CN102424694B - Preparation method of palladium complex and conjugated aromatic polymer - Google Patents
Preparation method of palladium complex and conjugated aromatic polymer Download PDFInfo
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- CN102424694B CN102424694B CN201110327662.6A CN201110327662A CN102424694B CN 102424694 B CN102424694 B CN 102424694B CN 201110327662 A CN201110327662 A CN 201110327662A CN 102424694 B CN102424694 B CN 102424694B
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Abstract
The invention provides a palladium complex of general formula (I) or general formula (II), wherein, X represents halogen, L represents phosphorus ligand or nitrogenous ligand, G represents a sulfonic group, a carboxylic group, a phosphonate group, a hydroxy group or a polyether chain, G is positioned at para-position or meta-position of L, n represents a positive integer, and m represents 2, 3 or 4. The invention further provides a preparation method of the palladium complex, and a method for preparing a conjugated aromatic polymer by using a palladium complex catalyst. According to the invention, because a neutral hydrophilic substituent group is introduced to the palladium complex catalyst ligand, the palladium complex catalyst is amphiphilic and can simultaneously dissolved in water phase and organic phase; the catalyst undergoes oxidative addition with a polymer monomer easily, and can promote the transmetallation step to let the coupling polymerization reaction carry out continuously and rapidly, thus the conjugated aromatic polymer having high molecular weight is obtained. The conjugated aromatic polymer is represented as PdX2(L-Gn)2 (I) or Pd(L-Gn)m (II).
Description
Technical field
The present invention relates to catalyst field, particularly the preparation method of a kind of palladium complex and conjugated aromatic polymer.
Background technology
The reaction of Suzuki coupling polymerization refers under the effect of catalyzer, the linked reaction that organoboron compound and organohalogen compound carry out.This method was applied by Schluter the earliest in 1989, after this more than 20 years, small molecules linked reaction at catalyst activity, productive rate, simplifying the operation and optimizing the aspects such as reaction conditions has all obtained tremendous development, but aspect coupling polymerization, but rarely have improvement.It is catalyzer that existing coupling polymerization reaction normally adopts the tetrakis triphenylphosphine palladium of zeroth order, and polymerization single polymerization monomer reacts in the two-phase reaction system of organic phase and alkaline aqueous solution.The problem of this method is in reaction process, polymerization single polymerization monomer is dissolved in organic phase, the alkali playing a crucial role in catalyzed polymerization circulation is soluble in the aqueous phase, because the mutual solubility of nonpolar organic phase and water is poor, directly cause alkali in water extremely difficult with organic phase in intermediate contact reacts, thereby affect polymerization effect, directly cause the molecular weight of polymkeric substance on the low side.
In order to solve the problem that polymericular weight is low, prior art has been made many effort at aspects such as changing organic solvent and change catalyzer.For example: the United States Patent (USP) that the patent No. is US2008/0033146 proposed to adopt water soluble ligand TPPMS, TPPDS, TPPTS and Pd (OAc) in 2008
2the double-component catalyst system forming.In toluene/aqueous sodium carbonate system and add a small amount of ethanol as cosolvent, take and gather fluorenes as example, at TPPMS: Pd=4: under 1 catalyst system, the molecular weight of polymkeric substance is 37000g/mol.This patent also proposes, and in tetrahydrofuran (THF)/aqueous sodium carbonate (2/1) system, adopts the double-component catalyst system of this type of wetting ability part, at TPPMS: Pd=6: under 1 condition, the molecular weight of copolymer of fluorenes and three arylamine can reach 180000g/mol.
Although adopt wetting ability series part TPPMS, TPPDS, TPPTS and Pd (OAc)
2the double-component catalyst system forming, can improve the molecular weight of polymkeric substance, but there is disadvantageous effect in part and palladium metal salt dual-component catalyst that this method adopts: 1) in catalyst system part with sulfonate groups there is strong water-soluble and poor oil soluble, will make like this catalyzer be formed in water, and be difficult to enter organic phase, be unfavorable in polyreaction being oxidized addition with polymerization single polymerization monomer; 2) because part had strong water-soluble and poor oil soluble, when in polymerization process, palladium intermediate is positioned at two-phase interface, part is difficulty and the coordination of palladium intermediate extremely, causes palladium intermediate to decompose, assemble formation palladium black, and catalyzer is lost activity.Prevent from forming palladium black, must add excessive part.
Summary of the invention
The technical problem that the present invention solves is to provide a kind of palladium complex, makes it can catalyzed polymerization monomer in coupling polymerization reaction obtain the conjugated aromatic polymer of high molecular.
In view of this, the invention provides a kind of structure suc as formula shown in (I) or suc as formula the palladium complex shown in (II):
PdX
2(L-Gn)
2 (I)
Pd(L-Gn)
m (II)
Wherein:
X is halogen;
L is phosphine part or containing n-donor ligand;
G is sulfonic group, carboxylic acid group, phosphonate group, hydroxyl or polyether chain; The position of described G is in contraposition or a position of described L;
N is positive integer;
M is 2,3 or 4.
Preferably, described X is Cl.
Preferably, described L is phosphine part; Preferred, described L is triphenylphosphine.
Preferably, described n is 1.
Preferably, described m is 3.
The invention provides a kind of method of preparing conjugated aromatic polymer, comprising:
Under the effect of the palladium complex catalyst of described formula (I) or described formula (II), there is coupling polymerization reaction in organoboron compound and organohalogen compound, generate conjugated aromatic polymer in organic solvent and alkali lye;
PdX
2(L-Gn)
2 (I)
Pd(L-Gn)
m (II)
Wherein:
X is halogen;
L is phosphine part or containing n-donor ligand;
G is sulfonic group, carboxylic acid group, phosphonate group, hydroxyl or polyether chain etc.; The position of substituting group G is in contraposition or a position of L;
N is positive integer;
M is 2,3 or 4.
Preferably, described organoboron compound is 9,9-dioctyl-2,7-dibromo fluorenes, and described organohalogen compound is 9,9-dioctyl fluorene-2,7-bis-(propylene glycol boric acid ester).
Preferably, described organic solvent is toluene or tetrahydrofuran (THF).
Preferably, described alkali lye is wet chemical.
The invention provides a kind of amphipathic palladium complex catalyst, in the part of described palladium complex catalyst, introduced as carboxylic acid group, sulfonic group, phosphonate group, hydroxyl or polyether chain neutral hydrophilic substituent, catalyzer just has amphipathic like this, catalyzer can be soluble in the aqueous phase and organic phase when polyreaction simultaneously, in polymerization process amphipathic catalyzer both easily and polymerization single polymerization monomer be oxidized addition, promoted again metal transfer step, polyreaction just can be carried out continuously rapidly so simultaneously.In the present invention, the part of catalyzer has wetting ability and lipophilicity simultaneously, therefore when palladium intermediate is positioned at two-phase interface, the part using is amphipathic and very high at interface content owing to having, can be in time and the coordination of palladium intermediate, stop the formation of palladium black, polyreaction is carried out continuously, without adding again excess ligand.Therefore at amphipathic palladium complex catalyst described in reaction process, to coupling polyreaction, can play good katalysis, thereby obtain the conjugated aromatic polymer of high molecular.
Accompanying drawing explanation
Fig. 1 is the synthetic PdCl of the embodiment of the present invention 19
2(4-TPPMC)
2crystalline structure figure;
Fig. 2 is the synthetic PdCl of the embodiment of the present invention 20
2(3-TPPMC)
2crystalline structure figure;
Fig. 3 is the synthetic Pd of the embodiment of the present invention 34 (3-TPPMSH)
3crystalline structure figure;
Fig. 4 is the synthetic Pd of the embodiment of the present invention 35 (4-TPPMC)
3crystalline structure figure;
Fig. 5 is the synthetic Pd of the embodiment of the present invention 36 (3-TPPMC)
3crystalline structure figure.
Embodiment
In order further to understand the present invention, below in conjunction with embodiment, the preferred embodiment of the invention is described, but should be appreciated that these are described is for further illustrating the features and advantages of the present invention, rather than limiting to the claimed invention.
The embodiment of the invention discloses a kind of structure suc as formula the palladium complex shown in (I) or formula (II):
PdX
2(L-Gn)
n (I)
Pd(L-Gn)
m (II)
The title complex with formula (I) structure is amphipathic divalence palladium complex, and wherein, X is halogen, is preferably Cl; L is phosphine part or containing n-donor ligand, is preferably phosphine part, more preferably triphenylphosphine; G is sulfonic group, carboxylic acid group, phosphonate group, hydroxyl or polyether chain; The position of G is in contraposition or a position of L; N is positive integer, is preferably 1.
The title complex with formula (II) structure is amphipathic zeroth order palladium complex, and wherein, L is phosphine part or containing n-donor ligand, is preferably phosphine part, more preferably triphenylphosphine; G is sulfonic group, carboxylic acid group, phosphonate group, hydroxyl or polyether chain; The position of G is in contraposition or a position of L; N is positive integer, is preferably 1; M is 2,3 or 4, is preferably 3.
In part due to the palladium complex catalyst in above-mentioned formula (I) or formula (II), introduce neutral hydrophilic substituent sulfonic group, carboxylic acid group, phosphonate group, hydroxyl or polyether chain, thereby formed amphipathic part.Contrast with sulfonate groups, sulfonic group, carboxylic acid group, phosphonate group, hydroxyl or polyether chain have moderate wetting ability, above group and phosphine part or containing n-donor ligand bonding, obtain a kind of amphipathic part, this amphipathic part has wetting ability and lipophilicity simultaneously, therefore palladium complex catalyst has amphipathicly, so just makes palladium complex catalyst can be dissolved in organic solvent and alkali lye, is easy to and polymerization single polymerization monomer generation oxidative addition.When polyreaction is carried out, owing to there being amphipathic palladium complex catalyst in reaction system, palladium complex catalyst can be dissolved in organic phase and water simultaneously, therefore be oxidized the alkali reaction of addition intermediate radical easily and in water, make metal transfer step more fast, easily carry out, thereby guarantee the continuity of polyreaction, directly result can generate high-molecular weight polymer exactly.
Amphipathic palladium complex catalyst has two kinds of structures, and wherein amphipathic divalence palladium complex is synthetic as follows:
Palladium source PdX
2react in organic solvent with amphipathic ligand L-Gn, obtain the amphipathic divalence palladium complex of formula (I) structure:
PdX
2(L-Gn)
2 (I)
Wherein X is halogen, is preferably Cl; L is phosphine part or containing n-donor ligand, is preferably phosphine part, more preferably triphenylphosphine; G is sulfonic group, carboxylic acid group, phosphonate group, hydroxyl or polyether chain; G is in contraposition or a position of L; N is positive integer, is preferably 1.
The reaction expression of above-mentioned reaction process is as follows:
PdX
2+L-Gn→PdX
2(L-Gn)
2
In reaction expression, X is halogen, is preferably Cl; L is phosphine part or containing n-donor ligand, is preferably phosphine part, more preferably triphenylphosphine; G is sulfonic group, carboxylic acid group, phosphonate group, hydroxyl or polyether chain; The position of G is in contraposition or a position of L; N is positive integer, is preferably 1.
