CN106046046A - Preparation method of tris(trimethylsilyl)phosphite - Google Patents
Preparation method of tris(trimethylsilyl)phosphite Download PDFInfo
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- CN106046046A CN106046046A CN201610378764.3A CN201610378764A CN106046046A CN 106046046 A CN106046046 A CN 106046046A CN 201610378764 A CN201610378764 A CN 201610378764A CN 106046046 A CN106046046 A CN 106046046A
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- preparation
- tms
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- phosphite ester
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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
- C07F9/06—Phosphorus compounds without P—C bonds
- C07F9/08—Esters of oxyacids of phosphorus
- C07F9/141—Esters of phosphorous acids
- C07F9/1415—Compounds containing the structure P-O-acyl, P-O-heteroatom, P-O-CN
Abstract
The invention discloses a preparation method of tris(trimethylsilyl)phosphate. The preparation method comprises the steps that an alkane or ether solvent is selected, two reactants including alkali metal silicon alkoxide and phosphorus halide are added into the solvent according to the mole ratio of 1:1, and stirring is intensely conducted in the adding process; inorganic salt is removed through filtration, and reduced pressure distillation is conducted on the solution under the condition of 90 DEG C/20 mmHg to obtain the target product, wherein the purity of the product can reach 99.6% or above. Accordingly, industrialized production is achieved, and great market prospects and economic values are achieved.
Description
Technical field
The present invention relates to a kind of preparation method for high-purity three (TMS) phosphite ester.
Background technology
Three (TMS) phosphite ester is a kind of conventional medicine intermediate and organic reagent, and it is special to be mainly used in
Olefines or the synthesis of alkynes compounds.The most domestic industrial process that there is no mass, relies primarily on import.Examination
The batch import price of agent level product is about 30,000 yuan/kilogram, and the maximum packing price of retail market is about 10,000 yuan/100g.
From disclosed report, current only synthesis preparation method is (such as tetrahydrochysene furan at triethylamine and common solvents
Mutter, hexamethylene etc.) in the presence of, use the preparation method that trim,ethylchlorosilane reacts, concrete reaction mechanism reference with phosphorous acid
Following reaction equation:
Wherein, the effect of the hydrogen chloride of release in both condensation reactions after triethylamine plays absorption so that reaction is flat
Weighing apparatus moves to product direction.Real reaction process is divided into two steps: the first step, trim,ethylchlorosilane and the phosphorous acid of excess are first sloughed
Two HCl molecules form by-product (2), and this HCl molecule is absorbed by the excess of triethylamine in reaction system and forms triethylamine salt
Hydrochlorate；Second step, by-product (2) continues condensation formation target product (1) with trim,ethylchlorosilane, then releases a HCl molecule,
The latter reacts production hydrochlorate again with triethylamine.In actual fabrication process, first step reaction can be under conditions of backflow, relatively
Fast completes.And second step reaction, owing to the base strength of triethylamine self is not enough, it is impossible to promote product balance to produce to target completely
Thing (1) direction is moved.After reaction terminates, the selectivity about 70% of target product (1), by-product (2) is about 30%.To sum up
Described, prior art has the disadvantage in that response speed is relatively slow, needs to reflux 20 hours, the selectivity ability of target product (1)
Reach 70%；Course of reaction is controlled by balance, and in system, by-product (2) cannot be fully converted to target product (1)；Follow-up product
During product separating-purifying, need to consider the recovery of by-product (2)；Rely solely on filtration and cannot remove triethylamine hydrochloric acid completely
Salt, therefore in follow-up product separation process, the triethylamine hydrochloride that volatility is stronger makes industrialization produce continuously to be difficult to
Realize；During rectification under vacuum, both boiling points are more or less the same (under 20mmHg vacuum, boiling-point difference is less than 20 DEG C), by-product (2)
Purification to target product (1) causes certain interference；Market product purity on sale is the highest by 98%, produces without more than 99% high-purity
Product.Harsher application cannot be met.
Summary of the invention
For solving above-mentioned technical problem, the present invention passes through appropriate design process route, by simple raw material, it is possible to obtain
Obtain high-purity three (TMS) phosphite ester product, thus avoid highly difficult rectification, little for laboratory or industry
Batch obtains this compound and provides one conveniently means.
For reaching above-mentioned purpose, technical scheme is as follows:
The preparation method of a kind of three (TMS) phosphite ester, it is characterised in that including:
Step 1: choose alkanes or ethers as solvent；
Step 2: alkali metal silicon alkoxide is added to above-mentioned solvent according to mol ratio 1:1 with two kinds of reactants of phosphorus Halides,
It is stirred vigorously during adding simultaneously；
Step 3: be filtered to remove inorganic salt；
Step 4:90 DEG C/20mmHg decompression is distilled above-mentioned solution and is obtained target product.
Preferably, described alkali metal silicon alkoxide is trimethyl silicane potassium alcoholate, trimethyl silicane sodium alkoxide or lithium trimethylsilanolate.
Preferably, described alkali metal silicon alkoxide is trimethyl silicane potassium alcoholate.
