CN102114433B - Supported arsine catalyst as well as synthesizing method and application thereof in Wittig reaction - Google Patents

Supported arsine catalyst as well as synthesizing method and application thereof in Wittig reaction Download PDF

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CN102114433B
CN102114433B CN2010105596164A CN201010559616A CN102114433B CN 102114433 B CN102114433 B CN 102114433B CN 2010105596164 A CN2010105596164 A CN 2010105596164A CN 201010559616 A CN201010559616 A CN 201010559616A CN 102114433 B CN102114433 B CN 102114433B
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arsine
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CN102114433A (en
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唐勇
刘春荣
孙秀丽
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Shanghai Institute of Organic Chemistry of CAS
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Abstract

The invention relates to a polyethylene-supported arsine catalyst with a structural formula shown in the specification as well as a synthesizing method and application thereof. The catalyst is simple and convenient to synthesize, can be conveniently used for catalyzing an aldehyde or ketone Wittig reaction to synthesize olefin compounds, and can be recycled conveniently.

Description

Load arsine catalyst, synthetic method and the purposes in the Wittig reaction thereof
Technical field
The present invention relates to arsine catalyst, synthetic method and the application in the Wittig reaction thereof of polyethylene load.This catalyst is to be obtained by alkene and ethene combined polymerization under the effect of polyolefin catalyst containing arsenic, can react and realize for Wittig the recycling of catalyst.
background technology
People recognize very early, if phosphine catalyst is immobilized to macromolecule, can realize easily separating of phosphine oxide compound and reaction system.1972, the people such as Mckinley just loaded to ylide on crosslinked polystyrene, had realized phosphonium ylide Wittig reaction [McKinley, the S.V. of load; Rakshys, J.W.J.Chem.Soc., Chem.Commun., 1972,134].After reaction finishes, only need to filter just can remove the accessory substance phosphine oxide compound.But there is the problem of low conversion rate in reaction, and the conversion ratio of reaction is substantially all at (reaction equation 1) below 70%.
Reaction equation 1
Figure DEST_PATH_GSB00000521166000011
1979, the people such as Castells reported reaction [Castells, the J. of the phosphonium ylide of m-terephthal aldehyde, terephthalaldehyde and crosslinked loaded by polystyrene; Font, J.; Virgili, A.J.Chem.Soc., PerkinTrans.1,1979,1].The scope of ylide can be expanded to stable ylide.Reaction can solve the product purification problem, also can conveniently reclaim phosphine oxide compound, but still could not realize the recycling of phosphine, and reaction speed is slow, low conversion rate (reaction equation 2).
Reaction equation 2
Figure BSA00000360964500021
Nineteen eighty-three, the people such as W.T.Ford are synthetic [Bernard, the M. for natural products Ethyl Retinoate by the Wittig reagent of load; Ford, W.T.; Nelson, E.C.; J.Org.Chem., 1983,48,3164].When using two equivalent phosphines, the reaction time is 24 hours, and reaction can obtain 70% productive rate.The accessory substance phosphine oxide compound can be by removing by filter, and so just can avoid product degenerate when column chromatography for separation (reaction equation 3).
Reaction equation 3
Figure BSA00000360964500022
1998, the people such as S.Ley reacted the phosphine of crosslinked polystyrene load to [Bolli, M.H. for Wittig; Ley, S.V.J.Chem.Soc., Perkin Trans 1 1998,2243].The scope of substrate is also wider, and aromatic aldehyde is arranged, alkyl aldehydes and ketone.But reaction still exists reaction speed slow, the problem that the phosphonium salt consumption is large.Reaction needed is used the phosphonium salt reaction of 2.5-3.0 equivalent, and needs 24-28 hour (reaction equation 4).
Reaction equation 4
Figure BSA00000360964500031
2002, the people such as C.Gennari were used for building macrolides compound [Porta, E.L. by the ylide epoxidation reaction of crosslinked loaded by polystyrene; Et al.Tetrahedron Lett.2002,43,761].But productive rate is low, only have 53%, lower for being with substituent substrate, only have 15% (reaction equation 5).
Reaction equation 5
Figure BSA00000360964500032
2004, the people such as R.Schobert reported load research [Schobert, the R. of phosphonium ylide ketenes; Jagusch, C.; Melanophy, C.; Mullen, G.; Org.Biomol.Chem.2004,2,3524].They for the Wittig reaction, have obtained medium productive rate (reaction equation 6) by the ylide ketenes of polystyrene support.
2005, the people such as P.H.Toy were used for ylide epoxidation reaction [Choi, M.K.W. by the sulphur reagent of crosslinked loaded by polystyrene; Toy.P.H.Tetrahedron 2004,60, and 2875], wait until in having obtained that outstanding productive rate and catalyst can recycle and reuse at least 5 times.The sulphur reagent of the loaded by polystyrene of reaction needed 3 equivalents (reaction equation 7).
Reaction equation 6
Reaction equation 7
Figure BSA00000360964500042
In above-mentioned research, is no matter in the Wittig reaction or in little cyclization, all uses the ylide reagent of the carrier of equivalent, and the carrier used is mostly crosslinked polystyrene support, have some inferior positions:
1) need the reagent of a large amount of loads;
2) low reaction activity, long reaction time and the lower extent of reaction;
3), because crosslinked polystyrene is poorly soluble, reaction finishes the back loading thing and is difficult for separating with solid impurity.
For this reason, people start to attempt the carrier of the Ylide reaction using the macromolecule of solubility as load.2002, the yellow Wittig reaction (reaction equation of clank having reported the tellurium catalyst of a routine PEG load
8)[Z.-Z.Huang，Y.Song，W.Xia，Y.-H.Yu，Y.Tang，J.Org.Chem.2002，67，3096]。Multiple aldehyde, comprise aromatic aldehyde, assorted aromatic aldehyde and fatty aldehyde, can react preferably, mainly obtains trans product.But, during the PEG load, only have the end group can be functionalized, thereby cause load capacity lower and under alkali condition, also can cause PEG to decompose to cause the loss of ylide precursor, thereby can't realize the recycling of tellurium.
Reaction equation 8
Figure BSA00000360964500051
[J.Polym.Sci. in 1989; PartA:Polym.Chem.1989; 27; 4205]; the people such as Bergbreiter have prepared diphenylphosphine and the phosphorous acid diphenyl alkyl ester (reaction equation 9) of PE load in the mode of anionic polymerisation; and these two compounds are used for to rhodium, the olefin hydrogenation of palladium, niobium, nickel, ruthenium, tin, copper catalysis, olefin hydroformylation, Cyclopropanated, pure oxidation, Kharasch react, the serial reactions such as carbonylation of alkynes.Catalyst can be realized repeatedly recycling, and substantially keeps catalytic activity, and its efficiency is about 80% left and right of micromolecule catalyst.But there is low (the 0.2 mM of gram of load capacity in the method -1), the carrier molecule amount is hanged down the problem not easily separated, that reclaim that causes.
Reaction equation 9
Figure BSA00000360964500052
Ethene and polar monomer carry out the load that coordination polymerization can effectively realize organic catalyst, but the exploration of this respect is not also arranged at present, therefore, are necessary to utilize the organic catalyst of the method exploitation high capacity amount.
