CN103772444B - Divalent palladium coordination compound, conjugation arene compound and conjugation aromatic hydrocarbon polymer - Google Patents
Divalent palladium coordination compound, conjugation arene compound and conjugation aromatic hydrocarbon polymer Download PDFInfo
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Abstract
The invention provides a kind of divalent palladium coordination compound with formula (I), formula (II) or formula (III) structure and preparation method thereof.Present invention also offers conjugation arene compound with formula (IV) structure and preparation method thereof and the conjugation aromatic hydrocarbon polymer with formula (VI) structure and preparation method thereof.The present invention introduces the functional groups such as the alkyl of C1～C4, the alkoxyl of C1～C4, cyano group, nitro or aldehyde radical in aryl divalent palladium coordination compound, described aryl divalent palladium coordination compound is the most relatively stable, the most insensitive to oxygen and heat, coupling polymerization reaction can be carried out as catalyst AB type aromatic hydrocarbons and prepare conjugated aromatic polymer, make on the described conjugated aromatic polymer end of the chain containing described functional group；Conjugation aromatic compound containing described functional group can also be synthesized as reaction substrate and aromatic hydrocarbons.
Description
Technical field
The invention belongs to be conjugated aromatic hydrocarbon technical field, particularly relate to a kind of divalent palladium coordination compound, conjugation virtue
Fragrant hydrocarbon compound and conjugation aromatic hydrocarbon polymer.
Background technology
Conjugated polymer generally uses Pd (0) coordination compound or with the Pd (0) of Pd (II) compound in situ generation
Thing is the Suzuki coupling reaction synthesis of catalyst, and this synthetic method exists two problems: 1, Pd (0) urges
Agent is to oxygen, thermo-responsive, and inactivation forms palladium black the most in the reaction；2, the conjugated polymer structure of synthesis is not
Clearly, particularly functional group position and content is uncertain, can be difficult to by reactive group further in copolymer
Introduce and end group existing defects.
Activity chain type growth polymerization [okoyama A, Suzuki H, Kubota Y, Ohuchi K,
Higashimura H, Yokozawa T (2007) J Am Chem Soc23:7236-7237] it is applied to conjugation
Macroscopic single crystal can overcome drawbacks described above to a certain extent.In this polymerization process, in catalyst activity
The heart does not come off from high polymer main chain, but by " ring-walking " mechanism on conjugation aromatic rings
Shift and insert the carbon halogen bond of the monomer other end, form active end group and be polymerized further.This polymerization side
On the one hand method can be prepared and has the conjugated polymer that monodispersity, molecular weight are controlled, simultaneously it can be avoided that
Free catalytic active center produces and then is susceptible to precipitating metal element and the phenomenon that inactivates.But also
There are the following problems: the initiator 1, used is the unsaturated palladium compound of tri-butyl phosphine coordination, its
Poor stability, needs to use under harsh operating condition and store；2, due to the poor stability of initiator
It is difficult to introduce functional or there is the most reactive group.
Therefore, it is within the contemplation of the invention that synthesis contains functional group, stable, insensitive to oxygen and heat on aromatic ring
Divalent aryl palladium complex, further catalysis AB type aromatic monomer carries out coupling polymerization preparation each poly-
The compound end of the chain contains the conjugated polymer of above-mentioned functions group or reacts conjunction as reaction substrate and halogenated aryl hydrocarbon
Become the conjugation aromatic compound containing above-mentioned functions group.
Summary of the invention
In view of this, the technical problem to be solved in the present invention is to provide a kind of divalent palladium coordination compound, conjugation
Arene compound and conjugation aromatic hydrocarbon polymer, the divalent palladium coordination compound that the present invention provides contains function base
Group, it is possible to preparation contains conjugation arene compound or the conjugation aromatic hydrocarbon polymer of functional group.
The invention provides a kind of divalent palladium coordination compound with formula (I), formula (II) or formula (III) structure:
Wherein, Ar is aryl or polyaryl；
R is the alkyl of C1～C4, the alkoxyl of C1～C4, cyano group, nitro or aldehyde radical；
X is halogen.
Preferably, Ar is phenyl, xenyl or fluorenyl；X is bromine or iodine.
Present invention also offers a kind of conjugation arene compound with formula (IV) structure:
Ar1-Ar-R formula (IV)；
Wherein, Ar is aryl or polyaryl；
R is the alkyl of C1～C4, the alkoxyl of C1～C4, cyano group, nitro or aldehyde radical；
Ar1For aryl or polyaryl.
Preferably, described Ar is phenyl, xenyl or fluorenyl；Described Ar1For phenyl.
Present invention also offers the preparation method being conjugated arene compound described in technique scheme, bag
Include:
There is the divalent palladium coordination compound of formula (I) or formula (II) structure and the compound with formula V structure
Reaction, obtains being conjugated arene compound；
Wherein, Ar is aryl or polyaryl；
R is the alkyl of C1～C4, the alkoxyl of C1～C4, cyano group, nitro or aldehyde radical；
X is halogen；
Ar1For aryl or polyaryl.
Preferably, described divalent palladium coordination compound with the mol ratio of the compound with formula V structure is
1～2:1～2；The temperature of described reaction is 30 DEG C～80 DEG C, and the described response time is 1h～2h.
Present invention also offers a kind of conjugation aromatic hydrocarbon polymer with formula (VI) structure:
Wherein, Ar is aryl or polyaryl；
R is the alkyl of C1～C4, the alkoxyl of C1～C4, cyano group, nitro or aldehyde radical；
R2For hydrogen or halogen；
N is the degree of polymerization；
The number-average molecular weight of described conjugation aromatic hydrocarbon polymer is 5000～20000.
Preferably, described Ar is phenyl, xenyl or fluorenyl.
Present invention also offers the preparation side being conjugated aromatic hydrocarbon polymer described in a kind of technique scheme
Method, including:
The divalent palladium coordination compound with formula (III) structure reacts with the compound with formula (VII) structure,
Obtain being conjugated aromatic hydrocarbon polymer；
Wherein, Ar is aryl or polyaryl；
R is the alkyl of C1～C4, the alkoxyl of C1～C4, cyano group, nitro or aldehyde radical；
X is halogen.
Preferably, divalent palladium coordination compound with the mol ratio of the compound with formula (VII) structure is
0.005:0.1～10；The temperature of described reaction is room temperature～80 DEG C, and the described response time is 12h～24h.
Compared with prior art, the present invention introduce in aryl divalent palladium coordination compound C1～C4 alkyl,
The functional groups such as the alkoxyl of C1～C4, cyano group, nitro or aldehyde radical, described aryl divalent palladium coordination compound is not
The most relatively stable, the most insensitive to oxygen and heat, coupling can be carried out as catalyst AB type aromatic hydrocarbons and gather
Close reaction and prepare conjugated aromatic polymer, make on the described conjugated aromatic polymer end of the chain containing described function base
Group；Conjugation aromatic hydrocarbons chemical combination containing described functional group can also be synthesized as reaction substrate and aromatic hydrocarbons
Thing.Enable to be conjugated aromatic compound after introducing above-mentioned functions group or conjugated aromatic polymer has relatively
Good reactivity, thus the conjugation aromatic hydrocarbons chemical combination of stable performance is obtained by modified or further modification
Thing or conjugated aromatic polymer.It addition, the divalent palladium coordination compound with present invention offer carries out idol for catalyst
When joining polyreaction or react with aromatic hydrocarbons, it is possible to improve reaction condition, the step of simplification separating-purifying,
The product obtained has higher productivity.Idol is carried out for catalyst with the divalent palladium coordination compound that the present invention provides
The conjugated aromatic polymer end of the chain of connection polyreaction synthesis is functional group, compares traditional end-blocking mode,
Ensure that polymer each molecular backbone end of the chain is all blocked by this functional group, thus improve polymer
Performance.
