CN106496279A - The synthetic method of (1,5 cyclo-octadiene) two chloro palladium - Google Patents
The synthetic method of (1,5 cyclo-octadiene) two chloro palladium Download PDFInfo
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- CN106496279A CN106496279A CN201610812809.3A CN201610812809A CN106496279A CN 106496279 A CN106496279 A CN 106496279A CN 201610812809 A CN201610812809 A CN 201610812809A CN 106496279 A CN106496279 A CN 106496279A
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- octadiene
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- VYXHVRARDIDEHS-UHFFFAOYSA-N 1,5-cyclooctadiene Chemical compound C1CC=CCCC=C1 VYXHVRARDIDEHS-UHFFFAOYSA-N 0.000 title claims abstract description 40
- 239000004912 1,5-cyclooctadiene Substances 0.000 title claims abstract description 40
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 title claims abstract description 34
- 229910052763 palladium Inorganic materials 0.000 title claims abstract description 24
- -1 chloro palladium Chemical compound 0.000 title claims abstract description 23
- 238000010189 synthetic method Methods 0.000 title claims abstract description 13
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 42
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 27
- RRKODOZNUZCUBN-CCAGOZQPSA-N (1z,3z)-cycloocta-1,3-diene Chemical compound C1CC\C=C/C=C\C1 RRKODOZNUZCUBN-CCAGOZQPSA-N 0.000 claims abstract description 18
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 claims abstract description 18
- 229960004756 ethanol Drugs 0.000 claims abstract description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229960000935 dehydrated alcohol Drugs 0.000 claims abstract description 9
- 238000001914 filtration Methods 0.000 claims abstract description 7
- 238000005406 washing Methods 0.000 claims abstract description 6
- 238000001291 vacuum drying Methods 0.000 claims abstract 2
- 239000000243 solution Substances 0.000 claims description 29
- 238000006243 chemical reaction Methods 0.000 claims description 24
- 239000007787 solid Substances 0.000 claims description 17
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 claims description 10
- 238000010790 dilution Methods 0.000 claims description 5
- 239000012895 dilution Substances 0.000 claims description 5
- 239000000376 reactant Substances 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- 239000007864 aqueous solution Substances 0.000 claims 1
- 239000012467 final product Substances 0.000 claims 1
- 238000002360 preparation method Methods 0.000 abstract description 11
- 239000013078 crystal Substances 0.000 abstract description 5
- 230000007613 environmental effect Effects 0.000 abstract description 5
- 239000002994 raw material Substances 0.000 abstract description 5
- 239000002904 solvent Substances 0.000 abstract description 4
- 230000008901 benefit Effects 0.000 abstract description 3
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 125000001309 chloro group Chemical group Cl* 0.000 abstract description 2
- 238000000034 method Methods 0.000 abstract description 2
- 230000008569 process Effects 0.000 abstract description 2
- 239000003125 aqueous solvent Substances 0.000 abstract 1
- 239000000843 powder Substances 0.000 abstract 1
- 238000004781 supercooling Methods 0.000 abstract 1
- 239000003054 catalyst Substances 0.000 description 5
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 230000004044 response Effects 0.000 description 4
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 description 3
- 238000004587 chromatography analysis Methods 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 235000013399 edible fruits Nutrition 0.000 description 3
- 238000000921 elemental analysis Methods 0.000 description 3
- 239000007791 liquid phase Substances 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- 239000012046 mixed solvent Substances 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 238000001308 synthesis method Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- 230000001988 toxicity Effects 0.000 description 2
- 231100000419 toxicity Toxicity 0.000 description 2
- XILIYVSXLSWUAI-UHFFFAOYSA-N 2-(diethylamino)ethyl n'-phenylcarbamimidothioate;dihydrobromide Chemical compound Br.Br.CCN(CC)CCSC(N)=NC1=CC=CC=C1 XILIYVSXLSWUAI-UHFFFAOYSA-N 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 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 1
