CN114213466B - Method for in-situ preparation of (1, 5-cyclooctadiene) palladium dichloride - Google Patents
Method for in-situ preparation of (1, 5-cyclooctadiene) palladium dichloride Download PDFInfo
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- VYXHVRARDIDEHS-UHFFFAOYSA-N 1,5-cyclooctadiene Chemical compound C1CC=CCCC=C1 VYXHVRARDIDEHS-UHFFFAOYSA-N 0.000 title claims abstract description 43
- 239000004912 1,5-cyclooctadiene Substances 0.000 title claims abstract description 43
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 title claims abstract description 32
- 238000000034 method Methods 0.000 title claims abstract description 25
- 238000011065 in-situ storage Methods 0.000 title claims abstract description 15
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims abstract description 101
- 238000006243 chemical reaction Methods 0.000 claims abstract description 25
- 239000002904 solvent Substances 0.000 claims abstract description 20
- 238000010438 heat treatment Methods 0.000 claims abstract description 11
- 230000000536 complexating effect Effects 0.000 claims abstract description 9
- 238000005406 washing Methods 0.000 claims abstract description 4
- 229910052763 palladium Inorganic materials 0.000 claims description 35
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 32
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 28
- 239000000047 product Substances 0.000 claims description 19
- 238000003756 stirring Methods 0.000 claims description 17
- 239000000460 chlorine Substances 0.000 claims description 16
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 15
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 12
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 11
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 10
- 238000001914 filtration Methods 0.000 claims description 10
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 9
- 239000000706 filtrate Substances 0.000 claims description 9
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 8
- 229910052801 chlorine Inorganic materials 0.000 claims description 8
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical group [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 6
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 6
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 5
- 235000017550 sodium carbonate Nutrition 0.000 claims description 5
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 claims description 4
- 238000007865 diluting Methods 0.000 claims description 4
- 239000011736 potassium bicarbonate Substances 0.000 claims description 4
- 235000015497 potassium bicarbonate Nutrition 0.000 claims description 4
- 229910000028 potassium bicarbonate Inorganic materials 0.000 claims description 4
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 claims description 4
- 235000011121 sodium hydroxide Nutrition 0.000 claims description 4
- 239000012065 filter cake Substances 0.000 claims description 3
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 3
- 235000011181 potassium carbonates Nutrition 0.000 claims description 3
- 235000011118 potassium hydroxide Nutrition 0.000 claims description 3
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 3
- 235000017557 sodium bicarbonate Nutrition 0.000 claims description 3
- 238000001291 vacuum drying Methods 0.000 claims description 3
- 239000012535 impurity Substances 0.000 abstract description 9
- 239000002994 raw material Substances 0.000 abstract description 8
- 239000002815 homogeneous catalyst Substances 0.000 abstract description 6
- 238000004519 manufacturing process Methods 0.000 abstract description 5
- 238000003786 synthesis reaction Methods 0.000 abstract description 5
- 239000003814 drug Substances 0.000 abstract description 4
- 229940079593 drug Drugs 0.000 abstract description 4
- 230000015572 biosynthetic process Effects 0.000 abstract description 3
- 239000012847 fine chemical Substances 0.000 abstract description 3
- 229910000510 noble metal Inorganic materials 0.000 abstract description 3
- 239000005456 alcohol based solvent Substances 0.000 abstract description 2
- 239000003446 ligand Substances 0.000 abstract description 2
- 229910052751 metal Inorganic materials 0.000 abstract description 2
- 239000002184 metal Substances 0.000 abstract description 2
- 238000005580 one pot reaction Methods 0.000 abstract description 2
