CN106187657A - A kind of method of palladium magnesia-alumina hydrotalcite catalyzed Suzuki cross-coupling reaction - Google Patents
A kind of method of palladium magnesia-alumina hydrotalcite catalyzed Suzuki cross-coupling reaction Download PDFInfo
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Abstract
The method that the invention discloses a kind of palladium magnesia-alumina hydrotalcite catalyzed Suzuki cross-coupling reaction, with halogenated aryl hydrocarbon and aryl boric acid as raw material, with PdMgAl LDH houghite as catalyst, under conditions of phase transfer catalyst, alkali, additive and solvent exist, reaction generates biphenyl compound, wherein, the feature of described catalyst is: palladium Direct Bonding, on the flaggy of brucite, is evenly distributed, good stability.The method that the present invention provides, under the conditions of green reaction, efficient catalytic Suzuki cross-coupling reaction, catalyst preparation is simple, be prone to regeneration, reusable edible, effectively reduces palladium to end prod and the pollution of environment.
Description
Technical field
The invention belongs to organic synthesis new technical field, be specifically related to a kind of hydrotalcite catalyzed Suzuki of palladium magnesia-alumina and intersect
The method of coupling reaction.
Background technology
Biphenyl derivatives is the fine-chemical intermediate that a class is important, have been widely used for medicine, dyestuff, organic conductor,
The field such as quasiconductor and liquid crystal material ((a) Hassan, J.；Sevignon,M.；Gozzi,C.；Schulz,E.；Lemaire,
M.Chem.Rev.2002,102,1359-1470.).The various halogenated aryl hydrocarbons of palladium chtalyst and the Suzuki of aryl boric acid intersect even
Connection reaction be synthesize this compounds one of important method ((a) Suzuki, A.J.Organomet.Chem.2002,653,
83-90.(b)Littke,A.F.；Fu,G.C.Angew.Chem.Int.Ed.2002,41,4176-4211.(c)Suzuki,
A.J.Organomet.Chem.1999,576,147-168.).In Suzuki cross-coupling reaction, generally use homogeneous catalysis
Agent improves catalytic efficiency and reaction selectivity.But, homogeneous catalyst is difficult to recycling, causes precious metal palladium to flow in a large number
Lose.The separation difficulty of catalyst, product will necessarily be polluted by the palladium of residual.Therefore, design synthesizing activity height, selectivity
Loaded catalyst good, that be easily recycled is significant for being catalyzed Suzuki cross-coupling reaction.
To this end, be developed various carrier in recent years to prepare Novel Palladium catalyst, specifically include that activated carbon, metal
Oxide, aluminosilicate micro porous molecular sieve, earth silicon material, activated clay and polymer etc. ((a) Seki,
M.Synthesis2006,2975-2992.(b)Kitamura,Y.；Sako,S.；Tsutsui,A.；Monguchi,Y.；
Maegawa,T.；Kitade Y.；Sajiki,H.Adv.Synth.Catal.2010,352,718-730.(c)Hu,M.G.；An,
Z.W.；Du,W.S.；Li,J.；Gao,A.A.Chin.J.Chem.2007,25,1183-1186.(d)Liu,S.Y.；Li,H.Y.；
Shi,M.M.；Jiang,H.；Hu,X.L.；Li,W.Q.；Fu,L.；Chen,H.Z.Macromolecules 2012,45,9004-
9009.(e)Shylesh,S.；Schünemann,V.；Thiel,W.R.Angew.Chem.Int.Ed.2010,49,3428-
3459.(f)Grirrane,A.；Garcia,H.；Corma,A.J.Catal.2013,302,49-57.).Research shows, these
Load type palladium catalyst not only has higher catalysis activity and selectivity, and can recycle and reuse, and preferably overcomes
The deficiency of homogeneous catalyst.
But, still there is synthesis step complexity, catalytic reaction condition harshness, circulation in current this kind of load type palladium catalyst
The shortcomings such as utilization ratio is the highest, pollution products and environment, limit its range of application.Accordingly, it would be desirable to exploitation preparation technology is simple,
Recycle the high load type palladium catalyst of efficiency for Suzuki cross-coupling reaction.
