CN111039848A - Preparation method of 4, 4' -dicarbazolylbiphenyl - Google Patents
Preparation method of 4, 4' -dicarbazolylbiphenyl Download PDFInfo
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- CN111039848A CN111039848A CN201811198751.3A CN201811198751A CN111039848A CN 111039848 A CN111039848 A CN 111039848A CN 201811198751 A CN201811198751 A CN 201811198751A CN 111039848 A CN111039848 A CN 111039848A
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- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D209/00—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
- C07D209/56—Ring systems containing three or more rings
- C07D209/80—[b, c]- or [b, d]-condensed
- C07D209/82—Carbazoles; Hydrogenated carbazoles
- C07D209/86—Carbazoles; Hydrogenated carbazoles with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to carbon atoms of the ring system
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Abstract
The invention provides a preparation method of 4,4 ' -dicarbazolyl biphenyl, which is characterized in that under the action of a palladium catalyst coordinated by 2, 6-bis (2,4, 6-triisopropylphenyl) phenyl-dicyclohexylphosphine and an organic magnesium reagent, 4,4 ' -dichlorobiphenyl and carbazole are effectively coupled to generate the 4,4 ' -dicarbazolyl biphenyl. The method is characterized in that 2, 6-bis (2,4, 6-triisopropylphenyl) phenyl-dicyclohexylphosphine is used as a supporting ligand of a palladium catalyst.
Description
Technical Field
The invention relates to preparation of 4, 4' -dicarbazolyl biphenyl by palladium-catalyzed Buchwald-Hartwig coupling amination reaction, belonging to the field of organic synthesis.
Background
N-aryl carbazole is a compound commonly used in medicines, pesticides and organic photoelectric materials, wherein 4, 4' -dicarbazolyl biphenyl is a key chemical component of an OLED device. The traditional preparation method is an Ullmann reaction catalyzed by copper, but the reaction condition is harsh, the dosage of the catalyst is large, the post-treatment is difficult, and the product purity often cannot meet the requirements of photoelectric materials. Buchwald and Hartwig developed palladium-catalyzed C-N bond coupling reactions, also known as Buchwald-Hartwig coupled amination reactions, widely used in amination reactions of halogenated aromatic hydrocarbons at the end of the last century, but reports on palladium-catalyzed carbazole-to-halogenated aromatic hydrocarbon coupling reactions are rare [ 1) G. Man, et al, J. Am. chem. Soc., 1998, 120,827; 2) J.F. Hartwig, et al, J. org. chem., 1999, 64, 5575; 3) D.W. Old, et al, org. Lett. 2002, 2, 1403; 4) M. Watanabe, et al, Tetrahedron Lett.,2000, 41, 481; 5) G.A. Grasa, et al, J. org. chem. 2001, 66, zu. 7729; Syntradron Lett. K.652, J. Adv. 652, 2008. The main reason is that the P-pi conjugation between the N atom in carbazole and the benzene ring makes the N atom have low nucleophilic ability, making carbazole a very challenging coupling substrate. In these reported references, the catalyst is often used in amounts as high as five percent (5 mol%).
In patent WO 2013/032035, Takasago, japan in 2013, described that a phosphine ligand (2, 2-diphenyl-1-methyl-cyclopropyl-1) -di-tert-butylphosphine (cBRIDP) developed by the company was superior in performance to the biphenol phosphine ligand developed by Buchwald, et al, a college of labor and science of ma, in the palladium-catalyzed coupling reaction of carbazole with chlorinated aromatic hydrocarbon. The technology is an advanced technology for preparing the N-aryl carbazole derivative in the world at present. Patents by Takasago corporation describe: at 145oAnd C, catalyzing the reaction of 4,4 '-dibromobiphenyl and carbazole by using a catalytic system of 0.2 mol% of allyl palladium chloride and 0.4 mol% of cBRIDP phosphine ligand, and preparing the 4, 4' -dicarbazolyl biphenyl by using methyl magnesium chloride as a base with the yield of 97%.
