CN114437142B - Preparation method of crotyl palladium chloride dimer - Google Patents
Preparation method of crotyl palladium chloride dimer Download PDFInfo
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- CN114437142B CN114437142B CN202210188690.2A CN202210188690A CN114437142B CN 114437142 B CN114437142 B CN 114437142B CN 202210188690 A CN202210188690 A CN 202210188690A CN 114437142 B CN114437142 B CN 114437142B
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- Prior art keywords
- palladium chloride
- crotyl
- reaction
- chloride
- cyclooctadiene
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- 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 title claims abstract description 29
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 claims abstract description 42
- 238000006243 chemical reaction Methods 0.000 claims abstract description 39
- VYXHVRARDIDEHS-UHFFFAOYSA-N 1,5-cyclooctadiene Chemical compound C1CC=CCCC=C1 VYXHVRARDIDEHS-UHFFFAOYSA-N 0.000 claims abstract description 30
- 239000004912 1,5-cyclooctadiene Substances 0.000 claims abstract description 30
- YTKRILODNOEEPX-NSCUHMNNSA-N crotyl chloride Chemical compound C\C=C\CCl YTKRILODNOEEPX-NSCUHMNNSA-N 0.000 claims abstract description 28
- 238000000034 method Methods 0.000 claims abstract description 21
- 230000035484 reaction time Effects 0.000 claims abstract description 13
- 239000002904 solvent Substances 0.000 claims abstract description 11
- 238000001914 filtration Methods 0.000 claims abstract description 10
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 57
- 239000012065 filter cake Substances 0.000 claims description 7
- 239000000706 filtrate Substances 0.000 claims description 6
- 239000007810 chemical reaction solvent Substances 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 3
- 239000011261 inert gas Substances 0.000 claims description 3
- 239000002699 waste material Substances 0.000 abstract description 7
- 238000000605 extraction Methods 0.000 abstract description 6
- 238000009776 industrial production Methods 0.000 abstract description 2
- 238000011112 process operation Methods 0.000 abstract description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- 239000007787 solid Substances 0.000 description 10
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 8
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 6
- 239000000463 material Substances 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 239000003054 catalyst Substances 0.000 description 4
- 238000011068 loading method Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 235000011164 potassium chloride Nutrition 0.000 description 4
- 239000001103 potassium chloride Substances 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 239000000539 dimer Substances 0.000 description 3
- 239000012074 organic phase Substances 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000012452 mother liquor Substances 0.000 description 2
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 230000036632 reaction speed Effects 0.000 description 2
- 239000010888 waste organic solvent Substances 0.000 description 2
- 239000002351 wastewater Substances 0.000 description 2
- 241001448862 Croton Species 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- -1 that is Substances 0.000 description 1
- 230000009466 transformation 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 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 preparation method of a crotyl palladium chloride dimer, which uses 1, 5-cyclooctadiene to participate in the reaction of palladium chloride and crotyl chloride to prepare the crotyl palladium chloride dimer. Wherein, the 1, 5-cyclooctadiene accelerates the reaction process, greatly shortens the reaction time, and shortens the reaction time from 24 hours to 3 hours in the prior art. And the complex processes of extraction, desolventizing and the like in the prior art are changed into simple filtration, so that the post-treatment process is greatly simplified, and the process operation is simple and convenient. The invention has high yield, high product purity, 4 times of the productivity of the prior art, and the solvent can be directly used for the next reaction, no three wastes are generated, and the process is environment-friendly, and is particularly suitable for large-scale industrial production.
Description
Technical Field
The invention relates to a preparation method of a crotyl palladium chloride dimer, belonging to the technical field of organic synthesis.
Background
The crotyl palladium chloride dimer plays an important role in modern organic synthesis and practical application, is mainly used as a catalyst in Suzuki, heck, negishi and other coupling reactions, and has very wide application in the synthesis of liquid crystal materials, optical functional complexes and other substances.