Brucite (Layered Double Hydroxides is called for short LDHs) is that a class has answering of typical layered structure
Close metal hydroxides, become the great research potential of class and a novel-section for application prospect because of the structure of its uniqueness and performance
Material, at ion exchange, absorption, medicine, functional material, is especially widely used at Supramolecular Assembling and catalytic field
((a)Wang,Q.；O'Hare,D.Chem.Rev.2012,112,4124-4155.(b)He,S.；An,Z.；Wei,M.；Evans,
D.G.；Duan,X. Chem.Commun.2013,49,5912-5920.(c)Xu,Z.P.；Zhang,J.；Adebajo,M.O.；
Zhang,H.；Zhou,C.H.Appl.Clay Sci.2011,53,139-150.(d)Fan,G.L.；Li,F.；Evans,D.G.；
Duan,X.Chem.Soc.Rev.2014,43,7040-7066.(e)Li,C.M.；Wei,M.；Evans,D.G.；Duan,
X.small 2014,10,4469-4486.).Template effect based on brucite and hollow structure feature thereof prepare support type
Catalyst, can effective divided catalytic site, improve catalytic efficiency.But the palladium catalyst with brucite as carrier is used at present
The research of Suzuki cross-coupling reaction is the most few, and is to be prepared by simple absorption, impregnating method, makes palladium on carrier
Poor stability, cause palladium to end prod and the pollution of environment.Accordingly, it would be desirable to continue to develop new technology to improve palladium at carrier
On stability, ensure catalysis activity while, can effectively reduce the loss of palladium, solve it and pollution of product and environment is asked
Topic.
Summary of the invention
It is contemplated that for problem present in above-mentioned technical Analysis, developed one and utilized palladium magnesia-alumina brucite to urge
Change the new method of Suzuki cross-coupling reaction.The method uses double chemical coprecipitation techniques by Pd (II) Direct Bonding at brucite
Flaggy on, be prepared for PdMgAl-LDH houghite catalyst, under the conditions of green reaction, efficient catalytic Suzuki intersects even
Connection reaction.Compared with the prior art, the method can effectively reduce Pd loss in course of reaction, reduce Pd to end prod and
The pollution of environment.Particularly PdMgAl-LDH houghite catalyst is prepared, is regenerated simply, reusable edible, economical and efficient, ring
Border is friendly.
The present invention adopts the following technical scheme that
The method that the invention provides a kind of palladium magnesia-alumina hydrotalcite catalyzed Suzuki cross-coupling reaction, is characterized in:
With halogenated aryl hydrocarbon and aryl boric acid as raw material, with PdMgAl-LDH houghite as catalyst, at phase transfer catalyst, alkali, add
Under conditions of adding agent and solvent existence, reaction generates biphenyl compound, and the feature of described catalyst is: palladium Direct Bonding is at water
On the flaggy of Talcum, be evenly distributed, good stability.Preferably, double chemical coprecipitation technique that drips is used to prepare the described of structural integrity
PdMgAl-LDH houghite catalyst.Described halogenated aryl hydrocarbon includes iodo, bromo and chlorinated aromatic hydrocarbons.
Its reaction equation is as follows:
Wherein Ar and Ar ' is phenyl, and methyl, methoxyl group, acetyl group, nitro substituted-phenyl or the fragrance such as pyridine, pyrimidine are miscellaneous
Ring group；X is I, Br, Cl etc..
Use double described PdMgAl-LDH houghite catalyst dripping the different palladium content of chemical coprecipitation technique preparation, this catalysis
Agent well-crystallized.Preferably, described double drip coprecipitation methods specifically comprise the following steps that metal nitrate mixed salt solution (A) and
Aqueous slkali (B) is simultaneously added dropwise in reactor, and maintaining the pH in reaction system is 9.3～9.8 (preferably 9.5), drips complete, will
Gained reaction system is aged 10～15h at 95～105 DEG C (preferably 100 DEG C), filters, washs, obtains PdMgAl-LDH after drying
Houghite.
Preferably, described dried grinding further is sieved and is obtained PdMgAl-LDH houghite catalyst.
Preferably, described metal nitrate mixed salt solution (A) is Pd (NO3)2、Mg(NO3)2With Al (NO3)3Mixing molten
Liquid, wherein, the bivalent metal ion (M in described metal nitrate mixed salt solution2+) and trivalent metal ion (M3+) mol ratio
For 3:1；Described aqueous slkali (B) is NaOH, Na2CO3The mixed solution of composition.
