CN1401667A - heterocyclic polymer-contg. carried palladium complex and use thereof in Heck reaction - Google Patents
heterocyclic polymer-contg. carried palladium complex and use thereof in Heck reaction Download PDFInfo
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- CN1401667A CN1401667A CN 02139082 CN02139082A CN1401667A CN 1401667 A CN1401667 A CN 1401667A CN 02139082 CN02139082 CN 02139082 CN 02139082 A CN02139082 A CN 02139082A CN 1401667 A CN1401667 A CN 1401667A
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Abstract
A heterocycle-containing high-molecular material carried metal Pd complex is prepared from polyacrylic nitrile as skeleton, grafting or cross-linking by imidazoline or oxazoline, and reacting with metal Pd salt. It can be used in Heck reaction with high catalyst efficiency, simple operation, cyclic use and no pollution.
Description
(1) technical field: the present invention relates to a kind of functional high-polymer loaded metal palladium complex, in more detail, what relate to macromolecule loading contains tetrahydroglyoxaline, oxazoline macromolecule metal palladium complex and the application in Heck reaction thereof.
(2) background technology: the organometallic complex catalyzer can show high-level efficiency and highly selective under mild conditions, but homogeneous catalyst is difficult to separate with product after reaction usually, reclaim and regeneration use difficulty, and when meeting water and air, easily decompose, easily adhere to reactor wall, very big to the corrodibility of equipment.
Polymer with functional group reacts with simple transition metal or its title complex under certain reaction conditions, the loaded catalyst that generates polymer binding metal complexes then can be avoided the shortcoming of above homogeneous catalyst, it have certain relative stability, operation simple, can reclaim and re-use and characteristics such as low production cost.Wohrle D has commented metal complexes and organic polymer has been mixed several method [Kaneko M with the macromolecule loading metal complexes that obtains to link to each other with macromolecular compound with the simple physics effect, Wohrle D (1988), Adv.Polym.Sci 84:141].
Other has a class is that palladium metal and polymer are the polymkeric substance (palladium metal is positioned on the high molecular main chain) of organic coordination.The shortcoming of these polymkeric substance is insoluble and infusibility (as four sulfosalt classes) [Reynolds J.R, Lillya C.P, Chen J.C.W91987] Macromol.20:1184; Schumater R.R, Engler E.M (1977), J.Am.Chem.Soc.99:5521; Tec B.K, Wudl F, Hauser J.J, Kruger A (1977) J.Am.Chem.Soc.99:4862].Obviously, this family macromolecule metal complexes is not only synthetic, purification difficult, and catalytic site is few in solvent, and it is less to be able to possibility of its application with catalyzer.
Also having a class is to be bonded to metal complexes on the polymer carrier by part or metal ion.As poly-SiO
2Palladium is reduced into simple substance [Pomogailo A.D, Klyuev M.V (1985) Izv Akad Nauk SSSR Ser Khim 1716] when-gr-(4-vinylpridine) and palladium salt formation title complex.Can also chain palladium metal ion [Freidlin LKH, Nazarova NM, Litvin EF.Annamuradova MA. (1978) Iza Akad Nauk SSSR, Ser Khim 2465] by the coordination of amide group on the polymer segment.
Also be to have done more research aspect the inorganic polymer metal palladium complex.PdCl
2With SiO
2The coordination of-gr-Polyvinyl carbazole is in conjunction with having formed a kind of inorganic polymer metal palladium complex [Yanzhu Z, YongjunLi, Lingzhi W, Yingyan J (1982) Fundamental reseach organomet.chem..Proc.China-Japan-U.S.Trilateral Semin.Peking, June 1980 N4:Beijing etc.P.77].Pd
2+Also can be at SiO
2The surface combines [Royer G.P, Wen-sheiung Chow, Hatton K.S. (1985) J.Mol.Catal 31:1] with the PEI coordination.In addition, on the magnesia powder behind the loaded metal palladium thing, at 60 ℃ of palladium catalysts [Kiyotomi K, Masoto H, and Toshinobu I, J.Moleular Catalysis, 63 (1990), L33] that obtain at high temperature to react use with hydrogen reducing.
