JP2008201730A - Method for producing aromatic compound - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for producing a formylpyrene derivative in a high yield, becoming an intermediate, in an aromatic compound useful in an electronic material. <P>SOLUTION: The method for producing an aromatic compound having a specific structure comprises introducing a formyl group to the aromatic ring of the aromatic compound having the specific structure in the presence of a trifluoromethanesulfonic acid anhydride by using a formamide group-containing compound as a formylating agent. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

    The present invention relates to a production method for obtaining a formylpyrene derivative by formylating a pyrene derivative.

Pyrene compounds are expected as useful materials for electronic information materials because of their electrical properties. Among these, formylpyrene derivatives have a wide range of uses as intermediates for various pyrene compounds. Formylation of aromatic compounds has been carried out for a long time (see, for example, Non-Patent Documents 1 to 3), but even when attempting to formylate pyrene using these methods, the reaction yield is low and industrial. Not happy with the production. Therefore, development of a production method for obtaining a formylpyrene derivative with high yield is demanded.
Journal of Chemical Society Chemical Communication (USA), 1990, 1571 Journal of American Chemical Society (USA), 1938, 60, 2555-2559 Journal of American Chemical Society (USA), 1942, 64, 1666-1669

  The present invention provides a method for producing a formylpyrene derivative in high yield.

  That is, the present invention provides a fragrance of an aromatic compound represented by the general formula (2) using a compound having a formamide group represented by the general formula (1) as a formylating agent in the presence of trifluoromethanesulfonic anhydride. It is a manufacturing method of the aromatic compound represented by General formula (3) manufactured by introduce | transducing a formyl group on a ring.

Ar ^{1 in the} general formula (1) represents an aryl group. R ¹ is an organic group selected from the group consisting of hydrogen, an alkyl group, an allyl group, and an aryl group. R ^{2 to} R ^{10 in the} general formulas (2) and (3) may be the same or different, and are hydrogen, alkyl group, allyl group, aralkyl group, aryl group, halogen, group having an ester bond, alkoxy group, formyl. An organic group selected from the group consisting of a group, an amino group, and a hydroxyl group.

  According to the present invention, a formylpyrene derivative can be produced with high yield.

In the general formula (1), Ar ¹ represents an aryl group. The aryl group represents an aromatic hydrocarbon group, preferably an aromatic hydrocarbon group having 6 to 12 carbon atoms. Examples include, but are not limited to, a phenyl group, a 1-naphthyl group, a 2-naphthyl group, and the like. R ¹ is an organic group selected from the group consisting of hydrogen, an alkyl group, an allyl group, and an aryl group. Here, the alkyl group represents a linear or branched saturated aliphatic hydrocarbon group, and is preferably a saturated aliphatic hydrocarbon group having 1 to 6 carbon atoms. Examples include, but are not limited to, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a sec-butyl group, a tert-butyl group, and a pentyl group. The allyl group represents a linear or branched unsaturated aliphatic hydrocarbon group, preferably an unsaturated aliphatic hydrocarbon group having 2 to 6 carbon atoms. Examples include, but are not limited to, a vinyl group, a propenyl group, an isopropenyl group, a 2-methyl-1-propenyl group, a 1,3-butadienyl group, and an ethynyl group. Specific examples of the aryl group selected by R ¹ are the same as the specific examples of the aryl group of Ar ¹ . Specific examples of the compound represented by the general formula (1) are given below.

In the compounds represented by the general formula (2) and the general formula (3), R ^{2 to} R ¹⁰ may be the same or different, and hydrogen, alkyl group, allyl group, aralkyl group, aryl group, halogen, ester bond And an organic group selected from the group consisting of an alkoxy group, a formyl group, an amino group, and a hydroxyl group. Here, the alkyl group and the allyl group are the same as those described for R ¹ in the general formula (1). The aryl group represents an aromatic hydrocarbon group, preferably an aromatic hydrocarbon group having 6 to 12 carbon atoms, which is substituted with an alkyl group, a halogen, a group having an ester bond, an alkoxy group, an amino group, a hydroxyl group, or the like. May be. For example, although a toluyl group, 4-t-butylphenyl group, etc. are mentioned, it is not limited to these. In addition, the group having an ester bond is represented by a general formula —COOR (R is an alkyl group or an aryl group), and examples thereof include, but are not limited to, ethyl ester and phenyl ester. Specific examples of the compound represented by the general formula (3) are given below.