- 230000001988 toxicity Effects 0.000 abstract 1
- 231100000419 toxicity Toxicity 0.000 abstract 1
- 238000005481 NMR spectroscopy Methods 0.000 description 19
- 239000007787 solid Substances 0.000 description 13
- 238000001228 spectrum Methods 0.000 description 9
- VYXHVRARDIDEHS-QGTKBVGQSA-N (1z,5z)-cycloocta-1,5-diene Chemical compound C\1C\C=C/CC\C=C/1 VYXHVRARDIDEHS-QGTKBVGQSA-N 0.000 description 8
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 5
- 229910052799 carbon Inorganic materials 0.000 description 5
- 239000001257 hydrogen Substances 0.000 description 5
- 229910052739 hydrogen Inorganic materials 0.000 description 5
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 229910021645 metal ion Inorganic materials 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 229910052759 nickel Inorganic materials 0.000 description 4
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- 238000002354 inductively-coupled plasma atomic emission spectroscopy Methods 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 2
- 230000001133 acceleration Effects 0.000 description 2
- -1 acetaldehyde, pyridine derivatives Chemical class 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- WXNOJTUTEXAZLD-UHFFFAOYSA-L benzonitrile;dichloropalladium Chemical compound Cl[Pd]Cl.N#CC1=CC=CC=C1.N#CC1=CC=CC=C1 WXNOJTUTEXAZLD-UHFFFAOYSA-L 0.000 description 2
- QARVLSVVCXYDNA-UHFFFAOYSA-N bromobenzene Chemical compound BrC1=CC=CC=C1 QARVLSVVCXYDNA-UHFFFAOYSA-N 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 238000005859 coupling reaction Methods 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 239000003002 pH adjusting agent Substances 0.000 description 2
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- 235000002639 sodium chloride Nutrition 0.000 description 2
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 2
- 238000010189 synthetic method Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- VZSRBBMJRBPUNF-UHFFFAOYSA-N 2-(2,3-dihydro-1H-inden-2-ylamino)-N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]pyrimidine-5-carboxamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C(=O)NCCC(N1CC2=C(CC1)NN=N2)=O VZSRBBMJRBPUNF-UHFFFAOYSA-N 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- 239000002083 C09CA01 - Losartan Substances 0.000 description 1
- 238000005577 Kumada cross-coupling reaction Methods 0.000 description 1
- 239000005517 L01XE01 - Imatinib Substances 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- 238000006069 Suzuki reaction reaction Methods 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 150000001345 alkine derivatives Chemical class 0.000 description 1
- 230000029936 alkylation Effects 0.000 description 1
- 238000005804 alkylation reaction Methods 0.000 description 1
- 125000000746 allylic group Chemical group 0.000 description 1
- 230000009435 amidation Effects 0.000 description 1
- 238000007112 amidation reaction Methods 0.000 description 1
- 238000005576 amination reaction Methods 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000000259 anti-tumor effect Effects 0.000 description 1
- 150000001499 aryl bromides Chemical class 0.000 description 1
- 238000006254 arylation reaction Methods 0.000 description 1
- YCOXTKKNXUZSKD-UHFFFAOYSA-N as-o-xylenol Natural products CC1=CC=C(O)C=C1C YCOXTKKNXUZSKD-UHFFFAOYSA-N 0.000 description 1
- 229960000074 biopharmaceutical Drugs 0.000 description 1
- 238000001460 carbon-13 nuclear magnetic resonance spectrum Methods 0.000 description 1
- 230000006315 carbonylation Effects 0.000 description 1
- 238000005810 carbonylation reaction Methods 0.000 description 1
- 238000010668 complexation reaction Methods 0.000 description 1
- 238000007333 cyanation reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 229930013356 epothilone Natural products 0.000 description 1
- 150000003883 epothilone derivatives Chemical class 0.000 description 1
- 238000006266 etherification reaction Methods 0.000 description 1
- 229940080856 gleevec Drugs 0.000 description 1
- 150000004795 grignard reagents Chemical class 0.000 description 1
- 231100000086 high toxicity Toxicity 0.000 description 1
- KTUFNOKKBVMGRW-UHFFFAOYSA-N imatinib Chemical compound C1CN(C)CCN1CC1=CC=C(C(=O)NC=2C=C(NC=3N=C(C=CN=3)C=3C=NC=CC=3)C(C)=CC=2)C=C1 KTUFNOKKBVMGRW-UHFFFAOYSA-N 0.000 description 1