Since palladium metal is rare and expensive, the development of a coupling reaction process with low catalyst consumption is an important subject in green chemistry research. The invention discovers that the palladium-catalyzed Buchwald-Hartwig coupling amination method can be effectively promoted by applying a triple aromatic phosphine supporting ligand (CN 201810187687.2) developed by the inventor, the activity of the triple aromatic phosphine supporting ligand in the coupling reaction of catalyzing 4, 4' -dichlorobiphenyl and carbazole is obviously higher than that of a cBRIDP phosphine-supported palladium system of Takasago company, and therefore, the dosages of palladium and phosphine ligands are respectively obviously less than that of the cBRIDP phosphine-supported palladium system of the Takasago company.
Disclosure of Invention
DISCLOSURE OF THE INVENTION
In a first aspect, the invention provides a method for preparing 4,4 '-dicarbazolylbiphenyl by using a palladium catalyst to realize a coupling reaction between 4, 4' -dichlorobiphenyl and carbazole under the promotion of an organic magnesium reagent.
In a second aspect, the supporting ligand of the palladium catalyst system used in the present invention is a tris-arylmono-phosphine ligand having the general formula Ia and Ib or mixtures thereof:
wherein
Ar is selected from (C6-C20) aryl, which may have 1 to 3 substituents independently selected from (C1-C6) alkyl, -O (C1-C6) alkoxy, -N (C1-C6)2Dialkylamino or (C6-C10) aryl (wherein the aryl may also have 1 to 3 substituents independently selected from (C1-C6) alkyl, -O (C1-C6) alkoxy or-N (C1-C6)2A substituent of a dialkylamino group);
R1selected from H, (C1-C6) alkyl, -O (C1-C6) alkoxy or-N (C1-C6)2A dialkylamino group;
R2and R3Each independently selected from (C1-C10) alkyl, (C3-C10) cycloalkyl, (5-11 membered) heterocycloalkyl, (C6-C20) aryl, (C4-C20) heteroaryl or-CH2(C6-C10) arylmethylene, here (C3-C10) cycloalkyl, (5-11 membered) heterocycloalkyl, (C6-C20) aryl, (C4-C20) heteroaryl and-CH2(C6-C10) the arylmethylene group may have 1 to 3 groups independently selected from (C1-C6) alkyl or-O (C1-C6) alkoxy-N (C1-C6)2A substituent of dialkylamino, where the heteroatom in heteroaryl is selected from O, N or an S atom.
In a third aspect, the tris-biaryl phosphines used in the present invention include those of the following structure.
In a fourth aspect, the palladium catalyst system used in the present invention is prepared from palladium source [2, 6-bis (2,4, 6-triisopropylphenyl) phenyl-dicyclohexylphosphine and allyl palladium (II) chloride, cinnamyl palladium (II) chloride, palladium acetate, dimeric [ 2' -amino-2-biphenyl-
-C, N-Palladium (II) chloride]Or is a complex [ tris (aryl) phosphine [)](allyl-
) Palladium chloride (II) is stirred in tetrahydrofuran, toluene or xylene solvent for 0.5 to 2 hours at room temperature according to a certain proportion to form a catalytic system; in some cases, 5 to 10 equivalents of water (based on palladium) are also added to 100oC, heating for 2 to 5 minutes to form a catalytic system; sometimes the complex [2, 6-bis (2,4, 6-triisopropylphenyl) phenyl-dicyclohexylphosphine is prepared first](allyl-
) Palladium (II) chloride, optionally with the addition of 2, 6-bis (2,4, 6-triisopropylphenyl) phenyl-dicyclohexylphosphine ligand; sometimes, the triple arylphosphine and the palladium source are directly added into the reaction system. Wherein the ratio of phosphine ligand to palladium may be from 1:1 to 3:1 and the amount of palladium is from 0.1 to 0.3mol% (based on 4, 4' -dichlorobenzene).
