CN113262816B - Catalytic system and method for synthesizing benzo [1,2-b:4,5-b' ] dibenzofuran by using same - Google Patents

Catalytic system and method for synthesizing benzo [1,2-b:4,5-b' ] dibenzofuran by using same Download PDF

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CN113262816B
CN113262816B CN202110589998.3A CN202110589998A CN113262816B CN 113262816 B CN113262816 B CN 113262816B CN 202110589998 A CN202110589998 A CN 202110589998A CN 113262816 B CN113262816 B CN 113262816B
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dibenzofuran
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palladium
dichlorobenzene
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CN113262816A (en
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吴忠凯
朱叶峰
杨修光
张玲
裴晓东
骆艳华
申保金
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Sinosteel Nanjing New Material Research Institute Co Ltd
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Abstract

The invention discloses a catalytic system and a method for synthesizing benzo [1,2-b:4,5-b' ] dibenzofuran by using the catalytic system, belonging to the technical field of chemistry. It comprises the following steps: s1: feeding: 1, 4-cyclohexanedione, o-dichlorobenzene, palladium salt, silver salt and ligand are added into a reaction vessel at one time in an inert atmosphere; s2: the reaction: heating the mixture obtained in the step S1, and reacting for a period of time; s3: and (3) collecting: after o-dichlorobenzene is recovered, solvent extraction is added, and the organic layer is desolventized and recrystallized to obtain the benzo [1,2-b:4,5-b' ] dibenzofuran compound. The invention uses 1, 4-cyclohexanedione, o-dichlorobenzene as basic reaction raw material, palladium salt and silver salt as co-catalyst, adopts metal catalyzed multi-step coupling strategy to construct benzo [1,2-b:4,5-b' ] dibenzofuran, has mild reaction condition, simple and easily obtained raw material, high atom utilization rate and high reaction yield.

Description

Catalytic system and method for synthesizing benzo [1,2-b:4,5-b' ] dibenzofuran by using same
Technical Field
The invention belongs to the technical field of chemistry, and particularly relates to a catalytic system and a method for synthesizing benzo [1,2-b:4,5-b' ] dibenzofuran by using the catalytic system.
Background
Dibenzofuran (dibenzofuran) is an important coal tar extract and is an important organic chemical intermediate. The synthesis and chemical modification are always hot spots in modern synthetic chemistry research, and can be widely applied to pesticides, medicines and materials due to the special physicochemical properties of the derivatives. Benzo [1,2-b:4,5-b' ] dibenzofuran is one class of derivatives with characteristics; the organic light emitting diode has great application prospect in the synthesis of OLED materials and molecular devices thereof due to the great conjugate planeness and the action of oxygen atoms.
Historically, lesimple et al (1866) first synthesized with triphenolphosphate and limestone to give dibenzofuran, the first demonstration of its presence in coal tar by Kreamer et al (1901). Dibenzofuran may also be extracted from wash oil or anthracene oil fractions of coal tar. In the prior art, the research methods for synthesizing dibenzofuran and derivatives thereof are mainly divided into two types: dehydration condensation synthesis method using biphenol as substrate; the method uses diphenyl ether compound as skeleton. The ring closure is generally carried out by adopting a mode of in-situ construction of a C-O bond to obtain the compound, and the following methods mainly exist:
method I: kawaguchi et al reported an example of a palladium-catalyzed synthesis of benzo [1,2-b:4,5-b' ] dibenzofuran (J.org.chem.2017, 72,5119). The method is characterized in that a C-O bond is directly constructed in situ through palladium catalysis, so that a furan ring is synthesized, and two furan rings are directly constructed through a two-time coupling process, so that a target product is obtained in 71% yield. In addition, the patent (CN 105348240A) takes m-xylylene ether as a raw material, boric acid is prepared by low-temperature reaction of butyl lithium, the boric acid is prepared into a derivative, and then the derivative and o-bromophenol undergo Suzuki coupling reaction, deprotection and ring closure to obtain the dibenzofuran compound.