Amphipathic zeroth order palladium complex is synthetic as follows:
Under the effect of reductive agent, palladium source PdX
2react in organic solvent with amphipathic ligand L-Gn, obtain the amphipathic zeroth order palladium complex of formula (II) structure:
Pd(L-Gn)
m (II)
Wherein L is phosphine part or containing n-donor ligand, is preferably phosphine part, more preferably triphenylphosphine; G is sulfonic group, carboxylic acid group, phosphonate group, hydroxyl or polyether chain, is preferably sulfonic group, carboxylic acid group or phosphonate group; G is in contraposition or a position of L; N is positive integer, is preferably 1; M is 2,3 or 4, is preferably 3.Preferably, all amphipathic zeroth order palladium complexes, to air and temperature sensitive, need argon gas cryopreservation.
The synthetic reaction expression of above-mentioned amphipathic zeroth order palladium complex is as follows:
Wherein X is halogen, is preferably Cl; L is phosphine part or containing n-donor ligand, is preferably phosphine part, more preferably triphenylphosphine; G is sulfonic group, carboxylic acid group, phosphonate group, hydroxyl or polyether chain, is preferably sulfonic group, carboxylic acid group or phosphonate group; G is in contraposition or a position of L; N is positive integer, is preferably 1; M is 2,3 or 4, is preferably 3.
Above-mentioned reaction is the building-up reactions of amphipathic palladium complex, and wherein amphipathic ligand L-Gn is synthetic in accordance with the following methods:
Wherein L is phosphine part or containing n-donor ligand, is preferably phosphine part; G is sulfonic group, carboxylic acid group, phosphonate group, hydroxyl or polyether chain; N is positive integer, is preferably 1.
When the substituting group of amphipathic part is sulfonic group, amphipathic part is synthetic as follows: phosphine part and oleum react, and obtains containing sulfonic amphipathic part.Phosphine part is preferably triphenylphosphine.
When the substituting group of amphipathic part is carboxylic acid group, amphipathic part is synthetic as follows: phosphine part and concentrated hydrochloric acid react, and obtains the amphipathic part containing carboxylic acid group.Phosphine part is preferably 4-(diphenylphosphine) cyanobenzene or 3-(diphenylphosphine) cyanobenzene.
When the substituting group of amphipathic part is phosphonate group, amphipathic part is synthetic as follows: phosphine part and hydrochloric acid react, and obtains the amphipathic part containing phosphonate group.Phosphine part is preferably sodium phosphate.
When the substituting group of amphipathic part is hydroxyl, amphipathic part is synthetic as follows: the amine of phosphine part and hydroxyl reacts, and obtains the amphipathic part of hydroxyl.Phosphine part is preferably 4-(diphenylphosphine) phenylformic acid or 3-(diphenylphosphine) phenylformic acid; The amine of hydroxyl is preferably thanomin or diethanolamine.
When the substituting group of amphipathic part is polyether chain, amphipathic part is synthetic as follows: phosphine part and bis ether chain secondary amine react, and obtains the amphipathic part containing polyether chain.Phosphine part is preferably 4-(diphenylphosphine) phenylformic acid or 3-(diphenylphosphine) phenylformic acid, and bis ether chain secondary amine is preferably di-alcohol dme amine.
The present invention also provides a kind of method of preparing conjugated aromatic polymer, comprising:
Under the effect of the palladium complex catalyst of formula (I) or formula (II), there is coupling polymerization reaction in organoboron compound and organohalogen compound, generate conjugated aromatic polymer in organic solvent and alkali lye;
PdX
2(L-Gn)
2 (I)
Pd(L-Gn)
m (II)
Wherein X is halogen, is preferably Cl; L is phosphine part or containing n-donor ligand, is preferably phosphine part, more preferably triphenylphosphine; G is sulfonic group, carboxylic acid group, phosphonate group, hydroxyl or polyether chain; The position of G is in contraposition or a position of L; N is positive integer, is preferably 1; M be 2,3 or 4, m be preferably 3.
According to the present invention, polymerization system comprises organoboron compound, organohalogen compound, organic solvent, alkali lye and amphipathic palladium complex catalyst.
In the present invention, organoboron compound is preferably 9,9-dioctyl fluorene-2,7-bis-(propylene glycol boric acid ester), and organohalogen compound is preferably 9,9-dioctyl-2,7-dibromo fluorenes.
The organic solvent of coupling polymerization reaction comprises aliphatic hydrocarbon, aromatic hydrocarbons, higher alcohols or ethers; According to the present invention, organic solvent is preferably toluene, tetrahydrofuran (THF), methylene dichloride and mixed solvent thereof; More preferably toluene or tetrahydrofuran (THF).Solute in alkali lye comprises oxyhydroxide, phosphoric acid salt, carbonate, acetate, alkoxide and primary amine, secondary amine, the tertiary amine of basic metal or alkaline-earth metal; The present invention is preferably Cs
2cO
3, K
2cO
3, Na
2cO
3, Li
2cO
3, Bu
4nF, CsF, KF; K more preferably
2cO
3.
In polymerization system, preferably add solubility promoter, solubility promoter adopts the organic solvent miscible with water, comprises nitrile, amides, lower alcohol, sulfoxide type or cyclic ethers class.
The present invention preferably adopts alkali lye to account for 1%～90% of polymerization system, and more preferably 20%～50%.It is (1～50) that the present invention preferably adopts the mole dosage proportional range of alkali and monomer: 1, more preferably (10～30): 1.The present invention preferably adopts the consumption of catalyzer to account for 0.2%～0.5% of polymerization system, and more preferably 0.3%.Reaction times, the present invention was preferably 12h～48h, more preferably 12h.
The present invention also provides and has adopted amphipathic palladium complex catalyst, 9,9-dioctyl fluorene-2,7-bis-(propylene glycol boric acid ester) and 9,9-dioctyl-2, the reaction of 7-dibromo fluorenes generation coupling polymerization, in toluene/wet chemical reaction system, the conjugated aromatic polymer that acquisition molecular weight is 120000-180000g/mol; In tetrahydrofuran (THF)/wet chemical reaction system, the conjugated aromatic polymer that acquisition molecular weight is 400000-600000g/mol.
In order further to understand the present invention; below in conjunction with embodiment, to palladium complex catalyst provided by the invention, palladium complex catalyst preparation method and utilize palladium complex catalyst to prepare high molecular conjugated aromatic polymer to be described in detail, protection scope of the present invention is not limited by the following examples.
Synthesizing of embodiment 1:3-(diphenylphosphine) Phenylsulfonic acid (3-TPPMSH)
In 250ml tri-neck round-bottomed flasks, add 20ml oleum (Oleum), under argon gas atmosphere, in ice-water bath, add the triphenylphosphine (PPh of 10g in batches
3), be stirred to after whole dissolvings, be warming up to 93 ℃ of stirring reaction 2h.Be cooled to after room temperature, add 20g ice and 100ml distilled water, add the NaOH aqueous solution that reaction solution is adjusted to neutrality, separate out white solid, after filtration, by distilled water recrystallization twice, obtain 3g brilliant white crystal powder sodium sulfonate part, the productive rate of sodium sulfonate part is 20%.Sodium sulfonate part is dissolved in methanol hydrochloride solution and obtains 3-TPPMSH, and reaction formula is shown in following formula:
Intermediate product sodium sulfonate part is carried out to nuclear magnetic resonance spectroscopy, and characterization result is as follows:
1hNMR (D
2o, 300MHz): δ=7.00-7.50 (m, 12H), 7.62 (d, J=7.2Hz, 1H), 7.70ppm (s, 1H);
31p{
1h}NMR (D
2o, 161.9Hz): δ=-6.43ppm (s).elemental analysis calcd(％)for C
18H
14NaO
4PS·H
2O：C 56.54，H 4.22，；found：C 55.74，H 4.119。Hence one can see that, and TPPMS can successfully be prepared.
Synthesizing of embodiment 2:4-(diphenylphosphine) phenylformic acid (4-TPPMC)
In 500ml tri-neck round-bottomed flasks; the KOH and the 300ml dimethyl sulfoxide (DMSO) (DMSO) that under argon shield, add 6g; add after 10.4ml diphenylphosphine, obtain red reaction solution, at room temperature stir 2h; add 7.26g p-Fluorophenyl cyanide; reaction solution produces white precipitate immediately, stirs after 0.5h, and sedimentation and filtration is also used twice of recrystallizing methanol; obtain 13.75g brilliant white crystal 4-(diphenylphosphine) cyanobenzene, the productive rate of 4-(diphenylphosphine) cyanobenzene is 80%.Product 4-(diphenylphosphine) cyanobenzene is carried out to nuclear magnetic resonance spectroscopy, and characterization result is as follows:
1h NMR (CDCl
3, 300MHz): δ=7.30-7.39 (m, 12H), 7.57ppm (d, J=6.9Hz, 2H);
31p{
1h}NMR (CDCl
3, 161.9Hz): δ=-4.67ppm (s).Hence one can see that, and 4-(diphenylphosphine) cyanobenzene can successfully be prepared.
In 250ml tri-neck round-bottomed flasks, under argon shield, add 4-(diphenylphosphine) cyanobenzene and the 100ml concentrated hydrochloric acid of 13.75g, reaction solution is in 110 ℃ of stirring reaction 1h.Be cooled to after room temperature, add 100ml distilled water to separate out immediately white precipitate, after sedimentation and filtration, by recrystallizing methanol twice, obtain 11g brilliant white crystal 4-TPPMC, the productive rate of 4-TPPMC is 75%, and reaction formula is shown in following formula:
Product 4-TPPMC is carried out to nuclear magnetic resonance spectroscopy, and characterization result is as follows:
1h NMR (CDCl
3, 300MHz): δ=7.33-7.38 (m, 12H), 8.025ppm (d, J=8.4Hz, 2H);
31p{
1h}NMR (CDCl
3, 161.9Hz): δ=-4.93ppm (s).MALDI-TOF(m/z)：305.2[M-H]
-。Hence one can see that, and 4-TPPMC can successfully be prepared.
Synthesizing of embodiment 3:3-(diphenylphosphine) phenylformic acid (3-TPPMC)
In 500ml tri-neck round-bottomed flasks; under argon shield, add 6gKOH and 300ml dimethyl sulfoxide (DMSO) (DMSO); add after 10.4ml diphenylphosphine, obtain red reaction solution, at room temperature stir 2h; add fluorobenzonitrile between 7.26g; reaction solution produces white precipitate immediately, stirs after 0.5h, and sedimentation and filtration is also used twice of recrystallizing methanol; obtain 12g brilliant white crystal 3-(diphenylphosphine) cyanobenzene, 3-(diphenylphosphine) cyanobenzene productive rate is 70%.Product 3-(diphenylphosphine) cyanobenzene is carried out to nuclear magnetic resonance spectroscopy, and characterization result is as follows:
1h NMR (CDCl
3, 400MHz): δ=7.27-7.31 (m, 4H), 7.375 (d, J=5.2Hz, 6H), 7.44 (d, J=7.6Hz, 1H), 7.48-7.55 (m, 2H), 7.60ppm (d, J=7.6Hz, 1H);
31p{
1h}NMR (CDCl
3, 161.9Hz): δ=-5.83ppm (s).Hence one can see that, and 3-(diphenylphosphine) cyanobenzene can successfully be prepared.
