CN104549504B - A kind of NHC-metal-glyoxaline structure type catalyst and preparation method thereof - Google Patents
A kind of NHC-metal-glyoxaline structure type catalyst and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a kind of NHC metal imidazole structured catalyst and preparation method thereof, the method comprises the following steps: filtrate, to dissolving, is MY with formula after filtration by the presence of the first solvent and the under agitation mixing of (1) imidazole salts and alkali2(MeCN)2Or MY2(PhCN)2Transition metal salt in the presence of the second solvent, carry out first step synthetic reaction under agitation；(2) imidazoles is dissolved in the 3rd solvent, is then added in the solution of step (1) gained, and carry out second step synthetic reaction under agitation.The method using the present invention is synthesized by two-step process NHC Pd glyoxaline structure type catalyst, and end product need not silicagel column and separates, beneficially large-scale production.
Description
Technical field
The present invention relates to the synthesis of N-heterocyclic carbine (NHC) metallic catalyst, more particularly it relates to an NHC-
The preparation method of metal-glyoxaline structure type catalyst.
Background technology
2011, the Shao Lixiong of Wenzhou University disclosed N-heterocyclic carbine (NHC)-metal in patent CN102153592A
The catalyst of palladium-glyoxaline structure, its structure is shown below:
The most in two years, Shao Li hero seminar and Lu Jianmei seminar demonstrate it with Metal Palladium (Pd) catalyst successively
Catalytic performance, mainly for coupling reaction, its structure is shown below:
Patent CN102153592A and article Synthesis, demonstrate it right in 2011,19,3138-3142.
Suzuki-Miyaura coupling reaction has and is well catalyzed activity.
Patent CN102432411A demonstrates its catalysis activity to aryl chloride with the coupling reaction of alkylamine.
Patent CN102816041A demonstrates it catalysis of benzyl chloride with phenylboric acid Suzuki-Miyaura coupling is lived
Property.
Article Tetrahedron, 2011,67(29), 5150-5155. and article Tetrahedron, 2012,68
(10), 2414-2420. demonstrates it catalysis of the C-N coupling reaction between aryl chloride and morphine and aminated compounds is lived
Property.
Article The Journal of Organic Chemistry, 2012,77(15), 6608-6614. demonstrates it
P-TOLUENE SULFO ACID 99's ester is active with the catalysis of aryl boric acid coupling reaction.
Article The Journal of Organic Chemistry, 2012,77(20), 9236-9239. demonstrates it
Aryl chloride can be catalyzed and with amide, C-N coupling reaction occurs.
Article Journal of Organometallic Chemistry, demonstrates it right in 2012,700,132-134.
The catalysis activity of Hiyama reaction.
Article Organic letters, 2013,15(6), 1254-1257. and article Synthesis, 2012,44(5),
711-716. demonstrates it and with aryl chloride, C-C coupling reaction can occur with activated carbonyl α position hydrogen.
Article Tetrahedron, 2012,68(29), 5806-5809. demonstrates it and can be catalyzed phenylboric acid in water
Generation benzophenone is reacted with benzoyl oxide.
Visible, catalysis scope and catalysis activity all ratios of the catalyst of this kind of NHC-Pd-glyoxaline structure are more prominent, but,
" one kettle way " that use in building-up process needs to use silicagel column to separate in last handling process, and process is loaded down with trivial details, is unfavorable for
Large-scale production.
Therefore, it is directed to this catalyst defect present in the building-up process, the invention provides a kind of novel azepine
The preparation method of ring Cabbeen (NHC)-metal-glyoxaline structure type catalyst.
Summary of the invention
It is an object of the invention to overcome in prior art and prepare N-heterocyclic carbine (NHC)-metal-imidazole catalyst process
Present in productivity relatively low and need silicagel column to carry out separating and being not easy to the defect synthesized in a large number, it is provided that Yi Zhongxin
The preparation method of N-heterocyclic carbine (the NHC)-metal of type-glyoxaline structure type catalyst.
