CN103073581B - Method for compositing alkyl phosphonic acid dialkyl ester - Google Patents
Method for compositing alkyl phosphonic acid dialkyl ester Download PDFInfo
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- CN103073581B CN103073581B CN201310014964.7A CN201310014964A CN103073581B CN 103073581 B CN103073581 B CN 103073581B CN 201310014964 A CN201310014964 A CN 201310014964A CN 103073581 B CN103073581 B CN 103073581B
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Abstract
A method for compositing alkyl phosphonic acid dialkyl ester is characterized in that phosphorous acid trialkyl ester is taken as a raw material and alkyl phosphonic acid dialkyl ester is composited under alkali conditions through catalyst. The specific compositing steps are as follows: phosphorous acid trialkyl ester, alkali, catalyst are added in a container in sequence, a reflux reaction is performed, and the pressure is controlled to be within 1.2 to 1.4 MPa; and when the reaction is over, underpressure distillation is performed, distillate is collected, and then alkyl phosphonic acid dialkyl ester is obtained. Phosphorous acid trialkyl ester used in the method, which is taken as the raw material, is low in cost and easy to get; and the method has the advantages of high productivity and simplicity in operation and is more suitable for mass production.
Description
Technical field
The invention belongs to chemical field, be specifically related to a kind of synthetic method of dialkyl alkylphosphonate.
Background technology
Dialkyl alkylphosphonate is widely used in the fire-retardant of polyurethane foam plastics, unsaturated polyester resin, epoxy resin and furan resin material.Such as, methyl-phosphoric acid dimethyl ester can be used as the main intermediate of the organophosphorus pesticide synthesis such as Cao An Phosphonium.Traditional dialkyl alkylphosphonate is mainly obtained by Michaelis-Arbuzov rearrangement reaction synthesis under alkylating reagent catalytic action with trialkyl phosphite.
The people such as Slaton take trialkyl phosphite as raw material, obtain dialkyl methyl phosphonate with iodomethane catalyst adding under the condition such as hot reflux, microwave irradiation by Michaelis-Arbuzov rearrangement reaction.Productive rate is 75%, but iodomethane is very expensive, and boiling point is low, and unstable, can not recycle, cost is higher.
The people such as Liu Zhiguo take alkyl phosphite as raw material, and methyl alkylbenzenesulfonate is that catalyst obtains alkyl phosphonic acid acid dialkyl ester by Michaelis-Arbuzov rearrangement reaction, and this reaction yield is 80%, but catalyst is not easy to obtain.
The people such as Renard find that trialkyl phosphite also the similar on-the-spot form catalysis Michaelis-Arbuzov rearrangement reaction producing methylating reagent can obtain alkyl phosphonic acid acid dialkyl ester under trimethyl iodate silicon, trimethyl silicon bromide and trimethyl silicane triflate catalytic condition, reaction time is 72h, and reaction yield is 68%.This reaction will use TMSOTf and BF
3.OEt
2, be inconvenient to store, the simultaneous reactions time is longer.Therefore, industrialization is more difficult.
The people such as Anh P. Vu carry out Michaelis-Becker Reactive Synthesis with alkyl phosphite or hypophosphorous acid dialkyl and iodomethane and obtain alkyl base phosphate dialkyl ester productive rate is about 60%, and this reaction needed uses ionic liquid [the bmim] [BF that price is higher
4] as solvent, also will use sodium metal in addition as catalyst, therefore this route is not suitable for suitability for industrialized production.
Manisha utilizes alkyl phosphonic acid and correspondent alcohol, at the diatomite of p-methyl benzenesulfonic acid modification or chlorination modified silica gel, esterification occurs under low-temperature catalyzed effect can obtain dialkyl alkylphosphonate, and productive rate is about 85%.But first the method must obtain alkyl phosphonic acid, and cost of material is higher, diatomite or silica gel to be used simultaneously, increase operation easier.
Muller uses fluoroalkyl phosphine oxide and esters of silicon acis to react also can prepare dialkyl alkylphosphonate, and reaction yield is 80%.SiF can be produced in course of reaction
4and HF, therefore require higher to industrial equipment, thus increase production cost.In addition, fluoroalkyl phosphine oxide is not easy synthesis and obtains.
The people such as Dunach can synthesize alkyl phosphonic acid dimethyl ester to react 10 min with the peroxide tertiary alcohol under alkyl dialkyl phosphite room temperature, because will use peroxide, make cost too high, also can affect industrial production safety simultaneously, be not suitable for suitability for industrialized production.
Summary of the invention
The object of this invention is to provide a kind of synthetic method of dialkyl alkylphosphonate, be characterized in that technological process is simple, cost is low, reaction is easy to control, and is suitable for suitability for industrialized production.
