CN106179333A - A kind of method of palladium magnesia-alumina hydrotalcite catalyzed Sonogashira cross-coupling reaction - Google Patents

A kind of method of palladium magnesia-alumina hydrotalcite catalyzed Sonogashira cross-coupling reaction Download PDF

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CN106179333A
CN106179333A CN201610542093.XA CN201610542093A CN106179333A CN 106179333 A CN106179333 A CN 106179333A CN 201610542093 A CN201610542093 A CN 201610542093A CN 106179333 A CN106179333 A CN 106179333A
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catalyst
ldh
reaction
pdmgal
palladium
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郭佃顺
于凯
赵梅
黄丹丹
吕晶
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Shandong Normal University
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Abstract

The method that the invention discloses a kind of palladium magnesia-alumina hydrotalcite catalyzed Sonogashira cross-coupling reaction, with halogenated aryl hydrocarbon and terminal alkyne as raw material, with PdMgAl LDH houghite as catalyst, it is not necessary to cuprous salt makees alkine compounds in reaction under conditions of promoter generates；Wherein, the feature of described catalyst is: palladium Direct Bonding, on the flaggy of brucite, is evenly distributed, good stability.The present invention, under conditions of existing without cuprous salt, uses PdMgAl LDH catalyst to be catalyzed Sonogashira cross-coupling reaction, environmental protection in water.Catalyst provided by the present invention preparation is simple, regeneration easily, can be recycled, cheap efficiently, effectively reduce palladium to end prod and the pollution of environment, to expanding, its application in pharmaceutical synthesis is significant.

Description

A kind of method of palladium magnesia-alumina hydrotalcite catalyzed Sonogashira cross-coupling reaction
Technical field
The invention belongs to organic synthesis new technical field, be specifically related to a kind of palladium magnesia-alumina hydrotalcite catalyzed The method of Sonogashira cross-coupling reaction.
Background technology
Transition metal-catalyzed terminal alkyne with the Sonogashira cross-coupling reaction of halogenated aryl hydrocarbon or alkenyl halide is Construct the effective ways of carbon-carbon bond, be widely used in the conjunction of natural product, new drug, new material and fine-chemical intermediate Become ((a) Chinchilla, R.；Nájera,C.Chem.Rev.2007,107,874-922.(b)Siemsen,P.； Livingston,R.C.；Diederich,F.Angew.Chem.Int.Ed.2000,39,2632-2557.).But, traditional Sonogashira cross-coupling reaction be make catalyst with precious metal palladium, cuprous salt makees promoter, amine makees alkali or solvent bar Under part, using homogeneous catalysis, not only catalyst cannot reuse, reaction cost high, and precious metal necessarily pollutes end Product (particularly medicine) and environment.Additionally, along with Organometallic Chemistry and the fast development of methodology of organic synthesis, Ren Menshe Meter has synthesized many can be as the organometallic complex of homogeneous catalyst, although improve its catalysis activity and selectivity, but This type of catalyst has corrosiveness to metallic reactors, poor at air and water stability, separates and reclaims difficulty, limiting Its range of application.Therefore, research catalytic efficiency height, selectivity catalyst system and catalyzing good, environmental protection have highly important theory Meaning and practical value ((a) Bedford, R.B.；Cazin,C.S.J.；Holder,D.Coord.Chem.Rev.2004,248, 2283-2321.(b)Littke,A.F.；Fu,G.C.J.Am.Chem.Soc.2001,123,6989-7000.(c)Welch, C.J.；Albaneze-Walker,J.；Leonard,W.R.；Biba,M.；DaSilva,J.；Henderson,D.；Laing, B.；Mathre,D.J.；Spencer,S.；Bu,X.；Wang,T.Org.Process Res.Dev.2005,9,198-205.).