- 239000002253 acid Substances 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 150000001345 alkine derivatives Chemical class 0.000 description 1
- 125000000746 allylic group Chemical group 0.000 description 1
- 125000003118 aryl group Chemical group 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
- 230000009286 beneficial effect Effects 0.000 description 1
- 229960000074 biopharmaceutical Drugs 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- SNHMUERNLJLMHN-UHFFFAOYSA-N iodobenzene Chemical compound IC1=CC=CC=C1 SNHMUERNLJLMHN-UHFFFAOYSA-N 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 125000001160 methoxycarbonyl group Chemical group [H]C([H])([H])OC(*)=O 0.000 description 1
- 150000002923 oximes Chemical class 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a kind of green, economy, (the 1 of environmental protection, 5 cyclo-octadiene) two chloro palladiums synthetic method, palladium chloride is adopted in preparation process for raw material, with after dissolving with hydrochloric acid with 1,5 cyclo-octadiene (COD) are reacted in the aqueous solvent of environmental protection and ethanol, yellow or lurid crystal powder is obtained after supercooling, filtration, washing, filtration, process of vacuum drying, as (1,5 cyclo-octadiene) two chloro palladium；Preparation method in the present invention, selects relatively inexpensive palladium chloride, greatly reduces the cost of whole production process, while the water and dehydrated alcohol that employ environmental protection make solvent, embody the advantage of environmentally friendly preparation theory and green syt.
Description
Technical field
The present invention relates to one kind with 1,5- cyclo-octadiene for part noble metal catalyst preparation method, specifically (1,
5- cyclo-octadiene)-two chloro palladiums green synthesis method.
Background technology
Palladium atom has the d electronic configurations of the platinum family element of uniqueness because of which, can form the organic metal of a class special construction
Coordination compound, so as to promote being smoothed out for many chemical reactions, is petrochemical industry, fine chemistry industry, environmental improvement and bio-pharmaceuticals
Important catalyst.
(1,5- cyclo-octadiene)-two chloro palladium ([Pd (COD) Cl2]) it is a kind of important noble metal catalyst, due to which
Have unique catalytic property, raw material cheap and easy to get, have the advantages that multiple catalytic effects, therefore, [Pd (COD) Cl2] conduct
Catalyst has caused the extensive concern of academia and industrial quarters, after research and testing, has been widely used for all kinds of having
Machine synthetic reaction carries out the preparation of important medicine and fine chemical product, such as catalyzing and synthesizing for various C-O keys, C-N keys and C-C keys
Process.[Pd(COD)Cl2] the Heck coupling reactions of catalysis alkynes and alkene are commonly used for, the Suzuki of aromatic bromide is coupled
The allylic substitution reaction of reaction, oxime and allyl ester, and the methoxycarbonyl group reaction of iodobenzene etc..
(1,5- cyclo-octadiene)-two chloro palladium as catalyst cause the condition of above-mentioned reaction become gently, yield improve,
Selective long-range DEPT, with important using value and market prospect.
But the report obtained with regard to the synthesis of (1,5- cyclo-octadiene)-two chloro palladium simultaneously seldom, mainly applies the acid of chlorine palladium
Sodium is used as initial reaction raw materials, but the market price of the reaction raw materials is expensive, therefore can only be in experiment in preparation process
Carry out under the scale of room, if carrying out commercial production, cost is very high, and during dissolving 1,5- cyclo-octadiene, make
Solvent is made with tetrahydrofuran, although can be very good to dissolve, but there is certain toxicity due to tetrahydrofuran, therefore can be to ring
Border affects.The invention discloses a kind of economy, environmentally friendly synthesis method, it is achieved that environmentally friendly preparing is excellent
Gesture.
Content of the invention
It is an object of the invention to provide a kind of economy, the synthetic method of (1,5- cyclo-octadiene)-two chloro palladium of environmental protection, from
Fundamentally solve the problems, such as that existing preparation method expensive starting materials, pollution are larger.
