CN106046057A - Azacyclocarbene metal coordination polymer and preparation method thereof, and application of azacyclocarbene metal coordination polymer as catalyst - Google Patents
Azacyclocarbene metal coordination polymer and preparation method thereof, and application of azacyclocarbene metal coordination polymer as catalyst Download PDFInfo
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Abstract
The invention specifically relates to an azacyclocarbene metal coordination polymer and a preparation method thereof, and application of the azacyclocarbene metal coordination polymer as a catalyst, belonging to the technical field of preparation and application of heterogeneous catalysts. The azacyclocarbene metal coordination polymer provided in the invention has a general structural formula (I) and can be prepared by reacting a bis(imidazole) salt with a metal precursor under alkaline conditions and carrying out coordination assembling. The azacyclocarbene metal coordination polymer is applicable to catalysis of oxydehydrogenation of a variety of alcohols and derivatives thereof, carbohydrate compounds, cellulose or lignin and to high-efficiency preparation of lactic acid and derivatives thereof. The novel self-loaded catalytic system integrates the advantages of homogeneous catalysis and heterogeneous catalysis, and can realize high-efficiency, high-selectivity and considerable conversion of biomass polyol raw materials under mild conditions; and the catalyst has the advantages of high-efficiency recovery, repeated usability, etc., and has good application prospect in preparation of lactic acid and hydrogen by using industrial catalysis approaches.
Description
Technical field
The invention belongs to heterogeneous catalysis preparation and application technical field, relate to a class novel nitrogen heterocyclic carbene metal coordination polymer, its preparation method and the application as catalyst.
Background technology
Many alcohol compounds and derivant thereof the most extensively come from nature, and just can conveniently obtain some cheap natural small molecule compounds by the simple conversion of biomass (such as cellulose, lignin, the waste material of production biodiesel in agricultural residue straw).Converted by the dehydrogenation of alcoholic compounds many to little molecule, not only can prepare the fine chemical product of some high added values easily, and for solve current serious rely on oil energy industry faced by relevant issues be significant.Preparing polyol converting waste material currently with natural polyol and biodiesel becomes the method for plateform molecules lactic acid of high added value mainly by biofermentation.Although fermentation method has, selectivity is good, the advantage of mild condition, but there is also that the purity requirement to raw material is high, convert time-consuming long, conversion ratio is low, enzyme easy in inactivation difficulty reclaims, be easily generated a large amount of refuse, reaction scale is difficult to amplify, cross dilute due to production concentration and cause stubborn problems such as being difficult to post processing.It is, thus, sought for new technology and method substitute traditional fermentation process so that polyol can facilitate, efficiently, leniently be converted into lactic acid, become in recent years probe into focus and difficult point.
Transition metal-catalyzed material catalysis polyol is utilized to prepare, by oxidative dehydrogenation, the new technique that lactic acid technology is a kind of biomass economy of rising in recent years.Silicon dioxide carried gold-platinum bimetallic heterogeneous catalysis is taken the lead in being applied to this field, but this kind of support type inorganic nano catalyst system and catalyzing yet suffers from that conversion ratio is low, reaction selectivity is poor, reaction temperature is too high, need to use the problems such as a large amount of highly basic.Prepare the reaction of lactic acid reported until utilizing the beginning of this year homogeneous double phosphine pincer ruthenium catalysts to be applied to glycerol, but only up to obtain about 60% selectively produce lactic acid, in addition to reaction conversion ratio is the highest, simultaneous reactions system also can generate multiple by-product.Phosphine ligands is because of its synthesis trouble, expensive, on air and water unstable, impact on factors such as environment are unfriendly simultaneously, it is difficult to be applied in actual production.Therefore, how to combine the homogeneous and advantage of heterogeneous catalysis, design and develop the catalyst system and catalyzing that a class is brand-new, realizing the biomass materials such as glycerol under gentle reaction condition while selective conversion efficient, high, it is possible to reclaiming and reuse transition metal-catalyzed material efficiently becomes academia and industrial quarters focus of attention.
Summary of the invention
It is an object of the present invention to provide that first stability is good, urge activity high, can high efficiente callback and reusable N-heterocyclic carbine metal coordination polymer.
Further object is that the preparation method that above-mentioned N-heterocyclic carbine metal coordination polymer is provided.
The present invention still another purpose is that the application providing above-mentioned N-heterocyclic carbine metal coordination polymer as catalyst.
