CN105175217A - Method for synthesizing polycyclic aromatic hydrocarbon by directly coupling Grignard reagent of halogenated compounds with halogenated compound by recyclable modified palladium on carbon - Google Patents
Method for synthesizing polycyclic aromatic hydrocarbon by directly coupling Grignard reagent of halogenated compounds with halogenated compound by recyclable modified palladium on carbon Download PDFInfo
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Abstract
The invention provides a method for synthesizing polycyclic aromatic hydrocarbon by directly coupling a Grignard reagent of halogenated compounds with the halogenated compound by recyclable modified palladium on carbon. After flowing back and water separating through an organic solvent which is capable of realizing azeotropy with water through non-halogenated hydrocarbon, a catalyst Pd/C is added with organic phosphine ligand for complexing, so that a catalyst (organic phosphine ligand complex Pd/C) is obtained, the halogenated compound as a starting material and magnesium are subjected to Grignard reaction under 10DEG C to 90DEG C, so that the Grignard reagent is obtained, the catalyst is then added to carry out coupling reaction with the halogenated compound, and thereby the coupling product (polycyclic aromatic hydrocarbon) is obtained. The method adopts one-step reaction, the synthesis cost is low, the method is environment-friendly, the process is simple, and the method is a more efficient, cleaner synthesis process for the polycyclic aromatic hydrocarbon.
Description
Technical field
The invention belongs to liquid crystal intermediates, OLED intermediate and fine chemical product technical field, especially relate to a kind of method that can reclaim modification palladium carbon again and the direct coupling halides of halides Grignard reagent be synthesized to polycyclic aromatic hydrocarbon.
Background technology
Polycyclic aromatic hydrocarbon compound obtains important application as type material in OLED field, and gone on the market in small-size screen display, market is burning hot, and large size is also in laboratory development success, and listing meter can be treated day.The synthesis of polycyclic aromatic hydrocarbon compound has important actual application value.Obtain linked reaction in OLED field and mainly contain Suzuk linked reaction and form linked reaction.Suzuk coupling be a little that selectivity is good, impurity is few.Shortcoming is that reactions steps is many, and need to prepare boric acid, equipment is special, and cost is high, and element utilization ratio is low, as synthetic route 1, and synthesis target product
classical way.Form linked reaction is as far back as 20 century 70s, Kochi and Tamura just have studied a series of halohydrocarbon and Grignard reagent carries out coupling under transition metal-catalyzed, start further investigation thus, people had done many-sided Exploration & stu dy to linked reaction in recent years, and had made some progress.
Synthetic route 1
Synthetic route 1 Problems existing has, synthetic route is long, two-step reaction, needs the specific installation of very low temperature, and the compound VII that the first step generates needs with hydrochloric acid hydrolysis, separatory extracts, dry concentrated, recrystallization just can be met the raw material of second step reaction, and aftertreatment produces spent acid, waste water, environmental pollution is large, and the Pd class catalyzer that second step reacts used is tetra-triphenylphosphine palladium, Palladous chloride, PdCO
3deng synthesis, expensive, not easily preserve, and can not recycle, compound VI yield of generation is low, and cost is high, and unfriendly to environment.This synthetic route is the classical main flow route of current suzuki reaction.
Summary of the invention
The object of the invention is to improve the deficiency of prior art and a kind of facility is provided, workable, synthesis cycle is short, synthetic environment is friendly, element utilization ratio is high can reclaim the method for modification palladium carbon to halides Grignard reagent direct coupling halides synthesis polycyclic aromatic hydrocarbon again.