In the present invention, the molecular formula of (1,5- cyclo-octadiene)-two chloro palladium is C8H12Cl2Pd, its structural formula are as follows：
；
Synthesis is somebody's turn to do under the concrete operations of (1,5- cyclo-octadiene)-two chloro palladium：
（1）Palladium chloride is added in hydrochloric acid solution, is dissolved under the conditions of 40-80 DEG C, after dissolving, add dehydrated alcohol dilution,
Obtain the ethanol solution hydrochloride of palladium chloride；
（2）1,5- cyclo-octadiene (COD) is added in ethanol water, stirring at normal temperature dissolves, and obtains 1,5- cyclo-octadiene
(COD) ethanol-water solution；
（3）By step（1）In obtained by solution, be added drop-wise to step（2）In the ethanol-water solution of 1,5- cyclo-octadiene (COD),
Reaction temperature is controlled at 45-60 DEG C after being added dropwise to complete, continue reaction 0.5-3 hours, after completion of the reaction, reactant liquor is naturally cold
But to room temperature, yellow crystals in observing response bottle, occur, after filtration, with the absolute ethanol washing solid of ice, gained solid is true
Empty dry, yield is weighed and calculate after drying, that is, complete the preparation of (1,5- cyclo-octadiene)-two chloro palladium.
In above-mentioned synthetic method, the concentration of hydrochloric acid solution for being used is 4-6mol/L.
In above-mentioned synthetic method, the consumption for dissolving the hydrochloric acid solution of palladium chloride is 10-30 times of palladium chloride quality, dilute
The consumption of the dehydrated alcohol that releases is 1-10 times of hydrochloric acid volume.
In above-mentioned synthetic method, the dehydrated alcohol that the solvent used by solid is ice is washed.
In above-mentioned synthetic method, the mol ratio of palladium chloride and 1,5- cyclo-octadiene is 1:1-1.5.
The ethanol water is ethanol and water by volume 1:1-2:1 ratio is mixed to prepare.
Beneficial effects of the present invention are embodied in：
1st, described according to invention, the use of the relatively low palladium chloride of price is raw material, reduces cost；
2nd, without High Temperature High Pressure, reaction condition is gentle, and step is simple, is suitable for industrialized production for the course of reaction in invention；
3rd, used in reacting, solvent is second alcohol and water, small toxicity and low cost, it is to avoid industrial pollution, embodies green syt
Advantage.
Specific embodiment
The present invention is described in further detail below by embodiment, but the scope of the present invention be not limited to described interior
Hold.
Embodiment 1：The preparation method of (1,5- cyclo-octadiene)-two chloro palladium, comprises the following steps：
A, palladium chloride 3.5466g (20mmol) is added to 56.6g concentration be 4mol/L hydrochloric acid in, molten under the conditions of 45 DEG C
Solution, adds the dilution of 116.4mL dehydrated alcohol, obtains the ethanol solution hydrochloride of palladium chloride after dissolving；
B, by 2.16g 1,5- cyclo-octadiene (COD) is added in the mixed solvent of second alcohol and water, stirring at normal temperature dissolve, obtain 1,
The ethanol-water solution of 5- cyclo-octadiene (COD)；
C, by the solution obtained by step a, be added drop-wise in step b in the water and ethanol solution of 1,5- cyclo-octadiene (COD), drip
Plus after the completion of by reaction temperature control at 45 DEG C, continue reaction 1 hour, after completion of the reaction, reactant liquor is naturally cooled to room temperature,
There are yellow crystals to occur in observing response bottle, after filtration, with the absolute ethanol washing solid of ice, gained solid is vacuum dried, dry
Yellow solid 5.36g, yield 93.8% is weighed after dry.
(1,5- cyclo-octadiene)-two chloro palladium prepared by the present embodiment is yellow or light yellow solid, and which is tied
Fruit is analyzed, and is measured with XT-4 melting point detectors, is as a result 205 DEG C or so beginning blackening, starts to melt between 209-210 DEG C
Solution；Efficient liquid phase chromatographic analysis are obtained, purity=98.1%；Elemental analysis data is (%): C, 33.61; H, 4.23; Pd
37.25.