In this way, the palladium magnesia-alumina hydrotalcite catalyst PdMgAl-LDH of synthesis, wherein Pd (II) Direct Bonding exists
On the flaggy of brucite；Preferably, from the point of view of catalytic effect, Pd accounts for 0.10%～4.00% in total catalyst weight, enters one
Preferably, it is 0.50%～3.00% (w/w) that Pd accounts in total catalyst weight to step.
Preferably, the alkali that described reaction uses is potassium carbonate.
Preferably, described phase transfer catalyst is quaternary ammonium salt；Further preferred quaternary ammonium salt is cetyl trimethyl bromine
Change ammonium (CTAB).
Preferably, described solvent is one or both the combination in water, ethanol, toluene, and further preferred solvent is
Water.
Preferably, described additive is sodium ascorbate, and wherein, sodium ascorbate is by the Pd on brucite flaggy2+In situ
It is reduced to Pd0, efficient catalytic Suzuki cross-coupling reaction.
It is further preferred that when chlorinated aromatic hydrocarbons and aryl boric acid coupling reaction, additive ethylenediaminetetraacetic acid need to be added
Disodium (Na2H2EDTA)。
Preferably, the consumption of described catalyst is (with Pd2+Meter) it is 0.20mol%～1.00mol% of halogenated aryl hydrocarbon.Other
The consumption of reaction raw materials can be determined according to conventional Suzuki reaction and practical situation and adjust.
Preferably, from the point of view of this is synthesized the efficiency of compound, described reaction temperature is that room temperature is to 80 DEG C.
Preferably, from the point of view of this is synthesized the efficiency of compound, the described response time is 1～48h.
Preferably, catalyst at least can be applied mechanically 7 times, and activity is held essentially constant.
Preferably, after PdMgAl-LDH catalysqt deactivation, it can be made to regenerate through simple acid-alkali treatment, its configuration with
Catalysis activity keeps constant.
PdMgAl-LDH catalyst prepared by the present invention, below the activity employing of its catalysis Suzuki cross-coupling reaction
Program is evaluated:
Taking a certain amount of PdMgAl-LDH catalyst, with 3.0mL water as solvent, 2.00mmol potassium carbonate is alkali,
0.10mmol CTAB is phase transfer catalyst, and 0.01mmol sodium ascorbate is additive, add 1.00mmol halogenated aryl hydrocarbon and
1.10mmol aryl boric acid, at N2In 80 DEG C of catalytic reactions under atmosphere.Thin layer chromatography is followed the tracks of, and reaction separates target product after terminating.
The present invention also provide for a kind of palladium magnesia-alumina brucite as catalyst catalysis Suzuki cross-coupling reaction in
Application, is characterized in: described palladium magnesia-alumina brucite uses above-mentioned double method dripping co-precipitation to prepare.
The PdMgAl-LDH catalyst that the present invention provides application in catalysis Suzuki cross-coupling reaction, has abandoned biography
The preparation method of system brucite loaded palladium catalyst (first prepares brucite, the most again by palladium by simple absorption or dipping
Load on brucite etc. method), use and double drip chemical coprecipitation techniques by palladium Direct Bonding on the flaggy of brucite, not only palladium
Be evenly distributed, good stability, and simplify the preparation process of catalyst.The PdMgAl-LDH catalyst of present invention offer and biography
System brucite loaded palladium catalyst structurally has a great difference, applies in Suzuki cross-coupling reaction, both ensure that
Catalysis activity, effectively reduces again the loss of Pd, decreases it to end prod and the pollution of environment.
The present invention also provides for a kind of catalyst regeneration method, is characterized in: comprise the catalyst of inactivation through soda acid
Process the step of regeneration.Preferably, catalyst recovery process specifically comprise the following steps that will inactivation PdMgAl-LDH catalyst first
Then and aqueous slkali remove organic residue by washing with alcohol, then obtain metal nitrate mixed solution by salpeter solution nitre solution,
Being simultaneously added dropwise in reactor, maintaining the pH in reaction system is 9.3～9.8, drips complete, by gained reaction system 95～
105 DEG C ageing 10～15h, filter, wash, be dried, grind after must regenerate PdMgAl-LDH houghite catalyst.This catalyst
Renovation process simple to operate, the catalyst structure form of regeneration with catalysis activity keep constant.
