CN102875596B - Preparation method of tricyclohexyl phosphine - Google Patents
Preparation method of tricyclohexyl phosphine Download PDFInfo
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- CN102875596B CN102875596B CN201210399055.5A CN201210399055A CN102875596B CN 102875596 B CN102875596 B CN 102875596B CN 201210399055 A CN201210399055 A CN 201210399055A CN 102875596 B CN102875596 B CN 102875596B
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- 0 *C1CCCCC1 Chemical compound *C1CCCCC1 0.000 description 1
- SQDGPLNZHYWEOB-UHFFFAOYSA-N C(CC1)CCC1C(C1CCCCC1)C1CCCCC1 Chemical compound C(CC1)CCC1C(C1CCCCC1)C1CCCCC1 SQDGPLNZHYWEOB-UHFFFAOYSA-N 0.000 description 1
- WLPUWLXVBWGYMZ-UHFFFAOYSA-N C(CC1)CCC1P(C1CCCCC1)C1CCCCC1 Chemical compound C(CC1)CCC1P(C1CCCCC1)C1CCCCC1 WLPUWLXVBWGYMZ-UHFFFAOYSA-N 0.000 description 1
- UAEPNZWRGJTJPN-UHFFFAOYSA-N CC1CCCCC1 Chemical compound CC1CCCCC1 UAEPNZWRGJTJPN-UHFFFAOYSA-N 0.000 description 1
Abstract
The invention relates to a preparation method of tricyclohexyl phosphine, which comprises the following steps: reacting a cyclohexyl Grignard reagent and phosphorus trihalide, dropwisely adding a saturated strongly-acidic weakly-alkaline inorganic salt water solution at low temperature to carry out quenching, adding tetrafluoroboric acid to prepare a salt, and resolving the salt with triethylamine to obtain the tricyclohexyl phosphine, wherein the cyclohexyl Grignard reagent is prepared by carrying out Grignard reaction on halogenated cyclohexane and magnesium metal under inert gas shielding. According to the invention, the product is subjected to after-treatment by a chemical process; the tetrafluoroboric acid firstly reacts with tricyclohexyl phosphine to form a salt to completely extract the tricyclohexyl phosphine from the reaction solution, and the salt is resolved with the triethylamine. The invention has very obvious beneficial effects, and greatly enhances the preparation yield; and the prepared product has the advantages of high purity, high quality and low preparation cost.
Description
Technical field
The present invention relates to a kind of preparation method of tricyclohexyl phosphine, belong to technical field of organic synthesis.
Background technology
Tricyclohexyl phosphine plays wide application in modern organic synthesis and practical application, it is used for Buchwald mainly as part, in the linked reactions such as Suzuki, have in the synthesis of the materials such as organic catalyst, transition metal compound catalizer, sun-screening agent, light functional complexes and apply very widely.In the synthesis of these materials, tricyclohexyl phosphine is especially needed to have higher purity and good quality.
Up to now, in order to obtain the tricyclohexyl phosphine of high purity, high yield, the preparation scheme that there has been proposed many tricyclohexyl phosphines is attempted.Have bibliographical information cyclohexyl grignard reagent and phosphorus trichloride to react, after having reacted, low temperature drips aqueous ammonium chloride solution, and by extracted with diethyl ether, concentrated, underpressure distillation, obtains white crystal.It is relatively stable that this route respectively walks reaction, controls than being easier to, but drawback to be aftertreatment cumbersome, due to tricyclohexyl phosphine extremely unstable in atmosphere, be easily oxidized, therefore product can not extract completely, thus causing productive rate lower, product purity is low, poor quality.
Also useful bibliographical information cyclohexyl grignard reagent and phosphorus trichloride react, and after having reacted, low temperature drips aqueous ammonium chloride solution, by extracted with diethyl ether, concentrates half, adds CS
2solid is separated out, after dissolve with ethanol, and concentrating under reduced pressure.The method aftertreatment is more complicated, and still there is the problems such as product yield is low, product purity is not high.