Embodiment 2：The preparation method of (1,5- cyclo-octadiene)-two chloro palladium, comprises the following steps：
A, palladium chloride 7.0932g (40mmol) is added to 146.2g concentration be 5mol/L hydrochloric acid in, under the conditions of 55 DEG C
Dissolving, adds the dilution of 466.2mL dehydrated alcohol, obtains the ethanol solution hydrochloride of palladium chloride after dissolving；
B, by 5.18g 1,5- cyclo-octadiene (COD) is added in the mixed solvent of second alcohol and water, stirring at normal temperature dissolve, obtain 1,
The ethanol-water solution of 5- cyclo-octadiene (COD)；
C, by the solution obtained by step a, be added drop-wise in step b in the water and ethanol solution of 1,5- cyclo-octadiene (COD),
Reaction temperature is controlled at 55 DEG C after being added dropwise to complete, continue reaction 3 hours, after completion of the reaction, reactant liquor is naturally cooled to room
Temperature, has yellow crystals to occur in observing response bottle, after filtration, with the absolute ethanol washing solid of ice, gained solid is vacuum dried,
Light yellow solid 10.43g, yield 91.3% is weighed after drying.
(1,5- cyclo-octadiene)-two chloro palladium prepared by the present embodiment is yellow or light yellow solid, and which is tied
Fruit is analyzed, and is measured with XT-4 melting point detectors, is as a result 208 DEG C or so beginning blackening, starts to melt between 210-213 DEG C
Solution；Efficient liquid phase chromatographic analysis are obtained, purity=97.8%；Elemental analysis data is (%): C, 33.59; H, 4.21; Pd
37.31.
Embodiment 3：The preparation method of (1,5- cyclo-octadiene)-two chloro palladium, comprises the following steps：
A, palladium chloride 14.1864g (80mmol) is added to 269.7g concentration be 6mol/L hydrochloric acid in, under the conditions of 75 DEG C
Dissolving, adds the dilution of 1865.4mL dehydrated alcohol, obtains the ethanol solution hydrochloride of palladium chloride after dissolving.
B, by 12.96g 1,5- cyclo-octadiene (COD) is added in the mixed solvent of second alcohol and water, stirring at normal temperature dissolve,
Obtain the ethanol-water solution of 1,5- cyclo-octadiene (COD).
C, by the solution obtained by step a, be added drop-wise to the water and ethanol solution of 1,5- cyclo-octadiene (COD) in step b
In, reaction temperature is controlled at 65 DEG C after being added dropwise to complete, continue reaction 3 hours, after completion of the reaction, reactant liquor is naturally cooled to
Room temperature, has yellow crystals to occur in observing response bottle, after filtration, with the absolute ethanol washing solid of ice, gained solid vacuum is done
Dry, light yellow solid 22.18g, yield 97.1% is weighed after drying.
(1,5- cyclo-octadiene)-two chloro palladium prepared by the present embodiment is yellow or light yellow solid, and which is tied
Fruit is analyzed, and is measured with XT-4 melting point detectors, is as a result 206 DEG C or so beginning blackening, starts to melt between 209-212 DEG C
Solution；Efficient liquid phase chromatographic analysis are obtained, purity=97.9%；Elemental analysis data is (%): C, 33.62; H, 4.20; Pd
37.27.
It should be noted that above-mentioned is only specific embodiment of the invention, not it is used for the protection model for limiting the present invention
Enclose, on the basis of above-described embodiment, done equivalents belong to protection scope of the present invention.
