CN102268039A - Preparation method of phosphonium salt - Google Patents
Preparation method of phosphonium salt Download PDFInfo
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- CN102268039A CN102268039A CN2010101881304A CN201010188130A CN102268039A CN 102268039 A CN102268039 A CN 102268039A CN 2010101881304 A CN2010101881304 A CN 2010101881304A CN 201010188130 A CN201010188130 A CN 201010188130A CN 102268039 A CN102268039 A CN 102268039A
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Abstract
The invention relates to a preparation method of a phosphonium salt, in particular relates to improvement of a preparation process of a phosphonium salt. The preparation method is characterized by comprising the following steps: carrying out a reaction on an alkane Grignard reagent and phosphorous trichloride so as to generate trialkyl phosphine; directly adding alkyl halide in the reaction in the former step without hydrolysis and separation so as to synthesize the phosphonium salt; and finally, separating and purifying by utilizing a principle that the phosphonium salt can be transferred in an organic phase and a water phase under a certain condition. Compared with the existing technology that the phosphonium salt is synthesized by a Grignard method, the hydrolysis step after trialkyl phosphine is synthesized is omitted in the preparation method provided by the invention, thereby simplifying the synthesis process, saving labor power and material resources and avoiding the side reaction and loss which are possibly brought by a middle operation so that the yield is improved; and the final yield is up to about 80%.
Description
Technical field
The present invention relates to improvement, further say so about improving the method for productive rate by simplifying the synthetic quaternary alkylphosphonium salt technology of Grignard, further reducing production costs to quaternary alkylphosphonium salt preparation technology.
Background technology
Quaternary alkylphosphonium salt can be used for solvent, sterilant, tensio-active agent, catalyzer and antistatic agent etc.
The method of at present synthetic quaternary alkylphosphonium salt mainly is to make (Journal of Moleculer Catalysis A:Chemical, 256 (1-2), 295-300 by trialkyl phosphine and the reaction of haloalkane direct heating; 2006).And the preparation of trialkyl phosphine can have diverse ways, has by alkene and phosphuret-(t)ed hydrogen to carry out addition reaction preparation (CN1069029), prepares by grignard reaction in addition.Patent CN200310100174 discloses from haloalkane, with the go forward side by side method of one-step synthesis quaternary alkylphosphonium salt of the synthetic trialkyl phosphine of Grignard.The deficiency that this method exists mainly be operate also more loaded down with trivial details, particularly behind the synthetic trialkyl phosphine of Grignard, need cooling, hydrolysis, separatory, this process one side's complex operation, the labor intensive material resources are on the other hand owing to trialkyl phosphine influences yield to the generation that can cause some side reactions unavoidably that increases of the susceptibility operation link of air.
Summary of the invention
Purpose of the present invention is exactly the deficiency at above technology, by simplifying synthesis technique, further reduces production costs, and improves productive rate.
The present invention adopts to generate behind the trialkyl phosphine without hydrolysis treatment and to separate by grignard reaction and directly adds the haloalkane reaction and synthesize quaternary alkylphosphonium salt, and the last quaternary alkylphosphonium salt that utilizes again can separate and purifies under certain condition in the principle that organic phase and aqueous phase shift.It is characterized in that method provided by the invention comprises the steps: (1) haloalkane and the synthetic Grignard reagent of MAGNESIUM METAL reaction; (2) generate trialkyl phosphine with adding the phosphorus trichloride reaction in the Grignard reagent; (3) trialkyl phosphine is synthesized quaternary alkylphosphonium salt with the haloalkane reaction again.Specifically:
Step (1) is under protection of inert gas, and in ether solvent, MAGNESIUM METAL and haloalkane reaction generate Grignard reagent under iodine causes;
Step (2) is added drop-wise to phosphorus trichloride and a kind of solvent in the Grignard reagent that is cooled to below 0 ℃, drips off the back intensification and steams ether, about 1～3 hour of time spent;
The above reaction solution of step (3) directly adds the haloalkane reflux without cooling and processing, and temperature was reacted 6～24 hours at 120 ℃～150 ℃, obtained product through aftertreatment.
The proportioning of the said reaction mass MAGNESIUM METAL of the present invention, haloalkane, phosphorus trichloride, ether and inert solvent is same as the prior art, and the condition that preparation Grignard reagent Ji Geshi reagent and phosphorus trichloride react is also with reference to prior art.
In the step of the present invention (1), said ether solvent can expand to ether, nearly all ether solvent such as tetrahydrofuran (THF).
In the step of the present invention (2), said a kind of solvent is high boiling point inert solvents such as dimethylbenzene.
In the step of the present invention (3), said post-treating method is that to utilize quaternary alkylphosphonium salt be a kind of not only close ester but also hydrophilic compound, can come isolating in the principle that organic phase and aqueous phase shift under the common-ion effcet effect.Specifically, at first will be in the reaction solution add the acidic solution hydrolysis, layering produces common-ion effcet because of containing a large amount of chlorions in the water layer, and product is insoluble substantially and enter organic layer in water layer, discards water layer.Add the distilled water extracted products in the organic layer again, extract organic layer with distilled water again, merge water, product is at water layer at this moment, and pressure reducing and steaming water obtains product.