The object of the present invention is achieved like this, and a kind of method that can reclaim modification palladium carbon again and the direct coupling halides of halides Grignard reagent be synthesized to polycyclic aromatic hydrocarbon, is characterized in that synthetic route is as follows:
A, organophosphorus ligand complexing Pd/C(II) preparation:
Wherein: organophosphorus ligand is triphenylphosphine, 2-dicyclohexylphosphontetrafluoroborate-2', 4', 6'-tri isopropyl biphenyl, 4,5-two diphenylphosphine-9,9-dimethyl xanthene, normal-butyl two (1-adamantyl) phosphines;
B, modification palladium carbon organophosphorus ligand complexing Pd/C(II can be reclaimed again) synthesis to aromatic hydrocarbon Grignard reagent direct coupling halogenated aromatic (V) synthesis of coupling polycyclic aromatic hydrocarbon (VI):
Wherein: R=H, C1 ~ C7 alkane, aromatic hydrocarbon; X=Cl, Br, I; X`=Cl, Br, I; R`=H, F, Cl, Br, I, C1 ~ C7 alkane, aromatic hydrocarbon.
In order to realize object of the present invention further, can be described organophosphorus ligand complexing Pd/C(II) be prepared as follows shown in:
Wherein: organophosphorus ligand is triphenylphosphine, 2-dicyclohexylphosphontetrafluoroborate-2', 4', 6'-tri isopropyl biphenyl, 4,5-two diphenylphosphine-9,9-dimethyl xanthene, normal-butyl two (1-adamantyl) phosphines;
Catalyst P d/C(I in formula) be the Pd/C of aqueous industrial 40 ~ 70%; the effective content 0.5 ~ 10% of palladium; under having protection of inert gas; to reflux azeotropic dehydration with the organic solvent of water azeotropic in non-halogenated hydrocarbons; after moisture is less than 500ppm, adds 1mol ~ 6mol equivalent that organophosphorus ligand is palladium, carries out complex reaction 10min ~ 120min with 10 DEG C ~ 150 DEG C, obtain catalyzer organophosphorus ligand complexing Pd/C(II); can directly be with solvent to use, also can isolate rear use.
In order to realize object of the present invention further, can be described can reclaim modification palladium carbon organophosphorus ligand complexing Pd/C(II again) as follows to the route of polycyclic aromatic hydrocarbon Grignard reagent direct coupling halogenated aromatic (V) synthesis of coupling aromatic hydrocarbon (VI):
Wherein: R=H, C1 ~ C7 alkane, aromatic hydrocarbon; X=Cl, Br, I; X`=Cl, Br, I; R`=H, F, Cl, Br, I, C1 ~ C7 alkane, aromatic hydrocarbon.
In formula, R is hydrogen, the alkyl of carbonatoms 1 ~ 7, aromatic hydrocarbon, XCl, Br, I, and X` is Cl, Br, I; R` is H, F, Cl, Br, I, C1 ~ C7 alkane, aromatic hydrocarbon.This reaction is the continuous grignard linked reaction of single stage method, compound condensed ring halogenated aromatic (III) is at THF, in ether or other ether solvent, with 10 ~ 90 DEG C at there is grignard reaction and obtain compound Grignard reagent (IV), Grignard reagent dropwise is entered to be equipped with the mixed liquid of halogenated aromatic (V), mixed liquid is added with the catalyzer Phosphine ligands complexing Pd/C(II of 0.05% ~ 8.0% in advance) system in there is linked reaction, time for adding 10min ~ 200min, temperature of reaction 40 DEG C ~ 150 DEG C, reaction times 4 ~ 18h, stopped reaction, filtering catalyst Phosphine ligands complexing Pd/C(II), catalyzer can reclaim use, organic phase is washed to neutrality, then dry, cross post, concentrated, rectifying, recrystallization obtains product coupling aromatic hydrocarbon (VI), GC, LC analyzes, reaction conversion ratio 98.0% ~ 99.8%, synthesis yield 80.0 ~ 98.0%.
In order to realize object of the present invention further, can be described can reclaim modification palladium carbon organophosphorus ligand complexing Pd/C(II again) as follows to the route of aromatic hydrocarbon Grignard reagent direct coupling condensed ring halogenated aromatic (V) synthesis of coupling aromatic hydrocarbon (VI):
wherein: R=H, C1 ~ C7 alkane, aromatic hydrocarbon; X=Cl, Br, I; X`=Cl, Br, I; R`=H, F, Cl, Br, I, C1 ~ C7 alkane, aromatic hydrocarbon.