Therefore, that how to improve tricyclohexyl phosphine prepares productive rate, improves product purity, improves product quality, become one of tricyclohexyl phosphine preparation field technical problem urgently to be resolved hurrily.
Summary of the invention
The object of this invention is to provide a kind of preparation method of tricyclohexyl phosphine, the method chemically carries out aftertreatment to product, first react salify with Tetrafluoroboric acid and tricyclohexyl phosphine, tricyclohexyl phosphine is extracted completely from reaction solution, again with triethylamine solution salt, significantly can improve and prepare productive rate, and the product purity prepared is high, quality better, preparation cost is cheap.
The invention provides a kind of preparation method of tricyclohexyl phosphine, comprise: react with cyclohexyl Grignard reagent and phosphorus trihalide, drip after saturated strong acid weak base inorganic salt solution carries out cancellation under low temperature, add Tetrafluoroboric acid and make salt, then obtain tricyclohexyl phosphine with triethylamine solution salt.
According to a concrete but nonrestrictive embodiment of the present invention, cyclohexyl Grignard reagent is by cyclohexane halide under protection of inert gas, carries out grignard reaction in organic solvent prepare with MAGNESIUM METAL.
According to a concrete but nonrestrictive embodiment of the present invention, cyclohexane halide is chlorocyclohexane or bromocyclohexane.
According to a concrete but nonrestrictive embodiment of the present invention, phosphorus trihalide is phosphorus trichloride or phosphorus tribromide.
According to a concrete but nonrestrictive embodiment of the present invention, the mol ratio of cyclohexane halide and phosphorus trihalide is 1:0.2-0.36.
According to a concrete but nonrestrictive embodiment of the present invention, strong acid weak base inorganic salt are one or more in ammonium chloride, ammonium sulfate or ammonium nitrate.
According to a concrete but nonrestrictive embodiment of the present invention, the preparation method of tricyclohexyl phosphine comprises the following steps successively:
Under protection of inert gas, in reaction vessel, add magnesium chips and organic solvent, drip cyclohexane halide solution at 50-65 DEG C, at 30-70 DEG C of insulation 8-16 hour;
Reacting liquid temperature is down to 0-20 DEG C, and drip phosphorus trihalide solution, temperature controls at 10-35 DEG C, afterwards at 40-50 DEG C of insulation 0.5-3 hour;
In ice-water bath downhill reaction liquid, drip saturated strong acid weak base inorganic salt solution clarify to reaction solution, hold over night;
Under anhydrous and oxygen-free environment, transferred to by supernatant liquid and be added with in the reaction vessel of Tetrafluoroboric acid, under protection of inert gas, stir 20-60 minute, except desolventizing, add water solid and separate out, washing, obtains off-white color tricyclohexyl phosphine a tetrafluoro borate;
Tricyclohexyl phosphine a tetrafluoro borate is loaded in another reaction vessel, adds methyl alcohol or alcohol solvent, drip triethylamine, after dropwising at-50 ~-30 DEG C, be heated to reaction solution clarification, be down to room temperature, separate out solid, filter under anhydrous and oxygen-free environment, vacuum-drying, obtain tricyclohexyl phosphine.
According to a concrete but nonrestrictive embodiment of the present invention, the holding temperature of grignard reaction controls at 45-65 DEG C, and soaking time controls at 12-16 hour.
According to a concrete but nonrestrictive embodiment of the present invention, the soaking time dripped after phosphorus trihalide controls at 1-2 hour.
According to a concrete but nonrestrictive embodiment of the present invention, the organic solvent of grignard reaction is anhydrous tetrahydro furan or anhydrous methyl tetrahydrofuran (THF); Cyclohexane halide solution and phosphorus trihalide solution are their anhydrous tetrahydro furan or anhydrous methyl tetrahydrofuran solution respectively.
