CN112250715A - Preparation method of chloro (crotyl) (3-tert-butylphosphoryl) palladium (II) - Google Patents
Preparation method of chloro (crotyl) (3-tert-butylphosphoryl) palladium (II) Download PDFInfo
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- butylphosphine
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- MUJIDPITZJWBSW-UHFFFAOYSA-N palladium(2+) Chemical compound [Pd+2] MUJIDPITZJWBSW-UHFFFAOYSA-N 0.000 title claims abstract description 64
- -1 chloro (crotyl) Chemical group 0.000 title claims abstract description 53
- 238000002360 preparation method Methods 0.000 title abstract description 17
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 claims abstract description 48
- 238000003756 stirring Methods 0.000 claims abstract description 41
- ZMPSAJZWHPLTKH-HYTOEPEZSA-L (e)-but-2-ene;chloropalladium(1+) Chemical compound [Pd+]Cl.[Pd+]Cl.C\C=C\[CH2-].C\C=C\[CH2-] ZMPSAJZWHPLTKH-HYTOEPEZSA-L 0.000 claims abstract description 35
- BWHDROKFUHTORW-UHFFFAOYSA-N tritert-butylphosphane Chemical compound CC(C)(C)P(C(C)(C)C)C(C)(C)C BWHDROKFUHTORW-UHFFFAOYSA-N 0.000 claims abstract description 28
- YTKRILODNOEEPX-NSCUHMNNSA-N crotyl chloride Chemical compound C\C=C\CCl YTKRILODNOEEPX-NSCUHMNNSA-N 0.000 claims abstract description 23
- 238000001035 drying Methods 0.000 claims abstract description 20
- 239000007864 aqueous solution Substances 0.000 claims abstract description 19
- 238000001914 filtration Methods 0.000 claims abstract description 17
- 238000006243 chemical reaction Methods 0.000 claims abstract description 16
- 238000005406 washing Methods 0.000 claims abstract description 12
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 10
- 238000002156 mixing Methods 0.000 claims abstract description 10
- 239000003960 organic solvent Substances 0.000 claims abstract description 7
- 239000007788 liquid Substances 0.000 claims abstract description 3
- 239000012299 nitrogen atmosphere Substances 0.000 claims abstract description 3
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 24
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 22
- 238000000034 method Methods 0.000 claims description 22
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 21
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 15
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims description 12
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 12
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical group CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 9
- 238000001816 cooling Methods 0.000 claims description 9
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 6
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 6
- 238000001291 vacuum drying Methods 0.000 claims description 6
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical group [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 5
- 239000002274 desiccant Substances 0.000 claims description 5
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 5
- 239000002808 molecular sieve Substances 0.000 claims description 4
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 4
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims description 3
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 claims description 3
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 claims description 3
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 claims description 3
- 239000003208 petroleum Substances 0.000 claims description 3
- 125000003944 tolyl group Chemical group 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims 1
- WCJYTPVNMWIZCG-UHFFFAOYSA-N xylylcarb Chemical compound CNC(=O)OC1=CC=C(C)C(C)=C1 WCJYTPVNMWIZCG-UHFFFAOYSA-N 0.000 claims 1
- 239000000460 chlorine Substances 0.000 abstract description 28
- 229910052801 chlorine Inorganic materials 0.000 abstract description 19
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 abstract description 12
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 28
- 239000013078 crystal Substances 0.000 description 24
- 229910052763 palladium Inorganic materials 0.000 description 16
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 15
- 238000000921 elemental analysis Methods 0.000 description 13
- 239000007787 solid Substances 0.000 description 13
- 239000000843 powder Substances 0.000 description 11
- 238000004458 analytical method Methods 0.000 description 9
- 229910052757 nitrogen Inorganic materials 0.000 description 8
- 239000008367 deionised water Substances 0.000 description 7
- 229910021641 deionized water Inorganic materials 0.000 description 7
- 239000007789 gas Substances 0.000 description 7
- 238000004128 high performance liquid chromatography Methods 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- 239000012074 organic phase Substances 0.000 description 7
- 230000001681 protective effect Effects 0.000 description 7
- 239000012465 retentate Substances 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- 238000000926 separation method Methods 0.000 description 6