Method II: feofanov et al synthesized benzo [1,2-b:4,5-b' ] dibenzofuran (angelw.chem.int.ed.2021, 60,5199) using the SNAr strategy by means of a multi-step construction. By utilizing the higher electronegativity of fluorine atoms, a compound is formed with potassium tert-butyl alcohol, free radicals are formed through a single electron transfer strategy, and the target product is obtained in a yield of 81% through the processes of free radical addition, fluorine leaving, alkyl alkene leaving and SNAr.
Method III: patent (CN 110483533) reports nucleophilic substitution reactions under high temperature conditions to give benzo [1,2-b:4,5-b' ] dibenzofuran. The target product can be obtained by taking potassium carbonate as alkali and N-methyl pyrrolidone as solvent and reacting at the high temperature of 180 ℃.
Figure GDA0004120893240000021
In the above synthetic routes, the poly-biphenyl (method II) or poly-biphenyl (method I and method III) needs to be prepared in advance, and the biphenyl compounds (mainly Suzuki coupling) must be constructed by coupling, so that the atom utilization rate is low, and the cost of the reaction route is increased. The method I has long reaction time, needs four days of 100 ℃ reaction, and has high energy consumption and low reaction efficiency; in the method III, the target product is obtained in a mode of no metal catalytic ring, but the high temperature also causes darkening of the color of the reaction solution, and the difficulty of later purification is increased.
Therefore, a method for synthesizing benzo [1,2-b:4,5-b' ] dibenzofuran with high atom utilization rate needs to be developed to meet the increasing product demands, along with green economy, simple operation and mild conditions.
Disclosure of Invention
1. Problems to be solved
Aiming at the problems of high energy consumption, low reaction efficiency, low atom utilization rate and long preparation route of the existing benzo [1,2-b:4,5-b '] dibenzofuran, the invention provides a catalytic system and a method for synthesizing the benzo [1,2-b:4,5-b' ] dibenzofuran by using the same.
2. Technical proposal
In order to solve the problems, the technical scheme adopted by the invention is as follows:
a catalytic system for the synthesis of benzo [1,2-b:4,5-b' ] dibenzofuran comprising a complex catalyst comprising a palladium salt and a silver salt and a ligand for reducing the palladium salt.
Still further, the palladium salt: silver salt: the molar ratio of the ligand is 1 (1-3): (2-4).
Further, the palladium salt includes palladium acetate (Pd (OAc) 2 ) Tetratriphenylphosphine palladium (Pd (PPh) 4 ) Palladium chloride (PdCl) 2 ) Or one or more of dichloro di-tert-butyl- (4-dimethylaminophenyl) palladium phosphide.
Further, the silver salt includes silver acetate (AgOAc), silver trifluoroacetate (AgCO) 2 CF 3 ) Or one or more of silver triflate (AgOTf).
Further, the bipyridine type ligand comprises one or more of 1, 10-phenanthroline (1, 10-phen), bipyridine and alpha, alpha-terpyridine, and the phosphine ligand comprises tri-tert-butylphosphine, tricyclohexylphosphine (PCy) 3 ) One or more of, (R) -N, N-dimethyl-1- ((S) -2-diphenylphosphine) ferrocene ethylamine (Josiphos) or 2- (DI-1-adamantylphosphine) dimethylaminobenzene.
A method for synthesizing benzo [1,2-b:4,5-b' ] dibenzofuran by using the catalytic system comprises the following steps:
s1: feeding: 1, 4-cyclohexanedione, o-dichlorobenzene, a composite catalyst and a ligand are added into a reaction vessel at one time in an inert atmosphere;
s2: the reaction: heating the mixture obtained in the step S1, and reacting for a period of time;
s3: and (3) collecting: after o-dichlorobenzene is recovered, solvent extraction is added, and the organic layer is desolventized and recrystallized to obtain the benzo [1,2-b:4,5-b' ] dibenzofuran compound. The reaction formula is shown in figure 1.