Accompanying drawing explanation
Fig. 1 is the crystal structure schematic diagram of the divalent palladium coordination compound of the embodiment of the present invention 1 preparation；
Fig. 2 is the crystal structure schematic diagram of the divalent palladium coordination compound of the embodiment of the present invention 2 preparation；
Fig. 3 is the crystal structure schematic diagram of the divalent palladium coordination compound of the embodiment of the present invention 3 preparation；
Fig. 4 is the crystal structure schematic diagram of the divalent palladium coordination compound of the embodiment of the present invention 4 preparation；
Fig. 5 is the crystal structure schematic diagram of the divalent palladium coordination compound of the embodiment of the present invention 5 preparation；
Fig. 6 is the crystal structure schematic diagram of the divalent palladium coordination compound of the embodiment of the present invention 6 preparation；
Fig. 7 is the crystal structure schematic diagram of the divalent palladium coordination compound of the embodiment of the present invention 7 preparation；
Fig. 8 is the crystal structure schematic diagram of the divalent palladium coordination compound of the embodiment of the present invention 8 preparation；
Fig. 9 is the crystal structure schematic diagram of the divalent palladium coordination compound of the embodiment of the present invention 9 preparation；
Figure 10 is the crystal structure schematic diagram of the divalent palladium coordination compound of the embodiment of the present invention 10 preparation；
Figure 11 is the crystal structure schematic diagram of the divalent palladium coordination compound of the embodiment of the present invention 11 preparation；
Figure 12 is the crystal structure schematic diagram of the divalent palladium coordination compound of the embodiment of the present invention 13 preparation；
Figure 13 is the mass spectral analysis figure of the polyfluorene that the embodiment of the present invention 22 prepares；
Figure 14 is the mass spectral analysis figure of the polyfluorene that the embodiment of the present invention 23 prepares；
Figure 15 is the mass spectral analysis figure of the polyfluorene that the embodiment of the present invention 24 prepares；
Figure 16 is the mass spectral analysis figure of the polyfluorene that the embodiment of the present invention 25 prepares；
Figure 17 is the mass spectral analysis figure of the polyfluorene that the embodiment of the present invention 26 prepares；
Figure 18 is the mass spectral analysis figure of the polyfluorene that the embodiment of the present invention 27 prepares.
Detailed description of the invention
The invention provides a kind of divalent palladium coordination compound with formula (I), formula (II) or formula (III) structure:
Wherein, Ar is aryl or polyaryl；
R is the alkyl of C1～C4, the alkoxyl of C1～C4, cyano group, nitro or aldehyde radical；
X is halogen.
The divalent palladium coordination compound that the present invention provides can have formula (I), formula (II) or formula (III) structure,
Wherein, the divalent palladium coordination compound with formula (I) or formula (II) structure can be as reaction substrate and aromatic hydrocarbons
Conjugation aromatic compound containing described functional group is synthesized, there is the divalent palladium of formula (III) structure
Coordination compound can carry out coupling polymerization reaction preparation conjugation aromatic hydrocarbons polymerization as catalyst AB type aromatic hydrocarbons
Thing, makes on the described conjugated aromatic polymer end of the chain containing described functional group.
In the divalent palladium coordination compound that the present invention provides, Ar is aryl or polyaryl, preferably phenyl, connection
Phenyl or fluorenyl, more preferably phenyl.R be the alkyl of C1～C4, the alkoxyl of C1～C4, cyano group,
Nitro or aldehyde radical, preferably methyl, ethyl, butyl, methoxyl group, cyano group, nitro or aldehyde radical.X is
Halogen, preferably bromine or iodine.
The divalent palladium coordination compound that the present invention provides is plane quadrilateral structure, with Suzuki coupling reaction mechanism
(Norio Miyaura;Akira Suzuki;Chem Rev.1995,95,2457-2483.) proposed in bivalence
The molecular configuration that palladium intermediate product is had is consistent.
In the present invention, the divalent palladium coordination compound described in formula (I) structure is prepared in accordance with the following methods:
Four (triphenylphosphine) closes palladium (0) and has the halogenated aryl hydrocarbon of formula a structure and react in organic solvent,
Obtain the divalent palladium coordination compound with formula (I) structure；
R-Ar-X formula a；
In formula a, Ar is aryl or polyaryl；
R is the alkyl of C1～C4, the alkoxyl of C1～C4, cyano group, nitro or aldehyde radical；
X is halogen.
The reaction equation that four (triphenylphosphine) closes palladium (0) and the halogenated aryl hydrocarbon with formula a structure is as follows:
In above-mentioned course of reaction, organic solvent is preferably toluene, and four (triphenylphosphine) closes palladium (0) and tool
The mol ratio having the halogenated aryl hydrocarbon of formula a structure is preferably 1:5～10, and reaction temperature is preferably 60 DEG C～90 DEG C,
Response time is preferably 2h～5h.After completion of the reaction, remove organic solvent, use ether washing, then with two
After chloromethanes/Diethyl ether recrystallization, i.e. can obtain the divalent palladium coordination compound with formula (I) structure.
In the present invention, the divalent palladium coordination compound described in formula (II) structure is prepared in accordance with the following methods:
Four (cyclohexyl phosphine) closes palladium (0) and has the halogenated aryl hydrocarbon of formula a structure and react in organic solvent,
Obtain the divalent palladium coordination compound with formula (II) structure；
R-Ar-X formula a；
In formula a, Ar is aryl or polyaryl；
R is the alkyl of C1～C4, the alkoxyl of C1～C4, cyano group, nitro or aldehyde radical；
X is halogen.
The reaction equation that four (cyclohexyl phosphine) closes palladium (0) and the halogenated aryl hydrocarbon with formula a structure is as follows:
In above-mentioned course of reaction, organic solvent is preferably toluene, and four (cyclohexyl phosphine) closes palladium (0) and tool
The mol ratio having the halogenated aryl hydrocarbon of formula a structure is preferably 1:5～10, and reaction temperature is preferably 60 DEG C～90 DEG C,
Response time is preferably 2h～5h.After completion of the reaction, remove organic solvent, use ether washing, then with two
After chloromethanes/Diethyl ether recrystallization, i.e. can obtain the divalent palladium coordination compound with formula (II) structure.
Described four (cyclohexyl phosphine) closes palladium (0) and prepares the most in accordance with the following methods:
Palladium chloride and cyclohexyl phosphine react in organic solvent, add after hydrazine hydrate continues reaction and obtain
Closing palladium (0) to four (cyclohexyl phosphine), course of reaction is as follows:
In above-mentioned course of reaction, organic solvent be preferably toluene, palladium chloride and cyclohexyl phosphine mole
Ratio preferably 1:3～7, the reaction temperature of palladium chloride and cyclohexyl phosphine is preferably 100 DEG C～130 DEG C, reaction
Time is preferably 20min～40min；After completion of the reaction, add hydrazine hydrate, after continuing reaction, obtain four (rings
Hexyl phosphine) close palladium (0).
In the present invention, the divalent palladium coordination compound described in formula (III) structure is prepared in accordance with the following methods:
Two (three (o-methyl-phenyl-phosphine)) closes palladium (0) and has the halogenated aryl hydrocarbon of formula a structure at organic solvent
Middle reaction, obtains the divalent palladium coordination compound with formula (III) structure；
R-Ar-X formula a；
In formula a, Ar is aryl or polyaryl；
R is the alkyl of C1～C4, the alkoxyl of C1～C4, cyano group, nitro or aldehyde radical；
X is halogen.
