CN102977151B - The preparation method of two (tricyclohexyl phosphine) palladium chloride - Google Patents
The preparation method of two (tricyclohexyl phosphine) palladium chloride Download PDFInfo
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Abstract
The present invention relates to a kind of preparation method of two (tricyclohexyl phosphine) palladium chloride, comprise: under anaerobic, tricyclohexyl phosphine is dissolved in organic solvent, at room temperature, drip the dilute hydrochloric acid solution of palladium chloride, after dropwising, at room temperature stir 2-6 hour, filter, washing leaching cake, dry, obtain two (tricyclohexyl phosphine) palladium chloride of yellow solid powder-product.Wherein, raw material tricyclohexyl phosphine by cyclohexane halide is made cyclohexyl Grignard reagent, can react with phosphorus trihalide, drips after saturated strong acid weak base inorganic salt solution carries out cancellation under low temperature, add Tetrafluoroboric acid and make salt, then prepare with triethylamine solution salt.Preparation cost is reduced about one times by the inventive method, and simple to operate, can obtain high yield, highly purified two (tricyclohexyl phosphine) palladium chloride.
Description
Technical field
The present invention relates to a kind of preparation method of two (tricyclohexyl phosphine) palladium chloride, belong to technical field of organic synthesis.
Background technology
Two (tricyclohexyl phosphine) palladium chloride is a kind of important catalyzer in chemical reaction, be widely used in all kinds of linked reactions that chlorinated aromatic hydrocarbons participates in, as Firooznia etc. utilizes two (tricyclohexyl phosphine) palladium chloride catalyst boric acid ester and 1-methoxyl group-2-chlorobenzene, obtain moderate yield (43%).Two (tricyclohexyl phosphine) palladium chloride also has a wide range of applications at medicine and organic synthesis field.
The aqueous solution of tetrachloro-palladium acid sodium is mainly added in the methanol solution of tricyclohexyl phosphine and reacts by the preparation method of two (tricyclohexyl phosphine) palladium chloride at present, filters afterwards and obtains two (tricyclohexyl phosphine) palladium chloride product.This method reaction is more stable, easy control, but owing to there being the existence of sodium ion, replace the space occupying palladium ion, make the ability of palladium ion absorption reaction thing-tricyclohexyl phosphine influenced, be unfavorable for generating " active compound ", the drawbacks such as product purity is low, low yield that cause the method to exist.
The method also having one to prepare two (tricyclohexyl phosphine) palladium chloride is added in the THF solution of tricyclohexyl phosphine by two (second Jing) palladium chloride, and reflux, obtains yellow powder product.Also there is the problems such as the poor product quality, the purity that obtain is low in the method.
Therefore, seek preparation cost method low, simple to operate to prepare two (tricyclohexyl phosphine) palladium chlorides of high yield, high purity, high-quality, become one of two (tricyclohexyl phosphine) palladium chloride 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 two (tricyclohexyl phosphine) palladium chloride, the dilute hydrochloric acid solution of the method Palladous chloride and thricyclohexyl phosphine reaction, significantly reduce preparation cost, and simple to operate, the product yield obtained is high, purity is high, quality is good.
The invention provides a kind of preparation method of two (tricyclohexyl phosphine) palladium chloride, comprising: under anaerobic, tricyclohexyl phosphine is dissolved in organic solvent; At room temperature, drip the dilute hydrochloric acid solution of palladium chloride, wherein the mol ratio of palladium chloride and tricyclohexyl phosphine is 1:2-3, and the concentration of dilute hydrochloric acid is 5-20 quality %; At room temperature stir 2-6 hour after dropwising, filter, washing leaching cake, dry, obtain two (tricyclohexyl phosphine) palladium chloride.
According to a concrete but nonrestrictive embodiment of the present invention, wherein the mol ratio of palladium chloride and tricyclohexyl phosphine is 1:2-2.5.
According to a concrete but nonrestrictive embodiment of the present invention, the organic solvent wherein dissolving tricyclohexyl phosphine is at least one in acetone, methyl alcohol and ethanol.
According to a concrete but nonrestrictive embodiment of the present invention, wherein the concentration of dilute hydrochloric acid is 5-15 quality %.
According to a concrete but nonrestrictive embodiment of the present invention, wherein churning time is 3-5 hour.
According to a concrete but nonrestrictive embodiment of the present invention, wherein the preparation of tricyclohexyl phosphine comprises the following steps:
Cyclohexane halide is made 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.