Still further, the molar ratio of 1, 4-cyclohexanedione to o-dichlorobenzene is 1 (3-6), said 1, 4-cyclohexanedione: o-dichlorobenzene: palladium salt: silver salt: the molar ratio of the ligand is 1: (3-6): 0.005: (0.005-0.015): (0.01-0.02).
Furthermore, the inert atmosphere in S1 is a nitrogen atmosphere, and an argon atmosphere may be used, which is used to prevent the ligand from being oxidized into a phosphine oxide compound, thereby losing the catalytic performance of the enhanced Pd salt, and no starting species such as zero-valent palladium can be obtained.
Further, the reaction temperature in S2 is 100 ℃, and the reaction time is 6-10h.
Furthermore, in the step S3, the solvent is water and ethyl acetate, preferably, the volume ratio of water to ethyl acetate is 3:4, and dichloromethane or chloroform can be used to separate and purify the product.
The invention uses palladium salt and silver salt as co-catalyst, adopts metal catalyzed multi-step coupling strategy to construct benzo [1,2-b:4,5-b ]']Dibenzofuran has the following reaction mechanism: first, pd 2+ Pd (0) is generated under the reduction of phosphine ligand, then the Pd (0) and o-dichlorobenzene are subjected to oxidative addition to generate aryl Pd species, meanwhile, under the catalysis of silver salt, alpha-H bond of 1, 4-cyclohexanedione is activated, further silver salt intermediate is generated, the silver salt intermediate is subjected to transmetallization with aryl Pd species, the Coupling of C-C bond (Suzuki Coupling-Path I) is realized, and the obtained intermediate is subjected to Ag reaction + Under the action of (a) to form a phenoxide intermediate in Pd 0 Under the action of which the intramolecular C-O bond is formed to form a first furan nucleus precursor (Path II), and then the substrate is subjected to Path I and Path II again to obtain a Birch-reduced product containing two furan fragments, which has a high activity in the allylic SP position 3 Conversion of the C-H bond with silver salt to form an allyl silver salt intermediate, subsequent transfer metallization with Pd to provide a Pd-containing species intermediate, and subsequent β -H elimination to provide the benzo [1,2-b:4,5-b ]']Dibenzofuran. The reaction mechanism is shown in FIG. 2.
Wherein, the palladium salt has the functions of realizing the construction of C-C bond and C-O bond and dehydrogenation process; the silver salt has the function of activating SP 3 C-H bond, forming intermediate of C-Ag bond, and carrying out transfer metallization with Pd, thereby realizing coupling of C-C bond and beta-H elimination aromatization; the ligand has the functions of reducing Pd salt, filling the ligand lone pair electron into the Pd p orbit, improving electronegativity, increasing steric hindrance and enhancing Pd catalytic activity, and the synergistic effect of the three is that the two are co-catalyzed, thereby realizing 1+1>2, effectively increasing the catalytic reaction efficiency through the synergistic effect of the two, realizing continuous and rapid construction of multiple bonds, and directly constructing two furan ring slices by a one-pot method through the construction and aromatization processes of C-C bonds and C-O bonds in a multi-step coupling mode in the reaction process.
3. Advantageous effects
Compared with the prior art, the invention has the beneficial effects that:
(1) Compared with the reported method, the method does not need to synthesize the polychlorinated biphenyl compounds in advance, only needs commercially available basic organic chemical raw materials such as ketone and O-dichlorobenzene, and directly constructs two furan ring slices through the construction and aromatization processes of C-C bond and C-O bond in a multi-step coupling mode;
(2) The invention uses 1, 4-cyclohexanedione and o-dichlorobenzene as basic reaction raw materials, palladium salt and silver salt as co-catalysts, and adopts a metal-catalyzed multi-step coupling strategy to construct benzo [1,2-b:4,5-b' ] dibenzofuran, the reaction conditions are mild, the raw materials are simple and easy to obtain, the atom utilization rate is high, and the reaction yield is high;
(3) The preparation method of the benzo [1,2-b:4,5-b' ] dibenzofuran parent body can obtain the target product with high yield and high purity by a co-catalysis strategy of palladium and silver salt at 100 ℃ without adding equivalent alkali, and the method has the advantages of mild condition, low raw material cost, simple operation, high benefit, environmental protection and easy industrial production of enterprises.