For solving the problems of the technologies described above, the technical solution adopted in the present invention is: a kind of synthetic method of dialkyl alkylphosphonate, take trialkyl phosphite as raw material, at catalyst, and synthesis of alkyl dialkyl alkylphosphonate under alkali condition, reaction equation is:
In formula, R is alkyl.
Concrete synthesis step is: under inert gas shielding, adds trialkyl phosphite, alkali, catalyst successively in a reservoir, back flow reaction; controlled pressure is followed the tracks of after reaction terminates at 1.2-1.4MPa, GC, decompression distillation; collect cut, obtain dialkyl alkylphosphonate.
Described trialkyl phosphite can be Trimethyl phosphite, triethyl phosphite, triphenyl phosphite or the aromatic radical tris phosphite containing any organic side chain, and R is alkyl.
Described alkali is inorganic base or organic amine.
Described catalyst is compound of benzene nitriles, and its phenyl ring can with various alkyl, chlorine, nitro or hydrogen.
Described catalyst is to 6-chlorophenyl nitrile.
Described inert gas is nitrogen or argon gas.
The present invention is compared with existing synthetic method, and the method that raw material is cheap and easy to get, productive rate is high, simple to operate, is applicable to the needs of large-scale production.
The method that this invention is set forth, the catalyst of use easily obtains, and reaction pressure is lower, and the reaction time is short, for industrialization creates good condition, thus saves production power cost and the cost of raw material.
Detailed description of the invention
Further illustrate the present invention below in conjunction with embodiment, but embodiment is only the present invention is described, instead of is limited.
Example 1:
Under nitrogen protection, in the round-bottomed flask of 25mL, add the Trimethyl phosphite of 5mmol successively, 10 mg potash, 20 mg cyanophenyls; heating reflux reaction, maintaining pressure is after 1.2-1.4MPa, GC tracking reaction terminates, decompression distillation; collect cut, product namely, productive rate is 88.9%.
Example 2:
Under inert nitrogen gas shield; the triethyl phosphite of 5mmol is added successively in the round-bottomed flask of 25mL; 10 mg sodium carbonate, 15 mg o-chloro benzonitriles, heating reflux reaction; maintenance pressure is 1.2-1.4MPa; after GC tracking reaction terminates, decompression distillation, collects cut; namely product, productive rate is 92.6%.
Example 3:
Under inert nitrogen gas shield; the tripropyl phosphite of 5mmol is added successively in the round-bottomed flask of 25mL; 10 mg NaOH, 15 mg o-chloro benzonitriles, heating reflux reaction; maintenance pressure is 1.2-1.4MPa; after GC tracking reaction terminates, decompression distillation, collects cut; namely product, productive rate is 91.5%.
Example 4:
Under inert nitrogen gas shield; the tripropyl phosphite of 5mmol is added successively in the round-bottomed flask of 25mL; 15 mg potassium hydroxide, 20 mg o-chloro benzonitriles, heating reflux reaction; maintenance pressure is 1.2-1.4MPa; after GC tracking reaction terminates, decompression distillation, collects cut; namely product, productive rate is 90.8%.
Example 5:
Under inert nitrogen gas shield; the tributyl phosphite of 5mmol is added successively in the round-bottomed flask of 25mL; 15 mg potassium hydroxide, 15 mg o-chloro benzonitriles, heating reflux reaction; maintenance pressure is 1.2-1.4MPa; after GC tracking reaction terminates, decompression distillation, collects cut; namely product, productive rate is 94.2%.
Example 6:
Under inert argon gas shield; the tributyl phosphite of 5mmol is added successively in the round-bottomed flask of 25mL; 15 mg potash, 25 mg to 6-chlorophenyl nitrile, heating reflux reaction; maintenance pressure is 1.2-1.4MPa; after GC tracking reaction terminates, decompression distillation, collects cut; namely product, productive rate is 92.7%.
Example 7:
Under inert nitrogen gas shield; the Trimethyl phosphite of 5mmol is added successively in the round-bottomed flask of 25mL; 10 mg triethylamines, 30 mg to 6-chlorophenyl nitrile, heating reflux reaction; maintenance pressure is 1.2-1.4MPa; after GC tracking reaction terminates, decompression distillation, collects cut; namely product, productive rate is 95.6%.
Example 8:
Under inert nitrogen gas shield; the Trimethyl phosphite of 5mmol is added successively in the round-bottomed flask of 25mL; 10 mg diethylamine, 25 mg p-nitrophenyl nitriles, heating reflux reaction; maintenance pressure is 1.2-1.4MPa; after GC tracking reaction terminates, decompression distillation, collects cut; namely product, productive rate is 91.1%.
Example 9:
Under inert argon gas shield; the tributyl phosphite of 5mmol is added successively in the round-bottomed flask of 25mL; 15 mg potash, 25 mg o-chloro benzonitriles, heating reflux reaction; maintenance pressure is 1.2-1.4MPa; after GC tracking reaction terminates, decompression distillation, collects cut; namely product, productive rate is 92.7%.