Two (three (o-methyl-phenyl-phosphine)) closes palladium (0) with the reaction equation of the halogenated aryl hydrocarbon with formula a structure such as
Under:
In above-mentioned course of reaction, organic solvent is preferably toluene, and two (three (o-methyl-phenyl-phosphine)) closes
Palladium (0) is preferably 1:1～3 with the mol ratio of the halogenated aryl hydrocarbon with formula a structure, and the temperature of described reaction is preferred
For room temperature, the time of reaction is preferably 3h～8h.After completion of the reaction, remove organic solvent, use dichloromethane
After/normal hexane recrystallization, i.e. can obtain the divalent palladium coordination compound with formula (III) structure.
Wherein, described two (three (o-methyl-phenyl-phosphine)) conjunction palladium (0) can be prepared in accordance with the following methods:
Palladium chloride and three (o-methyl-phenyl-) phosphine react, and obtain two (three (o-methyl-phenyl-s)
Phosphine) palladium chloride；
Described two (three (o-methyl-phenyl-) phosphine) palladium chlorides and three (o-methyl-phenyl-) phosphine are at hydrogen-oxygen
Change and react under the effect of sodium and ethanol, generate two (three (o-methyl-phenyl-phosphine)) and close palladium (0).
The building-up process that two (three (o-methyl-phenyl-phosphine)) closes palladium (0) is as follows:
First palladium chloride is dissolved in acetonitrile, adds three (o-methyl-phenyl-) phosphines and acetone is carried out
Reaction, the temperature of described reaction is preferably room temperature, described palladium chloride and three (o-methyl-phenyl-) phosphine
Mol ratio is preferably 1:2～4；The acetonitrile solution of palladium chloride and the acetone soln of three (o-methyl-phenyl-) phosphine
After mixing, stirring reaction can form yellow transparent solution at ambient temperature, and generates lemon yellow solid,
The lemon yellow solid sucking filtration that will obtain, with washing with acetone, i.e. can get two pure (three (adjacent methyl
Phenyl) phosphine) palladium chloride.
Described two (three (o-methyl-phenyl-) phosphine) palladium chloride is dissolved in three (o-methyl-phenyl-) phosphine
In toluene solution, add under stirring condition in the solution of sodium hydroxide and dehydrated alcohol formation and react,
Obtain two (three (o-methyl-phenyl-phosphine)) close palladium (0), it is not necessary to carry out any post processing, can with there is formula
The halogenated aryl hydrocarbon of a structure reacts.Described two (three (o-methyl-phenyl-) phosphine) palladium chlorides and three (neighbours
Aminomethyl phenyl) reaction temperature of phosphine is preferably 80 DEG C～100 DEG C, and the response time is preferably 2h～8h, described
The mol ratio of two (three (o-methyl-phenyl-) phosphine) palladium chlorides and three (o-methyl-phenyl-) phosphine is preferably
1:0.7～1.2.
Present invention also offers a kind of conjugation arene compound with formula (IV) structure:
Ar1-Ar-R formula (IV)；
Wherein, Ar is aryl or polyaryl, preferably phenyl, xenyl or fluorenyl, more preferably phenyl；
R is the alkyl of C1～C4, the alkoxyl of C1～C4, cyano group, nitro or aldehyde radical, preferably methyl,
Ethyl, butyl, methoxyl group, cyano group, nitro or aldehyde radical；
Ar1For aryl or polyaryl, preferably phenyl, xenyl or fluorenyl, more preferably phenyl.
Containing functional group in the conjugation arene compound that the present invention provides, it is easy to modify.
Present invention also offers the preparation method being conjugated arene compound described in technique scheme, bag
Include:
There is the divalent palladium coordination compound of formula (I) or formula (II) structure and the compound with formula V structure
Reaction, obtains being conjugated arene compound；
Wherein, Ar is aryl or polyaryl；
R is the alkyl of C1～C4, the alkoxyl of C1～C4, cyano group, nitro or aldehyde radical；
X is halogen；
Ar1For aryl or polyaryl.
The divalent palladium coordination compound with formula (I) structure is anti-with what the compound with formula V structure reacted
Answer formula as follows:
The divalent palladium coordination compound with formula (II) structure is anti-with what the compound with formula V structure reacted
Answer formula as follows:
There is the divalent palladium coordination compound of formula (I) or formula (II) structure and the compound with formula V structure
Reacting in organic solvent under the effect of catalyst, wherein, described organic solvent can be toluene,
Catalyst includes solution of potassium carbonate and Aliguat336.The divalent palladium with formula (I) or formula (II) structure is joined
Compound is preferably 1～2:1～2, more preferably 1:1, instead with the mol ratio of the compound with formula V structure
Answering temperature to be preferably 30 DEG C～80 DEG C, more preferably 60 DEG C, the response time is preferably 1h～2h.React complete
After, the product obtained is carried out post separation, i.e. can obtain the conjugation fragrance with formula (IV) structure
Hydrocarbon compound, yield is 99%～100%.
Present invention also offers a kind of conjugation aromatic hydrocarbon polymer with formula (VI) structure:
Wherein, Ar is aryl or polyaryl, preferably phenyl, xenyl or fluorenyl, more preferably phenyl；
R is the alkyl of C1～C4, the alkoxyl of C1～C4, cyano group, nitro or aldehyde radical, preferably methyl,
Ethyl, butyl, methoxyl group, cyano group, nitro or aldehyde radical；
R2For hydrogen or halogen, preferably hydrogen or bromine；
N is the degree of polymerization；
The number-average molecular weight of described conjugation aromatic hydrocarbon polymer is 5000～20000, preferably 8000～12000.
Containing functional group in the conjugation aromatic hydrocarbon polymer that the present invention provides, it is easy to modify.
Present invention also offers the preparation side being conjugated aromatic hydrocarbon polymer described in a kind of technique scheme
Method, including:
The divalent palladium coordination compound with formula (III) structure reacts with the compound with formula (VII) structure,
Obtain being conjugated aromatic hydrocarbon polymer；
Wherein, Ar is aryl or polyaryl；
R is the alkyl of C1～C4, the alkoxyl of C1～C4, cyano group, nitro or aldehyde radical；
X is halogen.
As a example by X is as bromine, there is the divalent palladium coordination compound of formula (III) structure and there is formula (VII) structure
Compound reaction reaction equation as follows:
There is the divalent palladium coordination compound of formula (III) structure and there is the compound of formula V structure at catalyst
Effect under react in organic solvent, wherein, described organic solvent can be toluene, catalyst
Including solution of potassium carbonate and Aliguat336.There is the divalent palladium coordination compound of formula (III) structure and there is formula V
The mol ratio of the compound of structure is preferably 0.005:0.1～10, more preferably 0.005:0.2～5, reaction temperature
Being preferably room temperature～80 DEG C, more preferably 60 DEG C, the response time is preferably 12h～24h.After completion of the reaction,
The product obtained is settled, i.e. can obtain the conjugation aromatic hydrocarbon polymerization with formula (VI) structure
Thing, the number-average molecular weight of the polymer obtained is 5000～20000.
The present invention introduces the alkyl of C1～C4, the alkoxyl of C1～C4, cyanogen in aryl divalent palladium coordination compound
The functional groups such as base, nitro or aldehyde radical, described aryl divalent palladium coordination compound is the most relatively stable, to oxygen and
Heat is the most insensitive, can carry out coupling polymerization reaction preparation conjugation aromatic hydrocarbons as catalyst AB type aromatic hydrocarbons
Polymer, makes on the described conjugated aromatic polymer end of the chain containing described functional group；Can also be as reaction
Substrate and aromatic hydrocarbons are synthesized the conjugation aromatic compound containing described functional group.Introduce above-mentioned functions base
Enable to be conjugated aromatic compound after Tuan or conjugated aromatic polymer has preferable reactivity, thus
It is polymerized by modified or modification acquisition stable performance further conjugation aromatic compound or conjugation aromatic hydrocarbons
Thing.It addition, with the present invention provide divalent palladium coordination compound for catalyst carry out coupling polymerization reaction or with
During aromatic hydrocarbons reaction, it is possible to improving reaction condition, the step of simplification separating-purifying, the product obtained has relatively
High productivity.Carry out what coupling polymerization was synthesized with the divalent palladium coordination compound that the present invention provides for catalyst
The conjugated aromatic polymer end of the chain is functional group, compares traditional end-blocking mode, it is possible to ensure that polymer is every
The individual molecular backbone end of the chain is all blocked by this functional group, thus improves the performance of polymer.