Preferably, hot ethanol washing is used to remove organic residue.
Preferably, the mass fraction of described salpeter solution is 20%.
The invention has the beneficial effects as follows:
The present invention use double drip a chemical coprecipitation technique prepare PdMgAl-LDH houghite catalyst, outstanding feature be by
Pd (II) is bound directly on the flaggy of brucite, is effectively increased palladium stability in brucite, it is achieved that green high-efficient
Catalysis Suzuki cross-coupling reaction, not only reduces palladium loss in the reaction, and reduces palladium to end prod and ring
The pollution in border.Such catalyst preparation process is simple, reusable, easy and simple to handle, and production efficiency is high.Particularly catalyst loses
After work, it can be made to regenerate through simple acid-alkali treatment, catalysis activity keeps constant, substantially increases the utilization effect of precious metal palladium
Rate.
Accompanying drawing explanation
Fig. 1 is catalyst PdMgAlLDH-1 (a), the XRD spectra of PdMgAl-LDH-2 (b) and PdMgAl-LDH-3 (c).
Fig. 2 is PdMgAl-LDH-1 (a), the TEM spectrogram of PdMgAl-LDH-2 (b) and PdMgAl-LDH-3 (c).
Fig. 3 is the EDX spectrogram of hydrotalcite catalyst PdMgAl-LDH-1.
Detailed description of the invention
Below in conjunction with specific embodiment, the present invention being expanded on further, embodiments of the invention are merely to illustrate the present invention's
Technical scheme, rather than limit the scope of the present invention.
Embodiment 1
The preparation of catalyst PdMgAl-LDH-1 (0.50%Pd, w/w):
Weigh Mg (NO3)2·6H2O(4.590g,17.90mmol)、A1(NO3)3·9H2O(2.251g,6.00mmol)、Pd
(NO3)2·6H2O(0.027g,0.10mmol)、HNO3(0.10mol/L, 1mL) is dissolved in 12.0mL deionized water, is made into mixed
Close saline solution (A)；NaOH(1.540g,38.50mmol)、Na2CO3(1.272g, 12.00mmol) is dissolved in 12.0mL deionized water
In, configuration aqueous slkali (B).(A) and (B) two kinds of solution are slowly added drop-wise to fill three mouthfuls of round bottoms of 9.0mL deionized water simultaneously
In flask, it is stirred vigorously, controls rate of addition, keep pH=9.5.Completion of dropwise addition, is aged 13h in 100 DEG C of water-baths, filters,
Solid water is washed till neutrality, 110 DEG C of dry 24h, obtains gray solid 2.012g, finely ground, sieving for standby.
Embodiment 2
The preparation of catalyst PdMgAl-LDH-2 (2.58%Pd, w/w):
Weigh Mg (NO3)2·6H2O(4.487g,17.50mmol)、A1(NO3)3·9H2O(2.251g,6.00mmol)、Pd
(NO3)2·6H2O(0.133g,0.50mmol)、HNO3(0.10mol/L, 1.0mL) configuration saline solution (A)；NaOH(1.540g,
38.50mmol)、Na2CO3(1.272g, 12.00mmol) configuration aqueous slkali (B), subsequent step, with embodiment 1, obtains gray powder
End 2.012g.
Embodiment 3
Catalyst PdMgAl-LDH-1 regeneration preparation PdMgAl-LDH-3:
First apply mechanically catalyst PdMgAl-LDH-1 that 10 secondary responses (seeing embodiment 4) inactivate afterwards (2.000g,
0.46%Pd, w/w) remove organic residue with hot ethanol washing, then by the catalyst nitric acid nitre solution of 11.0mL 20%,
Obtain settled solution (A)；NaOH(3.200g,80.00mmol),Na2CO3(1.272g, 12.00mmol) configuration aqueous slkali (B).
Subsequent step, with embodiment 1, obtains PdMgAl-LDH-3 catalyst 1.966g, Lycoperdon polymorphum Vitt powder, wherein (w/w) Han 0.44%Pd.
From the XRD spectra (Fig. 1) of PdMgAl-LDH it can be seen that 2 θ=11.6, near 23.2,34.8,60.5 and 62.0 °
All present the characteristic diffraction peak of brucite, compare with LDHs standard spectrum (JCPDS 51-1525), each diffraction peak intensity of XRD
Greatly, peak shape is sharp-pointed, and symmetry is good, shows that the catalyst crystal degree of preparation and regeneration is preferable；There is no other impurity peaks, explanation
Catalyst purity is high.
