CN102381916B - Synthesis method of beta, beta-diaryl alkene - Google Patents

Synthesis method of beta, beta-diaryl alkene Download PDF

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CN102381916B
CN102381916B CN201110241729.4A CN201110241729A CN102381916B CN 102381916 B CN102381916 B CN 102381916B CN 201110241729 A CN201110241729 A CN 201110241729A CN 102381916 B CN102381916 B CN 102381916B
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iodobenzene
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CN102381916A (en
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陈万芝
许代超
吕春欣
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Zhejiang University ZJU
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Abstract

The invention discloses a synthesis method of beta, beta-diaryl alkene, which comprises the following steps that: in an organic acid solvent, in the presence of a palladium catalyst and a silver salt, a halogenated aromatic hydrocarbon and an end alkenyl compound are subjected to a coupling reaction to obtain the beta, beta-diaryl alkene, wherein the organic acid solvent is acetic acid, the palladium catalyst is palladium acetate, the silver salt is silver acetate, silver carbonate or silver oxide, the halogenated aromatic hydrocarbon is iodo aromatic hydrocarbon, and the coupling reaction is operated at a reaction temperature of 80 to 130 DEG C for 0.25 to 24 hours. With the method, the environmentally friendly organic acid is used as the solvent, and the silver salt is used as an additive; and the method has the advantages of small amount of catalyst, mild reaction conditions, simple post-treatment, and high yield of a product, without adding other ligands and the like.

Description

A β, the synthetic method of beta-diaryl alkene
Technical field
The present invention relates to organic chemical synthesis field, relate in particular to a kind of β, the synthetic method of beta-diaryl alkene.
Background technology
β, the olefin(e) compound of beta-diaryl is the important intermediate during some drugs synthesizes.As there is compound (Synthesis and α-Glucosidase Inhibitory Activity of Cinnamic Amides.Chin.J.Org.Chem.2007 in the cinnamide of alpha-glucoside inhibiting activity, 27,5 (in Chinese)), its synthetic related important intermediate is β, beta-diaryl propionic ester.In addition, ((a) Diphenylpropionic acids as new AT (1) selective angiotensin II antagonists.J.Med.Chem.1996,39 in other some medicines synthesize, 2197. (b) Eur.Pat.EP 612,741,1994.Chem.Abstr.1995,122,314547p. (c) US Pat.US 4,342,781,1982.Chem.Abstr.1982,97,215790w.), all relate to this class β, beta-diaryl alkene intermediate.This compounds can be synthetic by conventional Witting reaction, but this method step is various, and classes of compounds that can be synthetic is very limited.In recent years, along with the research and development of Heck reaction, the diarylization of utilizing Heck to react to realize alkenyl compound can overcome these shortcomings, yet remains a challenge by the vinyl compound of synthetic this type of diaryl of Heck coupling one kettle way.
Owing to increasing the substituting group of two keys, will greatly weaken the reactivity worth of the further arylation of alkene, therefore classical intermolecular Heck reaction is mainly confined to single arylation (the The heck reaction as a sharpening stone of palladium catalysis.Chem.Rev..2000 to terminal olefin, 100,3009-3066.), by β, beta-diaryl is combined to current also few (Brase, the S. reporting of vinyl compound that polyaryl replaces; De Meijere, A.In Handbook of Organopalladium Chemistry for Organic Synthesis; Negishi, E.I.de Meijere, A., Eds.; Wiley:New York, 2002; Pp 1179-1208.).In Heck work in early days, with methyl acrylate and excessive iodobenzene, with palladium and P (o-tol) 3for catalyzer, in acetonitrile, reflux within 21 hours, obtain 78% 3,3-diphenylacrylate methyl esters (Palladium-Catalyzed Vinylic Hydrogen Substitution Reactions with Aryl, Benzyl, and Styryl Halides.J.Org.Chem.1978,43,2952.).And the β reporting recently; the method that beta-diaryl is combined to the vinyl compound that polyaryl replaces all need to be carried out under the existence with expensive phosphine part or carbenes; and need to just can complete under as nitrogen or argon shield at rare gas element, and comparatively responsive to water in a lot of situation.((a)Controlled?mono?and?double?Heck?reactions?in?water?catalyzed?by?an?oxime-derived?palladacycle.Tetrahedron?Lett.2004，45，1833.(b)Mono-and?beta?beta-double-heck?reactions?of?alpha，beta-unsaturated?carbonyl?compounds?in?aqueous?media.J.Org.Chem.2005，70，2005.(c)Heck?reaction?catalysed?by?palladium?supported?with?an?electron-rich?benzimidazolylidene?generated?in?situ：remarkable?ligand?electronic?effects?and?controllable?mono-and?di-arylation.New?J.Chem.，2006，30，803.)。In addition, the diarylization reaction of end alkenyl compound also needs than the higher temperature of reaction of single arylation reaction, therefore this class reaction is mostly carried out in high boiling solvent, as DMF, ionic liquid or need under high pressure carry out ((a) Heck reaction of beta-substituted acrylates in ionic liquids catalyzed by a Pd-benzothiazole carbene complex.Tetrahedron, 2001, 57, 6071. (b) Highly efficient, recyclable Pd (II) catalysts with bisimidazole ligands for the heck reaction in ionic liquids.Org.Lett.2003, 5, 3209. (c) Heck reaction catalysed by palladium supported with an electron-rich benzimidazolylidene generated in situ:remarkable ligand electronic effects and controllable mono-and di-arylation.New J.Chem.2006, 30, 803. (d) Effects of High-Pressure on the Heck Reaction-Is It Possible to Control Dehydropalladation of Alkylpalladium Intermediates Having Beta-Hydrogens.Tetrahedron Lett.1995, 36, (31), 5547.).The shortcoming of these methods shows that reaction conditions is still comparatively harsh, has limited its widespread use.
Silver salt has important effect in intramolecular Heck reaction as additive, as promoted cyclisation (The asymmetric Heck reaction.Tetrahedron 1997, 53, (22), 7371.), isomerization (the Palladium-Catalyzed Alpha-Arylation of Vinyl Butyl Ether with Aryl Halides.Tetrahedron Lett 1991 that suppresses alkene, 32, (14), 1753.), improve speed of reaction (Alpha-Regioselectivity in Palladium-Catalyzed Arylation of Acyclic Enol Ethers.J Org Chem 1992, 57, (5), 1481.) etc.And silver salt is applied to the research at present of intermolecular Heck reaction system also seldom.In Hallberg and colleague's thereof early stage research, find that Silver Nitrate can suppress the desiliconization base process that thiazolinyl silane and halogenated aryl hydrocarbon occur in coupling process, and to speed of reaction (the The Effect of Added Silver-Nitrate on the Palladium-Catalyzed Arylation of Allyltrimethylsilanes.J Org Chem 1985 that also improves, 50, (20), 3896.).In addition, the Heck that the thallium salt that produces similar effect with silver salt is applied to electron rich vinyl compound reacts, can improve to a certain extent regioselectivity (the Alpha-Regioselectivity in Palladium-Catalyzed Arylation of Acyclic Enol Ethers.J.Org.Chem.1992 of reaction, 57, (5), 1481.), but strong toxicity is restricted the application of thallium salt.
Linked reaction comprises that the solvent that Heck reacts conventional is that polar aprotic solvent is as acetonitrile (PCTInt.Appl.2007148135.), N, dinethylformamide (Palladium-catalyzed Heck reaction under thermomorphic mode.Tetrahedron Lett.2008, 49 (2): 371.), N, N-N,N-DIMETHYLACETAMIDE (Heck reaction in aqueous medium using Amberlite IRA-400 (basic) .Green Chem.2002, 4 (4): 347.), N-Methyl pyrrolidone (Ethylenediamine-Functionalized Resin-Supported Pd (0) Complex:An Effective and Recyclable Catalyst for Heck Vinylation.Chinese J.Chem.2006, 24 (10): 1309.).These solvents promote reaction also can cause severe contamination to environment when carrying out, and adopt to environment better, the organic acid solvent that is cheaply easy to get is if HOAc etc. is as solvent, can avoid this defect of Heck linked reaction.
Although the report that relevant Heck linked reaction is carried out in protonic solvent is many, but be that water is used together with solubility promoter mostly, N for example, dinethylformamide-water (Aqueous DMF-Potassium Carbonate as a Substitute for Thallium and Silver Additives in the Palladium-Catalyzed Conversion of Aryl Bromides to Acetyl Arenes.J.Org.Chem.2001, 66:4340.), alcohol-water (Palladium (II) chloride/EDTA-catalyzed biaryl homo-coupling of aryl halides in aqueous medium in the presence of ascorbic acid.Tetrahedron Lett.2006, 7625.) 47 (43): the mixed solvent such as, about the Heck reaction in pure water medium, also there is research, but generally need to add some special additives, as phase-transfer catalyst, tensio-active agent (Remarkably facile Heck and Suzuki reactions in water using a simple cationic surfactant and ligand-free palladium catalysts.Tetrahedron Lett.2005, 46:3557.) etc., cause catalyst system to have certain limitation in organic synthesis application, and adopt acid stronger organic acid solvent as the solvent of HOAc as this reaction, there is no at present report, this is because in common Heck reaction, alkali is absolutely necessary, and thereby organic acid can make the reaction of alkali complete failure be difficult to occur.
And silver salt is applied to intermolecular Heck reaction system, and take acetic acid as solvent, can greatly promote the diarylization reaction of end alkenyl compound.Only need the palladium of catalytic amount and need not add any part, in air, reacting, can be efficient, the acquisition β of high yield, beta-diaryl alkene.
Summary of the invention
The invention provides a kind of β, the synthetic method of beta-diaryl alkene, so that the comparatively friendly organic acid of environment is made to solvent, under catalyzer and silver salt existence, without adding any part, by Double-Heck mono-step linked reaction, by halogenated aryl hydrocarbon and end alkenyl compound, efficiently synthesize β, beta-diaryl alkene, preparation technology is simple, and reaction effect is good.