For solving above-mentioned technical problem, the aza ring carbine metal coordination polymer that embodiments of the present invention are provided, its structure is as shown in logical formula I:
And:
Wherein:
M is transition metal；
V, W are each independently N or CH；
X, Y are each independently O, N-G, CH ,-CH=CH-,-C ≡ C-, carbon number be 0～8 alkane group, to phenyl, a phenyl, adjacent phenyl, Isosorbide-5-Nitrae-divinyl phenyl, Isosorbide-5-Nitrae-diacetylene phenyl, xenyl, 1,4-methylene phenyl or 9,10-anthryl；Described G is blocking group, and described blocking group is: cyclic alkane base, benzyl, aryl, tertbutyloxycarbonyl, benzoyl or the benzyl chloroformate that chain alkyl that carbon number is 1～12, carbon number are 5～7；
Z is halogen anion, tetrafluoroborate, hexafluoro-phosphate radical or hexafluoroantimonic anion；
L is assistant ligand；
R be carbon number be 1～12 chain alkyl, carbon number be 5～7 cyclic alkane base, benzyl or aryl；
M represents the number of repetitive in linker, and m is 0 or natural number；
N represents the number comprising monomer in N-heterocyclic carbine metal coordination polymer, and n is the natural number more than or equal to 2.
Preferably, in the structure of the N-heterocyclic carbine metal coordination polymer that embodiments of the present invention are provided, transition metal represented by M can be Ag, Au, Cu, Ir, Mn, Mo, Ni, Os, Rh, Ru, Pd or Zn, and assistant ligand can be halogen, carbonyl, phenyl ring, cyclopentadienyl ring, cyclo-octadiene, hydroxyl, water, carbonate, acetate, acetylacetone,2,4-pentanedione anion or all kinds of Phosphine ligands.
The above-mentioned N-heterocyclic carbine metal coordination polymer that embodiments of the present invention are provided, be a kind of based on rigidity bidentate nitrogen heterocycle carbine ligand, there is strong σ donor and the N-heterocyclic carbine metal coordination polymer of weak π acceptor property, have good stability, urge activity high, can high efficiente callback and the advantage such as reuse.
Embodiments of the present invention provide the preparation method of above-mentioned N-heterocyclic carbine metal coordination polymer simultaneously, the steps include: to utilize the Neo Heliopan AP shown in logical formula II to react with metal precursor in the basic conditions, assembled by coordination and prepare the N-heterocyclic carbine metal coordination polymer shown in logical formula I；
Its reaction equation is as follows:
And:
Wherein:
M is transition metal；
V, W are each independently N or CH；
X, Y are each independently O, N-G, CH ,-CH=CH-,-C ≡ C-, carbon number be 0～8 alkane group, to phenyl, a phenyl, adjacent phenyl, Isosorbide-5-Nitrae-divinyl phenyl, Isosorbide-5-Nitrae-diacetylene phenyl, xenyl, 1,4-methylene phenyl or 9,10-anthryl；Described G is blocking group, and described blocking group is: cyclic alkane base, benzyl, aryl, tertbutyloxycarbonyl, benzoyl or the benzyl chloroformate that chain alkyl that carbon number is 1～12, carbon number are 5～7；
Z is halogen anion, tetrafluoroborate, hexafluoro-phosphate radical or hexafluoroantimonic anion；
L is assistant ligand；
R be carbon number be 1～12 chain alkyl, carbon number be 5～7 cyclic alkane base, benzyl or aryl；
M represents the number of repetitive in linker, and m is 0 or natural number；
N represents the number comprising monomer in N-heterocyclic carbine metal coordination polymer, and n is the natural number more than or equal to 2.
Embodiments of the present invention provided in the coordination poly-merization preparing this N-heterocyclic carbine metal coordination polymer, metal precursor is MXaLb, wherein, a is 0,1 or 2；B is 0,1 or 2；The definition of M, X, L is as hereinbefore.Specifically, used in this reaction metal precursor is preferably: Ag2O、AgBF4、AuCl(SMe2)、Cu2O、CuI、Ni(OAc)2、NiCl2、PtCl2、K2PtCl4、CoCl(PPh3)3、CoCl2、FeCl2、MnCl2、ZnCl2、OsH6(t-Bu3P)2、[Ir(COD)Cl]2、[Ir(COD)OMe]2、IrCl3·3H2O, [IrCp*Cl2]2、Ir(CO)2(acac)、Pd(OAc)2、PdCl2(CH3CN)2、RuCl3、[Ru(COD)Cl]2、[Ru(p-cymene)Cl2]2、[Ru(benzene)Cl2]2、[Rh(COD)Cl]2Deng.It addition, alkali used in this reaction can be NaOH, NaH, KOH, t-BuOK, LDA, LiHMDS or KHMDS.Part is 1:1～1:4 with the molar ratio of transition metal, organic solvent needed for reaction can select dichloromethane, chloroform, toluene, benzene, oxolane, methyl tertiary butyl ether(MTBE), acetonitrile, N, dinethylformamide, N,N-dimethylacetamide, methyl pyrrolidone or dimethyl sulfoxide equal solvent；In some cases, the mixed liquor of two to three kinds of organic solvent above-mentioned can provide more preferable polymerization result.Temperature required generally 0～150 DEG C of above-mentioned coordination poly-merization, the response time is recommended as 1～24 hour.