- 238000009616 inductively coupled plasma Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- SNHMUERNLJLMHN-UHFFFAOYSA-N iodobenzene Chemical compound IC1=CC=CC=C1 SNHMUERNLJLMHN-UHFFFAOYSA-N 0.000 description 1
- INQOMBQAUSQDDS-UHFFFAOYSA-N iodomethane Chemical compound IC INQOMBQAUSQDDS-UHFFFAOYSA-N 0.000 description 1
- 229960000519 losartan potassium Drugs 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 125000001160 methoxycarbonyl group Chemical group [H]C([H])([H])OC(*)=O 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 150000002923 oximes Chemical class 0.000 description 1
- 239000001103 potassium chloride Substances 0.000 description 1
- 235000011164 potassium chloride Nutrition 0.000 description 1
- 235000010333 potassium nitrate Nutrition 0.000 description 1
- 239000004323 potassium nitrate Substances 0.000 description 1
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 description 1
- 229910052939 potassium sulfate Inorganic materials 0.000 description 1
- 235000011151 potassium sulphates Nutrition 0.000 description 1
- OXCMYAYHXIHQOA-UHFFFAOYSA-N potassium;[2-butyl-5-chloro-3-[[4-[2-(1,2,4-triaza-3-azanidacyclopenta-1,4-dien-5-yl)phenyl]phenyl]methyl]imidazol-4-yl]methanol Chemical compound [K+].CCCCC1=NC(Cl)=C(CO)N1CC1=CC=C(C=2C(=CC=CC=2)C2=N[N-]N=N2)C=C1 OXCMYAYHXIHQOA-UHFFFAOYSA-N 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000007363 ring formation reaction Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 235000010344 sodium nitrate Nutrition 0.000 description 1
- 239000004317 sodium nitrate Substances 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 238000010183 spectrum analysis Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 150000003613 toluenes Chemical group 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 System
- C07F15/0006—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic System compounds of the platinum group
- C07F15/006—Palladium compounds
Abstract
The invention relates to a method for preparing (1, 5-cyclooctadiene) palladium dichloride in situ, belonging to the technical field of noble metal homogeneous catalyst preparation. The invention prepares (1, 5-cyclooctadiene) palladium dichloride by an in-situ method, and the raw material is palladium powder, so that the cost of the raw material is lower. The solvents and medicines used in the preparation process are conventional acid-base and alcohol solvents, so that the preparation method is low in toxicity and price, and suitable for industrial mass production. Meanwhile, the dosage of the ligand 1, 5-cyclooctadiene can be effectively reduced by adding the complexing promoter, so that the cost is reduced, and the environment-friendly requirement is met. In addition, the preparation process does not need high-temperature heating, the reaction condition is easy to realize, the steps are simple and convenient, the product yield is higher, the washing is easy, and a plurality of synthesis steps are directly prepared by a one-pot serial connection method. The product has the characteristics of low metal impurity content and the like, meets the use requirement of a homogeneous catalyst, and is suitable for serving as the homogeneous catalyst in the organic synthesis reaction of various medicines and fine chemical products.
Description
Technical Field
The invention relates to a method for preparing (1, 5-cyclooctadiene) palladium dichloride in situ, belonging to the technical field of noble metal homogeneous catalyst preparation.
Background
Palladium (Pd) is a fifth-period VIIIB element, has a unique d electronic configuration, has the advantages of high activity, good selectivity, mild reaction conditions, relatively low price and the like as a catalyst, is widely applied to cyclization, arylation, alkylation, carbonylation, cyanation, amidation, amination, etherification and other reactions, obtains 2010 Nobel chemical rewards in coupling reactions, and lays the role of the palladium in the fields of petrochemical industry, fine chemical industry, environmental management, biopharmaceuticals and the like, and the action of difficult shaking is achieved at one time. According to incomplete statistics, about 30% of chemical pharmacy, such as losartan potassium, gleevec, anti-tumor Epothilone and the like, and many chemical raw materials, such as acetaldehyde, pyridine derivatives, vinyl acetate and the like, and organic light-emitting diode (OLED) and the like, are reacted by the catalyst.
