Method for preparing phosphite ester compounds through reactive rectification coupling |
| CN103801400A (en) * | 2014-03-07 | 2014-05-21 | 中国天辰工程有限公司 | Process for synthesizing mono-phosphite metal coordination catalyst by coupling reactive distillation and magnetically-stabilized bed |
| CN114903879A (en) * | 2022-06-23 | 2022-08-16 | 东北大学 | Application of 3-alkyl phenol derivative in preparation of product for preventing or treating hyperlipidemia and related metabolic diseases |
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- 2013-08-16 CN CN201310359444XA patent/CN103396438A/en active Pending
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| RAJESH K. PANDEY，ET AL.: "Wittig-Horner Approach for the Synthesis of Tamoxifen", 《SYNTHETIC COMMUNICATIONS》 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103724370A (en) * | 2013-12-31 | 2014-04-16 | 中国天辰工程有限公司 | Method for preparing phosphite ester compounds through reactive rectification coupling |
| CN103801400A (en) * | 2014-03-07 | 2014-05-21 | 中国天辰工程有限公司 | Process for synthesizing mono-phosphite metal coordination catalyst by coupling reactive distillation and magnetically-stabilized bed |
| CN103801400B (en) * | 2014-03-07 | 2015-12-02 | 中国天辰工程有限公司 | A kind of reactive distillation synthesizes the technique of single phosphite ester Metal complex catalysts with magnetic stablizing bed coupling |
| CN114903879A (en) * | 2022-06-23 | 2022-08-16 | 东北大学 | Application of 3-alkyl phenol derivative in preparation of product for preventing or treating hyperlipidemia and related metabolic diseases |
| CN114903879B (en) * | 2022-06-23 | 2023-10-31 | 东北大学 | Use of 3-hydrocarbylphenol derivatives for the preparation of products for the prevention or treatment of hyperlipidaemia and related metabolic disorders |
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Application publication date: 20131120 |