Specifically, the laboratory operating procedures of this preparation reaction is as follows: at room temperature, the Neo Heliopan AP (aza ring carbene precursor) of the rigidity shown in logical formula II and respective metal precursor are dissolved in N, in dinethylformamide or other optional solvents, being added dropwise over the tetrahydrofuran solution of corresponding alkali, when there being brown color precipitation to produce, reaction system continues stirring, when TLC monitoring is less than imidazole salts or Cabbeen, reaction stops.After cooling, filter, wash, vacuum dried after obtain logical N-heterocyclic carbine metal coordination polymer shown in formula I.
The reaction mechanism of above-mentioned preparation process is as follows:
First Neo Heliopan AP is pulled out hydrogen under the effect of alkali, forms active Cabbeen species.Carbenes and metal precursor generation ligand exchange afterwards, part or anion X that in metal precursor, coordination ability is more weak are left away, and form double card guest-metal-complexing species, and this happens over and over again thus constructs metal organic coordination polymer by self assembly mode.Such metal organic coordination polymer dissolubility in common organic solvents and water is the most very poor, can form Precipitation.
Have verified that through experiment, logical N-heterocyclic carbine metal coordination polymer shown in formula I, in the case of linker, M, V, W, X, Y, Z, L, R, m, the n in its structure is various definition described previously herein or substituent group, all can be prepared by above-mentioned coordination poly-merization.
Furthermore, it is necessary to supplement, as the Neo Heliopan AP of aza ring carbene precursor, following reaction scheme can be used to prepare:
As a example by the synthesis of benzo Neo Heliopan AP, with 1,2,4,5-tetramino benzene hydrochlorides are raw material, generate benzo double imidazoles for solvent in 100 DEG C of reactions cyclization in 36 hours with formic acid.With sodium hydride for alkali one pot of double imidazoles bromide of the formation substituted benzo of the tetrabutyl under conditions of bromination of n-butane.The document referred to is: [J.Mater.Chem., 2010,20,5709 5714].
As a example by 3,3 '-bisbenzimidazolium salt: with 3,3 ', 4,4 ' tetra-amino-biphenyls are raw material, generate 3 for solvent in 100 DEG C of reactions cyclization in 36 hours with formic acid, 3 '-bisbenzimidazole.With sodium hydride for the alkali one pot of formation tetrabutyl substituted 3,3 '-bisbenzimidazolium salt bromide under conditions of bromination of n-butane.The document referred to is: [J.Am.Chem.Soc.2005,127,12496-12497].
Embodiments of the present invention also provide for the application as the catalyst of oxidative dehydrogenation of the above-mentioned N-heterocyclic carbine metal coordination polymer.Further, this kind of application is the above-mentioned N-heterocyclic carbine metal coordination polymer oxidative dehydrogenation for catalytic alcohol or derivatives thereof, saccharide compound, cellulose or lignin；Above-mentioned oxidative dehydrogenation can be used for the preparation of lactic acid or derivatives thereof.Further, the method for this catalytic applications is: under nitrogen atmosphere, in the reaction system of reaction substrate, alkali and water composition, add described N-heterocyclic carbine metal coordination polymer as catalyst, agitating heating is reacted, and discharges hydrogen, and prepared lactic acid or derivatives thereof；Wherein, reaction substrate is alcohol or derivatives thereof, saccharide compound, cellulose or lignin.In above-mentioned reaction, the consumption proportion situation of reaction substrate, alkali, water and catalyst is: the consumption of alkali can be 1～40mmol/mmol substrate, and the consumption proportion of water can be 0～15mL/mmol substrate, and the consumption of catalyst can be 1 × 10-6～1mmol/mmol substrate, temperature required generally 25～290 DEG C, the response time is recommended as 1～96 hour.Visible, in above-mentioned catalytic reaction, the catalytic efficiency of N-heterocyclic carbine metal coordination polymer catalyst provided by the present invention is high.
Specifically, the specific operation process that lactic acid is prepared in N-heterocyclic carbine metal coordination polymer catalytic oxidative dehydrogenation reaction embodiments of the present invention provided is as follows:
Under nitrogen atmosphere, the N-heterocyclic carbine metal coordination polymer that addition embodiments of the present invention are provided in reaction vessel successively is as supported catalyst, reaction substrate, alkali and a certain amount of water, the post-heating that stirs reacts, and reaction has hydrogen and releases during carrying out.When no longer there being hydrogen to release, show that reaction terminates.System is down to room temperature, after being centrifuged with low-speed centrifugal device, pours out supernatant, the conversion ratio warp of products therefrom1The amount of H NMR and hydrogen release determines.Reclaim supported catalyst, after organic solvent, washing, vacuum dried rear standby.