(1, 5-cyclooctadiene) Palladium dichloride (Pd (COD) Cl) 2 ) Is an important palladium homogeneous catalyst and is widely concerned by academia and industry. Its molecular formula C 8 H 12 Cl 2 Pd, molecular weight 285.51, melting point 210 ℃, insolubility in water, easy dissolution in organic solvents such as dichloromethane and chloroform, etc., has been applied to organic synthesis reactions of various medicines and fine chemical products, such as Heck coupling reactions of alkyne or alkene, suzuki coupling reactions of arylboronic acid esters or arylbromides with methyl iodide to form functionalized toluene derivatives, allylic substitution reactions of oxime with allyl esters, methoxycarbonyl reactions of iodobenzene, kumada cross coupling of bromobenzene with Grignard reagents to form star-shaped oligothiophenes, etc.
However, pd (COD) Cl is currently concerned 2 Few synthetic processes have been reported and Robert J.Angelici reported synthetic methods using bis (benzonitrile) palladium dichloride or sodium chloropalladate as starting materials. Such raw materials are expensive and labor intensiveThe cost of the industrial production is high, and simultaneously, a large amount of organic solvents with high toxicity such as tetrahydrofuran and the like are required to be used, so that the environment is adversely affected. Chinese patent CN106496279a discloses and reports a synthetic method which is economical and environment-friendly. They take palladium dichloride as raw material, after steps of acid dissolution, etc., the Pd (COD) Cl is obtained by reaction in the mixed solvent of water and ethanol 2 . However, the method has longer production process through the preparation, separation, combination and purification process of palladium dichloride.
Disclosure of Invention
The invention aims to overcome the defects in the prior art and provides a method for directly preparing (1, 5-cyclooctadiene) palladium dichloride from palladium powder in situ. The method is green and environment-friendly, does not need high-temperature heating, has easily-reached reaction conditions, short production period, simple and convenient operation and high yield.
In order to achieve the above purpose, the present invention mainly provides the following technical solutions:
a method for preparing (1, 5-cyclooctadiene) palladium dichloride in situ, which comprises the following steps:
(1) Adding palladium powder into a reactor, adding hydrochloric acid into the reactor, stirring, then introducing chlorine, heating to react at 20-50 ℃ for 2-4 hours, and obtaining palladium solution I after the reaction is completed;
(2) Filtering the palladium solution I obtained in the step (1), adding a pH regulator into the filtrate under the stirring condition to regulate the pH of the filtrate to 2-4, and continuing to react for 2-5h to obtain a palladium solution II;
(3) Diluting the palladium solution II obtained in the step (2) by 5-10 times by using an alcohol solvent, adding a complexing accelerator, then dropwise adding a 1, 5-cyclooctadiene solution at room temperature, and continuing to react for 2-5h after the dropwise adding is finished;
(4) Filtering the product obtained in the step (3), washing a filter cake with an alcohol solvent, and vacuum drying to obtain the (1, 5-cyclooctadiene) palladium dichloride.
Preferably, in the step (1), the purity of the palladium powder is not lower than 99.95%, the volume usage of hydrochloric acid is 4-8 times of the mass of the palladium powder, the mass concentration of hydrochloric acid is 37.5%, the micro positive pressure of chlorine is 0.01-0.05MPa, and the stirring speed is 200-500rpm.
Preferably, in the step (2), the pH adjuster is at least one of sodium carbonate, sodium bicarbonate, sodium hydroxide, potassium carbonate, potassium bicarbonate and potassium hydroxide.
Preferably, in the step (3), a constant pressure dropping funnel is used for dropping the 1, 5-cyclooctadiene solution, and the dropping speed is 2-5 drops/s.
Preferably, in step (3), the solvent of the 1, 5-cyclooctadiene solution is an alcoholic solvent;
preferably, in the step (3), the alcohol solvent is at least one of methanol, ethanol and isopropanol.
