CN103193573A - Method for removing by-product in a palladium-catalyzed coupling reaction in situ - Google Patents
Method for removing by-product in a palladium-catalyzed coupling reaction in situ Download PDFInfo
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- CN103193573A CN103193573A CN2013101143987A CN201310114398A CN103193573A CN 103193573 A CN103193573 A CN 103193573A CN 2013101143987 A CN2013101143987 A CN 2013101143987A CN 201310114398 A CN201310114398 A CN 201310114398A CN 103193573 A CN103193573 A CN 103193573A
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- 238000000034 method Methods 0.000 title claims abstract description 34
- 238000005859 coupling reaction Methods 0.000 title claims abstract description 31
- 239000006227 byproduct Substances 0.000 title claims abstract description 21
- 238000011065 in-situ storage Methods 0.000 title abstract 2
- 238000006243 chemical reaction Methods 0.000 claims abstract description 48
- 150000003863 ammonium salts Chemical class 0.000 claims abstract description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 12
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 72
- 229910052763 palladium Inorganic materials 0.000 claims description 32
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 27
- 239000002253 acid Substances 0.000 claims description 15
- 239000011230 binding agent Substances 0.000 claims description 13
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 12
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 11
- 238000006069 Suzuki reaction reaction Methods 0.000 claims description 11
- 238000007341 Heck reaction Methods 0.000 claims description 10
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 8
- WGYKZJWCGVVSQN-UHFFFAOYSA-N propylamine Chemical compound CCCN WGYKZJWCGVVSQN-UHFFFAOYSA-N 0.000 claims description 5
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 4
- 238000006411 Negishi coupling reaction Methods 0.000 claims description 4
- 238000006619 Stille reaction Methods 0.000 claims description 4
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 4
- 239000000377 silicon dioxide Substances 0.000 claims description 4
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 3
- NSOXQYCFHDMMGV-UHFFFAOYSA-N Tetrakis(2-hydroxypropyl)ethylenediamine Chemical compound CC(O)CN(CC(C)O)CCN(CC(C)O)CC(C)O NSOXQYCFHDMMGV-UHFFFAOYSA-N 0.000 claims description 3
- 229960001701 chloroform Drugs 0.000 claims description 3
- BAVYZALUXZFZLV-UHFFFAOYSA-N mono-methylamine Natural products NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 claims description 3
- 239000000376 reactant Substances 0.000 claims description 3
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 claims description 2
- URLKBWYHVLBVBO-UHFFFAOYSA-N Para-Xylene Chemical compound CC1=CC=C(C)C=C1 URLKBWYHVLBVBO-UHFFFAOYSA-N 0.000 claims description 2
- 229910002796 Si–Al Inorganic materials 0.000 claims description 2
- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 claims description 2
- 229960001545 hydrotalcite Drugs 0.000 claims description 2
- 229910001701 hydrotalcite Inorganic materials 0.000 claims description 2
- 239000002808 molecular sieve Substances 0.000 claims description 2
- 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 2
- 239000002904 solvent Substances 0.000 claims description 2
- 125000000250 methylamino group Chemical group [H]N(*)C([H])([H])[H] 0.000 claims 1
- 239000003054 catalyst Substances 0.000 abstract description 11
- UKVIEHSSVKSQBA-UHFFFAOYSA-N methane;palladium Chemical compound C.[Pd] UKVIEHSSVKSQBA-UHFFFAOYSA-N 0.000 abstract description 11
- 230000003197 catalytic effect Effects 0.000 abstract description 8
- 238000004519 manufacturing process Methods 0.000 abstract description 2
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- YCOXTKKNXUZSKD-UHFFFAOYSA-N as-o-xylenol Natural products CC1=CC=C(O)C=C1C YCOXTKKNXUZSKD-UHFFFAOYSA-N 0.000 description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 8
- SNHMUERNLJLMHN-UHFFFAOYSA-N iodobenzene Chemical compound IC1=CC=CC=C1 SNHMUERNLJLMHN-UHFFFAOYSA-N 0.000 description 8
- 239000000463 material Substances 0.000 description 5
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 4
- 239000004327 boric acid Substances 0.000 description 4
- 238000004587 chromatography analysis Methods 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 239000007791 liquid phase Substances 0.000 description 4
- 238000010792 warming Methods 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 208000012839 conversion disease Diseases 0.000 description 3
- 229910052814 silicon oxide Inorganic materials 0.000 description 3
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 150000005826 halohydrocarbons Chemical class 0.000 description 2