In 250ml tri-neck round-bottomed flasks, under argon shield, add 3-(diphenylphosphine) cyanobenzene and the 100ml concentrated hydrochloric acid of 12g, reaction solution is in 110 ℃ of stirring reaction 1h.Be cooled to after room temperature, add 100ml distilled water to separate out immediately white precipitate, after sedimentation and filtration, by recrystallizing methanol twice, obtain 9g brilliant white crystal 3-TPPMC, the productive rate of 3-TPPMC is 70%, and reaction formula is shown in following formula:
Product 3-TPPMC is carried out to nuclear magnetic resonance spectroscopy, and characterization result is as follows:
1h NMR (CDCl
3, 300MHz): δ=7.31-7.36 (m, 10H), 7.47 (m, 2H), 8.06ppm (t, J=7.2Hz, 2H);
31p{
1h}NMR (CDCl
3, 161.9Hz): δ=-5.94ppm (s); MALDI-TOF (m/z): 305.1[M-H]
-.Hence one can see that, and 3-TPPMC can successfully be prepared.
Synthesizing of embodiment 4:4-(diphenylphosphine) benzenephosphonic acid (4-TPPMP)
In being furnished with the 100ml tri-neck round-bottomed flasks of prolong, add 4-(diphenylphosphine) bromobenzene, 40ml toluene, 0.89gHP (O) of 2g (OEt)
2with 0.65g triethylamine, add 70mgPd (TPP) after substituting gas
4, reaction solution is heated to 80 ℃ and stirs 48h.Reaction solution after stirring is cooled to after room temperature, organic phase washed several times with water, anhydrous sodium sulfate drying filters, and concentrates and obtains 3.24g yellow oil, and gained yellow oil is suc as formula the first intermediate product shown in 2a.The productive rate of 2a is 60%.
Product 2a is carried out to nuclear magnetic resonance spectroscopy, and characterization result is as follows:
31p{
1h}NMR (CDCl
3, 161.9Hz): δ=-3.8 (P
iII), 19.4 (P
v) ppm.Hence one can see that, and 2a can successfully be prepared.
The 2a of 2.8g is dissolved in after 50ml methylene dichloride, adds 6.5gMe
3siBr, underpressure distillation after stirring at room 12h, last product is dissolved in 50ml acetone, adds stirring at room 2h after little water.Underpressure distillation, except after desolventizing, adds the dense NaOH aqueous solution of 20ml again.Mixed solution is poured in ethanol, separates out yellow solid, after washing with alcohol is dry, obtains Alendronate part 3a, and the productive rate of 3a is 70%.
Product 3a is carried out to nuclear magnetic resonance spectroscopy, and characterization result is as follows:
31p{
1h}NMR (D
2o, 161.9Hz): δ=-5.5 (P
iII), 12.0 (P
v) ppm.Hence one can see that, and 3a can successfully be prepared.
Alendronate part 3a is dissolved in methanol hydrochloride solution, obtains 4-TPPMP.Above-mentioned series reaction is shown in following formula:
Synthesizing of embodiment 5:4-(diphenylphosphine) benzoyl thanomin (4-TPPMN)
In being furnished with the 250ml tri-neck round-bottomed flasks of prolong, the 4-TPPMC and the 100mlMeOH that add 3g, after substituting gas, add the 1ml vitriol oil, reaction solution is heated to 70 ℃ and stirs 6h, then add triethylamine that reaction solution is adjusted to after neutrality, add 10ml, 160mmol thanomin, substitute after gas, reaction solution is heated to 70 ℃ and stirs 12h.After reaction solution after stirring is cooled to room temperature, solvent is steamed, with methylene dichloride dilution after washing for several times, organic phase anhydrous sodium sulfate drying filters, separated with silicagel column after concentrating, and obtains 2.45g white solid 4-TPPMN.The productive rate of 4-TPPMN is 70%.The reaction formula of above-mentioned reaction process is shown below:
Product 4-TPPMN is carried out to nuclear magnetic resonance spectroscopy, and characterization result is as follows:
1h NMR (CDCl
3, 300MHz): δ=7.735 (dd, J=4.2Hz, 2H), 7.38-7.28 (m, 12H), 6.91 (s, 1H), 3.81 (t, J=4.8Hz, 2H), 3.61 (d, J=3.9Hz, 2H), 2.97ppm (s, 1H);
31p{
1h}NMR (CDCl
3, 162MHz): δ=-5.76ppm (s); MALDI-TOF (m/z): 350.1[M+H]
+.Hence one can see that, and 4-TPPMN can successfully be prepared.
Synthesizing of embodiment 6:3-(diphenylphosphine) benzoyl thanomin (3-TPPMN)
In being furnished with the 250ml tri-neck round-bottomed flasks of prolong, add 3g 3-TPPMC and 100ml MeOH, after substituting gas, add the 1ml vitriol oil, reaction solution is heated to 70 ℃ and stirs 6h, then add triethylamine that reaction solution is adjusted to after neutrality, add 10ml, 160mmol thanomin, substitutes after gas reaction solution and is heated to 70 ℃ and stirs 12h.After reaction solution after stirring is cooled to room temperature, solvent is steamed, with methylene dichloride dilution after washing for several times, organic phase anhydrous sodium sulfate drying filters, separated with silicagel column after concentrating, and obtains 2.15g white solid 3-TPPMN.The productive rate of 3-TPPMN is 62%.The reaction formula of above-mentioned reaction process is shown below:
Product 3-TPPMN is carried out to nuclear magnetic resonance spectroscopy, and the characterization result of product 3-TPPMN is as follows:
1h NMR (CDCl
3, 300MHz): δ=7.75 (br, 2H), 7.36-7.24 (m, 12H), 6.65 (s, 1H), 3.75 (t, J=4.9Hz, 2H), 3.54ppm (q, J=5.4Hz, 2H),
31p{
1h}NMR (CDCl
3, 162MHz): δ=-5.67ppm (s); MALDI-TOF (m/z): 350.1[M+H]
+.Hence one can see that, and 3-TPPMN can successfully be prepared.
Synthesizing of embodiment 7:4-(diphenylphosphine) benzoyl diethanolamine (4-TPPMDN)
In being furnished with the 250ml tri-neck round-bottomed flasks of prolong, add 3g 4-TPPMC and 100ml MeOH, after substituting gas, add the 1ml vitriol oil, reaction solution is heated to 70 ℃ and stirs 6h, then add triethylamine that reaction solution is adjusted to after neutrality, add 10ml, 95mmol diethanolamine, substitutes after gas reaction solution and is heated to 70 ℃ and stirs 12h.After being cooled to room temperature, solvent is steamed, with methylene dichloride dilution after washing for several times, organic phase anhydrous sodium sulfate drying filters, concentrated rear separated with silicagel column, obtains 2.91g white solid 4-TPPMDN.The productive rate of 4-TPPMDN is 74%.The reaction formula of above-mentioned reaction process is shown below:
Product 4-TPPMDN is carried out to nuclear magnetic resonance spectroscopy, and characterization result is as follows:
1h NMR (CDCl
3, 400MHz): δ=7.47 (d, J=6.8Hz, 2H), 7.38-7.30 (m, 12H), 4.00 (br, 2H), 3.73 (br, 4H), 3.48ppm (br, 2H);
31p{
1h}NMR (CDCl
3, 162MHz): δ=-5.77ppm (s); MALDI-TOF (m/z): 394.1[M+H]
+.Hence one can see that, and 4-TPPMDN can successfully be prepared.
Synthesizing of embodiment 8:3-(diphenylphosphine) benzoyl diethanolamine (3-TPPMDN)
In being furnished with the 250ml tri-neck round-bottomed flasks of prolong, add 3g 3-TPPMC and 100ml MeOH, after substituting gas, add the 1ml vitriol oil, reaction solution is heated to 70 ℃ and stirs 6h, then add triethylamine that reaction solution is adjusted to after neutrality, add 10ml, 95mmol diethanolamine, substitutes after gas reaction solution and is heated to 70 ℃ and stirs 12h.After reaction solution after stirring is cooled to room temperature, solvent is steamed, with methylene dichloride dilution after washing for several times, organic phase anhydrous sodium sulfate drying filters, separated with silicagel column after concentrating, and obtains 2.55g white solid 3-TPPMDN.The productive rate of 3-TPPMDN is 65%.The reaction formula of above-mentioned reaction process is shown below:
Product 3-TPPMDN is carried out to nuclear magnetic resonance spectroscopy, and the characterization result of product 3-TPPMDN is as follows:
1h NMR (CDCl
3, 300MHz): δ=7.49 (tt, J=7.2Hz, 1H), 7.37-7.30 (m, 13H), 3.95 (br, 2H), 3.62 (br, 4H), 3.36ppm (br, 2H);
31p{
1h}NMR (CDCl
3, 162MHz): δ=-5.65ppm (s); MALDI-TOF (m/z): 394.1[M+H]
+.Hence one can see that, and 3-TPPMDN can successfully be prepared.
Embodiment 9:4-TPPND1's is synthetic
In 100ml round-bottomed flask, add 1.53g 4-TPPMC and 20ml methylene dichloride (DCM), after dissolving completely, reaction flask is placed in ice-water bath, then adds 1.44g EDC HCl, and mixed solution stirs in a moment, adds 1ml, 7.5mmol triethylamine (NEt
3) and 10ml containing the DCM solution of 1.0g di-alcohol dme amine, substitute destiny time, under argon shield, at 0 ℃, stir after 2h, room temperature continues to stir 24h.After reaction finishes, separated with silicagel column, obtain 0.31g colorless oil product 4-TPPND1.The productive rate of 4-TPPND 1 is 74%.The reaction formula of above-mentioned reaction process is shown below:
Product 4-TPPND1 is carried out to nuclear magnetic resonance spectroscopy, and characterization result is as follows:
1h NMR (CDCl
3, 300MHz): δ=7.39-7.28 (m, 14H), 3.70 (d, J=28.5Hz, 4H), 3.48 (d, J=30.0Hz, 4H), 3.37 (s, 3H), 3.26ppm (s, 3H);
31p{
1h}NMR (CDCl
3, 162MHz): δ=-5.76ppm (s); MALDI-TOF (m/z): 422.2[M+H]
+.Hence one can see that, and 4-TPPND1 can successfully be prepared.
Embodiment 10:3-TPPND1's is synthetic
In 100ml round-bottomed flask, add 1.53g 3-TPPMC and 20ml DCM, after dissolving completely, reaction flask is placed in ice-water bath, then adds 1.44g EDC HCl, and mixed solution stirs in a moment, adds 1ml, 7.5mmol NEt
3with the DCM solution of 10ml containing the di-alcohol dme amine of 1.0g, substitute destiny time, under argon shield, at 0 ℃, stir after 2h, room temperature continues to stir 24h.Reaction finishes rear separated with silicagel column, obtains 0.29g colorless oil product 3-TPPND1.The productive rate of 3-TPPND1 is 71%.The reaction formula of above-mentioned reaction process is shown below:
Product 3-TPPND1 is carried out to nuclear magnetic resonance spectroscopy, and the structural characterization of product 3-TPPND1 is as follows:
1h NMR (CDCl
3, 300MHz): δ=7.37-7.27 (m, 14H), 3.63 (d, J=27.6Hz, 4H), 3.40 (br, 2H), 3.31 (s, 3H), 3.24 (br, 2H), 3.14ppm (s, 3H);
31p{
1h}NMR (CDCl
3, 162MHz): δ=-5.49ppm (s); MALDI-TOF (m/z): 422.2[M+H]
+.Hence one can see that, and 3-TPPND1 can successfully be prepared.
