CN110407872A - The method of alkyl chlorination phosphonic acids list alkyl ester co-producing high-purity phosphorus oxychloride - Google Patents
The method of alkyl chlorination phosphonic acids list alkyl ester co-producing high-purity phosphorus oxychloride Download PDFInfo
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- CN110407872A CN110407872A CN201910676467.0A CN201910676467A CN110407872A CN 110407872 A CN110407872 A CN 110407872A CN 201910676467 A CN201910676467 A CN 201910676467A CN 110407872 A CN110407872 A CN 110407872A
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- alkyl
- phosphorus oxychloride
- chlorination
- phosphonic acids
- solvent
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/10—Halides or oxyhalides of phosphorus
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic System
- C07F9/02—Phosphorus compounds
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/38—Phosphonic acids RP(=O)(OH)2; Thiophosphonic acids, i.e. RP(=X)(XH)2 (X = S, Se)
- C07F9/42—Halides thereof
- C07F9/425—Acid or estermonohalides thereof, e.g. RP(=X)(YR)(Hal) (X, Y = O, S; R = H, or hydrocarbon group)
Abstract
The invention discloses a kind of methods of alkyl chlorination phosphonic acids list alkyl ester co-producing high-purity phosphorus oxychloride, the following steps are included: (1) reacts phosphorus pentachloride and alkyl phosphonic acid dialkyl in a solvent, the mixture of alkyl chlorination phosphonic acids list alkyl ester and phosphorus oxychloride containing solvent is obtained；Gas phase monochloro methane or monochlorethane are generated in reaction process；(2) the gas phase monochloro methane or monochlorethane, solvent, alkyl chlorination phosphonic acids list alkyl ester and the phosphorus oxychloride that generate in reaction are separated and recovered.The present invention is to prepare alkyl chlorination phosphonic acids list alkyl ester simultaneously with phosphorus pentachloride and alkyl phosphonic acid dialkyl reaction, produce the mixture of a large amount of phosphorus oxychloride and solvent, have found suitable recovery method, the phosphorus oxychloride of co-producing high-purity, it can get preferable economic benefit, while reducing the discharge of the three wastes.
Description
Technical field
The present invention relates to a kind of methods of alkyl chlorination phosphonic acids list alkyl ester co-producing high-purity phosphorus oxychloride.
Background technique
Phosphorus oxychloride is the raw material for manufacturing organophosphorus pesticide Spanon, it can also be used to produce diphenyl 2 ethylhexyl phosphate, phosphoric acid
The phosphates such as triethyl and production plastic plasticizer, are alternatively arranged as the chlorinating agent, catalyst and uranium ore extractant of organic synthesis, In
There is important application in Chemical Manufacture.
Phosphorus pentachloride is a kind of important chlorination reagent, it can with hydroxy compounds, carboxylic acid, carbonyls, alkene,
Compound, sulfonic acid and its salt, silicon compound containing lone pair electrons etc. carry out chlorination reaction, and the activity of phosphorus pentachloride is very big, it
Displacement reaction is fiercer, and reaction generates phosphorus oxychloride.
Summary of the invention
It is abundant to phosphorus oxychloride during preparing alkyl chlorination phosphonic acids list alkyl ester that the purpose of the present invention is to provide one kind
The method of the alkyl chlorination phosphonic acids list alkyl ester co-producing high-purity phosphorus oxychloride of recycling.
The technical solution of the invention is as follows:
A kind of method of alkyl chlorination phosphonic acids list alkyl ester co-producing high-purity phosphorus oxychloride, it is characterized in that: the following steps are included:
(1) phosphorus pentachloride and alkyl phosphonic acid dialkyl are reacted in a solvent, obtains the alkyl chlorination containing solvent
The mixture of phosphonic acids list alkyl ester and phosphorus oxychloride；Gas phase monochloro methane or monochlorethane are generated in reaction process；
Reaction equation:
(2) to the gas phase monochloro methane or monochlorethane generated in reaction, using pressure recovery after condensation, washing, drying；
(3) mixture of alkyl chlorination the phosphonic acids list alkyl ester and phosphorus oxychloride containing solvent generated to reaction, is subtracted
Pressure distillation, steaming thing are the mixture of solvent and phosphorus oxychloride, and residue is alkyl chlorination phosphonic acids list alkyl ester；
(4) atmospheric distillation is carried out to the mixture of step (3) obtained solvent and phosphorus oxychloride, first steamed low-boiling molten
Agent can be back to next secondary response, and remaining is phosphorus oxychloride and a small amount of high-boiling-point impurity, then is evaporated under reduced pressure, and reception evaporates
Part obtains high-purity phosphorus oxychloride.