The mixed type macromolecule ligand seldom uses, have only vinylformic acid and-or right-divinyl benzene copolymer grafted SiO
2With PdCl
2And H
2PtCl
6Bonding [Xiang-Yao Guo, Hui-Juan Zong, Yong-Jun Li, Ying-Yan Jiang (1984) Makromol.Chem.Rapid Commum.5:507].
Jia C.G etc. has synthesized Pd-PAN (polyacrylonitrile) catalyzer that palladium directly links to each other with itrile group: nitrogen palladium ratio is 20,60 ℃ were reacted 4 hours, and each palladium and two itrile group coordinations are co-catalyst then with the cupric chloride, the catalysis formoxy-changes into and is ketone, has recycled 5 times and still can obtain 100% yield.[Jia?C.G，Jin?F.Y，Pan?H.Q，Macromol.Chem.Phys.1994，195(9)，751]。Also have with Palladous chloride immobilized to cyanogen on the polyimide PI-CN, be co-catalyst with the cupric chloride equally, can be recycled 6 times [Ahn J.H, SherringtonD.C, Macromolecules, 1996,29 (11)].The polybenzimidazole of Palladous chloride and cyanomethylation is reacted, palladium still links to each other with itrile group nitrogen with coordinate bond, this kind catalyzer need be co-catalyst with the cupric chloride still, but when comparatively high temps (120 ℃), still have advantages of high catalytic activity, recycle [Tang H.G, Sherrington D.C, Polymer 7 times, 1993,34 (13) 2821].
Being that the macromolecule loading palladium complex of carrier is existing many with the polystyrene is applied to various organic reactions.[Bruner?H，Bailar?J.C.Jr，Inorg.Chem.1973，12，1465；Piffman?C.U.Jr，Wuu?S.K，JacobsonS.E，J.Catal.1976，44，87]?。
The examples of many successful that palladium metal is carried on the various polymer carriers has a lot, but their not only synthetic difficulties, and the overwhelming majority all contains phosphino-.[Kaneda?K，Kurosaki?H，Terasawa?M，Imanaka?T，Ternish?S，J.Org.Chem.1981，46，2356][Trost?B.M，Warner?R.W，J.Am.Chem.Soc.1982，104，6112][Berghreiter?D.E，Chen?B，Lynch?T.J，J.Org.Chem.1983，48，4179][Kaneda?K，Terasawa?M，Imanaka?T，Teranash?S，J.organomet.Chem.1978，162，403][Anderson?C.M，Karablas?K，Hallberg?A，J.Org.Chem.1985，50，3891][Trost?B.M，Keinen?E，J.Am.Chem.Soc.1978，22，7779][Anderson?Honwen?H，Kao?T.Y，Synthesis?1991，539][Kaneda?K，Kurasaki?H，Terasawa?M，Imanaka?T，Teranish?S，J.Catalysis?1978，51，406][Pittman?C.U，Quoch?N，J.Organomet.Chem.1978，539][Larsson?R，J.Catalysis，1983，81，179][Su-Bum?Jang，Tetrahedron?Letter，1997，38，1793][Su-Bum?Jang，Tetrahedron?Letter，1997，38，4421]
Macromolecule loading palladium catalyst described in the notification number CN1064477 (being used for the synthetic organic acid of normal pressure carbonylation) need to add a certain amount of alkali metal hydroxide, and polymer carrier (PVPd, PPO, PSu, PPA etc.) cost is higher relatively.Macromolecule loading palladium catalyst described in the notification number CN1094022 (being used for hydrodehalogenation) is a solubility, and is also unfavorable to the aftertreatment of reaction, and only contains a kind of ligating atom (N), and catalytic activity point is less.Catalyzer among the notification number CN1289759 (being used for carbonylation reaction), not only raw material (PVPd) cost is higher, needs bimetal catalysis altogether, also contains environmentally harmful phosphine class material.Catalyzer among notification number CN1146984 and the CN1151908 then just is impregnated into palladium on the matrix material of inorganics silicon-dioxide, though can make catalyzer when relatively-high temperature, its synthesis step is many, and also needs co-catalyst.The synthesis step that these catalyzer have is many, cost is higher, also needs co-catalyst, and what have contains environmentally harmful phosphine class material.