Summary of the invention
The arsine catalyst and the synthetic method thereof that the purpose of this invention is to provide a kind of polyethylene load;
Purpose provided by the invention be the arsine catalyst of above-mentioned polyethylene load for the synthetic olefin(e) compound of catalysis Wittig reaction, comprise the purposes to the Methoxycinnamate series compound with sun-screening function;
The arsine catalyst of a kind of polyethylene load provided by the invention has active high, the characteristics that can conveniently recycle, be a kind of structural formula following containing the arsine macromolecular compound:
Figure BSA00000360964500061
Wherein,
R 1, R 2the straight chain of C1-C20 or the alkyl that contains side chain or aromatic group; The optional position of described aromatic group can be replaced by one or more substituted radicals individually or simultaneously, and each substituted radical is the alkyl with 1 to 10 carbon atom, the alkoxyl with 1 to 10 carbon atom or amido (R 3) 2n-, there is ester group, the CF of 1 to 10 carbon atom 3or halogen, substituted radical can be identical, also can be different; R 3be the straight chain of C1-C7 or the alkyl that contains side chain or aromatic group, the optional position of described aromatic group can be individually or simultaneously by one or more R 5group replaces, each R 5group is the alkyl with 1 to 5 carbon atom, alkoxyl, the CF with 1 to 5 carbon atom 3or halogen, substituted radical can be identical, also can be different;
Described aromatic group is phenyl or naphthyl;
The molecular weight that the numerical value of X and y meets containing the arsine macromolecular compound is 2000-40000, and arsenic content is 0.1-15 % by mole;
N is 0 to 20 integer; The integer of preferred 3-9;
Described halogen is fluorine, chlorine, bromine or iodine.
For reaching more excellent effect, R 1, R 2straight chain or the alkyl that contains side chain or the aromatic group of preferred C1-C10; The optional position of described aromatic group can be replaced by one or more substituted radicals individually or simultaneously, and each substituted radical is the alkyl with 1 to 5 carbon atom, the alkoxyl with 1 to 5 carbon atom or amido (R 3) 2n-, there is ester group, the CF of 1 to 5 carbon atom 3or halogen, substituted radical can be identical, also can be different; The molecular weight that the numerical value of X and y meets containing the arsine macromolecular compound is 2000-20000, and arsenic content is 0.5-10mol%; N is 0 to 10 integer; R 3be the straight chain of C1-C7 or the alkyl that contains side chain or phenyl, the optional position of phenyl individually or simultaneously can be by one or more R 5group replaces, and each substituted radical is the alkyl with 1 to 5 carbon atom, alkoxyl, the CF with 1 to 5 carbon atom 3or halogen, substituted radical can be identical, also can be different;
Catalyst of the present invention is to be obtained by alkene and the combined polymerization of ethene under the olefin polymerization catalysis effect containing arsine, and concrete grammar is as follows:
1)
Figure BSA00000360964500071
react and within 1-72 hour, obtain solution A in subzero 78 to 100 degree in organic solvent with the trialkylaluminium reagent of equivalent; The preferred aluminium ethide of described trialkylaluminium reagent, triisobutyl aluminium or MAO, the preferred toluene of organic solvent;
2) after A step 1) obtained is added to solvent, pass into ethene in system, pressure is 0.1-10MPa, then adds co-catalyst and ethylene rolymerization catalyst, under 0 ℃ to 100 ℃ condition, carries out polymerase 10 .1-2.0 hour; Described co-catalyst is the metal reagents such as MAO, MMAO, triethyl aluminum or diethyl aluminum chloride, and the mol ratio of described co-catalyst and ethylene rolymerization catalyst is 1-10000/1; Wherein
Figure BSA00000360964500072
concentration be the 0.1-99.0 mol/L; Described MAO means MAO, and MMAO means the MAO of modifying; Described solvent can be halogenated hydrocarbons, for example carrene, 1,2-dichloroethanes, oxolane, toluene or methyl alcohol etc.; Halogenated hydrocarbons can be carrene or 1,2-dichloroethanes.
3) after polymerization completes, can add acidifying ethanol cancellation reaction, stir, filter to reclaim and obtain the arsine catalyst of load.
Described solvent can be halogenated hydrocarbons, varsol, ethyl acetate, oxolane or ethanol; The preferred toluene of varsol, n-hexane, cyclohexane or normal heptane;
R 1, R 2with n, define as previously mentioned.
Described ethylene rolymerization catalyst is patent ZL02110844.7, ZL01126323.7, the structure of report in 200610025918.7,200610026765.8,200610026766.2,200710045131.1.
The arsine catalyst of polyethylene load of the present invention can the Wittig reaction of high activity ground catalysis aldehydes or ketones obtain polysubstituted alkene under the diazonium decomposing agents exists.
Described diazonium decomposing agents is metallic compound, preferred acetic acid rhodium, and Fe (Tcpp) Cl most preferably, wherein the structural formula of Fe (Tcpp) Cl is:
Figure BSA00000360964500081
wherein, R=P-C 6h 4.
Described diazonium compound is ethyl diazoacetate, diazobenzene ethyl ketone, diazonium ethyl propionate, the different monooctyl ester of diazoacetic acid, benzyl diazonium, diazomethane etc., preferably ethyl diazoacetate
Wherein, the molar ratio of Fe (Tcpp) Cl and aldehydes or ketones is 1-2.5: 1000; The molar ratio of diazonium compound and aldehydes or ketones is 1.5-3: 1; Reducing agent is PMHS, diphenyl silane, and the molar ratio of reducing agent and aldehydes or ketones is 0.3-2.5: 1; The consumption of arsine catalyst is: 0.05-100 % by mole; PMHS means polymethyl hydrogen siloxane.
By the method can synthesize efficiently have sun-screening function to the Methoxycinnamate compounds, for example, in preference, the method for selection is as follows:
1.Schlenk add diazonium decomposing agents and arsine catalyst in bottle, displacement nitrogen three times;
2. add anisic aldehyde, solvent (can be toluene, carrene, 1,2-dichloroethanes), rise to reaction temperature;
3. be added dropwise to the solution of diazonium compound and reducing agent (PMHS or diphenyl silane), reaction adds a little ethanol cancellation cessation reaction after finishing.After being down to room temperature, add the arsine catalyst of benzinum or n-hexane wash load, filter the gained solid, but Vacuum Concentration dried recovered arsine catalyst reacting for next round.Filtrate is concentrated can be to the Methoxycinnamate compounds by column chromatography for separation.
The arsine catalyst of polyethylene load of the present invention is a kind of organic catalyst of high capacity amount, not only synthetic convenient, and the Wittig reaction of the effectively catalysis aldehyde of energy, ketonic compound generates olefin(e) compound, and the consumption of the arsine catalyst of polyethylene load is minimum can be to 0.05mol%.And in reaction, under room temperature condition, load arsine catalyst does not substantially dissolve in some solvents, and while rising to reaction temperature, catalyst can well dissolve, reaction is homogeneous system, and end reaction is while finishing to be down to room temperature, catalyst can be realized easily and the separating of reaction system, therefore can realize homogeneous reaction, out-phase is separated, thereby realizes easily the recycling of catalyst and reduce residual in product of arsine catalyst.The catalyst activity reclaimed can retain, and catalytic activity can at least be retained to the 10th and take turns.