In order to further illustrate the present invention, the divalent palladium coordination compound that the present invention provided below in conjunction with embodiment,
Conjugation aromatic compound and conjugated aromatic polymer are described in detail.
Embodiment 1
Under argon shield, 100mL Schlenk bottle adds 1.155g tetra-(triphenylphosphine) and closes palladium (0)
(Pd(PPh3)4) (1mmol), 7mmol parabromotoluene, 0.5246g triphenyl phosphorus (PPh3)(2mmol)
With 35mL toluene, electromagnetic agitation, react 4h at 85 DEG C, after temperature is down to room temperature, remove toluene,
Wash (3 × 10mL) with ether, drain and obtain white powder；White powder is heavily tied through dichloromethane/ether
Crystalline substance, obtains 0.448g clear crystal, and yield is 55.9%.
Being analyzed described clear crystal, result is as follows:
1H NMR(400MHz,CDCl3):δ7.52-7.47(m,12H,C6H5P),7.32-7.29(m,
6H,C6H5P),7.24-7.20(m,12H,C6H5P),6.43(d,2H,4-MeC6H4Pd,J=8.0Hz),
6.07(d,2H,4-MeC6H4Pd,J=7.6Hz),1.92(s,3H,4-CH3C6H4Pd).31P{1H}NMR
(162MHz,CDCl3):δ22.8。
It follows that described clear crystal is: (PPh3)2Pd(C6H4Me-4)Br。
Described clear crystal is carried out single crystal diffraction analysis, and it is the embodiment of the present invention that result sees Fig. 1, Fig. 1
The crystal structure schematic diagram of the divalent palladium coordination compound of 1 preparation.
Embodiment 2
Under argon shield, 100mL Schlenk bottle adds 1.155g tetra-(triphenylphosphine) and closes palladium (0)
(Pd(PPh3)4) (1mmol), 7mmol is to bromine ethylbenzene, 0.5246g triphenyl phosphorus (PPh3)(2mmol)
With 35mL toluene, electromagnetic agitation, react 4h at 85 DEG C, after temperature is down to room temperature, remove toluene,
Wash (3 × 10mL) with ether, drain and obtain white powder；White powder is heavily tied through dichloromethane/ether
Crystalline substance, obtains 0.461g clear crystal, and yield is 56.5%.
Being analyzed described clear crystal, result is as follows:
1H NMR(400MHz,CDCl3):δ7.52-7.47(m,12H,C6H5P),7.32-7.28(m,6H,
C6H5P),7.24-7.20(m,12H,C6H5P),6.47(d,2H,4-EtC6H4Pd,J=8.4Hz),6.09(d,
2H,4-EtC6H4Pd,J=7.6Hz),2.20(q,2H,CH3CH2C6H4Pd,J=7.6Hz),1.00(t,3H,
CH3CH2C6H4Pd,J=7.6Hz).31P{1H}NMR(162MHz,CDCl3):δ23.1.
It follows that described clear crystal is: (PPh3)2Pd(C6H4Et-4)Br。
Described clear crystal is carried out single crystal diffraction analysis, and it is the embodiment of the present invention that result sees Fig. 2, Fig. 2
The crystal structure schematic diagram of the divalent palladium coordination compound of 2 preparations.
Embodiment 3
Under argon shield, 100mL Schlenk bottle adds 1.155g tetra-(triphenylphosphine) and closes palladium (0)
(Pd(PPh3)4) (1mmol), 7mmol p-bromobenzaldehyde, 0.5246g triphenyl phosphorus (PPh3)(2mmol)
With 35mL toluene, electromagnetic agitation, react 4h at 85 DEG C, after temperature is down to room temperature, remove toluene,
Wash (3 × 10mL) with ether, drain and obtain white powder；White powder is heavily tied through dichloromethane/ether
Crystalline substance, obtains 0.487g clear crystal, and yield is 59.7%.
Being analyzed described clear crystal, result is as follows:
1H NMR(400MHz,CDCl3):δ9.51(s,1H,-CHO),7.55-7.50(m,12H,
C6H5P),7.34-7.30(m,6H,C6H5P),7.26-7.22(m,12H,C6H5P),6.90(d,2H,
4-CHOC6H4Pd,J=8.0Hz),6.65(d,2H,4-CHOC6H4Pd,J=8.0Hz).31P{1H}
NMR(162MHz,CDCl3):δ23.3.
It follows that described clear crystal is: (PPh3)2Pd(C6H4CHO-4)Br。
Described clear crystal is carried out single crystal diffraction analysis, and it is the embodiment of the present invention that result sees Fig. 3, Fig. 3
The crystal structure schematic diagram of the divalent palladium coordination compound of 3 preparations.
Embodiment 4
Under argon shield, 100mL Schlenk bottle adds 1.155g tetra-(triphenylphosphine) and closes palladium (0)
(Pd(PPh3)4) (1mmol), 7mmol is to Brominal, 0.5246g triphenyl phosphorus (PPh3)(2mmol)
With 35mL toluene, electromagnetic agitation, react 4h at 85 DEG C, after temperature is down to room temperature, remove toluene,
Wash (3 × 10mL) with ether, drain and obtain white powder；White powder is heavily tied through dichloromethane/ether
Crystalline substance, obtains 0.489g clear crystal, and yield is 60.1%.
Being analyzed described clear crystal, result is as follows:
1H NMR(400MHz,CDCl3):δ7.57-752(m,12H,C6H5P),7.40-7.36(m,6H,
C6H5P),7.31-7.27(m,12H,C6H5P),6.82(d,2H,4-CNC6H4Pd,J=8.4Hz),6.43
(d,2H,4-CNC6H4Pd,J=8.0Hz).31P{1H}NMR(162MHz,CDCl3):δ23.4.
It follows that described clear crystal is: (PPh3)2Pd(C6H4CN-4)Br。
Described clear crystal is carried out single crystal diffraction analysis, and it is the embodiment of the present invention that result sees Fig. 4, Fig. 4
The crystal structure schematic diagram of the divalent palladium coordination compound of 4 preparations.
Embodiment 5
Under argon shield, 100mL Schlenk bottle adds 1.155g tetra-(triphenylphosphine) and closes palladium (0)
(Pd(PPh3)4) (1mmol), 7mmol p-Nitrobromobenzene, 0.5246g triphenyl phosphorus (PPh3)(2mmol)
With 35mL toluene, electromagnetic agitation, react 4h at 85 DEG C, after temperature is down to room temperature, remove toluene,
Wash (3 × 10mL) with ether, drain and obtain white powder；White powder is heavily tied through dichloromethane/ether
Crystalline substance, obtains 0.554g clear crystal, and yield is 66.5%.
Being analyzed described clear crystal, result is as follows:
1H NMR(400MHz,CDCl3):δ7.57-752(m,12H,C6H5P),7.36-7.33(m,6H,
C6H5P),7.28-7.24(m,12H,C6H5P),7.00(d,2H,4-NO2C6H4Pd,J=8.4Hz),6.86
(d,2H,4-NO2C6H4Pd,J=8.0Hz).31P{1H}NMR(162MHz,CDCl3):δ23.2.