During second time circulation, containing in the reaction tube reclaiming supported catalyst being dried, rejoin reaction substrate, alkali and a certain amount of water, carry out reacting and post processing according to the condition that previous reaction is identical.So circular response about 15 to 20 times, the selectivity of reaction and conversion ratio can't occur how much changing.As can be seen here, catalyst provided by the present invention can realize reclaiming and recycling well.
What deserves to be explained is, the catalyticing mechanism of above-mentioned catalytic reaction is:
Glycols substrate obtains adjacent diketone intermediate through twice dehydrogenation oxidation under the effect of catalyst, three alcohols substrates under the effect of catalyst through once oxidation dehydrogenation, obtain Alpha-hydroxy aldehyde, aldehyde radical enol intermediate is obtained again after once eliminating dehydration, enol is rearranged to more stable ketone form structure, the most also obtains adjacent diketone intermediate.There are 3 C-C bond fissions in more than ternary polyol or sugar under the effect of catalyst, generates glyceraldehyde, be dehydrated further, and isomerization generates adjacent diketone intermediate.Polysaccharide and oligosaccharide generate monosaccharide through basic hydrolysis, and monosaccharide occurs 3 C-C bond fissions under the effect of catalyst again, generate glyceraldehyde, are dehydrated further, and isomerization generates adjacent diketone intermediate.Adjacent diketone intermediate obtains 'alpha '-hydroxy acids through the reaction of intramolecular cannizaro under alkali effect.Have verified that through experiment, alcohol or derivatives thereof, saccharide compound, cellulose or lignin are as reaction substrate, under the catalytic action of N-heterocyclic carbine metal coordination polymer provided by the present invention, efficient oxidative dehydrogenation all can occur, prepare lactic acid or derivatives thereof.
To sum up, the present invention utilizes the double imidazoles aza ring carbene precursor of bridging of rigidity as a kind of bridging bidentate ligand, by the way of coordination assembles, a kind of novel self-supported catalyst it is efficiently prepared under suitable conditions with metal precursor, it is achieved thereby that the selective oxidation dehydrogenation reaction of polyol biolobic material raw material.This kind of novel self-supported catalyst is convieniently synthesized, has homodisperse catalytic active center, shows the highest catalysis activity in multiclass converts.It addition, the dissolubility that this kind of coordination polymer type catalyst is in common solvents is extremely low, not only can carry out product easily and separate with catalyst, and can repeatedly reclaim and reuse, meet demand of industrial production, effectively reduce the heavy metal pollution to environment.
It is that a class novel nitrogen heterocyclic carbene metal coordination assembles supported catalyst that the present invention designs the N-heterocyclic carbine metal coordination polymer of synthesis, and the catalytic oxidative dehydrogenation that can be used for various biomass polyol and derivant, saccharide compound, cellulose or lignin reacts, efficiently prepares lactic acid.Owing to this kind of novel self-supported catalyst system and catalyzing stability is high, insoluble in most organic solvent and water, can apply to multiclass heterogeneous catalytic reaction, thus the advantage combining homogeneous catalysis and heterogeneous catalysis, it is not only able to realize the many raw polyols of biomass selectivity efficient, high, substantial amounts of conversion under mild conditions, and there is high efficiente callback and the advantage being recycled for multiple times.It is difficult to efficiently for current biomass material, the problem of high selective conversion, this kind of stable novel heterogeneous self-supported catalyst is utilized not only to achieve polyol and many 01 derivatives, saccharide compound, the conversion in a mild condition of the biomass material such as cellulose or lignin, thus efficiently, highly selective prepares Important Platform molecule lactic acid, and with the carrying out of catalytic reaction, efficiently output hydrogen, new solution route is proposed for solving current energy resource supply relevant issues, the most this kind of novel self-supported catalyst is at the energy, catalysis, the aspect of material shows fabulous using value.
Accompanying drawing explanation
Fig. 1 is the double imidazoles bromide of tetrabutyl benzo prepared in embodiment 11H NMR spectra；
Fig. 2 is the double imidazoles bromide of tetrabutyl benzo prepared in embodiment 113C NMR spectra；
Fig. 3 is the IR spectrogram of the double imidazoles bromide of tetrabutyl benzo prepared in embodiment 1；
The novel nitrogen heterocyclic carbene metal coordination that Fig. 4 is prepared in embodiment 2 assembles the IR spectrogram of supported catalyst 4a；
The novel nitrogen heterocyclic carbene metal coordination that Fig. 5 is prepared in embodiment 3 assembles the IR spectrogram of supported catalyst 4b；
The novel nitrogen heterocyclic carbene metal coordination that Fig. 6 is prepared in embodiment 4 assembles the IR spectrogram of supported catalyst 4c；
The novel nitrogen heterocyclic carbene metal coordination that Fig. 7 is prepared in embodiment 5 assembles the IR spectrogram of supported catalyst 4d；
The novel nitrogen heterocyclic carbene metal coordination that Fig. 8 is prepared in embodiment 6 assembles the IR spectrogram of supported catalyst 4e；
Fig. 9 is that in embodiment 11, novel nitrogen heterocyclic carbene metal coordination assembling supported catalyst 4d efficiently prepares lactic acid products therefrom for the oxidative dehydrogenation of catalyzing glycerol1H NMR spectra (containing the internal standard).