In formula, R is hydrogen, the alkyl of carbonatoms 1 ~ 7, aromatic hydrocarbon, and X is Cl, Br, I, and R` is F, Cl, Br, I, C1 ~ C7 alkane, aromatic hydrocarbon.This reaction is the continuous grignard linked reaction of single stage method, compound condensed ring halogenated aromatic (III) is at THF, in ether or other ether solvent, with 10 ~ 90 DEG C at there is grignard reaction and obtain compound Grignard reagent (IV), Grignard reagent dropwise is entered to be equipped with the mixed liquid of halogenated aromatic (V), mixed liquid is added with the catalyzer Phosphine ligands complexing Pd/C(II of 0.05% ~ 8.0% in advance) system in there is linked reaction, time for adding 10min ~ 200min, temperature of reaction 40 DEG C ~ 150 DEG C, reaction times 4 ~ 18h, stopped reaction, filtering catalyst Phosphine ligands complexing Pd/C(II), catalyzer can reclaim use, organic phase is washed to neutrality, then dry, cross post, concentrated, rectifying, recrystallization obtains product coupling aromatic hydrocarbon (VI), GC, LC analyzes, reaction conversion ratio 98.0% ~ 99.8%, synthesis yield 80.0 ~ 98.0%.
Compared with the prior art the present invention has following distinguishing feature and effect: the present invention on the basis of existing synthetic route, provide one more convenient, can operate strong, synthesis cycle is short, environmental friendliness, synthetic route that element utilization ratio is high.Synthetic method of the present invention adopts single stage method, simple to operate, because reactions steps reduces, effectively can improve reaction yield, element utilization ratio improves, reduce energy consumption and artificial, adopt solution palladium carbon cleverly to carry out organophosphorus complexing on the other hand and obtain raw catalyst, solve linked reaction moisture problem and catalyst recovery problem, catalyzer Phosphine ligands complexing Pd/C(II to obtain) carry out linked reaction, speed of response is fast, the selectivity generating target product is high, almost there is no the generation of side reaction, and the catalyzer organophosphorus ligand complexing Pd/C(II used) cheap, can repeatedly recovery, compared with former literature procedures, this patent route is the synthetic method of thinking novelty, practical, completely can industrialization, synthetic route is as follows:
Wherein: organophosphorus ligand=triphenylphosphine, 2-dicyclohexylphosphontetrafluoroborate-2', 4', 6'-tri isopropyl biphenyl, 4,5-two diphenylphosphine-9,9-dimethyl xanthene, normal-butyl two (1-adamantyl) phosphines.
Wherein: R=C1 ~ C7 alkane, aromatic hydrocarbon; X=Cl, Br, I; X`=Cl, Br, I; R`=H, F, Cl, Br, I, C1 ~ C7 alkane, aromatic hydrocarbon.
Said synthesis route, compared with the classical way of synthetic route 1, has in following advantage:
1, shorten reactions steps and cycle, become 1 step from 2 original steps reactions and complete;
2, secondly new catalyzer organophosphorus ligand complexing Pd/C(II is used), preparation is simple, cheap, environmental friendliness, can time use, active high, the linked reaction time is short, selectivity is high, and product compound coupling aromatic hydrocarbon (VI) purity of generation is high, so total recovery is high.
3, single stage method reacts the acid esterification hydrolytic process saved in traditional technology, makes this reaction entirety environmentally friendly, and element utilization ratio improves, and synthesis cycle shortens.
Accompanying drawing illustrates:
Fig. 1 is the present invention 4
`-bromo-1-phenylnaphthalene
1hNMR schemes.
Fig. 2 is 9-phenylanthracene of the present invention
1hNMR schemes.
Fig. 3 is 9-Alpha-Naphthyl anthracene of the present invention
1hNMR schemes.
Fig. 4 is the present invention 9,10-bis--Alpha-Naphthyl anthracene
1hNMR schemes.