The accompanying drawing explanation
Fig. 1 is the nmr analysis figure of embodiment 3 supported catalysts PE-1.Result shows As mole of insertion rate 6.5%.
Fig. 2 is the nmr analysis figure of embodiment 4 supported catalysts PE-2.Result shows As mole of insertion rate 0.3%.
Specific implementation method:
Following example has shown not ipsilateral of the present invention, and given data comprise the synthetic of catalyst, the application of catalyst in the Wittig reaction.Unless stated otherwise, reaction is all carried out under nitrogen or argon atmospher.Raw material and solvent are all used the standard method purification process.Institute responds and all uses thin layer silica gel chromatogram tracking, the High Performance Thin Layer Chromatography silica gel plate that uses the Yantai chemical institute to produce, and ultraviolet, iodine cylinder or potassium permanganate colour developing, rapid column chromatography carries out on silica gel H, and eluant, eluent is benzinum and ethyl acetate.In experiment, institute's serviceability temperature meter is not calibrated, 1h NMR and 13c NMR, at Varian EM-300, measures on Varian EM-400 and Bruker DPX-300 type NMR.Infrared spectrum is by measuring on Bio Rad FTS-185 type infrared spectrum analyser.Conventional mass spectrum is measured on HP-5958A type mass spectrograph.Elementary analysis is measured by Shanghai analysis center of organic institute.High polymer, by the alliance-GPC-2000 gel permeation chrommatograph, is usingd polystyrene as the standard sample determining molecular weight.Fe (Tcpp) Cl quality is by the weighing of ten thousand/balance (0.00001g).Polyolefin catalyst is according to document ZL02110844.7, ZL01126323.7, disclosed method preparation in 200610025918.7,200610026765.8,200610026766.2,200710045131.1.
Embodiment 1: the preparation of the different monooctyl ester of acetoacetate:
Sodium acetate (0.369g, 4.5mmol) join in the there-necked flask that air exhaust head and constant pressure funnel are housed, add ketene dimer (7.56g after substituting gas 3 times, 90mmol) and acetonitrile (50.0mL), cryosel is bathed and is cooled to-5 ℃, then by constant pressure funnel, adds isooctanol (11.7g, 90mmol), stir 3 as a child, rise to room temperature, stirring is spent the night.TLC stops reaction after following the tracks of the raw material disappearance.Add water and the extraction of ether separatory, collect diethyl ether solution, wash 2 times, after saturated common salt washing once, anhydrous magnesium sulfate drying spends the night, and after concentrating, is directly used in next step reaction.
Add the different monooctyl ester of back gained acetoacetate and acetonitrile (250mL) in 500mL egg type bottle, ice bath stirred after 15 minutes, add triethylamine (18.9mL, 135mmol), then add methylsulfonyl nitrine (15g, 124.8mmol), to react 30 minutes recession deicings and bathe, stirred overnight at room temperature is followed the tracks of and is reacted completely to TLC.Add the extraction of ether separatory, water merges diethyl ether solution after washing 2 times with ether, and anhydrous sodium sulfate drying concentrates and is directly used in next step reaction.
The different monooctyl ester of previous step gained diazonium acetoacetate is placed in 250mL egg type bottle, add sodium hydroxide solution (10%, 75mL) and diethyl ether solution (75mL), react after 3 days and stop reaction.Add water and the extraction of ether separatory, washing diethyl ether solution 2 times, anhydrous sodium sulfate drying after saturated common salt washing once, concentrated.Decompression distillation, obtain product 7.6g, and productive rate is 41%.
1H?NMR(300MHz，CDCl 3)δ4.68(s，1H)，4.02(d，J＝6.0Hz，2H)，1.52(m，1H)，1.34-1.18(m，6H)，0.834(m，6H).
Embodiment 2: arsine monomer synthetic
Figure BSA00000360964500112
Under condition of ice bath, by 10-hendecene-1-alcohol (11.6mL, 60mmol) and anhydrous pyridine (30mL) join in 100ml egg type bottle, after being uniformly mixed and dissolving each other, add paratoluensulfonyl chloride (13.75g, 72mmol), ice bath stirred after 6 hours, the TLC plate follow the tracks of to show fundamental reaction (PE: EA=6: 1, potassium permanganate colour developing) fully.Filter, add the 100ml ether in filtrate, with after 2N hydrochloric acid (100mL*4) washing diethyl ether solution.Anhydrous sodium sulphate, dry organic layer.Revolve most of ether, column chromatography for separation, solvent is PE: EA=10: 1, obtain product 15.26g, productive rate is 79%.
1H?NMR(300MHz，CDCl 3/TMS)：δ7.79(d，J＝7.8Hz，2H)，7.34(d，J＝8.4Hz，2H)，5.87-5.73(m，1H)，5.02-4.91(m，2H)，4.02(t，J＝6.3Hz，2H)，2.45(s，3H)，2.06-2.00(m，2H)，1.65-1.57(m，2H)，1.39-1.23(brs，12H)。
Ph 3As+Li→Ph 2AsLi
A 250mL there-necked flask is received on biexhaust pipe by an air exhaust head, the heating gun heating vacuumizes simultaneously, after cooling, change nitrogen, by triphenylarsine (21.49g, 70mmol) with cutting thin lithium bar, (kerosene soaks, 2.612g, 373.2mmol) join in there-necked flask, vacuumize, after changing nitrogen three times, cryosel adds oxolane (140mL) after bathing and being chilled to-14 ℃, stir after 1 hour, removing cryosel bathes, stirring at room 3 hours, double-ended needle is transferred in the 250mL cock bottle of substituting nitrogen, then slowly splash into tert-butyl chloride (7.6ml under ice bath, 70mmol), after stirring is spent the night, be directly used in next step reaction.
Install air exhaust head and constant pressure funnel additional on 250mL tri-neck round-bottomed flasks, the heating gun heating vacuumizes simultaneously, after cooling, changes nitrogen, by p-methyl benzenesulfonic acid 10-hendecene-1-ester (15.6g, 47mmol) join in there-necked flask, after displacement nitrogen three times, add oxolane (30ml), under ice bath is cooling, slowly splash into diphenyl arsine lithium (120ml) by constant pressure funnel, after stirring 17 hours 1h NMR follows the tracks of and shows that reaction is substantially complete.Oxolane is removed in decompression, adds carrene to filter, and with carrene, washes solid 3 times, combined dichloromethane solution, and after reduced pressure concentration, (eluent is PE: EA=20: 1), obtain product 14.51g, productive rate is 92% to column chromatography for separation.
1H?NMR(300MHz，CDCl 3/TMS)：δ7.45-7.40(m，4H)7.34-7.30(m，6H)，5.89-5.75(m，1H)，5.04-4.92(m，2H)，2.08-2.00(m，4H)，1.51-1.30(m，6H)，1.24(brs，8H)
Embodiment 3: the polyethylene support of arsine
The pretreatment of arsine monomer:
Add monomer (5.01g, 13.2mmol) in the cock bottle, after displacement nitrogen, add toluene (18ml), dry ice-propanone is bathed cooling, drips triisobutyl aluminium (4mL, 16mmol), is made into the solution of 0.5M, and stirring is spent the night, and naturally rises to room temperature.