Detailed description of the invention
For making the object, technical solutions and advantages of the present invention clearer, below in conjunction with accompanying drawing, the embodiments of the present invention are explained in detail.But, it will be understood by those skilled in the art that in each embodiment of the present invention, in order to make reader be more fully understood that, the application proposes many ins and outs.But, even if there is no these ins and outs and many variations based on following embodiment and amendment, it is also possible to realize the application each claim technical scheme required for protection.
The preparation of double imidazoles bromide 3a (aza ring carbene precursor) of embodiment 1 tetrabutyl benzo
Under room temperature, according to adding 1,2,4,5-tetramino benzene hydrochlorides 1 (284mg), formic acid (10mL) in 50mL round-bottomed flask.It is heated to 100 DEG C to react 36 hours.It is cooled to room temperature, is neutralized to neutrality by NaOH solution, filter precipitation and dry.Precipitation is transferred to 50mL standard Schlenk bottle, under nitrogen protection, is sequentially added into NaH (80mg, 60%), toluene 5mL and is heated to 110 DEG C of reactions 1 disappearance.It is cooled to room temperature, adds 1-n-butyl bromide (1mL), DMF (5mL), be heated to 110 DEG C of reactions and disappear to raw material for 4 hours.It is cooled to room temperature, is filtered to remove inorganic salt, obtain double imidazoles bromide 3a of tetrabutyl benzo with methylene chloride-methanol recrystallization.Productivity: 530mg, 98%.Characterization of The Products1H NMR spectra,13C NMR spectra and IR spectrogram are respectively as shown in accompanying drawing 1,2 and 3.
1H NMR (400MHz, DMSO) δ=10.18 (s, 2H), 9.05 (s, 2H), 4.61 (t, J=7.2,8H), 2.04 1.90 (m, 8H), 1.39 (dd, J=15.2,7.5,8H), 0.95 (t, J=7.4,12H).
13C NMR (101MHz, DMSO) δ=145.86,130.58,99.89,47.60,30.87,19.45,13.90.
IR (KBr pellet) ν 418.99,503.26,520.31,531.05,558.23,587.46,618.84,651.77,668.94,877.40,1021.32,1084.04,1104.94,1297.04,1384.37,1396.73,1448.48,1460.20,1578.89,1629.13,2955.97,2991.71,3074.74,3454.87cm-1
The preparation of embodiment 2 novel nitrogen heterocyclic carbene metal coordination assembling supported catalyst 4a:
Under nitrogen atmosphere is protected, in 50mL standard Schlenk bottle, add Neo Heliopan AP (aza ring carbene precursor) 3a (0.54g) of rigidity successively, [Ir (COD) Cl]2(0.33g), the tetrahydrofuran solution (1M, 2mL) of DMF (5mL), LiHMDS, the post-heating back flow reaction that stirs 12 hours, there is a large amount of yellow-brown solid to separate out, stop heating and reaction system is cooled to room temperature.Filter after reaction system adds 10mL distilled water, solid distilled water wash, after vacuum drying, obtain yellow-brown solid, be N-heterocyclic carbine metal coordination and assemble supported catalyst 4a, productivity: 0.62g, 91%.The IR spectrogram of Characterization of The Products is as shown in Figure 4.
IR (KBr pellet) ν 405.42,421.75,456.15,522.18,533.36,659.46,746.89,825.44,880.87,1083.56,1255.34,1346.66,1377.52,1438.53,1464.41,1552.37,1580.34,1628.99,2950.02,3416.80cm-1
The preparation of embodiment 3 novel nitrogen heterocyclic carbene metal coordination assembling supported catalyst 4b:
Under nitrogen atmosphere is protected, in 50mL standard Schlenk bottle, add Neo Heliopan AP (aza ring carbene precursor) 3b (0.68g) of rigidity successively, [Ir (COD) Cl]2(0.33g), the tetrahydrofuran solution (1M, 2mL) of DMF (5mL), LiHMDS, the post-heating back flow reaction that stirs 12 hours, there is a large amount of yellow-brown solid to separate out, stop heating and reaction system is cooled to room temperature.Filter after reaction system adds 10mL distilled water, solid distilled water wash, after vacuum drying, obtain yellow-brown solid, be N-heterocyclic carbine metal coordination and assemble supported catalyst 4b, productivity: 0.82g, 99%.The IR spectrogram of Characterization of The Products is as shown in Figure 5.