Preferably, in the step (3), the complexing promoter is at least one of sodium nitrate, sodium chloride, sodium bicarbonate, sodium sulfate, potassium nitrate, potassium chloride, potassium bicarbonate and potassium sulfate.
Preferably, in the step (3), the addition amount of the complexing promoter is 0.1% -1% of the mass of the palladium powder.
Preferably, in the step (3), the mass of the 1, 5-cyclooctadiene is 1.2-1.5 times of the mass of the palladium powder.
Preferably, in step (3), the mass concentration of the 1, 5-cyclooctadiene solution is 23% -45%.
Preferably, in the step (4), the alcohol solvent is the same as the alcohol solvent in the step (3).
Pd (COD) Cl obtained by the invention 2 Wherein the content of noble metal palladium is more than or equal to 37.1 percent, the product yield is more than or equal to 98.0 percent, and the mass contents of impurity metal ions Ni, cu, cd, cr, ir, pt, au, rh and other impurities are all less than 40ppm.
The product is subjected to nuclear magnetic resonance hydrogen spectrum and carbon spectrum analysis, and the result is that
1 H NMR(CDCl3):δ＝6.32(4H)，δ＝2.92(4H)，δ＝2.57(4H)；
13 C NMR (CDCl 3): δ=116.7 (4C), δ=31.0 (4C); the results are consistent with those reported in the literature for nuclear magnetic resonance hydrogen spectrum and carbon spectrum of (1, 5-cyclooctadiene) palladium dichloride.
Advantageous effects
(1) The in-situ method of the inventionPreparation of homogeneous catalyst Pd (COD) Cl 2 The raw material is palladium powder, and compared with the prior art which uses palladium dichloride, sodium chloropalladate or bis (benzonitrile) palladium dichloride as the raw material, the method can achieve the purposes of reducing the cost of the raw material and shortening the synthesis process.
(2) The solvents and medicines used in the invention are conventional acid-base and alcohol solvents, have low toxicity and low cost, and are suitable for industrial mass production.
(3) The pH regulator used in the invention is at least one of sodium carbonate, sodium bicarbonate, sodium hydroxide, potassium carbonate, potassium bicarbonate and potassium hydroxide, and the precipitate obtained by using the pH regulator is easy to dissolve in hydrochloric acid, the product yield is high, and the sodium salt is easy to wash.
(4) The invention can effectively reduce the dosage of the ligand 1, 5-cyclooctadiene by adding the complexing promoter, reduces the cost and meets the requirements of environmental protection.
(5) The method does not need high-temperature heating in the process, the reaction condition is easy to realize, the steps are simple and convenient, the product yield is high, and a plurality of synthesis steps are directly prepared by a one-pot serial connection method.
Drawings
FIG. 1 is a schematic diagram of the structure of (1.5-cyclooctadiene) palladium dichloride.
FIG. 2 is (1.5-cyclooctadiene) palladium dichloride of example 1 1 H NMR spectrum schematic.
FIG. 3 is (1.5-cyclooctadiene) palladium dichloride of example 1 13 C NMR spectrum schematic.
Detailed Description
The present invention will be further described with reference to specific examples, but the scope of the present invention is not limited thereto.
The invention discloses a method for directly preparing (1, 5-cyclooctadiene) palladium dichloride from metal palladium powder in situ, which is environment-friendly, does not need high-temperature heating, and has the advantages of easy achievement of reaction conditions, short production period, simple and convenient operation and high yield. The preparation method comprises the following steps: (1) Adding palladium powder into hydrochloric acid, stirring, introducing chlorine gas, and heating to dissolve to obtain palladium solution I; (2) Filtering the palladium solution I, and regulating the pH to 2-4 to obtain palladium solution II; (3) Diluting the palladium solution II with an alcohol solvent, adding a complexing accelerator, and continuously dropwise adding the 1, 5-cyclooctadiene dissolved by the alcohol solvent at room temperature until the reaction is complete; (4) Finally, the yellow solid is filtered, washed and dried in vacuum to obtain the product.