The preparation of supported catalysts PE-1:
Figure BSA00000360964500122
Dry Schlenk bottle displacement ethylene gas three times.Flow down at ethylene gas, add toluene (70mL), control oil bath temperature and be 30 ℃ and stir 10 minutes, make solution reach assigned temperature and ethene is saturated.The arsine monomer (0.5M, 24mL) of triisobutyl aluminium protection, stir 2 minutes, adds co-catalyst (MMAO) (1.9M, 15.0mL), stirs 2 minutes.Add the toluene solution (3.5 μ mol/ml, 8.0mL) of metallic catalyst to start timing simultaneously.After polyase 13 0 minute, cut off rapidly the ethene air-flow, add 5% alcohol hydrochloric acid solution (5mL) cancellation polymerisation.Reactant mixture is poured in a large amount of 5% alcohol hydrochloric acid solution, under normal temperature, stirs and spends the night.Filter successively and wash with 5% alcohol hydrochloric acid solution and ethanol, collect high polymer, in 50 ℃ of vacuum drying 24 hours.Obtain product 4.60g, M n6000 g/mols, As mole of insertion rate 6.5%.
Embodiment 4
The preparation of supported catalysts PE-2:
The autoclave displacement nitrogen of high temperature drying three times.Under stream of nitrogen gas, add arsine monomer (0.5M, 24mL), co-catalyst (MMAO) (1.9M, 15.0mL) and polyolefin catalyst 1 structure of toluene (75mL), triisobutyl aluminium protection to be
Figure BSA00000360964500132
toluene solution (3.5 μ mol/ml, 8.0mL), controlling oil bath temperature is 30 ℃, passes into high-pressure ethylene (1.1Mpa), makes solution reach assigned temperature and ethene is saturated.Start timing, polymerization, after 1 hour, is cut off rapidly the ethene air-flow simultaneously, adds 5% alcohol hydrochloric acid solution (3mL) cancellation polymerisation.Reactant mixture is poured in a large amount of 5% alcohol hydrochloric acid solution, under normal temperature, stirs and spends the night.Filter successively and wash with 5% alcohol hydrochloric acid solution and ethanol, collect high polymer, in 50 ℃ of vacuum drying 24 hours.Obtain product 4.1g, M nbe 8000 g/mols, mole insertion rate of arsine is 0.3mol%.
Prepared after the same method PE-3, PE-4:
Figure BSA00000360964500141
The aldehyde of embodiment 5:PE-1 catalysis and the reaction of ethyl diazoacetate
Figure BSA00000360964500142
General operation: Fe (Tcpp) Cl (four rubigan porphyrin iron chloride) (63mg, 0.07mmol), the PE-1 of catalytic amount, aldehyde (30mmol) join in the Schlenk bottle, add PMHS (hydrogen containing siloxane) (2.5mL after displacement nitrogen 3 times, 39mmol), then add toluene (20mL), be warming up to 80 ℃, take ethyl diazoacetate (5.6g, 48mmol) be dissolved in toluene (10mL), with syringe pump, the toluene solution of the ethyl diazoacetate for preparing be added drop-wise to (8h) in reaction system. 1h NMR stops reaction, the evaporating column chromatography after following the tracks of and reacting completely.
Synthesizing of E-3-(4-chlorphenyl) ethyl acrylate (3a)
Figure BSA00000360964500143
PE-1(0.5mol％)。Productive rate: 97%.E/Z＞99/1. 1H?NMR(300MHz，CDCl 3/TMS)：δ7.62(d，J＝16.5Hz，1H)，7.46-7.43(m，2H)，7.36-7.33(m，2H)，6.40(d，J＝16.0Hz，1H)，4.26(q，J＝7.2Hz，2H)，1.33(t，J＝6.9Hz，3H).
Synthesizing of E-3-(4-bromophenyl) ethyl acrylate (3b)
Figure BSA00000360964500151
PE-1(0.1mol％)。Productive rate: 94%.E/Z＞99/1. 1H?NMR(300MHz，CDCl 3/TMS)：δ7.63(d，J＝16.0Hz，1H)，7.53-7.50(m，2H)，7.40-7.37(m，2H)，6.43(d，J＝16.0Hz，1H)，4.27(q，J＝7.2Hz，2H)，1.34(t，J＝7.2Hz，3H).
Synthesizing of E-3-ethyl phenylacrylate (3c)
Figure BSA00000360964500152
PE-1(0.8mol％)。Productive rate: 92%.E/Z＞99/1. 1H?NMR(300MHz，CDCl 3/TMS)：，δ7.64(d，J＝16.0Hz，1H)，7.50-7.46(m，2H)，7.35-7.32(m，3H)，6.39(d，J＝16.0Hz，1H)，4.22(q，J＝7.2Hz，2H)，1.29(t，J＝7.2Hz，3H).
Synthesizing of E-3-(4-nitrobenzophenone) ethyl acrylate (3d)
Figure BSA00000360964500153
PE-1(0.3mol％)。Productive rate: 97%.E/Z＞99/1. 1H?NMR(300MHz，CDCl 3/TMS)：δ8.26(d，J＝9.0Hz，2H)，7.75-7.67(m，3H)，6.57(d，J＝16.0Hz，1H)，4.31(q，J＝7.1Hz，2H)，1.36(t，J＝7.2Hz，3H).
Synthesizing of E-3-(4-cyano-phenyl) ethyl acrylate (3e)
Figure BSA00000360964500154
PE-1(0.03mol％)。Productive rate: 97%.E/Z＞99/1. 1H?NMR(300MHz，CDCl 3/TMS)：δ7.71-7.60(m，5H)，6.53(d，J＝16.2Hz，1H)，4.29(q，J＝7.2Hz，2H)，1.35(t，J?＝7.2Hz，3H).
Synthesizing of E-3-(4-trifluoromethyl) ethyl acrylate (3f)
Figure BSA00000360964500161
PE-1(0.01mol％)。Productive rate: 95%.E/Z＞99/1. 1H?NMR(300MHz，CDCl 3/TMS)：δ＝7.70(d，J＝16.0Hz，1H)，7.64-7.61(m，4H)，6.52(d，J＝16.0Hz，1H)，4.22(q，J＝7.1Hz，2H)，1.35(t，J＝7.2Hz，3H). 19F?NMR(300MHz，CDCl 3/TMS)：，δ-63.3.
Synthesizing of E-3-(4-methoxyphenyl) ethyl acrylate (3g)
PE-1(0.03mol％)。Productive rate: 97%.E/Z＞99/1. 1H?NMR(300MHz，CDCl 3/TMS)：δ7.66(d，J＝16.0Hz，1H)，7.47(d，J＝12.0Hz，2H)，6.90(d，J＝8.4Hz，2H)，6.33(d，J＝15.6Hz，1H)，4.26(q，J＝7.1Hz，2H)，3.82(s，3H)，1.34(t，J＝6.9Hz，3H).
Synthesizing of E-3-(3-chlorphenyl) ethyl acrylate (3h)
Figure BSA00000360964500163
PE-1(0.03mol％)。Productive rate: 97%.E/Z＞99/1. 1H?NMR(300MHz，CDCl3/TMS)：?δ7.61(d，J＝16.5Hz，1H)，7.51(s，1H)，7.40-7.06(m，3H)，6.43(d，J＝15.9Hz，1H)，4.27(q，J＝7.1Hz，2H)，1.34(t，J＝7.3Hz，3H).