- 150000007524 organic acids Chemical class 0.000 description 2
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- 239000000843 powder Substances 0.000 description 2
- 230000004044 response Effects 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 239000007810 chemical reaction solvent Substances 0.000 description 1
- 238000006880 cross-coupling reaction Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- -1 halogenated aryl hydrocarbon Chemical class 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- SNHMUERNLJLMHN-IDEBNGHGSA-N iodobenzene Chemical group I[13C]1=[13CH][13CH]=[13CH][13CH]=[13CH]1 SNHMUERNLJLMHN-IDEBNGHGSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229930014626 natural product Natural products 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 238000006053 organic reaction Methods 0.000 description 1
- 239000012450 pharmaceutical intermediate Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 125000006308 propyl amino group Chemical group 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- ITMCEJHCFYSIIV-UHFFFAOYSA-M triflate Chemical compound [O-]S(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-M 0.000 description 1
- 229930195735 unsaturated hydrocarbon Natural products 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
本发明公开了一种原位去除钯催化偶联反应中副产物的方法。该方法包括如下步骤：向所述钯催化偶联反应的反应体系中加入含水的多孔介质，即可去除所述钯催化偶联反应中的副产物；所述钯催化偶联反应中加入缚酸剂。本发明提供的方法，通过在偶联反应体系中加入含水的多孔介质使得反应过程中所形成的铵盐被含水的多孔介质吸收，有效地降低了副产物铵盐在反应体系中的浓度，大大降低了铵盐的析出，从而使钯碳催化剂在有机溶液中能够稳定地发挥催化效用。本发明提供的方法简便有效，成本低廉，易于实现工业化生产。The invention discloses a method for removing by-products in a palladium-catalyzed coupling reaction in situ. The method comprises the following steps: adding a water-containing porous medium to the reaction system of the palladium-catalyzed coupling reaction to remove by-products in the palladium-catalyzed coupling reaction; agent. In the method provided by the invention, the ammonium salt formed in the reaction process is absorbed by the porous medium containing water by adding a water-containing porous medium in the coupling reaction system, effectively reducing the concentration of the by-product ammonium salt in the reaction system, greatly The precipitation of the ammonium salt is reduced, so that the palladium-carbon catalyst can stably exert its catalytic effect in the organic solution. The method provided by the invention is simple and effective, has low cost and is easy to realize industrialized production.
Description
Technical field
The present invention relates to a kind of original position and remove the method for by product in the palladium catalyzed coupling reaction, belong to technical field of organic synthesis.
Background technology
The C-C key construct the important technology field that belongs in the organic synthesis, the palladium catalyzed coupling reaction is constructed the simple and practical chemical reaction of a class of C-C key just, comprises Suzuki reaction, Heck reaction, Negishi reaction and Stille reaction etc.Utilize the palladium catalyzed coupling reaction, many pharmaceutical intermediates and some natural products can more easily carry out synthetic, commonly used are used for the synthetic organic reaction of C-C thereby opened up one for synthetic chemistry.Palladium carbon is because of its high reactivity and be easy to preparation and recovery, is widely used in the palladium catalyzed coupling reaction as catalyzer.Yet; the palladium catalyzed coupling reaction has by-product acids and produces in reaction is carried out; the carrying out that the generation of acid has a strong impact on reaction makes the speed of reaction reduce; therefore people can add alkaline acid binding agent usually and come the acid that produces in the neutralization reaction process; thereby make reaction forward move the raising reaction conversion ratio, organic acid binding agent commonly used mainly contains alkaline organic compounds such as pyridine, triethylamine, diethylamine.But, often because the existence of organic acid binding agent, the acid that generates in the reaction process is by in the acid binding agent and can generate ammonium salt, this ammonium salt is insoluble to reaction solvent usually, when reaching certain value, the concentration of ammonium salt can from reaction system, separate out, ammonium salt is optionally separated out at catalyst surface and is wrapped palladium-carbon catalyst catalyzer is lost activity, and causes reaction conversion ratio to reduce.Therefore, the problem of separating out that how to solve the by product ammonium salt that the palladium catalyzed coupling reaction produces becomes one of technical problem that palladium catalyzed coupling reaction field needs to be resolved hurrily.