Embodiment 11:
Reaction expression is as follows:
1, the first intermediate product 1b's is synthetic
In being furnished with the 250ml tri-neck round-bottomed flasks of constant pressure funnel, add 16.8g diethanolamine and 50ml dimethyl formamide (DMF), mixed solution is cooled to 0 ℃.22.32g triphenylmethyl chloride slowly splashes into the above-mentioned mixed solution that is cooled to 0 ℃ after being dissolved in 100ml DCM, and reaction solution is continued to stir 24h at low temperatures.Recover after room temperature, add after ether washing repeatedly, separate out a large amount of white precipitates.Filtering-depositing obtains 19.5g white solid 1b with DCM/PE recrystallization.The productive rate of the first intermediate product 1b is 70%.
The first intermediate product 1b is carried out to nuclear magnetic resonance spectroscopy, and characterization result is as follows:
1hNMR (CDCl
3, 300MHz): δ=7.55 (d, J=7.2Hz, 6H), 7.26 (t, J=7.5Hz, 6H), 7.16 (t, J=7.2Hz, 3H), 3.78 (t, J=6.3Hz, 4H), 2.57ppm (t, J=6.3Hz, 4H).Hence one can see that, and the first intermediate product 1b can successfully be prepared.
2, the second intermediate product 2b's is synthetic
In 500ml round-bottomed flask, add 110mmol oxyethyl group mono-methyl and 150ml THF, 13.2g NaOH adds in round-bottomed flask after being dissolved in 60ml water, mixed solution is placed in ice-water bath, slowly splashes into 150ml containing the THF solution of 41.8g p-methyl benzene sulfonic chloride under low temperature.Then continue at room temperature to stir 4h.Reaction solution adds after distilled water diluting, extracted with diethyl ether, and after organic phase washed several times with water, anhydrous sodium sulfate drying, filtration and concentrated, obtain colourless oil liquid 2b, and the productive rate of the second intermediate product 2b is 95～99%.
The second intermediate product 2b is carried out to nuclear magnetic resonance spectroscopy, and characterization result is as follows:
TsOCH
2CH
2OMe(TsO1)：
1H NMR(CDCl3，300MHz)：δ＝7.76(d，J＝8.1Hz，2H)，7.31(d，J＝7.8Hz，2H)，4.11(t，J＝4.5Hz，2H)，3.53(t，J＝4.8Hz，2H)，3.26(s，3H)，2.40ppm(s，3H)。
TsO(CH
2CH
2O)
2Me(TsO2)：
1H NMR(CDCl
3，300MHz)：δ＝7.80(d，J＝8.1Hz，2H)，7.34(d，J＝7.8Hz，2H)，4.17(t，J＝4.8Hz，2H)，3.69(t，J＝5.1Hz，2H)，3.58(t，J＝3.9Hz，2H)，3.48(t，J＝4.2Hz，2H)，3.35(s，3H)，2.4ppm(s，3H)。
TsO(CH
2CH
2O)
3Me(TsO3)：
1H NMR(CDCl
3，300MHz)：δ＝7.74(d，J＝8.4Hz，2H)，7.29(d，J＝8.4Hz，2H)，4.10(t，J＝4.5Hz，2H)，3.63(t，J＝4.8Hz，2H)，3.56(t，J＝3.9Hz，6H)，3.47(t，J＝3.3Hz，2H)，3.31(s，3H)，2.39ppm(s，3H)。Hence one can see that, and the second intermediate product 2b can successfully be prepared.
3, the 3rd intermediate product 3b's is synthetic
In 250ml round-bottomed flask, add the dense NaOH aqueous solution of 30ml and 0.5g Tetrabutyl amonium bromide, the first intermediate product 1b and the second intermediate product 2b mixing are dissolved in after 50mlTHF, add in reaction flask reaction solution return stirring 18h.Be cooled to after room temperature, add after distilled water diluting, extracted with diethyl ether, after organic phase washed several times with water, anhydrous sodium sulfate drying, filtration and concentrated, separated with silicagel column, obtain colourless oil liquid 3b, the productive rate of the 3rd intermediate product 3b is 70-75%.
The 3rd intermediate product 3b is carried out to nuclear magnetic resonance spectroscopy, and characterization result is as follows:
TPCN[(CH
2CH
2O)
2Me]
2(TPN2)：
1H NMR(CDCl
3，300MHz)：δ＝7.48(d，J＝7.8Hz，6H)，7.22(t，J＝7.2Hz，6H)，7.11(t，J＝7.5Hz，3H)，3.61(t，J＝7.2Hz，4H)，3.52-3.47(m，8H)，3.34(s，6H)，2.56ppm(t，J＝7.2Hz，4H)。
TPCN[(CH
2CH
2O)
3Me]
2(TPN3)：
1H NMR(CDCl
3，300MHz)：δ＝7.51(t，J＝7.8Hz，6H)，7.23(t，J＝7.8Hz，6H)，7.13(t，J＝7.5Hz，3H)，3.62-3.52(m，20H)，3.37(s，6H)，2.55ppm(t，J＝6.9Hz，4H)。
TPCN[(CH
2CH
2O)
4Me]
2(TPN4)：
1H NMR(CDCl
3，300MHz)：δ＝7.50(d，J＝7.8Hz，6H)，7.21(t，J＝7.8Hz，6H)，7.11(t，J＝7.2Hz，3H)，3.62-3.51(m，28H)，3.34(s，6H)，2.52ppm(t，J＝6.0Hz，4H)。Hence one can see that, and the 3rd intermediate product 3b can successfully be prepared.
4,4b's is synthetic
The diluted hydrochloric acid aqueous solution that adds 20ml 5% in 100ml round-bottomed flask, the 3rd intermediate product 3b is dissolved in after 40ml methyl alcohol, is added dropwise in reaction flask, separates out immediately white precipitate, reaction solution stirring at room 15min.After sedimentation and filtration, methyl alcohol in filtrate is boiled off, water is with after extracted with diethyl ether several, saturated aqueous sodium carbonate is neutralized to neutrality, and underpressure distillation, except anhydrating, adds DCM stirring at room 2h, elimination is not after dissolved solids, organic phase anhydrous sodium sulfate drying, filtration and concentrated, obtain colorless oil product 4b, and the productive rate of 4b is 60-70%.
Product 4b is carried out to nuclear magnetic resonance spectroscopy, and characterization result is as follows:
HN[(CH
2CH
2O)
2Me]
2(HN2)：
1H NMR(CDCl
3，300MHz)：δ＝3.63-3.60(m，8H)，3.57-3.55(m，4H)，3.39(br，6H)，2.84ppm(br，4H)。
HN[(CH
2CH
2O)
3Me]
2(HN3)：
1H NMR(CDCl
3，600MHz)：δ＝3.86(t，J＝5.4Hz，4H)，3.70-3.68(m，4H)，3.67-3.64(m，8H)，3.56-3.54(m，4H)，3.38(s，6H)，3.19ppm(t，J＝5.4Hz，4H)。
HN[(CH
2CH
2O)
4Me]
2(HN4)：
1H NMR(CDCl
3，300MHz)：δ＝3.60-3.48(m，28H)，3.32(br，6H)，2.75ppm(t，J＝3.3Hz，4H)。Hence one can see that, and 4b can successfully be prepared.
Embodiment 12:4-TPPND2's is synthetic
In 100ml round-bottomed flask, add 1.53g 4-TPPMC and 20ml DCM, after dissolving completely, reaction flask is placed in ice-water bath, then adds 1.44g EDC HCl, and mixed solution stirs in a moment, adds 1ml, the NEt of 7.5mmol
3with the DCM solution of 10ml containing 1.66g HN2, substitute destiny time, under argon shield, at 0 ℃, stir after 2h, at room temperature continue to stir 24h.Reaction finishes rear separated with silicagel column, obtains 0.35g colorless oil product 4-TPPND2, and the productive rate of 4-TPPND2 is 69%.
Product 4-TPPND2 is carried out to nuclear magnetic resonance spectroscopy, and characterization result is as follows:
1h NMR (CDCl
3, 300MHz): δ=7.37-7.24 (m, 14H), 3.73 (br, 4H), 3.60-3.44 (m, 12H), 3.36 (s, 3H), 3.29ppm (s, 3H);
31p{
1h}NMR (CDCl
3, 162MHz): δ=-5.79ppm (s); MALDI-TOF (m/z): 510.2[M+H]
+.Hence one can see that, and 4-TPPND2 can successfully be prepared.
Embodiment 13:3-TPPND2's is synthetic
In 100ml round-bottomed flask, add 1.53g 3-TPPMC and 20ml DCM, raw material dissolves rear reaction flask completely and is placed in ice-water bath, then adds 1.44g EDC HCl, and mixed solution stirs in a moment, adds 1ml, 7.5mmol NEt
3with the DCM solution of 10ml containing 1.66g HN2.Substitute destiny time, under argon shield, at 0 ℃, stir after 2h, at room temperature continue to stir 24h.Reaction finishes rear separated with silicagel column, obtains 0.34g colorless oil product 3-TPPND2, and the productive rate of 3-TPPND2 is 67%.
3-TPPND2 is carried out to nuclear magnetic resonance spectroscopy, and characterization result is as follows:
1hNMR (CDCl
3, 300MHz): δ=7.39-7.29 (m, 14H), 3.72 (br, 4H), 3.60 (br, 2H), 3.59-3.43 (br, 10H), 3.36ppm (s, 6H);
31p{
1h}NMR (CDCl
3, 162MHz): δ=-5.48ppm (s); MALDI-TOF (m/z): 510.2[M+H]
+.Hence one can see that, and 3-TPPND2 can successfully be prepared.
Embodiment 14:4-TPPND3's is synthetic
In 100ml round-bottomed flask, add 1.53g 4-TPPMC and 20mlDCM, after dissolving completely, reaction flask is placed in ice-water bath, then adds 1.44g EDC HCl, and mixed solution stirs in a moment, adds 1ml, 7.5mmol NEt
3with the DCM solution of 10ml containing 2.32g HN3.Substitute destiny time, under argon shield, at 0 ℃, stir after 2h, at room temperature continue to stir 24h.Reaction finishes rear separated with silicagel column, obtains 0.40g colorless oil product 4-TPPND3, and the productive rate of 4-TPPND3 is 67%.
4-TPPND3 is carried out to nuclear magnetic resonance spectroscopy, and characterization result is as follows:
1h NMR (CDCl
3, 300MHz): δ=7.39-7.29 (m, 14H), 3.75 (br, 4H), 3.69-3.52 (br, 20H), 3.35ppm (s, 6H);
31p{
1h}NMR (CDCl
3, 162MHz): δ=-5.81ppm (s); MALDI-TOF (m/z): 598.2[M+H]
+.Hence one can see that, and 4-TPPND3 can successfully be prepared.
Embodiment 15:3-TPPND3's is synthetic
In 100ml round-bottomed flask, add 1.53g 3-TPPMC and 20ml DCM, after dissolving completely, reaction flask is placed in ice-water bath, then adds 1.44g EDC HCl, and mixed solution stirs in a moment, adds 1ml, 7.5mmol NEt
3with the DCM solution of 10ml containing 2.32g HN3.Substitute destiny time, under argon shield, at 0 ℃, stir after 2h, at room temperature continue to stir 24h.Reaction finishes rear separated with silicagel column, obtains 0.38g colorless oil product 3-TPPND3, and the productive rate of 3-TPPND3 is 65%.