IR (KBr pellet) ν 703.40,1028.18,1083.90,1205.39,1384.09,1453.98,1477.94,1497.01,1648.38,3440.47cm-1
The preparation of embodiment 4 novel nitrogen heterocyclic carbene metal coordination assembling supported catalyst 4c:
Under nitrogen atmosphere is protected, in 50mL standard Schlenk bottle, add Neo Heliopan AP (aza ring carbene precursor) 3c (0.3g) of rigidity successively, [Ir (COD) Cl]2(0.33g), the tetrahydrofuran solution (1M, 2mL) of DMF (5mL), LiHMDS, the post-heating back flow reaction that stirs 12 hours, there is a large amount of yellow-brown solid to separate out, stop heating and reaction system is cooled to room temperature.Filter after reaction system adds 10mL distilled water, solid distilled water wash, after vacuum drying, obtain yellow-brown solid, be N-heterocyclic carbine metal coordination and assemble supported catalyst 4c, productivity: 0.5g, 98%.The IR spectrogram of Characterization of The Products is as shown in Figure 6.
IR(KBr pellet)ν455.20,763.95,1023.98,1273.33,1383.97,1523.04,1571.54,1629.33,2932.07,3432.38cm-1
The preparation of embodiment 5 novel nitrogen heterocyclic carbene metal coordination assembling supported catalyst 4d:
Under nitrogen atmosphere is protected, in 50mL standard Schlenk bottle, add Neo Heliopan AP (aza ring carbene precursor) 3d (0.4g), Ir (CO) of rigidity successively2(acac) (0.35g), the tetrahydrofuran solution (1M of DMF (5mL), LiHMDS, 2mL), the post-heating back flow reaction that stirs 12 hours, has a large amount of yellow-brown solid to separate out, and stops heating and reaction system is cooled to room temperature.Filter after reaction system adds 10mL distilled water, solid distilled water wash, after vacuum drying, obtain yellow-brown solid, be N-heterocyclic carbine metal coordination and assemble supported catalyst 4d, productivity: 0.54g, 99%.The IR spectrogram of Characterization of The Products is as shown in Figure 7.
IR (KBr pellet) ν 418.22,424.01,599.84,1084.05,1257.84,1383.96,1465.51,1629.09,2273.14,3443.20cm-1
The preparation of embodiment 6 novel nitrogen heterocyclic carbene metal coordination assembling supported catalyst 4e:
Under nitrogen atmosphere is protected, in 50mL standard Schlenk bottle, add Neo Heliopan AP (aza ring carbene precursor) 3d (0.4g) of rigidity, [Ru (p-cymene) Cl successively2]2(0.33g), the tetrahydrofuran solution (1M, 2mL) of DMF (5mL), LiHMDS, the post-heating back flow reaction that stirs 12 hours, there is a large amount of yellow-brown solid to separate out, stop heating and reaction system is cooled to room temperature.Filter after reaction system adds 10mL distilled water, solid distilled water wash, after vacuum drying, obtain yellow-brown solid, be N-heterocyclic carbine metal coordination and assemble supported catalyst 4e, productivity: 0.82g, 99%.The IR spectrogram of Characterization of The Products is as shown in Figure 8.
IR(KBr pellet)ν1618.18,1629.25,1636.50,1647.23,1653.86,2342.04,2360.15,3441.96,3567.51,3588.03,3619.96,3629.56cm-1
The coordination of embodiment 7 novel nitrogen heterocyclic carbene metal assembles supported catalyst 4c and efficiently prepares lactic acid for the oxidative dehydrogenation being catalyzed glucose:
Under nitrogen atmosphere is protected; have in the centrifuge tube of gas storage device to connection successively; add N-heterocyclic carbine metal coordination and assemble supported catalyst 4c (0.0045mmol); glucose (15mmol); potassium hydroxide (16.5mmol) and water (1mL); being heated with stirring to 115 DEG C react 24 hours, reaction has hydrogen and releases during carrying out.Reaction is cooled to about 80 DEG C after terminating, and adds a small amount of water dilute reaction solution and removes gas storage device, continuing to be cooled to room temperature, pours out supernatant after being centrifuged with low-speed centrifugal device, and supported catalyst reclaims with after distilled water wash repeatedly.Merging aqueous solution, after concentration, addition Sodium acetate trihydrate is as internal standard, and generating lactic acid yield with nuclear magnetic resonance measuring is 69%.
The coordination of embodiment 8 novel nitrogen heterocyclic carbene metal assembles supported catalyst 4c and efficiently prepares lactic acid for the oxidative dehydrogenation being catalyzed fructose:
Under nitrogen atmosphere is protected; have in the centrifuge tube of gas storage device to connection successively; add N-heterocyclic carbine metal coordination and assemble supported catalyst 4c (0.0045mmol); fructose (15mmol); potassium hydroxide (16.5mmol) and water (1mL); being heated with stirring to 115 DEG C react 24 hours, reaction has hydrogen and releases during carrying out.Reaction is cooled to about 80 DEG C after terminating, and adds a small amount of water dilute reaction solution and removes gas storage device, continuing to be cooled to room temperature, pours out supernatant after being centrifuged with low-speed centrifugal device, and supported catalyst reclaims with after distilled water wash repeatedly.Merging aqueous solution, after concentration, addition Sodium acetate trihydrate is as internal standard, and generating lactic acid yield with nuclear magnetic resonance measuring is 62%.
