CN109232664A - A kind of crystal structure and synthetic method of esters Pd-NHC molecular complex - Google Patents
A kind of crystal structure and synthetic method of esters Pd-NHC molecular complex Download PDFInfo
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- CN109232664A CN109232664A CN201811325032.3A CN201811325032A CN109232664A CN 109232664 A CN109232664 A CN 109232664A CN 201811325032 A CN201811325032 A CN 201811325032A CN 109232664 A CN109232664 A CN 109232664A
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- 150000002148 esters Chemical class 0.000 title claims abstract description 44
- 239000013078 crystal Substances 0.000 title claims abstract description 22
- 238000010189 synthetic method Methods 0.000 title claims abstract description 16
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims abstract description 27
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims abstract description 26
- 239000007787 solid Substances 0.000 claims abstract description 22
- 239000002904 solvent Substances 0.000 claims abstract description 18
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims abstract description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 15
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims abstract description 13
- 239000012046 mixed solvent Substances 0.000 claims abstract description 13
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000003446 ligand Substances 0.000 claims abstract description 12
- 235000002639 sodium chloride Nutrition 0.000 claims abstract description 12
- 239000003054 catalyst Substances 0.000 claims abstract description 11
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims abstract description 10
- 150000007942 carboxylates Chemical class 0.000 claims abstract description 10
- 238000001704 evaporation Methods 0.000 claims abstract description 10
- 229910052751 metal Inorganic materials 0.000 claims abstract description 10
- 239000002184 metal Substances 0.000 claims abstract description 10
- 239000012074 organic phase Substances 0.000 claims abstract description 10
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910052763 palladium Inorganic materials 0.000 claims abstract description 8
- 150000003839 salts Chemical class 0.000 claims abstract description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims abstract description 7
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims abstract description 5
- 239000012299 nitrogen atmosphere Substances 0.000 claims abstract description 5
- 238000005406 washing Methods 0.000 claims abstract description 5
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims description 8
- 235000011164 potassium chloride Nutrition 0.000 claims description 4
- 239000001103 potassium chloride Substances 0.000 claims description 4
- 239000011780 sodium chloride Substances 0.000 claims description 4
- 239000012071 phase Substances 0.000 claims description 3
- 239000003814 drug Substances 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 238000002360 preparation method Methods 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims description 2
- -1 N, N'- bis- (4- carboethoxyphenyl)-imidazoles chlorate imidazolium chloride Chemical class 0.000 claims 1
- 230000004048 modification Effects 0.000 abstract description 6
- 238000012986 modification Methods 0.000 abstract description 6
- 230000003197 catalytic effect Effects 0.000 description 11
- 238000006243 chemical reaction Methods 0.000 description 11
- 238000006555 catalytic reaction Methods 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 6
- 239000011521 glass Substances 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 238000005160 1H NMR spectroscopy Methods 0.000 description 4
- ZZYYOHPHSYCHQG-UHFFFAOYSA-N 2-bromo-4-methylbenzoic acid Chemical compound CC1=CC=C(C(O)=O)C(Br)=C1 ZZYYOHPHSYCHQG-UHFFFAOYSA-N 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 238000006073 displacement reaction Methods 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 125000000524 functional group Chemical group 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- HXITXNWTGFUOAU-UHFFFAOYSA-N phenylboronic acid Chemical compound OB(O)C1=CC=CC=C1 HXITXNWTGFUOAU-UHFFFAOYSA-N 0.000 description 3
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-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
- 150000001335 aliphatic alkanes Chemical group 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- NAEZZAYITXEWSN-UHFFFAOYSA-M ethyl 4-[3-(4-ethoxycarbonylphenyl)imidazol-3-ium-1-yl]benzoate chloride Chemical compound [Cl-].C(C)OC(=O)C1=CC=C(C=C1)[N+]1=CN(C=C1)C1=CC=C(C=C1)C(=O)OCC NAEZZAYITXEWSN-UHFFFAOYSA-M 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 101100030361 Neurospora crassa (strain ATCC 24698 / 74-OR23-1A / CBS 708.71 / DSM 1257 / FGSC 987) pph-3 gene Proteins 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 125000005907 alkyl ester group Chemical group 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 238000002447 crystallographic data Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000002815 homogeneous catalyst Substances 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 150000004702 methyl esters Chemical class 0.000 description 1
- 230000005311 nuclear magnetism Effects 0.000 description 1