3-TPPND3 is carried out to nuclear magnetic resonance spectroscopy, and characterization result is as follows:
1h NMR (CDCl
3, 300MHz): δ=7.39-7.28 (m, 14H), 3.71 (br, 4H), 3.62 (br, 8H), 3.54 (s, 6H), 3.44 (br, 4H), 3.37ppm (br, 8H);
31p{
1h}NMR (CDCl
3, 162MHz): δ=-5.50ppm (s); MALDI-TOF (m/z): 598.2[M+H]
+.Hence one can see that, and 3-TPPND3 can successfully be prepared.
Embodiment 16:4-TPPND4's is synthetic
In 100ml round-bottomed flask, add 1.53g 4-TPPMC and 20ml DCM, after dissolving completely, reaction flask is placed in ice-water bath, then adds 1.44g EDC HCl, and mixed solution stirs in a moment, adds 1ml, 7.5mmol NEt
3with the DCM solution of 10ml containing 2.98g HN4.Substitute destiny time, under argon shield, at 0 ℃, stir after 2h, room temperature continues to stir 24h.Reaction finishes rear separated with silicagel column, obtains 0.45g colorless oil 4-TPPND4, and the productive rate of 4-TPPND4 is 66%.
4-TPPND4 is carried out to nuclear magnetic resonance spectroscopy, and characterization result is as follows:
1h NMR (CDCl
3, 300MHz): δ=7.39-7.29 (m, 14H), 3.74 (br, 4H), 3.64-3.51 (br, 28H), 3.36ppm (s, 6H);
31p{
1h}NMR (CDCl
3, 162MHz): δ=-5.82ppm (s); MALDI-TOF (m/z): 686.3[M+H]
+.Hence one can see that, and 4-TPPND4 can successfully be prepared.
Embodiment 17:3-TPPND4's is synthetic
In 100ml round-bottomed flask, add 1.53g 3-TPPMC and 20ml DCM, after dissolving completely, reaction flask is placed in ice-water bath, then adds 1.44g EDC HCl, and mixed solution stirs in a moment, adds 1ml, 7.5mmol NEt
3with the DCM solution of 10ml containing 2.98g HN4.Substitute destiny time, under argon shield, at 0 ℃, stir after 2h, at room temperature continue to stir 24h.Reaction finishes rear separated with silicagel column, obtains 0.44g colorless oil product 3-TPPND4, and the productive rate of 3-TPPND4 is 64%.
3-TPPND4 is carried out to nuclear magnetic resonance spectroscopy, and characterization result is as follows:
1h NMR (CDCl
3, 300MHz): δ=7.38-7.28 (m, 14H), 3.70 (br, 4H), 3.62 (br, 16H), 3.55-3.52 (m, 6H), 3.44-3.37 (m, 12H);
31p{
1h}NMR (CDCl
3, 162MHz): δ=-5.51ppm (s); MALDI-TOF (m/z): 686.3[M+H]
+.Hence one can see that, and 3-TPPND4 can successfully be prepared.
Embodiment 18:PdCl
2(3-TPPMSH)
2synthesizing of divalence palladium complex
The PdCl that adds 0.177g in 100ml single necked round bottom flask
2with 30ml CH
3cN, at room temperature stirs after 6h and all dissolves, and after the amphipathic part 3-TPPMSH of 2mmol is dissolved in 10ml methyl alcohol, adds in reaction flask, after mixed solution stirring at room 0.5h, add a large amount of ether, after the yellow mercury oxide of separating out filters, with ethyl alcohol recrystallization, obtain the orange-yellow crystal PdCl of 0.61g
2(3-TPPMSH)
2, PdCl
2(3-TPPMSH)
2productive rate be 70%.To product P dCl
2(3-TPPMSH)
2carry out nuclear magnetic resonance spectroscopy, characterization result is as follows:
1hNMR (D
2o, 400MHz): δ=7.25-7.35 (m, 10H), 7.38-7.45 (m, 14H), 7.82 (d, J=7.6Hz, 2H), 7.88ppm (d, J=12.0Hz, 2H);
31p{
1h}NMR (D
2o, 161.9Hz): δ=36.97ppm (s).elemental analysis calcd(％)forC
36H
30Cl
2O
6P
2PdS
2·2H
2O：C 48.15，H 3.82；found：C，48.06，H，3.84。Hence one can see that PdCl
2(3-TPPMSH)
2can successfully prepare.
Embodiment 19:PdCl
2(4-TPPMC)
2synthesizing of divalence palladium complex
The PdCl that adds 0.177g in 100ml single necked round bottom flask
2with 30ml CH
3cN, all dissolves after stirring at room 6h, after the amphipathic part 4-TPPMC of 2mmol is dissolved in 10ml methyl alcohol, adds in reaction flask, after mixed solution stirring at room 0.5h, add a large amount of ether, after the yellow mercury oxide of separating out filters, use THF recrystallization, obtain 0.68g glassy yellow crystal PdCl
2(4-TPPMC)
2, PdCl
2(4-TPPMC)
2productive rate be 87%.
To product P dCl
2(4-TPPMC)
2carry out nuclear magnetic resonance spectroscopy, characterization result is as follows:
1hNMR (DMSO-d
6, 300MHz): δ=7.32-7.56 (m, 12H), 7.63-7.70 (m, 12H), 7.98ppm (d, J=8.1Hz, 4H);
31p{
1h}NMR (DMSO-d
6, 161.9Hz): δ=28.51ppm (s).elemental analysis calcd(％)for C
38H
30Cl
2O
4P
2Pd：C，57.78；H，3.83；found：C，57.69，H，4.02。Crystalline structure figure is shown in accompanying drawing 1.Hence one can see that PdCl
2(4-TPPMC)
2can successfully prepare.
Example 20:PdCl
2(3-TPPMC)
2synthesizing of divalence palladium complex
The PdCl that adds 0.177g in 100ml single necked round bottom flask
2with 30ml CH
3cN, at room temperature stirs after 6h and all dissolves.After the amphipathic part 3-TPPMC of 2mmol is dissolved in 10ml methyl alcohol, add in reaction flask, after mixed solution stirring at room 0.5h, add a large amount of ether, the yellow mercury oxide of separating out is used THF recrystallization after filtering, and obtains 0.67g glassy yellow crystal PdCl
2(3-TPPMC)
2, PdCl
2(3-TPPMC)
2productive rate be 85%.
To PdCl
2(3-TPPMC)
2carry out nuclear magnetic resonance spectroscopy, characterization result is as follows:
1h NMR (DMSO-d
6, 300MHz): δ=7.29-7.36 (m, 2H), 7.48-7.74 (m, 22H), 8.05 (d, J=7.8Hz, 2H), 8.19ppm (t, J=5.7Hz, 2H);
31p{
1h}NMR (CDCl
3, 161.9Hz): δ=24.03ppm (s).elemental analysis calcd(％)forC
38H
30C
12O
4P
2Pd·2THF：C 59.27，H 4.76；found：C，59.11，H，4.76。Crystalline structure figure is shown in accompanying drawing 2.Hence one can see that PdCl
2(3-TPPMC)
2can successfully prepare.
Embodiment 21:PdCl
2(4-TPPMP)
2synthesizing of divalence palladium complex
In 100ml single necked round bottom flask, add 0.177g PdCl
2with 30ml CH
3cN, all dissolves after stirring at room 6h, after the amphipathic part 4-TPPMP of 2mmol is dissolved in 10ml methyl alcohol, adds in reaction flask, after mixed solution stirring at room 0.5h, add a large amount of ether, after the yellow mercury oxide of separating out filters, with ethyl alcohol recrystallization, obtain 0.52g yellow crystals PdCl
2(4-TPPMP)
2, PdCl
2(4-TPPMP)
2productive rate be 61%.
To PdCl
2(4-TPPMP)
2carry out nuclear magnetic resonance spectroscopy, characterization result is as follows:
1h NMR (D
2o, 400MHz): δ=7.36-7.44 (m, 10H), 7.40-7.49 (m, 14H), 7.91 (d, J=7.6Hz, 2H), 7.92ppm (d, J=12.0Hz, 2H);
31p{
1h}NMR (D
2o, 161.9Hz): δ=37.67 (P
iII), 22.4ppm (P
v).elemental analysis calcd(％)forC
36H
32Cl
2O
6P
4Pd·2H
2O：C，48.16；H，4.04；found：C，48.10，H，3.98。Hence one can see that PdCl
2(4-TPPMP)
2can successfully prepare.
Embodiment 22:PdCl
2(4-TPPMN)
2synthesizing of divalence palladium complex
In 100ml single necked round bottom flask, add 0.177g PdCl
2with 30ml CH
3cN, all dissolves after stirring at room 6h, after the amphipathic part 4-TPPMN of 2mmol is dissolved in 10ml methyl alcohol, adds in reaction flask, after mixed solution stirring at room 0.5h, add a large amount of ether, after the yellow mercury oxide of separating out filters, use ethanol/methylene recrystallization, obtain 0.62g yellow crystals PdCl
2(4-TPPMN)
2, PdCl
2(4-TPPMN)
2productive rate be 71%.
To PdCl
2(4-TPPMN)
2carry out nuclear magnetic resonance spectroscopy, characterization result is as follows:
1h NMR (DMSO-d
6, 300MHz): δ=8.54 (t, J=5.7Hz, 2H), 7.86 (d, J=7.8Hz, 4H), 7.65-7.26 (m, 24H), 3.45 (t, J=6.0Hz, 4H), 3.28ppm (t, J=6.0Hz, 4H);
31p{
1h}NMR (DMSO-d
6, 161.9Hz): δ=24.42ppm (s).elemental analysis calcd(％)for C
42H
40Cl
2N
2O
4P
2Pd：C，57.58；H，4.60；found：C，57.63，H，4.559。Hence one can see that PdCl
2(4-TPPMN)
2can successfully prepare.
Embodiment 23:PdCl
2(3-TPPMN)
2synthesizing of divalence palladium complex
In 100ml single necked round bottom flask, add 0.177g PdCl
2with 30ml CH
3cN, all dissolves after stirring at room 6h, after the amphipathic part 3-TPPMN of 2mmol is dissolved in 10ml methyl alcohol, adds in reaction flask, after mixed solution stirring at room 0.5h, add a large amount of ether, after the yellow mercury oxide of separating out filters, use ethanol/methylene recrystallization, obtain 0.65g yellow crystals PdCl
2(3-TPPMN)
2, PdCl
2(3-TPPMN)
2productive rate be 74%.
To PdCl
2(3-TPPMN)
2carry out nuclear magnetic resonance spectroscopy, characterization result is as follows:
1h NMR (CDCl
3, 300MHz): δ=8.37 (br, 2H), 7.87-7.40 (m, 24H), 6.94 (br, 2H), 3.70 (br, 4H), 3.51ppm (br, 4H);
31p{
1h}NMR (CDCl
3, 161.9Hz): δ=23.30ppm (s).elemental analysis calcd(％)for C
42H
40Cl
2N
2O
4P
2Pd：C，57.58；H，4.60；found：C，57.83，H，4.506。Hence one can see that PdCl
2(3-TPPMN)
2can successfully prepare.