- 239000000243 solution Substances 0.000 description 4
- 239000002815 homogeneous catalyst Substances 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 150000001350 alkyl halides Chemical class 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 2
- 238000005580 one pot reaction Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- KZPYGQFFRCFCPP-UHFFFAOYSA-N 1,1'-bis(diphenylphosphino)ferrocene Chemical compound [Fe+2].C1=CC=C[C-]1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=C[C-]1P(C=1C=CC=CC=1)C1=CC=CC=C1 KZPYGQFFRCFCPP-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 238000003477 Sonogashira cross-coupling reaction Methods 0.000 description 1
- 238000006069 Suzuki reaction reaction Methods 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 150000003842 bromide salts Chemical class 0.000 description 1
- 230000006315 carbonylation Effects 0.000 description 1
- 238000005810 carbonylation reaction Methods 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 238000006880 cross-coupling reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 150000004694 iodide salts Chemical class 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- QMFVLQXRHBTDSH-UHFFFAOYSA-N tritert-butylphosphane Chemical compound CC(C)(C)P(C(C)(C)C)C(C)(C)C.CC(C)(C)P(C(C)(C)C)C(C)(C)C QMFVLQXRHBTDSH-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
- C07F15/0006—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table compounds of the platinum group
- C07F15/006—Palladium compounds
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
The invention discloses a preparation method of chloro (crotyl) (3-tert-butylphosphorus) palladium (II), which comprises the following steps: step one, dropwise adding crotyl chloride into a palladium chloride aqueous solution in a nitrogen atmosphere, and stirring for reaction at the temperature of 20-50 ℃; step two, extracting the reacted system by using an extracting agent, separating liquid, drying and concentrating to obtain a crotyl palladium chloride dimer; and step three, mixing and stirring the organic solvent, the tri-tert-butylphosphine and the crotyl palladium chloride dimer for reaction for 7 to 15 hours at the temperature of between 30 and 50 ℃, filtering, washing and drying in vacuum to obtain the chloro (crotyl) (3-tert-butylphosphine) palladium (II). The invention provides a preparation method of chlorine (crotyl) (3-tert-butylphosphorus) palladium (II), which is simple and easy to implement, green and environment-friendly, and has high yield, wherein the purity of the prepared chlorine (crotyl) (3-tert-butylphosphorus) palladium (II) is more than or equal to 99%, and the yield is more than 91%.
Description
Technical Field
The invention belongs to the technical field of chemical synthesis, and particularly relates to a preparation method of chloro (crotyl) (3-tert-butylphosphorus) palladium (II).
Background
In recent years, the use of noble metal catalysts represented by palladium in organic synthesis has been rapidly developed, and homogeneous catalysts exhibit excellent performance particularly in some special reactions. For example, Pd (dppf) Cl as a catalyst in preparation of aryl borates corresponding to bromides and iodides by Suzuki coupling reaction2And Pd (PPh) for use in Sonogashira coupling reaction3)Cl2In addition, Pd homogeneous catalysts are widely used in carbonylation of halogenated compounds, preparation of aldehydes from alkyl halides, production of carboxylic acids or amides, and reaction of alkyl halides with acetylene to produce acetylene compounds with increased carbon chains.
Chloro (crotyl) (3-tert-butylphosphine) palladium (II) is an important Pd homogeneous catalyst, and is mainly used in coupling reactions such as the cross-coupling of aryl groups with vinyl chloride, for example, Suzuki, Kumada, Negishi, Buchwald, and the like. Therefore, the method for synthesizing the chloro (crotyl) (3-tert-butylphosphine) palladium (II) which is simple in route, low in cost and environment-friendly has important significance.
Disclosure of Invention
The technical problem to be solved by the present invention is to provide a method for preparing chloro (crotyl) (3-tert-butylphosphine) palladium (II) in view of the above-mentioned shortcomings of the prior art. The method comprises the steps of firstly reacting a palladium chloride solution with crotyl chloride to generate a crotyl palladium chloride dimer, and then directly reacting the crotyl palladium chloride dimer with tri-tert-butylphosphine through a one-pot method to obtain chlorine (crotyl) (3-tert-butylphosphine) palladium (II), wherein the preparation method is simple and easy to implement, green and environment-friendly, and high in yield, and the purity of the prepared chlorine (crotyl) (3-tert-butylphosphine) palladium (II) is more than or equal to 99%, and the yield is more than 91%.