  Each process of the manufacturing method of the derivative | guide_body of this invention is given and an example is demonstrated. First, a cooling tube and a stirrer are set in a three-necked flask having an appropriate volume, and a formylating agent represented by the general formula (1), an aromatic compound represented by the general formula (2) and a solvent are charged, To do. Next, trifluoromethanesulfonic anhydride is added dropwise while stirring the mixed solution at room temperature in a nitrogen atmosphere, and the mixture is heated and stirred at a predetermined temperature (reaction temperature) and a predetermined time (reaction time). After completion of the reaction, the reaction solution is cooled to room temperature, and water and a solvent are added to extract the organic layer. The solvent is distilled off from the obtained organic layer with an evaporator, and column purification is performed to obtain the desired product.

  The formylating agent represented by the general formula (1) is used in an amount of 1 to 6 equivalents, preferably 1.5 to 3 equivalents, relative to the aromatic compound represented by the general formula (2).

  The trifluoromethanesulfonic anhydride is used in an amount of 1 to 4 equivalents, preferably 1.1 to 2 equivalents, relative to the aromatic compound represented by the general formula (2).

  The solvent used in the above production method is not particularly limited as long as it does not interfere with the reaction, and examples thereof include o-dichlorobenzene and p-dichlorobenzene. The amount of the solvent is not particularly limited, but if the amount of the solvent (ml) is in the range of 0.7 to 70 ml / g with respect to the weight (g) of the aromatic compound represented by the general formula (2), The production is small and the reaction can be completed quickly.

  The above reaction temperature can be carried out in the range of 0 to 120 ° C., but usually in the range of 60 to 110 ° C., more preferably in the range of 80 to 100 ° C., little by-product is produced, and the reaction can be completed quickly.

  The reaction time is not particularly limited and can be appropriately selected depending on the reaction temperature. Usually, the reaction time is preferably about 15 minutes to 3 hours because the reaction is completed.

  Hereinafter, the present invention will be described with reference to examples and comparative examples.

Example 1
Under a nitrogen atmosphere at room temperature, 1 g (2.6 mmol) of 1,6-di (4-methylphenyl) pyrene and 0.82 g (6.07 mmol) of N-methylformanilide were added to 7 ml of o-dichlorobenzene and stirred. While adding 0.85 g (3.01 mmol) of trifluoromethanesulfonic anhydride. The mixture was heated and stirred at 100 ° C. for 3 hours under a nitrogen atmosphere. The reaction solution was cooled to room temperature, and 50 ml of o-dichlorobenzene and 50 ml of water were added to extract the organic layer. The organic layer was washed twice with 50 ml of water and then evaporated to remove the solvent to obtain a solid. The obtained solid was purified by a column (filler: silica gel, solvent: dichloromethane / hexane), and 0.86 g (1) of 1,6-di (4-methylphenyl) -3-formylpyrene (the following compound (A)). .99 mmol) (yield 76.6%).
1H-NMR (CDCl3, ppm): 10.78 (s, 1H), 9.38 (d, 1H), 8.47-8.05 (m, 6H), 7.57 (d, 4H), 7 .40 (d, 4H), 2.52 (s, 6H).

Example 2
Under a nitrogen atmosphere at room temperature, 1 g (2.6 mmol) of 1,6-di (4-methylphenyl) pyrene and 1.03 g (5.22 mmol) of N, N-diphenylformamide were added to 7 ml of o-dichlorobenzene, While stirring, 0.85 g (3.01 mmol) of trifluoromethanesulfonic anhydride was added. The mixture was heated and stirred at 100 ° C. for 3 hours under a nitrogen atmosphere. The post-treatment was carried out in the same manner as in Example 1 to obtain 0.84 g (2.03 mmol) (yield 78.1%) of 1,6-di (4-methylphenyl) -3-formylpyrene.

