CN101274942A - Preparation of aryl phosphate - Google Patents
Preparation of aryl phosphate Download PDFInfo
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- CN101274942A CN101274942A CNA2007100569972A CN200710056997A CN101274942A CN 101274942 A CN101274942 A CN 101274942A CN A2007100569972 A CNA2007100569972 A CN A2007100569972A CN 200710056997 A CN200710056997 A CN 200710056997A CN 101274942 A CN101274942 A CN 101274942A
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- reaction
- binding agent
- phosphorus oxychloride
- polar solvent
- acid binding
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Abstract
The invention provides a preparation method of mono-aryl phosphate. An acid binding agent is dropped into a non-polar solvent containing phenols and phosphorus oxychloride, reacting at low temperature, so as to acquire the mono-aryl substitutional phosphate. The method avoids the generation of disubstituted compounds and trisubstituted compounds. Products obtained by the method have high purity, high yield and simple preparation technique.
Description
Invention field:
The present invention relates to a kind of method that in non-polar solvent, prepares aryl phosphate.
Background of invention:
As everyone knows, phosphorus oxychloride is a kind of very active chemical reagent, and it very easily reacts with various phenols, generates aryl phosphate ester.But three active chlorine atoms are arranged in the phosphorus oxychloride molecule, and it very easily forms a substitution compound (A), two substitution compounds (B), three substitution compounds (C) with various phenolic compounds in reaction, is a mixture thereby make reaction product.Both a large amount of wastes is former
(R in the formula
1, R
2: Cl, Br, H, R
3:-NO
2,-OAc)
Material has reduced the yield of single substitution product again, and makes follow-up separation means become complicated.This is one and perplexs the very troubling problem in chemical boundary for a long time.
In order to solve this difficult problem, the chemist has thought many methods both at home and abroad for a long time, as phenolic compound being made corresponding salt, then with excessive phosphorus oxychloride reaction, perhaps according to people's such as AndrewWilliams method (J.Chem.Soc. (B), 1971,1973-79), phosphorus oxychloride and phenols are made into pyridine solution respectively, the pyridine solution of phenols is added drop-wise in the phosphorus oxychloride pyridine solution.Yet all these methods all fail well to address this problem, and finally can only obtain containing the mixture of three kinds of substitution products.
In order to solve this difficult problem, inventor herein imagination can be dissolved in a large number as the reaction raw materials phosphorus oxychloride in the non-polar solvent such as benzene class, another reaction raw materials phenols then in non-polar solvent solubleness very little, be equivalent to the excessive existence of phosphorus oxychloride mole ratio in non-polar solvent, the generation of the substitution product that is highly advantageous to like this.Acid binding agent then adopts the mode of dropping, and controls reaction speed is carried out slowly.Temperature of reaction should be controlled at lesser temps, the reactive behavior between the restriction raw material.These measures all help the generation of a substitution product.And a replacement phosphoric acid ester that generates all is insoluble in the non-polar solvent, very easily breaks away from from reaction system, makes reaction terminating in single replacement stage.Experimental results show that this imagination is correct, and obtain completely success, most products are single substitution product, and two replace, trisubstitution product content is atomic, thereby saved raw material, improved yield, reduced cost.
Summary of the invention:
The invention provides a kind of method for preparing aryl phosphate.It mainly comprises: in the non-polar solvent that contains phosphorus oxychloride and phenols, drip acid binding agent, and reaction at a lower temperature, thereby obtain the phosphoric acid ester that highly purified single aryl replaces.
The used non-polar solvent of the present invention comprises benzene,toluene,xylene etc., and its consumption should be 5～10 times of reactant weight.Used non-polar solvent should dissolve phosphorus oxychloride, then is slightly soluble or insoluble to phenols, thereby forms a suspendible system.Its temperature of reaction should be lower, and scope is between 0～30 ℃, preferably between 10～20 ℃.Used acid binding agent comprises tertiary amine class organic basess such as pyridine, triethylamine, also comprises mineral alkalis such as NaOH, KOH.The acid binding agent of this reaction should adopt the dropping mode.Temperature should be controlled at below 30 ℃ when dripping acid binding agent, preferably between 10～20 ℃.The raw material phenols of this reaction and the mole ratio of phosphorus oxychloride should be between 1: 5, preferably between 1: 1～1: 1.2.