(3) summary of the invention: in order to overcome the deficiency of present macromolecule loading palladium catalyst, the invention provides that a kind of catalytic efficiency height, synthesis material are easy to get, operation is easy and can be repeatedly used, do not contain again phosphine pollution-free, environment-friendly type, contain heterocyclic polymer loaded metal palladium complex and the application in the Heck reaction thereof.
Technical scheme of the present invention realizes in the following manner: a kind of heterocyclic polymer loaded metal palladium complex that contains, it is by the preparation of following raw material and step: (A) by the general goods polyacrylonitrile be skeleton, (B) through the tetrahydroglyoxaline grafting or crosslinked, (C) form macromolecule loading metal palladium complex (being designated hereinafter simply as first kind of macromolecule loading metal palladium complex of the present invention) with the palladium metal reactant salt.Palladium salt is palladium, Palladous chloride, Palladous chloride lithium.
Technical scheme of the present invention can also following manner realize: a kind of heterocyclic polymer loaded metal palladium complex that contains, it is prepared by following raw material and step: be skeleton by the general goods polyacrylonitrile (A), (B) through the tetrahydroglyoxaline grafting or crosslinked after, (C) grafting Shang oxazoline coordinating group again, (D) tetrahydroglyoxaline in institute's grafting is with/Huo oxazoline and palladium reactant salt form macromolecule metal palladium complex (being designated hereinafter simply as second kind of macromolecule loading metal palladium complex of the present invention).
Palladium salt is palladium, Palladous chloride, Palladous chloride lithium.
Technical scheme of the present invention can also realize by following manner: a kind of heterocyclic polymer loaded metal palladium complex that contains, it is prepared by following raw material and step: be skeleton by the general goods polyacrylonitrile (A), (B) through the tetrahydroglyoxaline grafting or crosslinked after, (C) the part itrile group is hydrolyzed into carboxyl or its esters, and (D) tetrahydroglyoxaline in institute's grafting and/or carboxyl and palladium reactant salt form macromolecule metal palladium complex (being designated hereinafter simply as the third macromolecule loading metal palladium complex of the present invention).
Palladium salt is palladium, Palladous chloride, Palladous chloride lithium.
Technical scheme of the present invention can also realize by following manner: be skeleton by the general goods polyacrylonitrile (A), (B) through the tetrahydroglyoxaline grafting or crosslinked after, (C) oxazoline coordinating group in the grafting again, (D) the part itrile group is hydrolyzed into carboxyl or its esters, and (E) tetrahydroglyoxaline in institute's grafting is with/Huo oxazoline and carboxyl or its esters and palladium reactant salt form macromolecule metal palladium complex (being designated hereinafter simply as the 4th kind of macromolecule loading metal palladium complex of the present invention).
The hydrolysis salt is ammonium salt, sodium salt; Palladium salt is that palladium, Palladous chloride reach, the Palladous chloride lithium.
Grafting or crosslinked tetrahydroglyoxaline are to be solvent with ethylene glycol or other many alcohol, obtain with the polyamines polyene reaction at 100 ℃ at least, and the ratio of polyacrylonitrile and polyamines polyene is in 1: 5, and grafting and crosslinking rate are good with 10-45%.
Polyamines polyene be quadrol, diethylenetriamine, triethylene tetramine, tetraethylene pentamine with or their mixture.