The coordination of embodiment 9 novel nitrogen heterocyclic carbene metal assembles supported catalyst 4d and efficiently prepares lactic acid for the oxidative dehydrogenation being catalyzed microcrystalline Cellulose:
Under nitrogen atmosphere is protected; have in the centrifuge tube of gas storage device to connection successively; add N-heterocyclic carbine metal coordination and assemble supported catalyst 4d (0.0045mmol); microcrystalline Cellulose (2.7g); potassium hydroxide (16.5mmol) and water (10mL); being heated with stirring to 115 DEG C react 24 hours, reaction has hydrogen and releases during carrying out.Reaction is cooled to about 80 DEG C after terminating, and adds a small amount of water dilute reaction solution and removes gas storage device, continuing to be cooled to room temperature, pours out supernatant after being centrifuged with low-speed centrifugal device, and supported catalyst reclaims with after distilled water wash repeatedly.Merging aqueous solution, after concentration, addition Sodium acetate trihydrate is as internal standard, and generating lactic acid yield with nuclear magnetic resonance measuring is 21%.
The coordination of embodiment 10 novel nitrogen heterocyclic carbene metal assembles supported catalyst 4d and efficiently prepares lactic acid for the oxidative dehydrogenation of catalytic water soluble starch:
Under nitrogen atmosphere is protected; have in the centrifuge tube of gas storage device to connection successively; add N-heterocyclic carbine metal coordination and assemble supported catalyst 4d (0.0045mmol); water soluble starch (2.7g); potassium hydroxide (16.5mmol) and water (10mL); being heated with stirring to 115 DEG C react 24 hours, reaction has hydrogen and releases during carrying out.Reaction is cooled to about 80 DEG C after terminating, and adds a small amount of water dilute reaction solution and removes gas storage device, continuing to be cooled to room temperature, pours out supernatant after being centrifuged with low-speed centrifugal device, and supported catalyst reclaims with after distilled water wash repeatedly.Merging aqueous solution, after concentration, addition Sodium acetate trihydrate is as internal standard, and generating lactic acid yield with nuclear magnetic resonance measuring is 29%.
The coordination of embodiment 11 novel nitrogen heterocyclic carbene metal assembles supported catalyst 4d and efficiently prepares lactic acid for the oxidative dehydrogenation of catalyzing glycerol:
Under nitrogen atmosphere is protected; have in the centrifuge tube of gas storage device to connection successively; add N-heterocyclic carbine metal coordination and assemble supported catalyst 4d (0.0045mmol); glycerol (15mmol); potassium hydroxide (16.5mmol) and water (0.3mL); being heated with stirring to 115 DEG C react 24 hours, reaction has hydrogen and releases during carrying out.Reaction is cooled to about 80 DEG C after terminating, and adds a small amount of water dilute reaction solution and removes gas storage device, continuing to be cooled to room temperature, pours out supernatant after being centrifuged with low-speed centrifugal device, and supported catalyst reclaims with after distilled water wash repeatedly.Merging aqueous solution, after concentration, addition Sodium acetate trihydrate is as internal standard, and generating lactic acid yield with nuclear magnetic resonance measuring is 96%, can be confirmed this productivity according to the amount releasing hydrogen further.Products therefrom1H NMR spectra is as shown in Figure 9.
The coordination of embodiment 12 novel nitrogen heterocyclic carbene metal assembles supported catalyst 4d and is used for being catalyzed propylene glycol oxidative dehydrogenation and efficiently prepares lactic acid:
Under nitrogen atmosphere is protected; have in the centrifuge tube of gas storage device to connection successively; add N-heterocyclic carbine metal coordination and assemble supported catalyst 4d (0.0045mmol); propylene glycol (15mmol); potassium hydroxide (16.5mmol) and water (0.3mL); being heated to 115 DEG C to react 24 hours, reaction has hydrogen and releases during carrying out.Reaction is cooled to about 80 DEG C after terminating, and adds a small amount of water dilute reaction solution and removes gas storage device, continuing to be cooled to room temperature, pours out supernatant after being centrifuged with low-speed centrifugal device, and supported catalyst reclaims with after distilled water wash repeatedly.Merging aqueous solution, after concentration, addition Sodium acetate trihydrate is as internal standard, and generating lactic acid yield with nuclear magnetic resonance measuring is 48%, can be confirmed this productivity according to the amount releasing hydrogen further.