Drawings
The technical solution of the present invention will be described in further detail below with reference to the accompanying drawings and examples, but it should be understood that these drawings are designed for the purpose of illustration only and thus are not limiting the scope of the present invention.
FIG. 1 is a reaction equation of the present invention;
FIG. 2 is a diagram of the reaction mechanism of the present invention;
FIG. 3 shows the present invention 1 H-NMR spectrum; 1 H NMR(400MHz,CD 2 Cl 2 )δ8.11(s,2H),8.09–8.04(m,2H),7.61(d,J＝8.2Hz,2H),7.57–7.47(m,2H),7.40(dd,J＝11.3,4.6Hz,2H)；
FIG. 4 is a HPLC chart of example 1 of the present invention; a represents benzo [1,2-b:4,5-b' ] dibenzofuran.
Detailed Description
The following detailed description of exemplary embodiments of the invention is of exemplary embodiments in which the invention may be practiced. While these exemplary embodiments are described in sufficient detail to enable those skilled in the art to practice the invention, it is to be understood that other embodiments may be realized and that various changes to the invention may be made without departing from the spirit and scope of the invention. The following more detailed description of the embodiments of the invention is not intended to limit the scope of the invention, as claimed, but is merely illustrative and not limiting of the invention's features and characteristics in order to set forth the best mode of carrying out the invention and to sufficiently enable those skilled in the art to practice the invention. Accordingly, the scope of the invention is limited only by the attached claims.
Benzo [1,2-b:4,5-b '] dibenzofuran is a special derivative of dibenzofuran, and can be used for synthesizing OLED materials and molecular devices thereof due to the fact that the benzo [1,2-b:4,5-b' ] dibenzofuran has larger conjugation planarity and contains lone pair electron oxygen atoms. In the prior art, the synthesis of benzo [1,2-b:4,5-b' ] dibenzofuran generally requires the preparation of a polydifluorobenzene (method II) or a polydiphenol compound in advance, thereby increasing the cost of a reaction route and having low atom utilization rate. According to the invention, palladium salt and silver salt are used as a co-catalyst, through a multi-step coupling mode, two furan ring slices are directly constructed through a C-C bond and C-O bond construction and aromatization process by a one-pot method, and the benzo [1,2-b:4,5-b' ] dibenzofuran disclosed by the invention is prepared, and the nuclear magnetic spectrum is shown as figure 3.
Wherein, table 1 shows experimental parameters and product yields of the various embodiments of the present invention.
TABLE 1 Experimental parameters and product yields for various examples of the invention
Figure GDA0004120893240000051
Example 1
112.13g of 1, 4-cyclohexanedione (Mr=112.13, 99%,1 mol), 1.12g of palladium acetate (Mr= 224.15, 99%,5 mmol), 0.834g of silver acetate (Mr= 166.91, 99%,5 mmol), 2.023g of tri-tert-butylphosphine (Mr= 202.32, 99%,10 mmol), 588g of o-dichlorobenzene (Mr=147.0, 99%,4 mol) were added to a 1L four-necked flask under nitrogen atmosphere, the temperature was raised to 100℃at 500rmp, the reaction was carried out for 7h, monitored by Thin Layer Chromatography (TLC), after the completion of the reaction, unreacted o-dichlorobenzene was removed by distillation under reduced pressure after filtration of insoluble matters, and water and ethyl acetate (water: ethyl acetate=150 ml:200 ml), the organic layer is desolventized to obtain crude product, toluene is used for recrystallization to obtain 48.81g of benzo [1,2-b:4,5-b ' ] dibenzofuran, the content and yield of the prepared benzo [1,2-b:4,5-b ' ] dibenzofuran are measured by HPLC, the content is 99.1%, the yield is 18.9%, as shown in fig. 4, wherein a represents benzo [1,2-b:4,5-b ' ] dibenzofuran, the peak outlet time is 5.868min, the peak area is 8420.3, the B represents impurities, the peak outlet time is 10.968min, the peak area is 80.3, and the purity is 99.1%.