Preferably, described phosphorus Halides is Phosphorous chloride. or phosphorus tribromide.
Preferably, described phosphorus Halides is Phosphorous chloride..
Preferably, the solvent in described step 1 is oxolane, hexamethylene, ether or toluene.
Preferably, the solvent in described step 1 is oxolane.
The invention have the benefit that more environmental protection in production process, reluctant triethylamine hydrochloride will not be generated；
It is swift in response, the most equilibrium limited, can be rapidly completed, without other by-products, product selectivity 100%；Later separation is simple,
The product quality obtained is high, and purity can reach more than 99.8%.
Detailed description of the invention
Below in conjunction with the embodiment of the present invention, the technical scheme in the embodiment of the present invention is clearly and completely described.
The present invention passes through appropriate design process route, by simple raw material, it is possible to obtain high-purity three (trimethyl silicane
Alkyl) phosphite ester product, thus avoid highly difficult rectification, obtaining this compound for laboratory or industry small lot provides
One conveniently means.
Embodiment one: choose oxolane as solvent, by trimethyl silicane potassium alcoholate and two kinds of reactants of Phosphorous chloride. according to
Mol ratio 1:1 is added in above-mentioned solvent, is stirred vigorously simultaneously, is filtered to remove potassium chloride during adding, in 90 DEG C/
Under the conditions of 20mmHg, the above-mentioned solution of decompression distillation obtains target product, and the purity of target product can reach more than 99.8%.
Embodiment two: choose oxolane as solvent, by trimethyl silicane potassium alcoholate and two kinds of reactants of phosphorus tribromide according to
Mol ratio 1:1 is added in above-mentioned solvent, is stirred vigorously simultaneously, is filtered to remove potassium bromide during adding, in 90 DEG C/
Under the conditions of 20mmHg, the above-mentioned solution of decompression distillation obtains target product, and the purity of target product can reach more than 99.7%.
Embodiment three: choose oxolane as solvent, by trimethyl silicane sodium alkoxide and two kinds of reactants of Phosphorous chloride. according to
Mol ratio 1:1 is added in above-mentioned solvent, is stirred vigorously, filtration from sodium chloride during adding simultaneously, in 90 DEG C/
Under the conditions of 20mmHg, the above-mentioned solution of decompression distillation obtains target product, and the purity of target product can reach more than 99.7%.
Embodiment four: choose oxolane as solvent, by trimethyl silicane sodium alkoxide and two kinds of reactants of phosphorus tribromide according to
Mol ratio 1:1 is added in above-mentioned solvent, is stirred vigorously simultaneously, is filtered to remove sodium bromide during adding, in 90 DEG C/
Under the conditions of 20mmHg, the above-mentioned solution of decompression distillation obtains target product, and the purity of target product can reach more than 99.7%.
Embodiment five: choose oxolane as solvent, by lithium trimethylsilanolate and two kinds of reactants of Phosphorous chloride. according to
Mol ratio 1:1 is added in above-mentioned solvent, is stirred vigorously simultaneously, is filtered to remove lithium chloride during adding, in 90 DEG C/
Under the conditions of 20mmHg, the above-mentioned solution of decompression distillation obtains target product, and the purity of target product can reach more than 99.7%.
Embodiment six: choose oxolane as solvent, by lithium trimethylsilanolate and two kinds of reactants of phosphorus tribromide according to
Mol ratio 1:1 is added in above-mentioned solvent, is stirred vigorously simultaneously, is filtered to remove potassium chloride during adding, in 90 DEG C/
Under the conditions of 20mmHg, the above-mentioned solution of decompression distillation obtains target product, and the purity of target product can reach more than 99.7%.
Embodiment seven: choosing cyclohexane give is solvent, by two kinds of reactants of trimethyl silicane potassium alcoholate and Phosphorous chloride. according to rubbing
You ratio 1:1 adds in above-mentioned solvent, is stirred vigorously simultaneously, is filtered to remove potassium chloride during adding, in 90 DEG C/
Under the conditions of 20mmHg, the above-mentioned solution of decompression distillation obtains target product, and the purity of target product can reach more than 99.7%.
Embodiment eight: choose toluene as solvent, by trimethyl silicane potassium alcoholate and two kinds of reactants of Phosphorous chloride. according to mole
Add to above-mentioned solvent than 1:1, be stirred vigorously during adding simultaneously, be filtered to remove potassium chloride, in 90 DEG C/20mmHg
Under the conditions of decompression distill above-mentioned solution obtain target product, the purity of target product can reach more than 99.7%.
Embodiment nine: choose ether as solvent, by trimethyl silicane potassium alcoholate and two kinds of reactants of Phosphorous chloride. according to mole
Add to above-mentioned solvent than 1:1, be stirred vigorously during adding simultaneously, be filtered to remove potassium chloride, in 90 DEG C/20mmHg
Under the conditions of decompression distill above-mentioned solution obtain target product, the purity of target product can reach more than 99.7%.