The method comprises the following specific steps:
(1) Adding palladium powder with purity of more than or equal to 99.95% into a reactor, adding hydrochloric acid into the reactor, stirring, introducing chlorine, and heating for reaction. Wherein the mass consumption of the hydrochloric acid is 3-10 times of the mass of the palladium powder, the micro positive pressure of the chlorine is 0.01-0.05MPa, the stirring speed is 200-500rpm, the heating temperature is 20-50 ℃, the reaction time is 2-4h, and no macroscopic solid is at the bottle bottom after the reaction is finished, so that the palladium solution I is obtained.
(2) And (3) filtering the palladium solution I obtained in the step (1), adding a pH regulator into the filtrate under the stirring condition to regulate the pH of the filtrate to 2-4, and continuing to react for 2-5h after the addition is finished to obtain a palladium solution II. When the pH adjuster is added, a large amount of heat and bubbles may be evolved due to the reaction of acid and base or the like.
(3) Diluting the palladium solution II obtained in the step (2) by 5-10 times by using an alcohol solvent, then adding a complexation promoter, then adding a 1, 5-cyclooctadiene solution, and dropwise adding at room temperature to generate yellow solid. Wherein the drop acceleration is controlled to be 2-5 drops/s. After the dripping is finished, the reaction is continued for 2 to 5 hours.
The solvent of the 1, 5-cyclooctadiene solution is an alcohol solvent, and a constant pressure dropping funnel is used when the 1, 5-cyclooctadiene solution is added dropwise;
(4) Filtering the product obtained in the step (3), washing the filter cake which is yellow solid with alcohol solvent for 3-5 times, and vacuum drying to obtain Pd (COD) Cl 2 。
Example 1
(1) 100g of palladium powder with the purity of more than or equal to 99.95 percent is added into a reactor, 500mL of hydrochloric acid with the mass concentration of 37.5 percent (the volume usage of the hydrochloric acid is 5 times of the mass of the palladium powder) is added into the reactor, the mixture is stirred, chlorine is introduced into the reactor until the pressure is 0.01MPa, and the reaction is heated, wherein the stirring speed is set to 400rpm, the heating temperature is 25 ℃, and the reaction is carried out for 4 hours; after the reaction was completed, no solid was observed at the bottom of the flask with naked eyes, to obtain palladium solution I.
(2) And (3) filtering the palladium solution I obtained in the step (1), adding sodium bicarbonate in batches under the stirring condition, adjusting the pH of the filtrate to 4, and continuing to react for 3 hours after the addition to obtain a palladium solution II.
(3) The palladium solution II obtained in the step (2) was diluted with 5L of methanol (10-fold), and then 1g of sodium hydrogencarbonate was added. 120g of 1, 5-cyclooctadiene was dissolved in 500ml of methanol (mass concentration of 1, 5-cyclooctadiene solution: 23%) and added to a constant pressure dropping funnel, and the dropping speed was controlled to 3 drops/s at room temperature, resulting in a yellow solid. After the dripping is finished, the reaction is continued for 3 hours.
(4) Finally, the yellow solid is filtered, washed by methanol and dried in vacuum to obtain (1.5-cyclooctadiene) palladium dichloride, and the product yield is 98.0%.
The palladium content in the product is 37.11 percent as measured by an inductively coupled plasma emission spectrometer (ICP-OES), and the mass content of impurity ions such as impurity metal ions Ni, cu, cd, cr, ir, pt, au, rh is less than 40ppm. The structural diagram of the obtained (1, 5-cyclooctadiene) palladium dichloride product is shown in figure 1, and nuclear magnetic resonance is performed 1 The H NMR spectrum is schematically shown in fig. 2, and the result is: 400MHz- 1 H NMR(CDCl 3 ): δ=6.32 (d, 4H), 2.92 (m, 4H), 2.57 (m, 4H); nuclear magnetic resonance 13 The C NMR spectrum is schematically shown in FIG. 3, and the results are: 13 c NMR (CDCl 3): δ= 116.74, 31.0. As can be seen from FIGS. 2 and 3, the structure of the obtained (1.5-cyclooctadiene) palladium dichloride product is schematically shown in FIG. 1, which is consistent with the nuclear magnetic resonance hydrogen spectrum and carbon spectrum of the (1.5-cyclooctadiene) palladium dichloride literature.