One of solution to the problems described above is that Metal Palladium or palladium complex are loaded to inorganic or organic polymer carrier On, such as SiO2, zeolite, activated carbon, ((a) Seki, the M.Synthesis 2006,2975-2992. (b) such as polymer Hosseini-Sarvari,M.；Razmi,Z.；Doroodmand,M.M.Appl.Catal.A:Gen.2014,475,477- 486.(c)Shylesh,S.；Schünemann,V.；Thiel,W.R.Angew.Chem.Int.Ed.2010,49,3428- 3459.(d)Polshettiwar,V.；Len C.；Fihri,A.Coord.Chem.Rev.2009,253,2599-2626.(e) Khalafi-Nezhad,A.；Panahi, F.Green Chem.2011,13,2408-2415.), it is catalyzed under heterogeneous conditions Sonogashira cross-coupling reaction.Research shows, load type palladium catalyst has substantially had both inorganic matter and urged as heterogeneous Agent and metal organic complex, as the advantage of homogeneous catalyst, are catalyzed activity and selectivity higher, and corrosivity is less, and Easily recycle and reuse, meet the requirement of Green Chemistry.
But, current load type palladium catalyst still suffers from preparation process complexity, catalytic reaction condition is harsh, recycle effect The shortcomings such as rate is the highest, pollution products and environment.Accordingly, it would be desirable to develop new carrier, design efficient, green, preparation is simple, can The load type palladium catalyst recycled, improves the efficiency of catalysis Sonogashira 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 its distinctive structure and performance Material, at ion exchange, absorption, medicine, functional material, the particularly field such as Supramolecular Assembling and catalysis is widely used ((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.).In recent years, template effect based on brucite and hollow structure feature are prepared respectively Kind of loaded catalyst, can effectively divided catalytic site, raising catalytic efficiency.But, it is used for being catalyzed Sonogashira and intersects The brucite loaded palladium catalyst research of coupling reaction is the most few, and is mainly prepared by simple absorption, impregnating method, Can not be fixed on the flaggy of brucite by palladium, the stability making palladium load on brucite is bad, fails to solve palladium to end Product and the pollution problem of environment.
Therefore, research new type water Talcum loaded palladium catalyst is needed badly so that it is can intersect even by efficient catalytic Sonogashira Connection reaction, can effectively reduce again the loss of palladium, solves palladium to problems such as the pollutions of product and environment.
Summary of the invention
It is contemplated that for problem present in above-mentioned technical Analysis, developed a kind of palladium magnesia-alumina hydrotalcite catalyst The new method of catalysis Sonogashira cross-coupling reaction.The method characteristic based on brucite, uses double chemical coprecipitation techniques By Pd (II) Direct Bonding on the flaggy of brucite, it is prepared for PdMgAl-LDH houghite catalyst, without cuprous salt Under conditions of making promoter, can be with efficient catalytic Sonogashira cross-coupling reaction.Compared with prior art, the method Can effectively reduce Pd loss in course of reaction, reduce it to end prod and the pollution of environment.Particularly PdMgAl- LDH catalyst preparation process is simple, can be recycled, regenerate easy, environmental friendliness.
The present invention adopts the following technical scheme that
The invention provides the side of a kind of palladium magnesia-alumina hydrotalcite catalyst catalysis Sonogashira cross-coupling reaction Method, is characterized in: with halogenated aryl hydrocarbon 1 and terminal alkyne 2 as raw material, with PdMgAl-LDH houghite as catalyst, it is not necessary to sub- Mantoquita reacts alkine compounds 3 in generating in water under conditions of making promoter, wherein, the feature of described catalyst is: palladium is straight Connect on the flaggy being bonded in brucite, be evenly distributed, good stability.Preferably, a double chemical coprecipitation technique is used to prepare structure complete Whole described PdMgAl-LDH houghite catalyst.Described halogenated aryl hydrocarbon includes iodo, bromo and chlorinated aromatic hydrocarbons.
The structural formula of described halogenated aryl hydrocarbon as indicated with 1, as indicated with 2, close the structural formula of described terminal alkyne by described interior ethynylation As indicated at 3, its reaction equation is as follows for the structural formula of thing:
Wherein, Ar is phenyl, methyl, methoxyl group, acetyl group, nitro substituted-phenyl or the fragrant heterocyclic radical such as pyridine, pyrimidine； X is I, Br, Cl；R is phenyl, n-pro-pyl, C (CH3)2OH, ferrocenyl.
Use double described PdMgAl-LDH houghite catalyst dripping the different palladium content of coprecipitation method preparation, this catalysis Agent well-crystallized.Preferably, described double drip coprecipitation methods specifically comprise the following steps that under agitation, by metal nitrate Mixed solution (A) and aqueous slkali (B) are simultaneously added dropwise in reactor, and maintaining the pH in reaction system is 9.3～9.8 (preferably 9.5), drip complete, gained reaction system is aged 10～15h at 95～105 DEG C (preferably 100 DEG C), filter, wash, be dried After obtain PdMgAl-LDH 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%～5.00% in total catalyst weight.