The reaction temperature of step (1) is -30~30 DEG C；Phosphorus pentachloride is to be added portionwise under nitrogen protection or molten with solvent
It is added dropwise after being added dropwise or dissolve after solution.
Solvent described in step (1) be the halogenated alkanes such as methylene chloride, 1,2- dichloroethanes, carbon tetrachloride, carbon disulfide,
Hexamethylene, benzene, toluene etc..
Alkyl phosphonic acid dialkyl described in step (1) refers toThe alkyl such as R=-CH3 ,-C2H5 replace alkane
Base, R1=-CH3 ,-C2H5；R, R1 can be identical or different.
The molal weight of alkyl phosphonic acid dialkyl and phosphorus oxychloride ratio is 1:0.99~1.05 in step (1)；
The method of step (4) rectifying separates solvent and phosphorus oxychloride, then is evaporated under reduced pressure, and receives fraction, obtains
The phosphorus oxychloride of high-purity.
The present invention is produced while preparing alkyl chlorination phosphonic acids list alkyl ester with phosphorus pentachloride and alkyl phosphonic acid dialkyl reaction
The mixture for having given birth to a large amount of phosphorus oxychloride and solvent has found suitable recovery method, and the phosphorus oxychloride of co-producing high-purity can
Preferable economic benefit is obtained, while reducing the discharge of the three wastes.The present invention is raw using phosphorus pentachloride and alkyl phosphonic acid dialkyl
At the mixture of alkyl chlorination phosphonic acids list alkyl ester and phosphorus oxychloride, further according to the different physical characteristic of material in mixture, technology
Step-by-step processing is carried out to property, to produce the phosphorus oxychloride of high-content while corresponding phosphonic chloride is made.
Below with reference to embodiment, the invention will be further described.
Specific embodiment
Embodiment 1:
By in 150ml dichloroethanes and 40g dimethyl methyl phosphonate investment tetra- mouthfuls of reaction flasks of 500ml, starting is stirred, simultaneously
Cooling feed liquid is to 0 DEG C or so, under nitrogen protection, phosphorus pentachloride 68g is added in three times, controls 0-5 DEG C of feed liquid temperature, finish,
It carrying out insulation reaction 0.5 hour, is then evaporated under reduced pressure, steaming thing is the mixture 225g of dichloroethanes and phosphorus oxychloride,
Residue is 47g methyl chloride methyl-phosphonate；To the gas phase monochloro methane generated in reaction, using condensation, washing, it is dry after press
It retracts and receives；The mixture of atmospheric distillation solvent 225g dichloroethanes and phosphorus oxychloride first steams low boiling point dichloroethanes 170g, can
It is back to next secondary response；Remaining is phosphorus oxychloride and a small amount of high-boiling-point impurity, then is evaporated under reduced pressure, and receives fraction and obtains three
Chlorethoxyfos 43g, detection level 98.1%, remaining high-boiling components 8g.
Embodiment 2:
By in 150ml dichloroethanes and 44.5g ethylphosphonic acid dimethyl ester investment tetra- mouthfuls of reaction flasks of 500ml, starting is stirred, together
When cooling feed liquid to 0 DEG C or so, under nitrogen protection, phosphorus pentachloride 68g is added in three times, controls 0-5 DEG C of feed liquid temperature, add
Finish, carry out insulation reaction 0.5 hour, be then evaporated under reduced pressure, steaming thing is the mixture of dichloroethanes and phosphorus oxychloride
226g, residue are 50g ethylmercury chloride methyl-phosphonate；To the gas phase monochloro methane generated in reaction, using condensation, washing, do
Pressure recovery after dry；The mixture of atmospheric distillation solvent 226g dichloroethanes and phosphorus oxychloride, first steams low boiling point dichloroethanes
171g can be back to next secondary response；Remaining is phosphorus oxychloride and a small amount of high-boiling-point impurity, then is evaporated under reduced pressure, and is received
Fraction obtains phosphorus oxychloride 42g, detection level 98.3%, remaining high-boiling components 8.2g.