A β, the synthetic method of beta-diaryl alkene, comprising:
In organic acid solvent, under the existence of palladium catalyst and silver salt, halogenated aryl hydrocarbon and end alkenyl compound obtain β through linked reaction, beta-diaryl alkene;
Wherein, described halogenated aryl hydrocarbon is suc as formula the compound shown in (1); Described end alkenyl compound is suc as formula the compound shown in (2); Described β, beta-diaryl alkene is suc as formula the compound shown in (3):
Figure BDA0000085199480000041
X is-I or-Br;
R 1for aromatics group, described aromatics group is phenyl, substituted-phenyl, naphthyl, substituted naphthyl, heterocycle or substituted heterocycle;
R 1' be aromatics group, described aromatics group is phenyl, substituted-phenyl, naphthyl, substituted naphthyl, heterocycle or substituted heterocycle;
R 1with R 1' identical or not identical;
R 2for carboxyl, ester group, aldehyde radical, ketone group, itrile group, phenyl, substituted-phenyl, naphthyl, substituted naphthyl, heterocycle or substituted heterocycle;
R 3for-H, C 1～C 40alkyl, ester group, aldehyde radical, ketone group or itrile group.
Preferably, described halogenated aryl hydrocarbon is suc as formula the compound shown in (4); Described end alkenyl compound is suc as formula the compound shown in (5) or formula (6); Described β, beta-diaryl alkene is suc as formula the compound shown in (7) or formula (8):
Figure BDA0000085199480000051
X is-I or-Br;
R 4for ortho position, a position or para-orientation-H ,-CH 3,-OCH 3,-F ,-Cl ,-Br ,-CHO ,-COCH 3,-COOMe ,-COOC 2h 5,-COOH or-NO 2;
R 4' be ortho position, a position or para-orientation-H ,-CH 3,-OCH 3,-F ,-Cl ,-Br ,-CHO ,-COCH 3,-COOMe ,-COOC 2h 5,-COOH or-NO 2;
R 4with R 4' identical or not identical;
R 5for-H, C 1～C 40alkyl ,-Ph ,-Ar ,-OCH 2ph ,-OCH 2ar or-OR 7, R wherein 7for C 1～C 40alkyl;
R 6for ortho position, a position or para-orientation-H ,-CH 3,-OCH 3,-F ,-Cl ,-Br ,-CHO ,-COCH 3,-COOMe ,-COOC 2h 5,-COOH or-NO 2.
More preferably, the radicals X of described halogenated aryl hydrocarbon is-I.Halogenated aryl hydrocarbon is in Heck repercussion study, to use the earliest and a most classical class reaction substrate.Their speed of reaction sorts by size and is generally: iodo aromatic hydrocarbons > aryl bromide > > chlorinated aromatic hydrocarbons.The speed of response of iodo aromatic hydrocarbons is the fastest, and products collection efficiency is also the highest; And take aryl bromide as the raw material reaction time longer, product combined coefficient is low.
Described end alkenyl compound can also be the derivative suc as formula compound shown in (5) or formula (6) or the compound that other end contains carbon-carbon double bond.More preferably, described end alkenyl compound is acrylate, vinylbenzene or substituted phenylethylene.
Preferably, described halogenated aryl hydrocarbon can have one or both.If reacted by a kind of halogenated aryl hydrocarbon and end alkenyl compound, can obtain two β that substituted aryl is identical, beta-diaryl alkene; If the first halogenated aryl hydrocarbon of the first amount by same substance and the reaction of end alkenyl compound generate single arylation product, do not need separation to add the second halogenated aryl hydrocarbon to continue reaction, can obtain two β that substituted aryl is different, beta-diaryl alkene, is called " one pot of two-step approach ".Following reaction formula is for adopting the synthetic a kind of asymmetrical β of the inventive method, the reaction process of beta-diaryl alkene:
Figure BDA0000085199480000061
R 1with R 1different
Described organic acid solvent is the compound of general formula R-COOH or the aqueous solution of R-COOH, and wherein R is-H, C 1～C 4alkyl or-CF 3; Preferably, in the aqueous solution of described compound R-COOH, the concentration of volume percent of compound R-COOH is 50～99%; More preferably, described organic acid solvent is acetic acid.
Described palladium catalyst is palladium, Palladous chloride, Pd 2(dba) 3, one or more mixtures in Palladous nitrate, palladous oxide, palladium hydroxide, palladous sulfate, two (methyl ethyl diketone) palladium, two (acetonitrile) Palladous chloride; Preferably, described palladium catalyst is palladium.
Described silver salt is one or more mixtures in Silver monoacetate, silver carbonate, silver suboxide, trifluoroacetic acid silver, Trisilver phosphate, silver trifluoromethanesulfonate; Preferably, described silver salt is Silver monoacetate, silver carbonate or silver suboxide.Under the existence of silver salt, do not need to add part, only need simple reaction conditions can efficiently complete Double-Heck reaction.Because part is all more expensive, and unstable, need to just can react under as the protection of nitrogen or argon gas at rare gas element, severe reaction conditions, thereby limited its widespread use.Although silver salt is also comparatively expensive, can not have part under the efficient diarylization reaction that promotes end alkenyl compound, during reaction, do not need protection of inert gas, and insensitive to water yet.Silver salt effect is different from general Heck and reacts conventional alkali, although its acting in conjunction mechanism is all the haloid acid generating in capture reaction, but silver salt can promote the formation of this high reactivity reaction intermediate of ArPdOAc before alkene inserts, thereby greatly promote the efficiency of reaction.
In every mmole end alkenyl compound consumption, the addition of described halogenated aryl hydrocarbon is 2～5mmol, and the addition of palladium is 0.005～0.05mmol, and the addition of silver salt is counted 2.0～3.1mmol with silver ions.With excessive halogenated aryl hydrocarbon, react with end alkenyl compound, can obtain the alkene that polyaryl replaces.
In every mmole end alkenyl compound consumption, the consumption of described organic acid solvent is 1～5mL; Preferably, in every mmole end alkenyl compound consumption, the consumption of described organic acid solvent is 3mL.Reduce solvent load and can accelerate speed of reaction; And select this solvent load, can guarantee that all reactants, catalyzer, the equal stabilizing dissolved of silver salt are in solvent.
The temperature of reaction of described linked reaction is 80～130 ℃, and the reaction times is 0.25～24 hour.Different according to reactant feed or catalyst type, can select different temperature of reaction or reaction times, so that reaction is more complete, obtain higher product yield.Conventionally, rising temperature of reaction can add the speed of fast response, Reaction time shorten.
In the inventive method, product postprocessing and Structural Identification process comprise: after being finished by thin-layer chromatography or gas-chromatography tracking reaction, in reaction solution, add ethyl acetate and methylene dichloride, cross leaching filtrate, filtrate is removed desolventizing through rotary evaporation, then through column chromatography for separation, obtains β, beta-diaryl alkene; To the compound of gained carry out mass spectrum, infrared, 1h NMR or 13c NMR characterizes, and obtains the structural information of product.Target product amount/initial end alkenyl compound that the yield of product obtains with reality is converted into the amount of target product completely and calculates.
The inventive method adopts environment amenable organic acid as solvent, and take silver salt as additive, by the synthetic β of Double-Heck mono-step linked reaction, beta-diaryl alkene, have catalyst levels few, without adding other parts, reaction conditions is simply gentle, aftertreatment is simple, product yield advantages of higher.