The other factors that forms the macromolecule metal palladium complex has following several:
In first kind of macromolecule loading metal palladium complex of the present invention, tetrahydroglyoxaline grafting and crosslinking rate are 1% when following, because of coordinating group few, carrying capacity to palladium is very poor, when tetrahydroglyoxaline grafting and crosslinking rate greater than 45% the time, it is very hard and crisp that macromolecular material becomes, mechanical property is subjected to havoc, though it is the coordination carrying capacity to palladium is very strong, inadvisable because of having a strong impact on its reusability.So, the grafting of tetrahydroglyoxaline or crosslinking rate with in the 10-45% scope for well, be best with 20-30%.
In the factor that influences grafting or crosslinking rate, the Temperature Influence maximum, below 100 ℃ the time, reaction is carried out very slowly, and more than 150 ℃ the time, reaction is carried out too soon.So this be reflected at 100-150 ℃ down reaction 2-3 hour for well.
The adding of ethylene glycol is to be purpose to disperse polyamines polyene to impel the formation of tetrahydroglyoxaline ring and dissolving by product ammonia.When no ethylene glycol solvent, polyamines polyene is grafted to the ratio that macromolecular material gets on the non-crosslinked chain will be increased greatly, and the product catalytically inactive (comparative example 2) after chain polyamines polyene class and the coordination of palladium chelating.Ethylene glycol more than 1: 2, was good with 1: 1 to 5: 1 o'clock to the add-on of amine.
Palladium, Palladous chloride or Palladous chloride lithium should at room temperature carry out with the polymer carrier reaction that contains the tetrahydroglyoxaline part.Water can produce bigger disadvantageous effect to reaction, makes the hydrolysis and running off before coordination reaction takes place of palladium salt.In general general solvent, the solvability of palladium salt is all not so good, and methyl alcohol to the dissolving power of palladium salt still can, and cost is low, toxicity forms for a short time and is first-selection.(as refluxing in the methyl alcohol) palladium formed stopping property title complex prevention internal layer functional group rapidly at polymer surface and participates in coordination when temperature of reaction was high, and palladium only stockpiles on the surface like this, and its stability reduces, and it is serious to run off when repeated use and washing.And speed slows down when room temperature reaction, the not only dentate and the palladium coordination on surface in the polymer carrier, and the dentate of internal layer has also participated in coordination reaction after swelling, so palladium more firmly is combined on the macromolecular material, helps its regeneration and use.The coordination ratio of tetrahydroglyoxaline dentate and palladium should be best at 2: 1 to 1: 2 in the scope.
In second kind of macromolecule loading metal palladium complex, because of macromolecular material also needs oxazoline group in the grafting, so the grafting of tetrahydroglyoxaline and crosslinkedly should control lowlyer.The grafting of tetrahydroglyoxaline and crosslinking reaction are with first kind of polymer carrier, but tetrahydroglyoxaline grafting and crosslinking rate are good with 10-20%.When being reflected at 120 ℃, the reaction times was best with 2 hours.Jie Zhi oxazoline is that exsiccant grafting and the crosslinked macromolecular material of crossing tetrahydroglyoxaline are soaked in the thanomin, gets 50-130 ℃ of reaction 0.5-2 hour.The operation steps of graft reaction is the same with crosslinked tetrahydroglyoxaline with grafting.But need not to add solvent, the ammonia that reaction produces can be removed with the dilute hydrochloric acid neutralization.The mechanical property that temperature of reaction is too high, overlong time all can have a strong impact on macromolecular material was best with 110-115 ℃, 1 hour.The method of calculation of oxazoline percentage of grafting are the percentage of grafting method of calculation of tetrahydroglyoxaline roughly the same, and percentage of grafting for well, is the best with 40% with 10-100%.Tetrahydroglyoxaline Yu the ratio of oxazoline (mol ratio, down with) between 1: 3 to 3: 1, when cooperating (load) palladium, reaction conditions is the load-reaction of first kind of macromolecular material roughly the same, but at lesser temps and the long period cooperates the amount of palladium can be more.Because of there being a large amount of Sauerstoffatoms to be grafted on the macromolecular material, not only the polymer chain flexibility is improved, if the grafting amount is too big, also can cause macromolecular material to be partly dissolved.Because of oxygen give the electronics coordination ability very strong, so this material carries out manyly than first kind of macromolecular material when the coordination palladium easily, at room temperature placing spends the night get final product most of product.When coordination (load) was reacted, tetrahydroglyoxaline was Yu the proportioning of oxazoline sum and palladium metal is between 2: 1 to 1: 2.