The existing method for preparing the crotyl palladium chloride dimer is to take palladium chloride as a starting material, form an ionic state with potassium chloride, then complex with the crotyl chloride to generate the crotyl palladium chloride dimer, then extract the crotyl palladium chloride dimer with dichloromethane, desolventize the organic phase and dry the organic phase to obtain the crotyl palladium chloride dimer. Although the yield is higher, the reaction time is too long, and usually 24 hours are needed for completion; the post-treatment needs extraction, desolventizing and other steps, which is complicated; it also requires a large amount of water to dissolve the solid raw materials or as a reaction solvent, thus resulting in low productivity accompanied by waste water and waste organic solvent.
How to shorten the production time of the crotyl palladium chloride dimer, simplify the post-treatment, improve the productivity, avoid the generation of three wastes and solve the technical problem in the preparation field of the crotyl palladium chloride dimer.
Disclosure of Invention
The invention aims to provide a novel preparation method of a crotyl palladium chloride dimer, which has the advantages of greatly shortening the reaction time, improving the productivity, simplifying the post-treatment process, generating no three wastes and effectively solving the problems in the prior art.
The invention provides a preparation method of a crotyl palladium chloride dimer, which is characterized in that 1, 5-cyclooctadiene participates in the reaction of palladium chloride and crotyl chloride to prepare the crotyl palladium chloride dimer shown in a formula (I)
。
According to a specific but non-limiting embodiment of the present invention, the preparation method comprises: under the protection of inert gas, adding palladium chloride, 1, 5-cyclooctadiene, crotyl chloride and toluene into a reaction container, reacting for more than 0.5 hours at the temperature of 70-100 ℃, naturally cooling to 0-30 ℃, filtering, and drying a filter cake to obtain the crotyl palladium chloride dimer shown in the formula (I).
According to a specific, but non-limiting embodiment of the present invention, wherein the molar ratio of 1, 5-cyclooctadiene to palladium chloride is greater than 0.5:1.
according to a specific but non-limiting embodiment of the present invention, wherein the molar ratio of 1, 5-cyclooctadiene to palladium chloride is between 1 and 1.5:1.
according to a specific, but non-limiting embodiment of the present invention, wherein the molar ratio of crotyl chloride to palladium chloride is greater than 1:1.
according to a specific, but non-limiting embodiment of the present invention, wherein the molar ratio of crotyl chloride to palladium chloride is from 1 to 1.5:1.
according to a specific but non-limiting embodiment of the present invention, toluene is the reaction solvent.
According to a specific, but non-limiting embodiment of the present invention, wherein the mass ratio of toluene to palladium chloride is greater than 3:1.
according to a specific but non-limiting embodiment of the present invention, toluene is not added to the reaction, and an excess of crotyl chloride is used as a solvent.
According to a specific but non-limiting embodiment of the present invention, the reaction time is 2 to 5 hours.
The beneficial effects of the invention are mainly as follows:
1. according to the invention, 1, 5-cyclooctadiene is used for participating in the reaction of palladium chloride and crotyl chloride, and the 1, 5-cyclooctadiene plays a role of a catalyst, so that the reaction process is accelerated, the reaction time is greatly shortened, and the reaction time is shortened to about 3 hours from 24 hours in the prior art.
2. The auxiliary materials of the invention are all liquid, and the product has no other solid impurities except the solid of the crotyl palladium chloride dimer, so that the complicated processes of extraction, desolventizing and the like in the prior art are changed into simple filtration, the post-treatment is greatly simplified, the process operation is simple and convenient, and the invention is especially suitable for large-scale industrial production.
3. The solvent consumption of the invention is small, and the productivity of the invention is 4 times that of the prior art with the same solvent amount or the same reaction vessel; the solvent can be directly used for the next reaction without treatment, so that three wastes are not generated, and the process is environment-friendly.