Embodiment
Embodiment 1 prepares β by iodobenzene and ethyl propenoate, β-diphenyl-ethyl acrylate
By palladium 1.2mg (0.005mmol), Silver monoacetate 173mg (1.05mmol), Glacial acetic acid 1.5mL, iodobenzene 0.408g (2mmol), ethyl propenoate 50mg (0.5mmol) successively joins with stirring in the 25mL reaction tubes of magneton, stirring heating, 110 ℃ of reactions 4 hours; After reaction finishes, cooling, add each 10mL of ethyl acetate and methylene dichloride, to filter, filtrate is spin-dried for concentrated, and column chromatography for separation obtains product β, β-diphenyl-ethyl acrylate 118mg, yield 94%. 1H?NMR(400MHz，CDCl 3，ppm)：δ7.43-7.41(m，3H)，7.38-7.37(m，1H)，7.35-7.34(m，4H)，7.26-7.25(m，2H)，6.42(s，1H)，4.10(q，J＝7.2Hz，2H)，1.15(t，J＝7.2Hz，3H). 13C?NMR(100MHz，CDCl 3，ppm)：δ166.1，156.5，140.8，139.0，129.4，129.1，128.4，128.3，128.1，127.9，117.5，60.0，13.0.IR：2980，1719，1616，1491，1445，1368，1262，1154，1033，865，770，695，615cm -1.MS(EI，m/z)252(M +，75％)，207(100％)，178(99％)，152(32％)，105(25％)。
Embodiment 2 is by methyl iodobenzene and ethyl propenoate are prepared to β, β-bis--(p-methylphenyl) ethyl propenoate
By palladium 1.2mg (0.005mmol), Silver monoacetate 173mg (1.05mmol), Glacial acetic acid 1.5mL, to methyl iodobenzene 0.436g (2mmol), ethyl propenoate 50mg (0.5mmol) successively joins with stirring in the 25mL reaction tubes of magneton, stirring heating, 110 ℃ of reactions 4 hours; After reaction finishes, cooling, add each 10mL of ethyl acetate and methylene dichloride, to filter, filtrate is spin-dried for concentrated, and column chromatography for separation obtains product β, β-bis--(p-methylphenyl) ethyl propenoate 136mg, yield 97%. 1H?NMR(400MHz，aceton-d 6，ppm)：δ7.17-7.11(m，6H)，7.01-6.99(d，J＝8.0Hz，2H)，6.24(s，1H)，3.94(q，J＝7.1Hz，2H)，2.32(s，3H)，2.28(s，3H)，1.03(t，J＝7.2Hz，3H). 13C?NMR(100MHz，CDCl 3，ppm)：δ166.2，1569，139.6，138.3，137.9，136.1，129.2，129.0，128.5，128.3，116.2，59.9，21.4，21.2，14.1.IR：2980，1719，1605，1510，1447，1368，1263，1150，1036，875，818，723cm -1.MS(EI，m/z)280(M +，100％)，235(90％)，208(87％)，193(50％)，119(56％)。
Embodiment 3 prepares β by a methyl iodobenzene and ethyl propenoate, β-bis--(aminomethyl phenyl) ethyl propenoate
By palladium 1.2mg (0.005mmol), Silver monoacetate 173mg (1.05mmol), Glacial acetic acid 1.5mL, between methyl iodobenzene 0.436g (2mmol), ethyl propenoate 50mg (0.5mmol) successively joins with stirring in the 25mL reaction tubes of magneton, stirring heating, 110 ℃ of reactions 4 hours; After reaction finishes, cooling, add each 10mL of ethyl acetate and methylene dichloride, to filter, filtrate is spin-dried for concentrated, and column chromatography for separation obtains product β, β-bis--(aminomethyl phenyl) ethyl propenoate 129mg, yield 92%. 1H?NMR(400MHz，CDCl 3，ppm)：δ7.34-7.30(t，1H)，7.28-7.19(m，4H)，7.14-7.12(d，1H)，7.08-7.06(m，2H)，6.38(d，J＝0.8，1H)，4.11(q，J＝7.2，2H)，2.40(s，3H)，2.37(s，3H)，1.17(t，J＝7.2Hz，3H). 13C?NMR(100MHz，CDCl 3，ppm)：δ166.2，156.8，140.9，139.0，137.9，137.3，130.1，129.6，128.8，128.2，127.6，126.3，125.6，117.2，59.9，21.4，21.3，14.0.IR：2979，1721，1603，1447，1367，1274，1189，1153，1094，1037，873，786，701，658cm -1.MS(EI，m/z)280(M +，98％)，235(100％)，208(73％)，192(58％)，119(51％)。
Embodiment 4 is by methoxyl group iodobenzene and ethyl propenoate are prepared to β, β-bis--(p-methoxyphenyl) ethyl propenoate
By palladium 1.2mg (0.005mmol), Silver monoacetate 173mg (1.05mmol), Glacial acetic acid 1.5mL, to methoxyl group iodobenzene 0.468g (2mmol), ethyl propenoate 50mg (0.5mmol) successively joins with stirring in the 25mL reaction tubes of magneton, stirring heating, 110 ℃ of reactions 12 hours; After reaction finishes, cooling, add each 10mL of ethyl acetate and methylene dichloride, to filter, filtrate is spin-dried for concentrated, and column chromatography for separation obtains product β, β-bis--(p-methoxyphenyl) ethyl propenoate 87mg, yield 56%. 1H?NMR(400MHz，aceton-d 6，ppm)：δ7.28-7.26(m，2H)，7.13-7.10(m，2H)，6.96-6.92(m，4H)，6.22(s，1H)，4.00(q，J＝7.1Hz，2H)，3.85(s，3H)，3.83(s，3H)，1.11(t，J＝7.0Hz，3H). 13C?NMR(100MHz，CDCl 3，ppm)：δ166.4，160.8，159.7，156.4，133.8，131.2，130.9，130.0，114.8，113.7，113.2，59.8，55.3，55.1，14.1.IR：2958，2837，1714，1598，1509，1461，1369，1290，1245，1144，1030，831，745cm -1.MS(EI，m/z)312(M +，50％)，267(28％)，240(54％)，135(83％)，124(100％)，109(84％)。
Embodiment 5 prepares β by meta-methoxy iodobenzene and ethyl propenoate, β-bis--(m-methoxyphenyl) ethyl propenoate
By palladium 1.2mg (0.005mmol), Silver monoacetate 173mg (1.05mmol), Glacial acetic acid 1.5mL, meta-methoxy iodobenzene 0.468g (2mmol), ethyl propenoate 50mg (0.5mmol) successively joins with stirring in the 25mL reaction tubes of magneton, stirring heating, 110 ℃ of reactions 4 hours; After reaction finishes, cooling, add each 10mL of ethyl acetate and methylene dichloride, to filter, filtrate is spin-dried for concentrated, and column chromatography for separation obtains product β, β-bis--(m-methoxyphenyl) ethyl propenoate 153mg, yield 98%. 1H?NMR(400MHz，CDCl 3，ppm)：δ7.33-7.23(m，2H)，6.95-6.91(m，3H)，6.88(s，1H)，6.834(d，J＝7.2Hz，1H)，6.78(s，1H)，6.39(s，1H)，4.09(q，J＝7.2Hz，2H)，3.80(s，3H)，3.78(s，3H)，1.14(t，J＝7.2Hz，3H). 13CNMR(100MHz，CDCl 3，ppm)：δ165.9，159.5，159.1，155.8，141.9，140.2，129.3，128.8，121.5，120.7，117.7，114.7，114.6，113.9，113.5，60.0，55.2，55.1，13.9.IR：2939，2835，1719，1578，1485，1458，1429，1367，1284，1244，1211，1155，1038，866，781，696cm -1.MS(EI，m/z)312(M +，100％)，267(70％)，239(69％)，135(30％)。
Embodiment 6 is by fluorine iodobenzene and ethyl propenoate are prepared to β, β-bis--(to fluorophenyl) ethyl propenoate
By palladium 1.2mg (0.005mmol), Silver monoacetate 173mg (1.05mmol), Glacial acetic acid 1.5mL, to fluorine iodobenzene 0.444g (2mmol), ethyl propenoate 50mg (0.5mmol) successively joins with stirring in the 25mL reaction tubes of magneton, stirring heating, 110 ℃ of reactions 4 hours; After reaction finishes, cooling, add each 10mL of ethyl acetate and methylene dichloride, to filter, filtrate is spin-dried for concentrated, and column chromatography for separation obtains product β, β-bis--(to fluorophenyl) ethyl propenoate 131mg, yield 91%.M.p.57-58℃. 1H?NMR(400MHz，CDCl 3，ppm)：δ7.31-7.27(m，2H)，7.22-7.19(m，2H)，7.13-7.02(m，4H)，6.33(s，1H)，4.10(q，J＝7.1Hz，2H)，1.18(t，J＝7.2Hz，3H). 13C?NMR(100MHz，CDCl 3，ppm)：δ165.8，163.6(d， 1J CF＝248Hz)，162.8(d， 1J CF＝246Hz)，154.4，136.8(d， 4J CF＝3.1Hz)，134.5(d， 4J CF＝2.6Hz)，131.0(d， 3J CF＝7.9Hz)，130.2(d， 3J CF＝8.3Hz)，117.5，115.5(d， 2J CF＝21Hz)，115.0(d， 2J CF＝21Hz)，60.2，14.0.IR：2984，1714，1597，1505，1262，1225，1149，1031，876，835cm -1.MS(EI，m/z)288(M +，80％)，243(100％)，215(61％)，195(30％)，123(45％)。
Embodiment 7 prepares β by a fluorine iodobenzene and ethyl propenoate, β-bis--(fluorophenyl) ethyl propenoate
By palladium 1.2mg (0.005mmol), Silver monoacetate 173mg (1.05mmol), Glacial acetic acid 1.5mL, between fluorine iodobenzene 0.444g (2mmol), ethyl propenoate 50mg (0.5mmol) successively joins with stirring in the 25mL reaction tubes of magneton, stirring heating, 110 ℃ of reactions 4 hours; After reaction finishes, cooling, add each 10mL of ethyl acetate and methylene dichloride, to filter, filtrate is spin-dried for concentrated, and column chromatography for separation obtains product β, β-bis--(fluorophenyl) ethyl propenoate 141mg, yield 98%. 1H?NMR(400MHz，CDCl 3，ppm)：δ7.41-7.29(m，2H)，7.14-7.06(m，3H)，7.02-6.92(m，3H)，6.40(s，1H)，4.09(q，J＝7.1Hz，2H)，1.15(t，J＝7.2Hz，3H). 13C?NMR(100MHz，CDCl 3，ppm)：δ165.4，162.6(d， 1J CF＝245Hz)，162.4(d， 1J CF＝246Hz)，153.3，142.2(d， 3J CF＝7.4Hz)，140.4(d， 3J CF＝7.7Hz)，130.0(d， 3J CF＝8.5Hz)，129.6(d， 3J CF＝7.6Hz)，124.8(d， 4J CF＝2.1Hz)，123.7(d， 4J CF＝2.0Hz)，119.0，116.4(d， 2J CF＝22Hz)，116.1(d， 2J CF＝22Hz)，115.2(d， 2J CF＝16Hz)，115.0(d， 2J CF＝18Hz)，60.3，13.8.IR：2983，1720，1613，1582，1483，1442，1369，1266，1227，1188，1155，1116，1034，960，908，870，820，785，663cm -1.MS(EI，m/z)288(M +，76％)，243(100％)，215(74％)，195(28％)。
