CN104860986A - Preparation method of tris(trimethylsilyl)phosphite - Google Patents
Preparation method of tris(trimethylsilyl)phosphite Download PDFInfo
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- CN104860986A CN104860986A CN201410062968.7A CN201410062968A CN104860986A CN 104860986 A CN104860986 A CN 104860986A CN 201410062968 A CN201410062968 A CN 201410062968A CN 104860986 A CN104860986 A CN 104860986A
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Abstract
The invention discloses a preparation method of tris(trimethylsilyl)phosphate; through selection of an alkane or ether solvent, two reactants of an alkali metal silicon alkoxide and phosphorus halide are added to the above solvent in accordance with the molar ratio of 1:1, and vigorous stirring is carried out in the process of adding; and finally an inorganic salt is filtered to remove, and the solution is subjected to reduced pressure distillation under the condition of 90 DEG C/20 mmHg to obtain the target product, wherein the purity of the product can reach more than 99.6%. Industrialized production is achieved, and the preparation method has huge market prospects and economic values.
Description
Technical field
The present invention relates to a kind of preparation method for high purity three (TMS) phosphorous acid ester.
Background technology
Three (TMS) phosphorous acid ester is a kind of conventional medicine intermediate and organic reagent, is mainly used in the synthesis of special olefines or alkynes compounds.The domestic industrial process that there is no mass, mainly relies on import at present.The batch import price of grade 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 under the existence of triethylamine and common solvents (as tetrahydrofuran (THF), hexanaphthene etc.), adopt the preparation method that trimethylchlorosilane and phosphorous acid react, concrete reaction mechanism is with reference to following reaction equation: wherein, the effect of the hydrogenchloride discharged in both condensation reactions after triethylamine plays and absorbs, makes molecular balance move to product direction.Real reaction process is divided into two steps: the first step, and excessive trimethylchlorosilane and phosphorous acid are first sloughed two HCl molecules and formed by product (2), and this HCl molecule is absorbed formation triethylamine hydrochloride by the excess of triethylamine in reaction system; Second step, by product (2) and trimethylchlorosilane continue condensation and form target product (1), then release a HCl molecule, and the latter reacts with triethylamine and produces hydrochloride.In actual fabrication process, the first step reaction under the condition of backflow, can complete faster.And second step reaction, because the base strength of triethylamine self is not enough, product balance cannot be promoted and move to target product (1) direction completely.After reaction terminates, the selectivity about 70% of target product (1), by product (2) is about 30%.In sum, there is following shortcoming in prior art: speed of response is comparatively slow, and need backflow 20 hours, the selectivity of target product (1) just can reach 70%; Reaction process is by balancing control, and in system, by product (2) cannot be converted into target product (1) completely; In follow-up product separation purification process, need the recovery considering by product (2); Only rely on filtration cannot remove triethylamine hydrochloride completely, therefore in follow-up product separation process, the triethylamine hydrochloride that volatility is stronger makes industrialization continuous seepage be difficult to realize; In rectification under vacuum process, both boiling points are more or less the same (under 20mmHg vacuum tightness, boiling-point difference is less than 20 DEG C), and the purification of by product (2) to target product (1) causes certain interference; Market product purity on sale is the highest by 98%, without more than 99% high purity product.Harsher application cannot be met.
Summary of the invention
For solving the problems of the technologies described above, the present invention is by appropriate design operational path, by simple raw material, high purity three (TMS) phosphorous acid ester product can be obtained, thus avoid highly difficult rectifying, provide one conveniently means for laboratory or industrial short run obtain this compound.
For achieving the above object, technical scheme of the present invention is as follows:
A kind of preparation method of three (TMS) phosphorous acid ester, is characterized in that, bag
Draw together:
Step 1: choose alkanes or ethers as solvent;
Step 2: basic metal silicon alkoxide and Phosphorates phosphorus Halides two kinds of reactants are added in above-mentioned solvent according to mol ratio 1:1, the vigorous stirring while of in the process of adding;
Step 3: cross and filter inorganic salt;
The above-mentioned solution of step 4:90 DEG C/20mmHg underpressure distillation obtains target product.
Preferably, described basic metal silicon alkoxide is trimethyl silicane potassium alcoholate, trimethyl silicane sodium alkoxide or lithium trimethylsilanolate.
Preferably, described basic metal silicon alkoxide is trimethyl silicane potassium alcoholate.