PdMgAl-LDH catalyst prepared by the present invention, its catalysis activity uses procedure below to be evaluated:
Weigh a certain amount of PdMgAl-LDH catalyst, add 1.00mmol halogenated aryl hydrocarbon, 1.10mmol terminal alkyne, In the mixture of 2.00mmol potassium carbonate, 0.10mmol quaternary ammonium salt, 0.01mmol sodium ascorbate and 3.0mL water, at N2Atmosphere Under in 80 DEG C of catalytic reactions.Thin layer chromatography is followed the tracks of, and reaction separates target product after terminating.
Preferably, the alkali that described reaction uses is potassium carbonate, it is not necessary to organic base.
Preferably, the solvent that described reaction uses is water, it is not necessary to organic solvent.
Preferably, the additive of described reaction is sodium ascorbate and quaternary ammonium salt；It is further preferred that described quaternary ammonium salt is Cetyl trimethylammonium bromide (CTAB), wherein, sodium ascorbate is by the Pd on brucite flaggy2+In-situ reducing is Pd0, high Effect catalysis Sonogashira cross-coupling reaction.
It is further preferred that when chlorinated aromatic hydrocarbons and terminal alkyne 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 Sonogashira 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, described PdMgAl-LDH catalyst at least can be applied mechanically 5 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.
The PdMgAl-LDH catalyst that the present invention provides application in catalysis Sonogashira cross-coupling reaction, gets rid of Abandoned traditional brucite loaded palladium catalyst preparation method (the most first prepare brucite, the most again by palladium by simple absorption or Impregnating method loads on brucite), use double chemical coprecipitation technique that drips palladium one step to be bonded on the flaggy of brucite, not only Being evenly distributed of palladium, good stability, and simplify the synthesis step of catalyst.The PdMgAl-LDH catalyst that the present invention provides Structurally it is very different with tradition brucite loaded palladium catalyst, applies in Sonogashira cross-coupling reaction, both Ensure that catalysis activity, effectively reduce again the loss of Pd, decrease it to end prod and the pollution of environment.
Present invention also offers the renovation process of a kind of catalyst, be characterized in: comprise the catalyst of inactivation through peracid Alkali processes the step of regeneration.Preferably, catalyst recovery process specifically comprise the following steps that will inactivation PdMgAl-LDH catalyst 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.This catalysis Agent renovation process is simple to operate, and the catalyst structure form after regeneration keeps constant with catalysis activity.
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 uses double chemical coprecipitation technique that drips to prepare PdMgAl-LDH houghite catalyst, and its characteristic is by Pd (II) Direct Uniform is bonded on the flaggy of brucite, improves Pd stability in brucite, is realizing effectively catalysis While Sonogashira cross-coupling reaction, greatly reduce Pd loss in course of reaction, decrease Pd and end is produced Product and the pollution of environment.PdMgAl-LDH catalyst preparation process is simple, through simple filtration after using, reusable, produces Efficiency is high, easy to operate.After especially PdMgAl-LDH catalysqt deactivation, simple acid-alkali treatment can be passed through so that it is regeneration, And be catalyzed activity and keep constant.The method of the present invention is significant to expanding its application in pharmaceutical synthesis.
Accompanying drawing explanation
Fig. 1 is PdMgAl-LDH-1 (a), the XRD spectra of PdMgAl-LDH-2 (b) and PdMgAl-LDH-3 (c).
Fig. 2 is PdMgAl-LDH-1 (a), PdMgAl-LDH-2 (b), MgAl-LDH's (c) and PdMgAl-LDH-3 (d) TEM spectrogram.
Fig. 3 is the EDX spectrogram of 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 brucite MgAl-LDH:
Weigh Mg (NO3)2·6H2O(4.256g,18.00mmol)、A1(NO3)3·9H2O (2.251g, 6.00mmol) is molten In 12.0mL deionized water, it is made into mixing salt solution (A)；Separately take NaOH (1.536g, 38.40mmol), Na2CO3(1.272g, 12.00mmol) it is dissolved in 12.0mL deionized water, proportionaling alkali-forming solution (B).Under agitation, by (A) and (B) two kinds of solution Slowly it is added drop-wise to fill in the three neck round bottom flask of 9.0mL deionized water simultaneously, controls rate of addition, keep the pH of reaction system =9.5.Completion of dropwise addition, is aged 13h in 100 DEG C of water-baths, filters, and solid water is washed till neutrality, 110 DEG C of dry 24h, obtains white solid Body 1.924g, finely ground, sieving for standby.