Example 3
Under a nitrogen atmosphere at room temperature, 0.53 g (2.62 mmol) of pyrene and 0.73 g (5.41 mmol) of N-methylformanilide were added to 7 ml of o-dichlorobenzene, and trifluoromethanesulfonic anhydride 0 was added while stirring. .85 g (3.01 mmol) was added. The mixture was heated and stirred at 100 ° C for 3 hours in a nitrogen atmosphere. The post-treatment was performed in the same manner as in Example 1 to obtain 0.46 g (1.99 mmol) (yield 76%) of 1-formylpyrene (the following compound (B)).
1H-NMR (CDCl3, ppm): 10.70 (s, 1H), 9.06 (d, 1H), 8.10-7.86 (m, 7H), 7.74 (d, 1H).

Example 4
Under a nitrogen atmosphere at room temperature, 0.53 g (2.62 mmol) of pyrene and 1.02 g (5.17 mmol) of N, N-diphenylformamide were added to 7 ml of o-dichlorobenzene, and trifluoromethanesulfonic anhydride was stirred. 0.8 g (2.84 mmol) was added. The mixture was heated and stirred at 100 ° C for 3 hours in a nitrogen atmosphere. The post-treatment was performed in the same manner as in Example 1 to obtain 0.48 g (2.08 mmol) (yield 79.4%) of 1-formylpyrene (compound (B)).

Example 5
Under a nitrogen atmosphere at room temperature, 0.53 g (2.62 mmol) of pyrene and 0.9 g (5.24 mmol) of N- (2-naphthyl) formamide were added to 7 ml of o-dichlorobenzene, and trifluoromethanesulfonic acid was stirred. Anhydrous 0.8 g (2.84 mmol) was added. The mixture was heated and stirred at 100 ° C. for 3 hours under a nitrogen atmosphere. The post-processing similar to Example 1 was performed, and 0.43 g (1.86 mmol) (yield 71%) of 1-formyl pyrene (compound (B)) was obtained.

Example 6
Under a nitrogen atmosphere at room temperature, 1.09 g (2.62 mmol) of 1,6-di (4-methoxyphenyl) pyrene and 1.02 g (5.17 mmol) of N, N-diphenylformamide were added in 7 ml of o-dichlorobenzene. In addition, trifluoromethanesulfonic anhydride 0.8 g (2.84 mmol) was added with stirring. The mixture was heated and stirred at 100 ° C. for 3 hours under a nitrogen atmosphere. After the same post-treatment as in Example 1, 0.79 g (1.79 mmol) of 1,6-di (4-methoxyphenyl) -3-formylpyrene (the following compound (C)) (yield 68.4%) Got.
1H-NMR (CDCl3, ppm): 10.77 (s, 1H), 9.39 (d, 1H), 8.47-8.03 (m, 6H), 7.60 (d, 4H), 7 .14 (d, 4H), 3.97 (s, 6H).

Example 7
Under a nitrogen atmosphere at room temperature, 1.22 g (2.62 mmol) of 1,6-di (4-tert-butylphenyl) pyrene and 1.02 g (5.17 mmol) of N, N-diphenylformamide in 7 ml of o-dichlorobenzene ) And 0.8 g (2.84 mmol) of trifluoromethanesulfonic anhydride was added with stirring. The mixture was heated and stirred at 100 ° C. for 3 hours under a nitrogen atmosphere. The same post-treatment as in Example 1 was carried out, and 0.99 g (1.99 mmol) (yield 76%) of 1,6-di (4-t-butylphenyl) -3-formylpyrene (compound (D)) was obtained. Obtained.
1H-NMR (CDCl3, ppm): 10.79 (s, 1H), 9.40 (d, 1H), 8.50-8.06 (m, 6H), 7.63-7.59 (dd, 8H), 1.52 (s, 18H).

Comparative Example 1
Under a nitrogen atmosphere at room temperature, 0.53 g (2.62 mmol) of pyrene and 0.49 g (6.71 mmol) of N, N-dimethylformamide were added to 7 ml of o-dichlorobenzene, and 0.43 g of phosphorus oxychloride was stirred with stirring. (2.81 mmol) was added. The mixture was heated and stirred at 100 ° C for 3 hours in a nitrogen atmosphere. The post-treatment was carried out in the same manner as in Example 1 to obtain 0.01 g (0.04 mmol) of 1-formylpyrene (yield 1.5%).