The invention provides the preparation method of a kind of NHC-metal-glyoxaline structure type catalyst, the method includes following step
Rapid:
(1) the mixing extremely dissolving under agitation in the presence of the first solvent by the imidazole salts shown in formula (I) and alkali, filters
After be MY by filtrate and formula2(MeCN)2Or MY2(PhCN)2Transition metal salt in the presence of the second solvent under agitation
Carry out first step synthetic reaction,
Formula (I),
Wherein, R1And R2Group is identical or different, and is each independently alkyl or its isomer, the aryl of C1-C6, takes
For aryl or naphthyl；X is I-、Br-、Cl-Or BF4 -；Y is I-、Br-、Cl-、NO3 -Or CH3COO-；M be silver, nickel, palladium, cobalt, rhodium or
Ruthenium；
(2) imidazoles shown in formula (II) is dissolved in the 3rd solvent, is then added in the solution of step (1) gained, and
Carry out second step synthetic reaction under agitation,
Formula (II),
Wherein, R3Alkyl or its isomer, aryl, substituted aryl or naphthyl for C1-C6.
According to the preparation method of N-heterocyclic carbine (NHC)-metal-glyoxaline structure type catalyst that the present invention provides, in system
During Bei, it is synthesized by two-step process NHC-Pd-glyoxaline structure type catalyst, and end product need not silicagel column and separates, profit
In large-scale production, overcoming post processing in prior art needs to use silicagel column to separate, and process is loaded down with trivial details, and is separating
During have a certain amount of catalyst decompose loss shortcoming.
Other features and advantages of the present invention will be described in detail in detailed description of the invention part subsequently.
Accompanying drawing explanation
Fig. 1 is data X-ray (the X crystalline substance that the embodiment of the present invention 1 prepares obtained NHC-Pd-glyoxaline structure type catalyst
Body diffraction) structure chart.
Detailed description of the invention
Hereinafter the detailed description of the invention of the present invention is described in detail.It should be appreciated that described herein specifically
Embodiment is merely to illustrate and explains the present invention, is not limited to the present invention.
The invention provides the preparation method of a kind of NHC-metal-glyoxaline structure type catalyst, the method includes following step
Rapid:
(1) the mixing extremely dissolving under agitation in the presence of the first solvent by the imidazole salts shown in formula (I) and alkali, filters
After be MY by filtrate and formula2(MeCN)2Or MY2(PhCN)2Transition metal salt in the presence of the second solvent under agitation
Carry out first step synthetic reaction,
Formula (I),
Wherein, R1And R2Group is identical or different, and can be each independently alkyl or its isomer, the virtue of C1-C6
Base, substituted aryl or naphthyl；X can be I-、Br-、Cl-Or BF4 -；Y is I-、Br-、Cl-、NO3 -Or CH3COO-；M can be silver,
Nickel, palladium, cobalt, rhodium or ruthenium；
(2) imidazoles shown in formula (II) is dissolved in the 3rd solvent, is then added in the solution of step (1) gained, and
Carry out second step synthetic reaction under agitation,
Formula (II),
R3Can be alkyl or its isomer, aryl, substituted aryl or the naphthyl of C1-C6.
In the case of according to the invention it is preferred to, in formula (I), R1And R2Group is identical or different, and can be independently of one another
Alkyl or its isomer, aryl, substituted aryl or naphthyl for C1-C6；X can be I-、Br-、Cl-.Leading at transition metal salt
In formula, Y can be I-、Br-Or Cl-；M can be palladium.In formula (II), R3Can be alkyl or its isomer, the virtue of C1-C6
Base, substituted aryl or naphthyl.
In the case of according to the invention it is preferred to, described imidazole salts can be iodate 1-(1-methyl) ethyl-3-phenylimidazole,
Double (the 2,4,6-of bromination 1,3-diisopropyl imidazoles, chlorination 1,3-diphenyl-imidazole, chlorination 1,3-diethyl imidazolium or chlorination 1,3-
Trimethylphenyl) imidazoles；Described transition metal salt can be PdI2(MeCN)2、PdBr2(MeCN)2、PdCl2(MeCN)2、PdI2
(PhCN)2、PdBr2(PhCN)2And PdCl2(PhCN)2In one or more.