In the third high sub-loaded metal palladium complex of the present invention, in the hydrolysis carboxyl so that obtain to be similar to the catalytic activity point of simple small molecules palladium.Small molecules palladium itself has catalytic activity to Heck reaction, and the structure that can generate similar palladium that combines of the carboxyl of macromolecule loading or its esters and palladium salt, the palladium compound of this structure can react with tetrahydroglyoxaline palladium thing concerted catalysis Heck.Do not add other acid or alkaline catalysts during itrile group hydrolysis in the present invention, only the alkalescence of the tetrahydroglyoxaline that generates to some extent gets final product.Hydrolysis degree should be controlled very for a short time, and water-soluble fine because of hydrolysate can be caused a large amount of losses when washing.So the add-on of water should be in the 1-5% scope, with 2% for well.Hydrolysis can be adopted one kettle way, i.e. grafting need not to separate after eating the azoles quinoline, directly adds required water gaging to reaction system again.Tetrahydroglyoxaline grafting before the hydrolysis can be the same with first kind of polymer carrier with crosslinking rate, also can be low slightly, can keep physical strength preferably 20% with interior.The carboxyl of tetrahydroglyoxaline and itrile group hydrolysis or the ratio of its salt are between 2: 1 to 1: 2, when coordination (load) is reacted, they together and the proportioning of palladium metal be between 2: 1 to 1: 2.
In the 4th kind of macromolecule loading metal palladium complex of the present invention, in the same hydrolysis carboxyl so that obtain to be similar to the structure of simple small molecules palladium.The present invention is to be characteristics with the tetrahydroglyoxaline palladium Wu, oxazoline palladium thing that synthesizes many catalytic activity points to greatest extent and carboxylic acid palladium.The catalysis Heck reaction more efficiently of the synergy of many catalytic activity points.Grafting of the present invention and crosslinked tetrahydroglyoxaline are in 15%, and Jie Zhi oxazoline is in 30%.Amount of water in the 1-5% scope, with 2% for well.The ratio of tetrahydroglyoxaline, oxazoline, carboxyl or its salt is between 1: 1: 1 to 2: 6: 1.They together and the proportioning of palladium metal be between 2: 1 to 1: 2.
The coordination of functionalized macromolecular material and palladium salt or load-reaction are to carry out between room temperature to 65 ℃ (boiling point of methyl alcohol).Coordination reaction need not to stir, but can intermittently shake.
(4) description of drawings:
Fig. 1 is the synthetic synoptic diagram of four kinds of polymer carriers (I, II, III, IV).
Fig. 2 is four kinds of macromolecule loading metal palladium complex structural representations.
A is that SEM photo, B behind the loaded metal palladium are polymer carrier IISEM photo among Fig. 3.
(5) embodiment:
Reach comparative example by the following examples and illustrate in greater detail the present invention.When not being particularly limited among the embodiment, the ratio of reactive material is a mass ratio, and tetrahydroglyoxaline, oxazoline percentage of grafting or content calculate by heavy method of difference and volumetry, and the itrile group hydrolysis can not be calculated by the heavy method of difference because of being partly dissolved, and only controls with the water yield that adds.Palladium content is respectively by heavy method of difference and aas determination.SEM photo TMS-2 sem observation, shooting.IR measures on the PE580B infrared spectrometer.The TG collection of illustrative plates obtains on PE TG one 2 hot analytical balances.The tensile strength of fiber and elongation are by GB GB/T14335-93, and the method for GB/T14337-93 regulation is measured on INSTRON4465 type universal testing machine.
Tetrahydroglyoxaline is Ji the oxazoline assay
Tetrahydroglyoxaline is Ji oxazoline formation synoptic diagram is as follows:
Scheme 1 tetrahydroglyoxaline, oxazoline forms synoptic diagram
Through the tetrahydroglyoxaline grafting and crosslinked after PAN by and treatment process like the polyamines response class and thanomin react, can get the carrier of Jie Zhi oxazoline.