- 150000002895 organic esters Chemical group 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 150000003222 pyridines Chemical class 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000002390 rotary evaporation Methods 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 230000003335 steric effect Effects 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 238000000844 transformation Methods 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/22—Organic complexes
- B01J31/2265—Carbenes or carbynes, i.e.(image)
- B01J31/2269—Heterocyclic carbenes
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/30—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group
- C07C67/333—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by isomerisation; by change of size of the carbon skeleton
- C07C67/343—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
- C07B2200/00—Indexing scheme relating to specific properties of organic compounds
- C07B2200/13—Crystalline forms, e.g. polymorphs
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Pyridine Compounds (AREA)
Abstract
The invention belongs to catalyst technical fields, disclose a kind of esters Pd-NHC molecular complex and synthetic method, in nitrogen atmosphere or air, carboxylate ligand, divalent palladium ionic metal salt, chloride, pyridine and pyridine derivate solvent are placed in conventional closed container, are heated 10-2000 minutes；It is cooled to room temperature, vacuum evaporating solvent obtains solid residue；Obtained solid residue is dissolved in the mixed solvent of methylene chloride and water, through the isolated organic phase of separatory funnel；By gained organic phase 5% copper-bath and saturated common salt water washing, it is dried using anhydrous sodium sulfate, vacuum evaporating solvent obtains solid residue；Obtained solid residue is recrystallized in the in the mixed solvent of chloroform and n-hexane, obtains the crystal of Pd-NHC molecule.The present invention synthesizes the Pd-NHC molecular complex of carboxylate functional group modification and obtains its crystal structure.
Description
Technical field
The invention belongs to catalyst technical field more particularly to a kind of crystal structure of esters Pd-NHC molecular complex with
Synthetic method.
Background technique
Currently, the prior art commonly used in the trade is such that
Pd-NHC molecular complex is a kind of important Metal Organic Molecular catalyst, this kind of compound not only catalytic performance
It is superior, and can be also stabilized in the air for having humidity.The Typical Representative of this kind of Pd-NHC molecular complex has PEPPSI
Type catalyst (C.Valent et al, Angew.Chem.Int.Ed.2012,51,3314-3332).It is urged in PEPPSI type
In agent molecular structure, organic alkane functional group can significantly regulate and control its catalytic activity by space steric effect.But it is this kind of to urge
Agent is homogeneous catalyst, and catalysis reaction needs to use organic solvent that is volatile, being more toxic, catalysate and catalyst point
From difficulty, and it is unable to repeated recycling utilize.
Organic ester functional group hydrolyzes under acid or alkaline conditions generates water-soluble product.Pd-NHC points of ester modification
Catalysis reaction can be realized in water after sub- complex compound hydrolysis, and is easy to separate with organic catalysis product, and realizes repeatedly weight
It is multiple to utilize.Therefore, this kind of esters Pd-NHC molecular complex can be considered as a kind of environmental-friendly green catalyst.Esters
The research of Pd-NHC molecular complex is seldom.E.Steeples et al. reports 3 alkyl esters Pd-NHC molecular complex (New
J.Chem., 2016,40,4922-4930), and the reaction of the multiple catalysis in water phase is realized.But catalytic activity is compared
PEPPSI type catalyst is poor, this is possible as the electronics knot that Arrcostab flexible does not have regulation NHC molecule ligand
The ability of structure.Therefore, how the esters Pd-NHC molecular complex of synthesis catalytic performance efficiency is an important technological challenge.
Inventors etc. once reported an example esters Pd-NHC molecular complex (Duan et al, Appl Organometal
Chem.2018；32:e4444.), higher catalytic activity is illustrated compared to the equal catalyst of traditional Pd (PPh3) 4.In report
In compound, iodide costly have been used.Therefore, it is necessary to synthesize a kind of low in cost, catalytic performance on this basis
Efficiently, environmental-friendly esters Pd-NHC molecular complex.
In conclusion problem of the existing technology is:
(1) in the prior art, the Pd-NHC molecular complex of organic functional group modification does not have better catalytic activity, existing
There is Pd-NHC molecular complex in technology not have the electronic structure of regulation NHC molecule ligand.
(2) in the prior art, a kind of low in cost, efficient ester of catalytic performance cannot be provided using cheap chloride
Class Pd-NHC molecular complex.
Solve the meaning of above-mentioned technical problem:
The esters Pd-NHC molecule that it is an object of that present invention to provide an examples is low in cost, catalytic performance is efficient, environmental-friendly
Complex compound.