According to the present invention, described alkali can be potassium hexamethyldisilazide (KHMDS), sodium hexamethyldisilazide,
KHCO3、K2CO3、Na2CO3、Cs2CO3、NaHCO3、CH3COOK、CH3ONa, NaOH, KOH, potassium tert-butoxide (KOtAnd the tert-butyl alcohol Bu)
Sodium (NaOtBu) one or more in.Under preferable case, described alkali can be potassium hexamethyldisilazide (KHMDS),
K2CO3、Cs2CO3、KOtBu and NaOtOne or more in Bu.
According to the present invention, described first solvent, described second solvent and described 3rd solvent can be identical or differ,
And can be each the one or many in toluene, THF, 1,4-dioxane, normal hexane, dichloromethane and 1,2-dichloroethanes
Kind.Preferable case is as follows, and described first solvent, described second solvent and described 3rd solvent can be identical or differ, and respectively
From being one or more in toluene, 1,4-dioxane and dichloromethane.
According to the present invention, described stirring condition can be: stir speed (S.S.) is 50-1500 rev/min.
According to the present invention, the condition of described first step synthetic reaction can be: the condition of described first step synthetic reaction is:
Reaction temperature is-10-100 DEG C, preferably 30-80 DEG C, and the response time is 30-360 minute, preferably 60-240 minute；Described
The condition of synthetic reaction is for the second time: reaction temperature is-10-100 DEG C, preferably 30-40 DEG C, and the response time is that 20-120 divides
Clock, preferably 30-90 minute.
According to the present invention, described imidazole salts can be 1:1-3 with the mol ratio of described alkali, and described transition metal salt is with described
The mol ratio of imidazole salts can be 1:1-5, and described transition metal salt can be 1:0.1-1 with the mol ratio of described imidazoles.Preferably
In the case of, described imidazole salts can be 1:1-2 with the mol ratio of described alkali, and described transition metal salt rubs with described imidazole salts
Your ratio can be 1:1-2, and described transition metal salt can be 1:0.3-1 with the mol ratio of described imidazoles.
According to the present invention, described filtration is not particularly limited, and can be the filter types commonly used of those skilled in the art,
In the present invention, it is preferably and filters with kieselguhr.
According to the present invention, also needing to the product to being obtained and concentrate in this preparation method, described concentration is the most concrete
Limit, can be the condensing mode commonly used of those skilled in the art.
According to the present invention, in a certain detailed description of the invention, N-heterocyclic carbine (NHC)-metal-glyoxaline structure of the present invention
The preparation method of type catalyst specifically includes following steps:
(1) at temperature is-10-100 DEG C, imidazole salts and alkali mix under agitation to the most molten in the presence of the first solvent
Solving, recycle silicon diatomaceous earth filters, and is MY by filtrate and formula after filtration2(MeCN)2Or MY2(PhCN)2Transition metal salt second
First step synthetic reaction is carried out under agitation in the presence of solvent；Concrete course of reaction is as follows:
Wherein, by structural formula it isShown imidazole salts and alkali are 50-in stir speed (S.S.) in the first solvent
Under conditions of 1500, mixing is to dissolving, and is preferably and stirs 30-360 minute under this stir speed (S.S.)；Then, filter with kieselguhr,
After filtration, it is MX by filtrate and formula2(MeCN)2Or MX2(PhCN)2Transition metal salt mix in the second solvent, stirring
30-120 minute；
(2) at temperature is-10-100 DEG C, by imidazolesIt is dissolved in the 3rd solvent, is then added dropwise over
In the first step in the solution (or suspension) of gained solid, under conditions of stir speed (S.S.) is 50-1500 rev/min, stir 20-
120 minutes, solution was clarified, and solution is concentrated to give faint yellow solid；Concrete course of reaction is as follows:
Hereinafter will be described the present invention by embodiment.
The chemical drugs used in the following Examples and Comparative Examples is purchased from lark prestige Science and Technology Ltd..