Example 2
112.13g of 1, 4-cyclohexanedione (Mr=112.13, 99%,1 mol), 0.887g of palladium chloride (Mr=177.33, 99%,5 mmol), 1.104g of silver trifluoroacetate (Mr= 220.88, 99%,5 mmol), 1.80g of 1, 10-phenanthroline (Mr= 180.21, 99%,10 mmol), 735g of o-dichlorobenzene (Mr=147.0, 99%,5 mol), the addition of the feed, the temperature up to 100 ℃, the rotation speed 500rmp, the reaction for 8h, monitoring by Thin Layer Chromatography (TLC), filtering the insoluble substances after the reaction, distilling off unreacted o-dichlorobenzene under reduced pressure, extracting the residue with water: ethyl acetate=150 mL:200 mL), and dissolving the organic layer to obtain a crude product, which is recrystallized from toluene to obtain 35 84 g of benzo [1,2-b:4,5-b' ] dibenzofuran, the content of 99.0%, 28.9%.
Example 3
In a 500mL four-necked flask, 56.07g of 1, 4-cyclohexanedione (Mr=112.13, 99%,0.5 mol), 2.889g of tetrakis triphenylphosphine palladium (Mr= 1155.56, 99%,2.5 mmol), 0.642g of silver triflate (Mr= 256.94, 99%,2.5 mmol), 1.42g of PCy were charged under nitrogen atmosphere at room temperature 3 (Mr= 280.43, 99%,5 mmol), 294g o-dichlorobenzene (Mr=147.0, 99%,2 mol) was added, the temperature was raised to 100℃at 500rmp, the reaction was carried out for 8h, and monitoring by Thin Layer Chromatography (TLC)After the reaction, the insoluble matter was filtered and distilled under reduced pressure to remove unreacted o-dichlorobenzene, the residue was extracted with water and ethyl acetate (water: ethyl acetate=150 ml:200 ml), the organic layer was desolventized to give a crude product, and toluene was recrystallized to give 63.15g of benzo [1,2-b:4,5-b ]']Dibenzofuran content 99.1% and yield 48.9%.
Example 4
56.07g of 1, 4-cyclohexanedione (Mr=112.13, 99%,0.5 mol), 1.77g of di-tert-butyl- (4-dimethylaminophenyl) palladium dichloride (Mr= 708.08, 99%,2.5 mmol), 0.642g of silver triflate (Mr= 256.94, 99%,2.5 mmol), 2.21g of Josiphos (Mr= 441.33, 99%,5 mmol), 367.5g of o-dichlorobenzene (Mr=147.0, 99%,2.5 mol), the temperature is raised to 100 ℃, the reaction is carried out for 8 hours, thin Layer Chromatography (TLC) is carried out, unreacted o-dichlorobenzene is removed by reduced pressure distillation after filtration of the insoluble substances, water and ethyl acetate (water: 150mL:200 mL) are added to extract, and organic desolventization gives a crude product which is recrystallized from toluene to obtain 101.88g of benzo [1,2-b, 4-b, 5-b, 3.9% of benzofuran content, 99% and 9% of benzofuran content.
Example 5
56.07g of 1, 4-cyclohexanedione (Mr=112.13, 99%,0.5 mol), 1.77g of DI-tert-butyl- (4-dimethylaminophenyl) palladium dichloride (Mr= 708.08, 99%,2.5 mmol), 0.642g of silver triflate (Mr= 256.94, 99%,2.5 mmol), 2.11g of 2- (DI-1-adamantylphosphine) dimethylaminobenzene (Mr= 421.6, 99%,5 mmol), 367.5g of o-dichlorobenzene (Mr=147.0, 99%,2.5 mol) are added, the temperature is raised to 100 ℃, the rotation speed is 500rmp, the reaction is monitored for 8h, after the reaction is finished by Thin Layer Chromatography (TLC), unreacted o-dichlorobenzene is removed by filtration, the residue is extracted with water and ethyl acetate (water: ethyl acetate=150:200 mL), the crude product is obtained by organic desolventizing, and the crude product is recrystallized to obtain 117.38g of benzo [1,2-b, 2-99.9% of benzofurans, 2-5% of benzofurans, and the yield of 2.9% of 2-4-dihydrofurans is obtained.