Claims (6)
1. a kind of method of alkyl chlorination phosphonic acids list alkyl ester co-producing high-purity phosphorus oxychloride, it is characterized in that: the following steps are included:
(1) phosphorus pentachloride and alkyl phosphonic acid dialkyl are reacted in a solvent, obtains the alkyl chlorination phosphonic acids containing solvent
The mixture of single alkyl ester and phosphorus oxychloride；Gas phase monochloro methane or monochlorethane are generated in reaction process；
(2) to the gas phase monochloro methane or monochlorethane generated in reaction, using pressure recovery after condensation, washing, drying；
(3) mixture of alkyl chlorination the phosphonic acids list alkyl ester and phosphorus oxychloride containing solvent generated to reaction, carries out decompression steaming
It evaporates, steaming thing is the mixture of solvent and phosphorus oxychloride, and residue is alkyl chlorination phosphonic acids list alkyl ester；
(4) atmospheric distillation is carried out to the mixture of step (3) obtained solvent and phosphorus oxychloride, first steams low-boiling solvent,
It can be back to next secondary response, remaining is phosphorus oxychloride and a small amount of high-boiling-point impurity, then is evaporated under reduced pressure, and receives fraction and obtains
High-purity phosphorus oxychloride.
2. the method for alkyl chlorination phosphonic acids list alkyl ester co-producing high-purity phosphorus oxychloride according to claim 1, it is characterized in that:
The reaction temperature of step (1) is -30~30 DEG C；Phosphorus pentachloride is to be added portionwise or drip under nitrogen protection after being dissolved with solvent
Add.
3. the method for alkyl chlorination phosphonic acids list alkyl ester co-producing high-purity phosphorus oxychloride according to claim 1, it is characterized in that:
Solvent described in step (1) be include methylene chloride, 1,2- dichloroethanes, the halogenated alkane of carbon tetrachloride, carbon disulfide, hexamethylene
Alkane, benzene or toluene.
4. the method for alkyl chlorination phosphonic acids list alkyl ester co-producing high-purity phosphorus oxychloride according to claim 1, it is characterized in that:
Alkyl phosphonic acid dialkyl described in step (1) refers toR=-CH3、-C2H5Equal alkyl replace alkyl, R1=-
CH3、-C2H5；R,R1It can be identical or different.
5. the method for alkyl chlorination phosphonic acids list alkyl ester co-producing high-purity phosphorus oxychloride according to claim 1, it is characterized in that:
The molal weight of alkyl phosphonic acid dialkyl and phosphorus oxychloride ratio is 1:0.99~1.05 in step (1).
6. the method for alkyl chlorination phosphonic acids list alkyl ester co-producing high-purity phosphorus oxychloride according to claim 1, it is characterized in that:
The method of step (4) rectifying separates solvent and phosphorus oxychloride, then is evaporated under reduced pressure, and receives fraction, obtains high-purity
Phosphorus oxychloride.
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Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100522967C (en) * | 2002-02-01 | 2009-08-05 | 阿里亚德基因治疗公司 | Phosphorus-containing compounds & uses thereof |
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- 2019-07-25 CN CN201910676467.0A patent/CN110407872A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100522967C (en) * | 2002-02-01 | 2009-08-05 | 阿里亚德基因治疗公司 | Phosphorus-containing compounds & uses thereof |
Non-Patent Citations (3)
| Title |
|---|
| YONG XU等: "Chemical Synthesis and Molecular Recognition of ChemicalSynthesis and Molecular Recognition of Phosphatase-Resistant Analogues of Phosphatidylinositol-3-phosphate", 《J.AM.CHEM.SOC.》 * |
| 尹志刚 主编: "《有机磷化合物》", 31 March 2011, 北京：化学工业出版社 * |
| 赵临襄 主编: "《化学制药工艺学 （第4版）》", 31 August 2015, 北京:中国医药科技出版社 * |
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