Can be seen that along with the increase of Pd content, cell parameter a increases, and shows gold on laminate from cell parameter a of table 1, c
Belonging to the distance between ion to strengthen, the arranging density of atom reduces.Reason is Pd2+Ionic radius relatively big, enter veneer structure,
It is octahedra to have supportted big on laminate, makes laminate be distorted caused.From the TEM spectrogram (Fig. 2) of PdMgAl-LDH it can be seen that flaggy
After a small amount of Pd of upper insertion, brucite is still in irregular flat disc-shaped, and diameter is about 50～150nm.The EDX of PdMgAl-LDH
Spectrogram (Fig. 3) shows that Pd has been incorporated into brucite flaggy.
The structural parameters of table 1 PdMgAl-LDH catalyst
aA=2d110.bC=3d003.
Embodiment 4
Applying mechanically of biphenyl and catalyst is prepared in iodobenzene and phenylboric acid reaction:
Equipped with in two mouthfuls of round-bottomed flasks of magneton, add catalyst PdMgAl-LDH-1 (43mg, 0.20mol%Pd),
Sodium ascorbate (2mg, 0.01mmol), potassium carbonate (256mg, 2.00mmol), CTAB (36mg, 0.10mmol), phenylboric acid
(134mg, 1.00mmol), N2After gas displacement, it is sequentially added into iodobenzene (0.11mL, 1.00mmol), water (3.0mL).N2Delay under atmosphere
Slowly being warming up to 80 DEG C, TLC follows the tracks of reaction.After reaction 2h terminates, leach catalyst with sand core funnel, with ethyl acetate washing catalysis
Agent, merges organic facies and is washed to neutrality, anhydrous MgSO with saturated common salt4Being dried, remove solvent under reduced pressure, residue column chromatography divides
From (ethyl acetate/petroleum ether=1:20, Rf=0.6), white solid 144mg, productivity 93%, m.p.:69-70 DEG C of .IR are obtained
(neat,cm-1)νmax:1569,1470,723,688.1H NMR(300MHz,CDCl3, TMS): δ 7.61 (d, J=6.90Hz,
4H, ArH), 7.46 (t, J=7.35Hz, 4H, ArH), 7.36 (t, J=7.35Hz, 2H, ArH).13C NMR(75MHz,CDCl3,
TMS):δ141.30,128.80,127.30,127.22.HR-MS(APCI):m/z[M+H]+:calcd for C12H11:
155.0861,found:155.0866.
Repeat to apply mechanically 7 times by above-mentioned steps by catalyst PdMgAl-LDH-1, productivity is respectively 94%, 93%, 93%,
92%, 90%, 89% and 88%, activity is held essentially constant.
Embodiment 5
Biphenyl is prepared in bromobenzene and phenylboric acid reaction:
Preparation method, with embodiment 4, is used bromobenzene (0.10mL, 1.00mmol) instead and is replaced iodobenzene.After reaction 12h terminates, post
Chromatography (ethyl acetate/petroleum ether=1:20, Rf=0.6), white solid 139mg, productivity 90% are obtained.Characterize data with real
Execute example 4.
Embodiment 6
Biphenyl is prepared in chlorobenzene and phenylboric acid reaction:
Equipped with in two mouthfuls of round-bottomed flasks of magneton, add catalyst PdMgAl-LDH-2 (41mg, 1.00mol%Pd),
Sodium ascorbate (2mg, 0.01mmol), potassium carbonate (256mg, 2.00mmol), CTAB (36mg, 0.10mmol), Na2H2EDTA
(34mg, 0.10mmol), phenylboric acid (134mg, 1.00mmol), N2Gas displacement after, be sequentially added into chlorobenzene (0.11mL,
1.00mmol), water (3mL).N2Being to slowly warm up to 80 DEG C under atmosphere, TLC follows the tracks of reaction.After reaction 48h terminates, use sand core funnel
Leach catalyst, use ethyl acetate washing catalyst, merge organic facies and be washed to neutrality, anhydrous MgSO with saturated common salt4Dry
Dry, remove solvent, residue column chromatography for separation (ethyl acetate/petroleum ether=1:20, R under reduced pressuref=0.6), white solid is obtained
127mg, productivity 82%.Characterize data consistent with Example 4.