Preferably, described Phosphorates phosphorus Halides is phosphorus trichloride or phosphorus tribromide.
Preferably, described Phosphorates phosphorus Halides is phosphorus trichloride.
Preferably, the solvent in described step 1 is tetrahydrofuran (THF), hexanaphthene, ether or toluene.
Preferably, the solvent in described step 1 is tetrahydrofuran (THF).
Beneficial effect of the present invention is: comparatively environmental protection in production process, can not generate reluctant triethylamine hydrochloride; Be swift in response, not by equilibrium-limited, can complete fast, without other by products, product selectivity 100%; Later separation is simple, and the quality product obtained is high, and purity can reach more than 99.8%.
Embodiment
Be clearly and completely described to the technical scheme in the embodiment of the present invention below.
The present invention is by appropriate design operational path, by simple raw material, high purity three (TMS) phosphorous acid ester product can be obtained, thus avoid highly difficult rectifying, provide one conveniently means for laboratory or industrial short run obtain this compound.
Embodiment one: choose tetrahydrofuran (THF) as solvent, trimethyl silicane potassium alcoholate and phosphorus trichloride two kinds of reactants are added in above-mentioned solvent according to mol ratio 1:1, the vigorous stirring while of in the process of adding, cross and filter Repone K, under 90 DEG C/20mmHg condition, the above-mentioned solution of underpressure distillation obtains target product, and the purity of target product can reach more than 99.8%.
Embodiment two: choose tetrahydrofuran (THF) as solvent, trimethyl silicane potassium alcoholate and phosphorus tribromide two kinds of reactants are added in above-mentioned solvent according to mol ratio 1:1, the vigorous stirring while of in the process of adding, cross and filter Potassium Bromide, under 90 DEG C/20mmHg condition, the above-mentioned solution of underpressure distillation obtains target product, and the purity of target product can reach more than 99.7%.
Embodiment three: choose tetrahydrofuran (THF) as solvent, trimethyl silicane sodium alkoxide and phosphorus trichloride two kinds of reactants are added in above-mentioned solvent according to mol ratio 1:1, the vigorous stirring while of in the process of adding, filtration from sodium chloride, under 90 DEG C/20mmHg condition, the above-mentioned solution of underpressure distillation obtains target product, and the purity of target product can reach more than 99.7%.
Embodiment four: choose tetrahydrofuran (THF) as solvent, trimethyl silicane sodium alkoxide and phosphorus tribromide two kinds of reactants are added in above-mentioned solvent according to mol ratio 1:1, the vigorous stirring while of in the process of adding, cross and filter Sodium Bromide, under 90 DEG C/20mmHg condition, the above-mentioned solution of underpressure distillation obtains target product, and the purity of target product can reach more than 99.7%.
Embodiment five: choose tetrahydrofuran (THF) as solvent, lithium trimethylsilanolate and phosphorus trichloride two kinds of reactants are added in above-mentioned solvent according to mol ratio 1:1, the vigorous stirring while of in the process of adding, cross and filter lithium chloride, under 90 DEG C/20mmHg condition, the above-mentioned solution of underpressure distillation obtains target product, and the purity of target product can reach more than 99.7%.
Embodiment six: choose tetrahydrofuran (THF) as solvent, lithium trimethylsilanolate and phosphorus tribromide two kinds of reactants are added in above-mentioned solvent according to mol ratio 1:1, the vigorous stirring while of in the process of adding, cross and filter Repone K, under 90 DEG C/20mmHg condition, the above-mentioned solution of underpressure distillation obtains target product, and the purity of target product can reach more than 99.7%.
Embodiment seven: choosing cyclohexane give is solvent, trimethyl silicane potassium alcoholate and phosphorus trichloride two kinds of reactants are added in above-mentioned solvent according to mol ratio 1:1, the vigorous stirring while of in the process of adding, cross and filter Repone K, under 90 DEG C/20mmHg condition, the above-mentioned solution of underpressure distillation obtains target product, and the purity of target product can reach more than 99.7%.
Embodiment eight: choose toluene as solvent, trimethyl silicane potassium alcoholate and phosphorus trichloride two kinds of reactants are added in above-mentioned solvent according to mol ratio 1:1, the vigorous stirring while of in the process of adding, cross and filter Repone K, under 90 DEG C/20mmHg condition, the above-mentioned solution of underpressure distillation obtains target product, and the purity of target product can reach more than 99.7%.