Synthesizing of E-3-(3-nitrobenzophenone) ethyl acrylate (3i)
Figure BSA00000360964500171
PE-1(0.03mol％)。Productive rate: 97%.E/Z＞99/1. 1H?NMR(300MHz，CDCl 3/TMS)：δ8.37(s，1H)，8.24-8.20(m，1H)，7.82(d，J＝8.4Hz，1H)，7.71(d，J＝16.2Hz，1H)，7.57(t，J＝7.8Hz，1H)，6.55(d，J＝15.9Hz，1H)，4.28(q，J＝7.1Hz，2H)，1.34(t，J＝7.3Hz，3H).
Synthesizing of E-3-(2-aminomethyl phenyl) ethyl acrylate (3j)
Figure BSA00000360964500172
PE-1(0.8mol％)。Productive rate: 98%.E/Z＞99/1. 1H?NMR(300MHz，CDCl3/TMS)：δ＝8.00(d，J＝16.0Hz，1H)，7.58-7.55(m，1H)，7.30-7.20(m，3H)，6.38(d，J＝16.0Hz，1H)，4.29(q，J＝7.2Hz，2H)，2.46(s，3H)，1.36(t，J＝7.3Hz，3H).
Synthesizing of E-3-(2-nitrobenzophenone) ethyl acrylate (3k)
Figure BSA00000360964500173
PE-1(0.8mol％)。Productive rate: 98%.E/Z＞99/1. 1H?NMR(300MHz，CDCl3/TMS)：δ8.14-8.04(m，2H)，7.67-7.63(m，2H)，7.58-7.52(m，1H)，6.37(d，J＝16.0Hz，?1H)，4.30(q，J＝7.2Hz，2H)，1.34(t，J＝7.3Hz，3H).
Synthesizing of E-3-(2,4-dichlorophenyl) ethyl acrylate (3l)
PE-1(0.8mol％)。Productive rate: 90%.E/Z>99/1. 1h NMR (300MHz, CDCl 3/ TMS): δ 8.02 (d, J=16.0Hz, 1H), 7.55 (d, J=8.4Hz, 1H), 7.44 (s, 1H), 6.41 (d, J=16.0Hz, 1H), 4.28 (q, J=7.1Hz, 2H), 1.34 (t, J=6.6Hz, 3H).
Synthesizing of E-3-(2,6-dichlorophenyl) ethyl acrylate (3m)
Figure BSA00000360964500182
PE-1(0.8mol％)。Productive rate: 94%.E/Z>99/1. 1h NMR (300MHz, CDCl 3/ TMS): δ 7.80 (d, J=16.0Hz, 1H), 7.36 (d, J=6.6Hz, 2H), (7.20 t, J=6.6Hz, 1H), 6.60 (d, J=16.2Hz, 1H), (4.30 q, J=7.2Hz, 2H), 1.36 (t, J=6.9Hz, 3H).
Synthesizing of E-3-(2-furyl) ethyl acrylate (3n)
Figure BSA00000360964500183
PE-1(0.8mol％)。Productive rate: 91%.E/Z>99/1. 1h NMR (300MHz, CDCl 3/ TMS): δ 7.49-7.41 (m, 2H), 6.62-6.61 (m, 1H), 6.48-6.46 (m, 1H), 6.33 (d, J=15.9Hz, 1H), 4.25 (q, J=7.2Hz, 2H), 1.33 (t, J=7.2Hz, 3H).
Synthesizing of E-3-(2-naphthyl) ethyl acrylate (3o)
Figure BSA00000360964500191
PE-1(0.8mol％)。Productive rate: 94%.E/Z>99/1. 1h NMR (300MHz, CDCl 3/ TMS): δ 8.54 (d, J=15.9Hz, 1H), 7.92-7.87 (m, 2H), 7.78-7.76 (m, 1H), 7.61-7.47 (m, 4H), 6.54 (d, J=15.6Hz, 1H), (4.33 q, J=7.2Hz, 2H), 1.39 (t, J=6.9Hz, 3H).
Synthesizing of E-5-(phenyl) penta-2-olefin(e) acid ethyl ester (3p)
Figure BSA00000360964500192
PE-1(0.8mol％)。Productive rate: 95%.E/Z>99/1. 1h NMR (300MHz, CDCl 3/ TMS): δ 7.23-7.08 (m, 4H), 6.97-6.77 (m, 1H), 5.79-5.73 (m, 1H), (4.09 q, J=7.2Hz, 2H), 2.68 (t, J=7.2Hz, 3H), (2.47-2.39 m, 2H), 1.19 (t, J=7.2Hz, 3H).
Synthesizing of E-3-cyclohexyl-ethyl acrylate (3q)
Figure BSA00000360964500193
PE-1(0.8mol％)。Productive rate: 91%.E/Z>99/1. 1h NMR (300MHz, CDCl 3/ TMS): δ 6.92 (dd, J=6.9,15.8Hz, 1H), 5.77 (dd, J=15.8,1.0Hz, 1H), 4.19 (q, J=7.1Hz, 2H), 2.20-2.15 (m, 1H), 1.78-1.64 (m, 4H), 1.36-1.12 (m, 9H).
Synthesizing of E-2-decylenic acid ethyl ester (3r)
Figure BSA00000360964500194
PE-1(0.8mol％)。Productive rate: 92%.E/Z>99/1. 1h NMR (300MHz, CDCl 3/ TMS): δ 7.03-6.92 (m, 1H), 5.82 (dt, J=15.6,1.0Hz, 1H), 4.19 (q, J=7.1 Hz, 2H), 2.24-2.16 (m, 2H); (1.51-1.27 m, 13H), 0.89 (t, J=6.9Hz, 3H).
The E-6-phenoxy group oneself-2-olefin(e) acid ethyl ester (3s) synthetic
Figure BSA00000360964500201
PE-1(0.8mol％)。Productive rate: 91%.E/Z>99/1. 1h NMR (400MHz, CDCl 3/ TMS): δ 7.38-6.29 (m, 5H), 7.02-6.94 (m, 1H), (5.84 d, J=15.6Hz, 1H), 4.52 (s, 2H), 4.20 (q, J=7.2Hz, 2H), (3.51 t, J=6.0Hz, 2H), 2.33 (q, J=7.2Hz, 2H), 1.82-1.75 (m, 2H), (1.30 q, J=7.2Hz, 3H).
(E) synthesizing of-3-(4-(2,2-dimethyl-1,3-dioxolane)) ethyl acrylate (3t)
Figure BSA00000360964500202
PE-1(0.8mol％)。Productive rate: 86%.E/Z>99/1.ee value is measured (OJ hand-type post, isopropyl alcohol/n-hexane=98/2,0.7mL/min, 230nm by HPLC; t r(major)=13.78min, t r(minor)=13.78min) 95%ee, 1h NMR (300MHz, CDCl 3/ TMS): δ 6.88 (dd, J=15.6,6.0Hz, 1H), (6.10 d, J=16.2Hz, 1H), 4.67 (dd, J=15.6,5.7Hz, 1H), 4.25-4.17 (m, 3H), 3.68 (t, J=7.8Hz, 1H), (1.45 s, 3H), 1.41 (s, 3H), (1.30 q, J=6.9Hz, 3H).