Embodiment 24:PdCl
2(4-TPPMDN)
2synthesizing of divalence palladium complex
In 100ml single necked round bottom flask, add 0.177g PdCl
2with 30ml CH
3cN, all dissolves after stirring at room 6h, after the amphipathic part 4-TPPMDN of 2mmol is dissolved in 10ml methyl alcohol, adds in reaction flask, after mixed solution stirring at room 0.5h, add a large amount of ether, after the yellow mercury oxide of separating out filters, use ethanol/methylene recrystallization, obtain 0.74g yellow crystals PdCl
2(4-TPPMDN)
2, PdCl
2(4-TPPMDN)
2productive rate be 77%.
To PdCl
2(4-TPPMDN)
2carry out nuclear magnetic resonance spectroscopy, characterization result is as follows:
1h NMR (DMSO-d
6, 300MHz): δ=7.63-7.45 (m, 24H), 7.27 (t, J=7.8Hz, 2H), 3.56 (br, 4H), 3.46 (br, 8H), 3.26ppm (br, 4H);
31p{
1h}NMR (DMSO-d
6, 161.9Hz): δ=23.40ppm (s).elemental analysis calcd(％)forC
46H
48Cl
2N
2O
6P
2Pd·H
2O：C，56.25；H，5.13；found：C，56.24，H，4.922。Hence one can see that PdCl
2(4-TPPMDN)
2can successfully prepare.
Embodiment 25:PdCl
2(3-TPPMDN)
2synthesizing of divalence palladium complex
In 100ml single necked round bottom flask, add 0.177g PdCl
2with 30ml CH
3cN, all dissolves after stirring at room 6h, after the amphipathic part 3-TPPMDN of 2mmol is dissolved in 10ml methyl alcohol, adds in reaction flask, after mixed solution stirring at room 0.5h, add a large amount of ether, after the yellow mercury oxide of separating out filters, use ethanol/methylene recrystallization, obtain 0.68g yellow crystals PdCl
2(3-TPPMDN)
2, PdCl
2(3-TPPMDN)
2productive rate be 72%.
To PdCl
2(3-TPPMDN)
2carry out nuclear magnetic resonance spectroscopy, characterization result is as follows:
1h NMR (CDCl
3, 300MHz): δ=8.11 (q, J=6.6Hz, 2H), 7.76 (tt, J=16.2Hz, 6H), 7.55-7.33 (m, 16H), 7.18 (t, J=5.7Hz, 2H), 3.93 (br, 4H), 3.71 (br, 4H), 3.39ppm (br, 8H);
31p{
1h}NMR (CDCl
3, 161.9Hz): δ=23.93ppm (s).elemental analysis calcd(％)for C
46H
48Cl
2N
2O
6P
2Pd·H
2O：C，56.25；H，5.13；found：C，56.90，H，5.078。Hence one can see that PdCl
2(3-TPPMDN)
2can successfully prepare.
Embodiment 26:PdCl
2(4-TPPND1)
2synthesizing of divalence palladium complex
In 100ml single necked round bottom flask, add 0.177g PdCl
2with 30ml CH
3cN, all dissolves after stirring at room 6h, after the amphipathic part 4-TPPND1 of 2mmol is dissolved in 10ml methyl alcohol, adds in reaction flask, after mixed solution stirring at room 0.5h, add a large amount of ether, after the yellow mercury oxide of separating out filters, use ethanol/methylene recrystallization, obtain 0.68g yellow crystals PdCl
2(4-TPPND1)
2, PdCl
2(4-TPPND 1)
2productive rate be 75%.
To PdCl
2(4-TPPND1)
2carry out nuclear magnetic resonance spectroscopy, characterization result is as follows:
1h NMR (CDCl
3, 300MHz): δ=7.75-7.65 (m, 12H), 7.49-7.38 (m, 16H), 3.70 (d, J=30.0Hz, 8H), 3.45 (d, J=24.6Hz, 8H), 3.65 (s, 6H), 3.22ppm (s, 6H);
31p{
1h}NMR (CDCl
3, 161.9Hz): δ=22.97ppm (s).elementalanalysis calcd(％)for C
50H
56C
12N
2O
6P
2Pd·H
2O：C，57.84；H，5.63；found：C，57.97，H，5.595。Hence one can see that PdCl
2(4-TPPND 1)
2can successfully prepare.
Embodiment 27:PdCl
2(3-TPPNDl)
2synthesizing of divalence palladium complex
In 100ml single necked round bottom flask, add 0.177g PdCl
2with 30ml CH
3cN, all dissolves after stirring at room 6h, after the amphipathic part 3-TPPND1 of 2mmol is dissolved in 10ml methyl alcohol, adds in reaction flask, after mixed solution stirring at room 0.5h, add a large amount of ether, after the yellow mercury oxide of separating out filters, use ethanol/methylene recrystallization, obtain 0.73g yellow crystals PdCl
2(3-TPPND1)
2, PdCl
2(3-TPPND1)
2productive rate be 72%.
To PdCl
2(3-TPPND1)
2carry out nuclear magnetic resonance spectroscopy, characterization result is as follows:
1h NMR (CDCl
3, 300MHz): δ=7.73 (q, J=6.3Hz, 10H), 7.61 (t, J=5.7Hz, 2H), 7.52-7.38 (m, 16H), 3.70 (br, 4H), 3.60 (br, 4H), 3.42 (br, 4H), 3.32 (s, 6H), 3.20 (br, 4H), 3.06ppm (s, 6H);
31p{
1h}NMR (CDCl
3, 161.9Hz): δ=23.48ppm (s).elemental analysis calcd(％)forC
50H
56C
12N
2O
6P
2Pd：C，58.86；H，5.53，found：C，58.81；H，5.564。Hence one can see that PdCl
2(3-TPPNDl)
2can successfully prepare.
Embodiment 28:PdCl
2(4-TPPND2)
2synthesizing of divalence palladium complex
In 100ml single necked round bottom flask, add 0.177g PdCl
2with 30ml CH
3cN, all dissolves after stirring at room 6h, after the amphipathic part 4-TPPND2 of 2mmol is dissolved in 10ml methyl alcohol, adds in reaction flask, after mixed solution stirring at room 0.5h, add a large amount of ether, after the yellow mercury oxide of separating out filters, separated with silicagel column, obtain 0.93g yellow liquid PdCl
2(4-TPPND2)
2, PdCl
2(4-TPPND2)
2productive rate be 78%.
To PdCl
2(4-TPPND2)
2carry out nuclear magnetic resonance spectroscopy, characterization result is as follows:
1h NMR (CDCl
3, 300MHz): δ=7.72-7.62 (m, 12H), 7.44-7.36 (m, 16H), 3.73 (br, 8H), 3.61 (br, 4H), 3.49 (br, 12H), 3.40 (br, 8H), 3.35 (s, 6H), 3.26ppm (s, 6H);
31p{
1h}NMR (CDCl
3, 161.9Hz): δ=22.98ppm (s).Hence one can see that PdCl
2(4-TPPND2)
2can successfully prepare.
Embodiment 29:PdCl
2(3-TPPND2)
2synthesizing of divalence palladium complex
In 100ml single necked round bottom flask, add 0.177g PdCl
2with 30ml CH
3cN, all dissolves after stirring at room 6h, after the amphipathic part 3-TPPND2 of 2mmol is dissolved in 10ml methyl alcohol, adds in reaction flask, after mixed solution stirring at room 0.5h, add a large amount of ether, after the yellow mercury oxide of separating out filters, separated with silicagel column, obtain 0.86g yellow liquid PdCl
2(3-TPPND2)
2, PdCl
2(3-TPPND2)
2productive rate be 72%.
To PdCl
2(3-TPPND2)
2carry out nuclear magnetic resonance spectroscopy, characterization result is as follows:
1h NMR (CDCl
3, 300MHz): δ=7.72 (q, J=6.3Hz, 10H), 7.59 (t, J=5.1Hz, 2H), 7.53-7.38 (m, 16H), 3.71 (br, 8H), 3.58 (br, 4H), 3.48-3.41 (m, 10H), 3.34 (br, 10H), 3.30ppm (s, 12H);
31p{
1h}NMR (CDCl
3, 161.9Hz): δ=23.46ppm (s).Hence one can see that PdCl
2(3-TPPND2)
2can successfully prepare.
Embodiment 30:PdCl
2(4-TPPND3)
2synthesizing of divalence palladium complex
In 100ml single necked round bottom flask, add 0.177g PdCl
2with 30ml CH
3cN, all dissolves after stirring at room 6h, after the amphipathic part 4-TPPND3 of 2mmol is dissolved in 10ml methyl alcohol, adds in reaction flask, after mixed solution stirring at room 0.5h, add a large amount of ether, after the yellow mercury oxide of separating out filters, separated with silicagel column, obtain 0.97g yellow liquid PdCl
2(4-TPPND3)
2, PdCl
2(4-TPPND3)
2productive rate be 71%.
To PdCl
2(4-TPPND3)
2carry out nuclear magnetic resonance spectroscopy, characterization result is as follows:
1h NMR (CDCl
3, 300MHz): δ=7.75-7.66 (m, 12H), 7.47-7.41 (m, 16H), 3.75 (br, 8H), 3.65 (br, 12H), 3.54-3.49 (m, 28H), 3.35 (s, 6H), 3.33ppm (s, 6H);
31p{
1h}NMR (CDCl
3, 161.9Hz): δ=23.00ppm (s).Hence one can see that PdCl
2(4-TPPND3)
2can successfully prepare.
Embodiment 31:PdCl
2(3-TPPND3)
2synthesizing of divalence palladium complex
In 100ml single necked round bottom flask, add 0.177g PdCl
2with 30ml CH
3cN, all dissolves after stirring at room 6h, after the amphipathic part 3-TPPND3 of 2mmol is dissolved in 10ml methyl alcohol, adds in reaction flask, after mixed solution stirring at room 0.5h, add a large amount of ether, after the yellow mercury oxide of separating out filters, separated with silicagel column, obtain 0.93g yellow liquid PdCl
2(3-TPPND3)
2, PdCl
2(3-TPPND3)
2productive rate be 68%.
To PdCl
2(3-TPPND3)
2carry out nuclear magnetic resonance spectroscopy, characterization result is as follows:
1h NMR (CDCl
3, 300MHz): δ=7.75-7.69 (m, 10H), 7.60-7.49 (m, 8H), 7.41 (br, 10H), 3.70 (br, 8H), 3.60-3.44 (m, 40H), 3.34ppm (s, 12H);
31p{
1h}NMR (CDCl
3, 161.9Hz): δ=23.44ppm (s).Hence one can see that PdCl
2(3-TPPND3)
2can successfully prepare.
Embodiment 32:PdCl
2(4-TPPND4)
2synthesizing of divalence palladium complex
In 100ml single necked round bottom flask, add 0.177g PdCl
2with 30ml CH
3cN, all dissolves after stirring at room 6h, after the amphipathic part 4-TPPND4 of 2mmol is dissolved in 10ml methyl alcohol, adds in reaction flask, after mixed solution stirring at room 0.5h, add a large amount of ether, after the yellow mercury oxide of separating out filters, separated with silicagel column, obtain 1.02g yellow liquid PdCl
2(4-TPPND4)
2, PdCl
2(4-TPPND4)
2productive rate be 66%.