In a third aspect, the organomagnesium reagent is MgR2Or RMgX, wherein R may be selected from methyl, ethyl, propyl, or phenyl, and X is selected from chlorine, bromine, or iodine.
Fourth aspect, 4, 4' -dichlorobiphenyl, carbazole and organomagnesium reagents (based on MgR)2Or the amount of R in RMgX) in a ratio of 1:2:2 to 1:3:3, preferably 1:2.02:2.03 to 1:2.2: 2.3.
In a fifth aspect, the reaction medium may be one or a mixture of tetrahydrofuran, dioxane, and xylene.
In the sixth aspect, the reaction temperature may be 60 to 180 deg.CoC is preferably in the range of 90 to 150oC。
In the seventh aspect, the reaction time may be in the range of 0.1 to 24 hours, preferably 0.5 to 6 hours.
In an eighth aspect, the reaction pressure may be from 1 to 50 atmospheres, and is typically less than 10 atmospheres.
The present invention can be illustrated in further detail by the following examples, but it is not intended that the present invention be limited to these examples.
Example 1.
To a dry 50 mL Schlenk flask, under inert gas, add the stirrer, add carbazole (0.368 g, 2.2 mmol) and xylene (3 mL), cool to 5 deg.C, add methyl magnesium chloride (3.0M in THF, 2.3mmol, 0.77 mL) dropwise via syringe (about 1.5 min), stir for 15 min after addition, and transfer to a glove box for use.
In a glove box, 4' -dichlorobiphenyl (0.223 g, 1.0 mmol), complex [2, 6-bis (2,4, 6-triisopropylphenyl) phenyl-dicyclohexylphosphine were added to a pressure-resistant tube](allyl-
) Palladium (II) chloride (0.86 mg,0.001 mmol), 2, 6-bis (2,4, 6-triisopropylphenyl) phenyl-dicyclohexylphosphine (0.68 mg,0.001 mmol) and 0.13 mL dodecane (as internal standard for GC analysis) were dissolved in 1 mL xylene. The Schlenk bottle reaction solution is transferred into a pressure resistant tube at room temperature, sealed and reacted for 3 hours at 145 ℃ in an oil bath. The reaction mixture was filtered through silica gel and celite, the filtrate was concentrated under reduced pressure, and the residue was purified by silica gel column chromatography (petroleum ether: ethyl acetate = 10:1) to obtain 0.47 g of a white solid with a yield of 98%.
1H NMR (400 MHz, CDCl3) δ: 8.22 (d, J = 7.7 Hz, 4H), 7.92 (d, J = 8.4Hz, 4H), 7.73 (d, J = 8.4 Hz, 4H), 7.56 (d, J = 8.2 Hz, 4H), 7.53 – 7.45 (m,4H), 7.37 (dd, J = 10.9, 3.9 Hz, 4H).
13C NMR (101 MHz, CDCl3) δ: 140.9, 139.3, 137.3, 128.5, 127.5, 126.1,123.5, 120.4, 120.2, 109.9.
Example 2.
To a dry 50 mL Schlenk flask, under inert gas, add the stirrer, add carbazole (0.368 g, 2.2 mmol) and xylene (3 mL), cool to 5 deg.C, add methyl magnesium chloride (3.0M in THF, 2.3mmol, 0.77 mL) dropwise via syringe (about 1.5 min), stir for 15 min after addition, and transfer to a glove box for use.