Embodiment
Embodiment 1, a kind of method that can reclaim modification palladium carbon again and the direct coupling halides of halides Grignard reagent be synthesized to polycyclic aromatic hydrocarbon, its synthetic route is as follows:
Wherein catalyzer has Phosphine ligands complexing Pd/C(II) preparation be: under the protection of rare gas element, to in 100ml tri-mouthfuls of reaction flasks that mechanical stirring, reflux condensation mode drying tube are housed, add the Pd/C0.3g of moisture 56% successively, toluene 50ml, be warming up to 110 DEG C, reflux water-dividing 120min, is cooled to 90 DEG C, adds organophosphorus ligand triphenylphosphine 0.0008mol, be warming up to 110 DEG C, stirring 80min, be cooled to 30 DEG C, obtain catalyzer organophosphorus ligand complexing Pd/C(II) system is stand-by;
4
`the preparation of-bromo-1-phenylnaphthalene is: under the protection of rare gas element; to in the 100ml reaction flask that mechanical stirring, reflux condensation mode drying tube, feed hopper are housed; add magnesium powder 0.0500mol; THF10ml; add iodine one, drip the mixed liquid of condensed ring halogenated aromatic (III) 1-bromonaphthalene 0.0433mol, THF26ml, dropwise; back flow reaction 1h, obtains Grignard reagent (IV) 1-magnesium bromide naphthalene stand-by.
Under the protection of rare gas element; be equipped with in the 250ml reaction flask of mechanical stirring, reflux condensation mode drying tube, feed hopper to another and add 4-bromo-iodobenzene 0.0432mol; add above-mentioned stand-by catalyzer organophosphorus ligand complexing Pd/C(II) system; again the dropping of above-mentioned stand-by Grignard reagent (IV) is entered reaction system; control 50 ~ 85 DEG C of reaction 10h; stopped reaction; filtering catalyst organophosphorus ligand complexing Pd/C(II); catalyzer can reclaim and use next time; organic phase is washed to neutrality, dry, cross post, concentrated, distillation, recrystallization obtain product 4
`-bromo-1-phenylnaphthalene (VI), GC analyzes main content 99.2%, LC and analyzes main content 98.9%, yield, 78.3%.GC-MS(m/z:282,284 [M]+, 204,127), ultimate analysis: measured value (calculated value) C:67.88(67.87); H:3.92(3.92); Br:28.21(28.22) and
1hNMR (400MHz, CDCl3) confirms.
Embodiment 2, a kind of method that can reclaim modification palladium carbon again and the direct coupling halides of halides Grignard reagent be synthesized to polycyclic aromatic hydrocarbon, its synthetic route is as follows:
Wherein catalyzer organophosphorus ligand complexing Pd/C(II) preparation be: under the protection of rare gas element; to in 100ml tri-mouthfuls of reaction flasks that mechanical stirring, reflux condensation mode drying tube are housed; add Pd/C0.3g (moisture 56%) successively; toluene 50ml; be warming up to 110 DEG C; reflux water-dividing 120min; be cooled to 90 DEG C; add organophosphorus ligand 2-dicyclohexylphosphontetrafluoroborate-2', 4', 6'-tri isopropyl biphenyl 0.0005mol; be warming up to 110 DEG C; stirring 60min, be cooled to 30 DEG C, obtain catalyzer organophosphorus ligand complexing Pd/C(II) system is stand-by.
The preparation of 9-phenylanthracene is: under the protection of rare gas element; to in the 100ml reaction flask that mechanical stirring, reflux condensation mode drying tube, feed hopper are housed; add magnesium powder 0.0503mol; THF10ml; add iodine one, drip the mixed liquid of halogenated aromatic (III) bromobenzene 0.0440mol, THF26ml, dropwise; back flow reaction 2h, obtains Grignard reagent (IV) magnesium bromide benzene stand-by.