The calculating of tetrahydroglyoxaline content: 1, the heavy method of difference: calculate the amount of institute's grafted tetrahydroglyoxaline according to the weight difference of macromolecular material before and after the graft reaction, it is as follows to calculate general formula:
X: tetrahydroglyoxaline content (mmol/g), W: reaction back polymer carrier quality (mg), W
0: PAN quality (mg) before the reaction, Mi: the molecular weight of tetrahydroglyoxaline, Mn: the molecular weight of itrile group.2, volumetry: the polymer carrier of the grafting of certain mass W being crossed tetrahydroglyoxaline is soaked in certain volume and concentration (N
1V
1) acidic solution in, after the soaked overnight, the soak solution that extracts part is with standard NaOH solution (N
2V
2) titration is to neutral.Be calculated as follows tetrahydroglyoxaline content:
C: tetrahydroglyoxaline content (mmol/g), N
1V
1Acid concentration of soak-out material (N) and volume (ml), N
2V
2: concentration of standard alkali lye (N) and volume (ml), W be by the quality of soak-out material (g), V: extract the volume (ml) of part soak solution, 2: the number of N atom in the tetrahydroglyoxaline.
Tetrahydroglyoxaline grafting and crosslinking rate are calculated as follows:
I%: tetrahydroglyoxaline grafting and crosslinking rate, W: reaction back polymer carrier quality (mg), W
0: PAN quality (mg) before the reaction.
Oxazoline is measured the method with tetrahydroglyoxaline.
With add a certain proportion of water in the oxazoline afterreaction system, can generate carboxylic carrier at grafting and crosslinked tetrahydroglyoxaline simultaneously.
The itrile group hydrolysis is calculated by adding the water yield:
N%: itrile group degree of hydrolysis, W: reaction back polymer carrier quality (mg), Mn: the molecular weight of itrile group, Mw: the molecular weight of water, Ww: the quality of adding (mg).
Synthetic vectors: the PAN of certain mass is joined in polyamines, ethylene glycol or the thanomin in ratio shown in the table 1, be warming up to design temperature, behind the insulation certain hour, added a certain amount of water stoichiometric number again ten minutes, then PAN is pulled out (leaching), squeeze only, immerse again in the deionized water, through soaking-squeeze till clean-infusion showing neutrality to the aqueous solution for several times.Weigh after pulling oven dry out, calculate grafting and crosslinking rate.
Table 1, embodiment 1-8: contain the synthetic of coordinating group polymer carrier
| Sequence number | ????PAN | Polyamines 4 | ???Glycol | Thanomin | Water 3 | Temperature ℃ 1 | Time h 1 | Product (carrier) | Heterocycle content 1-2??(mmol/g) |
| ??1 | 1 (fiber) | ??15 | ??10 | ??0 | ?0 | ??120 | ??2 | ??(I) | ??1.85 |
| ??2 | 1 (fiber) | ??15 | ??20 | ??20 | ??0 | ??120/115 | ??2/0.5 | ??(III) | ??1.70/1.57 |
| ??3 | 1 (fiber) | ??15 | ??20 | ??0 | ??0.01 | ??130 | ??1.5 | ??(II) | ??1.66 |
| ??4 | 1 (fiber) | ??15 | ??20 | ??30 | ??0.02 | ??120/120 | ??1/1 | ??(IV) | ??1.52/2.10 |
| ??5 | 1 (cloth) | ??5 | ??20 | ??0 | ??0.05 | ??130 | ??1.5 | ??(II) | ??1.62 |
| ??6 | 1 (rope yarn) | ??10 | ??15 | ??25 | ??0 | ??135 | ??1.5/1.5 | ??(III) | ??2.02/3.0 |
| ??7 | 1 (fiber) | ??20 | ??10 | ??40 | ??0.05 | ??120/110 | ??1/2 | ??(IV) | ??1.65/2.76 |
| ??8 | 1 (fiber) | ??5 | ??20 | ??35 | ??0 | ??115/110 | ??3/1 | ??(II) | ??1.69/2.33 |
1: "/" preceding to be the relevant data of grafting tetrahydroglyoxaline, the relevant data of back Shi Jie Zhi oxazoline.