In order to solve the technical problems, the invention adopts the technical scheme that: a method for preparing chloro (crotyl) (3-tert-butylphosphine) palladium (II), which is characterized by comprising the following steps:
step one, dripping crotyl chloride into a palladium chloride aqueous solution in a nitrogen atmosphere, and stirring and reacting for 10-24 h at the temperature of 20-50 ℃;
step two, cooling the system after the reaction in the step one, extracting with an extracting agent, separating liquid, drying, and concentrating to obtain a crotyl palladium chloride dimer;
and step three, mixing and stirring an organic solvent, tri-tert-butylphosphine and the crotyl palladium chloride dimer in the step two for reaction for 7 to 15 hours at the temperature of between 30 and 50 ℃, filtering, washing and drying in vacuum to obtain the chloro (crotyl) (3-tert-butylphosphine) palladium (II).
The preparation method of the palladium (crotyl) (3-tert-butylphosphine) chloride (II) is characterized in that the mass percentage of the palladium chloride in the palladium chloride aqueous solution in the step one is 20-40%, and the amount of the crotyl chloride is 2-3.5 times of that of the palladium chloride.
The preparation method of the chloro (crotyl) (3-tert-butylphosphor) palladium (II) is characterized in that the time for dripping the crotyl chloride in the step one is 30-60 min.
The preparation method of chloro (crotyl) (3-tert-butylphosphoryl) palladium (II) is characterized in that the mass of the extractant in the second step is 5 to 10 times of that of palladium chloride, and the extractant is ethyl acetate, methyl acetate, dichloromethane, chloroform or toluene.
The preparation method of the chlorine (crotyl) (3-tert-butylphosphorus) palladium (II) is characterized in that the mass of the dried drying agent in the step two is 0.4 to 1.4 times of the mass of the palladium element, the drying agent is anhydrous sodium sulfate, anhydrous calcium chloride, anhydrous magnesium sulfate or a molecular sieve, the concentration temperature is 25 to 40 ℃, and the vacuum degree of concentration is more than or equal to 0.09 MPa.
The preparation method of chloro (crotyl) (3-tert-butylphosphine) palladium (II) is characterized in that, in the step three, the mass of the organic solvent is 6 times to 12 times of that of the crotyl palladium chloride dimer, and the organic solvent is toluene or tetrahydrofuran.
The preparation method of chloro (crotyl) (3-tert-butylphosphine) palladium (II) is characterized in that the amount of the tri-tert-butylphosphine in the step III is 1.2 to 3 times of the amount of the crotyl palladium chloride dimer.
The preparation method of chloro (crotyl) (3-tert-butylphosphoryl) palladium (II) is characterized in that the washing in the step III is carried out by using diethyl ether, petroleum ether, n-hexane or n-heptane.
The preparation method of the chloro (crotyl) (3-tert-butylphosphor) palladium (II) is characterized in that the temperature of vacuum drying in the step III is 20-40 ℃, the vacuum degree of vacuum drying is 0.07-0.09 MPa, and the time of vacuum drying is 2-4 h.
The molecular formula of the chlorine (crotyl) (3-tert-butylphosphine) palladium (II) in the invention is C16H34ClPPd, its structural formula is:
compared with the prior art, the invention has the following advantages:
1. the invention provides a preparation method of chlorine (crotyl) (3-tert-butylphosphine) palladium (II), which comprises the steps of firstly reacting a palladium chloride solution with crotyl chloride to generate a crotyl palladium chloride dimer, and then directly reacting the crotyl palladium chloride dimer with tri-tert-butylphosphine through a one-pot method to obtain the chlorine (crotyl) (3-tert-butylphosphine) palladium (II).
The technical solution of the present invention is further described in detail with reference to the following examples.
Detailed Description
The crotyl chloride and tri-tert-butylphosphine (tri-tert-butylphosphine) in the following examples of the present invention are preferably purchased from Shanghai Demer medical science and technology, Inc.; the reagents and materials used in the following examples are all commercially available, and the experimental procedures in the following examples, which are not specified under specific conditions, were carried out according to conventional methods and conditions.