Embodiment 8 is by chloroiodobenzone and ethyl propenoate are prepared to β, β-bis--(rubigan) ethyl propenoate
By palladium 1.2mg (0.005mmol), Silver monoacetate 173mg (1.05mmol), Glacial acetic acid 1.5mL, to chloroiodobenzone 0.476g (2mmol), ethyl propenoate 50mg (0.5mmol) successively joins with stirring in the 25mL reaction tubes of magneton, stirring heating, 110 ℃ of reactions 4 hours; After reaction finishes, cooling, add each 10mL of ethyl acetate and methylene dichloride, to filter, filtrate is spin-dried for concentrated, and column chromatography for separation obtains product β, β-bis--(rubigan) ethyl propenoate 151mg, yield 94%.M.p.61-62℃. 1H?NMR(400MHz，CDCl 3，ppm)：δ7.37(d，J＝8.4Hz，2H)，7.30(d，J＝8.4Hz，2H)，7.21(d，J＝8.8Hz，2H)，7.14(d，J＝8Hz，2H)，6.34(s，1H)，4.08(q，J＝7.2Hz，2H)，1.16(t，J＝7.2Hz，3H). 13C?NMR(100MHz，CDCl 3，ppm)：δ165.6，154.0，138.8，136.8，135.7，134.4，130.5，129.4，128.7，128.2，118.1，60.2，14.0.IR：2984，1718，1693，1588，1489，1401，1367，1284，1167，1089，1033，1013，908，827，732cm -1.MS(EI，m/z)320(M +，71％)，275(100％)，248(69％)，212(83％)，176(66％)，139(49％)，128(53％)。
Embodiment 9 prepares β by a chloroiodobenzone and ethyl propenoate, β-bis--(chloro-phenyl-) ethyl propenoate
By palladium 1.2mg (0.005mmol), Silver monoacetate 173mg (1.05mmol), Glacial acetic acid 1.5mL, between chloroiodobenzone 0.476g (2mmol), ethyl propenoate 50mg (0.5mmol) successively joins with stirring in the 25mL reaction tubes of magneton, stirring heating, 110 ℃ of reactions 4 hours; After reaction finishes, cooling, add each 10mL of ethyl acetate and methylene dichloride, to filter, filtrate is spin-dried for concentrated, and column chromatography for separation obtains product β, β-bis--(chloro-phenyl-) ethyl propenoate 157mg, yield 98%. 1H?NMR(400MHz，CDCl 3，ppm)：δ7.35-7.30(m，3H)，7.25-7.21(m，2H)，7.16(s，1H)，7.11(d，J＝7.6Hz，1H)，7.06(d，J＝7.6Hz，1H)，6.33(s，1H)，4.04(q，J＝7.2Hz，2H)，1.10(t，J＝7.0Hz，3H). 13C?NMR(100MHz，CDCl 3，ppm)：δ165.3，153.1，141.9，140.0，134.6，134.0，129.7，129.6，129.3，129.0，128.4，128.0，127.3，126.3，119.3，60.3，13.9.IR：2981，1720，1619，1592，1564，1472，1419，1367，1346，1255，1158，1082，1033，875，788，698cm -1.HRMS(EI，m/z)Calcd?for?C 17H 14Cl 2O 2(M +)：320.0371，found：320.0373。
Embodiment 10 is by bromo-iodobenzene and ethyl propenoate are prepared to β, β-bis--(to bromophenyl) ethyl propenoate
By palladium 1.2mg (0.005mmol), Silver monoacetate 173mg (1.05mmol), Glacial acetic acid 1.5mL, to bromo-iodobenzene 0.564g (2mmol), ethyl propenoate 50mg (0.5mmol) successively joins with stirring in the 25mL reaction tubes of magneton, stirring heating, 110 ℃ of reactions 4 hours; After reaction finishes, cooling, add each 10mL of ethyl acetate and methylene dichloride, to filter, filtrate is spin-dried for concentrated, and column chromatography for separation obtains product β, β-bis--(to bromophenyl) ethyl propenoate 195mg, yield 95%.M.p.64-65℃. 1H?NMR(400MHz，CDCl 3，ppm)：δ7.48(d，J＝8.0Hz，2H)，7.42(d，J＝8.8Hz，2H)，7.10(d，J＝8.4Hz，2H)，7.04(d，J＝8.8Hz，2H)，6.31(s，1H)，4.04(q，J＝7.2Hz，2H)，1.12(t，J＝7.2Hz，3H). 13C?NMR(100MHz，CDCl 3，ppm)：δ165.5，154.0，139.2，137.2，131.6，131.2，130.8，129.7，124.1，122.6，118.1，60.2，14.0.IR：2983，1693，1582，1485，1396，1367，1282，1171，1104，1071，1031，1008，899，822，760cm -1.MS(EI，m/z)410(M +，100％)，365(94％)，338(82％)，258(69％)，256(71％)，176(94％)。
Embodiment 11 prepares β by a bromo-iodobenzene and ethyl propenoate, β-bis--(bromophenyl) ethyl propenoate
By palladium 1.2mg (0.005mmol), Silver monoacetate 173mg (1.05mmol), Glacial acetic acid 1.5mL, between bromo-iodobenzene 0.564g (2mmol), ethyl propenoate 50mg (0.5mmol) successively joins with stirring in the 25mL reaction tubes of magneton, stirring heating, 110 ℃ of reactions 4 hours; After reaction finishes, cooling, add each 10mL of ethyl acetate and methylene dichloride, to filter, filtrate is spin-dried for concentrated, and column chromatography for separation obtains product β, β-bis--(bromophenyl) ethyl propenoate 199mg, yield 97%. 1H?NMR(400MHz，CDCl 3，ppm)：δ7.55-7.49(m，2H)，7.45(d，J＝1.6Hz，1H)，7.36-7.35(m，1H)，7.28-7.26(m，1H)，7.23-7.18(m，2H)，7.16-7.13(m，2H)，6.36(s，1H)，4.08(q，J＝7Hz，2H)，1.14(t，J＝7.2Hz，3H). 13CNMR(100MHz，CDCl 3，ppm)：δ165.2，152.9，142.2，140.2，132.5，131.8，131.3，130.9，130.0，129.5，127.7，126.8，122.8，122.1，119.4，60.3，13.9.IR：2980，1719，1619，1558，1470，1416，1367，1345，1254，1157，1072，1033，994，875，785，697，670cm -1.HRMS(TOF?MS?EI +)：m/z?Calcd?for?C 17H 14Br 2O 2(M +)：407.9361，found：407.9362。
Embodiment 12 is by iodobenzene ethyl ketone and ethyl propenoate are prepared to β, β-bis--(to acetylphenyl) ethyl propenoate
By palladium 1.2mg (0.005mmol), Silver monoacetate 173mg (1.05mmol), Glacial acetic acid 1.5mL, to iodobenzene ethyl ketone 0.492g (2mmol), ethyl propenoate 50mg (0.5mmol) successively joins with stirring in the 25mL reaction tubes of magneton, stirring heating, 110 ℃ of reactions 4 hours; After reaction finishes, cooling, add each 10mL of ethyl acetate and methylene dichloride, to filter, filtrate is spin-dried for concentrated, and column chromatography for separation obtains product β, β-bis--(to acetylphenyl) ethyl propenoate 163mg, yield 97%.M.p.77-78℃. 1H?NMR(400MHz，CDCl 3，ppm)：δ8.00(d，J＝8.4Hz，2H)，7.90(d，J＝8.4Hz，2H)，7.36(d，J＝8.4Hz，2H)，7.31(d，J＝8.0Hz，2H)，6.48(s，1H)，4.07(q，J＝8.4Hz，2H)，2.63(s，3H)，2.59(s，3H)，1.14(t，J＝8.4Hz，3H). 13C?NMR(100MHz，CDCl 3，ppm)：δ197.5，197.3，165.3，154.0，144.2，143.3，137.5，136.6，129.2，128.4，128.3，128.1，119.8，60.4，26.65，26.62，13.9.IR：2960，1679，1603，1561，1406，1358，1264，1184，1027，956，886，837，683cm -1.HRMS(TOF?MS?EI +)：m/z?Calcd?for?C 21H 20O 4(M +)：336.1362，found：336.1359。
Embodiment 13 prepares 4,4 '-(3-oxyethyl group-3-oxo-1-propylene-1,1-phenylbenzene) methyl-formiate by 4-Iodobenzoic acid methyl esters and ethyl propenoate
By palladium 1.2mg (0.005mmol), Silver monoacetate 173mg (1.05mmol), Glacial acetic acid 1.5mL, to iodobenzene methyl benzoate 0.524g (2mmol), ethyl propenoate 50mg (0.5mmol) successively joins with stirring in the 25mL reaction tubes of magneton, stirring heating, 110 ℃ of reactions 4 hours; After reaction finishes, cooling, add each 10mL of ethyl acetate and methylene dichloride, to filter, filtrate is spin-dried for concentrated, and column chromatography for separation obtains product 4,4 '-(3-oxyethyl group-3-oxo-1-propylene-1,1-phenylbenzene) methyl-formiate 180mg, yield 98%.M.p.68-69℃. 1H?NMR(400MHz，CDCl 3，ppm)：δ8.08(d，J＝8.4，2H)，7.99(d，J＝8.4，2H)，7.34(d，J＝8.4，2H)，7.30-7.28(m，2H)，6.48(s，1H)，4.06(q，J＝7.2，2H)，3.94(s，3H)，3.92(s，3H)，1.12(t，J＝7.2，3H). 13C?NMR(100MHz，CDCl 3，ppm)：δ166.6，166.3，165.2，153.9，144.1，143.1，130.8，129.8，129.6，129.2，129.0，128.0，119.8，60.3，52.1，52.0，13.8.IR：2953，1711，1606，1436，1274，1162，1108，1017，898，773，733，702cm -1.HRMS(TOF?MS?EI +)：m/z?Calcd?for?C 21H 20O 6(M +)：368.1260，found：368.1257。
Embodiment 14 prepares β by adjacent methiodide benzene and ethyl propenoate, β-bis--(o-methyl-phenyl-) ethyl propenoate
By palladium 1.2mg (0.005mmol), Silver monoacetate 173mg (1.05mmol), Glacial acetic acid 1.5mL, adjacent methiodide benzene 0.436g (2mmol), ethyl propenoate 50mg (0.5mmol) successively joins with stirring in the 25mL reaction tubes of magneton, stirring heating, 110 ℃ of reactions 12 hours; After reaction finishes, cooling, add each 10mL of ethyl acetate and methylene dichloride, to filter, filtrate is spin-dried for concentrated, and column chromatography for separation obtains product β, β-bis--(o-methyl-phenyl-) ethyl propenoate 87mg, yield 62%. 1H?NMR(400MHz，CDCl 3，ppm)：δ7.24-7.07(m，8H)，6.12(s，1H)，4.04(q，J＝7.0Hz，2H)，2.33(s，3H)，2.15(s，3H)，1.08(t，J＝7.2Hz，3H). 13C?NMR(100MHz，CDCl 3，ppm)：δ165.8，156.1，140.6，139.5，135.6，135.4，131.1，130.0，129.8，129.0，128.2，127.8，125.7，125.2，122.1，60.0，20.8，19.8，13.9.IR：2979，1722，1702，1619，1454，1368，1252，1155，1033，882，761，729，625cm -1.HRMS(TOF?MS?EI +)：m/z?Calcd?for?C 19H 20O 2(M +)：280.1463，found：280.1457。