Summary of the invention
The purpose of this invention is to provide a kind of original position and remove the method for by product in the palladium catalyzed coupling reaction, this method can be improved the performance of palladium-carbon catalyst in linked reaction effectively, and the palladium catalyst activity is significantly improved.
Original position provided by the present invention is removed the method for by product in the palladium catalyzed coupling reaction, comprises the steps:
In the reaction system of described palladium catalyzed coupling reaction, add moisture porous medium, can remove the by product in the described palladium catalyzed coupling reaction;
Add acid binding agent in the described palladium catalyzed coupling reaction.
In the above-mentioned method, be before described palladium catalyzed coupling reaction, to add described moisture porous medium.
In the above-mentioned method, described palladium catalyzed coupling reaction can be in Suzuki reaction, Heck reaction, Stille reaction and the Negishi reaction at least a,
Wherein, the Suzuki reaction is the linked reaction that halogenated aryl hydrocarbon and organic boron carry out under the catalysis of palladium catalyst;
The Heck reaction generates the linked reaction of trans product under the palladium katalysis for halohydrocarbon and activation unsaturated hydrocarbons;
The Stille reaction is the cross-coupling reaction that organo-tin compound and the halohydrocarbon (or triflate) that does not contain β-hydrogen take place under palladium catalysis;
The linked reaction that Negishi reaction is carried out under palladium catalysis for unsaturated organic zinc reagent and aryl or ethyl halogenide.
In the above-mentioned method, described moisture porous medium can be in moisture gac, moisture porous silica, moisture Si-Al molecular sieve and the moisture hydrotalcite at least a.
In the above-mentioned method, the temperature of reaction of described palladium catalyzed coupling reaction can be 10～100 ° of C, specifically can be 60～90 ° of C, 60 ° of C, 80 ° of C, 85 ° of C or 90 ° of C.
In the above-mentioned method, the add-on of described moisture porous medium can be 1～5 times of total mass of the reactant of described palladium catalyzed coupling reaction, specifically can be 1～3 times, 1 times, 2 times or 3 times.
In the above-mentioned method, the water ratio of described moisture porous medium can be 10%～200%, specifically can be 80%～100%, 80% or 100%, and the water ratio among the present invention refers to that institute's water content accounts for the mass percent of porous medium.
In the above-mentioned method, described acid binding agent can be methylamine, ethamine, propylamine, quadrol, triethylamine or pyridine, and described by product is ammonium salt.
In the above-mentioned method, the solvent of described palladium catalyzed coupling reaction can be in toluene, p-Xylol, methylene dichloride and the trichloromethane at least a.
Method provided by the invention, make that by in the linked reaction system, adding moisture porous medium formed ammonium salt is absorbed by moisture porous medium in the reaction process, reduced the concentration of by product ammonium salt in reaction system effectively, greatly reduce separating out of ammonium salt, thereby make palladium catalyst in organic solution, can play consistently catalysis effectiveness.Method provided by the invention is simple and effective, and is with low cost, is easy to realize suitability for industrialized production.
Description of drawings
Fig. 1 is Suzuki-H system and Suzuki-N system catalyzed reaction transformation efficiency-time curve among the embodiment 1.
Fig. 2 is Suzuki-H system and Suzuki-N system catalyzed reaction transformation efficiency-time curve among the embodiment 2.
Fig. 3 is Heck-H system and Heck-N system catalyzed reaction transformation efficiency-time curve among the embodiment 3.
Fig. 4 is Heck-H system and Heck-N system catalyzed reaction transformation efficiency-time curve among the embodiment 4.
Embodiment
Employed experimental technique is ordinary method if no special instructions among the following embodiment.
Used material, reagent etc. if no special instructions, all can obtain from commercial channels among the following embodiment.
Among the following embodiment, adopt gas chromatograph (Agilent 6890 types) and high performance liquid chromatograph (Tianjin, island SHIMADZU10A-VP-PLUS model) analytical reaction thing transformation efficiency, productive rate, selectivity and catalytic cycle performance, test condition is: 70% methanol aqueous solution is as moving phase, flow velocity is 0.8ml/min, the C18 reverse-phase chromatographic column, detector is UV-detector, and the detection wavelength is 200nm.