2: be the volumetry income value.
3: hydrolysis and grafting heterocycle can carry out simultaneously.
4:1-6 number is triethylene tetramine, and 7-8 number is quadrol.
The loaded metal palladium: a certain amount of polymer carrier is soaked in the palladium salts solution, after the reaction of specified reaction conditions finishes in the table 2, product is leached, when embathing, product constant weight colourless with methyl alcohol repeatedly to solution till.Weigh after the vacuum-drying, survey palladium content.
Table 2, embodiment 9-14 macromolecule loading metal complexes (PSMC) synthetic
| Sequence number | Carrier | C PdCl2/methol | Temperature ℃ | Time h | Product | Pd content mmol/g |
| ?9 | (I) | Saturated solution | 25 | ?24 | ?PSMC-1 | ?0.78 |
| ?10 | (II) | 0.1g/l | 65 | ?3 | ?PSMC-2 | ?0.23 |
| ?11 | (III) | Saturated solution | 25 | ?24 | ?PSMC-3 | ?1.43 |
| ?12 | (IV) | Saturated solution | 25 | ?24 | ?PSMC-4 | ?1.84 |
| ?13 | (II) | Saturated solution | 25 | ?76 | ?PSMC-2a | ?1.04 |
| ?14 | (II) | Saturated solution | 65 | ?2 | ?PSMC-2b | ?0.82 |
Table 3, comparative example 1-3
Embodiment 15-18: the application of catalyzer in the Heck reaction.
| Sequence number | Part | C PdCl2/methol | Temperature ℃ | Time h | Product | Pd content mmol/g |
| ?1 | The PAN raw material | Saturated solution | 65 | ?2 | Do not have | 0 |
| ?2 | Triethylene tetramine | Full sharp solution | 25 | ?1 | ?MC-1 | 3.01 |
| ?3 | Tetrahydroglyoxaline | Full sharp solution | 25 | ?1 | ?MC-2 | 3.1 |
Palladium complex in above-mentioned macromolecule loading palladium complex and the comparative example is applied in the following reaction,
Gained result such as table 4, step is as follows:
With ArI, acrylate, triethylamine and palladium-containing catalyst in 1: 1.2: 1.2: the ratio of 1% (mol ratio) joins 1, and in the 4-dioxane solvent, reflux 8 hours is crossed silica-gel plate and isolated product, and vacuum is drained the back calculated yield.Products therefrom all reaches through ultimate analysis
1H-NMR test back is transconfiguration (J=16Hz of two protons in two keys).
Table 4, embodiment 15-18, catalysis Heck reaction result
A: be separation yield (pressing ArI calculates).B: the basic free of losses of catalyzer when reusing 20 times, yield still can reach＞and 99%.
| Sequence number | Catalyzer | Catalyst levels mol% | Temperature ℃ | Time h | ?R | Yield % a |
| ?15 | ?PSMC-1 | ?1 | ?101 | ?8 | ?CO 2Me | ?＞99 |
| ?16 | ?PSMC-2 | ?1 | ?101 | ?8 | ?CO 2Me | ?100b |
| ?17 | ?PSMC-3 | ?1 | ?101 | ?8 | ?CONH 2 | ?＞84 |
| ?18 | ?PSMC-4 | ?1 | ?101 | ?8 | ?CONH 2 | ?93 |
Comparative example 4-5 has illustrated that the tetrahydroglyoxaline palladium complex is the catalytic activity point in the macromolecule load catalyst.And the palladium complex of simple polyamines polyene does not have catalytic activity.Just the same among reaction conditions in the comparative example and the embodiment.The result of comparative example is as shown in table 5.