The used non-polar solvent of this reaction is benzene,toluene,xylene preferably.Phosphorus oxychloride has big solubleness in these non-polar solvents, and phenolic compound solubleness in these non-polar solvents is lower, formed mono-substituted phosphoric acid ester solubleness in these non-polar solvents is also lower simultaneously, even insoluble, the generation of the aryl phosphate that is highly advantageous to.
The temperature of reaction of this reaction should be controlled at a lower temperature and carry out, and generally at 0～30 ℃, preferably carries out under 10～20 ℃.
In non-polar solvent, the mole ratio of phenols and phosphorus oxychloride should be between 1: 5, preferably between 1: 1～1: 1.2.
Used non-polar solvent should be big excessive, and the weight ratio of they and raw material should be between 5: 1～10: 1.
Control reaction temperature is one of key of the present invention, and low temperature will help single generation that replaces phosphoric acid ester, and suppresses the generation of polysubstituted phosphoric acid ester.For making temperature of reaction be no more than 30 ℃, preferably be no more than 20 ℃, answer the rate of addition of strict control acid binding agent, reaction vessel cools off with ice or water-bath in case of necessity.
Below by specific embodiment the present invention is described.But point out that it is solvent that embodiment has only listed with toluene, control low-temp reaction, obtain the experiment condition of single substitution product best effect, the claim of patent of the present invention is not limited in these embodiments.
Embodiment 1: to acetylphenyl disodic alkaliine (PAP-PNa
2) preparation
Reaction equation:
Electronic stirring, dropping funnel and thermometer are installed on the 250ml there-necked flask, are added acetyl phenol 20.4g (0.15mol), toluene 110ml and POCl
327.6g (0.18mol), stirring and controlled temperature are below 20 ℃, drip 14.3g (0.18mol) pyridine solution, after pyridine all dropwises,, add 30ml water at stirring reaction 3h below 20 ℃, temperature is controlled at 10～20 ℃, hydrolysis reaction 1h separates water layer, with ethyl acetate extraction (3 * 50ml), united extraction liquid, in extracting solution, add sodium hydroxide solution (solution that 14g NaOH and 42ml water are made into), stir 10min, remove under reduced pressure behind the solvent the heavy 50.3g (theoretical amount 52.5g) of a solids, yield 95.8%, the water recrystallization gets needle crystal 40.3g, recrystallization yield 80.1%.
Ultimate analysis (molecular formula: C
8H
7O
5PN
A25H
2O, molecular weight: 350.17)
Theoretical value: C 27.27 H 4.89 P 8.95
Test value: C 27.31 H 4.98 P 8.72
1H NMR (D
2O, TMS) (see accompanying drawing 1):
δ：7.17，7.86(m，4H)；2.51(d，3H)。
1H NMR spectrum analysis is 2: 2: 3 from the ratio of the various as can be known numbers of hydrogen atoms of integrated curve, its numerical value sum just in time with target compound in number of hydrogen atoms meet.Know that by pairing hydrogen atom number of each peak group and peak shape in the hydrogen spectrum molecule is symmetric figure.The multiplet at δ 7.17, δ 7.86 places is 4 H on the phenyl ring, according to 4 residing environment of H, it can be divided into 2 groups, i.e. each 2 H of δ 7.17 and δ 7.86 places.Because the coupling between these two groups of H, these two groups of peaks are split be divided into 4 peaks.2 peaks at δ 2.51 places are 3 H on the methyl, and these 3 H are divided into 2 peaks because the coupling that is subjected to closing on one group of H on the phenyl ring is split.
IR (KBr), v/cm
-1(seeing accompanying drawing 2):
1678 (by force), 1264 (by force), 1144 (by force), 907 (by force), 1601 (in), 3434 (in), 1404 (weak), 1359 (weak).