3u's is synthetic
Figure BSA00000360964500203
The ee pH-value determination pH of 3u is measured (AD hand-type post, isopropyl alcohol/n-hexane=98/2,0.7mL/min, 230nm by HPLC; t r(major)=7.73min, t r(minor)=8.68min) 86%ee, productive rate: 89%.E/Z>99/1.ee value is measured (AD hand-type post, isopropyl alcohol/n-hexane=98/2,0.7mL/min, 230nm by HPLC; t r(major)=40.53min, t r(minor)=29.63min) 86%ee, 1h NMR (300MHz, CDCl 3/ TMS): δ 6.91-6.80 (m, 1H), 5.99-5.87 (m, 1H), 4.59-4.40 (m, 1H), 4.26-4.08 (m, 3H), 3.81 (dd, J=9.0,2.1Hz, 1H), 1.67-1.25 (m, 18H).
3v's is synthetic
Figure BSA00000360964500211
Productive rate: 92%.E/Z>99/1. 1h NMR (300MHz, CDCl 3/ TMS): δ 7.48-7.28 (m, 5H), 6.86-6.84 (m, 2H), 5.97 (d, J=15.0Hz, 1H), 4.22 (q, J=7.2Hz, 2H), 1.30 (q, J=7.2Hz, 3H).
The ketone of embodiment 6:PE-1 catalysis and the reaction of ethyl diazoacetate
Figure BSA00000360964500212
General operation: Fe (Tcpp) Cl (four rubigan porphyrin iron chloride) (6.3mg, 0.007mmol), PE-1, ketone (3.0mmol) join in the Schlenk bottle, add PMHS (hydrogen containing siloxane) (250.0 μ L after displacement nitrogen 3 times, 3.9mmol), then add toluene (2.0mL), be warming up to 80 ℃, take ethyl diazoacetate (0.56g, 4.8mmol) be dissolved in toluene (1.0mL), with syringe pump, the toluene solution of the ethyl diazoacetate for preparing is added drop-wise in reaction system. 1hNMR stops reaction, the evaporating column chromatography after following the tracks of and reacting completely.
5a's is synthetic:
Figure BSA00000360964500221
Polymer arsine consumption (20mg, 0.8mol%), time for adding: 8h, productive rate: 96%.E/Z>99/1. 1h NMR (300MHz, CDCl 3/ TMS): δ 7.43-7.26 (m, 5H), 6.61 (m, 1H), 4.04 (q, J=7.2Hz, 2H), 1.06 (q, J=7.2Hz, 3H). 19F?NMR(300MHz，CDCl 3/TMS)：δ＝-68.0.
5b's is synthetic:
Polymer arsine consumption (50mg, 2.0mol%), time for adding: 12h, productive rate: 92%. 1h NMR (300MHz, CDCl 3/ TMS): δ 5.60 (s, 1H), 4.14 (q, J=7.1Hz, 2H), 2.84-2.81 (m, 2H), 2.21-2.17 (m, 2H), 1.67-1.61 (m, 6H), 1.27 (q, J=7.2Hz, 3H).
5c's is synthetic:
Figure BSA00000360964500223
Polymer arsine consumption (50mg, 2.0mol%), time for adding: 12h, productive rate: 91%. 1h NMR (300MHz, CDCl 3/ TMS): δ 5.68 (s, 1H), 4.14 (q, J=7.1Hz, 1H), 3.79-3.72 (m, 4H), 3.00 (t, J=5.4Hz, 2H), 3.32 (t, J=5.4Hz, 2H), 1.27 (q, J=7.2Hz, 3H).
5d's is synthetic:
Polymer arsine consumption (50mg, 2.0mol%), time for adding: 12h, productive rate: 92%. 1h NMR (400MHz, CDCl 3/ TMS): δ 5.81 (s, 1H), 4.16 (q, J=7.2Hz, 2H), 2.80-2.76 (m, 2H), 2.47-2.43 (m, 2H), 1.78-1.65 (m, 4H), 1.29 (q, J=7.2Hz, 3H).
5e's is synthetic:
Figure BSA00000360964500231
Polymer arsine consumption (50mg, 2.0mol%), diazonium consumption 2.0 equivalents, time for adding: 24h, productive rate: 87%.E/Z=7/1. (E): 1h NMR (400MHz, CDCl 3/ TMS): δ 7.42-7.39 (m, 2H), 7.02-6.98 (m, 2H), 6.04 (s, 1H), 4.16 (q, J=7.2Hz, 2H), 2.50 (s, 3H), 1.25 (t, J=7.2Hz, 3H). 19f NMR (400MHz, CDCl 3/ TMS): δ-117.3
5f's is synthetic:
Polymer arsine consumption (125mg, 5.0mol%), diazonium consumption 3.0 equivalents, time for adding: 24h, productive rate: 82%. 1h NMR (300MHz, CDCl 3/ TMS): δ 7.39-7.20 (m, 10H), 6.37 (s, 1H), 4.06 (q, J=7.2Hz, 2H), 1.11 (t, J=7.2Hz, 3H).
5h's is synthetic:
Figure BSA00000360964500233
Polymer arsine consumption (50mg, 2.0mol%), diazonium consumption 2.0 equivalents, time for adding: 12h, productive rate: 90%.E/Z=1.7/1. (E): 1h NMR (300MHz, CDCl 3/ TMS): δ 5.9-5.75 (m, 1H), 5.67 (s, 1H), 5.08-4.96 (m, 2H), (4.15 q, J=7.2Hz, 2H), 2.24 (br, 4H), (2.17 s, 3H), 1.28 (t, J=7.2Hz, 3H). (Z): 1h NMR (300MHz, CDCl 3/ TMS): δ 5.9-5.75 (m, 1H), 5.67 (s, 1H), 5.08-4.96 (m, 2H), 4.14 (q, J=7.2Hz, 2H), 2.72 (t, J=7.2Hz, 2H), 2.24 (br, 2H), 1.90 (s, 3H), 1.27 (t, J=7.2Hz, 3H).
5i's is synthetic:
Figure BSA00000360964500241
Polymer arsine consumption (50mg, 2.0mol%), diazonium consumption 1.5 equivalents, time for adding: 12h, productive rate: 88%.E/Z=1.3/1.2Z, the 4E isomers: 1h NMR (300MHz, CDCl 3): δ 8.43 (d, J=16.2Hz, 1H), (7.52-7.55 m, 2H), 7.24-7.36 (m, 3H), 6.90 (d, J=16.2Hz, 1H), (5.75 s, 1H), 4.19 (q, J=7.2Hz, 2H), 2.11 (d, J=1.2Hz, 3H), 1.30 (t, J=7.2Hz, 3H); 2E, the 4E isomers: 1h NMR (300M Hz, CDCl 3): δ 7.45-7.48 (m, 2H), 7.26-7.38 (m, 3H), (6.94 d, J=16.2Hz, 1H), 6.81 (d, J=16.2,3Hz, 1H), 5.91 (s, 1H), 4.19 (q, J=7.2Hz, 2H), (2.41 d, J=1.5Hz, 3H), (1.31 t, J=7.2Hz, 3H).
