CN107602608A - A kind of preparation method of diethyl methyl-phosphonite - Google Patents
A kind of preparation method of diethyl methyl-phosphonite Download PDFInfo
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- CN107602608A CN107602608A CN201710882015.9A CN201710882015A CN107602608A CN 107602608 A CN107602608 A CN 107602608A CN 201710882015 A CN201710882015 A CN 201710882015A CN 107602608 A CN107602608 A CN 107602608A
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- phosphonite
- diethyl methyl
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- methyl
- alchlor
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Abstract
The present invention proposes a kind of synthetic method of diethyl methyl-phosphonite, and its processing step is as follows：First ternary complexes being prepared using phosphorus trichloride, alchlor and chloromethanes as raw material, then reacting with absolute ethyl alcohol after aluminum reduction to obtain diethyl methyl-phosphonite crude product, rectification under vacuum obtains sterling.The present invention directly prepares diethyl methyl-phosphonite by ternary complexes, need not move through intermediate methyl dichloro phosphorus, reduce the degree of danger of industrialized production, and react to obtain diethyl methyl-phosphonite by intermediate methyl dichloro phosphorus and ethanol, sodium chloride compared in traditional handicraft, reaction condition is gentleer, waste residue rate significantly reduces, and high income is up to 85%.
Description
Technical field
The present invention relates to diethyl methyl-phosphonite synthesis technical field, and in particular to a kind of diethyl methyl-phosphonite
Preparation method.
Background technology
It is a kind of liquid of colourless irritant smell under diethyl methyl-phosphonite normal temperature, is in a kind of important chemical industry
Mesosome, the synthesis available for new and effective herbicide glufosinate-ammonium.
The main method for preparing diethyl methyl-phosphonite at present has Ethanol Method, triethyl phosphite method and methyl dichloro
Phosphorus method.
Diethyl methyl-phosphonite synthesising process research [J] (fine-chemical intermediate, Wang Hong-Liang, Shao Shengfu, Xu Yun,
Deng .2005,35 (2):Report a kind of using phosphorus trichloride and ethanol as the preparation method of raw material in 54-56.), the two is tiing up acid
The lower generation diethoxy phosphorus chloride of agent DMA effect, then generate methyl phosphonous acid diethyl with methyl chloride reactive magnesium
Ester, separating-purifying, product purity 97.5%, yield 40.3% are carried out from suitable solvent.The route is during synthesis
Reaction condition is harsher, and product yield is relatively low, while causes production cost higher as catalyst using noble metal.
Methylisothiouronium methylphosphite diethylester synthesising process research [J] (Zhejiang Polytechnical University's journal, Ding Chengrong, Guo Weichen, Liang Hong
Fly, wait .2016,2:008.) phosphorus trichloride and triethyl phosphite are used as raw material in, is first prepared under composite catalyst catalysis
Chloro diethyl phosphite, then the diethyl methyl-phosphonite of content 97.6% is obtained with methyl chloride reactive magnesium, rectification under vacuum,
Overall yield of reaction 78.5%.The method substantially has no essential distinction with Ethanol Method, and triethyl phosphite can also be by tri-chlorination
It is prepared by phosphorus and ethanol synthesis.
Process for the preparation of alkylphosphonous acid diesters and/or
dialkylphosphinous acid esters:Adopted in US, US5128495 [P] (Scheffel G, Thiele are M.1992.)
By the use of 6-methyl phosphonic triamide as catalyst, catalysis phosphorus trichloride protochloride p diethylaminobenzoic acid is prepared with triethyl phosphite reaction
Ester, then act on obtaining diethyl methyl-phosphonite with grignard reagent, yield 87.1%, cost is high and technique is relatively hazardous, obtains
Product purity is not high.
Highy potent herbicide grass fourth phosphine intermediate MeP (OEt) 2 synthesis [J] (chemical industry in Jiangsu Province, Shi Hongxin, Lin Hui, Xiang Juping,
Deng .2005 (z1):One kind is reported in 106-107.) diethyl methyl-phosphonite is prepared by methyl dichloro phosphorus and ethanol synthesis
Method, methyl dichloro phosphorus first prepared by phosphorus trichloride and alchlor, chloromethanes reaction, then methyl is obtained with ethanol synthesis
Phosphonous acid diethylester, overall yield of reaction 76.7%.This route needs to use the higher methyl dichloro phosphorus of degree of danger, pair sets
Standby corrosion is extremely serious, and industrialization difficulty is larger.Intermediate methyl dichloro phosphorus production process produces a large amount of corrosivity waste residues, and
The intermediate is very active, meets water burning, sees air oxidation, production, transport, storage difficulty are big.