Summary of the invention
In view of the problems of the existing technology, the present invention provides a kind of crystal structures of esters Pd-NHC molecular complex
With synthetic method.
The invention is realized in this way a kind of esters Pd-NHC molecular complex, the esters Pd-NHC molecular complex
Object, structural formula are as follows:
Molecular formula: PdC25H25N3O4Cl2；Mw=608.81；Yellow column crystal；Dissolubility: solvable under heating state
In organic solvent, such as 1.4- dioxane, n,N-Dimethylformamide etc..The compound can be used for being catalyzed C-C, the coupling such as C-N
Reaction.
Another object of the present invention is to provide a kind of synthetic method of esters Pd-NHC molecular complex, specifically include with
Lower step:
Step 1: in nitrogen atmosphere or air, carboxylate ligand, divalent palladium ionic metal salt, chloride, pyridine and pyridine
Derivative solvent is placed in conventional closed container, is heated 10-2000 minutes；
Step 2: being cooled to room temperature, and vacuum evaporating solvent obtains solid residue；
Obtained solid residue: being dissolved in the mixed solvent of methylene chloride and water by step 3, isolated through separatory funnel
Organic phase；
Step 4: gained organic phase 5% copper-bath and saturated common salt water washing are carried out using anhydrous sodium sulfate
Dry, vacuum evaporating solvent obtains solid residue；
Step 5: obtained solid residue is recrystallized in the in the mixed solvent of chloroform and n-hexane, obtains Pd-NHC points
The crystal of son.
Further, in step 1, divalent palladium ionic metal salt is 0.05-1.0mmol.
Further, in step 1, preferred nitrogen protection.
Further, in step 1, carboxylate ligand are as follows:
Bis- (4- the carboethoxyphenyl)-imidazoles chlorate imidazolium chloride, 21.4mg- of N, N'-
428mg,0.05-1.0mmol。
Further, in step 1, the preferred sodium chloride of chloride, potassium chloride；0.1-2.0mmol.
Further, in step 1, pyridine derivate solvent 0.1-20ml.
Further, in step 1, conventional closed container, such as glass tube, reaction kettle.
Further, in step 3, the volume ratio of the mixed solvent of methylene chloride and water is 2:1.
Further, in step 5, the crystal of Pd-NHC molecule, yield 10-99%.
Further, the synthetic method chemical equation of the esters Pd-NHC molecular complex are as follows:
Another object of the present invention is to provide a kind of medicine using esters Pd-NHC molecular complex preparation to lead
The catalyst of domain production application.
Esters Pd-NHC molecular complex can efficient catalytic Suzuki-palace Pu reaction.It is as follows to react example:
Wherein, esters Pd-NHC molecular complex catalysis 4- methyl-bromobenzoate reacts empty with the Suzuki of phenyl boric acid-palace Pu
In gas, by 4- methyl-bromobenzoate (215.0mg, 1.0mmol, 1.0eq), phenyl boric acid (146.4mg, 1.2mmol, 1.2eq), carbon
Sour potassium (414.6mg, 3.0mmol, 3.0eq), esters Pd-NHC molecular catalyst potassium carbonate (0.61mg, 0.001mmol,
0.1eq%), dioxane (4.0mL, 46.9mmol, 46.9eq) is added in glass reactor together, sealing, and 85 degrees Celsius
Heating 24 hours.After cooling, wherein to glass reaction, 4.0mL methylene chloride is respectively added in two times, organic phase is transferred to round bottom
In flask, rotary evaporation in vacuo obtains solid residue.Solid residue is dry, it is used in combination1HNMR nuclear-magnetism determines 4- biphenyl-first
The yield of sour methyl esters is 90.3% (see Fig. 3).4- biphenyl-methyl formate1HNMR (400MHz, CDCl3): δ 8.10 (d, J=
8.3Hz, 2H), 7.66 (d, J=8.4Hz, 2H), 7.62 (d, J=7.4Hz, 2H), 7.47 (t, J=7.5Hz, 2H), 7.39 (t,
J=7.3Hz, 1H), 3.92 (s, 3H).
In conclusion advantages of the present invention and good effect are as follows:
The present invention has synthesized the Pd-NHC molecular complex of carboxylate functional group modification and has obtained its crystal
Structure.
Pd-NHC molecular complex of the present invention is a kind of important Metal Organic Molecular catalyst, and this kind of compound is not only urged
Change superior performance, and can be also stabilized in the air for having humidity.The Pd- of organic functional group (such as ester function group) modification
NHC molecular complex is possible to have better catalytic activity, this is because the presence of organic functional group can regulate and control NHC molecule
The electronic structure of ligand.
