CN102911205A - Method for preparing diisopropyl phosphonium chloride - Google Patents
Method for preparing diisopropyl phosphonium chloride Download PDFInfo
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- CN102911205A CN102911205A CN2012103923033A CN201210392303A CN102911205A CN 102911205 A CN102911205 A CN 102911205A CN 2012103923033 A CN2012103923033 A CN 2012103923033A CN 201210392303 A CN201210392303 A CN 201210392303A CN 102911205 A CN102911205 A CN 102911205A
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- Prior art keywords
- methyltetrahydrofuran
- phosphonium chloride
- isopropyl
- magnesium
- chloride
- Prior art date
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Abstract
The invention discloses a method for preparing diisopropyl phosphonium chloride. The method includes preparing diisopropyl phosphonium chloride by Grignard reagent and then synthetizing by taking isopropyl chloride, magnesium and phosphorus trichloride as raw materials, taking iodine as an initiator and taking 2-methyltetrahydrofuran as a solvent. The method has the advantages of reaction yield is high, purity of products is high, the reaction process is safe, the recovery rate of the solvent is high, and fewer pollutants are produced in reaction.
Description
Technical field
The present invention relates to the preparation method of di-isopropyl phosphonium chloride.
Background technology
The di-isopropyl phosphonium chloride is the important organic intermediate of preparation organic phosphine, be widely used in preparation organic phosphine sterilant, organic phosphine coordination body, the synthetic organo-metallic catalyst of thermoplastic elastomer, also can make the important component part of non-lethal weapon, it is used to synthesizing lithium ion secondary cell novel electrolytes salt fluoro-alkyl phosphonic acids lithium in recent years.
The method of synthetic di-isopropyl phosphonium chloride has a lot, mainly comprises metal deoxidization, phosgene reaction method, Grignard reagent synthesis method and yellow phosphorus reaction method.At present the Grignard reagent synthesis method is take chloroisopropane, magnesium and phosphorus trichloride as raw material, take ether or tetrahydrofuran (THF) as the synthetic di-isopropyl phosphonium chloride of solvent.
Preparation process comprises following reaction:
Mg+i-C
3H
7Cl→i-C
3H
7MgCl
2i-C
3H
7MgCl+PCl
3→(i-C
3H
7)
2PCl+2MgCl
2
Simple take ether as solvent method, raw material is inexpensive, and productive rate is higher, can arrive 55%～60%, but the ether boiling point is low, and is volatile, and danger is large and be unfavorable for preserving product, and the magnesium chloride of generation is difficult to suction filtration, should not be used for scale operation.The people such as Wang Fenghua. the research of the Synthesis of Chlorodiisopropylphosphine [J]. the Shandong chemical industry, 2007,36 (2): 32-35 discloses the method for the synthetic chloro diisopropyl phosphine of Grignard reagent method take tetrahydrofuran (THF) as solvent, the highest yield of mixture reaches 71.25%, but single substitution product by-products content is high, target product is 2.63 with single mol ratio that replaces by product: 1-6.85: 1, and the highest yield of converting as target product is 65.18%, product purity is not high.
Summary of the invention
The technical problem to be solved in the present invention provides a kind of preparation method of di-isopropyl phosphonium chloride.
The present invention goes out to adopt the standby di-isopropyl phosphonium chloride of Grignard reagent legal system, take chloroisopropane, magnesium and phosphorus trichloride as raw material, take iodine as initiator, the 2-methyltetrahydrofuran synthesizes as solvent.Reaction yield of the present invention is high, and product purity is high, and process is safer, and the recycled solvent rate is high, and the pollutent of generation is few.
The inventive method may further comprise the steps:
(1) synthetic chloro isopropyl-magnesium
A) by vacuumize, the method for nitrogen replacement removes the air in the reactor;
B) chloroisopropane and 2-methyltetrahydrofuran are with volume ratio 1: 2-1: 3 mix;
C) theoretical molar being counted 1.1-1.3 magnesium doubly adds in the reactor, add an amount of 2-methyltetrahydrofuran submergence magnesium grain, the grain iodine that adds amount of initiator, heating systems, when treating that temperature is increased to 60-80 ℃, add chloroisopropane and the 2-methyltetrahydrofuran mixed solution of cumulative volume 1%-5%, after question response causes, drip chloroisopropane and the 2-methyltetrahydrofuran mixed solution of residual content, be advisable with the reaction system slight boiling condition; Dropwise rear continuation and stir 0.5-2h, namely get the isopropylmagnesium chloride Grignard reagent, be transferred in the volumetric flask for subsequent use;
(2) synthetic di-isopropyl phosphonium chloride
A) be 1 with phosphorus trichloride and 2-methyltetrahydrofuran volume ratio: 5-1: 10 (are preferably 1: 6-1: in the mixed solution adding reactor 8), system is lowered the temperature, when treating that temperature is down to-40～-20 ℃ (being preferably-30～-20 ℃), drip the isopropylmagnesium chloride Grignard reagent of theoretical amount to system, dropwise, continue stirring reaction 0.5-2h;
B) reaction mixture is at N
2The lower suction filtration of protection, to white, filtrate is the mixed solution of di-isopropyl phosphonium chloride and 2-methyltetrahydrofuran with 2-methyltetrahydrofuran flush cake; Filter cake is that the magnesium chloride crystal is recyclable;
D) separating filtrate gets di-isopropyl phosphonium chloride product, reclaims the 2-methyltetrahydrofuran.