Example 10:
Under inert nitrogen gas shield; the tripropyl phosphite of 5mmol is added successively in the round-bottomed flask of 25mL; 15 mg dimethylamine, 25 mg to 6-chlorophenyl nitrile, heating reflux reaction; maintenance pressure is 1.2-1.4MPa; after GC tracking reaction terminates, decompression distillation, collects cut; namely product, productive rate is 96.2%.
Example 11:
Under inert nitrogen gas shield; the triethyl phosphite of 5mmol is added successively in the round-bottomed flask of 25mL; 10 mg potassium hydroxide, 20 mg p-nitrophenyl nitriles, heating reflux reaction; maintenance pressure is 1.2-1.4MPa; after GC tracking reaction terminates, decompression distillation, collects cut; namely product, productive rate is 90.8%.
Example 12:
Under inert argon gas shield; the Trimethyl phosphite of 5mmol is added successively in the round-bottomed flask of 25mL; 15 mg triethanolamines, 25 mg cyanophenyls, heating reflux reaction; maintenance pressure is 1.2-1.4MPa; after GC tracking reaction terminates, decompression distillation, collects cut; namely product, productive rate is 94.5%.
Example 13:
Under inert nitrogen gas shield; the tributyl phosphite of 5mmol is added successively in the round-bottomed flask of 25mL; 15 mg tripropyl amine (TPA)s, 30 mg o-chloro benzonitriles, heating reflux reaction; maintenance pressure is 1.2-1.4MPa; after GC tracking reaction terminates, decompression distillation, collects cut; namely product, productive rate is 89.3%.
Example 14:
Under inert argon gas shield; the tributyl phosphite of 5mmol is added successively in the round-bottomed flask of 25mL; 15 mg triethanolamines, 25 mg to 6-chlorophenyl nitrile, heating reflux reaction; maintenance pressure is 1.2-1.4MPa; after GC tracking reaction terminates, decompression distillation, collects cut; namely product, productive rate is 92.5%.
Claims (5)
1. a synthetic method for dialkyl alkylphosphonate, is characterized in that: be raw material with trialkyl phosphite, at catalyst, and synthesis of alkyl dialkyl alkylphosphonate under alkali condition, reaction equation is:
In formula, R is alkyl;
Described alkali is inorganic base or organic amine;
Described catalyst is compound of benzene nitriles, and its phenyl ring can with various alkyl, chlorine, nitro or hydrogen.
2. the synthetic method of dialkyl alkylphosphonate according to claim 1; it is characterized in that; concrete synthesis step is: under inert gas shielding; add trialkyl phosphite, alkali, catalyst successively in a reservoir, back flow reaction, controlled pressure is at 1.2-1.4MPa; after GC tracking reaction terminates; decompression distillation, collects cut, obtains dialkyl alkylphosphonate.
3. the synthetic method of dialkyl alkylphosphonate according to claim 1, is characterized in that, described trialkyl phosphite can be Trimethyl phosphite, triethyl phosphite.
4. the synthetic method of dialkyl alkylphosphonate according to claim 1, is characterized in that: described catalyst is to 6-chlorophenyl nitrile.
5. the synthetic method of dialkyl alkylphosphonate according to claim 2, is characterized in that: described inert gas is nitrogen or argon gas.
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Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103880881B (en) * | 2014-04-16 | 2016-05-18 | 苏州科技学院相城研究院 | A kind of preparation method of Dimethyl ally phosphite |
| CN107894480A (en) * | 2017-12-20 | 2018-04-10 | 上海建科检验有限公司 | A kind of GC-MS detection method of MOCA contents and its application |
| CN107973813B (en) * | 2018-01-04 | 2019-07-30 | 太和气体（荆州）有限公司 | A kind of synthetic method of trimethyl borine |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3855360A (en) * | 1972-08-21 | 1974-12-17 | Stauffer Chemical Co | Polyalkylene glycol alkyl or haloalkyl poly-phosphonates |
| CN1127755A (en) * | 1994-07-27 | 1996-07-31 | Basf公司 | Preparation of phosphonic esters |
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2013
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3855360A (en) * | 1972-08-21 | 1974-12-17 | Stauffer Chemical Co | Polyalkylene glycol alkyl or haloalkyl poly-phosphonates |
| CN1127755A (en) * | 1994-07-27 | 1996-07-31 | Basf公司 | Preparation of phosphonic esters |
Non-Patent Citations (1)
| Title |
|---|
| First use of benzyl phosphites in the Michaelis-Arbuzov reaction synthesis of mono-, di-, and triphosphate analogs;Mourad Saady et al.;《Helvetica Chimica Acta》;19951231;第78卷;670-678 * |
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