It follows that described clear crystal is: (PPh3)2Pd(C6H4NO2-4)Br。
Described clear crystal is carried out single crystal diffraction analysis, and it is the embodiment of the present invention that result sees Fig. 5, Fig. 5
The crystal structure schematic diagram of the divalent palladium coordination compound of 5 preparations.
Embodiment 6
Under argon shield, 100mL Schlenk bottle adds 1.155g tetra-(triphenylphosphine) and closes palladium (0)
(Pd(PPh3)4) (1mmol), 7mmol3-bromo nitrobenzene, 0.5246g triphenyl phosphorus (PPh3)(2mmol)
With 35mL toluene, electromagnetic agitation, react 4h at 85 DEG C, after temperature is down to room temperature, remove toluene,
Wash (3 × 10mL) with ether, drain and obtain white powder；White powder is heavily tied through dichloromethane/ether
Crystalline substance, obtains 0.510g clear crystal, and yield is 61.2%.
Being analyzed described clear crystal, result is as follows:
1H NMR(400MHz,CDCl3):δ7.58-7.53(m,12H,C6H5P),7.35-7.13(m,
21H,C6H5P and3-NO2C6H4Pd),6.39(t,1H,3-NO2C6H4Pd,J=7.6Hz).31P{1H}
NMR(162MHz,CDCl3):δ23.9.
It follows that described clear crystal is: (PPh3)2Pd(C6H4NO2-3)Br。
Described clear crystal is carried out single crystal diffraction analysis, and it is the embodiment of the present invention that result sees Fig. 6, Fig. 6
The crystal structure schematic diagram of the divalent palladium coordination compound of 6 preparations.
Embodiment 7
Under argon shield, 100mL Schlenk bottle adds 1.155g tetra-(triphenylphosphine) and closes palladium (0)
(Pd(PPh3)4) (1mmol), 7mmol2-bromo nitrobenzene, 0.5246g triphenyl phosphorus (PPh3)(2mmol)
With 35mL toluene, electromagnetic agitation, react 4h at 85 DEG C, after temperature is down to room temperature, remove toluene,
Wash (3 × 10mL) with ether, drain and obtain white powder；White powder is heavily tied through dichloromethane/ether
Crystalline substance, obtains 0.530g clear crystal, and yield is 63.6%.
Being analyzed described clear crystal, result is as follows:
1H NMR(400MHz,CDCl3):δ7.58-7.54(m,12H,C6H5P),7.44(d,1H,
2-NO2C6H4Pd,J=7.6Hz),7.34-7.30(m,6H,C6H5P),7.26-7.22(m,12H,C6H5P),
7.12(d,1H,2-NO2C6H4Pd,J=8.0Hz),6.66(t,1H,2-NO2C6H4Pd,J=7.2Hz),
6.52(t,1H,2-NO2C6H4Pd,J=7.6Hz),5.28(s,2H,CH2Cl2).31P{1H}NMR(162
MHz,CDCl3):δ21.5.
It follows that described clear crystal is: (PPh3)2Pd(C6H4NO2-2)Br。
Described clear crystal is carried out single crystal diffraction analysis, and it is the embodiment of the present invention that result sees Fig. 7, Fig. 7
The crystal structure schematic diagram of the divalent palladium coordination compound of 7 preparations.
Embodiment 8
Under argon shield, 100mL Schlenk bottle adds 0.1773g palladium chloride (PdCl2)(1
mmol)、5mmol PCy3With 35mL toluene, electromagnetic agitation, after reacting 30min at 120 DEG C, add
Enter 10mL hydrazine hydrate, obtain faint yellow toluene solution.After temperature is down to room temperature, pipette faint yellow first
Benzole soln, adds 7mmol parabromotoluene, reacts 4h at 85 DEG C；After temperature is down to room temperature, remove
Toluene solvant, washs (3 × 10mL) with ether, drains and obtain white powder；White powder after recrystallization,
Obtaining 0.415g clear crystal, yield is 49.5%.
Being analyzed described clear crystal, result is as follows:
1H NMR(400MHz,CDCl3):δ7.20(d,2H,4-MeC6H4Pd,J=7.2Hz),6.74(d,
2H,4-MeC6H4Pd,J=7.2Hz),2.20(s,3H,CH3C6H4Pd),2.06-1.05(m,66H,
C6H11P).31P{1H}NMR(162MHz,CDCl3):δ19.1.
It follows that described clear crystal is: (PCy3)2Pd(C6H4Me-4)Br。
Described clear crystal is carried out single crystal diffraction analysis, and it is the embodiment of the present invention that result sees Fig. 8, Fig. 8
The crystal structure schematic diagram of the divalent palladium coordination compound of 8 preparations.
Embodiment 9
Under argon shield, 100mL Schlenk bottle adds 0.1773g palladium chloride (PdCl2)(1
mmol)、5mmol PCy3With 35mL toluene, electromagnetic agitation, after reacting 30min at 120 DEG C, add
Enter 10mL hydrazine hydrate, obtain faint yellow toluene solution.After temperature is down to room temperature, pipette faint yellow first
Benzole soln, 7mmol is to Brominal in addition, reacts 4h at 85 DEG C；After temperature is down to room temperature, remove
Toluene solvant, washs (3 × 10mL) with ether, drains and obtain white powder；White powder after recrystallization,
Obtaining 0.243g clear crystal, yield is 28.6%.
Being analyzed described clear crystal, result is as follows:
1H NMR(400MHz,CDCl3):δ7.62(d,2H,4-CNC6H4Pd,J=8.0Hz),7.19(d,
2H,4-CNC6H4Pd,J=8.0Hz),2.04-0.84(m,66H,C6H11P).31P{1H}NMR(162
MHz,CDCl3):δ19.8.
It follows that described clear crystal is: (PCy3)2Pd(C6H4CN-4)Br。
Described clear crystal is carried out single crystal diffraction analysis, and it is the embodiment of the present invention that result sees Fig. 9, Fig. 9
The crystal structure schematic diagram of the divalent palladium coordination compound of 9 preparations.
Embodiment 10
Under argon shield, 100mL Schlenk bottle adds 0.1773g palladium chloride (PdCl2)(1
mmol)、5mmol PCy3With 35mL toluene, electromagnetic agitation, after reacting 30min at 120 DEG C, add
Enter 10mL hydrazine hydrate, obtain faint yellow toluene solution.After temperature is down to room temperature, pipette faint yellow first
Benzole soln, 7mmol is to bromine methoxybenzene in addition, reacts 4h at 85 DEG C；After temperature is down to room temperature,
Remove toluene solvant, wash (3 × 10mL) with ether, drain and obtain white powder；White powder is through heavily tying
After crystalline substance, obtaining 0.459g clear crystal, yield is 53.7%.
Being analyzed described clear crystal, result is as follows:
1H NMR(400MHz,CDCl3):δ7.21(d,2H,4-MeOC6H4Pd,J=8.4Hz),
7.25-7.16(m,5H,C7H8),6.62(d,2H,4-MeOC6H4Pd,J=8.0Hz),3.74(s,3H,
4-OCH3),1.91-1.05(m,99H,C6H11P and C18H33PO).31P{1H}NMR(162MHz,
CDCl3):δ19.4,49.5.
It follows that described clear crystal is: (PCy3)2Pd(C6H4OMe-4)Br。
Described clear crystal is carried out single crystal diffraction analysis, and it is that the present invention implements that result sees Figure 10, Figure 10
The crystal structure schematic diagram of the divalent palladium coordination compound of example 10 preparation.