To PdCl
2(4-TPPND4)
2carry out nuclear magnetic resonance spectroscopy, characterization result is as follows:
1h NMR (CDCl
3, 300MHz): δ=7.72-7.63 (m, 12H), 7.45-7.36 (m, 16H), 3.72 (br, 8H), 3.61-3.48 (m, 56H), 3.33ppm (s, 12H);
31p{
1h}NMR (CDCl
3, 161.9Hz): δ=23.01ppm (s).Hence one can see that PdCl
2(4-TPPND4)
2can successfully prepare.
Embodiment 33:PdCl
2(3-TPPND4)
2synthesizing of divalence palladium complex
In 100ml single necked round bottom flask, add 0.177g PdCl
2with 30ml CH
3cN, all dissolves after stirring at room 6h, after the amphipathic part 3-TPPND4 of 2mmol is dissolved in 10ml methyl alcohol, adds in reaction flask, after mixed solution stirring at room 0.5h, add a large amount of ether, after the yellow mercury oxide of separating out filters, separated with silicagel column, obtain 0.99g yellow liquid PdCl
2(3-TPPND4)
2, PdCl
2(3-TPPND4)
2productive rate be 64%.
To PdCl
2(3-TPPND4)
2carry out nuclear magnetic resonance spectroscopy, characterization result is as follows:
1h NMR (CDCl
3, 300MHz): δ=7.71 (q, J=5.7Hz, 10H), 7.56 (t, J=5.1Hz, 2H), 7.52-7.37 (m, 16H), 3.67 (br, 8H), 3.62-3.59 (br, 32H), 3.54-3.51 (m, 10H), 3.45-3.40 (m, 8H), 3.36 (s, 12H), 3.31ppm (br, 6H);
31p{
1h}NMR (CDCl
3, 161.9Hz): δ=23.46ppm (s).Hence one can see that PdCl
2(3-TPPND4)
2can successfully prepare.
Embodiment 34:Pd (3-TPPMSH)
3synthesizing of zeroth order palladium complex
Under argon shield, in the Schlenk of 100ml bottle, add the PdCl of 0.177g
2naCl with 0.116g, be heated to 70 ℃ and be cooled to room temperature after being dissolved in 1ml water, after being dissolved in 10ml methanolic hydrochloric acid solution, the amphipathic part 3-TPPMSH of 3mmol adds in reaction flask, after mixed solution stirring at room 0.5h, drip 2ml hydrazine hydrate and separate out with yellow mercury oxide, after sedimentation and filtration, with ether/methyl alcohol, spread crystallization, and obtain the orange-yellow monocrystalline Pd of 0.71g (3-TPPMSH)
3, Pd (3-TPPMSH)
3productive rate be 63%.
To Pd (3-TPPMSH)
3carry out nuclear magnetic resonance spectroscopy, characterization result is as follows:
1h NMR (CDCl
3, 400MHz): δ=7.28-7.53 (m, 9H), 7.62-7.69 (m, 3H), 8.02ppm (br, 30H);
31p{
1h}NMR (CDCl
3, 161.9Hz): δ=28.64ppm (s).Crystalline structure figure is shown in accompanying drawing 3.Hence one can see that Pd (3-TPPMSH)
3can successfully prepare.
Embodiment 35:Pd (4-TPPMC)
3synthesizing of zeroth order palladium complex
Under argon shield, in the Schlenk of 100ml bottle, add the PdCl of 0.177g
2naCl with 0.116g, be heated to 70 ℃ and be cooled to room temperature after being dissolved in 1ml water, after being dissolved in 10ml methyl alcohol, the amphipathic part 4-TPPMC of 3mmol adds in reaction flask, after mixed solution stirring at room 0.5h, drip 2ml hydrazine hydrate and separate out with yellow mercury oxide, after sedimentation and filtration, by recrystallizing methanol, obtain 0.85g glassy yellow crystal Pd (4-TPPMC)
3, Pd (4-TPPMC)
3productive rate be 83%.
To Pd (4-TPPMC)
3carry out nuclear magnetic resonance spectroscopy, characterization result is as follows:
1h NMR (DMSO-d
6, 400MHz): δ=7.07-7.12 (m, 24H), 7.23-7.24 (m, 6H), 7.53-7.64ppm (m, 12H);
31p{
1h}NMR (D
2o, 161.9Hz): δ=21.37 (s), 36.76ppm (s).Crystalline structure figure is shown in accompanying drawing 4.Hence one can see that Pd (4-TPPMC)
3can successfully prepare.
Embodiment 36:Pd (3-TPPMC)
3synthesizing of zeroth order palladium complex
Under argon shield, in the Schlenk of 100ml bottle, add the PdCl of 0.177g
2naCl with 0.116g, be heated to 70 ℃ and be cooled to room temperature after being dissolved in 1ml water, after being dissolved in 10ml methyl alcohol, the amphipathic part 3-TPPMC of 3mmol adds in reaction flask, after mixed solution stirring at room 0.5h, drip 2ml hydrazine hydrate and separate out with yellow mercury oxide, after sedimentation and filtration, by recrystallizing methanol, obtain 0.87g glassy yellow crystal Pd (3-TPPMC)
3, Pd (3-TPPMC)
3productive rate be 85%.
To Pd (3-TPPMC)
3carry out nuclear magnetic resonance spectroscopy, characterization result is as follows:
1h NMR (D
2o, 400MHz): δ=6.69 (br, 15H), 7.07 (br, 15H), 7.56-7.65ppm (m, 12H);
31p{
1h}NMR (D
2o, 161.9Hz): δ=21.93ppm (s).Crystalline structure figure is shown in accompanying drawing 5.Hence one can see that Pd (3-TPPMC)
3can successfully prepare.
Example 37:Pd (4-TPPMP)
3synthesizing of zeroth order palladium complex
Under argon shield, in the Schlenk of 100ml bottle, add the PdCl of 0.177g
2naCl with 0.116g, be heated to 70 ℃ and be cooled to room temperature after being dissolved in 1ml water, after being dissolved in 10ml methyl alcohol, the amphipathic part 4-TPPMP of 3mmol adds in reaction flask, after mixed solution stirring at room 0.5h, drip 2ml hydrazine hydrate and separate out with yellow mercury oxide, after sedimentation and filtration, by recrystallizing methanol, obtain 0.81g yellow crystals Pd (4-TPPMP)
3, Pd (4-TPPMP)
3productive rate be 72%.
To Pd (4-TPPMP)
3carry out nuclear magnetic resonance spectroscopy, characterization result is as follows:
1h NMR (D
2o, 400MHz): δ=6.66 (br, 15H), 7.01 (br, 15H), 7.33-7.45ppm (m, 12H);
31p{
1h}NMR (D
2o, 161.9Hz): δ=22.44 (P
iII), 35.21 (P
v) ppm.Hence one can see that Pd (4-TPPMP)
3can successfully prepare.
Embodiment 38: adopt PdCl
2(3-TPPMSH)
2in toluene/alkali lye two-phase system, catalyze and synthesize poly-fluorenes
In reaction flask, add 9 of 0.2742g, 9-dioctyl fluorene-2,9 of 7-bis-(propylene glycol boric acid ester), 0.2792g, 9-dioctyl-2,7-dibromo fluorenes and 0.3% PdCl
2(3-TPPMSH)
2rear argon replaces 0.5h, adds 8ml toluene and 2ml 2M K
2cO
3after the aqueous solution, 100 ℃ of stirring reaction 12h.Reaction solution is cooled to after room temperature, pours in methanol solution, separates out polymkeric substance, is dissolved in chloroform after sedimentation and filtration.After polymers soln washing, anhydrous Na
2sO
4dry 30min.Methanol solution sedimentation after filtering and concentrating, dry after filtering, obtain poly-fluorenes, productive rate is 88.8%.By GPC, determine the molecular weight of poly-fluorenes, Mn=145700, Mw=522700, PDI=3.58.
Embodiment 39: adopt PdCl
2(3-TPPMSH)
2in tetrahydrofuran (THF)/alkali lye two-phase system, catalyze and synthesize poly-fluorenes
In reaction flask, add 9 of 0.2742g, 9-dioctyl fluorene-2,9 of 7-bis-(propylene glycol boric acid ester), 0.2792g, 9-dioctyl-2,7-dibromo fluorenes and 0.3% PdCl
2(3-TPPMSH)
2rear argon replaces 0.5h, adds 8ml tetrahydrofuran (THF) and 8ml 2M K
2cO
3after the aqueous solution, 80 ℃ of stirring reaction 12h.Reaction solution is cooled to after room temperature, pours in methanol solution, separates out polymkeric substance, dry after filtering, and obtains poly-fluorenes, and productive rate is 82.2%.By GPC, determine the molecular weight of poly-fluorenes, Mn=454100, Mw=1672900, PDI=3.68.
Embodiment 40: adopt PdCl
2(4-TPPMC)
2in toluene/alkali lye two-phase system, catalyze and synthesize poly-fluorenes
In reaction flask, add 9 of 0.2742g, 9-dioctyl fluorene-2,9 of 7-bis-(propylene glycol boric acid ester), 0.2792g, 9-dioctyl-2,7-dibromo fluorenes and 0.3% PdCl
2(4-TPPMC)
2rear argon replaces 0.5h, adds 8ml toluene and 2ml 2M K
2cO
3after the aqueous solution, 100 ℃ of stirring reaction 12h.Reaction solution is cooled to after room temperature, pours in methanol solution, separates out polymkeric substance, is dissolved in chloroform after sedimentation and filtration.After polymers soln washing, anhydrous Na
2sO
4dry 30min.Methanol solution sedimentation after filtering and concentrating, dry after filtering, obtain poly-fluorenes, productive rate is 81.9%.By GPC, determine the molecular weight of polymkeric substance, Mn=122400, Mw=492300, PDI=4.02.
Embodiment 41: adopt PdCl
2(4-TPPMC)
2in tetrahydrofuran (THF)/alkali lye two-phase system, catalyze and synthesize poly-fluorenes
In reaction flask, add 9 of 0.2742g, 9-dioctyl fluorene-2,9 of 7-bis-(propylene glycol boric acid ester), 0.2792g, 9-dioctyl-2,7-dibromo fluorenes and 0.3% PdCl
2(4-TPPMC)
2rear argon replaces 0.5h, adds 8ml tetrahydrofuran (THF) and 8ml 2M K
2cO
3after the aqueous solution, 80 ℃ of stirring reaction 12h.Reaction solution is cooled to after room temperature, pours in methanol solution, separates out polymkeric substance, dry after filtering, and obtains poly-fluorenes, and productive rate is 90.1%.By GPC, determine the molecular weight of polymkeric substance, Mn=571700, Mw=1942900, PDI=3.40.
Embodiment 42: adopt PdCl
2(3-TPPMC)
2in toluene/alkali lye two-phase system, catalyze and synthesize poly-fluorenes
In reaction flask, add 9 of 0.2742g, 9-dioctyl fluorene-2,9 of 7-bis-(propylene glycol boric acid ester), 0.2792g, 9-dioctyl-2,7-dibromo fluorenes and 0.3% PdCl
2(3-TPPMC)
2rear argon replaces 0.5h, adds 8ml toluene and 2ml 2M K
2cO
3after the aqueous solution, 100 ℃ of stirring reaction 12h.Reaction solution is cooled to after room temperature, pours in methanol solution, separates out polymkeric substance, is dissolved in chloroform after sedimentation and filtration.After polymers soln washing, anhydrous Na
2sO
4dry 30min.Methanol solution sedimentation after filtering and concentrating, dry after filtering, obtain poly-fluorenes, productive rate is 92.3%.By GPC, determine the molecular weight of polymkeric substance, Mn=177500, Mw=525900, PDI=2.96.
