JP5381718B2 - Halopolycyclic aromatic compound and method for producing the same - Google Patents

Description

  The present invention relates to an intermediate of an organic synthetic compound, in particular, a halopolycyclic aromatic compound useful as an intermediate of an organic electroluminescent material, and a method for producing the same.

A useful intermediate is known in a method for synthesizing a dicarbazolyl polycyclic aromatic compound having a symmetrical form in which two carbazoyl groups are substituted. For example, in the case of dibenzofuran, 2,7-dibromodibenzofuran or 2,7-diiododibenzofuran can be used as a synthetic intermediate. (For example, refer nonpatent literature 1.)
However, when synthesizing a dicarbazolyl polycyclic aromatic compound having an asymmetric form, it is difficult to control the reaction if these intermediates are used, and simultaneously with 2-carbazolyl-7-halodibenzofuran in which only one carbazoyl group is substituted. There was a problem that the yield of the carbazoyl group substituted was by-produced and the yield was greatly reduced.
Kryska Anna et al. , J .; Chem. Res. Miniprint. 10; 2501-2517 (1999)

  Accordingly, the present invention has been made to solve the above-described problems, and is a halopolycyclic aromatic compound that is an intermediate useful in synthesizing a polycyclic aromatic compound having an asymmetric form in a high yield, and It is in providing the manufacturing method.

  The above problem could be solved by the following configuration.

  1. The manufacturing method of the halo polycyclic aromatic compound characterized by manufacturing the halo polycyclic aromatic compound represented by the following general formula [2] using the compound represented by the following general formula [1].

_(Wherein, R 1, _{R 2} represents a substituent, n1, n2 are _.R 3 represents an integer of 0 to 3, _{R 4} is .R ₃ and _{R 4} representing a human Dorokishi group or an alkoxy group each other bound good .X ₁ to form a ring with the .X ₂ representing an oxygen atom or a sulfur atom represents a halogen atom.)
2. The compound represented by the general formula [1] is reacted with a lithiating agent and then reacted with a boronic acid derivative to produce a halopolycyclic aromatic compound represented by the general formula [2]. 2. The method for producing a halopolycyclic aromatic compound as described in 1 above.

  3. A compound represented by the following general formula [2] and a compound represented by the following general formula [3] are reacted in the presence of a transition metal catalyst to produce a halopolycyclic aromatic compound represented by the following general formula [4]. A process for producing a halopolycyclic aromatic compound, characterized in that it is produced.

_(Wherein, R 1, _{R 2} represents a substituent, n1, n2 are _.R 3 represents an integer of 0 to 3, _{R 4} is .R ₃ and _{R 4} representing a human Dorokishi group or an alkoxy group each other binding to which may form a ring .X ₁ is the .X _2, X ₃ representing an oxygen atom or a sulfur atom is .Z represents a halogen atom to form an aromatic hydrocarbon ring or aromatic heterocyclic ring Represents a group of non-metallic atoms necessary for
4). A halopolycyclic aromatic compound represented by the following general formula [2].

_(Wherein, R 1, _{R 2} represents a substituent, n1, n2 are _.R 3 represents an integer of 0 to 3, _{R 4} is .R ₃ and _{R 4} representing a human Dorokishi group or an alkoxy group each other bound good .X ₁ to form a ring with the .X ₂ representing an oxygen atom or a sulfur atom represents a halogen atom.)
5). 5. The halopolycyclic aromatic compound according to the above 4, represented by the following general formula [5].
(In the formula, R ₁ and R ₂ represent a hydrogen atom or a methyl group. R ₃ and R ₄ represent a hydroxy group or an alkoxy group. R ₃ and R ₄ may be bonded to each other to form a ring. .X ₁ is .X ₂ representing an oxygen atom or a sulfur atom represents a halogen atom.)

  A halopolycyclic aromatic compound useful as an intermediate of an organic synthetic compound, particularly as an intermediate of an organic electroluminescent material, can be obtained in a high yield by the production method of the present invention.