The IR spectrum analysis on infrared spectrogram, 1678cm
-1Strong absorption peak is
Absorption peak; 1264cm
-1Strong absorption peak is the absorption peak of P=O; 1144cm
-1Strong absorption peak is the absorption peak of P-O-Ar; 907cm
-1Strong absorption peak is the absorption peak of two adjacent hydrogen on the phenyl ring; 1601cm
-1The absorption peak of medium tenacity is on the phenyl ring-the C=C-absorption peak; 3434cm
-1The absorption peak of medium tenacity broad is in the crystal water-OH absorption peak (sample contains crystal water); 1404cm
-1And 359cm
-1There is weak absorption peak to be-CH simultaneously
3Absorption peak.
Embodiment 2:2, the preparation of 6-two chloro-4-acetylphenyl phosphoric acid ester
Electronic stirring, dropping funnel and thermometer are installed on the 250ml there-necked flask, are added 2,6-two chloro-4-acetyl phenol 20.5g (0.1mol), toluene 110ml and POCl
318.4g (0.12mol); stirring also, controlled temperature drips 9.5g (0.12mol) pyridine solution, after pyridine all dropwises below 20 ℃; at stirring reaction 3h below 20 ℃; add 30ml water, temperature is controlled at 10～20 ℃, hydrolysis reaction 1h; separate water layer; (3 * 50ml), united extraction liquid adds anhydrous magnesium sulfate drying and spends the night with ethyl acetate extraction; the elimination siccative; get 2,6-two chloro-4-acetylphenyl phosphoric acid ester crude product 17.4g (theoretical amount 28.5g), yield 61.0% after removing solvent under reduced pressure; final product ethyl acetate/normal hexane recrystallization; get white crystals 14.6g, recrystallization yield 83.8%, m.p.175～177 ℃ decomposition.
Ultimate analysis (molecular formula: C
8H
7O
5Cl
2P, molecular weight: 285.0):
Theoretical value (%): C 33.71 H 2.45
Test value (%): C 34.08 H 2.70
1H?NMR(DMSO-D
6，TMS)：
δ：2.55(s，3H，CH
3)、δ：7.95(s，2H，ArH)、δ：6.87(s，br，2H，P-OH)。
IR(KBr)，v/c?m
-1：
2892(P-OH)，1658(C＝O)，1286(P＝O)，954(P-O)，739(C-Cl)。
Reference examples (O.A.Bessey and R.H.Love, J.Biol.Chem., 1952,196:175-178):
Add the solution that 200ml pyridine and 30ml phosphorus oxychloride are made in two mouthfuls of bottles of 1000ml, install and stir and separating funnel, cool off with ice bath, stir and drip the pyridine solution that 100ml contains the 27.8g p-NP down, behind the reaction 30min this mixed solution is poured in the 400ml cold water, add NaOH solution and make pH=7～8, temperature removes water and pyridine under reduced pressure when being no more than 60 ℃, residue is used 600ml respectively, the ethanolic soln of 300ml and 200ml ebullient 87% extracts, filtered while hot, filtrate is cooled off, obtain the product crystallization, filter and, wash with dehydrated alcohol and ether subsequently with cold 87% ethanolic soln washing, get a lurid crystallization after the drying and weigh 28～30g, purity 80～85%.
Then the aryl phosphate materials consumption of the present invention's preparation is few as can be seen by these specific embodiments, the yield height, and cost is low, and bigger social benefit is arranged.
Description of drawings:
Accompanying drawing 1 is to acetylphenyl disodic alkaliine (PAP-PNa
2)
1H NMR spectrogram.Accompanying drawing 2 is to acetylphenyl disodic alkaliine (PAP-PNa
2) the IR spectrogram.
Claims (7)
1. this patent provides a kind of method for preparing aryl phosphate.It mainly comprises: in the non-polar solvent that contains phosphorus oxychloride and phenols, drip acid binding agent, and reaction at a lower temperature, thereby obtain the phosphoric acid ester that highly purified single aryl replaces.