Beneficial effect of the present invention is mainly reflected in:
The present invention is directed to reaction product tricyclohexyl phosphine extremely unstable in atmosphere, easy oxidation, the feature of aftertreatment difficulty, use chemical process instead and aftertreatment is carried out to product, with Tetrafluoroboric acid and tricyclohexyl phosphine salify, tricyclohexyl phosphine is extracted completely from reaction solution, after Ficus caricaL is good, again with triethylamine solution salt, thus obtain high quality, high yield, highly purified tricyclohexyl phosphine product.
Preparation method of the present invention, relatively simple to product postprocessing, thus preparation cost is cheaper.
The present invention is because of reaction conditions gentleness, therefore operational safety.
Accompanying drawing explanation
Fig. 1 is tricyclohexyl phosphine a tetrafluoro borate
1h-NMR.
Fig. 2 is tricyclohexyl phosphine a tetrafluoro borate
31p-NMR.
Embodiment
Provided hereinafter concrete embodiment and further illustrate the present invention, but the present invention is not limited only to following embodiment.
The present inventor finds in long-term tricyclohexyl phosphine preparation research, due to tricyclohexyl phosphine extremely unstable in atmosphere, be easy to oxidized, if adopt conventional extraction purification method to carry out aftertreatment, tricyclohexyl phosphine can lose major part at last handling process, thus causes low yield.And the present inventor gropes through long-term experiment, studies discovery, react further with Tetrafluoroboric acid and product tricyclohexyl phosphine and make salt, after its Ficus caricaL is good, again with triethylamine solution salt, tricyclohexyl phosphine in last handling process can be avoided frequently to contact with air, be oxidized, decrease the trouble of aftertreatment.Contriver's years of researches result shows, selects triethylamine solution salt, and solution salt effect is very good, and the tricyclohexyl phosphine obtained is pure white crystal, and quality is very good, and purity is very high.The post-treating method of this salt adding, solution salt, can make productive rate significantly promote.
The present invention take cyclohexane halide as starting raw material, after making cyclohexyl grignard reagent, react with phosphorus trihalide, drip after saturated strong acid weak base inorganic salt solution carries out cancellation under low temperature, add Tetrafluoroboric acid and make salt, then obtain tricyclohexyl phosphine with triethylamine solution salt.Concrete synthetic route is as follows:
Wherein, starting halo hexanaphthene preferably uses chlorocyclohexane or bromocyclohexane, and phosphorus trihalide preferably uses phosphorus trichloride or phosphorus tribromide.The mol ratio of cyclohexane halide and phosphorus trihalide can be 1:0.2-0.36, preferred 1:0.28-0.33.
Below each reactions steps is described in detail.
1. the preparation of cyclohexyl Grignard reagent
Under rare gas element such as nitrogen protection, in reaction vessel, add magnesium chips and organic solvent as anhydrous tetrahydro furan (THF) or anhydrous methyl tetrahydrofuran (THF), magnesium chips is excessive a little, organic solvent submergence magnesium chips.Add several iodine grains, start mechanical stirring, at the 50-65 DEG C of organic solvent solution adding cyclohexane halide as anhydrous THF or anhydrous methyl tetrahydrofuran solution, first drip a small amount of, after causing grignard reaction, then drip, temperature maintains about 50-65 DEG C, after dropwising, and carries out being incubated and stirring.Reaction holding temperature controls at 30-70 DEG C, and preferred 45-65 DEG C, soaking time controls at 8-16 hour, preferred 12-16 hour.
2. the preparation of tricyclohexyl phosphine
Reacting liquid temperature is down to 0-20 DEG C, and drip the organic solvent solution of phosphorus trihalide as anhydrous tetrahydro furan or methyltetrahydrofuran solution, temperature controls at 10-35 DEG C, after dropwising, and 40-50 DEG C of insulation 0.5-3 hour, preferred 1-2 hour.
3. cancellation
Reaction solution is down to room temperature, drips saturated strong acid weak base inorganic salt solution under ice-water bath and clarify to reaction solution, hold over night.
Strong acid weak base inorganic salt solution can be ammonium chloride, ammonium sulfate or aqueous ammonium nitrate solution etc., and their aqueous solution shows slightly acidic, plays cancellation effect.Reaction solution drips saturated strong acid weak base inorganic salt solution and clarifies to reaction solution, layering, and form the organic matter layer on upper strata and the aqueous layer of lower floor, product tricyclohexyl phosphine is then in supernatant.