Embodiment 15 prepares β by O-methoxy iodobenzene and ethyl propenoate, β-bis--(o-methoxyphenyl) ethyl propenoate
By palladium 1.2mg (0.005mmol), Silver monoacetate 173mg (1.05mmol), Glacial acetic acid 1.5mL, O-methoxy iodobenzene 0.468g (2mmol), ethyl propenoate 50mg (0.5mmol) successively joins with stirring in the 25mL reaction tubes of magneton, stirring heating, 110 ℃ of reactions 12 hours; After reaction finishes, cooling, add each 10mL of ethyl acetate and methylene dichloride, to filter, filtrate is spin-dried for concentrated, and column chromatography for separation obtains product β, β-bis--(o-methoxyphenyl) ethyl propenoate 95mg, yield 61%. 1H?NMR(400MHz，CDCl 3，ppm)：δ7.29-7.23(m，2H)，7.11-7.03(m，2H)，6.92-6.84(m，4H)，6.48(s，1H)，4.03(q，J＝7.6Hz，2H)，3.72(s，3H)，3.70(s，3H)，1.08(t，J＝7.2Hz，3H). 13C?NMR(100MHz，CDCl 3，ppm)：δ166.3，157.3，156.5，149.4，130.8，130.3，129.7，129.62，129.58，128.8，121.9，120.3，120.0，111.6，110.7，59.6，55.58，55.56，14.0.IR：2939，2835，1718，1594，1489，1459，1435，1367，1245，1153，1109，1025，751cm -1.HRMS(TOFMS?EI +)：m/z?Calcd?for?C 19H 20O 4(M +)：312.1362，found：312.136。
Embodiment 16 prepares β by adjacent fluorine iodobenzene and ethyl propenoate, β-bis--(adjacent fluorophenyl) ethyl propenoate
By palladium 1.2mg (0.005mmol), Silver monoacetate 173mg (1.05mmo1), Glacial acetic acid 1.5mL, adjacent fluorine iodobenzene 0.444g (2mmol), ethyl propenoate 50mg (0.5mmol) successively joins with stirring in the 25mL reaction tubes of magneton, stirring heating, 110 ℃ of reactions 12 hours; After reaction finishes, cooling, add each 10mL of ethyl acetate and methylene dichloride, to filter, filtrate is spin-dried for concentrated, and column chromatography for separation obtains product β, β-bis--(adjacent fluorophenyl) ethyl propenoate 91mg, yield 63%. 1H?NMR(400MHz，CDCl 3，ppm)：δ7.34-7.30(m，2H)，7.15-7.04(m，6H)，6.48(s，1H)，4.09(q，J＝7.2Hz，2H)，1.14(t，J＝7.2Hz，3H). 13C?NMR(100MHz，CDCl 3，ppm)：δ165.2，160.1(d， 1J CF＝250Hz)，159.4(d， 1J CF＝246Hz)，144.0，130.8(d， 4J CF＝1.8Hz)，130.6(d， 3J CF＝7.9Hz)，130.3(d， 4J CF＝2.9Hz)，129.9(d， 3J CF＝8Hz)，128.1(d， 2J CF＝11.2Hz)，126.6(d， 2J CF＝15.1Hz)，124.1(d， 3J CF＝4.3Hz)，123.7(d， 3J CF＝5.9Hz)，123.5(d， 4J CF＝2.6Hz)，116.2(d， 2J CF＝22.8Hz)，115.2(d， 2J CF＝21.8Hz)，60.2，13.9.IR：2983，1722，1610，1578，1488，1450，1370，1254，1220，1171，1100，1032，756cm -1.HRMS(TOF?MS?EI +)：m/z?Calcd?for?C 17H 14F 2O 2(M +)：288.0962，found：288.0959。
Embodiment 17 prepares β by adjacent chloroiodobenzone and ethyl propenoate, β-bis--(Chloro-O-Phenyl) ethyl propenoate
By palladium 1.2mg (0.005mmol), Silver monoacetate 173mg (1.05mmol), Glacial acetic acid 1.5mL, adjacent chloroiodobenzone 0.476g (2mmol), ethyl propenoate 50mg (0.5mmol) successively joins with stirring in the 25mL reaction tubes of magneton, stirring heating, 110 ℃ of reactions 12 hours; After reaction finishes, cooling, add each 10mL of ethyl acetate and methylene dichloride, to filter, filtrate is spin-dried for concentrated, and column chromatography for separation obtains product β, β-bis--(Chloro-O-Phenyl) ethyl propenoate 80mg, yield 50%. 1H?NMR(400MHz，CDCl 3，ppm)：δ7.44-7.40(m，2H)，7.31-7.21(m，6H)，6.38(s，1H)，4.10(q，J＝6.8Hz，2H)，1.14(t，J＝7.2Hz，3H). 13C?NMR(100MHz，CDCl 3，ppm)：δ165.1，149.7，138.9，137.9，132.7，132.5，131.1，130.44，130.37，129.6，129.4，129.1，126.6，126.2，125.0，60.3，13.8.IR：2981，1720，1629，1469，1434，1368，1346，1283，1246，1171，1033，884，754，682cm -1.HRMS(TOF?MS?EI +)：m/z?Calcd?for?C 17H 14Cl 2O 2(M +)：320.0371，found：320.0360。
Embodiment 18 prepares β by iodobenzene and methyl acrylate, β-diphenylacrylate methyl esters
By palladium 1.2mg (0.005mmol), Silver monoacetate 173mg (1.05mmol), Glacial acetic acid 1.5mL, iodobenzene 0.408g (2mmol), methyl acrylate 43mg (0.5mmol) successively joins with stirring in the 25mL reaction tubes of magneton, stirring heating, 110 ℃ of reactions 4 hours; After reaction finishes, cooling, add each 10mL of ethyl acetate and methylene dichloride, to filter, filtrate is spin-dried for concentrated, and column chromatography for separation obtains product β, β-diphenylacrylate methyl esters 114mg, yield 96%. 1H?NMR(400MHz，CDCl 3，ppm)：δ7.43-7.42(m，3H)，7.38-7.34(m，5H)，7.27-7.25(m，2H)，6.42(s，1H)，3.65(s，3H). 13C?NMR(100MHz，CDCl 3，ppm)：δ166.4，157.0，140.8，138.8，129.5，129.1，128.4，128.3，128.2，127.9，116.8，51.2.IR：2948，1723，1616，1492，1439，1362，1263，1156，1015，972，875，770，695，619cm -1.MS(EI，m/z)238(M +，100％)，207(100％)，178(89％)，152(18％)，105(39％)，89(33％)，51(20％)。
Embodiment 19 prepares β by iodobenzene and isopropyl acrylate, β-diphenylacrylate isopropyl ester
By palladium 1.2mg (0.005mmol), Silver monoacetate 173mg (1.05mmol), Glacial acetic acid 1.5mL, iodobenzene 0.408g (2mmol), isopropyl acrylate 57mg (0.5mmol) successively joins with stirring in the 25mL reaction tubes of magneton, stirring heating, 110 ℃ of reactions 4 hours; After reaction finishes, cooling, add each 10mL of ethyl acetate and methylene dichloride, to filter, filtrate is spin-dried for concentrated, and column chromatography for separation obtains product β, β-diphenylacrylate methyl esters 130mg, yield 98%. 1H?NMR(400MHz，aceton-d 6，ppm)：δ7.35-7.26(m，8H)，7.14-7.12(m，2H)，6.31(s，1H)，4.78(m，1H)，0.99(d，6.4Hz，6H). 13C?NMR(100MHz，CDCl 3，ppm)：δ165.7，155.7，140.7，139.1，129.2，129.1，128.3，128.2，128.0，127.8，118.1，67.3，21.6.IR：2979，1714，1699，1616，1447，1368，1265，1168，1106，997，872，769，695em -1.MS(EI，m/z)266(M +，53％)，223(67％)，207(82％)，180(100％)，77(40％)，43(51％)。
Embodiment 20 prepares β by iodobenzene and n-butyl acrylate, the positive butyl ester of β-diphenylacrylate
By palladium 1.2mg (0.005mmol), Silver monoacetate 173mg (1.05mmol), Glacial acetic acid 1.5mL, iodobenzene 0.408g (2mmol), n-butyl acrylate 64mg (0.5mmol) successively joins with stirring in the 25mL reaction tubes of magneton, stirring heating, 110 ℃ of reactions 4 hours; After reaction finishes, cooling, add each 10mL of ethyl acetate and methylene dichloride, to filter, filtrate is spin-dried for concentrated, and column chromatography for separation obtains product β, β-diphenylacrylate methyl esters 137mg, yield 98%. 1H?NMR(400MHz，aceton-d 6，ppm)：δ7.35-7.29(m，6H)，7.26-7.24(m，2H)，7.14-7.12(m，2H)，6.32(s，1H)，3.92(t，J＝6.4Hz，2H)，1.39(m，2H)，1.17(m，2H)，0.81(t，J＝7.4Hz，3H). 13C?NMR(100MHz，CDCl 3，ppm)：δ166.2，156.3，140.8，139.0，129.3，129.1，128.3，128.2，128.0，127.8，117.5，64.0，30.4，19.0，13.7.IR：2958，1719，1699，1616，1492，1446，1357，1263，1154，1065，1027，769，695cm -1.MS(EI，m/z)280(M +，43％)，224(63％)，207(91％)，178(100％)，167(44％)，152(30％)，105(33％)，77(25％)，51(23％)。
Embodiment 21 prepares β by iodobenzene and benzyl acrylate, β-diphenylacrylate benzyl ester
By palladium 1.2mg (0.005mmol), Silver monoacetate 173mg (1.05mmol), Glacial acetic acid 1.5mL, iodobenzene 0.408g (2mmol), benzyl acrylate 81mg (0.5mmol) successively joins with stirring in the 25mL reaction tubes of magneton, stirring heating, 110 ℃ of reactions 4 hours; After reaction finishes, cooling, add each 10mL of ethyl acetate and methylene dichloride, to filter, filtrate is spin-dried for concentrated, and column chromatography for separation obtains product β, β-diphenylacrylate benzyl ester 152mg, yield 97%.M.p.174-175℃. 1H?NMR(400MHz，aceton-d 6，ppm)：δ7.41-7.34(m，6H)，7.36-7.30(m，5H)，7.24-7.19(m，4H)，6.46(s，1H)，5.04(s，2H). 13C?NMR(100MHz，CDCl 3，ppm)：δ165.9，157.1，140.8，138.9，135.9，129.5，129.2，128.45，128.42，128.4，128.3，128.2，128.1，128.0，117.1，66.0.IR：2960，1720，1616，1492，1448，1379，1356，1262，1143，1004，975，874，751，694cm -1.MS(EI，m/z)314(M +，17％)，296(18％)，168(26％)，254(37％)，207(55％)，178(65％)，91(100％)。
Embodiment 22 prepares β by iodobenzene and vinylformic acid, β-diphenylacrylate