Claims (5)
1. a kind of synthetic method of (1,5- cyclo-octadiene)-two chloro palladium, it is characterised in that comprise the following steps that：
（1）Palladium chloride is added in concentration 4-6 mol/L hydrochloric acid solutions, is dissolved under the conditions of 40-80 DEG C, added after dissolving
Dehydrated alcohol dilutes, and obtains the ethanol solution hydrochloride of palladium chloride；
（2）1,5- cyclo-octadiene is added in ethanol water, stirring at normal temperature dissolves, obtain the ethanol of 1,5- cyclo-octadiene-
Aqueous solution；
（3）By step（1）Obtained solution, is added drop-wise to step（2）In the ethanol-water solution of 1,5- cyclo-octadiene (COD), drop
Plus after the completion of at reaction temperature 45-60 DEG C continue reaction 0.5-3 hours, after completion of the reaction, reactant liquor is naturally cooled to room
Temperature, after filtration, with the absolute ethanol washing solid of ice, the vacuum drying of gained solid, obtains final product (1,5- cyclo-octadiene)-two chloro
Palladium.
2. the synthetic method of (1,5- cyclo-octadiene)-two chloro palladium according to claim 1, it is characterised in that：Dissolving two
The consumption of the hydrochloric acid solution of Palladous chloride. is 10-30 times of palladium chloride quality.
3. the synthetic method of (1,5- cyclo-octadiene)-two chloro palladium according to claim 1, it is characterised in that：Dilution is used
The amount of dehydrated alcohol be 1-10 times of hydrochloric acid volume.
4. the synthetic method of (1,5- cyclo-octadiene)-two chloro palladium according to claim 1, it is characterised in that：Dichloride
Palladium is 1 with the mol ratio of 1,5- cyclo-octadiene:1-1.5.
5. the synthetic method of (1,5- cyclo-octadiene)-two chloro palladium according to claim 1, it is characterised in that：Ethanol water
Solution is ethanol and water by volume 1:1-2:1 ratio is mixed to prepare.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110078771A (en) * | 2019-06-06 | 2019-08-02 | 江苏欣诺科催化剂有限公司 | A kind of preparation method of iridium catalyst |
| CN114213466A (en) * | 2021-11-18 | 2022-03-22 | 中国船舶重工集团公司第七一八研究所 | Method for in-situ preparation of (1, 5-cyclooctadiene) palladium dichloride |
| CN114605476A (en) * | 2022-02-28 | 2022-06-10 | 北京格林凯默科技有限公司 | Preparation method of allyl palladium chloride dimer |
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|---|---|---|---|---|
| JPS63264594A (en) * | 1987-04-21 | 1988-11-01 | Ajinomoto Co Inc | Antitumor agent |
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2016
- 2016-09-09 CN CN201610812809.3A patent/CN106496279A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS63264594A (en) * | 1987-04-21 | 1988-11-01 | Ajinomoto Co Inc | Antitumor agent |
Non-Patent Citations (1)
| Title |
|---|
| A.M.S. HOSSAIN ET AL: ""Synthesis and study of the catalytic applications in C–C coupling reactions of hybrid nanosystems based on alumina and palladium nanoparticles"", 《INORGANICA CHIMICA ACTA》 * |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110078771A (en) * | 2019-06-06 | 2019-08-02 | 江苏欣诺科催化剂有限公司 | A kind of preparation method of iridium catalyst |
| CN110078771B (en) * | 2019-06-06 | 2022-04-05 | 江苏欣诺科催化剂有限公司 | Preparation method of iridium catalyst |
| CN114213466A (en) * | 2021-11-18 | 2022-03-22 | 中国船舶重工集团公司第七一八研究所 | Method for in-situ preparation of (1, 5-cyclooctadiene) palladium dichloride |
| CN114213466B (en) * | 2021-11-18 | 2023-12-19 | 中国船舶重工集团公司第七一八研究所 | Method for in-situ preparation of (1, 5-cyclooctadiene) palladium dichloride |
| CN114605476A (en) * | 2022-02-28 | 2022-06-10 | 北京格林凯默科技有限公司 | Preparation method of allyl palladium chloride dimer |
| CN114605476B (en) * | 2022-02-28 | 2024-02-23 | 北京格林凯默科技有限公司 | Preparation method of allyl palladium chloride dimer |
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Application publication date: 20170315 |