Embodiment nine: choose ether as solvent, trimethyl silicane potassium alcoholate and phosphorus trichloride two kinds of reactants are added in above-mentioned solvent according to mol ratio 1:1, the vigorous stirring while of in the process of adding, cross and filter Repone K, under 90 DEG C/20mmHg condition, the above-mentioned solution of underpressure distillation obtains target product, and the purity of target product can reach more than 99.7%.
In technical scheme provided by the invention, in raw material, the compound such as trimethyl silicane potassium alcoholate, trimethyl silicane sodium alkoxide, lithium trimethylsilanolate, phosphorus tribromide, phosphorus trichloride realizes industrial mass manufacture all.Therefore, production cost is controlled.Under the prerequisite adopting trimethyl silicane potassium alcoholate (or trimethyl silicane sodium alkoxide, lithium trimethylsilanolate) slightly excessive, reaction process is similar to strong acid and highly basic interacts, and not by equilibrium-limited, 100% optionally generates target product and inorganic salt; Under suitable solvent helps, as tetrahydrofuran (THF), reaction can complete at normal temperatures instantaneously, and the certain heat of heat release; In product separation process, only have tetrahydrofuran solvent and target product, after inorganic salt simple filtration, this, after 90 DEG C/20mmHg underpressure distillation, obtains the target product of 99.7% purity easily.
Beneficial effect of the present invention is: comparatively environmental protection in production process, can not generate reluctant triethylamine hydrochloride; Be swift in response, not by equilibrium-limited, can complete fast, without other by products, product selectivity 100%; Later separation is simple, and the quality product obtained is high, and purity can reach more than 99.8%.
To be apparent for those skilled in the art to the multiple amendment of these embodiments, General Principle as defined herein can without departing from the spirit or scope of the present invention, realize in other embodiments.
Claims (7)
1. the preparation method of three (TMS) phosphorous acid ester, is characterized in that, bag
Draw together:
Step 1: choose alkanes or ethers as solvent;
Step 2: basic metal silicon alkoxide and Phosphorates phosphorus Halides two kinds of reactants are added in above-mentioned solvent according to mol ratio 1:1, the vigorous stirring while of in the process of adding;
Step 3: cross and filter inorganic salt;
The above-mentioned solution of step 4:90 DEG C/20mmHg underpressure distillation obtains target product.
2. the preparation method of a kind of three (TMS) phosphorous acid ester according to claim 1, it is characterized in that, described basic metal silicon alkoxide is trimethyl silicane potassium alcoholate, trimethyl silicane sodium alkoxide or lithium trimethylsilanolate.
3. the preparation method of a kind of three (TMS) phosphorous acid ester according to claim 1 and 2, it is characterized in that, described basic metal silicon alkoxide is trimethyl silicane potassium alcoholate.
4. the preparation method of a kind of three (TMS) phosphorous acid ester according to claim 1, it is characterized in that, described Phosphorates phosphorus Halides is phosphorus trichloride or phosphorus tribromide.
5. the preparation method of a kind of three (TMS) phosphorous acid ester according to claim 1, it is characterized in that, described Phosphorates phosphorus Halides is phosphorus trichloride.
6. the preparation method of a kind of three (TMS) phosphorous acid ester according to claim 1, it is characterized in that, the solvent in described step 1 is tetrahydrofuran (THF), hexanaphthene, ether or toluene.
7. the preparation method of one three (TMS) phosphorous acid ester according to claim 1 or 6, is characterized in that, the solvent in described step 1 is tetrahydrofuran (THF).
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| CN201410062968.7A CN104860986A (en) | 2014-02-25 | 2014-02-25 | Preparation method of tris(trimethylsilyl)phosphite |
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| CN201410062968.7A CN104860986A (en) | 2014-02-25 | 2014-02-25 | Preparation method of tris(trimethylsilyl)phosphite |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106046046A (en) * | 2016-05-31 | 2016-10-26 | 镇江中化聚氨酯工业设备有限公司 | Preparation method of tris(trimethylsilyl)phosphite |
| 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 (1)
| 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 |
-
2014
- 2014-02-25 CN CN201410062968.7A patent/CN104860986A/en active Pending
Patent Citations (1)
| 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 |
Non-Patent Citations (1)
| 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》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106046046A (en) * | 2016-05-31 | 2016-10-26 | 镇江中化聚氨酯工业设备有限公司 | Preparation method of tris(trimethylsilyl)phosphite |
| 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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Application publication date: 20150826 |