Example 6
In a 500mL four-necked flask, 56.07g of 1, 4-cyclohexanedione (Mr=112.13, 99%,0.5 mol), 2.889g of tetrakis triphenylphosphine palladium (Mr= 1155.56, 99%,2.5 mmol), 0.642g of silver triflate (Mr= 256.94, 99%,2.5 mmol), 2.11g of 2- (DI-1-adamantylphosphine) dimethylaminobenzene (Mr= 421.6, 99%,5 mmol), 294g of o-dichlorobenzene (Mr=147.0, 99%,2 mol), the temperature was raised to 100℃and the rotation speed was 500rmp, the reaction was carried out for 8 hours, after the completion of the reaction, the insoluble matter was filtered and distilled off under reduced pressure, and the residue was extracted with water and ethyl acetate (water: ethyl acetate: 150mL:200 mL), and the organic solvent was removed to obtain a crude product by toluene recrystallization to obtain 96.87g of benzo [1,2-b:4,5-b, 5' -benzofuran content of 1.99%, layer content of 1.75%).
Example 7
56.07g of 1, 4-cyclohexanedione (Mr=112.13, 99%,0.5 mol), 2.889g of tetrakis triphenylphosphine palladium (Mr= 1155.56, 99%,2.5 mmol), 1.28g of silver triflate (Mr= 256.94, 99%,5 mmol), 4.21g of 2- (DI-1-adamantylphosphine) dimethylaminobenzene (Mr= 421.6, 99%,10 mmol), 220.5g of o-dichlorobenzene (Mr=147.0, 99%,1.5 mol), the temperature was raised to 100℃after the addition, the reaction was carried out at 500rmp, the reaction was carried out for 10 hours, monitored by Thin Layer Chromatography (TLC), the unreacted o-dichlorobenzene was removed by distillation under reduced pressure after the filtration of the insoluble matter, and the residue was extracted with water and ethyl acetate (water: ethyl acetate: 150mL:200 mL), and the crude product was obtained by organic desolventizing and recrystallized from toluene to obtain 70.10g of benzo [1,2-b:4, 5' -b, 5% and 0.53% of benzofuran content, 0.53% layer yield.
Example 8
56.07g of 1, 4-cyclohexanedione (Mr=112.13, 99%,0.5 mol), 2.889g of tetrakis triphenylphosphine palladium (Mr= 1155.56, 99%,2.5 mmol), 1.93g of silver triflate (Mr= 256.94, 99%,7.5 mmol), 3.16g of 2- (DI-1-adamantylphosphine) dimethylaminobenzene (Mr= 421.6, 99%,7.5 mmol), 441g of o-dichlorobenzene (Mr=147.0, 99%,3 mol), the temperature was raised to 100℃and the rotation speed was 500rmp, the reaction was monitored by Thin Layer Chromatography (TLC), the insoluble matter was filtered and distilled off under reduced pressure after the reaction was completed, and water and ethyl acetate (water: ethyl acetate: 150mL:200 mL) were added to extract, and the organic desolventized to obtain crude product, which was recrystallized from toluene to obtain 74.02g of benzo [1,2-b:4,5-b, 5% and a benzofuran content of 99.56% in 1.56% layer.