Embodiment 11
Under argon shield, 100mL Schlenk bottle adds 0.1773g palladium chloride (PdCl2)(1
mmol)、5mmol PCy3With 35mL toluene, electromagnetic agitation, after reacting 30min at 120 DEG C, add
Enter 10mL hydrazine hydrate, obtain faint yellow toluene solution.After temperature is down to room temperature, pipette faint yellow first
Benzole soln, adds 7mmol para-bromoaniline, reacts 4h at 85 DEG C；After temperature is down to room temperature, remove
Toluene solvant, washs (3 × 10mL) with ether, drains and obtain white powder；White powder after recrystallization,
Obtaining 0.482g clear crystal, yield is 57.4%.
Being analyzed described clear crystal, result is as follows:
1H NMR(400MHz,CDCl3):δ7.12(d,2H,4-NH2C6H4Pd,J=4Hz),6.54(d,
2H,4-NH2C6H4Pd,J=8Hz),2.10-1.07(m,66H,C6H11P)31P{1H}NMR(162MHz,
CDCl3):δ19.7.
It follows that described clear crystal is: (PCy3)2Pd(C6H4NH2-4)Br。
Described clear crystal is carried out single crystal diffraction analysis, and it is that the present invention implements that result sees Figure 11, Figure 11
The crystal structure schematic diagram of the divalent palladium coordination compound of example 11 preparation.
Embodiment 12
0.1773g palladium chloride (1mmol) and 50mL acetonitrile, room temperature is added in 100mL reaction bulb
Stirring, to when forming red solution, adds 0.9131g tri-(o-methyl-phenyl-) phosphine (3mmol) and 50mL third
Ketone forms yellow transparent solution, and gradually has lemon yellow solid to separate out；Described lemon yellow solid is entered
Row sucking filtration, washing with acetone, obtain two (three (o-methyl-phenyl-) phosphine) palladium chloride.By described two (three (adjacent first
Base phenyl) phosphine) palladium chloride dissolves in 0.27g tri-(o-methyl-phenyl-) phosphine P (o-tol)3(0.9mmol) and 8mL
The solution of toluene composition, stirring is lower adds 0.071g sodium hydroxide (1.79mmol) and 8mL dehydrated alcohol,
It is warming up to 90 DEG C of reaction 5h, obtains yellow green product；By described yellow green product with 2.5mmol to bromine
Toluene mixes, and 5h is stirred at room temperature, then shifts toluene in 20mL toluene, the solid dichloro obtained
Methane/normal hexane recrystallization, obtains yellow solid product, and productivity is 58.7%.
Being analyzed described clear crystal, result is as follows:
1H NMR(400MHz,CDCl3):δ7.51-7.28(m,24H,P(o-tol)),7.08-6.31(m,8H,
4-CH3C6H4Pd),2.16(s,18H,P(o-tol)),1.99(s,6H,4-CH3C6H4Pd).31P
{1H}NMR(162MHz,CDCl3):27.9.
It follows that described clear crystal is: (P (o-tol)3)2Pd2(C6H4CH3-4)2Br2。
Embodiment 13
0.1773g palladium chloride (1mmol) and 50mL acetonitrile, room temperature is added in 100mL reaction bulb
Stirring, to when forming red solution, adds 0.9131g tri-(o-methyl-phenyl-) phosphine (3mmol) and 50mL third
Ketone forms yellow transparent solution, and gradually has lemon yellow solid to separate out；Described lemon yellow solid is entered
Row sucking filtration, washing with acetone, obtain two (three (o-methyl-phenyl-) phosphine) palladium chloride.By described two (three (adjacent first
Base phenyl) phosphine) palladium chloride dissolves in 0.27g tri-(o-methyl-phenyl-) phosphine P (o-tol)3(0.9mmol) and 8mL
The solution of toluene composition, stirring is lower adds 0.071g sodium hydroxide (1.79mmol) and 8mL dehydrated alcohol,
It is warming up to 90 DEG C of reaction 5h, obtains yellow green product；By described yellow green product with 2.5mmol to bromine
Butyl benzene mixes, and 5h is stirred at room temperature, then shifts toluene in 20mL toluene, and the solid obtained is with two
Chloromethanes/normal hexane recrystallization, obtains yellow solid product, and productivity is 54.6%.
Being analyzed described clear crystal, result is as follows:
1H NMR(400MHz,CDCl3):δ7.28-7.22(m,24H,P(o-tol)),7.06-6.49(m,8H,
4-tBuC6H4Pd),2.15(s,18H,P(o-tol)),1.08(s,18H,4-tBuC6H4Pd).31P
{1H}NMR(162MHz,CDCl3):28.0.
It follows that described clear crystal is: (P (o-tol)3)2Pd2(C6H4 tBu-4)2Br2。
Described clear crystal is carried out single crystal diffraction analysis, and it is that the present invention implements that result sees Figure 12, Figure 12
The crystal structure schematic diagram of the divalent palladium coordination compound of example 13 preparation.
Embodiment 14
0.1773g palladium chloride (1mmol) and 50mL acetonitrile, room temperature is added in 100mL reaction bulb
Stirring, to when forming red solution, adds 0.9131g tri-(o-methyl-phenyl-) phosphine (3mmol) and 50mL third
Ketone forms yellow transparent solution, and gradually has lemon yellow solid to separate out；Described lemon yellow solid is entered
Row sucking filtration, washing with acetone, obtain two (three (o-methyl-phenyl-) phosphine) palladium chloride.By described two (three (adjacent first
Base phenyl) phosphine) palladium chloride dissolves in 0.27g tri-(o-methyl-phenyl-) phosphine P (o-tol)3(0.9mmol) and 8mL
The solution of toluene composition, stirring is lower adds 0.071g sodium hydroxide (1.79mmol) and 8mL dehydrated alcohol,
It is warming up to 90 DEG C of reaction 5h, obtains yellow green product；By described yellow green product with 2.5mmol to bromine
Methoxybenzene mixes, and 5h is stirred at room temperature, then shifts toluene in 20mL toluene, and the solid obtained is used
Dichloromethane/normal hexane recrystallization, obtains yellow solid product, and productivity is 58.4%.
Being analyzed described clear crystal, result is as follows:
1H NMR(400MHz,CDCl3):δ7.48-7.29(m,24H,P(o-tol)),7.08-6.17(m,8H,
4-CH3OC6H4Pd),2.16(s,18H,P(o-tol)),3.54(s,6H,4-CH3OC6H4Pd).31P
{1H}NMR(162MHz,CDCl3):27.9.
It follows that described clear crystal is: (P (o-tol)3)2Pd2(C6H4OCH3-4)2Br2。
Embodiment 15
0.1773g palladium chloride (1mmol) and 50mL acetonitrile, room temperature is added in 100mL reaction bulb
Stirring, to when forming red solution, adds 0.9131g tri-(o-methyl-phenyl-) phosphine (3mmol) and 50mL third
Ketone forms yellow transparent solution, and gradually has lemon yellow solid to separate out；Described lemon yellow solid is entered
Row sucking filtration, washing with acetone, obtain two (three (o-methyl-phenyl-) phosphine) palladium chloride.By described two (three (adjacent first
Base phenyl) phosphine) palladium chloride dissolves in 0.27g tri-(o-methyl-phenyl-) phosphine P (o-tol)3(0.9mmol) and 8mL
The solution of toluene composition, stirring is lower adds 0.071g sodium hydroxide (1.79mmol) and 8mL dehydrated alcohol,
It is warming up to 90 DEG C of reaction 5h, obtains yellow green product；By described yellow green product with 2.5mmol to bromine
Benzaldehyde mixes, and 5h is stirred at room temperature, then shifts toluene in 20mL toluene, and the solid obtained is with two
Chloromethanes/normal hexane recrystallization, obtains yellow solid product, and productivity is 62.5%.
Being analyzed described clear crystal, result is as follows:
1H NMR(400MHz,CDCl3):δ9.64(s,2H,4-CHOC6H4Pd),7.33-7.23(m,
24H,P(o-tol)),7.17-6.99(m,8H,4-CHOC6H4Pd),2.35(s,18H,P(o-tol)).31P
{1H}NMR(162MHz,CDCl3):27.4.