4. salt-forming reaction
By reaction flask at the middle and upper levels clear liquid transfer under anhydrous and oxygen-free condition in another reaction vessel, add Tetrafluoroboric acid in advance in this reaction vessel and be replaced as rare gas element as nitrogen atmosphere by biexhaust pipe, the amount of Tetrafluoroboric acid should ensure that tricyclohexyl phosphine in solution can salify completely, after transfer, stirs 20-60 minute, make salt-forming reaction complete, removal of solvent under reduced pressure, adds water solid and separates out, solid washed with water 1-3 time, PE washes 1-2 time, filters and obtains off-white color tricyclohexyl phosphine a tetrafluoro borate.
5. separate reactant salt
Tricyclohexyl phosphine a tetrafluoro borate is loaded in another reaction vessel, add methyl alcohol or alcohol solvent, drip excessive triethylamine at-50 ~-30 DEG C, tricyclohexyl phosphine all solutions is separated out, after dropwising, be heated to reaction solution clarification, be down to room temperature, have solid to separate out, as filtered in bag glove under anhydrous and oxygen-free environment, vacuum-drying, obtains white crystal tricyclohexyl phosphine.
Above raw material all can be bought by commercially available approach and obtain.
By several specific embodiment, the present invention will be further described below.But following embodiment should not be construed as the concrete restriction to scope.
Embodiment one
Reaction flask is replaced as nitrogen atmosphere, adds 12.8g analytical pure magnesium chips and anhydrous THF, THF submergence magnesium chips.Add 1-2 grain iodine grain, start mechanical stirring, add the anhydrous THF solution 200mL of 59.3g analytical pure chlorocyclohexane at 60 DEG C, stop dripping after first dripping 20mL, after causing grignard reaction, then drip, temperature maintains 60 DEG C, after dropwising, and stirs 12 hours at 45 DEG C.
Reacting liquid temperature is down to 15 DEG C, drips 22g analytical pure PCl
3anhydrous THF solution 150mL, temperature controls at 25 DEG C, after dropwising, 45 DEG C insulation 1 hour.
Be down to room temperature again, under ice-water bath, drip saturated NH
4the Cl aqueous solution is clarified to reaction solution, hold over night.
By reaction flask at the middle and upper levels clear liquid be transferred in 500mL reaction flask by stainless steel pipe, add 70mL Tetrafluoroboric acid (concentration 40%) in this reaction flask in advance and be replaced as nitrogen atmosphere by biexhaust pipe, after transfer, stir 30 minutes, removal of solvent under reduced pressure, the solid that added water is separated out, solid washed with water 2 times, PE washes 1 time, filters, obtains off-white color tricyclohexyl phosphine a tetrafluoro borate.
Tricyclohexyl phosphine a tetrafluoro borate is loaded in 500mL reaction flask, adds methanol solvate 350mL, drip 50mL analytical pure triethylamine at-40 DEG C, after dropwising, be heated to reaction solution clarification, be down to room temperature, have solid to separate out.Filter in bag glove, vacuum-drying, obtain white crystal tricyclohexyl phosphine 38g, calculated yield is 84.6%, and obtaining product purity by XY-1A intelligence elemental analyser is 99.3%.
Because tricyclohexyl phosphine is very easily oxidized, be inconvenient to detection of setting the chessman on the chessboard according to the chess manual, therefore characterize its intermediate tricyclohexyl phosphine a tetrafluoro borate, as shown in Figure 1 and Figure 2, characterization result is as follows:
300MHz-
1H-NMR（CDCl3）：δ=1.2-1.5(m,9H);1.5-1.7(m,6H);1.7-1.85(M,3H);1.85-2.0(m,6H);2.0-2.1(m,6H);2.46-2.51(m,3H);5.85(dd,1H,
1J=474Hz)。
120MHz-
31P-NMR(CDCl
3):δ=28.2。
Embodiment two
Reaction flask is replaced as nitrogen atmosphere, adds 12.8g analytical pure magnesium chips and anhydrous THF, THF submergence magnesium chips.Add 1-2 grain iodine grain, start mechanical stirring, add the anhydrous THF solution 200mL of 59.3g analytical pure chlorocyclohexane at 60 DEG C, stop dripping after first dripping 20mL, after causing grignard reaction, then drip, temperature maintains 60 DEG C, after dropwising, and stirs 16 hours at 60 DEG C.