Example 2
(1) Adding 1kg of palladium powder with purity of more than or equal to 99.95% into a reactor, adding 8L of hydrochloric acid solution with mass concentration of 37.5% (the volume usage of hydrochloric acid is 8 times of the mass of palladium powder), stirring, introducing a small amount of chlorine gas to pressure of 0.04MPa, heating to 35 ℃ for reaction, and setting stirring speed to 300rpm; and (3) reacting for 3 hours, and obtaining the palladium solution I after the reaction is finished and no solid is visible at the bottom of the bottle.
(2) And (3) filtering the palladium solution I obtained in the step (1), adding sodium carbonate in batches under the stirring condition, adjusting the pH of the filtrate to 2, and continuing to react for 2 hours after the addition to obtain a palladium solution II.
(3) The palladium solution II obtained in the step (2) was diluted with 60L of ethanol (7.5-fold), and 5g of sodium carbonate was added. 1.5kg of 1, 5-cyclooctadiene was dissolved in 5L of ethanol (mass concentration of 1, 5-cyclooctadiene solution: 27%) and added to a constant pressure dropping funnel, and the mixture was continuously dropped at room temperature to give a yellow solid. Wherein the drop acceleration is controlled at 5 drops/s. After the dripping is finished, the reaction is continued for 2 hours.
(4) Finally, the yellow solid is filtered, washed by ethanol and dried in vacuum to obtain Pd (COD) Cl 2 The product yield was 98.1%.
The palladium content in the product is 37.12% by ICP-OES, and the mass content of impurity ions such as impurity metal ions Ni, cu, cd, cr, ir, pt, au, rh is less than 40ppm.
The structural diagram of the obtained (1, 5-cyclooctadiene) palladium dichloride product is shown in figure 1, and nuclear magnetic resonance is performed 1 The H NMR spectrum results were: 400MHz- 1 H NMR(CDCl 3 ): δ=6.32 (d, 4H), 2.92 (m, 4H), 2.57 (m, 4H); nuclear magnetic resonance 13 The C NMR spectrum results were: 13 c NMR (CDCl 3): δ= 116.74, 31.0. Is consistent with the nuclear magnetic resonance hydrogen spectrum and the carbon spectrum of the (1.5-cyclooctadiene) palladium dichloride literature.
Example 3
(1) 5kg of palladium powder with purity of more than or equal to 99.9% is added into a reactor, 20L of hydrochloric acid with mass concentration of 37.5% (the volume usage of the hydrochloric acid is 4 times of the mass of the palladium powder) is added into the reactor, the mixture is stirred, chlorine is introduced into the reactor until the pressure is 0.05MPa, the reactor is heated to 50 ℃ for reaction, and the stirring speed is 500rpm; and (3) reacting for 2 hours, and obtaining the palladium solution I after the reaction is finished, wherein no solid is visible at the bottom of the bottle.
(2) And (3) filtering the palladium solution I obtained in the step (1), slowly dropwise adding a sodium hydroxide solution with the concentration of 30% under the stirring condition, adjusting the pH of the filtrate to 3, and continuing to react for 4 hours after the completion of the addition to obtain a palladium solution II.
(3) The palladium solution II obtained in step (2) was diluted with 100L of isopropyl alcohol (5-fold), and 30g of sodium chloride was added. 6.5kg of 1, 5-cyclooctadiene was dissolved in 10L of isopropanol (mass concentration of 1, 5-cyclooctadiene solution: 45%) and added to a constant pressure dropping funnel, and the mixture was continuously dropped at room temperature to give a yellow solid. The dropping speed is controlled at 5 drops/s, and the reaction is continued for 4 hours after the dropping is completed.