Embodiment 7
Bromobenzene and phenylboric acid reaction are prepared biphenyl and are evaluated the activity of regenerated catalyst PdMgAl-LDH-3:
Preparation method, with embodiment 4, is used bromobenzene (0.10mL, 1.00mmol) instead and is made substrate, use PdMgAl-LDH-3 instead
(48mg, 0.20mol%Pd) makees catalyst.After reaction 12h terminates, column chromatography for separation (ethyl acetate/petroleum ether=1:20, Rf
=0.6), white solid 138mg, productivity 89% are obtained.Characterize data consistent with Example 4.
This example demonstrates that the catalysis activity of the catalyst PdMgAl-LDH-3 of regeneration keeps constant.
Embodiment 8
4-Nitrobromobenzene and phenylboric acid react prepares 4-nitrobiphenyl:
Preparation method, with embodiment 4, is used 4-Nitrobromobenzene (202mg, 1.00mmol) instead and is made substrate.After reaction 8h terminates,
Column chromatography for separation (ethyl acetate/petroleum ether=1:15, Rf=0.5), faint yellow solid 192mg is obtained, productivity 96%, m.p.:
114-116℃.IR(neat,cm-1)νmax:1591,1506,1396,847,733,691.1H NMR(300MHz,DMSO-d6,
TMS): δ 8.30 (d, J=9.00Hz, 2H, ArH), 7.96 (d, J=8.70Hz, 2H, ArH), 7.80-7.77 (m, 2H, ArH),
7.56-7.45(m,3H,ArH).13C NMR(75MHz,DMSO-d6,TMS):δ147.15,147.09,138.29,129.68,
129.50,128.30,127.71,124.52.HR-MS(ESI):m/z[M+H]+:calcd for C12H10NO2:200.0712,
found:200.0717.
Embodiment 9
4-chloronitrobenzene and phenylboric acid react prepares 4-nitrobiphenyl:
Preparation method, with embodiment 6, is used 4-chloronitrobenzene (158mg, 1.00mmol) instead and is made substrate.After reaction 32h terminates,
Column chromatography for separation (ethyl acetate/petroleum ether=1:15, Rf=0.5), obtain faint yellow solid 171mg, productivity 86%, characterize data
With embodiment 8.
Embodiment 10
4-bromoacetophenone and phenylboric acid react prepares 4-phenyl acetophenone:
Preparation method, with embodiment 4, is used 4-bromoacetophenone (199mg, 1.00mmol) instead and is made substrate.After reaction 8h terminates,
Column chromatography for separation (ethyl acetate/petroleum ether=1:15, Rf=0.5), white solid 182mg, productivity 93%, m.p.:120-are obtained
122℃.IR(cm-1)νmax:2919,1672,1592,1477,835,759,683.1H NMR(300MHz,CDCl3,TMS):δ
8.06 (d, J=8.40Hz, 2H, ArH), 7.71 (d, J=8.10Hz, 2H, ArH), 7.65 (d, 2H, J=6.90Hz, 2H,
ArH),7.40-7.52(m,3H,ArH),2.66(s,3H,-CH3).13C NMR(75MHz,CDCl3,TMS):δ197.75,
145.81,139.90,135.89,128.97,128.93,128.25,127.29,127.24,26.67.HR-MS(ESI):m/z
[M+H]+:calcd for C14H13O:197.0966,found:197.0961.
Embodiment 11
4-chloro-acetophenone and phenylboric acid react prepares 4-phenyl acetophenone:
Preparation method, with embodiment 6, is used 4-chloro-acetophenone (155mg, 1.00mmol) instead and is made substrate.Reaction 36h terminates
After, column chromatography for separation (ethyl acetate/petroleum ether=1:10, Rf=0.5), obtain white solid 165mg, productivity 84%, characterize number
According to same embodiment 10.