It follows that described clear crystal is: (P (o-tol)3)2Pd2(C6H4CHO-4)2Br2。
Embodiment 16
0.1773g palladium chloride (1mmol) and 50mL acetonitrile, room temperature is added in 100mL reaction bulb
Stirring, to when forming red solution, adds 0.9131g tri-(o-methyl-phenyl-) phosphine (3mmol) and 50mL third
Ketone forms yellow transparent solution, and gradually has lemon yellow solid to separate out；Described lemon yellow solid is entered
Row sucking filtration, washing with acetone, obtain two (three (o-methyl-phenyl-) phosphine) palladium chloride.By described two (three (adjacent first
Base phenyl) phosphine) palladium chloride dissolves in 0.27g tri-(o-methyl-phenyl-) phosphine P (o-tol)3(0.9mmol) and 8mL
The solution of toluene composition, stirring is lower adds 0.071g sodium hydroxide (1.79mmol) and 8mL dehydrated alcohol,
It is warming up to 90 DEG C of reaction 5h, obtains yellow green product；By described yellow green product with 2.5mmol to bromine
Cyanophenyl mixes, and 5h is stirred at room temperature, then shifts toluene in 20mL toluene, the solid dichloro obtained
Methane/normal hexane recrystallization, obtains yellow solid product, and productivity is 54.6%.
Being analyzed described clear crystal, result is as follows:
1H NMR(400MHz,CDCl3):δ7.51-7.34(m,24H,P(o-tol)),7.12-6.73(m,8H,
4-CNC6H4Pd),1.53(s,18H,P(o-tol)).31P{1H}NMR(162MHz,CDCl3):27.7.
It follows that described clear crystal is: (P (o-tol)3)2Pd2(C6H4CN-4)2Br2。
Embodiment 17
0.1773g palladium chloride (1mmol) and 50mL acetonitrile, room temperature is added in 100mL reaction bulb
Stirring, to when forming red solution, adds 0.9131g tri-(o-methyl-phenyl-) phosphine (3mmol) and 50mL third
Ketone forms yellow transparent solution, and gradually has lemon yellow solid to separate out；Described lemon yellow solid is entered
Row sucking filtration, washing with acetone, obtain two (three (o-methyl-phenyl-) phosphine) palladium chloride.By described two (three (adjacent first
Base phenyl) phosphine) palladium chloride dissolves in 0.27g tri-(o-methyl-phenyl-) phosphine P (o-tol)3(0.9mmol) and 8mL
The solution of Nitrobenzol composition, stirring is lower adds 0.071g sodium hydroxide (1.79mmol) and the anhydrous second of 8mL
Alcohol, is warming up to 90 DEG C of reaction 5h, obtains yellow green product；By described yellow green product and 2.5mmol
Parabromotoluene mixes, and 5h is stirred at room temperature, then shifts toluene in 20mL toluene, and the solid obtained is used
Dichloromethane/normal hexane recrystallization, obtains yellow solid product, and productivity is 65.2%.
Being analyzed described clear crystal, result is as follows:
1H NMR(400MHz,CDCl3):δ7.38-7.32(m,24H,P(o-tol)),7.18-6.84(m,8H,
4-NO2C6H4Pd),1.91(s,18H,P(o-tol)).31P{1H}NMR(162MHz,CDCl3):27.5.
It follows that described clear crystal is: (P (o-tol)3)2Pd2(C6H4NO2-4)2Br2。
Embodiment 18
Under argon shield, (the PPh of 1mol embodiment 5 preparation3)2Pd(C6H4NO2-4) Br, 1mol phenylboric acid
At 15mL toluene, 5mL (2mol/L) K2CO3Solution and 2 Aliguat336 mixing, in temperature 50
Reacting 12h under the conditions of DEG C, the product obtained is carried out post separation, obtains target product, productivity is 96%.
Being analyzed described target product, result is as follows:
1H NMR(400MHz,CDCl3,298K):δ8.29(d,2H,J=8.0Hz);7.73(d,2H,J=
8.0Hz);7.62(d,2H,J=8.0Hz);7.51-7.42(m,3H)。
It follows that described target product is 4-(4-NO2C6H4)Ph。
Embodiment 19
Under argon shield, (the PCy of 1mol embodiment 9 preparation3)2Pd(C6H4CN-4) Br, 1mol phenylboric acid
At 15mL toluene, 5mL (2mol/L) K2CO3Solution and 2 Aliguat336 mixing, in temperature 50
Reacting 12h under the conditions of DEG C, the product obtained is carried out post separation, obtains target product, productivity is 98%.
Being analyzed described target product, result is as follows:
1H NMR(400MHz,CDCl3,298K):δ7.73-7.66(m,4H)；7.58(d,2H,J=8.0
Hz);7.48(t,2H,J=4.0Hz);7.42(t,1H,J=4.0Hz)。
It follows that described target product is 4-(4-CNC6H4)Ph。
Embodiment 20
Under argon shield, (the PCy of 1mol embodiment 8 preparation3)2Pd(C6H4Me-4) Br, 1mol phenylboric acid
At 15mL toluene, 5mL (2mol/L) K2CO3Solution and 2 Aliguat336 mixing, in temperature 50
Reacting 12h under the conditions of DEG C, the product obtained is carried out post separation, obtains target product, productivity is 99%.
Being analyzed described target product, result is as follows:
1H NMR(400MHz,CDCl3,298K):δ7.57(d,2H,J=8.0Hz);7.48(d,2H,J
=8.0Hz);7.41(t,2H,J=8.0Hz);7.35-7.29(m,1H);7.24(d,2H,J=8.0Hz);
2.39(s,3H)。
It follows that described target product is 4-(4-MeC6H4)Ph。
Embodiment 21
Under argon shield, (the PPh of 1mol embodiment 2 preparation3)2Pd(C6H4Et-4) Br, 1mol phenylboric acid
At 15mL toluene, 5mL (2mol/L) K2CO3Solution and 2 Aliguat336 mixing, in temperature 50
Reacting 12h under the conditions of DEG C, the product obtained is carried out post separation, obtains target product, productivity is 99%.
Being analyzed described target product, result is as follows:
1H NMR(400MHz,CDCl3,298K):δ7.55(d,2H,J=8.0Hz);7.49(d,2H,J=
8.0Hz);7.38(t,2H,J=8.0Hz);7.30-7.22(m,3H);2.69-2.62(m,2H);1.25(t,3H,J
=8.0Hz)。
It follows that described target product is 4-(4-EtC6H4)Ph。
Embodiment 22
Under argon shield, 10ml toluene adds 0.5534g (1mmol) single bromo fluorenes borate, 1mmol
(the P (o-tol) of embodiment 12 preparation3)2Pd2(C6H4CH3-4)2Br2、3mL(2mol/L)K2CO3Solution and 2
Drip Aliguat336, at 30 DEG C, react 12h, after sedimentation, obtain polyfluorene.
Described polyfluorene carries out MALDI-TOF mass spectral analysis sign, and it is this that result sees Figure 13, Figure 13
The mass spectral analysis figure of the polyfluorene that inventive embodiments 22 prepares.
In Figure 13, the repetitive of polymer is fluorenes (2114.4-1725.9=388.5;2035.4-1646.7=
388.7…).Assuming repetitive n=6, end group is C6H4CH3During-4/Br, Mn=388.6×6+91.1
+ 79.9=2502.6, the mass spectra peak 2503.0 corresponding with Figure 13, differ 0.4；End group is
C6H4CH3During-4/H, Mn=388.6 × 6+91.1+1=2423.7, the mass spectra peak corresponding with figure
2423.9, differ 0.2.It follows that polymer is that to contain end group respectively be C6H4CH3-4/Br and
C6H4CH3Two kinds of polymer of-4/H.