The present invention is take magnesium, chloroisopropane, phosphorus trichloride as main raw material, and iodine is initiator, prepares the di-isopropyl phosphonium chloride take the 2-methyltetrahydrofuran as solvent, target product and single mol ratio height that replaces by product, and product yield is high, purity is high.The 2-methyltetrahydrofuran is higher than the boiling point of ether, and reaction process is safer, generates the solid by-product magnesium chloride, is convenient to suction filtration; Than tetrahydrofuran solvent, single replacement by product dichloro-sec.-propyl phosphine content is few, and product purity is higher, and the recycled solvent rate is high, and the pollutent of generation is few.The present invention had both improved the security of reaction, had also improved productive rate and the purity of di-isopropyl phosphonium chloride.
Embodiment
The invention will be further described below in conjunction with embodiment.
Embodiment 1
(1) synthetic chloro isopropyl-magnesium
Join in the constant pressure funnel after 500mL chloroisopropane and 1400mL2-methyltetrahydrofuran mixed, take by weighing 146.37g magnesium and join in the four-hole boiling flask, add 3g iodine and 100mL2-methyltetrahydrofuran submergence magnesium grain.
System temperature is raised to 80 ℃, drips the mixed solution of 50mL chloroisopropane and 2-methyltetrahydrofuran, begin to stir, treat that liquid color bleaches in the flask, during little boiling, show that reaction causes.Then slowly drip remaining chloroisopropane and 2-methyltetrahydrofuran mixed solution, the control rate of addition is that slight boiling condition is advisable, and continues after dropwising to stir 1h again, and stopped heating is cooled to room temperature, pours in the volumetric flask.Adopting the transformation efficiency (with respect to chloroisopropane) of the method mensuration isopropylmagnesium chloride Grignard reagent of acid base titration is 96.2%.
(2) synthetic di-isopropyl phosphonium chloride
To insert in the glycol/water cryostat pot with the four-hole boiling flask of thermometer, constant pressure funnel, and use liquid nitrogen as cooling fluid in the condensing coil, insert stirring rod, vacuumize, inflated with nitrogen displacement 2 times.Then add flatly nitrogen protection at four-hole bottle.
Get the 230mL phosphorus trichloride and the 1610mL2-methyltetrahydrofuran is added in the four-hole bottle by material hole, logical liquid nitrogen cooling is to-30 ℃.Mixing speed is 180r/min, drips isopropylmagnesium chloride Grignard reagent 1848g, and the control rate of addition makes temperature of reaction be controlled at-30～-25 ℃, and 3.5h dropwises, and withdraws the cryostat pot, continues to stir 1h.Suction filtration under the nitrogen protection, reaction mixture is at N
2Suction filtration under the protection is white to crystal color repeatedly with the flushing of 2-methyltetrahydrofuran, and filtrate is the mixed solution of di-isopropyl phosphonium chloride and 2-methyltetrahydrofuran, and target product is 57.12: 1 with single replacement by product mol ratio.
It is the water distilling apparatus of the 30mm*300mm fractional column of glass spring that filler is installed, the mixed solution of di-isopropyl phosphonium chloride and 2-methyltetrahydrofuran is heated to 80 ℃, reclaiming 2-methyl tetrahydrochysene furan solvent mutters, accept 150 ℃ of later cuts, obtain product di-isopropyl phosphonium chloride 298.5g, productive rate is 74.3%, and purity is 96.5%.Recovered solvent 2-methyltetrahydrofuran further distills, and can be recycled.
Embodiment 2
(1) synthetic chloro isopropyl-magnesium
Join in the constant pressure funnel after 500mL chloroisopropane and 1000mL2-methyltetrahydrofuran mixed, take by weighing 172.98g magnesium and join in the four-hole boiling flask, add 3g iodine and 120mL2-methyltetrahydrofuran submergence magnesium grain.
Drip the mixed solution of 16mL chloroisopropane and 2-methyltetrahydrofuran, initiation reaction continues after chloroisopropane and 2-methyltetrahydrofuran mixed solution dropwise to stir 2h again, and other are with embodiment 1.
The transformation efficiency of isopropylmagnesium chloride Grignard reagent is 97%.
(2) synthetic di-isopropyl phosphonium chloride
The 2-methyltetrahydrofuran drips isopropylmagnesium chloride Grignard reagent 1523g with being that the 1150mL temperature of reaction is controlled at-40～-35 ℃, dropwises, and withdraws the cryostat pot, continues to stir 2h.
Target product is 51.32: 1 with single replacement by product mol ratio, gets product 289.7g, product yield 71.5%, purity 96.2%.
Other are with embodiment 1.