Under the protection of rare gas element, to another, mechanical stirring is housed, reflux condensation mode drying tube, 9-bromine anthracene 0.0433mol is added in the 250ml reaction flask of feed hopper, add stand-by catalyzer organophosphorus ligand complexing Pd/C(II) system, the dropping of above-mentioned stand-by Grignard reagent (IV) is entered reaction system, 10h is reacted with 50 ~ 85 DEG C, stopped reaction, filtering catalyst organophosphorus ligand complexing Pd/C(II), catalyzer can reclaim and use next time, organic phase is washed to neutrality, dry, cross post, concentrated, distillation, recrystallization obtains product 9-phenylanthracene (VI), LC analyzes main content 98.9%, yield 78.3%.GC-MS(m/z:254 [M]+, 178,78), ultimate analysis: measured value (calculated value) C:94.50(94.45); H:5.53(5.55) and
1hNMR (400MHz, CDCl3) confirms.
Embodiment 3, a kind of method that can reclaim modification palladium carbon again and the direct coupling halides of halides Grignard reagent be synthesized to polycyclic aromatic hydrocarbon, its synthetic route is as follows:
Wherein catalyzer organophosphorus ligand complexing Pd/C(II) preparation be: under the protection of rare gas element; to in 100ml tri-mouthfuls of reaction flasks that mechanical stirring, reflux condensation mode drying tube are housed; add Pd/C0.3g (moisture 56%) successively; toluene 50ml; be warming up to 110 DEG C; reflux water-dividing 120min; be cooled to 90 DEG C; add two diphenylphosphine-9, the 9-dimethyl xanthene 0.0006mol of organophosphorus ligand 4,5-; be warming up to 110 DEG C; stirring 60min, be cooled to 30 DEG C, obtain catalyzer organophosphorus ligand complexing Pd/C(II) system is stand-by.
The preparation of 9-Alpha-Naphthyl anthracene is: under the protection of rare gas element; to in the 100ml reaction flask that mechanical stirring, reflux condensation mode drying tube, feed hopper are housed; add magnesium powder 0.0551mol; THF10ml; add iodine one, drip the mixed liquid of halogenated aromatic (III) 1-bromonaphthalene 0.0481mol, THF30ml, dropwise; back flow reaction 2h, Grignard reagent (IV) 1-magnesium bromide naphthalene is stand-by.
Under the protection of rare gas element, to another, mechanical stirring is housed, reflux condensation mode drying tube, halogenated aromatic (V) 9-iodine anthracene 0.0432mol is added in the 250ml reaction flask of feed hopper, add stand-by catalyst II system, the dropping of above-mentioned stand-by Grignard reagent (IV) is entered reaction system, 14h is reacted with 50 ~ 85 DEG C, stopped reaction, filtering catalyst organophosphorus ligand complexing Pd/C(II), catalyzer can reclaim and use next time, organic phase is washed to neutrality, dry, cross post, concentrated, distillation, recrystallization obtains product coupling aromatic hydrocarbon (VI) 9-Alpha-Naphthyl anthracene, LC analyzes main content 98.2%, yield 76.4%.GC-MS(m/z:304 [M]+, 178,128), ultimate analysis: measured value (calculated value) C:94.64(94.70); H:5.36(5.30) and
1hNMR (400MHz, CDCl3) confirms.
Embodiment 4, a kind of method that can reclaim modification palladium carbon again and the direct coupling halides of halides Grignard reagent be synthesized to polycyclic aromatic hydrocarbon, its synthetic route is as follows:
Wherein catalyzer organophosphorus ligand complexing Pd/C(II) preparation be: under the protection of rare gas element; to in 100ml tri-mouthfuls of reaction flasks that mechanical stirring, reflux condensation mode drying tube are housed; add Pd/C0.3g (moisture 56%) successively; toluene 50ml; be warming up to 110 DEG C; reflux water-dividing 120min; be cooled to 90 DEG C; add organophosphorus ligand normal-butyl two (1-adamantyl) phosphine 0.0006mol; be warming up to 110 DEG C; stirring 60min, be cooled to 30 DEG C, obtain catalyzer organophosphorus ligand complexing Pd/C(II) system is stand-by.
9; the preparation of 10-bis--Alpha-Naphthyl anthracene is: under the protection of rare gas element; to in the 100ml reaction flask that mechanical stirring, reflux condensation mode drying tube, feed hopper are housed; add magnesium powder 0.0551mol, THF10ml, add iodine one; drip the mixed liquid of halogenated aromatic (III) 1-bromonaphthalene 0.0481mol, THF30ml; dropwise, back flow reaction 2h, Grignard reagent (IV) 1-magnesium bromide naphthalene is stand-by.