Embodiment 12
4-toluene bromide and phenylboric acid react prepares 4-methyl biphenyl:
Preparation method, with embodiment 4, is used 4-toluene bromide (0.15mL, 1.00mmol) instead and is made substrate.After reaction 15h terminates,
Column chromatography for separation (ethyl acetate/petroleum ether=1:20, Rf=0.5), white solid 154mg, productivity 91%, m.p.:46-48 are obtained
℃.IR(cm-1)νmax:2912,1600,1478,821,749,685.1H NMR(300MHz,CDCl3, TMS): δ 7.63 (d, J=
7.20Hz, 2H, ArH), 7.54 (d, J=8.10Hz, 2H, ArH), 7.47 (t, J=7.50Hz, 2H, ArH), 7.36 (t, J=
7.35Hz, 1H, ArH), 7.30 (d, J=8.10Hz, 2H, ArH), 2.44 (s, 3H ,-CH3).13C NMR(75MHz,CDCl3,
TMS):δ141.24,138.43,137.06,129.54,128.77,127.23,127.04,21.16.HR-MS(APCI):m/z
[M+H]+:calcd for C13H13:169.1017,found:169.1013.
Embodiment 13
4-methoxybromobenzene and phenylboric acid react prepares 4-methoxyl biphenyl:
Preparation method, with embodiment 4, is used 4-methoxybromobenzene (0.13mL, 1.00mmol) instead and is made substrate.Reaction 8h terminates
After, column chromatography for separation (ethyl acetate/petroleum ether=1:12, Rf=0.5), white solid 171mg is obtained, productivity 93%, m.p.:
86-87℃.IR(neat,cm-1)νmax:2961,1600,1518,831,755,683.1H NMR(300MHz,CDCl3,TMS):δ
7.60-7.55 (m, 4H, ArH), 7.45 (t, J=7.50Hz, 2H, ArH), 7.33 (t, J=7.20Hz, 1H, ArH), 7.02 (d,
J=8.70Hz, 2H, ArH), 3.88 (s, 3H ,-CH3).13C NMR(75MHz,CDCl3,TMS):δ159.19,140.86,
133.81,128.72,128.16,126.74,126.66,114.24,55.34.HR-MS(APCI):m/z[M+H]+:calcd
for C13H13O:185.0966,found:185.0969.
Embodiment 14
5-Bromopyrimidine and phenylboric acid react prepares 5-phenyl pyrimidine:
Preparation method, with embodiment 4, is used 5-Bromopyrimidine (158mg, 1.00mmol) instead and is made substrate.After reaction 10h terminates, post
Chromatography (ethyl acetate/petroleum ether=2:3, Rf=0.5), faint yellow solid 148mg, productivity 95%, m.p.:50-52 are obtained
℃.IR(cm-1)νmax:1577,1497,1408,760,693.1H NMR(300MHz,CDCl3,TMS):δ9.22(s,1H,
PyrimH),8.97(s,2H,PyrimH),7.45-7.61(m,5H,ArH).13C NMR(75MHz,CDCl3,TMS):δ
157.49,154.91,134.36,134.29,129.44,129.02,127.00.HR-MS(APCI):m/z[M+H]+:calcd
for C10H9N2:157.0766,found:157.0762.
Embodiment 15
4-bromopyridine and phenylboric acid react prepares 4-phenylpyridine:
Preparation method, with embodiment 4, is used 4-bromopyridine hydrochloride (194mg, 1.00mmol) instead and is made substrate.Reaction 10h knot
Shu Hou, column chromatography for separation (ethyl acetate/petroleum ether=1:1, Rf=0.5), faint yellow solid 144mg is obtained, productivity 93%,
m.p.:77-78℃.IR(cm-1)νmax:1581,1474,755,678.1H NMR(300MHz,DMSO-d6,TMS):δ8.64(d,
J=6.00Hz, 2H, PyH), 7.80 (d, J=6.00Hz, 2H, PyH), 7.69-7.71 (m, 2H, PyH), 7.45-7.56 (m,
3H,ArH).13C NMR(75MHz,DMSO-d6,TMS):δ150.68,147.45,137.63,129.67,129.64,127.24,
121.66.HR-MS(ESI):m/z[M+H]+:calcd for C11H10N:156.0813,found:156.0809。
Claims (10)
1. a method for palladium magnesia-alumina hydrotalcite catalyzed Suzuki cross-coupling reaction, is characterized in that: with halogenated aryl hydrocarbon and virtue
Ylboronic acid is raw material, with PdMgAl-LDH houghite as catalyst, exists at phase transfer catalyst, alkali, additive and solvent
Under conditions of reaction generate biphenyl compound, wherein, the feature of described catalyst is: Pd (II) Direct Bonding is at brucite
On flaggy, it is evenly distributed, good stability.