2. according to claim 1, non-polar solvent of the present invention comprises benzene,toluene,xylene etc.Its consumption should be 5～10 times of reactant weight.
3. according to claim 1, the used non-polar solvent of the present invention should dissolve phosphorus oxychloride, then is slightly soluble or insoluble to phenols, thereby forms a suspendible system.
4. according to claim 1, temperature of reaction of the present invention should be lower, and its scope should be between 0～30 ℃, preferably between 10～20 ℃.
5. according to claim 1, acid binding agent of the present invention comprises tertiary amine class organic basess such as pyridine, triethylamine, also comprises mineral alkalis such as NaOH, KOH.
6. according to claim 1, the acid binding agent of this reaction should adopt the dropping mode.Temperature should be controlled at below 30 ℃ when dripping acid binding agent, preferably between 10～20 ℃.
7. according to claim 1, the raw material phenols of this reaction and the mole ratio of phosphorus oxychloride should be between 1: 5, between preferably 1: 1～1: 1.2.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2007100569972A CN101274942A (en) | 2007-03-26 | 2007-03-26 | Preparation of aryl phosphate |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2007100569972A CN101274942A (en) | 2007-03-26 | 2007-03-26 | Preparation of aryl phosphate |
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|---|---|
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Family
ID=39994832
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102807583A (en) * | 2011-06-02 | 2012-12-05 | 中国石油化工股份有限公司 | Synthesis methods of organophosphate ester and organophosphate salt |
| CN103980306A (en) * | 2014-04-28 | 2014-08-13 | 湖南大学 | Preparation method for hypophosphorous acid / phosphorous acid/ phosphate compounds by adopting P(O)-OH-contained compounds |
| CN105646577A (en) * | 2016-03-01 | 2016-06-08 | 苏州艾缇克药物化学有限公司 | Preparation method of aromatic phosphate compound |
| CN106146548A (en) * | 2015-04-17 | 2016-11-23 | 中山大学 | The preparation of a kind of aryloxy group phosphate ester list sodium salt and application |
| CN106588978A (en) * | 2016-12-03 | 2017-04-26 | 苏州大学 | Phosphate ester fire retardant based on biomass and preparation method thereof |
| CN112239478A (en) * | 2019-07-17 | 2021-01-19 | 杉杉新材料（衢州）有限公司 | Method for synthesizing asymmetric phosphate compound |
-
2007
- 2007-03-26 CN CNA2007100569972A patent/CN101274942A/en active Pending
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102807583A (en) * | 2011-06-02 | 2012-12-05 | 中国石油化工股份有限公司 | Synthesis methods of organophosphate ester and organophosphate salt |
| CN102807583B (en) * | 2011-06-02 | 2014-12-03 | 中国石油化工股份有限公司 | Synthesis methods of organophosphate ester and organophosphate salt |
| CN103980306A (en) * | 2014-04-28 | 2014-08-13 | 湖南大学 | Preparation method for hypophosphorous acid / phosphorous acid/ phosphate compounds by adopting P(O)-OH-contained compounds |
| CN106146548A (en) * | 2015-04-17 | 2016-11-23 | 中山大学 | The preparation of a kind of aryloxy group phosphate ester list sodium salt and application |
| CN106146548B (en) * | 2015-04-17 | 2020-12-29 | 中山大学 | Preparation and application of aryloxy phosphate monosodium salt |
| CN105646577A (en) * | 2016-03-01 | 2016-06-08 | 苏州艾缇克药物化学有限公司 | Preparation method of aromatic phosphate compound |
| CN106588978A (en) * | 2016-12-03 | 2017-04-26 | 苏州大学 | Phosphate ester fire retardant based on biomass and preparation method thereof |
| CN112239478A (en) * | 2019-07-17 | 2021-01-19 | 杉杉新材料（衢州）有限公司 | Method for synthesizing asymmetric phosphate compound |
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Open date: 20081001 |