Drawings
FIG. 1 is a nuclear magnetic resonance spectrum of a dimer of palladium chloride crotyl prepared in example 1 of the present invention.
Detailed Description
The following provides a detailed description of the present invention, but the present invention is not limited to the following embodiments.
Typically palladium chloride does not react directly with crotyl chloride, with no product formation. The inventor of the application has long-term research and found that if 1, 5-cyclooctadiene is added, palladium chloride and crotyl chloride can react rapidly to obtain crotyl palladium chloride dimer in the presence of 1, 5-cyclooctadiene. The 1, 5-cyclooctadiene plays a role of a catalyst, accelerates the reaction process, greatly shortens the reaction time, and can complete the reaction in only 3 hours. Moreover, the same reaction vessel had four times the loading of palladium chloride and four times the capacity of the prior art. Meanwhile, the post-treatment is carried out by simple filtration; the solvent can be directly used without three wastes, and has remarkable beneficial effects. The preparation of the crotyl palladium chloride dimer by using 1, 5-cyclooctadiene to participate in the reaction of palladium chloride and crotyl chloride is not reported in the literature at present, and the application is the first time.
The present invention thus provides a novel process for preparing a dimer of crotyl palladium chloride using 1, 5-cyclooctadiene to participate in the reaction of palladium chloride and crotyl chloride to prepare a dimer of crotyl palladium chloride. The reaction formula of the invention is as follows:
we have found that this reaction must be carried out with the addition of 1, 5-cyclooctadiene and only crotyl chloride does not react with palladium chloride. Moreover, by detecting the reaction components at a plurality of stages in the reaction process, the complex of palladium chloride and 1, 5-cyclooctadiene is not present in the reaction process all the time, so that the 1, 5-cyclooctadiene is presumed to act as a catalyst in the reaction, and the reaction process is accelerated.
Specifically, the method for preparing the crotyl palladium chloride dimer comprises the following steps: under the protection of inert gas, adding palladium chloride, 1, 5-cyclooctadiene, crotyl chloride and toluene into a reaction container, reacting for more than 0.5 hours at the temperature of 70-100 ℃, naturally cooling to 0-30 ℃, filtering, and drying a filter cake to obtain the crotyl palladium chloride dimer shown in the formula (I).
Wherein the molar ratio of 1, 5-cyclooctadiene to palladium chloride is generally greater than 0.5:1, preferably 1 to 1.5:1.
the molar ratio of crotyl chloride to palladium chloride is typically greater than 1:1, preferably 1 to 1.5:1.
toluene is a reaction solvent, and because toluene and crotyl chloride can be mutually dissolved, homogeneous phase reaction is easy to form, and the reaction speed can be increased. Typically the mass ratio of toluene to palladium chloride is greater than 3:1, preferably 4 to 5:1. in the actual reaction, toluene may be optionally added as a reaction solvent, that is, toluene may be added, or toluene may not be added, and an excessive amount of crotyl chloride may be used as a solvent.
The reaction time is preferably 2 to 5 hours.
The mother liquor after the reaction is toluene, 1, 5-cyclooctadiene and crotyl chloride which remain in the reaction, and the mother liquor can be directly used for the next reaction without treatment, so that three wastes are avoided.
According to the invention, 1, 5-cyclooctadiene is used for participating in the reaction of palladium chloride and crotyl chloride to prepare the crotyl palladium chloride dimer, so that the reaction speed is greatly increased, and the reaction time is shortened to 2-5 hours from 24 hours in the prior art; the solvent consumption of the invention is greatly reduced, and the loading capacity of the raw material palladium chloride in the same reaction vessel is greatly improved, which is four times that of the prior art, so that the productivity is four times that of the prior art; the yield of the invention can reach more than 98 percent, and the purity can reach 98 percent.
The invention will be further illustrated with reference to the following specific examples, but the invention is not limited to the following examples.
The experimental methods used in the above and the following examples are conventional methods unless otherwise specified.