Embodiment 2
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, 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 Lycoperdon polymorphum Vitt powder 1.954g。
Embodiment 3
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 4
The regeneration of catalyst:
First will apply mechanically catalyst PdMgAl-LDH-1 that 8 secondary responses (seeing embodiment 5) 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.
PdMgAl-LDH catalyst through XRD spectrum (Fig. 1) characterize, find 2 θ=11.6,23.2,34.8,60.5 and 62.0 ° attached The nearly characteristic diffraction peak all presenting brucite, compares with LDHs standard spectrum (JCPDS 51-1525), and each diffraction peak intensity is big, peak Shape is sharp-pointed, and symmetry is good, shows that preparation is preferable with the catalyst crystal degree of regeneration, does not has other impurity peaks, catalysis is described Agent purity is high.Can be seen that, along with the increase of Pd content, cell parameter a increases, shows on laminate from cell parameter a of table 1, c Distance between metal ion strengthens, and the arranging density of atom reduces.Reason is Pd2+Ionic radius relatively big, enter laminate knot Structure, has supportted big on laminate octahedra, makes laminate be distorted caused.(Fig. 2) is schemed it can be seen that plate from the TEM of PdMgAl-LDH After inserting a small amount of Pd on layer, brucite is still in irregular flat disc-shaped, and diameter is about 50～150nm.PdMgAl-LDH's EDX figure (Fig. 3) shows that Pd has been incorporated into brucite flaggy.
The structural parameters of table 1PdMgAl-LDH catalyst
aA=2d110.bC=3d003.
Embodiment 5
Applying mechanically of tolan and catalyst is prepared in iodobenzene and phenylacetylene 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), N2Gas is replaced, It is sequentially added into iodobenzene (0.11mL, 1.00mmol), water (3.0mL), phenylacetylene (0.12mL, 1.10mmol).N2Under atmosphere slowly Being warming up to 80 DEG C, TLC follows the tracks of reaction.After reaction 1h 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 167mg, productivity 94%, m.p.:58-59 DEG C of .IR are obtained (neat,cm-1)νmax:1596,1492,748,681.1H NMR(300MHz,CDCl3,TMS):δ7.58-7.55(m,4H, ArH),7.39-7.30(m,6H,ArH).13C NMR(75MHz,CDCl3,TMS):δ131.66,128.39,128.29, 123.37,89.47.HR-MS(APCI):m/z[M+H]+:calcd for C14H11:179.0861,found:179.0865.
Repeating to apply mechanically 5 times by above-mentioned steps by catalyst, reaction yield is respectively 92%, 93%, 90%, 88%, 87%, It is held essentially constant.After applying mechanically 5 times, in catalyst, the content of Pd is 0.48% (ICP mensuration), only lost the Pd of 0.02%, Prove that Pd is bonded on brucite flaggy effectively reduce its loss in course of reaction, reduce it to end prod and environment Pollution.
Embodiment 6
Tolan is prepared in bromobenzene and phenylacetylene reaction:
Method, with embodiment 5, changes bromobenzene (0.10mL, 1.00mmol) and replaces iodobenzene, react 12h, obtain white solid 166mg, productivity 93%, characterize data consistent with Example 5.
Embodiment 7
Tolan is prepared in chlorobenzene and phenylacetylene 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) N2Gas is replaced, and is sequentially added into chlorobenzene (0.11mL, 1.00mmol), water (3.0mL), phenylacetylene (0.12mL, 1.10mmol).N2Being to slowly warm up to 80 DEG C under atmosphere, TLC follows the tracks of reaction.After reaction 48h terminates, column chromatography for separation (ethyl acetate/petroleum ether=1:20, Rf=0.6), obtain white solid 147mg, productivity 82%, characterize data consistent with Example 5.