Embodiment 1
The first step: at temperature is 30 DEG C, by 62.8mg(0.2mmol) iodate 1-(1-methyl) ethyl-3-phenylimidazole
(structural formula is) and potassium hexamethyldisilazide (KHMDS) 43.9mg(0.22mmol) add
Enter to stirring in 5mL toluene and be completely dissolved for 60 minutes, filter with kieselguhr, by filtrate and 88.4mg(0.2mmol after filtration)
PdI2(MeCN)2Isosorbide-5-Nitrae-dioxane (15ml) solution mixing, at temperature is 30 DEG C, stir 30 minutes；Use kieselguhr mistake
Filter, concentrates filtrate after filtration, obtains orange solids 101.1mg, and productivity is 92.7%.
Second step: at temperature is 40 DEG C, the orange solid product 101.1mg(0.09mmol that will obtain in the first step) molten
Imidazoles is added under (suspension), stirring in 15ml dichloromethaneDichloro 26.7mg(0.182mmol)
Dichloromethane 10ml, stirs 60 minutes until solution clarification is yellow solution, is concentrated to give 127.6mg faint yellow solid, productivity
100%。
Embodiment 2
The first step: at temperature is 30 DEG C, by 46.4mg(0.2mmol) bromination 1, (structural formula is 3-diisopropyl imidazoles) and 33.7mg(0.3mmol) KOtBu to join in the toluene (5mL) stirring 90 minutes the most molten
Solve, with kieselguhr filter, by filtrate and 88.4mg(0.2mmol after filtration) PdBr2(MeCN)21,4-dioxane molten
(15ml) liquid mixing, stirs 60 minutes at temperature is 60 DEG C；Filter with kieselguhr, after filtration, filtrate is concentrated, obtain orange
Solid 78.7mg, productivity is 94.6%.
Second step: at temperature is 30 DEG C, the orange solid product 78.7mg(0.095mmol that will obtain in the first step) molten
Imidazoles is added under (suspension), stirring in 15ml dichloromethaneDichloromethane 20.9mg(0.19mmol)
Alkane solution 8ml, stirs 50 minutes until solution clarification is yellow solution, is concentrated to give 99.8mg faint yellow solid, productivity 100%.
Embodiment 3
The first step: at temperature is 30 DEG C, by 68.1mg(0.2mmol) chlorination 1, double (2,4, the 6-trimethylphenyl) miaow of 3-
Azoles and 43.9mg(0.22mmol) potassium hexamethyldisilazide (KHMDS) join and stir 180 minutes points in 5mL toluene
Clock is completely dissolved, with kieselguhr filter, by filtrate and 51.8mg(0.2mmol after filtration) PdCl2(MeCN)2Dioxane
Solution (15ml) mixes, and stirs 60 minutes at temperature is 80 DEG C；Filter with kieselguhr, after filtration, filtrate is concentrated, obtain orange
Color solid 87.8mg, productivity is 91.3%.
Second step: at temperature is 40 DEG C, by first step product as orange solid product 87.8mg(0.09mmol) it is dissolved in
In 15ml dichloromethane (suspension), stirring is lower adds 0.183mmol imidazoles26.4mg dichloromethane
Alkane solution 10ml, stirs 90 minutes until solution clarification is yellow solution, is concentrated to give 176.0mg faint yellow solid, productivity
100%。
Embodiment 4
The first step: at temperature is 30 DEG C, by 51.2mg(0.2mmol) chlorination 1,3-diphenyl-imidazole (structural formula) and 130.0mg(0.4mmol) Cs2CO3Join in 10mL normal hexane stir 120 minutes
Be completely dissolved, with kieselguhr filter, by filtrate and 84.3mg(0.22mmol after filtration) PdCl2(PhCN)2Oxolane molten
Liquid (15ml) mixes, and stirs 120 minutes at temperature is 80 DEG C；Filter with kieselguhr, after filtration, filtrate is concentrated, obtain orange
Solid 71.0mg, productivity is 89.7%.