By palladium 1.2mg (0.005mmol), Silver monoacetate 173mg (1.05mmol), Glacial acetic acid 1.5mL, iodobenzene 0.408g (2mmol), vinylformic acid 36mg (0.5mmol) successively joins with stirring in the 25mL reaction tubes of magneton, stirring heating, 110 ℃ of reactions 12 hours; After reaction finishes, cooling, add each 10mL of ethyl acetate and methylene dichloride, to filter, filtrate is spin-dried for concentrated, and column chromatography for separation obtains product β, β-diphenylacrylate 76mg, yield 68%.M.p.154-155℃. 1HNMR(400MHz，aceton-d 6，ppm)：δ10.53(s，1H)，7.34-7.32(m，6H)，7.28-7.27(m，2H)，7.17-7.15(m，2H)，6.35(s，1H). 13C?NMR(100MHz，CDCl 3，ppm)：δ171.4，159.1，140.8，138.4，129.8，129.3，128.6，128.5，128.4，127.9，116.5.IR：3023，1694，1666，1611，1491，1283，1213，923，869，773，694，626cm -1.MS(EI，m/z)224(M +，100％)，178(90％)，77(32％)，51(33％)。
Embodiment 23 is by methiodide benzene and vinylformic acid are prepared to β, β-bis--(p-methylphenyl) vinylformic acid
By palladium 1.2mg (0.005mmol), Silver monoacetate 173mg (1.05mmol), Glacial acetic acid 1.5mL, to methyl iodobenzene 0.436g (2mmol), vinylformic acid 36mg (0.5mmol) successively joins with stirring in the 25mL reaction tubes of magneton, stirring heating, 110 ℃ of reactions 12 hours; After reaction finishes, cooling, add each 10mL of ethyl acetate and methylene dichloride, to filter, filtrate is spin-dried for concentrated, and column chromatography for separation obtains product β, β-bis--(p-methylphenyl) 64mg, yield 51%.M.p.174-175℃(litt.：174℃) 42. 1H?NMR(400MHz，CDCl 3，ppm)：δ7.20-7.11(m，8H)，6.29(s，1H)，2.41(s，3H)，2.37(s，3H). 13C?NMR(100MHz，CDCl 3，ppm)：δ171.5，159.1，139.9，138.32，138.28，135.5，129.3，129.0，128.6，115.3，21.3，21.2.IR：2918，1690，1662，1596，1509，1418，1355，1284，1207，1187，1151，939，879，818，685cm -1.MS(EI，m/z)252(M +，100％)，207(35％)，162(52％)，115(72％)，105(63％)，91(63％)。
Embodiment 24 prepares triphenylethylene by iodobenzene and vinylbenzene
By palladium 1.2mg (0.005mmol), Silver monoacetate 173mg (1.05mmol), Glacial acetic acid 1.5mL, iodobenzene 0.408g (2mmol), vinylbenzene 52mg (0.5mmol) successively joins with stirring in the 25mL reaction tubes of magneton, stirring heating, 110 ℃ of reactions 15 minutes; After reaction finishes, cooling, add each 10mL of ethyl acetate and methylene dichloride, to filter, filtrate is spin-dried for concentrated, and column chromatography for separation obtains product triphenylethylene 118mg, yield 92%.M.p.69-70℃. 1H?NMR(400MHz，aceton-d 6，ppm)：δ7.33-7.27(m，8H)，7.14-7.09(m，5H)，7.02-6.98(m，3H). 13C?NMR(100MHz，CDCl 3，ppm)：δ143.5，142.6，140.4，137.4，130.4，129.6，128.7，128.3，128.0，127.7，127.6，127.5，126.8.MS(EI，m/z)256(M +，100％)，239(45％)，178(90％)，165(40％)。
Embodiment 25 prepares triphenylethylene by iodobenzene and triethoxy vinyl silanes
By palladium 1.2mg (0.005mmol), Silver monoacetate 173mg (1.05mmol), Glacial acetic acid 1.5mL, iodobenzene 0.408g (2mmol), triethoxy vinyl silanes 85mg (0.5mmol) successively joins with stirring in the 25mL reaction tubes of magneton, stirring heating, 110 ℃ of reactions 12 hours; After reaction finishes, cooling, add each 10mL of ethyl acetate and methylene dichloride, to filter, filtrate is spin-dried for concentrated, and column chromatography for separation obtains product triphenylethylene 52mg, yield 40%.M.p.69-70℃. 1HNMR(400MHz，aceton-d 6，ppm)：δ7.33-7.27(m，8H)，7.14-7.09(m，5H)，7.02-6.98(m，3H). 13C?NMR(100MHz，CDCl 3，ppm)：δ143.5，142.6，140.4，137.4，130.4，129.6，128.7，128.3，128.0，127.7，127.6，127.5，126.8.MS(EI，m/z)256(M +，100％)，239(45％)，178(90％)，165(40％)。
Embodiment 26 is by preparing 1,1,2-tri--(to bromobenzene) ethene to bromo-iodobenzene with to bromstyrol
By palladium 1.2mg (0.005mmol), Silver monoacetate 173mg (1.05mmol), Glacial acetic acid 1.5mL, to bromo-iodobenzene 0.566g (2mmol), bromstyrol 92mg (0.5mmol) is successively joined with stirring in the 25mL reaction tubes of magneton, stirring heating, at 110 ℃ of reaction 4h; After reaction finishes, cooling, add each 10mL of ethyl acetate and methylene dichloride, to filter, filtrate is spin-dried for concentrated, and column chromatography for separation obtains product 1,1,2-tri--(to bromobenzene) ethene 229mg, yield 93%.M.p.104-105℃. 1H?NMR(400MHz，CDCl 3，ppm)：δ7.49-7.44(m，4H)，7.30(d，J＝8.4Hz，2H)，7.16(d，J＝8.0Hz，2H)，7.05(d，J＝8.4Hz，2H)，6.91-6.88(m，3H). 13C?NMR(100MHz，CDCl 3，ppm)：δ141.5，141.1，138.3，135.6，132.1，132.0，131.5，131.3，131.0，129.2，127.8，122.1，121.1.MS(EI，m/z)494(M +，88％)，492(M +，91％)，334(47％)，332(49％)，252(100％)，126(85％)。
Embodiment 27 is by preparing 1,1,2-tri--(to chlorobenzene) ethene to chloroiodobenzone with to chloro-styrene
By palladium 1.2mg (0.005mmol), Silver monoacetate 173mg (1.05mmol), Glacial acetic acid 1.5mL, to chloroiodobenzone 0.476g (2mmol), chloro-styrene 69mg (0.5mmol) is successively joined with stirring in the 25mL reaction tubes of magneton, stirring heating, at 110 ℃ of reaction 4h; After reaction finishes, cooling, add each 10mL of ethyl acetate and methylene dichloride, to filter, filtrate is spin-dried for concentrated, and column chromatography for separation obtains product 1,1,2-tri--(to chlorobenzene) ethene 133mg, yield 74%.M.p.80-81℃. 1H?NMR(400MHz，CDCl 3，ppm)：δ7.32-7.26(m，4H)，7.21-7.19(m，2H)，7.14-7.08(m，4H)，6.94(d，J＝8.4Hz，2H)，6.87(s，1H). 13C?NMR(100MHz，CDCl 3，ppm)：δ141.2，140.9，137.9，135.2，133.8，132.8，131.7，130.7，129.1，128.9，128.5，128.4，127.7.MS(EI，m/z)362(M +，42％)，360(M +，100％)，358(M +，94％)，288(68％)，252(56％)，176(18％)，126(30％)，125(30％)。
Embodiment 28 is by methiodide benzene and p-methylstyrene are prepared to 1,1,2-tri--(to methylbenzene) ethene
By palladium 1.2mg (0.005mmol), Silver monoacetate 173mg (1.05mmol), Glacial acetic acid 1.5mL, to methiodide benzene 0.436g (2mmol), p-methylstyrene 59mg (0.5mmol) successively joins with stirring in the 25mL reaction tubes of magneton, stirring heating, at 110 ℃ of reaction 4h; After reaction finishes, cooling, add each 10mL of ethyl acetate and methylene dichloride, to filter, filtrate is spin-dried for concentrated, and column chromatography for separation obtains product 1,1,2-tri--(to methylbenzene) ethene 112mg, yield 75%.M.p.83-84℃. 1H?NMR(400MHz，CDCl 3，ppm)：δ7.21(d，J＝8.4Hz，2H)，7.15-7.08(m，6H)，6.94(s，4H)，6.87(s，1H)，2.38(s，3H)，2.35(s，3H)，2.27(s，3H). 13C?NMR(100MHz，CDCl 3，ppm)：δ141.7，141.1，137.8，137.2，137.0，136.3，134.9，130.4，129.5，129.4，129.0，128.8，127.6，127.2，21.4，21.2.MS(EI，m/z)298(M +，100％)，283(34％)，268(30％)，57(51％)。
Embodiment 29 is by preparing 1,1,2-tri--(to anisole) ethene to methoxyl group iodobenzene with to methoxy styrene
By palladium 1.2mg (0.005mmol), Silver monoacetate 173mg (1.05mmol), Glacial acetic acid 1.5mL, to methoxyl group iodobenzene 0.468g (2mmol), methoxy styrene 67mg (0.5mmol) is successively joined with stirring in the 25mL reaction tubes of magneton, stirring heating, at 110 ℃ of reaction 12h; After reaction finishes, cooling, add each 10mL of ethyl acetate and methylene dichloride, to filter, filtrate is spin-dried for concentrated, and column chromatography for separation obtains product 1,1,2-tri--(to anisole) ethene 78mg, yield 45%. 1H?NMR(400MHz，CDCl 3，ppm)：δ7.27(d，J＝9.2Hz，2H)，7.15(d，J＝8.0Hz，2H)，7.00(d，J＝8.4Hz，2H)，6.90-6.85(m，4H)，6.80(s，1H)，6.70(d，J＝8.8Hz，2H)，3.85(s，3H)，3.82(s，3H)，3.76(s，3H). 13C?NMR(100MHz，CDCl 3，ppm)：δ159.0，158.8，158.0，139.8，136.6，133.0，131.6，130.6，130.5，128.6，125.7，114.0，113.5，113.4，55.22，55.12，55.06.MS(EI，m/z)346(M +，100)，331(31％)，135(27％)。
Embodiment 30 by vinylbenzene successively and iodobenzene, methiodide benzene is prepared to 1,2-phenylbenzene-1-(p-methylphenyl) ethene