Detailed description of the invention
Fig. 1 is the Opacity in lens method flow diagram of esters Pd-NHC molecular complex provided in an embodiment of the present invention.
Fig. 2 is the molecule shown in the crystallographic axis C in the crystal of esters Pd-NHC molecular complex provided in an embodiment of the present invention
Accumulation graph.
Fig. 3 is esters Pd-NHC molecular complex catalysis 4- methyl-bromobenzoate and phenyl boric acid provided in an embodiment of the present invention
Suzuki-palace Pu reaction1HNMR map.
Specific embodiment
In order to make the objectives, technical solutions, and advantages of the present invention clearer, with reference to embodiments, to the present invention
It is further elaborated.It should be appreciated that the specific embodiments described herein are merely illustrative of the present invention, it is not used to
Limit the present invention.
Application principle of the invention is further elaborated with reference to the accompanying drawing；
The crystal molecular structure of esters Pd-NHC molecular complex provided in an embodiment of the present invention.It is as follows:
Model structure are as follows:
As shown in Figure 1, the synthetic method of esters Pd-NHC molecular complex provided in an embodiment of the present invention, specifically include with
Lower step:
S101: in nitrogen atmosphere or air, carboxylate ligand, divalent palladium ionic metal salt (0.05-1.0mmol), chlorination
Object, pyridine and pyridine derivate solvent are placed in conventional closed container, are heated 10-2000 minutes；
S102: being cooled to room temperature, and vacuum evaporating solvent obtains solid residue；
Obtained solid residue: being dissolved in the mixed solvent of methylene chloride and water by S103, is had through separatory funnel is isolated
Machine phase；
S104: gained organic phase 5% copper-bath and saturated common salt water washing are done using anhydrous sodium sulfate
Dry, vacuum evaporating solvent obtains solid residue；
S105: obtained solid residue is recrystallized in the in the mixed solvent of chloroform and n-hexane, obtains Pd-NHC molecule
Crystal.
In step S101, divalent palladium ionic metal salt provided in an embodiment of the present invention is 0.05-1.0mmol.
In step S101, preferred nitrogen protection provided in an embodiment of the present invention.
In step S101, carboxylate ligand provided in an embodiment of the present invention are as follows:
N, N '-bis (4-ethoxycarbonylphenyl) imidazolium chloride, 21.4mg-428mg,
0.05-1.0mmol。
In step S101, the preferred sodium chloride of chloride provided in an embodiment of the present invention, potassium chloride；0.1-2.0mmol.
In step S101, pyridine derivate solvent 0.1-20ml provided in an embodiment of the present invention.
In step S101, routine closed container provided in an embodiment of the present invention, such as glass tube, reaction kettle.
In step S103, the volume ratio of the mixed solvent of methylene chloride and water provided in an embodiment of the present invention is 2:1.
In step S105, the crystal of Pd-NHC molecule provided in an embodiment of the present invention, yield 10-99%.
As shown in Fig. 2, in the Opacity in lens route of esters Pd-NHC molecular complex provided in an embodiment of the present invention, are as follows:
As shown in Fig. 2, in the crystal of esters Pd-NHC molecular complex provided in an embodiment of the present invention shown in the crystallographic axis c
Packing of molecules figure.
The separation of esters Pd-NHC molecular complex exists in crystal.Along crystallographic axis c, there is typical case between adjacent Pyridine Molecules
π-π interaction, molecule face interplanar distance isAdjacent esters Pd-NHC molecular complex passes through this π-π oversubscription
Sub- active force and form three-dimensional close-packed structure.Application principle of the invention is carried out combined with specific embodiments below further detailed
It describes in detail bright；
Fig. 3 is esters Pd-NHC molecular complex catalysis 4- methyl-bromobenzoate and phenyl boric acid provided in an embodiment of the present invention
Suzuki-palace Pu reaction1HNMR map.
The invention will be further described combined with specific embodiments below.