Example 1
This example provides a method for preparing chloro (crotyl) (3-tert-butylphosphine) palladium (II), comprising the steps of:
step one, placing 17.7g of palladium chloride in a 250mL beaker, adding 35.4mL of concentrated hydrochloric acid, stirring at room temperature to dissolve the palladium chloride, and adding deionized water into the beaker to obtain a palladium chloride aqueous solution with the mass percentage of the palladium chloride of 25%; the concentrated hydrochloric acid is preferably 38 percent by mass; the room temperature is 20-25 ℃;
step two, placing the palladium chloride aqueous solution in the step one into a three-neck flask, introducing nitrogen as protective gas, dropwise adding 22.5g of crotyl chloride into the three-neck flask under the condition of stirring at 30 ℃, and stirring and reacting for 20 hours at the temperature of 30 ℃; the time for dripping the crotyl chloride is 30 min;
step three, cooling the system after the reaction in the step two to room temperature, mixing the cooled system with 150g of an extracting agent dichloromethane, stirring to fully mix, standing, layering, separating, adding 10g of anhydrous sodium sulfate into the organic phase obtained by separation to carry out drying for 2h, removing solids, concentrating the system after removing the solids under the conditions of 30 ℃ and a vacuum degree of more than or equal to 0.09MPa to obtain yellow powder which is crotyl palladium chloride dimer, wherein the mass of the yellow powder is 37.66 g;
and step four, directly adding 160g of tetrahydrofuran, 19.7g of the crotyl palladium chloride dimer obtained in the step three and 15.2g of tri-tert-butylphosphine into another three-neck flask, stirring and reacting at 40 ℃ for 10 hours, filtering, washing a retentate obtained by filtering with diethyl ether, and drying in vacuum at 40 ℃ and 0.07MPa for 2 hours to obtain a light yellow crystal, wherein the light yellow crystal is shown to be chloro (crotyl) (3-tert-butylphosphine) palladium (II) through elemental analysis, and the mass of the light yellow crystal is 18.67 g. The element analysis is carried out on a Saimer flying FlashSmart element analyzer, and the analysis result is as follows: 48.20% of C, 8.51% of H, 8.79% of Cl, 7.81% of P, Pd: 26.69% in accordance with the theoretical value of palladium (II) chloro (crotyl) (3-tert-butylphosphine) (C48.13%, H8.58%, Cl 8.88%, P7.76%, Pd 26.65%). High performance liquid chromatography analysis showed: the purity of chloro (crotyl) (3-tert-butylphosphine) palladium (II) was 99.3%.
In this example, the yield of crotyl palladium chloride dimer was 95.6%, and the yield of chloro (crotyl) (3-tert-butylphosphino) palladium (II) was 93.6%.
Storing chlorine (crotyl) (3-tert-butylphosphine) palladium (II) in an inert atmosphere at 2-8 ℃, wherein the inert atmosphere is nitrogen or argon.
Example 2
This example provides a method for preparing chloro (crotyl) (3-tert-butylphosphine) palladium (II), comprising the steps of:
step one, placing 17.7g of palladium chloride in a 250mL beaker, adding 35.4mL of concentrated hydrochloric acid, stirring at room temperature to dissolve the palladium chloride, and adding deionized water into the beaker to obtain a palladium chloride aqueous solution with the mass percentage of the palladium chloride of 20%; the concentrated hydrochloric acid is preferably 38 percent by mass;
step two, placing the palladium chloride aqueous solution obtained in the step one into a three-neck flask, introducing nitrogen as protective gas, dropwise adding 27g of crotyl chloride into the three-neck flask under the condition of stirring at 35 ℃, and stirring and reacting for 18 hours at the temperature of 35 ℃; the time for dripping the crotyl chloride is 30 min;
step three, cooling the system after the reaction in the step two to room temperature, mixing the cooled system with 180g of an extracting agent dichloromethane, stirring to fully mix, standing, layering, separating, adding 8g of anhydrous sodium sulfate into the organic phase obtained by separation to carry out drying for 3h, removing solids, concentrating the system after removing the solids under the conditions of 30 ℃ and a vacuum degree of more than or equal to 0.09MPa to obtain yellow powder which is crotyl palladium chloride dimer, wherein the mass of the yellow powder is 37.15 g;
and step four, directly adding 200g of tetrahydrofuran, 19.7g of the crotyl palladium chloride dimer obtained in the step three and 18.18g of tri-tert-butylphosphine into another three-neck flask, stirring and reacting at the temperature of 50 ℃ for 7 hours, filtering, washing a retentate obtained by filtering with diethyl ether, and drying in vacuum at the temperature of 40 ℃ and the vacuum degree of 0.07MPa for 3 hours to obtain a light yellow crystal, wherein the light yellow crystal is subjected to elemental analysis, and shows that the light yellow crystal is chloro (crotyl) (3-tert-butylphosphine) palladium (II), and the mass of the light yellow crystal is 18.45 g. The elemental analysis results are: 48.25% of C, 8.54% of H, 8.73% of Cl, 7.85% of P, Pd: 26.63% in accordance with the theoretical value of palladium (II) chloro (crotyl) (3-tert-butylphosphine) (C48.13%, H8.58%, Cl 8.88%, P7.76%, Pd 26.65%). High performance liquid chromatography analysis showed: the purity of chloro (crotyl) (3-tert-butylphosphine) palladium (II) was 99.0%.