Under the protection of rare gas element, to another, mechanical stirring is housed, reflux condensation mode drying tube, halogenated aromatic (V) 9-Alpha-Naphthyl-10-iodine anthracene 0.0442mol is added in the 250ml reaction flask of feed hopper, add stand-by catalyst II system, the dropping of above-mentioned stand-by Grignard reagent (IV) is entered reaction system, 18h is reacted with 50 ~ 85 DEG C, stopped reaction, filtering catalyst organophosphorus ligand complexing Pd/C(II), catalyzer can reclaim and use next time, organic phase is washed to neutrality, dry, cross post, concentrated, distillation, recrystallization obtains product coupling aromatic hydrocarbon (VI) 9, 10-bis--Alpha-Naphthyl anthracene, LC analyzes main content 98.5%, yield 75.4%.GC-MS(m/z:430 [M]+, 304,178,128), ultimate analysis: measured value (calculated value) C:94.74(94.85); H:5.16(5.15) and
1hNMR (400MHz, CDCl3) confirms.
Claims (4)
1. can reclaim the method for modification palladium carbon to halides Grignard reagent direct coupling halides synthesis polycyclic aromatic hydrocarbon again, it is characterized in that synthetic route is as follows:
A, organophosphorus ligand complexing Pd/C(II) preparation:
Wherein: organophosphorus ligand is triphenylphosphine, 2-dicyclohexylphosphontetrafluoroborate-2', 4', 6'-tri isopropyl biphenyl, 4,5-two diphenylphosphine-9,9-dimethyl xanthene, normal-butyl two (1-adamantyl) phosphines;
B, modification palladium carbon organophosphorus ligand complexing Pd/C(II can be reclaimed again) synthesis to aromatic hydrocarbon Grignard reagent direct coupling halogenated aromatic (V) synthesis of coupling polycyclic aromatic hydrocarbon (VI):
Wherein: R=H, C1 ~ C7 alkane, aromatic hydrocarbon; X=Cl, Br, I; X`=Cl, Br, I; R`=H, F, Cl, Br, I, C1 ~ C7 alkane, aromatic hydrocarbon.
2. according to claim 1ly a kind ofly can reclaim the method for modification palladium carbon to halides Grignard reagent direct coupling halides synthesis polycyclic aromatic hydrocarbon again, it is characterized in that described organophosphorus ligand complexing Pd/C(II) be prepared as follows shown in:
Wherein: organophosphorus ligand is triphenylphosphine, 2-dicyclohexylphosphontetrafluoroborate-2', 4', 6'-tri isopropyl biphenyl, 4,5-two diphenylphosphine-9,9-dimethyl xanthene, normal-butyl two (1-adamantyl) phosphines;
Catalyst P d/C(I in formula) be the Pd/C of aqueous industrial 40 ~ 70%; the effective content 0.5 ~ 10% of palladium; under having protection of inert gas; to reflux azeotropic dehydration with the organic solvent of water azeotropic in non-halogenated hydrocarbons; after moisture is less than 500ppm, adds 1mol ~ 6mol equivalent that organophosphorus ligand is palladium, carries out complex reaction 10min ~ 120min with 10 DEG C ~ 150 DEG C, obtain catalyzer organophosphorus ligand complexing Pd/C(II); can directly be with solvent to use, also can isolate rear use.