By product in embodiment 1, the removal Suzuki reaction
Prepare two parts of reaction systems: 5mmol iodobenzene and 10mmol phenylo boric acid are dissolved in the toluene of 50mL, add the Pd/C catalyzer of 0.1g5wt%, acid binding agent is triethylamine.
For the influence of comparative illustration the inventive method to the Suzuki reaction, a copy of it does not add any material, is designated as the Suzuki-N system; The a 2g water content that adds is 80% wet shaped activated carbon pressed powder in addition, is designated as the Suzuki-H system, and in this system, the addition of wet shaped activated carbon pressed powder is 1 times of total mass of iodobenzene and phenylo boric acid.Subsequently two parts of reaction systems are warming up to 80 ° of C, add the 10mmol triethylamine to open reaction, 15min samples at interval, adopts Tianjin, island 10A-VP-PLUS liquid-phase chromatographic analysis transformation efficiency.
Fig. 1 is the contrast of Suzuki reaction system catalytic kinetics curve, as can be seen from the figure, the consistent transformation efficiency of the two speed of response of 15min is all about 25% before the reaction beginning, proceed Suzuki-N system speed when reaction and will be slower than the Suzuki-H reaction system, when reaction proceeds to 1h, the reaction conversion ratio of the two is respectively 80.0% and 99.9%, does not tie up to reaction and carries out just reaching behind the 2h 100% and transform and add moisture activated carbon bodies.This phenomenon occurs and be because the HI reaction that generates in acid binding agent triethylamine and the reaction during reaction beginning generates ammonium salt, so the concentration of ammonium salt did not reach and separated out concentration and can not produce detrimentally affect to catalyzer this moment, when reaction is carried out gradually, the ammonium salt concentration that generates reaches certain value, since palladium-carbon catalyst in system be one well the deposition site make the by product ammonium salt optionally precipitate into the palladium carbon surface to have stoped reactant contact with palladium carbon, thereby make the reduction of palladium carbon catalytic activity.After adding moisture gac, ammonium salt in the system is because the solubleness in water is higher, these ammonium salts optionally are dissolved in and make the ammonium salt concentration of system reduce in the moisture porous, reduce ammonium salt and separated out possibility on palladium-carbon catalyst, thereby made the palladium-carbon catalyst to give full play to its catalysis effectiveness.So adding moisture porous activated carbon as can be seen is useful to palladium-carbon catalyst performance catalytic effect in the Suzuki reaction.
By product in embodiment 2, the removal Suzuki reaction
Prepare two parts of reaction systems: 5mmol iodobenzene and 10mmol phenylo boric acid are dissolved in the trichloromethane of 50ml, add the Pd/C catalyzer of 0.1g5wt%, acid binding agent is quadrol.
For the influence of comparative illustration the inventive method to the Suzuki reaction, a copy of it does not add any material, is designated as the Suzuki-N system; The a 2g water content that adds is 100% porous silica in addition, is designated as the Suzuki-H system, and in this system, the addition of porous silica is 1 times of total mass of iodobenzene and phenylo boric acid.Subsequently two parts of reaction systems are warming up to 60 ° of C, add the 10mmol triethylamine to open reaction, 15min samples at interval, adopts Tianjin, island 10A-VP-PLUS liquid-phase chromatographic analysis transformation efficiency.
Fig. 2 is Suzuki reaction system catalytic kinetics curve contrast, and as seen from the figure, the two speed of response is very nearly the same within reaction beginning half hour.But along with reaction is further carried out, its catalyzed reaction speed of Suzuki-H system is higher than the Suzuki-N system, and the Suzuki-H system transforms iodobenzene fully only needs 1.5h, and the Suzuki-N system then needs 2.5h.This has proved absolutely the superiority of Suzuki-H system.
By product in embodiment 3, the removal Heck reaction
Prepare two parts of reaction systems: 5mmol iodobenzene and 10mmol vinylbenzene are dissolved in the toluene of 30ml, add the Pd/C catalyzer of 0.1g5wt%, acid binding agent is pyridine.