  Hereinafter, the present invention will be described in more detail.

In general formula [1], general formula [2], general formula [3], and general formula [4], examples of the substituent represented by R ₁ and R ₂ include alkyl, cycloalkyl, alkenyl, aryl, Acylamino, sulfonamido, alkylthio, arylthio, halogen atom, heterocycle, sulfonyl, sulfinyl, phosphonyl, acyl, carbamoyl, sulfamoyl, cyano, alkoxy, aryloxy, heterocycleoxy, siloxy, acyloxy, carbamoyloxy, amino, alkylamino, Examples include imide, ureido, sulfamoylamino, alkoxycarbonylamino, alkoxycarbonylamino, aryloxycarbonylamino, alkoxycarbonyl, aryloxycarbonyl, carboxyl and the like.

X ₁ represents an oxygen atom, a sulfur atom or an imino group, and the imino group is preferably an imino group substituted with alkyl or aryl. Of these, preferred is an oxygen atom. The halogen atom represented by X ₂ is preferably a bromine atom.

R ₃ and R ₄ represent a hydroxy group or an alkoxy group. Examples of the alkoxy group represented by R ₃ and R ₄ include a methoxy group, and further —OC (CH ₃ ) ₂ C (CH ₃ ) ₂ O— and —OCH ₂ CH (CH ₃ ) forming a ring. CH ₂ O- and the like. Among the groups represented by R ₃ and R ₄ , preferred are a hydroxy group, —OC (CH ₃ ) ₂ C (CH ₃ ) ₂ O—, and more preferred is a hydroxy group.

  Examples of the aromatic hydrocarbon ring and aromatic heterocycle formed together with Z include, for example, a benzene ring, biphenyl ring, naphthalene ring, carbazole ring, furan ring, thiophene ring, pyridine ring, pyridazine ring, pyrimidine ring, pyrazine ring, Triazine ring, benzimidazole ring, oxadiazole ring, triazole ring, imidazole ring, pyrazole ring, thiazole ring, indole ring, benzimidazole ring, benzothiazole ring, benzoxazole ring, quinoxaline ring, quinazoline ring, phthalazine ring, carboline ring And a diazacarbazole ring (showing a ring in which one of the carbon atoms of the hydrocarbon ring constituting the carboline ring is further substituted with a nitrogen atom). Of these, preferred are a benzene ring and a carbazole ring.

  Any of the above groups may be further substituted with a substituent. Examples of the substituent include alkyl, cycloalkyl, alkenyl, aryl, acylamino, sulfonamido, alkylthio, arylthio, halogen atom, heterocycle, sulfonyl, Sulfinyl, phosphonyl, acyl, carbamoyl, sulfamoyl, cyano, alkoxy, aryloxy, heterocyclic oxy, siloxy, acyloxy, carbamoyloxy, amino, alkylamino, imide, ureido, sulfamoylamino, alkoxycarbonylamino, alkoxycarbonylamino, Examples include aryloxycarbonylamino, alkoxycarbonyl, aryloxycarbonyl, carboxyl and the like.

  Hereinafter, typical specific examples of the compounds represented by the general formula [1], the general formula [2], the general formula [3], and the general formula [4] are shown in the present invention, but the present invention is not limited thereto. is not.

  The compound represented by the general formula [2] can be obtained by reacting the general formula [1] with a lithiating agent and then reacting with a boronic acid derivative.

  Examples of the lithiating agent include methyl lithium, n-butyl lithium, sec-butyl lithium, t-butyl lithium, and n-hexyl lithium. Of these, n-butyllithium is preferred. Examples of the boronic acid derivative include trimethyl borate, tributyl borate, 2-isopropoxy-4,4,5,5-tetramethyl-1,3,2-dioxaborolane and the like. Of these, trimethyl borate is preferred.

  The reaction is usually preferably performed at -80 to 0 ° C, particularly preferably at -80 to -50 ° C.