Embodiment 3
(1) synthetic chloro isopropyl-magnesium
Drip the mixed solution of 100mL chloroisopropane and 2-methyltetrahydrofuran, initiation reaction continues after chloroisopropane and 2-methyltetrahydrofuran mixed solution dropwise to stir 0.5h again, and other are with embodiment 1.
The transformation efficiency of isopropylmagnesium chloride Grignard reagent is 95.5%.
(2) synthetic di-isopropyl phosphonium chloride
The 2-methyltetrahydrofuran is with being 2300mL.Temperature of reaction is controlled at-25～-20 ℃, drips isopropylmagnesium chloride Grignard reagent 1847g, dropwises, and withdraws the cryostat pot, continues to stir 0.5h.
Target product with single replace the by product mol ratio be 44.28: 1 product 262.5g, product yield 65.8%, purity 95.1%.
Other are with embodiment 1.
Claims (3)
1. method for preparing the di-isopropyl phosphonium chloride adopts the standby di-isopropyl phosphonium chloride of Grignard reagent legal system, take chloroisopropane, magnesium and phosphorus trichloride as raw material, it is characterized in that take iodine as initiator, the 2-methyltetrahydrofuran synthesizes as solvent.
2. the method for preparing the di-isopropyl phosphonium chloride according to claim 1 may further comprise the steps:
(1) synthetic chloro isopropyl-magnesium
A) by vacuumize, the method for nitrogen replacement removes the air in the reactor;
B) chloroisopropane and 2-methyltetrahydrofuran are with volume ratio 1: 2-1: 3 mix;
C) theoretical molar being counted 1.1-1.3 magnesium doubly adds in the reactor, add an amount of 2-methyltetrahydrofuran submergence magnesium grain, the grain iodine that adds amount of initiator, heating systems, when treating that temperature is increased to 60-80 ℃, add chloroisopropane and the 2-methyltetrahydrofuran mixed solution of cumulative volume 1%-5%, after question response causes, drip chloroisopropane and the 2-methyltetrahydrofuran mixed solution of residual content, be advisable with the reaction system slight boiling condition; Dropwise rear continuation and stir 0.5-2h, namely get the isopropylmagnesium chloride Grignard reagent, be transferred in the volumetric flask for subsequent use;
(2) synthetic di-isopropyl phosphonium chloride
A) be 1 with phosphorus trichloride and 2-methyltetrahydrofuran volume ratio: 5-1: 10 mixed solution adds in the reactor, with the system cooling, when treating that temperature is down to-40～-20 ℃, drip the isopropylmagnesium chloride Grignard reagent to system, dropwise, continue stirring reaction 0.5-2h;
B) reaction mixture suction filtration under the N2 protection, to white, filtrate is the mixed solution of di-isopropyl phosphonium chloride and 2-methyltetrahydrofuran with 2-methyltetrahydrofuran flush cake; Filter cake is that the magnesium chloride crystal is recyclable;
D) separating filtrate gets di-isopropyl phosphonium chloride product.
3. the method for preparing the di-isopropyl phosphonium chloride according to claim 2 is characterized in that phosphorus trichloride and 2-methyltetrahydrofuran volume ratio are for being 1: 6-1: 8, and the temperature that drips the isopropylmagnesium chloride Grignard reagent is-30～-20 ℃; The method of separating filtrate is distillation method, accepts 150 ℃ of later cuts.
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| CN2012103923033A CN102911205A (en) | 2012-09-28 | 2012-09-28 | Method for preparing diisopropyl phosphonium chloride |
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| CN2012103923033A CN102911205A (en) | 2012-09-28 | 2012-09-28 | Method for preparing diisopropyl phosphonium chloride |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1628122A (en) * | 2002-02-04 | 2005-06-15 | 北兴化学工业株式会社 | Process for producing tertiary phosphine having bulky hydrocarbon group bonded |
| CN1724548A (en) * | 2005-07-05 | 2006-01-25 | 南开大学 | Synthesis method of chloro diisopropyl phosphine |
| CN101704833A (en) * | 2009-11-16 | 2010-05-12 | 中唯炼焦技术国家工程研究中心有限责任公司 | Method for preparing trimethylsilyl acetylene |
-
2012
- 2012-09-28 CN CN2012103923033A patent/CN102911205A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1628122A (en) * | 2002-02-04 | 2005-06-15 | 北兴化学工业株式会社 | Process for producing tertiary phosphine having bulky hydrocarbon group bonded |
| CN1724548A (en) * | 2005-07-05 | 2006-01-25 | 南开大学 | Synthesis method of chloro diisopropyl phosphine |
| CN101704833A (en) * | 2009-11-16 | 2010-05-12 | 中唯炼焦技术国家工程研究中心有限责任公司 | Method for preparing trimethylsilyl acetylene |
Non-Patent Citations (2)
| Title |
|---|
| 王风花等: "氯代二异丙基膦合成工艺的研究", 《山东化工》, vol. 39, no. 2, 15 February 2007 (2007-02-15), pages 35 - 37 * |
| 郑睿等: "新型溶剂2-甲基四氢呋喃的合成和应用研究进展", 《精细化工中间体》, vol. 39, no. 2, 30 April 2009 (2009-04-30) * |
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Application publication date: 20130206 |