Second step: at temperature is 40 DEG C, by first step product as orange solid product 71.0mg(0.09mmol) it is dissolved in
In 15ml dichloromethane (suspension), stirring is lower adds 0.18mmol imidazoles14.7mg dichloromethane solution
10ml, stirs 30 minutes until solution clarification is yellow solution, is concentrated to give 86.0mg faint yellow solid, productivity 100%.
Embodiment 5
The first step: at temperature is 30 DEG C, by 32.0mg(0.2mmol) chlorination 1,3-diethyl imidazolium (structural formula) and 26.9mg(0.24mmol) KOtBu join in 10mL normal hexane stir 40 minutes the most molten
Solve, with kieselguhr filter, by filtrate and 64.8mg(0.25mmol after filtration) PdCl2(MeCN)2Tetrahydrofuran solution
(15ml) mixing, stirs 60 minutes at temperature is 80 DEG C；Filter with kieselguhr, after filtration, filtrate is concentrated, obtain orange solid
Body 51.2mg, productivity is 85.3%.
Second step: at temperature is 30 DEG C, by first step product as orange solid product 51.2mg(0.085mmol) it is dissolved in
In 15ml dichloromethane (suspension), stirring is lower adds 0.17mmol imidazoles13.9mg dichloromethane solution
10ml, stirs 40 minutes until solution clarification is yellow solution, is concentrated to give 65.0mg faint yellow solid, productivity 100%.
Comparative example 1
The structure preparing NHC-metal-glyoxaline structure type catalyst with embodiment 1 is identical, and institute's difference is that this is prepared
Method uses one-step method, is i.e. reacted by one-step synthesis, under nitrogen protection NHC imidazole salts
(0.21mmol), PdI2(0.2mmol), K2CO3(0.22mmol) with(0.82mmol) in anhydrous tetrahydro furan
Being heated to reflux 20 hours, the product silicagel column obtained after concentration carries out isolated faint yellow solid product, productivity 63%.
Comparative example 2
The method preparing NHC-metal-glyoxaline structure type catalyst with embodiment 1 is identical, and institute's difference is that this is prepared
The first step in method: use 40mg(0.2mmol) potassium hexamethyldisilazide (KHMDS) obtain orange solids 88.5mg,
Productivity is 81%.
Second step: stirring 30 minutes at 30 DEG C, productivity is 87%.
Comparative example 3
The method preparing NHC-metal-glyoxaline structure type catalyst with embodiment 1 is identical, and institute's difference is that this is prepared
The first step in method: 44.2mg(0.1mmol) PdI2(MeCN)2Productivity is 40%.
Second step: stirring 480 minutes at 40 DEG C, productivity is 100%.
Fig. 1 is NHC-Pd-glyoxaline structure crystal X-ray structure chart, as can be seen from this figure: the method using the present invention is real
Execute example 1 prepare obtained NHC-Pd-glyoxaline structure type catalyst cultivate the data result of monocrystalline gained prove this catalyst with
Designed is identical.
By the experimental result in embodiment 1-5 and comparative example 1-3, it can be deduced that two-step method used in the present invention
Make catalyst ultimate yield reach more than 90%, and overcome post processing in prior art and need to use silicagel column to separate,
It is unfavorable for large-scale production, and in separation process, has the shortcomings such as loss that a certain amount of catalyst decomposes.
Claims (12)
1. a preparation method for NHC-metal-glyoxaline structure type catalyst, the method comprises the following steps:
(1) imidazole salts shown in formula (I) and alkali and are mixed under agitation to dissolving, after filtration in the presence of the first solvent
It is MY by filtrate and formula2(MeCN)2Or MY2(PhCN)2Transition metal salt enter under agitation in the presence of the second solvent
Row first step synthetic reaction,
Wherein, R1And R2Identical or different, and it is each independently alkyl or its isomer, substituted aryl or the naphthyl of C1-C6；X
For I-、Br-、Cl-Or BF4 -；Y is I-、Br-、Cl-、NO3 -Or CH3COO-；M is silver, nickel, palladium, cobalt, rhodium or ruthenium；
(2) imidazoles shown in formula (II) is dissolved in the 3rd solvent, is then added in the solution of step (1) gained, and is stirring
Second step synthetic reaction is carried out under the conditions of mixing,
Wherein, R3Alkyl or its isomer, aryl, substituted aryl or naphthyl for C1-C6；
The product obtained is concentrated after also including second step synthetic reaction by described preparation method.