  The compound represented by the general formula [4] can be obtained by the reaction of the compound represented by the general formula [2] and the compound represented by the general formula [3] in the presence of a transition metal catalyst.

Examples of the transition metal catalyst include palladium complexes (PdCl ₂ , Pd (OAc) ₂ , Pd (PPh ₃ ) ₄ , PdCl ₂ dppf, Pd (dba) ₂ , Pd / C), nickel complexes (NiBr ₂ , NiBr _2). (PPh ₃ ) ₂ , Ni (acac) ₂ , Bis (1,5-cyclotadiene) Ni (0)), zinc and the like. Among these, a palladium complex is preferable.

Further, the following compounds may be added together with the metal catalyst. For example, quaternary ammonium salts (TBAF (tetrabutylammonium fluoride), tetraethylammonium iodide), 2,2′-bipyridine, tri (t-butyl) phosphine, DPPE (Bis (diphenylphosphino) ethane), DPPP (Bis ( diphenylphosphino) propane), DPPB (Bis (diphenylphosphino) butane), DPPF (1,1′-Bis (diphenylphosphino) ferrocene), PCy ₃ (Tricyclohexylphosphine) and the like.

  Furthermore, a base is used in the above reaction. Examples of the base include alkali metal salts (sodium carbonate, potassium carbonate, sodium hydrogen carbonate, cesium carbonate, cesium fluoride, etc.), amine derivatives (triethylamine, etc.) and the like.

  The reaction is usually preferably carried out at 60 to 130 ° C, particularly preferably 70 to 100 ° C.

  Hereinafter, the present invention will be specifically described with reference to examples. However, the embodiment of the present invention is not limited thereto.

Example 1 (Comparative Example)
<< Synthesis of Compound D >>

  Exemplified compound 1-1, 6.30 g, carbazole 2.9 g (× 0.9 mol), potassium carbonate 4.0 g (× 1.5 mol), Cu powder 3.68 g (× 3 mol), dehydrated DMAc 75 ml are mixed, and nitrogen is mixed. The mixture was stirred for 30 hours under an air stream (internal temperature: 145 to 147 ° C.). Insoluble matter was filtered under reduced pressure, and the filtrate was extracted with THF, and then the solvent was removed by distillation under reduced pressure. Purification by column chromatography (filler: silica gel, developing solution: toluene / n-hexane) gave 0.48 g (yield 6.0%) of Compound B.

Next, under a nitrogen stream, Compound B, 0.48 g, Compound C, 0.43 g, Ethylene glycol dimethyl ether 50 ml, 15% aqueous potassium carbonate solution 2.5 ml, Pd (Pph ₃ ) ₄ 0.080 g were charged and refluxed for 5 hours. did. The reaction solution was washed with water and filtered under reduced pressure. The resulting crude crystals were purified by column chromatography (silica gel, toluene / hexane) to obtain Compound D (0.13 g, yield 20.0%).

Example 2 (Example of the present invention)
<< Synthesis of Compound D >>

Under a nitrogen stream, 81.5 g of Exemplified Compound 1-1 was added to 1 L of dehydrated THF, and stirred and dissolved at an internal temperature of 25 to 30 ° C. Next, it was cooled to an internal temperature of −72 ° C. in a dry ice / acetone bath. 97.1 ml of n-BuLi (2.6M) was added dropwise at an internal temperature of −70 ° C. or less for 2.5 hours, and the mixture was stirred for 1 hour. Subsequently, 60.1 g of B (OCH ₃ ) _{3 was} added dropwise at an internal temperature of −70 ° C. or less for 1 hour to release the dry ice / acetone bath.

  Two hours later (internal temperature 20 ° C.), 10% HCl, 300 ml (× 3.3 mol) was added. It was transferred to a separatory funnel and washed with brine. The THF solution was concentrated under reduced pressure to form a slurry, acetonitrile was added thereto, and the precipitated crystals were filtered under reduced pressure to obtain 50.9 g (yield 70%) of Exemplary Compound 2-1.