Compare with the synthetic quaternary alkylphosphonium salt technology of existing Grignard, saved the step of the synthetic trialkyl phosphine posthydrolysis separatory of step (2), directly add the reaction that haloalkane synthesizes quaternary alkylphosphonium salt, so both simplified synthesis technique, save the man power and material, avoided the side reaction and the loss that may bring in the intermediary operation again, thereby than the productive rate of prior art about 70% by a relatively large margin raising has been arranged, ultimate yield can reach about 80%.
Embodiment
Embodiment 1
Under nitrogen protection; electronic stirring, thermometer are being housed; add 9 gram magnesium in the 1000mL four-hole bottle of constant pressure funnel and prolong respectively, 5.9 gram n-propylcarbinyl chloride and 100mL ether join 28.8 gram n-propylcarbinyl chlorides and 150mL dimethylbenzene in the dropping funnel again.Add an iodine in the four-hole bottle, add thermal initiation and stable back splash into n-propylcarbinyl chloride and dimethylbenzene gradually from dropping funnel mixed solution, heating also keeps reacting balance to carry out, approximately react two hours after, the magnesium chips primitive reaction is complete.Be cooled to below 0 ℃, begin to drip the mixed solution of 15.5 gram phosphorus trichlorides and 100mL dimethylbenzene and keep temperature of reaction below 0 ℃.Begin heat temperature raising after dripping off and simultaneously ether steamed, steam most of ether after temperature be elevated to gradually about 120 ℃, added 35 gram chloro-tetradecane back flow reaction this moment again 20 hours, temperature raises gradually and can reach about 140 ℃ between the reaction period.Reaction solution is cooled to below 40 ℃, slowly adds 5% dilute hydrochloric acid hydrolysis, and separatory keeps organic layer.Organic layer extracts three times with distilled water again, combining water layer, and pressure reducing and steaming water gets product, productive rate: 83.6%.
Embodiment 2
Under nitrogen protection; electronic stirring, thermometer are being housed; add 9 gram magnesium in the 1000mL four-hole bottle of constant pressure funnel and prolong respectively, 5.9 gram n-propylcarbinyl chloride and 100mL ether join 28.8 gram n-propylcarbinyl chlorides and 150mL dimethylbenzene in the dropping funnel again.Add an iodine in the four-hole bottle, add thermal initiation and stable back splash into n-propylcarbinyl chloride and dimethylbenzene gradually from dropping funnel mixed solution, heating also keeps reacting balance to carry out, approximately react two hours after, the magnesium chips primitive reaction is complete.Be cooled to below 0 ℃, begin to drip the mixed solution of 15.5 gram phosphorus trichlorides and 100mL dimethylbenzene and keep temperature of reaction below 0 ℃.Begin heat temperature raising after dripping off and simultaneously ether steamed, steam most of ether after temperature be elevated to gradually about 120 ℃, added 35 gram chloro-tetradecane back flow reaction this moment again 18 hours, temperature raises gradually and can reach about 140 ℃ between the reaction period.Reaction solution is cooled to below 40 ℃, slowly adds the aqueous ammonium chloride solution hydrolysis, and separatory keeps organic layer.Organic layer extracts three times with distilled water again, combining water layer, and pressure reducing and steaming water gets product, productive rate: 80.2%.
Embodiment 3
Under nitrogen protection; electronic stirring, thermometer are being housed; add 9 gram magnesium in the 1000mL four-hole bottle of constant pressure funnel and prolong respectively, 5.9 gram n-propylcarbinyl chloride and 100mL tetrahydrofuran (THF)s join 28.8 gram n-propylcarbinyl chlorides and 150mL dimethylbenzene in the dropping funnel again.Add an iodine in the four-hole bottle, add thermal initiation and stable back splash into n-propylcarbinyl chloride and dimethylbenzene gradually from dropping funnel mixed solution, heating also keeps reacting balance to carry out, approximately react two hours after, the magnesium chips primitive reaction is complete.Be cooled to below 0 ℃, begin to drip the mixed solution of 15.5 gram phosphorus trichlorides and 100mL dimethylbenzene and keep temperature of reaction below 0 ℃.Begin heat temperature raising after dripping off and simultaneously tetrahydrofuran (THF) steamed, steam most of tetrahydrofuran (THF) after temperature be elevated to gradually about 120 ℃, added 35 gram chloro-tetradecane back flow reaction this moment again 19 hours, temperature raises gradually and can reach about 140 ℃ between the reaction period.Reaction solution is cooled to below 40 ℃, slowly adds 5% dilute hydrochloric acid hydrolysis, and separatory keeps organic layer.Organic layer extracts three times with distilled water again, combining water layer, and pressure reducing and steaming water gets product, productive rate: 79.8%.