From above-mentioned prior art, the preparation technology of diethyl methyl-phosphonite is still to be improved, it is necessary to develop one kind
The complete efficient synthesis route of new height.
The content of the invention
For above-mentioned problem, the present invention proposes a kind of preparation method of diethyl methyl-phosphonite, with trichlorine
It is that raw material prepares ternary complexes to change phosphorus, alchlor and chloromethanes, and methyl phosphonous acid is then directly prepared by ternary complexes
Diethylester, it is not necessary to by intermediate methyl dichloro phosphorus, the degree of danger of industrialized production is reduced, and compared to traditional work
React to obtain diethyl methyl-phosphonite by intermediate methyl dichloro phosphorus and ethanol, sodium chloride in skill, reaction condition more heats
With waste residue rate significantly reduces, and high income is up to 85%.
AlCl3+PCl3+CH3Cl→[CH3PCl3]+[AlCl4]-
3[CH3PCl3]+[AlCl4]-+2Al→3CH3PCl2·5AlCl3
In order to realize above-mentioned purpose, the present invention uses following technical scheme：
A kind of preparation method of diethyl methyl-phosphonite, preparation method are as follows：
1) it is raw material to weigh appropriate phosphorus trichloride, alchlor and chloromethanes, using dichloromethane as solvent, is added closed
In reactor, heating response 6h, ternary complexes are made；
2) ternary complexes are first distilled in atmospheric conditions, reheating is warming up to 140 DEG C, is evaporated under reduced pressure, abundant precipitation
Solvent；
3) add aluminium powder several times into the ternary complexes after precipitation and carry out reduction reaction, obtain P3+Ternary complexing
Thing；
System is cooled to -20-10 DEG C after the completion of reduction reaction, then anhydrous second is slowly added dropwise thereto under nitrogen atmosphere
Alcohol, is incubated 1-3h after being added dropwise to complete, rectification under vacuum produces diethyl methyl-phosphonite.
Preferably, heating response temperature is 80-100 DEG C in step 1).
Preferably, it is 140-160 DEG C that aluminium powder adds specially guarantee reduction reaction temperature several times in step 3).
Preferably, it is -20-40 DEG C that specially guarantee reaction temperature, which is slowly added dropwise, in absolute ethyl alcohol in step 4).
Preferably, holding temperature is 0-40 DEG C in step 4).
Preferably, each raw material addition is as follows in step 1)：Phosphorus trichloride 79.8-80.5g, alchlor 107.3-
109.3g, chloromethanes 60g, dichloromethane 100mL.
Preferably, the mass ratio of aluminium powder addition and alchlor addition is 1 in step 3):7-9.
Preferably, the mol ratio of absolute ethyl alcohol addition and alchlor addition is 4-8 in step 4):1.
Phosphorus trichloride, alchlor and chloromethanes of the present invention are ternary complexes prepared by raw material, and structural formula is
[CH3PCl3]+[AlCl4]-, wherein phosphorus is with P5+Form is present, it is necessary to first use aluminum reduction into 3CH3PCl2·5AlCl3.The cooperation
Thing structure is sufficiently stable, and conventional method is difficult to destroy, and prior art is using in the metal salts, with its structure such as sodium chloride, potassium chloride
Aluminium chloride combine to form more stable NaAlCl4, by CH3PCl2Discharge.But the NaAlCl of its by-product4Impurity is more, place
It is big to manage difficulty.Scheme of the present invention is directly to participate in reacting by the complex after reduction, the CH in complex3PCl2With
Ethanol synthesis generates diethyl methyl-phosphonite, the AlCl discharged3In ethanol, rectifying obtains methyl phosphonous acid diethyl for dissolving
Ester, ethanol is reclaimed, while by-product aluminium chlorohydrate, solid byproducts reduce 60% compared to prior art.
Due to using above-mentioned technical scheme, the beneficial effects of the invention are as follows：The present invention with phosphorus trichloride, alchlor and
Chloromethanes is that raw material prepares ternary complexes, then directly prepares diethyl methyl-phosphonite by ternary complexes, it is not necessary to pass through
Intermediate methyl dichloro phosphorus is crossed, optimizes synthesis route, the separation of methyl dichloro phosphorus is avoided and collects, reduce
The degree of danger of industrialized production, and reacted compared in traditional handicraft by intermediate methyl dichloro phosphorus and ethanol, sodium chloride
Diethyl methyl-phosphonite is obtained, reaction condition is gentleer, and waste residue rate significantly reduces, and high income effectively reduces up to 85%
Industrial cost, synthesis controllability are strong.