Materials, reagents and the like used in the above and in the following examples are commercially available unless otherwise specified.
Example 1
Under the protection of nitrogen, 1200g of palladium chloride, 806g of 1, 5-cyclooctadiene, 675g of crotyl chloride, 6L of toluene and 80 ℃ are added into a 10L four-mouth bottle, the mixture is stirred for 3 hours, the temperature is naturally reduced to 20 ℃, filtration is carried out, a filter cake is dried to obtain 1307g of yellow solid crotyl palladium chloride dimer, the filtrate is directly sleeved for the next reaction, and the yield is 98 percent and the purity is 98 percent. FIG. 1 is a nuclear magnetic resonance spectrum of a palladium chloride dimer on crotyl prepared in example 1.
Example 2
Under the protection of nitrogen, 1200g of palladium chloride, 806g of 1, 5-cyclooctadiene, 675g of crotyl chloride and 6L of the filtrate of the example 1 are added into a 10L four-mouth bottle, the insufficient part is supplemented by toluene, the mixture is stirred for 2 hours at 80 ℃, the temperature is naturally reduced to 20 ℃, the mixture is filtered, a filter cake is dried to obtain 1320g of yellow solid crotyl palladium chloride dimer, the filtrate is directly sleeved for the next reaction, and the yield is 99% and the purity is 98%.
Example 3
Under the protection of nitrogen, 1200g of palladium chloride, 806g of 1, 5-cyclooctadiene and 6L of crotyl chloride are added into a 10L four-mouth bottle, stirred for 3 hours at 80 ℃, naturally cooled to 20 ℃, filtered, and a filter cake is dried to obtain 1307g of yellow solid crotyl palladium chloride dimer, and the filtrate is directly sleeved for the next reaction, so that the yield is 98%, and the purity is 98%.
Example 4
Under the protection of nitrogen, 1200g of palladium chloride, 366g of 1, 5-cyclooctadiene, 675g of crotyl chloride, 6L of toluene and 80 ℃ are added into a 10L four-mouth bottle, the mixture is stirred for 3 hours, the temperature is naturally reduced to 20 ℃, filtration is carried out, a filter cake is dried to obtain 1133g of yellow solid crotyl palladium chloride dimer, the filtrate is directly sleeved for the next reaction, and the yield is 85% and the purity is 98%. Since the amount of 1, 5-cyclooctadiene is reduced by more than half, the molar ratio of 1, 5-cyclooctadiene to palladium chloride is less than 0.5:1, the yield was lower than that of example 1.
Comparative example
Preparation of Croton Palladium chloride dimer by Prior Art methods
Under the protection of nitrogen, 300g of palladium chloride, 252g of potassium chloride and 6L of water are added into a 10L three-necked flask, stirred for 1 hour at 25 ℃, 492g of crotyl chloride is added dropwise, and stirred for 24 hours at room temperature; then 5L of dichloromethane is added for extraction, the organic phase is desolventized, and 300g of yellow solid is obtained after drying, and the yield is 90%.
The comparison of the above comparative example with inventive example 1 shows that:
1. the reaction time of the invention is shortened from 24 hours to 3 hours in the prior art, and the reaction time is greatly shortened.
2. The post-treatment of the invention is changed from the complicated processes of extraction, desolventizing and the like in the prior art into simple filtration. The reason is that the auxiliary materials are all liquid, the product is solid, and the auxiliary materials can be separated by filtration; the unreacted solid impurities such as potassium chloride in the prior art process products can only be separated by the complicated process of extraction and desolventizing.
3. The productivity of the invention is 4 times that of the prior art. The method has the advantages that the required solvent amount is small, the palladium chloride loading capacity of the method is 4 times that of the prior art, and the productivity is 4 times that of the prior art; in the prior art, a large amount of water is needed to dissolve potassium chloride or react, so that the loading capacity of palladium chloride is low and the productivity is low.