By palladium 1.2mg (0.005mmol), Silver monoacetate 173mg (1.05mmol), Glacial acetic acid 1.5mL, iodobenzene 0.102g (0.5mmol), vinylbenzene 52mg (0.5mmol) successively joins with stirring in the 25mL reaction tubes of magneton, stirring heating, after 110 ℃ of reaction 5min, cooling, add methiodide benzene 0.120g (0.55mmol), continue to spend the night 110 ℃ of reactions, column chromatography for separation obtains product 1,2-phenylbenzene-1-(p-methylphenyl) ethene 123mg, yield 91%.Products therefrom is cis-trans-isomer mixture, ratio trans/cis=72/28. 1H?NMR(400MHz，CDCl 3，ppm)：δ7.37-7.05(m，14H)，7.00-6.97(m，1H)，2.43-2.39(m，3H). 13C?NMR(100MHz，CDCl 3，ppm)：δ143.8，142.7，142.6，140.7，140.6，137.63，137.57，137.4，137.1，130.5，130.4，129.6，129.4，129.0，128.7，128.2，128.0，127.7，127.6，127.5，126.72，126.66，21.4，21.2.MS(EI，m/z)270(M +，100％)，255(33％)，178(30％)，126(13％)。
Embodiment 31 by vinylbenzene successively and iodobenzene, methoxyl group iodobenzene is prepared to 1,2-phenylbenzene-1-(p-methoxyphenyl) ethene
By palladium 1.2mg (0.005mmol), Silver monoacetate 173mg (1.05mmol), Glacial acetic acid 1.5mL, iodobenzene 0.102g (0.5mmol), vinylbenzene 52mg (0.5mmol) successively joins with stirring in the 25mL reaction tubes of magneton, stirring heating, after 110 ℃ of reaction 5min, cooling, add methoxyl group iodobenzene 0.129g (0.55mmol), continue to spend the night 110 ℃ of reactions, column chromatography for separation obtains product 1,2-phenylbenzene-1-(p-methoxyphenyl) ethene 114mg, yield 80%.Products therefrom is cis-trans-isomer mixture, ratio trans/cis=69/31. 1H?NMR(400MHz，CDCl 3，ppm)：δ7.37-7.04(m，12H)，6.94-6.88(m，3H)，3.87-3.84(m，3H). 13CNMR(100MHz，CDCl 3，ppm)：δ159.3，159.0，143.8，142.3，142.1，140.6，137.7，137.6，136.0，132.5，131.6，130.4，129.5，129.4，128.8，128.6，128.2，128.0，127.9，127.8，127.7，127.5，127.4，126.6，126.5，126.4，114.0，113.6，55.3，55.2.MS(EI，m/z)286(M +，100％)，178(13％)，165(21％)。
Embodiment 32 by vinylbenzene successively and iodobenzene, fluorine iodobenzene is prepared to 1,2-phenylbenzene-1-(to fluorophenyl) ethene
By palladium 1.2mg (0.005mmol), Silver monoacetate 173mg (1.05mmol), Glacial acetic acid 1.5mL, iodobenzene 0.102g (0.5mmol), vinylbenzene 52mg (0.5mmol) successively joins with stirring in the 25mL reaction tubes of magneton, stirring heating, after 110 ℃ of reaction 5min, cooling, add fluorine iodobenzene 0.122g (0.55mmol), continue to spend the night 110 ℃ of reactions, column chromatography for separation obtains product 1,2-phenylbenzene-1-(to fluorophenyl) ethene 124mg, yield 93%.Products therefrom is cis-trans-isomer mixture, ratio trans/cis=70/30. 1H?NMR(400MHz，CDCl 3，ppm)：δ7.39-7.31(m，5H)，7.26-7.14(m，5H)，7.09-6.95(m，5H). 13C?NMR(100MHz，CDCl 3，ppm)：δ162.4(d， 1J CF＝245.7Hz)，162.2(d， 1J CF＝245.7Hz)，143.3，141.6，140.2，139.59，139.57，137.2，136.2，132.2，132.1，130.3，129.5，129.3，129.2，128.7，128.6，128.3，128.1，128.0，127.7，127.62，127.57，126.9，126.8，115.6(d， 2J CF＝20.9Hz)，115.1(d， 2J CF＝21.5Hz).MS(EI，m/z)274(M +，100％)，196(34％)，178(33％)。
Embodiment 33 by vinylbenzene successively and iodobenzene, chloroiodobenzone is prepared to 1,2-phenylbenzene-1-(rubigan) ethene
By palladium 1.2mg (0.005mmol), Silver monoacetate 173mg (1.05mmol), Glacial acetic acid 1.5mL, iodobenzene 0.102g (0.5mmol), vinylbenzene 52mg (0.5mmol) successively joins with stirring in the 25mL reaction tubes of magneton, stirring heating, after 110 ℃ of reaction 5min, cooling, add to chloroiodobenzone 0.131g (0.55mmol), continue to spend the night 110 ℃ of reactions, column chromatography for separation obtains product 1,2-phenylbenzene-1-(rubigan) ethene 142mg, yield 98%.Products therefrom is cis-trans-isomer mixture, ratio trans/cis=77/23. 1H?NMR(400MH?z，CDCl 3，ppm)：δ7.38-7.15(m，12H)，7.07-7.05(m，2H)，7.01-6.978(m，1H). 13C?NMR(100MHz，CDCl 3，ppm)：δ143.0，141.9，141.4，141.3，139.9，138.8，137.1，133.3，131.9，129.5，129.1，128.8，128.7，128.5，128.3，128.1，127.7，127.6，127.0.MS(EI，m/z)292(M +，34％)，290(M +，100％)，253(40％)，178(45％)，126(24％)。
Embodiment 34 by vinylbenzene successively and iodobenzene, bromo-iodobenzene is prepared to 1,2-phenylbenzene-1-(to bromophenyl) ethene
By palladium 1.2mg (0.005mmol), Silver monoacetate 173mg (1.05mmol), Glacial acetic acid 1.5mL, iodobenzene 0.102g (0.5mmol), vinylbenzene 52mg (0.5mmol) successively joins with stirring in the 25mL reaction tubes of magneton, stirring heating, after 110 ℃ of reaction 5min, cooling, add to bromo-iodobenzene 0.156g (0.55mmol), continue to spend the night 110 ℃ of reactions, column chromatography for separation obtains product 1,2-phenylbenzene-1-(to bromophenyl) ethene 154mg, yield 92%.Products therefrom is cis-trans-isomer mixture, ratio trans/cis=76/24. 1H?NMR(400MHz，CDCl 3，ppm)：δ7.49-7.31(m，6H)，7.22-7.04(m，8H)，7.00-6.97(m，1H). 13C?NMR(100MHz，CDCl 3，ppm)：δ143.0，142.4，141.4，141.3，139.8，139.3，137.0，132.2，131.8，131.5，131.3，131.1，131.0，130.9，130.3，129.5，129.2，128.8，128.5，128.3，128.2，127.7，127.6，127.5，127.0，126.8，121.5.MS(EI，m/z)336(M +，99％)，334(M +，100％)，253(75％)，239(40％)，178(65％)，126(35％)。
Embodiment 35 prepares 1,2-phenylbenzene-1-(aminomethyl phenyl) ethene by vinylbenzene priority and iodobenzene, a methyl iodobenzene
By palladium 1.2mg (0.005mmol), Silver monoacetate 173mg (1.05mmol), Glacial acetic acid 1.5mL, iodobenzene 0.102g (0.5mmol), vinylbenzene 52mg (0.5mmol) successively joins with stirring in the 25mL reaction tubes of magneton, stirring heating, after 110 ℃ of reaction 5min, cooling, add a methiodide benzene 0.120g (0.55mmol), continue to spend the night 110 ℃ of reactions, column chromatography for separation obtains product 1,2-phenylbenzene-1-(tolyl) ethene 127mg, yield 94%.Products therefrom is cis-trans-isomer mixture, ratio trans/cis=73/27. 1H?NMR(400MHz，CDCl 3，ppm)：δ7.37-7.22(m，6H)，7.20-7.05(m，8H)，6.99(s，1H)，2，37-2.34(d，3H). 13C?NMR(100MHz，CDCl 3，ppm)：δ143.6，143.5，142.8，142.7，140.5，140.3，138.3，137.8，137.5，130.8，130.4，129.6，128.6，128.5，128.4，128.3，128.2，128.1，128.09，128.04，127.98，127.6，127.5，127.4，126.7，124.9，21.5，21.4.MS(EI，m/z)270(M +，100％)，255(31％)，178(33％)。
Embodiment 36 prepares 1,2-phenylbenzene-1-(m-methoxyphenyl) ethene by vinylbenzene priority and iodobenzene, meta-methoxy iodobenzene
By palladium 1.2mg (0.005mmol), Silver monoacetate 173mg (1.05mmol), Glacial acetic acid 1.5mL, iodobenzene 0.102g (0.5mmol), vinylbenzene 52mg (0.5mmol) successively joins with stirring in the 25mL reaction tubes of magneton, stirring heating, after 110 ℃ of reaction 5min, cooling, add meta-methoxy iodobenzene 0.129g (0.55mmol), continue to spend the night 110 ℃ of reactions, column chromatography for separation obtains product 1,2-phenylbenzene-1-(m-methoxyphenyl) ethene 138mg, yield 97%.Products therefrom is cis-trans-isomer mixture, ratio trans/cis=74/26. 1H?NMR(400MHz，CDCl 3，ppm)：δ7.36-7.20(m，6H)，7.14-7.02(m，5H)，6.978-6.75(m，4H)，3.77-3.70(m，3H). 13C?NMR(100MHz，CDCl 3，ppm)：δ159.6，145.0，142.5，140.3，137.3，130.4，129.8，129.6，129.5，129.2，128.7，128.4，128.3，128.2，128.0，127.6，127.5，126.8，122.9，120.3，115.6，113.5，113.4，112.9，55.21，55.17.MS(EI，m/z)286(M +，100％)，253(22％)，178(18％)，165(20％)，77(14％)。
Embodiment 37 prepares 1,2-phenylbenzene-1-(o-tolyl) ethene by vinylbenzene priority and iodobenzene, adjacent methyl iodobenzene
By palladium 1.2mg (0.005mmol), Silver monoacetate 173mg (1.05mmol), Glacial acetic acid 1.5mL, iodobenzene 0.102g (0.5mmol), vinylbenzene 52mg (0.5mmol) successively joins with stirring in the 25mL reaction tubes of magneton, stirring heating, after 110 ℃ of reaction 5min, cooling, add adjacent methyl iodobenzene 0.120g (0.55mmol), continue to spend the night 110 ℃ of reactions, column chromatography for separation obtains product 1,2-phenylbenzene-1-(o-methyl-phenyl-) ethene 83mg, yield 61%.Products therefrom is cis-trans-isomer mixture, ratio trans/cis=60/40. 1H?NMR(400MHz，CDCl 3，ppm)：δ7.34-6.63(m，15H)，2.14-2.06(m，3H). 13C?NMR(100MHz，CDCl 3，ppm)：δ144.0，143.0，142.3，141.4，140.2，139.7，137.4，137.3，136.6，136.3，130.5，130.4，130.2，130.1，129.9，129.4，129.0，128.4，128.2，128.1，128.0，127.7，127.44，127.39，127.1，126.9，126.8，126.6，126.4，125.7，20.5，19.7.MS(EI，m/z)270(M +，100％)，255(33％)，192(40％)，179(95％)。