Embodiment
To make the purpose, technical scheme and advantage of the embodiment of the present invention clearer, below in conjunction with the embodiment of the present invention,
Technical scheme in the embodiment of the present invention is clearly and completely described.Based on embodiments of the invention, the common skill in this area
The every other embodiment that art personnel are obtained under the premise of creative work is not made, belong to the model that the present invention protects
Enclose.
Synthesis route of the present invention is as follows：
The preparation of ternary complexes：
Alchlor and slightly excessive phosphorus trichloride are put into closed reactor, with dichloromethane, are passed through appropriate
Chloromethanes, at a certain temperature reaction a period of time, it is evaporated under reduced pressure desolvation.
The reduction of ternary complexes：
Ternary complexes are heated to 140 DEG C, in batches a small amount of repeatedly to add aluminium powder, control temperature is no more than 160 DEG C
(140-160 DEG C), 1/8 or so (1/7-1/9) of the alchlor quality of previous step input aluminium powder is added, is fully dropped after reaction
Temperature to 10 DEG C (- 20-10 DEG C) below.
The preparation of diethyl methyl-phosphonite：
The ethanol after water removal is slowly dropped in the ternary complexes after reduction under nitrogen protection, during control is added dropwise
Reaction temperature is no more than 40 DEG C (- 20-40 DEG C), is incubated 1-3h after being added dropwise at 0-40 DEG C, rectification under vacuum produces content
More than 97% diethyl methyl-phosphonite.
Embodiment 1：
80.1g alchlor 107.9g phosphorus trichlorides are put into closed reactor, using 100mL dichloromethane as molten
Agent, then 60g chloromethanes is passed through, reacted 6 hours at 80-100 DEG C.First air-distillation removes most of solvent, then slowly heating
To 140 DEG C of vacuum distillations.It is in batches a small amount of after abundant desolvation repeatedly to add aluminium powder, ternary complexes are reduced, control reaction
Temperature is 150 DEG C.- 10 DEG C fully are cooled to after reaction, 110.4g (2 times of theoretical amount) anhydrous second is slowly added dropwise under condition of nitrogen gas
Alcohol, it is 10 DEG C to control and process temperature is added dropwise, and is added dropwise to complete rear 20-30 DEG C of insulation 2h, and rectification under vacuum obtains 71.62g contents
98.1% diethyl methyl-phosphonite, total recovery 86.1% in terms of alchlor.
Embodiment 2：
80.2g alchlor 108.5g phosphorus trichlorides are put into closed reactor, using 100mL dichloromethane as molten
Agent, then 60g chloromethanes is passed through, reacted 6 hours at 80-100 DEG C.First air-distillation removes most of solvent, then slowly heating
To 140 DEG C of vacuum distillations.It is in batches a small amount of after abundant desolvation repeatedly to add aluminium powder, ternary complexes are reduced, control reaction
Temperature is 160 DEG C.- 20 DEG C fully are cooled to after reaction, 165.9g (3 times of theoretical amount) anhydrous second is slowly added dropwise under condition of nitrogen gas
Alcohol, it is 20 DEG C to control and process temperature is added dropwise, and is added dropwise to complete rear 30-40 DEG C of insulation 1h, and rectification under vacuum obtains 70.38g contents
98.9% diethyl methyl-phosphonite, total recovery 85.3% in terms of alchlor.
Embodiment 3：
79.8g alchlor 108.5g phosphorus trichlorides are put into closed reactor, using 100mL dichloromethane as molten
Agent, then 60g chloromethanes is passed through, reacted 6 hours at 80-100 DEG C.First air-distillation removes most of solvent, then slowly heating
To 140 DEG C of vacuum distillations.It is in batches a small amount of after abundant desolvation repeatedly to add aluminium powder, ternary complexes are reduced, control reaction
Temperature is 160 DEG C.0 DEG C fully is cooled to after reaction, 221g (4 times of theoretical amount) absolute ethyl alcohol is slowly added dropwise under condition of nitrogen gas,
It is 30 DEG C to control and process temperature is added dropwise, and is added dropwise to complete rear 30-40 DEG C of insulation 3h, and rectification under vacuum obtains 69.88g contents 97.5%
Diethyl methyl-phosphonite, total recovery 83.5% in terms of alchlor.
Embodiment 4：
80.5g alchlor 107.3g phosphorus trichlorides are put into closed reactor, using 100mL dichloromethane as molten
Agent, then 60g chloromethanes is passed through, reacted 6 hours at 80-100 DEG C.First air-distillation removes most of solvent, then slowly heating
To 140 DEG C of vacuum distillations.It is in batches a small amount of after abundant desolvation repeatedly to add aluminium powder, ternary complexes are reduced, control reaction
Temperature is 160 DEG C.0 DEG C fully is cooled to after reaction, 82.8g (1.5 times of theoretical amount) absolute ethyl alcohol is slowly added dropwise, control is added dropwise
Process temperature is 30 DEG C, is added dropwise to complete rear 30-40 DEG C of insulation 1h, and rectification under vacuum obtains the methyl Asia phosphine of 67.42g contents 96.7%
Diethyl phthalate, total recovery 79.9% in terms of alchlor.