Embodiment 23
Under argon shield, 10ml toluene adds 0.5534g (1mmol) single bromo fluorenes borate, 1mmol
(the P (o-tol) of embodiment 13 preparation3)2Pd2(C6H4 tBu-4)2Br2、3mL(2mol/L)K2CO3Solution and 2
Drip Aliguat336, at 30 DEG C, react 12h, after sedimentation, obtain polyfluorene.
Described polyfluorene carries out MALDI-TOF mass spectral analysis sign, and it is this that result sees Figure 14, Figure 14
The mass spectral analysis figure of the polyfluorene that inventive embodiments 23 prepares.
In Figure 14, the repetitive of polymer is fluorenes (2156.8-1768.1=388.7;2077.5-1689.9=
387.6…).Assuming repetitive n=6, end group is C6H4 tDuring Bu/Br, Mn=388.6×6+133.2+
79.9=2544.7, the mass spectra peak 2545.4 corresponding with figure, differ 0.7；End group is C6H4 tBu/H
Time, Mn=388.6 × 6+133.2+1=2465.8, the mass spectra peak 2466.2 corresponding with figure, difference
0.4.It follows that polymer is that to contain end group respectively be C6H4 tBu/Br and C6H4 tTwo kinds of Bu/H gather
Compound.
Embodiment 24
Under argon shield, 10ml toluene adds 0.5534g (1mmol) single bromo fluorenes borate, 1mmol
(the P (o-tol) of embodiment 14 preparation3)2Pd2(C6H4OCH3-4)2Br2、3mL(2mol/L)K2CO3Solution and
2 Aliguat336, react 12h at 30 DEG C, obtain polyfluorene after sedimentation.
Described polyfluorene carries out MALDI-TOF mass spectral analysis sign, and it is this that result sees Figure 15, Figure 15
The mass spectral analysis figure of the polyfluorene that inventive embodiments 24 prepares.
In Figure 15, the repetitive of polymer is fluorenes (2130.3-1741.7=388.6;2439.6-2051.1=
388.5…).Assuming repetitive n=6, end group is C6H4CH3During O/Br, Mn=388.6×6+107.1
+ 79.9=2518.6, the mass spectra peak 2518.8 corresponding with figure, differ 0.2；End group is C6H4CH3O/H
Time, Mn=388.6 × 6+107.1+1=2439.7, the mass spectra peak 2439.6 corresponding with figure, difference
0.1.It follows that polymer is that to contain end group respectively be C6H4CH3O/Br and C6H4CH3The two of O/H
Plant polymer.
Embodiment 25
Under argon shield, 10ml toluene adds 0.5534g (1mmol) single bromo fluorenes borate, 1mmol
(the P (o-tol) of embodiment 15 preparation3)2Pd2(C6H4CHO-4)2Br2、3mL(2mol/L)K2CO3Solution and 2
Drip Aliguat336, at 30 DEG C, react 12h, after sedimentation, obtain polyfluorene.
Described polyfluorene carries out MALDI-TOF mass spectral analysis sign, and it is this that result sees Figure 16, Figure 16
The mass spectral analysis figure of the polyfluorene that inventive embodiments 25 prepares.
In Figure 16, the repetitive of polymer is fluorenes (2517.2-2128.3=388.9;2437.9-2049.3=
388.6…).Assuming repetitive n=6, end group is C6H4During CHO/Br, Mn=388.6×6+105.1
+ 79.9=2516.6, the mass spectra peak 2517.2 corresponding with figure, differ 0.6；End group is C6H4CHO/H
Time, Mn=388.6 × 6+105.1+1=2437.7, the mass spectra peak 2437.9 corresponding with figure, difference
0.2.It follows that polymer is that to contain end group respectively be C6H4CHO/Br and C6H4Two kinds of CHO/H
Polymer.
Embodiment 26
Under argon shield, 10ml toluene adds 0.5534g (1mmol) single bromo fluorenes borate, 1mmol
(the P (o-tol) of embodiment 16 preparation3)2Pd2(C6H4CN-4)2Br2、3mL(2mol/L)K2CO3Solution and 2
Drip Aliguat336, at 30 DEG C, react 12h, after sedimentation, obtain polyfluorene.
Described polyfluorene carries out MALDI-TOF mass spectral analysis sign, and it is this that result sees Figure 17, Figure 17
The mass spectral analysis figure of the polyfluorene that inventive embodiments 26 prepares.
In Figure 17, the repetitive of polymer is fluorenes (2434.9-2046.2=388.7;2514.1-2125.4=
388.7…).Assuming repetitive n=6, end group is C6H4During CN/Br, Mn=388.6×6+102.1
+ 79.9=2513.6, the mass spectra peak 2514.1 corresponding with figure, differ 0.5；End group is C6H4CN/H
Time, Mn=388.6 × 6+102.1+1=2434.7, the mass spectra peak 2434.9 corresponding with figure, difference
0.2.It follows that polymer is that to contain end group respectively be C6H4CN/Br and C6H4Two kinds of CN/H gather
Compound.
Embodiment 27
Under argon shield, 10ml toluene adds 0.5534g (1mmol) single bromo fluorenes borate, 1mmol
(the P (o-tol) of embodiment 17 preparation3)2Pd2(C6H4NO2-4)2Br2、3mL(2mol/L)K2CO3Solution and 2
Drip Aliguat336, at 30 DEG C, react 12h, after sedimentation, obtain polyfluorene.
Described polyfluorene carries out MALDI-TOF mass spectral analysis sign, and it is this that result sees Figure 18, Figure 18
The mass spectral analysis figure of the polyfluorene that inventive embodiments 27 prepares.
In Figure 18, the repetitive of polymer is fluorenes (2145.5-1756.9=388.6;2454.8-2066.4=
388.4…).Assuming repetitive n=6, end group is C6H4NO2During/Br, Mn=388.6×6+122.1
+ 79.9=2533.6, the mass spectra peak 2554.8 corresponding with figure, differ 0.1；End group is C6H4NO2/H
Time, Mn=388.6 × 6+122.1+1=2454.7, the mass spectra peak 2434.9 corresponding with figure, difference
0.2.It follows that polymer is that to contain end group respectively be C6H4NO2/ Br and C6H4NO2Two kinds of/H
Polymer.
The above is only the preferred embodiment of the present invention, it is noted that general for the art
For logical technical staff, under the premise without departing from the principles of the invention, it is also possible to make some improvement and profit
Decorations, these improvements and modifications also should be regarded as protection scope of the present invention.
Claims (4)
1. there is the divalent palladium coordination compound of formula (III) structure:
Wherein, Ar is aryl or polyaryl；
R is cyano group or aldehyde radical；
X is halogen.
Divalent palladium coordination compound the most according to claim 1, it is characterised in that Ar be phenyl,
Xenyl or fluorenyl；X is bromine or iodine.
3. there is the preparation method of the conjugation aromatic hydrocarbon polymer of formula (VI) structure, including:
The divalent palladium coordination compound with formula (III) structure is anti-with the compound with formula (VII) structure
Should, obtain being conjugated aromatic hydrocarbon polymer；
Wherein, Ar is aryl or polyaryl；
R is cyano group or aldehyde radical；
X is halogen；
R2For hydrogen or halogen；
N is the degree of polymerization；
The number-average molecular weight of described conjugation aromatic hydrocarbon polymer is 5000～20000.
Preparation method the most according to claim 3, it is characterised in that divalent palladium coordination compound with
The mol ratio of the compound with formula (VII) structure is 0.005:0.1～10；The temperature of described reaction
For room temperature～80 DEG C, the described response time is 12h～24h.
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