The Opacity in lens process of esters Pd-NHC molecular complex provided in an embodiment of the present invention:
1. the synthesis of ligand: can refer to document synthesis (Duan et al, Appl Organometal Chem.2018；32:
e4444.)；
2. the synthesis of crystal: in nitrogen atmosphere or air (preferably nitrogen protection), carboxylate ligand (N, N '-bis (4-
Ethoxycarbonylphenyl) imidazolium chloride, 21.4mg-428mg, 0.05-1.0mmol), divalent palladium from
Sub- metal salt (0.05-1.0mmol), chloride (preferably sodium chloride, potassium chloride；0.1-2.0mmol), pyridine and pyridine derived
Object solvent (0.1-20ml) is placed in conventional closed container (such as glass tube, reaction kettle) and heats 10-2000 minutes.It is cooled to
Room temperature, vacuum evaporating solvent obtain solid residue.Obtained solid residue is dissolved in the mixed solvent (volume of methylene chloride and water
Than 2:1), the isolated organic phase of separatory funnel.Gained organic phase 5% copper-bath and saturated common salt water washing, gained
Organic phase is dry with anhydrous sodium sulfate, and vacuum evaporating solvent obtains solid residue.Obtained solid residue in chloroform and just oneself
The in the mixed solvent of alkane recrystallizes, and obtains the crystal of Pd-NHC molecule, yield 10-99%.
3. crystal structure is obtained by single crystal diffraction technology.Crystallographic data see the table below.
Table 1:Crystal data and structure refinement for 180808e.
Table 2:Atomic coordinates (x 10^4) and equivalent isotropic displacement
parameters(A^2 x 10^3)for 180808e.
U(eq)is defined as one third of the trace of the orthogonalized Uij
tensor.
Table 3:Bond lengths [A] and angles [deg] for 180808e.
Symmetry transformations used to generate equivalent atoms:#1-x,y,-z+
3/2
Table 4:Anisotropic displacement parameters (A^2 x 10^3) for 180808e.
The anisotropic displacement factor exponenttakes the form:-2pi^2[h^
2a*^2U11+...+2h k a*b*U12]
Table 5:Hydrogen coordinates (x 10^4) and isotropic displacement parameters
(A^2 x 10^3)for 180808e.
Table 6:Hydrogen bonds for 180808e [A and deg.]
The foregoing is merely illustrative of the preferred embodiments of the present invention, is not intended to limit the invention, all in essence of the invention
Made any modifications, equivalent replacements, and improvements etc., should all be included in the protection scope of the present invention within mind and principle.
Claims (8)
1. a kind of esters Pd-NHC molecular complex, which is characterized in that the esters Pd-NHC molecular complex, molecular formula knot
Structure is as follows:
2. a kind of synthetic method of esters Pd-NHC molecular complex as described in claim 1, which is characterized in that the esters
The synthetic method of Pd-NHC molecular complex, specifically includes the following steps:
Step 1: in nitrogen atmosphere or air, carboxylate ligand, divalent palladium ionic metal salt, chloride, pyridine and pyridine derived
Object solvent is placed in conventional closed container, is heated 10-2000 minutes；
Step 2: being cooled to room temperature, and vacuum evaporating solvent obtains solid residue；
Obtained solid residue: being dissolved in the mixed solvent of methylene chloride and water by step 3, isolated organic through separatory funnel
Phase；
Step 4: gained organic phase 5% copper-bath and saturated common salt water washing are done using anhydrous sodium sulfate
Dry, vacuum evaporating solvent obtains solid residue；
Step 5: obtained solid residue is recrystallized in the in the mixed solvent of chloroform and n-hexane, obtains Pd-NHC molecule
Crystal.
3. the synthetic method of esters Pd-NHC molecular complex as claimed in claim 2, which is characterized in that the step 1
In, divalent palladium ionic metal salt is 0.05-1.0mmol.
4. the synthetic method of esters Pd-NHC molecular complex as claimed in claim 2, which is characterized in that the step 1
In, carboxylate ligand are as follows:
N, N'- bis- (4- carboethoxyphenyl)-imidazoles chlorate imidazolium chloride, 21.4mg-428mg,
0.05-1.0mmol。
5. the synthetic method of esters Pd-NHC molecular complex as claimed in claim 2, which is characterized in that the step 1
In, chloride is sodium chloride, potassium chloride；0.1-2.0mmol；
Pyridine derivate solvent 0.1-20ml.
6. the synthetic method of esters Pd-NHC molecular complex as claimed in claim 2, which is characterized in that
In the step 3, the volume ratio of the mixed solvent of methylene chloride and water is 2:1.
7. the synthetic method of esters Pd-NHC molecular complex as claimed in claim 2, which is characterized in that the esters Pd-
The synthetic method chemical equation of NHC molecular complex are as follows:
8. a kind of chemistry using esters Pd-NHC molecular complex as described in claim 1 preparation, field of medicaments production application
Catalyst.
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