Comparative Example 2
Under a nitrogen atmosphere at room temperature, 0.53 g (2.62 mmol) of pyrene and 0.84 g (6.22 mmol) of N-methylformanilide were added to 7 ml of o-dichlorobenzene, and 0.48 g of phosphorus oxychloride ( 3.14 mmol) was added. The mixture was heated and stirred at 100 ° C. for 3 hours under a nitrogen atmosphere. Post-treatment was performed in the same manner as in Example 1 to obtain 0.05 g (0.22 mmol) of 1-formylpyrene (yield 8.4%).

Comparative Example 3
Under a nitrogen atmosphere at room temperature, 0.53 g (2.62 mmol) of pyrene and 1.03 g (5.22 mmol) of N, N-diphenylformamide were added to 7 ml of o-dichlorobenzene, and 0.49 g of phosphorus oxychloride was stirred with stirring. (3.2 mmol) was added. The mixture was heated and stirred at 100 ° C. for 3 hours under a nitrogen atmosphere. The post-treatment was performed in the same manner as in Example 1 to obtain 0.04 g (0.17 mmol) of 1-formylpyrene (yield 6.5%).

Comparative Example 4
Under a nitrogen atmosphere at room temperature, 0.53 g (2.62 mmol) of pyrene and 0.49 g (6.7 mmol) of N, N-dimethylformamide were added to 7 ml of o-dichlorobenzene, and trifluoromethanesulfonic anhydride was stirred. 0.83 g (2.94 mmol) was added. The mixture was heated and stirred at 100 ° C. for 3 hours under a nitrogen atmosphere. The post-treatment was performed in the same manner as in Example 1 to obtain 0.04 g (0.17 mmol) of 1-formylpyrene (yield 6.5%).

Comparative Example 5
Under a nitrogen atmosphere at room temperature, 0.53 g (2.62 mmol) of pyrene and 0.67 g (5.82 mmol) of N-formylmorpholine were added to 12 ml of o-dichlorobenzene, and trifluoromethanesulfonic anhydride 0. 84 g (2.98 mmol) was added. The mixture was heated and stirred at 100 ° C. for 3 hours under a nitrogen atmosphere. The post-treatment was performed in the same manner as in Example 1 to obtain 0.13 g (0.56 mmol) of 1-formylpyrene (yield 21.4%).

Comparative Example 6
Under a nitrogen atmosphere at room temperature, 0.53 g (2.62 mmol) of pyrene and 0.76 g (5.89 mmol) of N, N-diisopropylformamide were added to 7 ml of o-dichlorobenzene, and trifluoromethanesulfonic anhydride was stirred. 0.88 g (3.12 mmol) was added. The mixture was heated and stirred at 100 ° C. for 3 hours under a nitrogen atmosphere. The post-treatment was carried out in the same manner as in Example 1 to obtain 0.01 g (0.04 mmol) of 1-formylpyrene (yield 1.5%).

Claims (2)

A method for producing an aromatic compound represented by general formula (3), wherein a compound having a formamide group represented by general formula (1) is used as a formylating agent in the presence of trifluoromethanesulfonic anhydride. The manufacturing method of the aromatic compound which introduce | transduces a formyl group on the aromatic ring of the aromatic compound represented by General formula (2).

(Ar ^{1 in the} general formula (1) represents an aryl group. R ¹ is a group selected from the group consisting of hydrogen, an alkyl group, an allyl group, and an aryl group. R ^{2 in the} general formulas (2) and (3) to R ¹⁰ may be the same or different, are selected from hydrogen, alkyl group, aryl group, aralkyl group, aryl group, halogen, a group having an ester bond, an alkoxy group, a formyl group, an amino group, from the group consisting of hydroxyl group Organic group.) The method for producing an aromatic compound according to claim 1, wherein Ar ^{1 of the} compound represented by the general formula (1) is at least one selected from the group consisting of a phenyl group, a 1-naphthyl group, and a 2-naphthyl group. .