According to a concrete but nonrestrictive embodiment of the present invention, wherein cyclohexane halide is chlorocyclohexane or bromocyclohexane, phosphorus trihalide is phosphorus trichloride or phosphorus tribromide, and strong acid weak base inorganic salt are at least one in ammonium chloride, ammonium sulfate and ammonium nitrate.
According to a concrete but nonrestrictive embodiment of the present invention, wherein the preparation 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, wherein the mol ratio of cyclohexane halide and phosphorus trihalide is 1:0.2-0.36, and 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, wherein 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, 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.
Beneficial effect of the present invention is mainly reflected in:
The dilute hydrochloric acid solution of the present invention's Palladous chloride and thricyclohexyl phosphine reaction prepare two (tricyclohexyl phosphine) palladium chloride, other metallic cation except palladium metal is not introduced in reaction process, therefore overcome other metal ion and replace the problem occupying palladium ion space, palladium ion is made to be more prone to absorption reaction thing-tricyclohexyl phosphine and to generate " active compound ", thus productive rate is significantly promoted, the product purity obtained is high, quality better.Because of not containing other metallic impurity, ensure that product possesses good catalytic performance.
The present invention directly uses Palladous chloride for starting raw material, compared with the preparation method using tetrachloro-palladium acid sodium to be raw material with prior art, owing to directly using the dilute hydrochloric acid solution of Palladous chloride, first Palladous chloride need not be prepared into tetrachloro-palladium acid sodium, therefore the present invention significantly reduces production cost, is conducive to the reduction of two (tricyclohexyl phosphine) palladium chloride catalyzer price.
Preparation process of the present invention is simple to operate, stirs and can obtain high yield, highly purified product under normal temperature.
According to one embodiment of the invention, the preparation of tricyclohexyl phosphine is used chemical process instead and is carried out aftertreatment, namely uses Tetrafluoroboric acid and tricyclohexyl phosphine salify, is extracted completely by tricyclohexyl phosphine from reaction solution, after Ficus caricaL is good, then with triethylamine solution salt.The method overcome the shortcoming of tricyclohexyl phosphine extremely unstable, easily oxidation, aftertreatment difficulty in atmosphere, high yield, high purity, high-quality tricyclohexyl phosphine product can be obtained, and then obtain high yield, high purity, high-quality two (tricyclohexyl phosphine) palladium chloride.
Accompanying drawing explanation
Fig. 1 is two (tricyclohexyl phosphine) palladium chlorides
31p-NMR spectrogram (solvent: CDCl3).
Fig. 2 is two (tricyclohexyl phosphine) palladium chlorides
1h-NMR spectrogram (solvent: CDCl3).
Embodiment
Provided hereinafter concrete embodiment and further illustrate the present invention, but the present invention is not limited only to following embodiment.
The present invention take tricyclohexyl phosphine as raw material, at room temperature, drips the diluted hydrochloric acid aqueous solution (existing with the form of chloric acid palladium) of Palladous chloride, stirs, filter, obtain two (tricyclohexyl phosphine) palladium chloride of yellow solid powder-product.Concrete synthetic route is as follows:
Under anaerobic, tricyclohexyl phosphine is dissolved in organic solvent, at room temperature, drips the diluted hydrochloric acid aqueous solution of palladium chloride, have yellow solid to produce after dropwising, stirred at ambient temperature 2-6 hour, preferably stir 3-5 hour.By reacting liquid filtering, filter cake washing with acetone, dry, obtain two (tricyclohexyl phosphine) palladium chloride of yellow solid powder-product.
The mol ratio of above-mentioned reaction raw materials palladium chloride and tricyclohexyl phosphine can be 1:2-3, preferred 1:2-2.5.
Dissolve the organic solvent of tricyclohexyl phosphine and should select to dissolve the solvent that tricyclohexyl phosphine again can be water-soluble, as acetone, methyl alcohol, ethanol etc.The consumption of solvent is suitable so that tricyclohexyl phosphine can be made to be dissolved as completely.
Above-mentioned dilute hydrochloric acid concentration controls at 5%-20%(by mass percentage usually), preferred 5%-15%(is by mass percentage).Acid concentration is unsuitable too high or too low, and the too high meeting of acid concentration makes tricyclohexyl phosphine salify, and concentration is too low can not dissolve palladium chloride completely.The consumption of dilute hydrochloric acid is suitable so that palladium chloride can be made to be dissolved as completely.
On address raw material used in following embodiment and embodiment, reagent etc., if no special instructions, all can obtain from commercial channels.
Raw material tricyclohexyl phosphine is except using except commercially available prod, also can by cyclohexane halide be made 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 prepare with triethylamine solution salt.Wherein, cyclohexane halide 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 the preparation method of this tricyclohexyl phosphine is described in detail.