Embodiment 8
The activity rating of regenerated catalyst:
Method, with embodiment 5, makees substrate with bromobenzene (0.10mL, 1.00mmol), use instead PdMgAl-LDH-3 (48mg, 0.20mol%Pd) make catalyst.After reaction 12h terminates, column chromatography for separation (ethyl acetate/petroleum ether=1:20, Rf=0.6), Obtain white solid 165mg, productivity 92%, characterize data consistent with Example 5.It is demonstrated experimentally that regenerated catalyst activity keeps constant.
Embodiment 9
The preparation of 4-nitro tolan:
Preparation method, with embodiment 5, makees substrate with 4-Nitrobromobenzene (202mg, 1.00mmol).After reaction 10h terminates, post Chromatography (ethyl acetate/petroleum ether=1:10, Rf=0.5), faint yellow solid 212mg, productivity 95%, m.p.:118-are obtained 119℃.IR(neat,cm-1)νmax:2207,1586,1508,1339,853,756,685.1H NMR(300MHz,CDCl3, TMS): δ 8.22 (d, J=8.40Hz, 2H, ArH), 7.67 (d, J=8.40Hz, 2H, ArH), 7.57-7.55 (m, 2H, ArH), 7.41-7.39(m,3H,ArH).13C NMR(75MHz,CDCl3,TMS):δ147.02,132.25,131.84,130.26, 129.26,128.53,123.61,122.13,94.70,87.55.HR-MS(ESI):m/z[M+H]+:calcd for C14H10NO2:224.0712,found:224.0715.
Embodiment 10
The preparation of 4-acetyl group tolan:
Preparation method, with embodiment 5, is used 4-bromoacetophenone (199mg, 1.00mmol) instead and is made substrate.After reaction 10h terminates, Column chromatography for separation (ethyl acetate/petroleum ether=1:10, Rf=0.5), white solid 207mg, productivity 93%, m.p.:94-96 are obtained ℃.IR(cm-1)νmax:2216,1674,1594,1515,830,754,688.1H NMR(300MHz,CDCl3,TMS):δ7.96 (d, J=8.40Hz, 2H, ArH), 7.63 (d, J=8.40Hz, 2H, ArH), 7.56-7.59 (m, 2H, ArH), 7.38-7.40 (m,3H,ArH),2.63(s,3H,-CH3).13C NMR(75MHz,CDCl3,TMS):δ197.24,136.23,131.7, 131.74,128.80,128.43,128.26,122.68,92.70,88.60,26.57.HR-MS(ESI):m/z[M+H]+: calcd for C16H13O:221.0966,found:221.0962.
Embodiment 11
The preparation of 4-methyldiphenyl acetylene:
Preparation method, with embodiment 5, is used 4-toluene bromide (0.15mL, 1.00mmol) instead and is made substrate.After reaction 14h terminates, Column chromatography for separation (ethyl acetate/petroleum ether=1:20, Rf=0.5, obtain white solid 177mg, productivity 92%, m.p.:68-70 ℃.IR(cm-1)νmax:2917,2210,1584,1500,814,752,687.1H NMR(300MHz,CDCl3,TMS):δ7.51- 7.55 (m, 2H, ArH), 7.43 (d, J=8.10Hz, 2H, ArH), 7.33-7.37 (m, 3H, ArH), 7.16 (d, J=8.10Hz, 2H,ArH),2.37(s,3H,-CH3).13C NMR(75MHz,CDCl3,TMS):δ138.41,131.58,131.53,129.14, 128.34,128.10,123.53,120.24,89.60,88.76,21.53.HR-MS(APCI):m/z[M+H]+:calcd for C15H13:193.1017,found:193.1022.
Embodiment 12
The preparation of 4-methoxyl group tolan:
Preparation method, with embodiment 5, is used 4-bromoanisole (0.13mL, 1.00mmol) instead and is made substrate.Reaction 14h terminates After, column chromatography for separation (ethyl acetate/petroleum ether=1:15, Rf=0.5), white solid 194mg is obtained, productivity 93%, m.p.: 56-58℃.IR(neat,cm-1)νmax:2931,2207,1595,1501,832,751,687.1H NMR(300MHz,CDCl3, TMS): δ 7.55-7.48 (m, 4H, ArH), 7.37-7.33 (m, 3H, ArH), 6.90 (d, J=9.00Hz, 2H, ArH), 3.85 (s,3H,-CH3).13C NMR(75MHz,CDCl3,TMS):δ159.65,133.07,131.47,128.32,127.94, 123.64,115.43,114.02,89.39,88.08,55.32.HR-MS(APCI):m/z[M+H]+:calcd for C15H13O: 209.0966,found:209.0970.