4. The prior art process has the production of waste water and waste organic solvent; the solvent of the invention can be directly used for the next reaction, so that no three wastes are generated, and the invention belongs to a green environment-friendly process.
The foregoing is merely a specific application example of the present invention, and the protection scope of the present invention is not limited in any way. All technical schemes formed by equivalent transformation or equivalent substitution fall within the protection scope of the invention.
Claims (10)
1. A preparation method of a crotyl palladium chloride dimer is characterized in that 1, 5-cyclooctadiene is used for participating in the reaction of palladium chloride and crotyl chloride to prepare the crotyl palladium chloride dimer shown in a formula (I)
。
2. The preparation method according to claim 1, comprising: under the protection of inert gas, adding palladium chloride, 1, 5-cyclooctadiene, crotyl chloride and toluene into a reaction container, reacting for more than 0.5 hours at the temperature of 70-100 ℃, naturally cooling to 0-30 ℃, filtering, and drying a filter cake to obtain the crotyl palladium chloride dimer shown in the formula (I).
3. The process according to claim 1 or 2, wherein the molar ratio of 1, 5-cyclooctadiene to palladium chloride is greater than 0.5:1.
4. The process according to claim 3, wherein the molar ratio of 1, 5-cyclooctadiene to palladium chloride is 1 to 1.5:1.
5. The process according to claim 1 or 2, wherein the molar ratio of crotyl chloride to palladium chloride is greater than 1:1.
6. The process according to claim 2, wherein toluene is the reaction solvent.
7. The process according to claim 2, wherein the mass ratio of toluene to palladium chloride is greater than 3:1.
8. The production process according to claim 2, wherein toluene is not added in the reaction, and an excessive amount of crotyl chloride is used as a solvent.
9. The preparation method according to claim 2, wherein the reaction time is 2 to 5 hours.
10. The preparation method according to claim 2, wherein the filtered filtrate is directly used for the next reaction.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210188690.2A CN114437142B (en) | 2022-02-28 | 2022-02-28 | Preparation method of crotyl palladium chloride dimer |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210188690.2A CN114437142B (en) | 2022-02-28 | 2022-02-28 | Preparation method of crotyl palladium chloride dimer |
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| Publication Number | Publication Date |
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| CN114437142A CN114437142A (en) | 2022-05-06 |
| CN114437142B true CN114437142B (en) | 2024-02-23 |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1082248A (en) * | 1963-09-03 | 1967-09-06 | Ici Ltd | Improvements in and relating to the preparation of ªð-allylic palladium halide complexes |
| GB1287050A (en) * | 1970-09-16 | 1972-08-31 | Exxon Research Engineering Co | pi-ALLYLIC PALLADIUM COMPLEXES |
| CN110804074A (en) * | 2019-11-14 | 2020-02-18 | 西安凯立新材料股份有限公司 | Preparation method of allyl palladium chloride dimer |
| CN112250715A (en) * | 2020-10-29 | 2021-01-22 | 西安凯立新材料股份有限公司 | Preparation method of chloro (crotyl) (3-tert-butylphosphoryl) palladium (II) |
-
2022
- 2022-02-28 CN CN202210188690.2A patent/CN114437142B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1082248A (en) * | 1963-09-03 | 1967-09-06 | Ici Ltd | Improvements in and relating to the preparation of ªð-allylic palladium halide complexes |
| GB1287050A (en) * | 1970-09-16 | 1972-08-31 | Exxon Research Engineering Co | pi-ALLYLIC PALLADIUM COMPLEXES |
| CN110804074A (en) * | 2019-11-14 | 2020-02-18 | 西安凯立新材料股份有限公司 | Preparation method of allyl palladium chloride dimer |
| CN112250715A (en) * | 2020-10-29 | 2021-01-22 | 西安凯立新材料股份有限公司 | Preparation method of chloro (crotyl) (3-tert-butylphosphoryl) palladium (II) |
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