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.
Reacting liquid temperature is down to 0-20 DEG C, and drip the organic solvent solution of phosphorus trihalide as anhydrous tetrahydro furan or anhydrous methyl tetrahydrofuran 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.
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.
By reaction vessel 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.
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.
The preparation method of above-mentioned tricyclohexyl phosphine has applied for patent by applicant of the present invention on October 19th, 2012, and number of patent application is 201210399055.5, is quoted in full at this.Prepare tricyclohexyl phosphine by this method, productive rate is high, purity is high, and further with two (tricyclohexyl phosphine) palladium chloride of method preparation of the present invention, two (tricyclohexyl phosphine) the palladium chloride product purity obtained and quality can be better.
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 1
Reaction flask is replaced as nitrogen atmosphere, tricyclohexyl phosphine 15g(tricyclohexyl phosphine is added purchased from system in Beijing Jing Ze Wang Chemical Co., Ltd. in reaction flask, purity 98%) and ethanol 250mL, at room temperature, drip the 8wt% dilute hydrochloric acid solution 80mL of analytical pure palladium chloride 4g, yellow solid is had to produce after dropwising, stirred at ambient temperature 4h.By reacting liquid filtering, filter cake washing with acetone, dry, obtain two (tricyclohexyl phosphine) palladium chloride 14.5g of yellow solid powder-product, calculated yield is 88%, and obtaining product purity by ERBA-1106 elemental analyser is 99.0%.
With Palladous chloride: 91 yuan/g, tricyclohexyl phosphine: the calculation of price of 8 yuan/g, preparation cost of the present invention is: (Palladous chloride cost+tricyclohexyl phosphine cost+solvent cost)/product volume=33.6 yuan/g.
Embodiment 2
Reaction flask is replaced as nitrogen atmosphere, tricyclohexyl phosphine 200g(tricyclohexyl phosphine is added purchased from system in Beijing Jing Ze Wang Chemical Co., Ltd. in reaction flask, purity 98%) and methyl alcohol 3000mL, at room temperature, drip the 12wt% dilute hydrochloric acid solution 600mL of analytical pure palladium chloride 60.2g, yellow solid is had to produce after dropwising, stirred at ambient temperature 3h.By reacting liquid filtering, filter cake washing with acetone, dry, obtain two (tricyclohexyl phosphine) palladium chloride 223g of yellow solid powder-product, calculated yield is 89%, and obtaining product purity by ERBA-1106 elemental analyser is 99.1%.
Embodiment 3
Reaction flask is replaced as nitrogen atmosphere, tricyclohexyl phosphine 500g(tricyclohexyl phosphine is added purchased from system in Beijing Jing Ze Wang Chemical Co., Ltd. in reaction flask, purity 98%) and acetone 5000mL, at room temperature, drip the 15wt% dilute hydrochloric acid solution 900mL of analytical pure palladium chloride 150.5g, yellow solid is had to produce after dropwising, stirred at ambient temperature 4h.By reacting liquid filtering, filter cake washing with acetone, dry, obtain two (tricyclohexyl phosphine) palladium chloride 576.6g of yellow solid powder-product, calculated yield is 92%, and obtaining product purity by ERBA-1106 elemental analyser is 99.0%.
Embodiment 4
1. the preparation of tricyclohexyl phosphine
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 analytical pure chlorocyclohexane 59.3g 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 analytical pure PCl
3the anhydrous THF solution 150mL of 22g, temperature controls at 25 DEG C, and after dropwising, 45 DEG C are incubated 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 tricyclohexyl phosphine purity by XY-1A intelligence elemental analyser is 99.3%.The cost that the method prepares tricyclohexyl phosphine is 1.1 yuan/g.
And according to prior art, react with cyclohexyl Grignard reagent and phosphorus trichloride, after low temperature drips aqueous ammonium chloride solution, by extracted with diethyl ether, concentrated, the conventional post-treating method such as underpressure distillation obtains product, and counting yield yield is only about 40%, obtaining product purity by XY-1A intelligence elemental analyser is 98%, and preparation cost is at 1.9 yuan/g.The preparation method of above-mentioned tricyclohexyl phosphine is enough to the advantage being embodied in product yield, product purity and preparation cost aspect.
2. the preparation of pair (tricyclohexyl phosphine) palladium chloride
Reaction flask is replaced as nitrogen atmosphere, in reaction flask, add tricyclohexyl phosphine 20g and the acetone 300mL of above-mentioned preparation, at room temperature, drip the 10wt% dilute hydrochloric acid solution 100mL of analytical pure palladium chloride 5.75g, yellow solid is had to produce after dropwising, stirred at ambient temperature 5h.By reacting liquid filtering, filter cake washing with acetone, dry, obtain two (tricyclohexyl phosphine) palladium chloride 21.5g of yellow solid powder-product, calculated yield is 90%, and obtaining product purity by ERBA-1106 elemental analyser is 99.2%.