Table 5, comparative example 4-5
1: be separation yield (pressing ArI calculates).
| Sequence number | Catalyzer | Catalyst levels mol% | Temperature ℃ | Time h | ?R | Yield %1 |
| ?4 | ?MC-1 | ?2 | ?101 | ?10 | ?CO 2Me | ?0 |
| ?5 | ?MC-2 | ?1 | ?101 | ?4 | ?CO 2Me | ?100 |
Claims (9)
1. macromolecule loading metal palladium complex, it be (A) to have general goods polyacrylonitrile material be skeleton, through (B) tetrahydroglyoxaline grafting or crosslinked, (C) with the macromolecule loading metal palladium complex of palladium metal salt formation.
2. macromolecule loading metal palladium complex according to claim 1, it is characterized in that the percentage of grafting of tetrahydroglyoxaline or degree of crosslinking between 1-150%, temperature of reaction is 100-150 ℃, palladium content is between 0.05-3.5mmol/g.
3. macromolecule loading metal palladium complex, it is to have polyacrylonitrile material skeleton by containing (A), earlier through (B) tetrahydroglyoxaline grafting or crosslinked after, reaction goes up that (C) oxazoline coordinating group, (D) tetrahydroglyoxaline is with the macromolecule loading metal palladium complex of at least a heterocycle and palladium salt formation in the oxazoline again.
4. macromolecule loading metal palladium complex according to claim 3, the percentage of grafting that it is characterized in that tetrahydroglyoxaline are between 1-50%, and temperature of reaction is 100-150 ℃.
5. macromolecule loading metal palladium complex according to claim 3, Qi Te are levied the percentage of grafting of Zai Yu oxazoline between 10-150%, and temperature of reaction is 100-150 ℃, and palladium content is between 0.05-3.5mmol/g.
6. according to claim 1 and 3 described macromolecule loading metal palladium complexes, it is characterized in that polyacrylonitrile can be fiber, rope yarn, fabric, non-woven fabric and other sheet material etc., the palladium salt that participates in reaction is palladium, Palladous chloride or Palladous chloride lithium.
7. according to claim 1 and 3 described macromolecule loading metal palladium complexes, it is characterized in that polyacrylonitrile be the carboxyl that partial hydrolysis forms of 1%-5% mass ratio or its ammonium salt, sodium salt, sylvite with and with the title complex of palladium salt formation.
8. be applied to catalysis Heck reaction according to claim 1,3 described macromolecule loading metal palladium complexes.
9. be applied to catalysis Heck reaction according to the described macromolecule loading metal palladium complex of claim 7.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 02139082 CN1200008C (en) | 2002-09-20 | 2002-09-20 | Heterocyclic polymer-contg. carried palladium complex and use thereof in Heck reaction |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 02139082 CN1200008C (en) | 2002-09-20 | 2002-09-20 | Heterocyclic polymer-contg. carried palladium complex and use thereof in Heck reaction |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1401667A true CN1401667A (en) | 2003-03-12 |
| CN1200008C CN1200008C (en) | 2005-05-04 |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101890367A (en) * | 2010-05-28 | 2010-11-24 | 绍兴文理学院 | IPN load palladium metal catalyst, preparation method and application thereof in catalytic Heck coupling reaction |
| CN116174038A (en) * | 2023-03-06 | 2023-05-30 | 华北理工大学 | Polyaza ligand palladium functionalized fiber and preparation method and application thereof |
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2002
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101890367A (en) * | 2010-05-28 | 2010-11-24 | 绍兴文理学院 | IPN load palladium metal catalyst, preparation method and application thereof in catalytic Heck coupling reaction |
| CN116174038A (en) * | 2023-03-06 | 2023-05-30 | 华北理工大学 | Polyaza ligand palladium functionalized fiber and preparation method and application thereof |
| CN116174038B (en) * | 2023-03-06 | 2023-09-19 | 华北理工大学 | Polyaza ligand palladium functionalized fiber and preparation method and application thereof |
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| CN1200008C (en) | 2005-05-04 |
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