Reacting liquid temperature is down to 15 DEG C, drips 22g analytical pure PCl
3anhydrous THF solution 150mL, temperature controls at 25 DEG C, after dropwising, 40 DEG C insulation 2 hours.
Be down to room temperature again, under ice-water bath, drip saturated NH
4the Cl aqueous solution is clarified to reaction solution, hold over night.
By reaction flask at the middle and upper levels clear liquid be transferred in 500mL reaction flask by stainless steel pipe, add 70mL Tetrafluoroboric acid (concentration 40%) in this reaction flask in advance and be replaced as nitrogen atmosphere by biexhaust pipe, after transfer, stir 30 minutes, removal of solvent under reduced pressure, the solid that added water is separated out, solid washed with water 2 times, PE washes 1 time, filters, obtains off-white color tricyclohexyl phosphine a tetrafluoro borate.
Tricyclohexyl phosphine a tetrafluoro borate is loaded in 500mL reaction flask, adds alcohol solvent 350mL, drip 50mL analytical pure triethylamine at-40 DEG C, after dropwising, be heated to reaction solution clarification, be down to room temperature, have solid to separate out.Filter in bag glove, vacuum-drying, obtain white crystal tricyclohexyl phosphine 38.2g, calculated yield is 85%, and obtaining product purity by XY-1A intelligence elemental analyser is 99.5%.
Embodiment three
Reaction flask is replaced as nitrogen atmosphere, adds 195g analytical pure magnesium chips and anhydrous THF, THF submergence magnesium chips.Add 4-5 grain iodine grain, start mechanical stirring, add the anhydrous THF solution 3000mL of 950g analytical pure chlorocyclohexane by separating funnel at 60 DEG C in batches, stop dripping after first dripping 120mL, after causing grignard reaction, then drip, temperature maintains 60 DEG C, after dropwising, stir 14 hours at 50 DEG C.
Reacting liquid temperature is down to 20 DEG C, drips 352g analytical pure PCl
3anhydrous THF solution 800mL, temperature controls at 30 DEG C, after dropwising, 45 DEG C insulation 1 hour.
Be down to room temperature again, under ice-water bath, drip saturated NH
4nO
3the aqueous solution is clarified to reaction solution, hold over night.
By reaction flask at the middle and upper levels clear liquid be transferred in 10L reaction flask by stainless steel pipe, add 960mL Tetrafluoroboric acid (concentration 40%) in this reaction flask in advance and be replaced as nitrogen atmosphere by biexhaust pipe, after transfer, stir 30 minutes, removal of solvent under reduced pressure, the solid that added water is separated out, solid washed with water 2 times, PE washes 1 time, filters, obtains off-white color tricyclohexyl phosphine a tetrafluoro borate.
Tricyclohexyl phosphine a tetrafluoro borate is loaded in 10L reaction flask, adds methanol solvate 6000mL, drip 640mL analytical pure triethylamine at-25 DEG C, after dropwising, be heated to reaction solution clarification, be down to room temperature, have solid to separate out.Filter in bag glove, vacuum-drying, obtain white crystal tricyclohexyl phosphine 600g, calculated yield is 83.5%, and obtaining product purity by XY-1A intelligence elemental analyser is 99.4%.
Embodiment four
Reaction flask is replaced as nitrogen atmosphere, add 160g analytical pure magnesium chips and anhydrous THF, add 4-5 grain iodine grain, start mechanical stirring, add the anhydrous THF solution 3000mL of 741g analytical pure chlorocyclohexane at about 60 DEG C by separating funnel in batches, stop dripping after first dripping 120mL, after causing grignard reaction, then drip, temperature maintains about 60 DEG C, after dropwising, stir 16 hours at 50 DEG C.