Embodiment 5
1. the preparation of tricyclohexyl phosphine
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 analytical pure chlorocyclohexane 741g by separating funnel at about 60 DEG C 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 analytical pure PBr
3the anhydrous THF solution 700mL of 542g, temperature controls at 20 DEG C, and after dropwising, 45 DEG C are incubated 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 tricyclohexyl phosphine purity by XY-1A intelligence elemental analyser is 99.5%.
The preparation method of above-mentioned tricyclohexyl phosphine compared with prior art, is enough to the advantage being embodied in product yield, product purity and preparation cost aspect.
2. the preparation of pair (tricyclohexyl phosphine) palladium chloride
Reaction flask is replaced as nitrogen atmosphere, in reaction flask, add tricyclohexyl phosphine 250g and the acetone 3000mL of above-mentioned preparation, at room temperature, drip the 14wt% dilute hydrochloric acid solution 700mL of analytical pure palladium chloride 68.7g, yellow solid is had to produce after dropwising, stirred at ambient temperature 3h.By reacting liquid filtering, filter cake washing with acetone, dry, obtain two (tricyclohexyl phosphine) palladium chloride 259g of yellow solid powder-product, calculated yield is 90.5%, and obtaining product purity by ERBA-1106 elemental analyser is 99.3%.
Contrast experiment's example:
Two (tricyclohexyl phosphine) palladium chloride is synthesized: under anaerobic by existing method, the aqueous solution of tetrachloro-palladium acid sodium 6.3g is added in the methanol solution 300mL of 12g tricyclohexyl phosphine, stirred at ambient temperature 4h, filter, obtain yellow powder product 11.8g, calculated yield is 75%, obtains product purity 98.5% by ERBA-1106 elemental analyser.
With tetrachloro-palladium acid sodium: 100 yuan/g, tricyclohexyl phosphine: the calculation of price of 8 yuan/g, art methods cost is: (tetrachloro-palladium acid sodium cost+tricyclohexyl phosphine cost+solvent cost)/product volume=60.2 yuan/g.
This case embodiment 1 is suitable with above-mentioned art methods raw material dosage, and two (tricyclohexyl phosphine) palladium chloride product comparative results that two kinds of methods obtain are as follows:
| Product of the present invention | Prior art products | |
| Output | 14.5g | 11.8g |
| Yield | 88% | 75% |
| Purity | 99% | 98.5% |
| Cost | 33.6 yuan/g | 60.2 yuan/g |
Can see from above-mentioned contrast, about preparation cost of the present invention is only the half of prior art cost, and product yield improves 17.3% than prior art, and product purity of the present invention is higher.Therefore, with two (tricyclohexyl phosphine) palladium chloride of method preparation 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 (10)
1. the preparation method of two (tricyclohexyl phosphine) palladium chloride, 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, wherein the mol ratio of cyclohexane halide and phosphorus trihalide is 1:0.2-0.36, and 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 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;
Under anaerobic, tricyclohexyl phosphine is dissolved in organic solvent; At room temperature, drip the dilute hydrochloric acid solution of palladium chloride, wherein the mol ratio of palladium chloride and tricyclohexyl phosphine is 1:2-3, and the concentration of dilute hydrochloric acid is 5-20 quality %; At room temperature stir 2-6 hour after dropwising, filter, washing leaching cake, dry, obtain two (tricyclohexyl phosphine) palladium chloride.
2. method according to claim 1, wherein cyclohexane halide is chlorocyclohexane or bromocyclohexane.
3. 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.
4. method according to claim 1, wherein phosphorus trihalide is phosphorus trichloride or phosphorus tribromide.
5. 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.
6. method according to claim 1, wherein strong acid weak base inorganic salt are at least one in ammonium chloride, ammonium sulfate and ammonium nitrate.
7. method according to claim 1, wherein the mol ratio of palladium chloride and tricyclohexyl phosphine is 1:2-2.5.
8. method according to claim 1, the organic solvent wherein dissolving tricyclohexyl phosphine is at least one in acetone, methyl alcohol and ethanol.
9. method according to claim 1, wherein the concentration of dilute hydrochloric acid is 5-15 quality %.
10. method according to claim 1, stirs 3-5 hour after wherein dripping the dilute hydrochloric acid solution of palladium chloride.
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