Example 9
112.13g of 1, 4-cyclohexanedione (Mr=112.13, 99%,1 mol), 0.887g of palladium chloride (Mr=177.33, 99%,5 mmol), 1.104g of silver trifluoroacetate (Mr= 220.88, 99%,5 mmol), 1.56g of bipyridine (Mr= 156.18, 99%,10 mmol), 735g of o-dichlorobenzene (Mr=147.0, 99%,5 mol) were added to a 1L four-necked flask under nitrogen atmosphere, the temperature was raised to 100 ℃, the rotation speed was 500rmp, the reaction was carried out for 8 hours, monitored by Thin Layer Chromatography (TLC), unreacted o-dichlorobenzene was removed by distillation under reduced pressure after the reaction was completed, water and ethyl acetate (water: ethyl acetate=150 mL:200 mL) were added to extract, and the organic layer was desolventized to obtain crude benzo [1,2-b:4,5-b' ] dibenzofuran with a content of 27.89g and a yield of 99.0% by toluene recrystallization, 10.8%.
Example 10
112.13g of 1, 4-cyclohexanedione (Mr=112.13, 99%,1 mol), 0.887g of palladium chloride (Mr=177.33, 99%,5 mmol), 1.104g of silver trifluoroacetate (Mr= 220.88, 99%,5 mmol), 2.33g of alpha, alpha-terpyridine (Mr= 233.27, 99%,10 mmol), 735g of o-dichlorobenzene (Mr=147.0, 99%,5 mol), the addition of the feed, the temperature rise to 100 ℃, the rotation speed 500rmp, the reaction for 8h, monitoring by Thin Layer Chromatography (TLC), filtering the insoluble substances after the reaction, removing unreacted o-dichlorobenzene by reduced pressure distillation, extracting the residue with water: ethyl acetate=150 mL:200 mL), and carrying out solvent removal on the organic layer to obtain crude products, which are recrystallized from toluene to obtain 88.33g of benzo [1,2-b:4,5-b' ] dibenzofuran with the content of 99.1%, 34.2%.
Comparative example 1
56.07g of 1, 4-cyclohexanedione (Mr=112.13, 99%,0.5 mol), 1.77g of DI-tert-butyl- (4-dimethylaminophenyl) palladium dichloride (Mr= 708.08, 99%,2.5 mmol), 2.11g of 2- (DI-1-adamantylphosphine) dimethylaminobenzene (Mr= 421.6, 99%,5 mmol), 367.5g of o-dichlorobenzene (Mr=147.0, 99%,2.5 mol) are added to a 500mL four-necked flask under nitrogen atmosphere, the temperature is raised to 100 ℃, the rotation speed is 500rmp, the reaction is carried out for 10 hours, after the reaction is completed, unreacted o-dichlorobenzene is removed by distillation under reduced pressure after the insoluble matter is filtered, water and methylene chloride (water: 150mL:200 mL) are added for extraction, the organic layer GC-MS analysis, benzo [1,2-b:4,5-b' ] dibenzofuran is 5%.
Comparative example 2
56.07g of 1, 4-cyclohexanedione (Mr=112.13, 99%,0.5 mol), 1.77g of di-tert-butyl- (4-dimethylaminophenyl) palladium dichloride (Mr= 708.08, 99%,2.5 mmol), 0.642g of silver triflate (Mr= 256.94, 99%,2.5 mmol), 367.5g of o-dichlorobenzene (Mr=147.0, 99%,2.5 mol) are added to a 500mL four-necked flask at room temperature under nitrogen atmosphere, the temperature is raised to 100 ℃, the rotation speed is 500rmp, the reaction is carried out for 10 hours, after the reaction is finished, unreacted o-dichlorobenzene is removed by reduced pressure distillation, water and methylene dichloride (water: 150mL:200 mL) are added to the residue for extraction, and the organic layer GC-MS analysis is carried out, and benzo [1,2-b:4,5-b' ] dibenzofuran <5%.