2. the method for claim 1, is characterized in that: the reaction equation of described Suzuki reaction is as follows:
Wherein Ar and Ar ' is phenyl, methyl, methoxyl group, acetyl group, nitro substituted-phenyl or pyridine, pyrimidine fragrant heterocyclic radical；X
For I, Br or Cl.
3. the method for claim 1, is characterized in that: use double coprecipitation method that drips to prepare the described of structural integrity
PdMgAl-LDH houghite catalyst；Preferably, described double specifically comprising the following steps that of coprecipitation method will be containing Pd2+、
Mg2+And Al3+Metal nitrate mixed salt solution and aqueous slkali be simultaneously added dropwise in reactor, maintain the pH in reaction system to be
9.3～9.8, after dropping, gained reaction system is aged 10～15h at 95～105 DEG C, filters, wash, be dried, grind
After obtain PdMgAl-LDH houghite catalyst.
4. the method for claim 1, is characterized in that: Pd content in the catalyst is 0.10%～4.00% (w/w),
Preferably, Pd content in the catalyst is 0.50%～3.00% (w/w).
5. the method for claim 1, is characterized in that: the alkali that described reaction uses is potassium carbonate, and phase transfer catalyst is
Quaternary ammonium salt, preferred quaternary ammonium salt is cetyl trimethylammonium bromide (CTAB)；The solvent of described reaction is water, ethanol, toluene
In one or both combination, preferred solvent is water.
6. the method for claim 1, is characterized in that: the additive that described reaction uses is sodium ascorbate.
7. method as claimed in claim 6, is characterized in that: when for chlorinated aromatic hydrocarbons with aryl boric acid coupling reaction, described in add
Add agent and also include disodiumedetate (Na2H2EDTA)。
8. the method for claim 1, is characterized in that: the consumption of described catalyst is (with Pd2+Meter) it is halogenated aryl hydrocarbon
0.20mol%～1.00mol%.
9. the method for claim 1, is characterized in that: described reaction temperature be room temperature to 80 DEG C, the response time be 1～
48h。
10. a renovation process for catalyst, is characterized in that: comprise the step regenerated by the catalyst of inactivation through acid-alkali treatment
Suddenly；Preferably, after the catalysqt deactivation in the specifically comprising the following steps that any one of claim 1～9 of catalyst recovery process,
First remove organic residue by washing with alcohol, then obtain metal nitrate mixed solution by salpeter solution nitre solution, then molten with alkali
Liquid is simultaneously added dropwise in reactor, and maintaining the pH in reaction system is 9.3～9.8, drips complete, by gained reaction system 95
～105 DEG C ageing 10～15h, filter, wash, be dried, grind after must regenerate PdMgAl-LDH houghite catalyst.
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| CN112387294A (en) * | 2020-12-02 | 2021-02-23 | 丹阳恒安化学科技研究所有限公司 | Preparation method of palladium-loaded ammonium decamolybdate catalyst material |
| CN112387273A (en) * | 2020-12-02 | 2021-02-23 | 丹阳恒安化学科技研究所有限公司 | Preparation method of palladium-loaded carbon fiber catalyst material |
| CN113956883A (en) * | 2021-11-25 | 2022-01-21 | 北京化工大学 | Monoatomic/magnesium-aluminum hydrotalcite material and preparation method and application thereof |
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| CN101602011A (en) * | 2009-07-08 | 2009-12-16 | 华东师范大学 | A kind of renovation process of titanium-silicon molecular sieve catalyst |
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Cited By (3)
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| CN112387294A (en) * | 2020-12-02 | 2021-02-23 | 丹阳恒安化学科技研究所有限公司 | Preparation method of palladium-loaded ammonium decamolybdate catalyst material |
| CN112387273A (en) * | 2020-12-02 | 2021-02-23 | 丹阳恒安化学科技研究所有限公司 | Preparation method of palladium-loaded carbon fiber catalyst material |
| CN113956883A (en) * | 2021-11-25 | 2022-01-21 | 北京化工大学 | Monoatomic/magnesium-aluminum hydrotalcite material and preparation method and application thereof |
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