In this example, the yield of crotyl palladium chloride dimer was 94.3%, and the yield of chloro (crotyl) (3-tert-butylphosphino) palladium (II) was 92.5%.
Example 3
This example provides a method for preparing chloro (crotyl) (3-tert-butylphosphine) palladium (II), comprising the steps of:
step one, placing 17.7g of palladium chloride in a 250mL beaker, adding 35.4mL of concentrated hydrochloric acid, stirring at room temperature to dissolve the palladium chloride, and adding deionized water into the beaker to obtain a palladium chloride aqueous solution with the mass percentage of the palladium chloride of 35%; the concentrated hydrochloric acid is preferably 38 percent by mass;
step two, placing the palladium chloride aqueous solution obtained in the step one into a three-neck flask, introducing nitrogen as protective gas, dropwise adding 18.5g of crotyl chloride into the three-neck flask under the condition of stirring at 25 ℃, and stirring and reacting for 24 hours at the temperature of 25 ℃; the time for dripping the crotyl chloride is 30 min;
step three, cooling the system after the reaction in the step two to room temperature, mixing the cooled system with 120g of an extracting agent dichloromethane, stirring to fully mix, standing, layering, separating, adding 15g of anhydrous sodium sulfate into the organic phase obtained by separation to perform drying for 1.5h, removing solids, and concentrating the system at 35 ℃ under the condition that the vacuum degree is not less than 0.09MPa after the solids are removed to obtain yellow powder which is crotyl palladium chloride dimer and has the mass of 36.08 g;
and step four, directly adding 120g of tetrahydrofuran, 19.7g of the crotyl palladium chloride dimer obtained in the step three and 12.12g of tri-tert-butylphosphine into another three-neck flask, stirring and reacting at the temperature of 30 ℃ for 15 hours, filtering, washing a retentate obtained by filtering with diethyl ether, and drying in vacuum at the temperature of 30 ℃ and the vacuum degree of 0.09MPa for 4 hours to obtain a light yellow crystal, wherein the light yellow crystal is subjected to elemental analysis, and shows that the chlorine (crotyl) (3-tert-butylphosphine) palladium (II) is obtained, and the mass of the light yellow crystal is 18.21 g. The elemental analysis results are: 48.17% of C, 8.43% of H, 8.86% of Cl, 7.75% of P, Pd: 26.79% in accordance with theoretical values for palladium (II) chloro (crotyl) (3-tert-butylphosphine) (C48.13%, H8.58%, Cl 8.88%, P7.76%, Pd 26.65%). High performance liquid chromatography analysis showed: the purity of chloro (crotyl) (3-tert-butylphosphine) palladium (II) was 99.2%.
In this example, the yield of crotyl palladium chloride dimer was 91.6%, and the yield of chloro (crotyl) (3-tert-butylphosphino) palladium (II) was 91.3%.