Claims (5)
1. the method for the synthetic quaternary alkylphosphonium salt of a Grignard, it is characterized in that by directly adding the synthetic quaternary alkylphosphonium salt of haloalkane reaction without hydrolysis treatment with separating behind the grignard reaction generation trialkyl phosphine, the last quaternary alkylphosphonium salt that utilizes again can separate and purifies under certain condition in the principle that organic phase and aqueous phase shift, and specifically comprises following three steps:
Step (1): under protection of inert gas, in ether solvent, MAGNESIUM METAL and haloalkane reaction generate Grignard reagent under iodine causes;
Step (2): with phosphorus trichloride and a kind of solvent, be added drop-wise in the Grignard reagent that is cooled to below 0 ℃, drip off the back intensification and steam ether, about 1～3 hour of time spent;
Step (3): above reaction solution directly adds the haloalkane reflux without cooling and processing, and temperature was reacted 6～24 hours at 120 ℃～150 ℃, obtained product through aftertreatment.
2. according to the method for claim 1, it is characterized in that said a kind of solvent can be high boiling point inert solvents such as dimethylbenzene in the step (2).
3. according to the method for claim 1, it is characterized in that said ether can be ether, tetrahydrofuran (THF) etc. in the step (2).
4. according to the method for claim 1, it is characterized in that said post-treating method is at first will to add the acidic solution hydrolysis in the reaction solution in the step (3), layering discards water layer.Use distilled water extracted products three times in the organic layer again, merge water, pressure reducing and steaming water obtains product.
5. according to the method for claim 4, it is characterized in that said acidic solution can be dilute hydrochloric acid, aqueous ammonium chloride solution etc. in the step (3).
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| CN201010188130.4A CN102268039B (en) | 2010-06-01 | 2010-06-01 | Preparation method of phosphonium salt |
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| CN201010188130.4A CN102268039B (en) | 2010-06-01 | 2010-06-01 | Preparation method of phosphonium salt |
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| CN102268039A true CN102268039A (en) | 2011-12-07 |
| CN102268039B CN102268039B (en) | 2014-05-21 |
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| CN201010188130.4A Expired - Fee Related CN102268039B (en) | 2010-06-01 | 2010-06-01 | Preparation method of phosphonium salt |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102702258A (en) * | 2012-06-21 | 2012-10-03 | 南开大学 | Water removal method for quaternary phosphonium salt aqueous solution |
| CN105189522A (en) * | 2013-01-17 | 2015-12-23 | 伊赛欧尼克公司 | Low symmetry molecules and phosphonium salts, methods of making and devices formed there from |
| CN105330691A (en) * | 2015-12-08 | 2016-02-17 | 山东维天精细化工科技有限公司 | Synthetic method for triethylphosphine |
| CN107098933A (en) * | 2017-03-16 | 2017-08-29 | 安徽至善新材料有限公司 | A kind of synthetic method of tri-n-butyl phosphine Lei quaternary alkylphosphonium salts |
| CN112142788A (en) * | 2019-06-27 | 2020-12-29 | 南京韦福化工技术有限公司 | Preparation method of tri-n-butylphosphonium |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1607203A (en) * | 2003-10-15 | 2005-04-20 | 北京联众大地科技有限公司 | Method for synthesizing phosphonium salt by three organo-phosphines and alkyl halide hydrocarbon |
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2010
- 2010-06-01 CN CN201010188130.4A patent/CN102268039B/en not_active Expired - Fee Related
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1607203A (en) * | 2003-10-15 | 2005-04-20 | 北京联众大地科技有限公司 | Method for synthesizing phosphonium salt by three organo-phosphines and alkyl halide hydrocarbon |
Non-Patent Citations (2)
| Title |
|---|
| 王乃绪等: "三(十二烷基)膦的合成", 《沈阳化工学院学报》 * |
| 范庆松等: "季鏻盐杀菌剂的合成新方法与杀菌特性研究", 《云南化工》 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102702258A (en) * | 2012-06-21 | 2012-10-03 | 南开大学 | Water removal method for quaternary phosphonium salt aqueous solution |
| CN105189522A (en) * | 2013-01-17 | 2015-12-23 | 伊赛欧尼克公司 | Low symmetry molecules and phosphonium salts, methods of making and devices formed there from |
| CN105330691A (en) * | 2015-12-08 | 2016-02-17 | 山东维天精细化工科技有限公司 | Synthetic method for triethylphosphine |
| CN107098933A (en) * | 2017-03-16 | 2017-08-29 | 安徽至善新材料有限公司 | A kind of synthetic method of tri-n-butyl phosphine Lei quaternary alkylphosphonium salts |
| CN112142788A (en) * | 2019-06-27 | 2020-12-29 | 南京韦福化工技术有限公司 | Preparation method of tri-n-butylphosphonium |
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| CN102268039B (en) | 2014-05-21 |
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