The coordination of embodiment 13 novel nitrogen heterocyclic carbene metal assembles supported catalyst 4c and is used for being catalyzed propylene glycol carbonate oxidative dehydrogenation and efficiently prepares lactic acid:
Under nitrogen atmosphere is protected; have in the centrifuge tube of gas storage device to connection successively; add N-heterocyclic carbine metal coordination and assemble supported catalyst 4c (0.0045mmol); propylene glycol carbonate (15mmol); potassium hydroxide (16.5mmol) and water (0.3mL); being heated to 115 DEG C to react 24 hours, reaction has hydrogen and releases during carrying out.Reaction is cooled to about 80 DEG C after terminating, and adds a small amount of water dilute reaction solution and removes gas storage device, continuing to be cooled to room temperature, pours out supernatant after being centrifuged with low-speed centrifugal device, and supported catalyst reclaims with after distilled water wash repeatedly.Merging aqueous solution, after concentration, addition Sodium acetate trihydrate is as internal standard, and generating lactic acid yield with nuclear magnetic resonance measuring is 62%, can be confirmed this productivity according to the amount releasing hydrogen further.
It will be understood by those skilled in the art that the respective embodiments described above are to realize the specific embodiment of the present invention, and in actual applications, can to it, various changes can be made in the form and details, without departing from the spirit and scope of the present invention.
Claims (10)
1. aza ring carbine metal coordination polymer, its structure is as shown in logical formula I:
And:
Wherein:
M is transition metal；
V, W are each independently N or CH；
X, Y are each independently O, N-G, CH ,-CH=CH-, and-C ≡ C-, carbon number are 0～8
Alkane group, to phenyl, a phenyl, adjacent phenyl, 1,4-divinyl phenyl, 1,4-diacetylene
Phenyl, xenyl, 1,4-methylene phenyl or 9,10-anthryl；Described G is blocking group, described protection
Group is: cyclic alkane base that chain alkyl that carbon number is 1～12, carbon number are 5～7, benzyl,
Aryl, tertbutyloxycarbonyl, benzoyl or benzyl chloroformate；
Z is halogen anion, tetrafluoroborate, hexafluoro-phosphate radical or hexafluoroantimonic anion；
L is assistant ligand；
R be carbon number be 1～12 chain alkyl, carbon number be 5～7 cyclic alkane base, benzyl or
Aryl；
M represents the number of repetitive in linker, and m is 0 or natural number；
N represents the number comprising monomer in N-heterocyclic carbine metal coordination polymer, and n is for being more than or equal to
The natural number of 2.
N-heterocyclic carbine metal coordination polymer the most according to claim 1, it is characterised in that
Described transition metal is Ag, Au, Cu, Ir, Mn, Mo, Ni, Os, Rh, Ru, Pd or Zn.
N-heterocyclic carbine metal coordination polymer the most according to claim 1, it is characterised in that
Described assistant ligand be halogen, carbonyl, phenyl ring, cyclopentadienyl ring, cyclo-octadiene, hydroxyl, water, carbonate,
Acetate, acetylacetone,2,4-pentanedione anion or Phosphine ligands.
4. the preparation method of the N-heterocyclic carbine metal coordination polymer described in claim 1, its feature
It is that step is: utilize logical Neo Heliopan AP shown in formula II to react with metal precursor in the basic conditions,
Assembled by coordination and prepare the N-heterocyclic carbine metal coordination polymer shown in logical formula I；
Its reaction equation is as follows:
And:
Wherein, the definition of M, V, W, X, Y, Z, L, R, m, n and phase in claim 1
With.
Preparation method the most according to claim 4, it is characterised in that described metal precursor is
MXaLb, wherein, a is 0,1 or 2；B is 0,1 or 2；The definition of M, X, L is wanted with right
Ask identical in 1.
Preparation method the most according to claim 4, it is characterised in that described alkali be NaOH,
NaH, KOH, t-BuOK, LDA, LiHMDS or KHMDS.
7. the N-heterocyclic carbine metal coordination polymer described in claim 1 is as oxidative dehydrogenation
The application of catalyst.
Application the most according to claim 7, it is characterised in that described N-heterocyclic carbine metal is joined
Position polymer is for catalytic alcohol and the oxidative dehydrogenation of derivant, saccharide compound, cellulose or lignin thereof
Reaction.
Application the most according to claim 8, it is characterised in that described oxidative dehydrogenation is used for
The preparation of lactic acid or derivatives thereof.
Application the most according to claim 9, it is characterised in that the method for described catalytic applications is:
Under atmosphere of inert gases, in the reaction system of reaction substrate, alkali and water composition, add described azepine
Ring carbine metal coordination polymer reacts as catalyst, agitating heating, discharges hydrogen, and makes
Obtain lactic acid or derivatives thereof；Wherein, described reaction substrate is alcohol or derivatives thereof, saccharide compound, fibre
Dimension element or lignin.
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