The aldehyde ketone of embodiment 7:PE-1 catalysis and the reaction of diazobenzene ethyl ketone
Figure BSA00000360964500242
General operation: Fe (Tcpp) Cl (four rubigan porphyrin iron chloride) (6.3mg, 0.007mmol), PE-1, aldehyde (3.0mmol) join in the Schlenk bottle, add PMHS (hydrogen containing siloxane) (250.0 μ L after displacement nitrogen 3 times, 3.9mmol), then add toluene (2.0mL), be warming up to 80 ℃, take diazobenzene ethyl ketone (0.513g, 4.5mmol) be dissolved in toluene (1.0mL), with syringe pump, the toluene solution of the diazobenzene ethyl ketone for preparing is added drop-wise to (8h) in reaction system. 1h NMR stops reaction, the evaporating column chromatography after following the tracks of and reacting completely.
7a's is synthetic:
Figure BSA00000360964500251
Polymer arsine consumption (20mg, 0.8mol%), time for adding: 8h, productive rate: 96%.Z/E>99: 1, 1h NMR (300MHz, CDCl 3/ TMS): δ 8.03 (d, J=6.9Hz, 2H), 7.77 (d, J=16.0Hz, 1H), 7.61-7.50 (m, 6H), 7.41 (d, J=8.1Hz, 2H).
7b's is synthetic:
Polymer arsine consumption (20mg, 0.8mol%), time for adding: 8h, productive rate: 92%.Z/E>99: 1, 1h NMR (300MHz, CDCl 3/ TMS): δ 7.95-7.92 (m, 2H), 7.59-7.45 (m, 3H), 7.13-7.03 (m, 1H), (6.88 d, J=15.6Hz, 1H), (2.32 q, J=7.1Hz, 2H), (1.56-1.48 m, 2H), 1.36-1.32 (m, 4H), 0.93-0.88 (m, 3H).
7c's is synthetic:
Figure BSA00000360964500253
Polymer arsine consumption (50mg, 2.0mol%), time for adding: 12h, productive rate: 93%. 1h NMR (300MHz, CDCl 3/ TMS): δ 7.96-7.94 (m, 2H), 7.59-7.45 (m, 3H), 6.73 (s, 1H), (3.86 t, J=5.4Hz, 2H), 3.78 (q, J=5.4Hz, 2H), (3.00 t, J=5.4Hz, 2H), 2.47 (q, J=5.4Hz, 2H).
7d's is synthetic:
Figure BSA00000360964500261
Polymer arsine consumption (20mg, 0.8mol%), time for adding: 8h, productive rate: 91%. 1h NMR (300MHz, CDCl 3/ TMS): δ 7.84-7.81 (m, 4H), 7.59-7.51 (m, 3H), 7.44-7.38 (m, 4H). 19f NMR (300MHz, CDCl 3/ TMS): δ=-66.6.
The aldehyde ketone of embodiment 8:PE-1 catalysis and the reaction of diazonium propionic ester
Figure BSA00000360964500262
General operation: Fe (Tcpp) Cl (four rubigan porphyrin iron chloride) (6.3mg, 0.007mmol), PE-1, aldehyde (3.0mmol) join in the schlenk bottle, add PMHS (hydrogen containing siloxane) (250.0 μ L after displacement nitrogen 3 times, 3.9mmol), then add toluene (2.0mL), be warming up to 80 ℃, take the diazonium ethyl propionate and be dissolved in toluene (1.0mL), with syringe pump, the toluene solution of the diazobenzene ethyl ketone for preparing is added drop-wise to (8h) in reaction system.1HNMR stops reaction, the evaporating column chromatography after following the tracks of and reacting completely.
9a's is synthetic:
Figure BSA00000360964500263
Polymer arsine consumption (20mg, 0.8mol%), time for adding: 8h, productive rate: 91%.Z/E>99: 1, 1h NMR (300MHz, CDCl 3/ TMS): δ 7.63 (s, 1H), 7.39-7.31 (m, 4H), 4.28 (q, J=7.0Hz, 2H), 2.10 (s, 3H), 1.36 (t, J=7.2Hz, 3H).
9b's is synthetic:
Figure BSA00000360964500271
Polymer arsine consumption (20mg, 0.8mol%), time for adding: 8h, productive rate: 90%.Z/E=4.4: 1, 1h NMR (300MHz, CDCl 3/ TMS): δ 6.76 (dt, J=7.2,1.2Hz, 1H), 4.19 (q, J=7.0Hz, 2H), 2.16 (q, J=7.0Hz, 2H), 1.83 (s, 3H), 1.51-1.20 (m, 9H), 0.92-0.87 (m, 3H).
9c's is synthetic:
Figure BSA00000360964500272
Polymer arsine consumption (50mg, 2.0mol%), time for adding: 8h, productive rate: 91%. 1h NMR (300MHz, CDCl 3/ TMS): δ 4.19 (q, J=7.2Hz, 2H), 3.75-3.67 (m, 4H), 2.68-3.65 (m, 2H), 2.39-3.35 (m, 2H), 1.87 (s, 3H), 1.31 (t, J=7.2Hz, 3H).
9d's is synthetic:
Figure BSA00000360964500273
Polymer arsine consumption (20mg, 0.8mol%), time for adding: 8h, productive rate: 91%.Z/E=17/1. 1h NMR (300MHz, CDCl 3/ TMS): δ 7.29-7.14 (m, 5H), 3.81 (q, J=6.9Hz, 2H), 2.18 (m, 3H), 0.76 (t, J=7.2Hz, 3H).
9e's is synthetic:
Figure BSA00000360964500281
Polymer arsine consumption (50mg, 2.0mol%), time for adding: 8h, productive rate: 91%. 1h NMR (300MHz, CDCl 3/ TMS): δ 4.19 (q, J=7.2Hz, 2H), 2.42 (m, 2H), 2.21 (m, 2H), 1.86 (s, 3H), 1.59 (brs, 6H), 1.29 (t, J=7.2Hz, 3H).
The different monooctyl ester of diazoacetic acid of embodiment 9:PE-1 catalysis and the reaction of P-methoxybenzal-dehyde
Figure BSA00000360964500282
General operation: Fe (TcPP) Cl (6.3mg, 0.007mmol), PE-1 (20mg, 0.024mmol), 2g (506mg, 3.0mmol) join in the Schlenk bottle, add PMHS (hydrogen containing siloxane) (250.0 μ L after displacement nitrogen 3 times, 3.9mmol), then add toluene (2.0mL), be warming up to 80 ℃, take the different monooctyl ester (0.95g of diazoacetic acid, 4.8mmol) be dissolved in toluene (1.0mL), with syringe pump, the toluene solution of the ethyl diazoacetate for preparing is added drop-wise in reaction system. 1hNMR stops reaction, the evaporating column chromatography after following the tracks of and reacting completely.
Figure BSA00000360964500283
Productive rate: 94%. 1h NMR (300MHz, CDCl 3/ TMS): δ 7.63 (d, J=16.0Hz, 1H), 7.48 (d, J=12.0Hz, 2H), 6.90 (d, J=8.7Hz, 2H), 6.31 (d, J=15.6Hz, 1H), (4.10 m, 2H), 3.83 (S, 3H), (1.64-1.61 br, 1H), 1.43-1.32 (m, 8H), 0.94-0.87 (m, 6H).