Embodiment 38 prepares 1,2-phenylbenzene-1-(adjacent fluorophenyl) ethene by vinylbenzene priority and iodobenzene, adjacent fluorine iodobenzene
By palladium 1.2mg (0.005mmol), Silver monoacetate 173mg (1.05mmol), Glacial acetic acid 1.5mL, iodobenzene 0.102g (0.5mmol), vinylbenzene 52mg (0.5mmol) successively joins with stirring in the 25mL reaction tubes of magneton, stirring heating, after 110 ℃ of reaction 5min, cooling, add adjacent fluorine iodobenzene 0.122g (0.55mmol), continue to spend the night 110 ℃ of reactions, column chromatography for separation obtains product 1,2-phenylbenzene-1-(adjacent fluorophenyl) ethene 109mg, yield 82%.Products therefrom is immiscible compound, ratio trans/cis=60/40.(E)： 1H?NMR(400MHz，CDCl 3，ppm)：δ7.35-7.28(m，6H)，7.18-7.03(m，9H). 13C?NMR(100MHz，CDCl 3，ppm)：δ160.3(d， 1J CF＝246.7Hz)，142.1，137.0，136.0，132.3(d， 3J CF＝3Hz)，130.3，129.6(d， 3J CF＝8.6Hz)，129.0，128.3，128.1，127.8，127.6，127.1，126.7，124.4(d， 2J CF＝3.2Hz)，116.1(d， 2J CF＝21.6Hz).MS(EI，m/z)274(M +，100％)，252(24％)，196(14％)，178(22％)，165(16％)，126(13％).(Z)： 1H?NMR(400MHz，CDCl 3，ppm)：δ7.27-7.19(m，7H)，7.16-7.12(m，3H)，7.11-7.02(m，4H)，6.88(s，1H). 13C?NMR(100MHz，CDCl 3，ppm)：δ160.3(d， 1J CF＝248.1Hz)，140.2，137.1，137.0，131.6(d， 3J CF＝4.1Hz)，131.3(d， 3J CF＝3Hz)，129.8，129.5，129.0，128.9，128.4，128.0，127.4，127.1，127.0，123.8(d， 2J CF＝3.7Hz)，116.0(d， 2J CF＝23.1Hz).MS(EI，m/z)274(M +，100％)，252(24％)，196(14％)，178(22％)，165(16％)，126(13％)。
Embodiment 39 prepares 1,2-phenylbenzene-1-(Chloro-O-Phenyl) ethene by vinylbenzene priority and iodobenzene, adjacent chloroiodobenzone
By palladium 1.2mg (0.005mmol), Silver monoacetate 173mg (1.05mmol), Glacial acetic acid 1.5mL, iodobenzene 0.102g (0.5mmol), vinylbenzene 52mg (0.5mmol) successively joins with stirring in the 25mL reaction tubes of magneton, stirring heating, after 110 ℃ of reaction 5min, cooling, add adjacent chloroiodobenzone 0.131g (0.55mmol), continue to spend the night 110 ℃ of reactions, column chromatography for separation obtains product 1,2-phenylbenzene-1-(Chloro-O-Phenyl) ethene 98mg, yield 68%.Products therefrom is immiscible compound, ratio trans/cis=66/34.(E)： 1H?NMR(400MHz，CDCl 3，ppm)：δ7.39-7.34(m，2H)，7.25-7.15(m，12H)，6.70(s，1H). 13C?NMR(100MHz，CDCl 3，ppm)：δ142.9，140.4，139.6，136.8，133.4，131.7，131.6，130.0，129.9，129.5，128.6，128.2，128.0，127.3，127.1，126.6.MS(EI，m/z)292(M +，33％)，290(M +，100％)，255(82％)，239(40％)，178(36％)，126(34％).(Z)： 1H?NMR(400MHz，CDCl 3，ppm)：δ7.47(d，J＝8Hz)，7.34-7.23(m，8H)，7.16-7.14(m，4H)，7.02-7.00(m，2H). 13C?NMR(100MHz，CDCl 3，ppm)：δ141.5，139.4，139.1，136.9，134.2，132.0，130.1，129.6，129.0，128.4，128.1，127.6，127.2，127.1，126.5.MS(EI，m/z)292(M +，33％)，290(M +，100％)，255(82％)，239(40％)，178(36％)，126(34％)。
Embodiment 40 by vinylbenzene successively and iodobenzene, iodobenzene ethyl ketone is prepared to 1,2-phenylbenzene-1-(to acetylphenyl) ethene
By palladium 1.2mg (0.005mmol); Silver monoacetate 173mg (1.05mmol); Glacial acetic acid 1.5mL; iodobenzene 0.102g (0.5mmol); vinylbenzene 52mg (0.5mmol) successively joins with stirring in the 25mL reaction tubes of magneton; stirring heating; after 110 ℃ of reaction 5min; cooling; add iodobenzene ethyl ketone 0.135g (0.55mmol), continue to spend the night 110 ℃ of reactions, column chromatography for separation obtains product 1; 2-phenylbenzene-1-(to acetylphenyl) ethene 143mg, yield 96%.Products therefrom is cis-trans-isomer mixture, ratio trans/cis=82/18. 1H?NMR(400MHz，CDCl 3，ppm)：δ7.93-7.89(m，2H)，7.42-7.14(m，10H)，7.06-7.03(m，3H)，2.62-2.60(d，3H). 13C?NMR(100MHz，CDCl 3，ppm)：δ197.7，197.5，148.0，145.7，142.7，141.6，141.5，139.7，136.8，136.0，135.9，130.8，130.3，130.1，129.7，129.5，129.2，128.8，128.6，128.3，128.1，128.0，127.8，127.7，127.6，127.4，127.3，127.1，26.6.IR：3023，1679，1597，1491，1443，1407，1357，1265，1183，912，843，822，760，696，612cm -1.MS(EI，m/z)298(M +，100％)，283(60％)，253(24％)，239(27％)，178(14％)，126(12％)，77(9％)。
Embodiment 41 prepares 4-(1,2-diphenylacetylene) methyl benzoate by vinylbenzene priority and iodobenzene, 4-Iodobenzoic acid methyl esters
By palladium 1.2mg (0.005mmol); Silver monoacetate 173mg (1.05mmol); Glacial acetic acid 1.5mL; iodobenzene 0.102g (0.5mmol); vinylbenzene 52mg (0.5mmol) successively joins with stirring in the 25mL reaction tubes of magneton; stirring heating; after 110 ℃ of reaction 5min; cooling; add 4-Iodobenzoic acid methyl esters 0.144g (0.55mmol), continue to spend the night 110 ℃ of reactions, column chromatography for separation obtains product 1; 2-phenylbenzene-1-(to acetylphenyl) ethene 154mg, yield 98%.Products therefrom is cis-trans-isomer mixture, ratio trans/cis=81/19. 1H?NMR(400MHz，CDCl 3，ppm)：δ7.98-7.96(m，2H)，7.39-7.02(m，13H)，3.93-3.92(d，3H).13CNMR(100MHz，CDCl 3，ppm)：δ166.9，147.8，141.6，139.7，136.8，130.2，130.0，136.8，130.5，130.2，129.9，129.8，129.6，129.5，129.1，128.9，128.8，128.3，128.0，127.7，127.6，127.5，127.4，127.2，127.0，52.1，52.0.IR：3056，1714，1601，1492，1436，1407，1278，1179，1104，1018，860，768，728，695cm -1.MS(EI，m/z)314(M +，100％)，253(36％)，239(27％)，178(23％)，126(15％)，59(26％)。

Claims (5)

1. a β, the synthetic method of beta-diaryl alkene, comprising: in organic acid solvent, under the existence of palladium catalyst and silver salt, halogenated aryl hydrocarbon and end alkenyl compound obtain β through linked reaction, beta-diaryl alkene;
Wherein, described halogenated aryl hydrocarbon is compound as the formula (1); Described end alkenyl compound is compound as the formula (2); Described β, beta-diaryl alkene is compound as the formula (3):
Figure FDA0000428675120000011
X is-I or-Br;
R 1for aromatics group, described aromatics group is phenyl, substituted-phenyl, naphthyl, substituted naphthyl, heterocycle or substituted heterocycle;
R 1' be aromatics group, described aromatics group is phenyl, substituted-phenyl, naphthyl, substituted naphthyl, heterocycle or substituted heterocycle;
R 1with R 1' identical;
R 2for carboxyl, ester group, aldehyde radical, ketone group, itrile group, phenyl, substituted-phenyl, naphthyl, substituted naphthyl, heterocycle or substituted heterocycle;
R 3for-H, C 1～C 40alkyl, ester group, aldehyde radical, ketone group or itrile group;
Described organic acid solvent is acetic acid;
Described palladium catalyst is palladium;
Described silver salt is Silver monoacetate.
2. method according to claim 1, is characterized in that: described halogenated aryl hydrocarbon is compound as the formula (4); Described end alkenyl compound is suc as formula the compound shown in (5) or formula (6); Described β, beta-diaryl alkene is suc as formula the compound shown in (7) or formula (8):
Figure FDA0000428675120000021
X is-I or-Br;
R 4for-H or ortho position, a position or para-orientation-CH 3,-OCH 3,-F ,-Cl ,-Br ,-CHO ,-COCH 3,-COOMe ,-COOC 2h 5,-COOH or-NO 2;
R 4' be-H or ortho position, a position or para-orientation-CH 3,-OCH 3,-F ,-Cl ,-Br ,-CHO ,-COCH 3,-COOMe ,-COOC 2h 5,-COOH or-NO 2;
R 4with R 4' identical;
R 5for-H, C 1～C 40alkyl ,-Ar ,-OCH 2ar or-OR 7, R wherein 7for C 1～C 40alkyl;
R 6for-H or ortho position, a position or para-orientation-CH 3,-OCH 3,-F ,-Cl ,-Br ,-CHO ,-COCH 3,-COOMe ,-COOC 2h 5,-COOH or-NO 2.
3. method according to claim 1 and 2, is characterized in that: the radicals X of described halogenated aryl hydrocarbon is-I.
4. method according to claim 1, it is characterized in that: in every mmole end alkenyl compound consumption, the consumption of described organic acid solvent is 1～5mL, the addition of halogenated aryl hydrocarbon is 2～5mmol, the addition of palladium is 0.005～0.05mmol, and the addition of silver salt is counted 2.0～3.1mmol with silver ions.
5. method according to claim 1, is characterized in that: the temperature of reaction of described linked reaction is 80～130 ℃, and the reaction times is 0.25～24 hour.
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