In a glove box, Pd (dba) is added into a pressure-resistant tube2(1.15 mg, 0.002 mmol), 2, 6-bis (2,4, 6-triisopropylphenyl) phenyl-dicyclohexylphosphine (2.72 mg, 0.004 mmol) were dissolved in 1 mL of xylene, and further dissolved in 100 mL of xyleneoHeating under CFor 2 minutes, cool to room temperature and add 4, 4' -dichlorobiphenyl (0.223 g, 1.0 mmol) and 0.13 mL dodecane (as an internal standard for GC analysis). The Schlenk bottle reaction solution is transferred into a pressure resistant tube at room temperature, sealed and reacted for 12 hours at 145 ℃ in an oil bath. The reaction mixture was filtered through silica gel and celite, the filtrate was concentrated under reduced pressure, and the residue was purified by silica gel column chromatography (petroleum ether: ethyl acetate = 10:1) to obtain 0.44 g of a white solid in 91% yield.
Example 3.
To a dry 50 mL Schlenk flask, under inert gas, add the stirrer, add carbazole (0.368 g, 2.2 mmol) and xylene (3 mL), cool to 5 deg.C, add methyl magnesium chloride (3.0M in THF, 2.3mmol, 0.77 mL) dropwise via syringe (about 1.5 min), stir for 15 min after addition, and transfer to a glove box for use.
In a glove box, Pd (OAc) is added into a pressure-resistant tube2(0.67 mg, 0.003 mmol), 2, 6-bis (2,4, 6-triisopropylphenyl) phenyl-dicyclohexylphosphine (4.1 mg, 0.006 mmol) and water (0.27 uL, 1.5 mol%, 5.0 eq) were dissolved in 1 mL of xylene and then dissolved in 100 mL of xyleneoHeated at C for 3 minutes, cooled to room temperature, and added 4, 4' -dichlorobiphenyl (0.223 g, 1.0 mmol) and 0.13 mL dodecane (as an internal standard for GC analysis). The Schlenk bottle reaction solution is transferred into a pressure resistant tube at room temperature, sealed and reacted for 12 hours at 145 ℃ in an oil bath. The reaction mixture was filtered through silica gel and celite, the filtrate was concentrated under reduced pressure, and the residue was purified by silica gel column chromatography (petroleum ether: ethyl acetate = 10:1) to obtain 0.45 g of a white solid in 93% yield.
Example 4.
To a dry 50 mL Schlenk flask, under inert gas, add the stirrer, add carbazole (0.368 g, 2.2 mmol) and xylene (3 mL), cool to 5 deg.C, add methyl magnesium chloride (3.0M in THF, 2.3mmol, 0.77 mL) dropwise via syringe (about 1.5 min), stir for 15 min after addition, and transfer to a glove box for use.
In a glove box, to a pressure-resistant tube, diallyl palladium (II) chloride (0.18 mg, 0.0005mmol), 2, 6-bis (2,4, 6-triisopropylphenyl) phenyl-dicyclohexylphosphine (1.36 mg, 0.002 mmol) were added dissolved in 1 mL of xylene, stirred for 5 minutes, and 4, 4' -dichlorobiphenyl (0.223 g, 1.0 mmol) and 0.13 mL of dodecane (as an internal standard for GC analysis) were added. The Schlenk bottle reaction solution is transferred into a pressure resistant tube at room temperature, sealed and reacted for 12 hours at 145 ℃ in an oil bath. The reaction mixture was filtered through silica gel and celite, the filtrate was concentrated under reduced pressure, and the residue was purified by silica gel column chromatography (petroleum ether: ethyl acetate = 10:1) to obtain 0.46 g of a white solid in 95% yield.
Claims (10)
1. The invention provides a method for preparing 4,4 '-dicarbazolyl biphenyl by using a palladium catalyst to realize a coupling reaction between 4, 4' -dichlorobiphenyl and carbazole under the promotion of an organic magnesium reagent.