In the technical scheme that the present invention provides, trimethyl silicane potassium alcoholate, trimethyl silicane sodium alkoxide, trimethyl silanol in raw material
The compounds such as lithium, phosphorus tribromide, Phosphorous chloride. have realized industrial mass manufacture the most.Therefore, production cost is controlled.Use three
Under methyl silanol potassium (or trimethyl silicane sodium alkoxide, lithium trimethylsilanolate) slight excess of premise, course of reaction be similar to strong acid with
Highly basic interacts, and the most equilibrium limited, 100% has been selectively generating target product and inorganic salt；In suitable solvent side
Help down, such as oxolane, reaction can at normal temperatures moment complete, and the certain heat of heat release；In product separation process, only have
Tetrahydrofuran solvent and target product, after inorganic salt simple filtration, this is after 90 DEG C/20mmHg decompression distillation, it is easy to
Obtain the target product of 99.7% purity.
The invention have the benefit that more environmental protection in production process, reluctant triethylamine hydrochloride will not be generated；
It is swift in response, the most equilibrium limited, can be rapidly completed, without other by-products, product selectivity 100%；Later separation is simple,
The product quality obtained is high, and purity can reach more than 99.8%.
Multiple amendment to these embodiments will be apparent from, herein for those skilled in the art
Defined General Principle can realize without departing from the spirit or scope of the present invention in other embodiments.
Claims (7)
1. the preparation method of (TMS) phosphite ester, it is characterised in that including:
Step 1: choose alkanes or ethers as solvent；
Step 2: alkali metal silicon alkoxide is added to above-mentioned solvent according to mol ratio 1:1 with two kinds of reactants of phosphorus Halides, is adding
It is stirred vigorously during adding simultaneously；
Step 3: be filtered to remove inorganic salt；
Step 4:90 DEG C/20mmHg decompression is distilled above-mentioned solution and is obtained target product.
The preparation method of a kind of three (TMS) the most according to claim 1 phosphite ester, it is characterised in that institute
Stating alkali metal silicon alkoxide is trimethyl silicane potassium alcoholate, trimethyl silicane sodium alkoxide or lithium trimethylsilanolate.
The preparation method of a kind of three (TMS) the most according to claim 1 and 2 phosphite ester, its feature exists
In, described alkali metal silicon alkoxide is trimethyl silicane potassium alcoholate.
The preparation method of a kind of three (TMS) the most according to claim 1 phosphite ester, it is characterised in that institute
Stating phosphorus Halides is Phosphorous chloride. or phosphorus tribromide.
The preparation method of a kind of three (TMS) the most according to claim 1 phosphite ester, it is characterised in that institute
Stating phosphorus Halides is Phosphorous chloride..
The preparation method of a kind of three (TMS) the most according to claim 1 phosphite ester, it is characterised in that institute
Stating the solvent in step 1 is oxolane, hexamethylene, ether or toluene.
7., according to the preparation method of one three (TMS) phosphite ester described in claim 1 or 6, its feature exists
In, the solvent in described step 1 is oxolane.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106866728A (en) * | 2017-03-30 | 2017-06-20 | 石家庄圣泰化工有限公司 | The synthetic method of two (trimethyl silicon substrate) phosphite esters |
| CN109456361A (en) * | 2018-12-14 | 2019-03-12 | 常熟市常吉化工有限公司 | A kind of synthetic method of three (trialkyl silicon substrate) phosphite esters |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2010009754A1 (en) * | 2008-07-21 | 2010-01-28 | Momentive Performance Materials Gmbh | Curable silicone compositions comprising organo-silylphosphites |
| CN104860986A (en) * | 2014-02-25 | 2015-08-26 | 苏州正元新材料科技有限公司 | Preparation method of tris(trimethylsilyl)phosphite |
-
2016
- 2016-05-31 CN CN201610378764.3A patent/CN106046046A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2010009754A1 (en) * | 2008-07-21 | 2010-01-28 | Momentive Performance Materials Gmbh | Curable silicone compositions comprising organo-silylphosphites |
| CN104860986A (en) * | 2014-02-25 | 2015-08-26 | 苏州正元新材料科技有限公司 | Preparation method of tris(trimethylsilyl)phosphite |
Non-Patent Citations (2)
| Title |
|---|
| IRENEUSZ KOWNACKI ET AL.: "Tris(triorganosilyl)phosphites—New ligands controlling catalytic activity of Pt(0) complex in curing of silicone rubber", 《APPLIED CATALYSIS A: GENERAL》 * |
| YVES BERCHADSKY ET AL.: "Persilylated Phosphoranyl Radicals: The First Persistent Noncyclic Phosphoranyl Radicals", 《CHEM. EUR. J.》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106866728A (en) * | 2017-03-30 | 2017-06-20 | 石家庄圣泰化工有限公司 | The synthetic method of two (trimethyl silicon substrate) phosphite esters |
| CN109456361A (en) * | 2018-12-14 | 2019-03-12 | 常熟市常吉化工有限公司 | A kind of synthetic method of three (trialkyl silicon substrate) phosphite esters |
| CN109456361B (en) * | 2018-12-14 | 2021-08-24 | 苏州祺添新材料有限公司 | Synthesis method of tri (trihydrocarbylsilyl) phosphite ester |
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