The ethyl diazoacetate of embodiment 10:0.05mol%PE-1 catalysis and the reaction of 2-naphthaldehyde
Figure BSA00000360964500291
Fe (Tcpp) Cl (four rubigan porphyrin iron chloride) (6.3mg, 0.007mmol), PE-1 (10mg, 0.012mmol), 2-naphthaldehyde (3.74g, 24.0mmol) join in the Schlenk bottle, add PMHS (hydrogen containing siloxane) (2.0mL) after displacement nitrogen 3 times, then add toluene (2.0mL), be warming up to 80 ℃, taking ethyl diazoacetate is dissolved in toluene (1.0mL), with syringe pump by the ethyl diazoacetate (5.50g prepared, toluene solution 48mmol) is added drop-wise in reaction system, the ethyl diazoacetate consumption is 2.0 equivalents, when time for adding is 56h, conversion ratio 92%, productive rate is 88%.
The ethyl diazoacetate of embodiment 11:PE-2 catalysis and the reaction of 4-chloro-benzaldehyde
Figure BSA00000360964500292
Because the dissolubility of PE-4 is poor, under 80 ℃ of conditions, PE-2 (200mg) can not be dissolved in toluene fully, and 90 ℃ of next can finely dissolvings, thereby we attempt 90 ℃ as reaction temperature.
Operation
Fe (Tcpp) Cl (four rubigan porphyrin iron chloride) (6.3mg, 0.007mmol), PE-2 (200mg, 0.012mmol), 4-chloro-benzaldehyde (420mg, 3.0mmol) join in the schlenk bottle, add PMHS (hydrogen containing siloxane) (250 μ L) after displacement nitrogen 3 times, then add toluene (2.0mL), be warming up to 80 ℃, taking ethyl diazoacetate is dissolved in toluene (1.0mL), with syringe pump by the ethyl diazoacetate (0.56g prepared, 4.8mmol) toluene solution be added drop-wise in reaction system 1h NMR follows the tracks of and calculates conversion ratio.Reaction is down to room temperature after finishing, and adds a small amount of benzinum to impel the high polymer sedimentation to form larger blocks of solid, then adds a little ethanol to dissolve the oxidation product of unreacted PMHS (hydrogen containing siloxane) and PMHS (hydrogen containing siloxane).After sedimentation 2 hours, syringe extracts the upper strata stillness of night, then adds benzinum to wash solid, and supernatant liquor is extracted in sedimentation, and reduce pressure and remove solvent in the polymer environment afterwards for 3 times like this, the clear liquid of getting before merging, the evaporating column chromatography obtains product.And the experiment for next round by polymer, application so repeatedly.
The EDA consumption is 1.5 equivalents, when time for adding is 18h, and conversion ratio>99%, productive rate 92%
Recovery experiment: the 1st takes turns: productive rate 92% E/Z>99/1
The 2nd takes turns productive rate 93% E/Z>99/1
The 3rd takes turns productive rate 93% E/Z>99/1
The 4th takes turns productive rate 90% E/Z>99/1
The 5th takes turns productive rate 95% E/Z>99/1.

Claims (6)

1. the synthetic method of the arsine catalyst of a polyethylene load, it is characterized in that catalyst synthetic be by
Figure FSB00001020575100011
obtain with ethylene copolymerization, be specially:
1)
Figure FSB00001020575100012
contact 1-72 hour in subzero 78 to 100 degree with the trialkylaluminium reagent of equivalent in organic solvent, obtain solution A; Described trialkylaluminium reagent is triethyl aluminum, triisobutyl aluminium or MAO;
2) A is added in organic solvent, passes into ethene in system, and pressure is 0.1-10MPa, then adds co-catalyst and ethylene rolymerization catalyst, under 0 ℃ to 100 ℃ condition, carries out polymerization; Described co-catalyst is MAO, triethyl aluminum or the diethyl aluminum chloride of MAO, modification; The mol ratio of described co-catalyst and ethylene rolymerization catalyst is 1-10000/1;
3) after polymerization completes, add acidifying ethanol cancellation reaction, filter to obtain described arsine catalyst after stirring;
Described organic solvent is halogenated hydrocarbons, varsol, ethyl acetate, oxolane or ethanol; Varsol is toluene, n-hexane, cyclohexane or normal heptane;
The structural formula of described arsine catalyst is as follows:
Figure FSB00001020575100013
Wherein, R 1, R 2the straight chain of C1-C20 or the alkyl that contains side chain or R 4the aromatic group replaced; The optional position of described aromatic group is individually or simultaneously by R 4group replaces, each R 4substituted radical is the alkyl with 1 to 10 carbon atom, the alkoxyl with 1 to 10 carbon atom or amido (R 3) 2n-, there is ester group, the CF of 1 to 10 carbon atom 3or halogen, substituted radical is identical or different;
R 3be the straight chain of C1-C7 or the alkyl that contains side chain or aromatic group, the optional position of described aromatic group is individually or simultaneously by R 5group replaces, each R 5substituted radical is the alkyl with 1 to 5 carbon atom, alkoxyl, the CF with 1 to 5 carbon atom 3or halogen, substituted radical is identical or different;
Described aromatic group is phenyl or naphthyl;
The molecular weight that the numerical value of X and y meets containing the arsine macromolecular compound is 2000-40000, and arsenic content is 0.1-15mol%;
N is 0 to 20 integer;
Described halogen is fluorine, chlorine, bromine or iodine.
2. the synthetic method of the arsine catalyst of polyethylene load as claimed in claim 1, is characterized in that described R 1, R 2the straight chain of C1-C10 or the alkyl that contains side chain or R 4the aromatic group replaced; The optional position of described aromatic group is individually or simultaneously by R 4group replaces, described R 4substituted radical is the alkyl with 1 to 5 carbon atom, the alkoxyl with 1 to 5 carbon atom or amido (R 3) 2n-, there is ester group, the CF of 1 to 5 carbon atom 3or halogen; Described arsenic content is 0.5-10mol%; N is 0 to 10 integer; R 3be the straight chain of C1-C7, the alkyl that contains side chain or phenyl, the optional position of described phenyl is individually or simultaneously by R 5group replaces.
3. the purposes of the arsine catalyst of the polyethylene load that method prepares as claimed in claim 1, is characterized in that described catalyst is for the synthetic olefin(e) compound of catalysis aldehydes or ketones Ylide reaction.
4. a purposes as claimed in claim 3, while it is characterized in that described catalyst for the synthetic olefin(e) compound of aldehydes or ketones, the mol ratio of this catalyst and aldehydes or ketones is 1: 0.01%.
5. a purposes as claimed in claim 3, is characterized in that described aldehyde is anisic aldehyde, and described catalyst and anisic aldehyde and diazonium acetate obtain sun-screening agent to Methoxycinnamate under Fe (Tcp) Cl effect; Described Fe (Tcp) Cl has following structural formula:
Figure FSB00001020575100021
, wherein, R=P-C 6h 4.
6. a purposes as claimed in claim 3, is characterized in that described catalyst repeatedly reclaims, and reuses.
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