Reacting liquid temperature is down to 10 DEG C, drips 542g analytical pure PBr
3anhydrous THF solution 700mL, temperature controls at 20 DEG C, after dropwising, 45 DEG C insulation 2 hours.
Be down to room temperature again, under ice-water bath, drip saturated NH
4nO
3the aqueous solution is clarified to reaction solution, hold over night.
By reaction flask at the middle and upper levels clear liquid be transferred in 10L reaction flask by stainless steel pipe, add 750mL Tetrafluoroboric acid (concentration 40%) in this reaction flask in advance and be replaced as nitrogen atmosphere by biexhaust pipe, after transfer, stir 30 minutes, removal of solvent under reduced pressure, the solid that added water is separated out, solid washed with water 2 times, PE washes 1 time, filters, obtains off-white color tricyclohexyl phosphine a tetrafluoro borate.
Tricyclohexyl phosphine a tetrafluoro borate is loaded in 10L reaction flask, adds alcohol solvent 5000mL, drip 500mL analytical pure triethylamine at-40 DEG C, after dropwising, be heated to reaction solution clarification, be down to room temperature, have solid to separate out.Filter in bag glove, vacuum-drying, obtain white crystal tricyclohexyl phosphine 482g, calculated yield is 85.8%, and obtaining product purity by XY-1A intelligence elemental analyser is 99.5%.
Embodiment five
Reaction flask is replaced as nitrogen atmosphere, adds 160g analytical pure magnesium chips and anhydrous THF, THF submergence magnesium chips.Add 4-5 grain iodine grain, start mechanical stirring, add the anhydrous THF solution 3000mL of 1019g analytical pure bromocyclohexane by separating funnel at 60 DEG C in batches, stop dripping after first dripping 120mL, after causing grignard reaction, then drip, temperature maintains 60 DEG C, after dropwising, stir 14 hours at 50 DEG C.
Reacting liquid temperature is down to less than 20 DEG C, drips 542g analytical pure PBr
3anhydrous THF solution 700mL, temperature controls at 20 DEG C, after dropwising, 40 DEG C insulation 1 hour.
Be down to room temperature again, under ice-water bath, drip saturated (NH
4)
2sO
4the aqueous solution is clarified to reaction solution, hold over night.
By reaction flask at the middle and upper levels clear liquid be transferred in 10L reaction flask by stainless steel pipe, add 750mL Tetrafluoroboric acid (concentration 40%) in this reaction flask in advance and be replaced as nitrogen atmosphere by biexhaust pipe, after transfer, stir 30 minutes, removal of solvent under reduced pressure, the solid that added water is separated out, solid washed with water 2 times, PE washes 1 time, filters, obtains off-white color tricyclohexyl phosphine a tetrafluoro borate.
Tricyclohexyl phosphine a tetrafluoro borate is loaded in 10L reaction flask, 500mL triethylamine is dripped at-40 DEG C, after dropwising, be heated to reaction solution clarification, be down to room temperature, solid is had to separate out, filter in bag glove, vacuum-drying, obtain white crystal tricyclohexyl phosphine 480g, calculated yield is 85.5%, and obtaining product purity by XY-1A intelligence elemental analyser is 99.2%.
Comparative experimental example:
Below with existing method synthesizing tricyclic hexyl phosphine:
12g magnesium chips and anhydrous diethyl ether is added under nitrogen protection in reaction flask; add 1-2 grain iodine grain; the anhydrous ether solution 150mL of 43g chlorocyclohexane is added at about 60 DEG C; stop dripping after first dripping 15mL, after causing grignard reaction, then drip; temperature maintains about 60 DEG C; after dropwising, reflux 2 hours, slowly cool to room temperature.