Method the most according to claim 1, wherein, in formula (I), R1And R2Group is identical or different, and independently of one another
Alkyl or its isomer, aryl, substituted aryl or naphthyl for C1-C6；X is I-、Br-Or Cl-；Formula at transition metal salt
In, Y is I-、Br-Or Cl-；M is silver, nickel, palladium, cobalt, rhodium or ruthenium；In formula (II), R3For the alkyl of C1-C6 or its isomer,
Aryl, substituted aryl or naphthyl.
Method the most according to claim 1 and 2, wherein, described imidazole salts is iodate 1-(1-methyl) ethyl-3-phenyl miaow
Azoles, bromination 1,3-diisopropyl imidazoles, chlorination 1,3-diphenyl-imidazole, chlorination 1,3-diethyl imidazolium or chlorination 1,3-pair (2,
4,6-trimethylphenyl) imidazoles；Described transition metal salt is PdI2(MeCN)2、PdBr2(MeCN)2、PdCl2(MeCN)2、PdI2
(PhCN)2、PdBr2(PhCN)2And PdCl2(PhCN)2In one or more.
Method the most according to claim 1, wherein, described alkali is potassium hexamethyldisilazide, the silica-based amine of hexamethyl two
Base sodium, KHCO3、K2CO3、Na2CO3、Cs2CO3、NaHCO3、CH3COOK、CH3ONa, NaOH, KOH, potassium tert-butoxide and sodium tert-butoxide
In one or more.
Method the most according to claim 1, wherein, described alkali is potassium hexamethyldisilazide, K2CO3、Cs2CO3, tertiary fourth
One or more in potassium alcoholate and sodium tert-butoxide.
Method the most according to claim 1, wherein, described first solvent, described second solvent and described 3rd solvent phase
With or differ, respectively toluene, oxolane, Isosorbide-5-Nitrae-dioxane, normal hexane, dichloromethane and 1, in 2-dichloroethanes
One or more.
7. according to the method described in claim 1 or 6, wherein, described first solvent, described second solvent and described 3rd solvent
Identical or differ, respectively one or more in toluene, Isosorbide-5-Nitrae-dioxane and dichloromethane.
Method the most according to claim 1, wherein, described stirring condition is: stir speed (S.S.) is 50-1500 rev/min.
Method the most according to claim 1, wherein, the condition of described first step synthetic reaction is: reaction temperature is-10-
100 DEG C, the response time is 30-360 minute；The condition of described second step synthetic reaction is: reaction temperature is-10-100 DEG C, instead
It is 20-120 minute between Ying Shi.
Method the most according to claim 9, wherein, the condition of described first step synthetic reaction is: reaction temperature is 30-
80 DEG C, the response time is 60-240 minute；The condition of described second step synthetic reaction is: reaction temperature is 30-40 DEG C, during reaction
Between be 30-90 minute.
11. methods according to claim 1, wherein, described imidazole salts is 1:1-3 with the mol ratio of described alkali, described mistake
The mol ratio crossing slaine and described imidazole salts is 1:1-5, and described transition metal salt is 1:0.1-with the mol ratio of described imidazoles
1。
12. according to the method described in claim 1 or 11, and wherein, described imidazole salts is 1:1-2 with the mol ratio of described alkali, institute
The mol ratio stating transition metal salt and described imidazole salts is 1:1-2, and described transition metal salt is 1 with the mol ratio of described imidazoles:
0.3-1。
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| N-Heterocyclic Carbene-Amine Pt(II) Complexes, a New Chemical Space for the Development of Platinum-Based Anticancer Drugs;Myriem Skander等;《Journal of Medicinal Chemistry》;20100211;第53卷(第5期);第2146-2154页 * |
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| CN104549504A (en) | 2015-04-29 |
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