2. According to claim 1, the supporting ligands of the palladium catalyst systems used according to the invention are tertiaryarylmonophosphine ligands having the general formulae Ia and Ib or mixtures thereof:
wherein
Ar is selected from (C6-C20) aryl, which may have 1 to 3 substituents independently selected from (C1-C6) alkyl, -O (C1-C6) alkoxy, -N (C1-C6)2Dialkylamino or (C6-C10) aryl (wherein the aryl may also have 1 to 3 substituents independently selected from (C1-C6) alkyl, -O (C1-C6) alkoxy or-N (C1-C6)2A substituent of a dialkylamino group);
R1selected from H, (C1-C6) alkyl, -O (C1-C6) alkoxy or-N (C1-C6)2A dialkylamino group;
R2and R3Each independently selected from (C1-C10) alkyl, (C3-C10) cycloalkyl, (5-11 membered) heterocycloalkyl, (C6-C20) aryl, (C4-C20) heteroaryl or-CH2(C6-C10) arylmethylene, here (C3-C10) cycloalkyl, (5-11 membered) heterocycloalkyl, (C6-C20) aryl, (C4-C20) heteroaryl and-CH2(C6-C10) the arylmethylene group may have 1 to 3 groups independently selected from (C1-C6) alkyl or-O (C1-C6) alkoxy-N (C1-C6)2A substituent of dialkylamino group, wherein the hetero atom in the heteroaryl group is selected from O, N or S atom。
3. The invention according to the above claims uses a tris-biaryl phosphine comprising a tris-biaryl phosphine of the structure.
4. According to claim 1, the palladium source in the palladium catalyst system used in the present invention is allylpalladium (II) chloride, cinnamylpalladium (II) chloride, palladium acetate, dimeric [ 2' -amino-2-biphenyl-
-C, N-Palladium (II) chloride]Or a complex [ (trisarylphosphine) (allyl-
) Palladium chloride (II)]。
5. According to claim 1, the ratio of phosphine ligand to palladium in the palladium catalyst system used according to the invention can be from 1:1 to 3: 1.
6. According to claim 1, the organomagnesium reagent is MgR2Or RMgX, wherein R may be selected from methyl, ethyl, propyl, isopropyl or phenyl and X is selected from chlorine, bromine or iodine.
7. The reagents according to claim 1, 4, 4' -dichlorobiphenyl, carbazole and organomagnesium (based on MgR)2Or the amount of R in RMgX) is in a ratio of 1:2:2 to 1:3:3, preferably 1:2.02:2.03 to 1:2.2:2.3, and palladium is used in an amount of 0.1 to 0.3mol% (based on 4, 4' -dichlorobiphenyl).
8. In the preparation method provided by the invention, the reaction medium in the above claims can be tetrahydrofuran, dioxane, toluene or xylene.
9. In the preparation method provided by the invention, the reaction temperature in the above claims can be 60-180 DEGoC is preferably in the range of 90 to 150oC。
10. In the preparation method provided by the invention, the reaction time in the above claims can be in the range of 0.1-24 hours, preferably 0.5-6 hours.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103917522A (en) * | 2011-09-02 | 2014-07-09 | 高砂香料工业株式会社 | Process for producing n-(hetero)arylazoles |
| CN105859774A (en) * | 2016-04-12 | 2016-08-17 | 盘锦格林凯默科技有限公司 | Preparation method of phosphinobenzene compound |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103917522A (en) * | 2011-09-02 | 2014-07-09 | 高砂香料工业株式会社 | Process for producing n-(hetero)arylazoles |
| CN105859774A (en) * | 2016-04-12 | 2016-08-17 | 盘锦格林凯默科技有限公司 | Preparation method of phosphinobenzene compound |
Non-Patent Citations (2)
| Title |
|---|
| LAURA ORTEGA-MORENO ET AL.: "Synthesis, properties, and some rhodium, iridium, and platinum complexes of a series of bulky m-terphenylphosphine ligands", 《POLYHEDRON》 * |
| YUJI NAKAYAMA ET AL.: "An Efficient Synthesis of N-(Hetero)arylcarbazoles: Palladium-Catalyzed Coupling Reaction between (Hetero)aryl Chlorides and N-Carbazolylmagnesium Chloride", 《ADV. SYNTH. CATAL.》 * |
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