Embodiment 13
The preparation of 2-methyldiphenyl acetylene:
Preparation method, with embodiment 5, is used 2 bromo toluene (0.12mL, 1.00mmol) instead and is made substrate.After reaction 14h terminates, Column chromatography for separation (ethyl acetate/petroleum ether=1:20, Rf=0.6), colorless oil 157mg, productivity 82% are obtained.IR(cm-1) νmax:2919,2214,1597,1491,750,686.1H NMR(300MHz,CDCl3,TMS):δ7.51-7.58(m,3H,ArH), 7.36-7.41(m,3H,ArH),7.16-7.26(m,3H,ArH),2.54(s,3H,-CH3).13C NMR(75MHz,CDCl3, TMS):δ140.22,131.88,131.55,129.50,128.39,128.34,128.20,125.62,123.61,123.07, 93.39,88.39,20.78.HR-MS(APCI):m/z[M+H]+:calcd for C15H13:193.1017,found: 193.1014.
Embodiment 14
The preparation of 5-phenylacetylene base pyrimidine:
Preparation method, with embodiment 5, is used 5-Bromopyrimidine (158mg, 1.00mmol) instead and is made substrate.After reaction 12h terminates, post Chromatography (ethyl acetate/petroleum ether=1:3, Rf=0.5), yellow oil 165mg, productivity 92% are obtained.IR(cm-1)νmax: 2212,1598,1482,1408,759,687.1H NMR(300MHz,CDCl3,TMS):δ9.14(s,1H,PyrimH),8.86 (s,2H,PyrimH),7.54-7.57(m,2H,ArH),7.35-7.40(m,3H,ArH).13C NMR(75MHz,CDCl3, TMS):δ158.63,156.71,131.80,129.39,128.57,121.80,119.96,96.35,82.31.HR-MS (ESI):m/z[M+H]+:calcd for C12H9N2:181.0766,found:181.0761.
Embodiment 15
The preparation of 4-phenylethynylpyridin:
Preparation method, with embodiment 5, is used 4-bromopyridine hydrochloride (194mg, 1.00mmol) instead and is made substrate.Reaction 12h knot Shu Hou, column chromatography for separation (ethyl acetate/petroleum ether=1:3, Rf=0.6), faint yellow solid 163mg is obtained, productivity 91%, m.p.:93-95℃.IR(cm-1)νmax:2214,1577,1533,1406,754,689.1H NMR(300MHz,CDCl3,TMS): δ 8.62 (d, J=6.00Hz, 2H, PyH), 7.56-7.59 (m, 2H, PyH), 7.39-7.41 (m, 5H, ArH).13C NMR (75MHz,CDCl3,TMS):δ149.66,131.90,131.52,129.24,128.52,125.81,122.12,94.04, 86.68.HR-MS(ESI):m/z[M+H]+:calcd for C13H10N:180.0813,found:180.0815.
Embodiment 16
The preparation of phenylacetylene base ferrocene:
Preparation method with embodiment 5, use instead iodobenzene (0.11mL, 1.00mmol) and ferrocene acetylene (231mg, 1.10mmol) make substrate.After reaction 2h terminates, column chromatography for separation (ethyl acetate/petroleum ether=1:15, Rf=0.6), obtain dark red Color solid 276mg, productivity 96%, m.p.:117-119 DEG C of .IR (neat, cm-1)νmax:2196,1593,1488,690,751.1H NMR(300MHz,CDCl3,TMS):δ7.53-7.49(m,2H,ArH),7.36-7.32(m,3H,ArH),4.53(s,2H, FcH),4.27(s,7H,FcH).13C NMR(75MHz,CDCl3,TMS):δ131.43,128.30,127.68,123.98, 88.33,85.76,71.50,70.09,68.93,65.44.HRMS(APCI):m/z[M+H]+:calcd for C18H15Fe: 287.0523,found:287.0528.