Next, Example Compound 2-1, 11.7 g, Example Compound 3-3, 18.5 g, 10.4 g of potassium carbonate, DMSO, 600 ml are mixed under a nitrogen stream, and further PdCl ₂ dppf 1.60 g is added, and 90 The mixture was stirred at around 0 ° C for 2 hours. 100 ml of water was added, and the precipitated crystals were filtered under reduced pressure. The obtained crude crystals were purified by column chromatography (silica gel, toluene / hexane) to obtain Exemplified Compounds 4-3 and 10 g (yield 57.4%).

Next, 0.30 g of Pd (OAc) ₂ , 1.0 g of P (But) ₃ and 10 ml of dehydrated xylene were stirred at 40 ° C. for 10 minutes under a nitrogen stream. Exemplified Compound 4-3, 5.0 g, Exemplified Compound 3-3, 1.9 g, NaOBu-t, 1.2 g, and 100 ml of dehydrated xylene were added and refluxed for 4 hours. The reaction solution was washed with water and filtered under reduced pressure. The obtained crude crystals were purified by column chromatography (silica gel, toluene / hexane) to obtain 3.60 g (yield 61.4%) of Compound D.

  From Examples 1 and 2 which are manufacturing methods of an organic electroluminescent material (compound D), it can be seen that Example 2 which is a manufacturing method of the present invention clearly has a high yield.

Example 3 (Example of the present invention)
<< Synthesis of Exemplified Compound 4-8 >>

Under a nitrogen stream, Example Compound 1-6, 47.5 g, dehydrated THF, and 1 L were mixed and dissolved by stirring at an internal temperature of 25 to 30 ° C. Next, it was cooled to an internal temperature of −73 ° C. in a dry ice / acetone bath. n-BuLi (2.6 M) and 56.6 ml were added dropwise at an internal temperature of −70 ° C. or less for 2.5 hours, and the mixture was stirred for 1 hour. Subsequently, 28 g of boronic acid ester was added dropwise at an internal temperature of −70 ° C. or less for 1 hour to release the dry ice / acetone bath. It was transferred to a separatory funnel and washed with brine. The THF solution was concentrated under reduced pressure. Ethanol was added thereto, and the precipitated crystals were filtered under reduced pressure to obtain 21.1 g of exemplified compound 2-6. (Yield 39%)
Under nitrogen stream, Exemplified Compound 2-6, 15.4 g, Exemplified Compound 3-8, 15.5 g, Potassium Carbonate 10.4 g, DMSO, 600 ml were mixed, and PdCl ₂ dppf, 1.60 g was added, and 90 The mixture was stirred at around 0 ° C for 2 hours. 100 ml of water was added, and the precipitated crystals were filtered under reduced pressure. The obtained crude crystals were purified by column chromatography (silica gel, toluene / hexane) to obtain 8.4 g (yield 47.4%) of Exemplary Compound 4-8.

Example 4 (Example of the present invention)
<< Synthesis of Exemplified Compound 4-4 >>

Under a nitrogen stream, Exemplified Compound 1-3, 85.5 g, dehydrated THF, and 1 L were mixed and dissolved by stirring at an internal temperature of 25 to 30 ° C. Next, it was cooled to an internal temperature of −70 ° C. with a dry ice / acetone bath. n-BuLi (2.6M), 97.1 ml, was added dropwise at an internal temperature of −70 ° C. or less for 2.5 hours, followed by stirring for 1 hour. Subsequently, 60.1 g of B (OCH ₃ ) _{3 was} added dropwise over 1 hour at an internal temperature of −70 ° C. or less to release dry ice / acetone. Two hours later (internal temperature 20 ° C.), 10% HCl and 300 ml (× 3.3 mol) were added. It was transferred to a separatory funnel and washed with brine. The THF solution was concentrated under reduced pressure to form a slurry, acetonitrile was added thereto, and the precipitated crystals were filtered under reduced pressure to obtain Exemplified Compound 2-3 (39.9 g). (Yield 52%)
Next, under a nitrogen stream, Example Compound 2-3, 12.3 g, Example Compound 3-3, 18.5 g, 10.4 g of potassium carbonate, DMSO, 600 ml are mixed, and PdCl ₂ dppf, 1.60 g is added. The mixture was stirred at around 90 ° C. for 2 hours. 100 ml of water was added, and the precipitated crystals were filtered under reduced pressure. The obtained crude crystals were purified by column chromatography (silica gel, toluene / hexane) to obtain 8.3 g (yield 41%) of Exemplary Compound 4-4.