3. according to claim 1ly a kind ofly can reclaim the method for modification palladium carbon to halides Grignard reagent direct coupling halides synthesis polycyclic aromatic hydrocarbon again, it is characterized in that described to reclaim modification palladium carbon organophosphorus ligand complexing Pd/C(II again) as follows to the route of polycyclic aromatic hydrocarbon Grignard reagent direct coupling halogenated aromatic (V) synthesis of coupling aromatic hydrocarbon (VI):
Wherein: R=H, C1 ~ C7 alkane, aromatic hydrocarbon; X=Cl, Br, I; X`=Cl, Br, I; R`=H, F, Cl, Br, I, C1 ~ C7 alkane, aromatic hydrocarbon;
In formula, R is hydrogen, the alkyl of carbonatoms 1 ~ 7, aromatic hydrocarbon, XCl, Br, I, and X` is Cl, Br, I; R` is H, F, Cl, Br, I, C1 ~ C7 alkane, aromatic hydrocarbon;
This reaction is the continuous grignard linked reaction of single stage method, compound condensed ring halogenated aromatic (III) is at THF, in ether or other ether solvent, with 10 ~ 90 DEG C at there is grignard reaction and obtain compound Grignard reagent (IV), Grignard reagent dropwise is entered to be equipped with the mixed liquid of halogenated aromatic (V), mixed liquid is added with the catalyzer Phosphine ligands complexing Pd/C(II of 0.05% ~ 8.0% in advance) system in there is linked reaction, time for adding 10min ~ 200min, temperature of reaction 40 DEG C ~ 150 DEG C, reaction times 4 ~ 18h, stopped reaction, filtering catalyst Phosphine ligands complexing Pd/C(II), catalyzer can reclaim use, organic phase is washed to neutrality, then dry, cross post, concentrated, rectifying, recrystallization obtains product coupling aromatic hydrocarbon (VI), GC, LC analyzes, reaction conversion ratio 98.0% ~ 99.8%, synthesis yield 80.0 ~ 98.0%.
4. according to claim 1ly a kind ofly can reclaim the method for modification palladium carbon to halides Grignard reagent direct coupling halides synthesis polycyclic aromatic hydrocarbon again, it is characterized in that described to reclaim modification palladium carbon organophosphorus ligand complexing Pd/C(II again) as follows to the route of aromatic hydrocarbon Grignard reagent direct coupling condensed ring halogenated aromatic (V) synthesis of coupling aromatic hydrocarbon (VI):
wherein: R=H, C1 ~ C7 alkane, aromatic hydrocarbon; X=Cl, Br, I; X`=Cl, Br, I; R`=H, F, Cl, Br, I, C1 ~ C7 alkane, aromatic hydrocarbon;
In formula, R is hydrogen, the alkyl of carbonatoms 1 ~ 7, aromatic hydrocarbon, and X is Cl, Br, I, and R` is F, Cl, Br, I, C1 ~ C7 alkane, aromatic hydrocarbon;
This reaction is the continuous grignard linked reaction of single stage method, compound condensed ring halogenated aromatic (III) is at THF, in ether or other ether solvent, with 10 ~ 90 DEG C at there is grignard reaction and obtain compound Grignard reagent (IV), Grignard reagent dropwise is entered to be equipped with the mixed liquid of halogenated aromatic (V), mixed liquid is added with the catalyzer Phosphine ligands complexing Pd/C(II of 0.05% ~ 8.0% in advance) system in there is linked reaction, time for adding 10min ~ 200min, temperature of reaction 40 DEG C ~ 150 DEG C, reaction times 4 ~ 18h, stopped reaction, filtering catalyst Phosphine ligands complexing Pd/C(II), catalyzer can reclaim use, organic phase is washed to neutrality, then dry, cross post, concentrated, rectifying, recrystallization obtains product coupling aromatic hydrocarbon (VI), GC, LC analyzes, reaction conversion ratio 98.0% ~ 99.8%, synthesis yield 80.0 ~ 98.0%.
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| CN106824267A (en) * | 2017-01-25 | 2017-06-13 | 江西省汉氏贵金属有限公司 | A kind of Suzuki coupling reactions palladium-carbon catalyst and preparation method thereof |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106316745A (en) * | 2016-08-24 | 2017-01-11 | 苏州氟拓化工科技有限公司 | Preparing method of biphenyl compound |
| CN106824267A (en) * | 2017-01-25 | 2017-06-13 | 江西省汉氏贵金属有限公司 | A kind of Suzuki coupling reactions palladium-carbon catalyst and preparation method thereof |
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