Comparative example 3
56.07g of 1, 4-cyclohexanedione (Mr=112.13, 99%,0.5 mol), 0.642g of silver triflate (Mr= 256.94, 99%,2.5 mmol), 2.11g of 2- (DI-1-adamantylphosphine) dimethylaminobenzene (Mr= 421.6, 99%,5 mmol), 367.5g of o-dichlorobenzene (Mr=147.0, 99%,2.5 mol) were added to a 500mL four-necked flask under nitrogen atmosphere, the temperature was raised to 100℃at 500rmp, the reaction was carried out for 10 hours, after the reaction was completed, the insoluble matter was filtered, the unreacted o-dichlorobenzene was removed by distillation under reduced pressure, and water and methylene chloride (water: methylene chloride=150 mL:200 mL) were added to extract, and the organic layer was analyzed by GC-MS, and benzo [1,2-b:4,5-b' ] dibenzofuran <1%.
The present invention is not limited to the embodiments of the present invention. Specific examples are set forth herein to illustrate the structure and embodiments of the present invention, and the above examples are only for aiding in the understanding of the core concept of the present invention. It should be noted that it will be apparent to those skilled in the art that various modifications and adaptations of the invention can be made without departing from the principles of the invention and these modifications and adaptations are intended to be within the scope of the invention as defined in the following claims.

Claims (8)

1. A method for synthesizing benzo [1,2-b:4,5-b' ] dibenzofuran, characterized by comprising the steps of:
s1: feeding: 1, 4-cyclohexanedione, o-dichlorobenzene, a composite catalyst and a ligand are added into a reaction vessel at one time in an inert atmosphere; the composite catalyst comprises palladium salt and silver salt, and the ligand comprises bipyridine ligand or phosphine ligand, and is used for reducing the palladium salt;
s2: the reaction: heating the mixture obtained in the step S1, and reacting for a period of time at a reaction temperature of 100 ℃ for a reaction time of 6-10 h;
s3: and (3) collecting: after o-dichlorobenzene is recovered, solvent extraction is added, and the organic layer is desolventized and recrystallized to obtain the benzo [1,2-b:4,5-b' ] dibenzofuran compound.
2. A process for the synthesis of benzo [1,2-b:4,5-b' ] dibenzofuran according to claim 1, characterized in that said palladium salt: silver salt: the molar ratio of the ligand is 1 (1-3): (2-4).
3. The method for synthesizing benzo [1,2-b:4,5-b' ] dibenzofuran according to claim 1, wherein said palladium salt comprises one or more of palladium acetate, palladium tetraphenylphosphine, palladium chloride or palladium dichloro di-tert-butyl- (4-dimethylaminophenyl) phosphorus.
4. A method of synthesizing benzo [1,2-b:4,5-b' ] dibenzofuran according to claim 1, wherein said silver salt comprises one or more of silver acetate, silver trifluoroacetate or silver trifluoromethane sulfonate.
5. A method of synthesizing benzo [1,2-b:4,5-b' ] dibenzofuran according to claim 1, wherein said bipyridine-based ligand comprises one or more of 1, 10-phenanthroline, bipyridine and α, α, α -terpyridine, and said phosphine ligand comprises one or more of tri-tert-butylphosphine, tricyclohexylphosphine, (R) -N, N-dimethyl-1- ((S) -2-diphenylphosphine) ferrocenoethyl amine or 2- (DI-1-adamantylphosphine) dimethylaminobenzene.
6. A process for the synthesis of benzo [1,2-b:4,5-b' ] dibenzofuran according to claim 1, wherein the molar ratio of 1, 4-cyclohexanedione to o-dichlorobenzene is 1 (3-6), said 1, 4-cyclohexanedione: o-dichlorobenzene: palladium salt: silver salt: the molar ratio of the ligand is 1: (3-6): 0.005: (0.005-0.015): (0.01-0.02).
7. A process for the synthesis of benzo [1,2-b:4,5-b' ] dibenzofuran according to claim 1, wherein said inert atmosphere in S1 is a nitrogen atmosphere or an argon atmosphere.
8. The process for synthesizing benzo [1,2-b:4,5-b' ] dibenzofuran according to claim 1, wherein the solvent in step S3 is a mixed solvent of water and ethyl acetate, water and methylene chloride or water and chloroform.
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