Example 5 (Example of the present invention)
<< Synthesis of Exemplary Compound 4-1 >>

Under a nitrogen stream, Example Compound 3-1, 32.9 g, Example Compound 2-1, 64.0 g, Ethylene glycol dimethyl ether 1.5 L, Potassium carbonate 58.0 g, Water 350 ml, Pd (Pph ₃ ) ₄ 7.0 g Charged and refluxed for 12 hours. The precipitated crystals were filtered and dried. 4.8 L of THF was added and dissolved by heating. After removing insolubles, the solution was concentrated to 300 ml, 300 ml of acetonitrile was added dropwise and stirred for 1 hour. The precipitated crystals were filtered to obtain 40.3 g (yield 71.0%) of Exemplary Compound 4-1.

  Each compound in the examples was identified by MASS and NMR spectra to confirm that it was the target compound. Other exemplary compounds can also be synthesized according to the above method.

Claims (5)

The manufacturing method of the halo polycyclic aromatic compound characterized by manufacturing the halo polycyclic aromatic compound represented by the following general formula [2] using the compound represented by the following general formula [1].
_(Wherein, R 1, _{R 2} represents a substituent, n1, n2 are _.R 3 represents an integer of 0 to 3, _{R 4} is .R ₃ and _{R 4} representing a human Dorokishi group or an alkoxy group each other bound good .X ₁ to form a ring with the .X ₂ representing an oxygen atom or a sulfur atom represents a halogen atom.) The compound represented by the general formula [1] is reacted with a lithiating agent and then reacted with a boronic acid derivative to produce a halopolycyclic aromatic compound represented by the general formula [2]. The method for producing a halopolycyclic aromatic compound according to claim 1 . A compound represented by the following general formula [2] and a compound represented by the following general formula [3] are reacted in the presence of a transition metal catalyst to produce a halopolycyclic aromatic compound represented by the following general formula [4]. A process for producing a halopolycyclic aromatic compound, characterized in that it is produced.
_(Wherein, R 1, _{R 2} represents a substituent, n1, n2 are _.R 3 represents an integer of 0 to 3, _{R 4} is .R ₃ and _{R 4} representing a human Dorokishi group or an alkoxy group each other binding to which may form a ring .X ₁ is the .X _2, X ₃ representing an oxygen atom or a sulfur atom is .Z represents a halogen atom to form an aromatic hydrocarbon ring or aromatic heterocyclic ring Represents a group of non-metallic atoms necessary for A halopolycyclic aromatic compound represented by the following general formula [2].
_(Wherein, R 1, _{R 2} represents a substituent, n1, n2 are _.R 3 represents an integer of 0 to 3, _{R 4} is .R ₃ and _{R 4} representing a human Dorokishi group or an alkoxy group each other bound good .X ₁ to form a ring with the .X ₂ representing an oxygen atom or a sulfur atom represents a halogen atom.) The halopolycyclic aromatic compound according to claim 4 represented by the following general formula [5].
(Wherein R ₁ , R ₂ Represents a hydrogen atom or a methyl group. R ₃ , R ₄ Is a hydroxy group or Represents an alkoxy group. R ₃ And R ₄ May be bonded to each other to form a ring. X ₁ Is oxygen field Represents a child or sulfur atom. X ₂ Represents a halogen atom. )