18.3g PCl is dripped below 20 DEG C
3anhydrous ether solution, temperature controls, below 30 DEG C, at room temperature to stir 1 hour after dropwising, and then under ice-water bath, drips saturated NH
4cl aqueous hydrolysis, separates organic phase, by extracted with diethyl ether, concentrated, use oil pump underpressure distillation, collect cut 180-210 DEG C, obtain white crystal 14.9g, calculated yield is 40%, and obtaining product purity by XY-1A intelligence elemental analyser is 98%, required cost 1.9 yuan/g.
This case embodiment two raw material dosage is roughly the same with above-mentioned art methods, and the product comparative result that two kinds of methods obtain is as follows:
| Product of the present invention | Prior art products | |
| Output | 38.2g | 14.9g |
| Yield | 85% | 40% |
| Purity | 99.5% | 98% |
| Cost | 1.1 yuan/g | 1.9 yuan/g |
Passable as apparent from above-mentioned contrast, product yield of the present invention is doubled many than prior art, and the purity of product is apparently higher than the product purity of prior art, and preparation cost of the present invention declines to a great extent than prior art simultaneously.Therefore, prepare tricyclohexyl phosphine by method of the present invention, beneficial effect is very remarkable.
Below be only embody rule example of the present invention, protection scope of the present invention is not constituted any limitation.The technical scheme that all employing equivalents or equivalence are replaced and formed, all drops within rights protection scope of the present invention.
Claims (8)
1. a preparation method for tricyclohexyl phosphine, comprises the following steps successively:
Under protection of inert gas, carry out grignard reaction at 50-65 DEG C to dripping cyclohexane halide solution in containing the organic solvent of magnesium chips, at 30-70 DEG C of insulation 8-16 hour;
Reacting liquid temperature is down to 0-20 DEG C, and drip phosphorus trihalide solution, temperature controls at 10-35 DEG C, afterwards at 40-50 DEG C of insulation 0.5-3 hour;
In ice-water bath downhill reaction liquid, drip saturated strong acid weak base inorganic salt solution clarify to reaction solution, hold over night;
Under anhydrous and oxygen-free environment, transferred to by supernatant liquid in Tetrafluoroboric acid, under protection of inert gas, stir 20-60 minute, except desolventizing, add water solid and separate out, washing, obtains off-white color tricyclohexyl phosphine a tetrafluoro borate;
In tricyclohexyl phosphine a tetrafluoro borate, add methyl alcohol or alcohol solvent, drip triethylamine at-50 ~-30 DEG C, after dropwising, be heated to reaction solution clarification, be down to room temperature, separate out solid, filter under anhydrous and oxygen-free environment, vacuum-drying, obtain tricyclohexyl phosphine.
2. method according to claim 1, wherein cyclohexane halide is chlorocyclohexane or bromocyclohexane.
3. method according to claim 1, wherein phosphorus trihalide is phosphorus trichloride or phosphorus tribromide.
4. method according to claim 1, wherein the mol ratio of cyclohexane halide and phosphorus trihalide is 1:0.2-0.36.
5. method according to claim 1, wherein strong acid weak base inorganic salt are one or more in ammonium chloride, ammonium sulfate or ammonium nitrate.
6. method according to claim 1, wherein the holding temperature of grignard reaction controls at 45-65 DEG C, and soaking time controls at 12-16 hour.
7. method according to claim 1, the soaking time after wherein dripping phosphorus trihalide controls at 1-2 hour.
8. method according to claim 1, wherein the organic solvent of grignard reaction is anhydrous tetrahydro furan or anhydrous methyl tetrahydrofuran (THF); Cyclohexane halide solution and phosphorus trihalide solution are their anhydrous tetrahydro furan or anhydrous methyl tetrahydrofuran solution respectively.
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| WO2009013628A2 (en) * | 2007-07-26 | 2009-01-29 | Dynamit Nobel Gmbh Explosivstoff-Und Systemtechnik | Use of phosphonium salts in coupling reactions and process for their manufacture |
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| Title |
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| 杜三立等.三乙胺.《摄影印刷业化学药品大全》.印刷工业出版社,1993,第24页. * |
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