Example 4
This example provides a method for preparing chloro (crotyl) (3-tert-butylphosphine) palladium (II), comprising the steps of:
step one, placing 17.7g of palladium chloride in a 250mL beaker, adding 35.4mL of concentrated hydrochloric acid, stirring at room temperature to dissolve the palladium chloride, and adding deionized water into the beaker to obtain a palladium chloride aqueous solution with the mass percentage of the palladium chloride of 25%; the concentrated hydrochloric acid is preferably 38 percent by mass;
step two, placing the palladium chloride aqueous solution obtained in the step one into a three-neck flask, introducing nitrogen as protective gas, dropwise adding 27g of crotyl chloride into the three-neck flask under the stirring condition of 45 ℃, and stirring and reacting for 12 hours at the temperature of 45 ℃; the time for dripping crotyl chloride is 60 min;
step three, cooling the system after the reaction in the step two to room temperature, mixing the cooled system with 100g of ethyl acetate serving as an extracting agent, stirring to fully mix, standing, layering, separating, adding 10g of anhydrous magnesium sulfate into the organic phase obtained by separation to dry for 1.5h, removing solids, concentrating the system at the temperature of 30 ℃ and the vacuum degree of more than or equal to 0.09MPa after the solids are removed, and obtaining yellow powder which is crotyl palladium chloride dimer and has the mass of 37.07 g;
and step four, directly adding 120g of toluene, 19.7g of the crotyl palladium chloride dimer obtained in the step three and 25.2g of tri-tert-butylphosphine into another three-neck flask, stirring and reacting at the temperature of 35 ℃ for 12 hours, filtering, washing a retentate obtained by filtering with petroleum ether, and drying in vacuum at the temperature of 20 ℃ and the vacuum degree of 0.07MPa for 3 hours to obtain a light yellow crystal, wherein the light yellow crystal is subjected to elemental analysis, and shows that the light yellow crystal is chloro (crotyl) (3-tert-butylphosphine) palladium (II), and the mass of the light yellow crystal is 18.41 g. The elemental analysis results are: 48.11% of C, 8.59% of H, 8.68% of Cl, 7.79% of P, Pd: 26.83%, consistent with the theoretical values of chloro (crotyl) (3-tert-butylphosphine) palladium (II) (C48.13%, H8.58%, Cl 8.88%, P7.76%, Pd 26.65%). High performance liquid chromatography analysis showed: the purity of chloro (crotyl) (3-tert-butylphosphine) palladium (II) was 99.0%.
In this example, the yield of crotyl palladium chloride dimer was 94.1%, and the yield of chloro (crotyl) (3-tert-butylphosphino) palladium (II) was 92.3%.
Example 5
This example provides a method for preparing chloro (crotyl) (3-tert-butylphosphine) palladium (II), comprising the steps of:
step one, placing 17.7g of palladium chloride in a 250mL beaker, adding 35.4mL of concentrated hydrochloric acid, stirring at room temperature to dissolve the palladium chloride, and adding deionized water into the beaker to obtain a palladium chloride aqueous solution with the mass percentage of the palladium chloride of 40%; the concentrated hydrochloric acid is preferably 38 percent by mass;
placing the palladium chloride aqueous solution in the step one into a three-neck flask, introducing nitrogen as protective gas, dropwise adding 27g of crotyl chloride into the three-neck flask under the stirring condition at 50 ℃, and stirring and reacting for 10 hours at the temperature of 50 ℃; the time for dripping crotyl chloride is 60 min;
step three, cooling the system after the reaction in the step two to room temperature, mixing the cooled system with 170g of chloroform serving as an extracting agent, stirring to fully mix, standing, layering, separating, adding 5g of molecular sieve into the organic phase obtained by separation, drying for 2 hours, removing solids, concentrating the system after removing the solids under the conditions that the temperature is 40 ℃ and the vacuum degree is more than or equal to 0.09MPa, and obtaining yellow powder which is crotyl palladium chloride dimer and has the mass of 37.50 g;
and step four, directly adding 200g of toluene, 19.7g of the crotyl palladium chloride dimer obtained in the step three and 12.5g of tri-tert-butylphosphine into another three-neck flask, stirring and reacting at the temperature of 40 ℃ for 15 hours, filtering, washing a retentate obtained by filtering by using normal hexane, and drying in vacuum for 2 hours at the temperature of 40 ℃ and the vacuum degree of 0.08MPa to obtain a light yellow crystal, wherein the light yellow crystal is subjected to elemental analysis, and shows chlorine (crotyl) (3-tert-butylphosphine) palladium (II), and the mass of the light yellow crystal is 18.29 g. The elemental analysis results are: 48.30% of C, 8.45% of H, 8.68% of Cl, 7.92% of P, Pd: 26.65% in accordance with the theoretical value of palladium (II) chloro (crotyl) (3-tert-butylphosphine) (C48.13%, H8.58%, Cl 8.88%, P7.76%, Pd 26.65%). High performance liquid chromatography analysis showed: the purity of chloro (crotyl) (3-tert-butylphosphine) palladium (II) was 99.1%.
In this example, the yield of crotyl palladium chloride dimer was 95.2%, and the yield of chloro (crotyl) (3-tert-butylphosphino) palladium (II) was 91.7%.