Embodiment 43: adopt PdCl
2(3-TPPMC)
2in tetrahydrofuran (THF)/alkali lye two-phase system, catalyze and synthesize poly-fluorenes
In reaction flask, add 9 of 0.2742g, 9-dioctyl fluorene-2,9 of 7-bis-(propylene glycol boric acid ester), 0.2792g, 9-dioctyl-2,7-dibromo fluorenes and 0.3% PdCl
2(3-TPPMC)
2rear argon replaces 0.5h, adds 8ml tetrahydrofuran (THF) and 8ml 2M K
2cO
3after the aqueous solution, 80 ℃ of stirring reaction 12h, reaction solution is cooled to after room temperature, pours in methanol solution, separates out polymkeric substance, dry after filtering, and obtains poly-fluorenes, and productive rate is 87.1%.By GPC, determine the molecular weight of polymkeric substance, Mn=399200, Mw=825500, PDI=2.07.
Embodiment 44: adopt Pd (3-TPPMSH)
3in tetrahydrofuran (THF)/alkali lye two-phase system, catalyze and synthesize poly-fluorenes
In reaction flask, add 9 of 0.2742g, 9-dioctyl fluorene-2,9 of 7-bis-(propylene glycol boric acid ester), 0.2792g, 9-dioctyl-2,7-dibromo fluorenes and 0.3% Pd (3-TPPMSH)
3rear argon replaces 0.5h, adds 8ml tetrahydrofuran (THF) and 8ml 2M K
2cO
3after the aqueous solution, 80 ℃ of stirring reaction 12h.Reaction solution is cooled to after room temperature, pours in methanol solution, separates out polymkeric substance, dry after filtering, and obtains poly-fluorenes, and productive rate is 80.6%.By GPC, determine the molecular weight of polymkeric substance, Mn=197600, Mw=990600, PDI=5.01.
Embodiment 45: adopt Pd (4-TPPMC)
3in tetrahydrofuran (THF)/alkali lye two-phase system, catalyze and synthesize poly-fluorenes
In reaction flask, add 9 of 0.2742g, 9-dioctyl fluorene-2,9 of 7-bis-(propylene glycol boric acid ester), 0.2792g, 9-dioctyl-2,7-dibromo fluorenes and 0.3% Pd (4-TPPMC)
3rear argon replaces 0.5h, adds 8ml tetrahydrofuran (THF) and 8ml 2M K
2cO
3after the aqueous solution, 80 ℃ of stirring reaction 12h.Reaction solution is cooled to after room temperature, pours in methanol solution, separates out polymkeric substance, dry after filtering, and obtains poly-fluorenes, and productive rate is 79.1%.By GPC, determine the molecular weight of polymkeric substance, Mn=591900, Mw=2015700, PDI=3.40.
Embodiment 46: adopt Pd (3-TPPMC)
3in tetrahydrofuran (THF)/alkali lye two-phase system, catalyze and synthesize poly-fluorenes
In reaction flask, add 9 of 0.2742g, 9-dioctyl fluorene-2,9 of 7-bis-(propylene glycol boric acid ester), 0.2792g, 9-dioctyl-2,7-dibromo fluorenes and 0.3% Pd (3-TPPMC)
3, rear argon replaces 0.5h, adds 8ml tetrahydrofuran (THF) and 8ml 2M K
2cO
3after the aqueous solution, 80 ℃ of stirring reaction 12h.Reaction solution is cooled to after room temperature, pours in methanol solution, separates out polymkeric substance, dry after filtering, and obtains poly-fluorenes, productive rate 78.1%.By GPC, determine the molecular weight of polymkeric substance, Mn=419000, Mw=910000, PDI=2.17.
Embodiment 47: adopt PdCl
2(4-TPPMP)
2in toluene/alkali lye two-phase system, catalyze and synthesize poly-fluorenes
In reaction flask, add 9 of 0.2742g, 9-dioctyl fluorene-2,9 of 7-bis-(propylene glycol boric acid ester), 0.2792g, 9-dioctyl-2,7-dibromo fluorenes and 0.3% PdCl
2(4-TPPMP)
2rear argon replaces 0.5h, adds 8ml toluene and 2ml 2M K
2cO
3after the aqueous solution, 100 ℃ of stirring reaction 12h.Reaction solution is cooled to after room temperature, pours in methanol solution, separates out polymkeric substance, is dissolved in chloroform after sedimentation and filtration.After polymers soln washing, anhydrous Na
2sO
4dry 30min.Methanol solution sedimentation after filtering and concentrating, dry after filtering, obtain poly-fluorenes, productive rate is 86.5%.By GPC, determine polymericular weight, Mn=185700, Mw=602700, PDI=3.25.
Embodiment 48: adopt PdCl
2(4-TPPMP)
2in tetrahydrofuran (THF)/alkali lye two-phase system, catalyze and synthesize poly-fluorenes
In reaction flask, add 9 of 0.2742g, 9-dioctyl fluorene-2,9 of 7-bis-(propylene glycol boric acid ester), 0.2792g, 9-dioctyl-2,7-dibromo fluorenes and 0.3% PdCl
2(4-TPPMP)
2rear argon replaces 0.5h, adds 8ml tetrahydrofuran (THF) and 8ml 2M K
2cO
3after the aqueous solution, 80 ℃ of stirring reaction 12h, reaction solution is cooled to after room temperature, pours in methanol solution, dry after filtering, and obtains poly-fluorenes, and productive rate is 78.9%.By GPC, determine polymericular weight, Mn=551500, Mw=19018700, PDI=3.45.
Embodiment 49: adopt PdCl
2(4-TPPMN)
2in toluene/alkali lye two-phase system, catalyze and synthesize poly-fluorenes
In reaction flask, add 9 of 0.2742g, 9-dioctyl fluorene-2,9 of 7-bis-(propylene glycol boric acid ester), 0.2792g, 9-dioctyl-2,7-dibromo fluorenes and 0.3% PdCl
2(4-TPPMN)
2rear argon replaces 0.5h, adds 8ml toluene and 2ml 2M K
2cO
3after the aqueous solution, 100 ℃ of stirring reaction 12h.Reaction solution is cooled to after room temperature, pours in methanol solution, separates out polymkeric substance, is dissolved in chloroform after sedimentation and filtration.After polymers soln washing, anhydrous Na
2sO
4dry 30min.Methanol solution sedimentation after filtering and concentrating, dry after filtering, obtain poly-fluorenes, productive rate is 92.3%.By GPC, determine polymericular weight, Mn=170200, Mw=600400, PDI=3.52.
Embodiment 50: adopt PdCl
2(3-TPPMN)
2in toluene/alkali lye two-phase system, catalyze and synthesize poly-fluorenes
In reaction flask, add 9 of 0.2742g, 9-dioctyl fluorene-2,9 of 7-bis-(propylene glycol boric acid ester), 0.2792g, 9-dioctyl-2,7-dibromo fluorenes and 0.3% PdCl
2(3-TPPMN)
2rear argon replaces 0.5h, adds 8ml toluene and 2ml 2M K
2cO
3after the aqueous solution, 100 ℃ of stirring reaction 12h.Reaction solution is cooled to after room temperature, pours in methanol solution, separates out polymkeric substance, is dissolved in chloroform after sedimentation and filtration.After polymers soln washing, anhydrous Na
2sO
4dry 30min.Methanol solution sedimentation after filtering and concentrating, dry after filtering, obtain poly-fluorenes, productive rate is 93.2%.By GPC, determine polymericular weight, Mn=161700, Mw=500100, PDI=3.09.
Embodiment 51: adopt PdCl
2(4-TPPMDN)
2in toluene/alkali lye two-phase system, catalyze and synthesize poly-fluorenes
In reaction flask, add 9 of 0.2742g, 9-dioctyl fluorene-2,9 of 7-bis-(propylene glycol boric acid ester), 0.2792g, 9-dioctyl-2,7-dibromo fluorenes and 0.3% PdCl
2(4-TPPMDN)
2rear argon replaces 0.5h, adds 8ml toluene and 2ml 2M K
2cO
3after the aqueous solution, 100 ℃ of stirring reaction 12h.Reaction solution is cooled to after room temperature, pours in methanol solution, separates out polymkeric substance, is dissolved in chloroform after sedimentation and filtration.After polymers soln washing, anhydrous Na
2sO
4dry 30min.Methanol solution sedimentation after filtering and concentrating, dry after filtering, obtain poly-fluorenes, productive rate is 83.0%.By GPC, determine polymericular weight, Mn=98800, Mw=483900, PDI=4.69.
Embodiment 52: adopt PdCl
2(3-TPPMDN)
2in toluene/alkali lye two-phase system, catalyze and synthesize poly-fluorenes
In reaction flask, add 9 of 0.2742g, 9-dioctyl fluorene-2,9 of 7-bis-(propylene glycol boric acid ester), 0.2792g, 9-dioctyl-2,7-dibromo fluorenes and 0.3% PdCl
2(3-TPPMDN)
2rear argon replaces 0.5h, adds 8ml toluene and 2ml 2M K
2cO
3after the aqueous solution, 100 ℃ of stirring reaction 12h.Reaction solution is cooled to after room temperature, pours in methanol solution, separates out polymkeric substance, is dissolved in chloroform after sedimentation and filtration.After polymers soln washing, anhydrous Na
2sO
4dry 30min.Methanol solution sedimentation after filtering and concentrating, dry after filtering, obtain poly-fluorenes, productive rate is 93.8%.By GPC, determine polymericular weight, Mn=134500, Mw=493300, PDI=3.66.
The explanation of above embodiment is just for helping to understand method of the present invention and core concept thereof.It should be pointed out that for those skilled in the art, under the premise without departing from the principles of the invention, can also carry out some improvement and modification to the present invention, these improvement and modification also fall in the protection domain of the claims in the present invention.
Above-mentioned explanation to the disclosed embodiments, makes professional and technical personnel in the field can realize or use the present invention.To the multiple modification of these embodiment, will be apparent for those skilled in the art, General Principle as defined herein can, in the situation that not departing from the spirit or scope of the present invention, realize in other embodiments.Therefore, the present invention will can not be restricted to these embodiment shown in this article, but will meet the widest scope consistent with principle disclosed herein and features of novelty.
Claims (1)
1. a method of preparing conjugated aromatic polymer, comprising:
Under the effect of the palladium complex catalyst of described formula I or described formula II, 9,9-dioctyl fluorene-2,7-bis-(propylene glycol boric acid ester) and 9,9-dioctyl-2, there is coupling polymerization reaction in 7-dibromo fluorenes, generate conjugated aromatic polymer in organic solvent and wet chemical;
PdX
2(L-Gn)
2 (Ⅰ)
Pd(L-Gn)
m (Ⅱ)
Wherein:
X is halogen;
M is 3;
Described L-Gn is selected from
described organic solvent is toluene or tetrahydrofuran (THF).
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