(4) Finally, the yellow solid is filtered, washed by isopropanol and dried in vacuum to obtain the product with the yield of 98.4 percent.
The palladium content in the product is 37.12% by ICP-OES, and the mass content of impurity ions such as impurity metal ions Ni, cu, cd, cr, ir, pt, au, rh is less than 40ppm.
The structural diagram of the obtained (1, 5-cyclooctadiene) palladium dichloride product is shown in figure 1, and nuclear magnetic resonance is performed 1 The H NMR spectrum results were: 400MHz- 1 H NMR(CDCl 3 ): δ=6.32 (d, 4H), 2.92 (m, 4H), 2.57 (m, 4H); nuclear magnetic resonance 13 The C NMR spectrum results were: 13 c NMR (CDCl 3): δ= 116.74, 31.0. Is consistent with the nuclear magnetic resonance hydrogen spectrum and the carbon spectrum of the (1.5-cyclooctadiene) palladium dichloride literature.
The above description is only of the preferred embodiments of the present invention and is not intended to limit the present invention in any way. Those skilled in the art should be informed by logic analysis, reasoning, etc. according to the technical scheme or conception of the present invention.
Claims (6)
1. A method for preparing (1, 5-cyclooctadiene) palladium dichloride in situ, which is characterized by comprising the following steps:
(1) Adding palladium powder into a reactor, adding hydrochloric acid into the reactor, stirring, then introducing chlorine, heating to react at 20-50 ℃ for 2-4 hours, and obtaining palladium solution I after the reaction is completed;
(2) Filtering the palladium solution I obtained in the step (1), adding a pH regulator into the filtrate under the stirring condition to regulate the pH of the filtrate to 2-4, and continuing to react for 2-5h to obtain a palladium solution II;
(3) Diluting the palladium solution II obtained in the step (2) by 5-10 times by using an alcohol solvent, adding a complexing accelerator, then dropwise adding a 1, 5-cyclooctadiene solution at room temperature, and continuing to react for 2-5h after the dropwise adding is finished;
(4) Filtering the product obtained in the step (3), washing a filter cake with an alcohol solvent, and vacuum drying to obtain (1, 5-cyclooctadiene) palladium dichloride;
in the step (1), the purity of palladium powder is not lower than 99.95%, the volume consumption of hydrochloric acid is 4-8 times of the mass of palladium powder, the mass concentration of hydrochloric acid is 37.5%, the micro positive pressure of chlorine is 0.01-0.05MPa, and the stirring speed is 200-500rpm;
in the step (2), the pH regulator is at least one of sodium carbonate, sodium bicarbonate, sodium hydroxide, potassium carbonate, potassium bicarbonate and potassium hydroxide;
in the step (3), the complexing promoter is sodium bicarbonate; the addition amount of the complexing promoter is 0.1-1% of the mass of the palladium powder.
2. The method for in situ preparation of (1, 5-cyclooctadiene) palladium dichloride according to claim 1, wherein in the step (3), the solvent of the 1, 5-cyclooctadiene solution is an alcohol solvent.
3. The method for in-situ preparation of (1, 5-cyclooctadiene) palladium dichloride according to claim 1, wherein in the step (3), a constant pressure dropping funnel is used when 1, 5-cyclooctadiene solution is added dropwise, and the dropping speed is 2-5 drops/s.
4. The method for in situ preparation of (1, 5-cyclooctadiene) palladium dichloride according to claim 2, wherein in the step (3) and the step (4), the alcohol solvent is at least one of methanol, ethanol and isopropanol.
5. The method for in-situ preparation of (1, 5-cyclooctadiene) palladium dichloride according to claim 1, wherein in the step (3), the mass of the 1, 5-cyclooctadiene is 1.2-1.5 times of the mass of palladium powder.
6. The method for in situ preparation of (1, 5-cyclooctadiene) palladium dichloride according to claim 1, wherein the mass concentration of the 1, 5-cyclooctadiene solution in the step (3) is 23% -45%.
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