For the influence of comparative illustration the inventive method to the Heck reaction, a copy of it does not add any material, is designated as the Heck-N system; A adding 3g water content is 100% gac in addition, is designated as the Heck-H system, and in this system, the addition of gac is iodobenzene and cinnamic total mass 3 times.Subsequently two parts of reaction systems are warming up to 90 ° of C, add the 10mmol triethylamine to open reaction, 0.5h samples at interval, adopts Tianjin, island 10A-VP-PLUS liquid-phase chromatographic analysis transformation efficiency.
Fig. 3 is the contrast of Heck reaction system catalytic kinetics curve, as seen from the figure, for the Heck-H system, after proceeding to 1h, reaction surpasses the Heck-N system owing to added moisture gac Heck speed of reaction, the Heck-H system transforms fully only needs 3h Heck-N system then to need 4h, therefore can embody the superiority of Heck-H system.
By product in embodiment 4, the removal Heck reaction
Prepare two parts of reaction systems: 5mmol iodobenzene and 10mmol vinylbenzene are dissolved in the ethylbenzene of 30ml, add the Pd/C catalyzer of 0.1g5wt%, acid binding agent is propylamine.
For the influence of comparative illustration the inventive method to the Heck reaction, a copy of it does not add any material, is designated as the Heck-N system; A adding 2g water content is 80% mesopore silicon oxide in addition, is designated as the Heck-H system, and in this system, the addition of mesopore silicon oxide is iodobenzene and cinnamic total mass 2 times.Subsequently two parts of reaction systems are warming up to 85 ° of C, add the 10mmol triethylamine to open reaction, 0.5h samples at interval, adopts Tianjin, island 10A-VP-PLUS liquid-phase chromatographic analysis transformation efficiency.
Fig. 4 is the contrast of Heck reaction system catalytic kinetics curve, as seen from the figure, for the Heck-H system, because having added moisture mesopore silicon oxide Heck speed of reaction is higher than the Heck-N system, the Heck-H system transforms fully only needs 5h Heck-N system then to need 7h, therefore can embody the superiority of Heck-H system.
Claims (8)
1. original position is removed the method for by product in the palladium catalyzed coupling reaction, comprises the steps:
In the reaction system of described palladium catalyzed coupling reaction, add moisture porous medium, can remove the by product in the described palladium catalyzed coupling reaction;
Add acid binding agent in the described palladium catalyzed coupling reaction.
2. method according to claim 1 is characterized in that: described palladium catalyzed coupling reaction is at least a in Suzuki reaction, Heck reaction, Stille reaction and the Negishi reaction.
3. method according to claim 1 and 2, it is characterized in that: described moisture porous medium is at least a in moisture gac, moisture porous silica, moisture Si-Al molecular sieve and the moisture hydrotalcite.
4. according to each described method among the claim 1-3, it is characterized in that: the temperature of reaction of described palladium catalyzed coupling reaction is 10～100 ° of C.
5. according to each described method among the claim 1-4, it is characterized in that: the add-on of described moisture porous medium is 1～5 times of total mass of the reactant of described palladium catalyzed coupling reaction.
6. method according to claim 5 is characterized in that: the water ratio of described moisture porous medium is 10%～200%.
7. according to each described method among the claim 1-6, it is characterized in that: described acid binding agent is methylamine, ethamine, propylamine, quadrol, triethylamine or pyridine, and described by product is ammonium salt.
8. according to each described method among the claim 1-7, it is characterized in that: the solvent of described palladium catalyzed coupling reaction is at least a in toluene, p-Xylol, methylene dichloride and the trichloromethane.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108201897A (en) * | 2018-02-01 | 2018-06-26 | 黑龙江省科学院石油化学研究院 | The method that ultrasonic wave added local reduction way prepares SBA-15 loaded nanometer palladium catalysts |
-
2013
- 2013-04-03 CN CN2013101143987A patent/CN103193573A/en active Pending
Non-Patent Citations (2)
| Title |
|---|
| KLAUS KOHLER ET AL.: ""Highly Active Palladium/Activated Carbon Catalysts for Heck Reactions: Correlation of Activity, Catalyst Properties, and Pd Leaching"", 《 CHEM. EUR. J.》 * |
| 颜美 等: ""负载钯催化的Suzuki 偶联反应研究进展"", 《有机化学》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108201897A (en) * | 2018-02-01 | 2018-06-26 | 黑龙江省科学院石油化学研究院 | The method that ultrasonic wave added local reduction way prepares SBA-15 loaded nanometer palladium catalysts |
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