Embodiment 17
The preparation of 2-methyl 4-phenyl-3-butyne-2-alcohol:
Preparation method, with embodiment 5, uses iodobenzene (0.11mL, 1.00mmol) and 2-methyl-3-butyne-2-alcohol instead (0.11mL, 1.10mmol) makees substrate.After reaction 2h terminates, column chromatography for separation (ethyl acetate/petroleum ether=1:3, Rf=0.5, Obtain yellow oil 147mg, productivity 92%.IR(cm-1)νmax:3271,2207,1596,1486,753,690.1H NMR (300MHz,CDCl3,TMS):δ7.40-7.43(m,2H,ArH),7.29-7.32(m,3H,ArH),2.01(s,1H,-OH), 1.62(s,6H,-CH3).13C NMR(75MHz,CDCl3,TMS):δ131.63,128.22,122.76,93.82,82.14, 65.60,31.49.HR-MS(ESI):m/z[M+H]+:calcd for C11H13O:161.0966,found:161.0970.
Embodiment 18
The preparation of 1-phenyl-1-pentyne:
Preparation method, with embodiment 5, uses iodobenzene (0.11mL, 1.00mmol) and positive pentyne (0.11mL, 1.10mmol) instead Make substrate.After reaction 1.5h terminates, column chromatography for separation (ethyl acetate/petroleum ether=1:20, Rf=0.5), yellow oil is obtained 126mg, productivity 87%.IR(cm-1)νmax:2235,1598,1498,753,689.1H NMR(300MHz,CDCl3,TMS):δ 7.39-7.42 (m, 2H, ArH), 7.28-7.32 (m, 3H, ArH), 2.40 (t, J=6.90Hz, 2H ,-CH2),1.59-1.71 (m,2H,-CH2), 1.06 (t, J=7.35Hz, 3H ,-CH3).13C NMR(75MHz,CDCl3,TMS):δ131.53,128.14, 127.42,124.13,90.21,80.71,22.21,21.38,13.50.HR-MS(APCI):m/z[M+H]+:calcd for C11H13:145.1017,found:145.1021.
Embodiment 19:
The preparation of 4-nitro tolan:
Preparation method, with embodiment 7, is used 4-chloronitrobenzene (158mg, 1.00mmol) instead and is made substrate.After reaction 36h terminates, Column chromatography for separation (ethyl acetate/petroleum ether=1:10, Rf=0.5), obtain faint yellow solid 190mg, productivity 95%, characterize data With embodiment 9.
Embodiment 20
The preparation of 4-acetyl group tolan:
Preparation method, with embodiment 7, is used 4-chloro-acetophenone (155mg, 1.00mmol) instead and is made substrate.After reaction 36h terminates, Column chromatography for separation (ethyl acetate/petroleum ether=1:10, Rf=0.5), obtain white solid 174mg, productivity 79%, characterize data same Embodiment 10.

Claims (10)

1. a method for palladium magnesia-alumina hydrotalcite catalyzed Sonogashira cross-coupling reaction, is characterized in that: with halogenated aryl hydrocarbon With terminal alkyne be raw material, with PdMgAl-LDH houghite as catalyst, it is not necessary to cuprous salt is made under conditions of promoter anti- Interior alkine compounds should be generated；Wherein, the feature of described catalyst is: palladium Direct Bonding, on the flaggy of brucite, is evenly distributed, Good stability.
2. the method for claim 1, is characterized in that: the structural formula of described halogenated aryl hydrocarbon as indicated with 1, described terminal alkyne Structural formula as indicated with 2, as indicated at 3, its reaction equation is as follows for the structural formula of described interior alkine compounds:
Wherein, Ar is phenyl, methyl, methoxyl group, acetyl group, nitro substituted-phenyl or pyridine, pyrimidine fragrant heterocyclic radical；X is I, Br, Cl；R is phenyl, n-pro-pyl, C (CH3)2OH, ferrocenyl.
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%～5.00% (w/w).
5. the method for claim 1, is characterized in that: the alkali that described reaction uses is potassium carbonate, and the solvent of employing is water.
6. the method for claim 1, is characterized in that: the additive that described reaction uses is sodium ascorbate and quaternary ammonium Salt；Preferably, described quaternary ammonium salt is cetyl trimethylammonium bromide (CTAB).
7. method as claimed in claim 6, is characterized in that: when for the coupling reaction of chlorinated aromatic hydrocarbons, described additive also wraps 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 catalyst regeneration method, 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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