Embodiment 5：
80.1g alchlor 109.3g phosphorus trichlorides are put into closed reactor, using 100mL dichloromethane as molten
Agent, then 60g chloromethanes is passed through, reacted 6 hours at 80-100 DEG C.First air-distillation removes most of solvent, then slowly heating
To 140 DEG C of vacuum distillations.It is in batches a small amount of after abundant desolvation repeatedly to add aluminium powder, ternary complexes are reduced, control reaction
Temperature is 160 DEG C.10 DEG C fully are cooled to after reaction, 110.5g (2 times of theoretical amount) absolute ethyl alcohol is slowly added dropwise, control is added dropwise
Process temperature is 40 DEG C, is added dropwise to complete rear 30-40 DEG C of insulation 2h, and rectification under vacuum obtains the methyl Asia phosphine of 65.26g contents 97.9%
Diethyl phthalate, total recovery 78.3% in terms of alchlor.
The above embodiments are merely illustrative of the technical solutions of the present invention, rather than its limitations；Although with reference to the foregoing embodiments
The present invention is described in detail, it will be understood by those within the art that：It still can be to foregoing each implementation
Technical scheme described in example is modified, or carries out equivalent substitution to which part technical characteristic；And these modification or
Replace, the essence of appropriate technical solution is departed from the spirit and scope of various embodiments of the present invention technical scheme.
Claims (8)
1. a kind of preparation method of diethyl methyl-phosphonite, it is characterised in that preparation method is as follows：
1) it is raw material to weigh appropriate phosphorus trichloride, alchlor and chloromethanes, using dichloromethane as solvent, adds confined reaction
In device, heating response 6h, ternary complexes are made；
2) ternary complexes are first distilled in atmospheric conditions, reheating is warming up to 140 DEG C, is evaporated under reduced pressure, abundant precipitation solvent；
3) add aluminium powder several times into the ternary complexes after precipitation and carry out reduction reaction, obtain P3+Ternary complexes；
4) system is cooled to -20-10 DEG C after the completion of reduction reaction, then absolute ethyl alcohol is slowly added dropwise thereto under nitrogen atmosphere,
1-3h is incubated after being added dropwise to complete, rectification under vacuum produces diethyl methyl-phosphonite.
2. the preparation method of diethyl methyl-phosphonite according to claim 1, it is characterised in that：Heating is anti-in step 1)
It is 80-100 DEG C to answer temperature.
3. the preparation method of diethyl methyl-phosphonite according to claim 1, it is characterised in that：Aluminium powder point in step 3)
Repeatedly add is specially to ensure that reduction reaction temperature is 140-160 DEG C.
4. the preparation method of diethyl methyl-phosphonite according to claim 1, it is characterised in that：Anhydrous second in step 4)
Alcohol, which is slowly added dropwise, specially ensures that reaction temperature is -20-40 DEG C.
5. the preparation method of diethyl methyl-phosphonite according to claim 1, it is characterised in that：Insulation temperature in step 4)
Spend for 0-40 DEG C.
6. the preparation method of the diethyl methyl-phosphonite according to claim any one of 1-5, it is characterised in that step 1)
In each raw material addition it is as follows：Phosphorus trichloride 79.8-80.5g, alchlor 107.3-109.3g, chloromethanes 60g, dichloromethane
100mL。
7. the preparation method of diethyl methyl-phosphonite according to claim 6, it is characterised in that：Aluminium powder adds in step 3)
The mass ratio of dosage and alchlor addition is 1:7-9.
8. the preparation method of diethyl methyl-phosphonite according to claim 1, it is characterised in that：Anhydrous second in step 4)
The mol ratio of alcohol addition and alchlor addition is 4-8:1.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113387981A (en) * | 2021-06-22 | 2021-09-14 | 辽宁陶普唯农化工有限公司 | Novel synthesis method of diethyl phosphite |
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2017
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| CN102372738A (en) * | 2010-08-14 | 2012-03-14 | 李坚 | Application of LJ reaction in preparation of wittig reagent and glufosinate-ammonium |
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Cited By (1)
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| CN113387981A (en) * | 2021-06-22 | 2021-09-14 | 辽宁陶普唯农化工有限公司 | Novel synthesis method of diethyl phosphite |
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