Example 6
This example provides a method for preparing chloro (crotyl) (3-tert-butylphosphine) palladium (II), comprising the steps of:
step one, placing 17.7g of palladium chloride in a 250mL beaker, adding 35.4mL of concentrated hydrochloric acid, stirring at room temperature to dissolve the palladium chloride, and adding deionized water into the beaker to obtain a palladium chloride aqueous solution with the mass percentage of the palladium chloride of 40%; the concentrated hydrochloric acid is preferably 38 percent by mass;
step two, placing the palladium chloride aqueous solution obtained in the step one into a three-neck flask, introducing nitrogen as protective gas, dropwise adding 32g of crotyl chloride into the three-neck flask under the condition of stirring at 20 ℃, and stirring and reacting for 10 hours at the temperature of 20 ℃; the time for dripping crotyl chloride is 45 min;
step three, cooling the system after the reaction in the step two to room temperature, mixing the cooled system with 170g of extracting agent toluene, stirring to fully mix, standing, layering, separating, adding 15g of anhydrous calcium chloride into the separated organic phase, drying for 2.5h, removing solids, concentrating the system at 25 ℃ under the condition that the vacuum degree is not less than 0.09MPa, wherein the obtained yellow powder is crotyl palladium chloride dimer and the mass of the yellow powder is 37.14 g;
and step four, directly adding 225g of toluene, 19.7g of the crotyl palladium chloride dimer obtained in the step three and 30.4g of tri-tert-butylphosphine into another three-neck flask, stirring and reacting at the temperature of 40 ℃ for 15 hours, filtering, washing a retentate obtained by filtering with n-heptane, and drying in vacuum at the temperature of 40 ℃ and the vacuum degree of 0.08MPa for 2 hours to obtain a light yellow crystal, wherein the light yellow crystal is subjected to elemental analysis, and shows chlorine (crotyl) (3-tert-butylphosphine) palladium (II), and the mass of the light yellow crystal is 18.25 g. The elemental analysis results are: 48.30% of C, 8.45% of H, 8.68% of Cl, 7.92% of P, Pd: 26.65% in accordance with the theoretical value of palladium (II) chloro (crotyl) (3-tert-butylphosphine) (C48.13%, H8.58%, Cl 8.88%, P7.76%, Pd 26.65%). High performance liquid chromatography analysis showed: the purity of chloro (crotyl) (3-tert-butylphosphine) palladium (II) was 99.1%.
In this example, the yield of crotyl palladium chloride dimer was 94.3%, and the yield of chloro (crotyl) (3-tert-butylphosphino) palladium (II) was 91.5%.
Example 7
This example provides a method for preparing chloro (crotyl) (3-tert-butylphosphine) palladium (II), comprising the steps of:
step one, placing 17.7g of palladium chloride in a 250mL beaker, adding 35.4mL of concentrated hydrochloric acid, stirring at room temperature to dissolve the palladium chloride, and adding deionized water into the beaker to obtain a palladium chloride aqueous solution with the mass percentage of the palladium chloride of 40%; the concentrated hydrochloric acid is preferably 38 percent by mass;
step two, placing the palladium chloride aqueous solution obtained in the step one into a three-neck flask, introducing nitrogen as protective gas, dropwise adding 32g of crotyl chloride into the three-neck flask under the condition of stirring at 20 ℃, and stirring and reacting for 10 hours at the temperature of 20 ℃; the time for dripping crotyl chloride is 45 min;
step three, cooling the system after the reaction in the step two to room temperature, mixing the cooled system with 170g of methyl acetate serving as an extracting agent, stirring to fully mix, standing, layering, separating, adding 10g of molecular sieve into the organic phase obtained by separation, drying for 1.5h, removing solids, concentrating the system after removing the solids under the conditions that the temperature is 25 ℃, and the vacuum degree is not less than 0.09MPa, wherein the obtained yellow powder is crotyl palladium chloride dimer and the mass of the yellow powder is 37.34 g;
and step four, directly adding 225g of tetrahydrofuran, 19.7g of the crotyl palladium chloride dimer obtained in the step three and 30.4g of tri-tert-butylphosphine into another three-neck flask, stirring and reacting at the temperature of 45 ℃ for 7 hours, filtering, washing a retentate obtained by filtering with n-heptane, and drying in vacuum at the temperature of 30 ℃ and the vacuum degree of 0.08MPa for 3 hours to obtain a light yellow crystal, wherein the light yellow crystal is subjected to elemental analysis, and shows that the light yellow crystal is chloro (crotyl) (3-tert-butylphosphine) palladium (II), and the mass of the light yellow crystal is 18.35 g. The elemental analysis results are: 48.30% of C, 8.45% of H, 8.68% of Cl, 7.92% of P, Pd: 26.65% in accordance with the theoretical value of palladium (II) chloro (crotyl) (3-tert-butylphosphine) (C48.13%, H8.58%, Cl 8.88%, P7.76%, Pd 26.65%). High performance liquid chromatography analysis showed: the purity of chloro (crotyl) (3-tert-butylphosphine) palladium (II) was 98.0%.
In this example, the yield of crotyl palladium chloride dimer was 94.8%, and the yield of chloro (crotyl) (3-tert-butylphosphino) palladium (II) was 92.0%.
The above description is only a preferred embodiment of the present invention, and is not intended to limit the present invention, and all simple modifications, changes and equivalent structural changes made to the above embodiment according to the technical spirit of the present invention still fall within the protection scope of the technical solution of the present invention.
Claims (9)
1. A method for preparing chloro (crotyl) (3-tert-butylphosphine) palladium (II), which is characterized by comprising the following steps:
step one, dripping crotyl chloride into a palladium chloride aqueous solution in a nitrogen atmosphere, and stirring and reacting for 10-24 h at the temperature of 20-50 ℃;
step two, cooling the system after the reaction in the step one, extracting with an extracting agent, separating liquid, drying, and concentrating to obtain a crotyl palladium chloride dimer;
and step three, mixing and stirring an organic solvent, tri-tert-butylphosphine and the crotyl palladium chloride dimer in the step two for reaction for 7 to 15 hours at the temperature of between 30 and 50 ℃, filtering, washing and drying in vacuum to obtain the chloro (crotyl) (3-tert-butylphosphine) palladium (II).
2. The method for preparing chloro (crotyl) (3-tert-butylphosphine) palladium (II) as claimed in claim 1, wherein the mass percentage of palladium chloride in the palladium chloride aqueous solution in step one is 20-40%, and the amount of crotyl chloride is 2-3.5 times that of palladium chloride.
3. The method for preparing chloro (crotonyl) (3-tert-butylphosphine) palladium (II) according to claim 1, wherein the time for dropping crotonyl chloride in step one is 30-60 min.
4. The method for preparing chloro (crotyl) (3-tert-butylphosphine) palladium (II) as claimed in claim 1, wherein the mass of the extractant in step two is 5 times to 10 times that of palladium chloride, and the extractant is ethyl acetate, methyl acetate, dichloromethane, chloroform or toluene.
5. The method for preparing chloro (crotyl) (3-tert-butylphosphor) palladium (II) according to claim 1, wherein the drying in step two is performed with a drying agent, the drying agent has a mass 0.4 to 1.4 times that of the palladium element, and the drying agent is anhydrous sodium sulfate, anhydrous calcium chloride, anhydrous magnesium sulfate or molecular sieve; and in the second step, the concentration temperature is 25-40 ℃, and the vacuum degree of concentration is more than or equal to 0.09 MPa.
6. The method for preparing chloro (crotyl) (3-tert-butylphosphine) palladium (II) according to claim 1, wherein the mass of the organic solvent in step three is 6 times to 12 times that of the crotyl palladium chloride dimer, and the organic solvent is toluene or tetrahydrofuran.
7. The method for preparing chloro (crotyl) (3-tert-butylphosphine) palladium (II) according to claim 1, wherein the amount of tri-tert-butylphosphine in step III is 1.2 to 3 times the amount of crotylpalladium chloride dimer substance.
8. The method for preparing chloro (crotyl) (3-tert-butylphosphine) palladium (II) as claimed in claim 1, wherein the washing in step three is with diethyl ether, petroleum ether, n-hexane or n-heptane.
9. The method for preparing chloro (crotyl) (3-tert-butylphosphine) palladium (II) as claimed in claim 1, wherein the temperature of vacuum drying in step three is 20-40 ℃, the vacuum degree of vacuum drying is 0.07-0.09 MPa, and the time of vacuum drying is 2-4 h.
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| CN114437142A (en) * | 2022-02-28 | 2022-05-06 | 北京格林凯默科技有限公司 | Preparation method of crotyl palladium chloride dimer |
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| CN114437142A (en) * | 2022-02-28 | 2022-05-06 | 北京格林凯默科技有限公司 | Preparation method of crotyl palladium chloride dimer |
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