JP5529407B2 - 1,3,5-triazine compound and method for producing the same - Google Patents

Description

  The present invention relates to a 1,3,5-triazine compound having a 3,5-dihalo-substituted phenyl group useful as an intermediate of an organic electronic material that can be used for an organic electroluminescence device and the like, and a method for producing the same.

  The 1,3,5-triazine compound having a 3,5-dihalo-substituted phenyl group of the present invention is a novel compound, and there has been no report on its production method. The 1,3,5-triazine compound of the present invention is a 1,3,5-triazine derivative having a 3,5-disubstituted phenyl group that exhibits high performance as an organic electronic material used in an organic electroluminescent device (for example, a patent It is useful as an intermediate of Reference 1).

  Further, as a compound similar to the 1,3,5-triazine compound of the present invention, a 1,3,5-triazine derivative having a 3,5-dibromo-2-hydroxyphenyl group has been disclosed (for example, Patent Documents). 2 and 3) is different from the 1,3,5-triazine compound of the present invention in that it has a hydroxyl group at the 2-position of the phenyl group. Furthermore, generally, it is not preferable in terms of durability and conductivity that a hydroxyl group remains as an organic electronic material.

  Further, although 1,3,5-triazine derivatives having a dihalophenyl group are disclosed (for example, see Patent Document 4), the substitution position of the halogen atom is not limited, and the 3,5-dihalo substitution of the present invention is not limited. There is no mention of phenyl groups.

Japanese Patent Application No. 2007-104808 U.S. Pat. No. 3,321,698 US Pat. No. 3,211,699 JP 2007-137829 A

  The present invention provides a 1,3,5-triazine compound useful as an intermediate for efficiently producing an organic electronic material that can be used in an organic electroluminescent device or the like.

  As a result of intensive studies to solve the above problems, the present inventors have found that the 1,3,5-triazine compound of the present invention has a 1,5-disubstituted phenyl group useful as an electron transport material. The present invention was completed by finding that it can be an effective intermediate of the 1,3,5-triazine compound.

  That is, the present invention relates to the general formula (1)

(In the formula, R ¹ , R ² and R ³ each independently represents a hydrogen atom or a methyl group. X represents a chlorine atom, a bromine atom or an iodine atom. Ar represents an optionally substituted aromatic group. Represents a hydrocarbon group.)
And a 1,3,5-triazine compound having a 3,5-dihalo-substituted phenyl group represented by the formula:

  The present invention also provides a general formula (2)

(In the formula, R ¹ , R ² , R ³ , X and Ar are the same as described above. Y ⁻ represents a counter anion.)
Wherein the oxonium salt represented by the general formula (1) is reacted with an ammonia source

(Wherein R ¹ , R ² , R ³ , X and Ar are the same as described above.)
It is related with the manufacturing method of the 1,3,5-triazine compound which has a 3,5- dihalo substituted phenyl group shown by these.

  The present invention also provides a general formula (3)

(Wherein R ¹ , R ² , R ³ and X are the same as described above.)
Acid chloride represented by the general formula (4)

(In the formula, Ar is the same as described above.)
Is reacted with an aromatic nitrile represented by the general formula (2)

(In the formula, R ¹ , R ² , R ³ , X, Ar and Y ⁻ are the same as described above.)
The oxonium salt represented by the general formula (1) is obtained and then reacted with an ammonia source.

(Wherein R ¹ , R ² , R ³ , X and Ar are the same as described above.)
It is related with the manufacturing method of the 1,3,5-triazine compound which has a 3,5- dihalo substituted phenyl group shown by these.

  Furthermore, the present invention relates to a general formula (3)

(Wherein R ¹ , R ² , R ³ and X are the same as described above.)
Acid chloride represented by the general formula (4)

(In the formula, Ar is the same as described above.)
Wherein the aromatic nitrile represented by the general formula (2) is reacted in the presence of a Lewis acid.

(In the formula, R ¹ , R ² , R ³ , X, Ar and Y ⁻ are the same as described above.)
It is related with the manufacturing method of the oxonium salt shown by these.

In the 1,3,5-triazine compound having a 3,5-dihalo-substituted phenyl group represented by the general formula (1) of the present invention, R ¹ , R ² and R ³ are each independently a hydrogen atom or a methyl group R ¹ and R ³ are preferably hydrogen atoms in that they are easy to synthesize and have good reaction yield in the subsequent production of organic electronic materials.

  X represents a chlorine atom, a bromine atom or an iodine atom, and is preferably a chlorine atom or a bromine atom from the viewpoint of easy synthesis and good reaction yield in the subsequent production of an organic electronic material.

  Examples of the optionally substituted aromatic hydrocarbon group represented by Ar include a phenyl group which may be substituted, a naphthyl group which may be substituted, an anthranyl group which may be substituted, May be a perylenyl group which may be substituted and a triphenylenyl group which may be substituted, which is easy to synthesize and has a good reaction yield in the subsequent production of an organic electronic material. An naphthyl group which may be substituted is preferred.

  Examples of the optionally substituted phenyl group represented by Ar include a phenyl group, a p-tolyl group, an m-tolyl group, an o-tolyl group, a p-trifluoromethylphenyl group, an m-trifluoromethylphenyl group, o-trifluoromethylphenyl group, 2,4-dimethylphenyl group, 3,5-dimethylphenyl group, mesityl group, 2-ethylphenyl group, 3-ethylphenyl group, 4-ethylphenyl group, 2,4-diethyl Phenyl group, 3,5-diethylphenyl group, 2-propylphenyl group, 3-propylphenyl group, 4-propylphenyl group, 2,4-dipropylphenyl group, 3,5-dipropylphenyl group, 2-isopropyl Phenyl group, 3-isopropylphenyl group, 4-isopropylphenyl group, 2,4-diisopropylphenyl group, 3,5-diisopropyl Pyrphenyl group, 2-butylphenyl group, 3-butylphenyl group, 4-butylphenyl group, 2,4-dibutylphenyl group, 3,5-dibutylphenyl group, 2-tert-butylphenyl group, 3-tert-butyl Phenyl group, 4-tert-butylphenyl group, 2,4-di-tert-butylphenyl group, 3,5-di-tert-butylphenyl group, biphenyl-4-yl group, biphenyl-3-yl group, biphenyl 2-yl group, 2-methylbiphenyl-4-yl group, 3-methylbiphenyl-4-yl group, 2′-methylbiphenyl-4-yl group, 4′-methylbiphenyl-4-yl group, 2, 2'-dimethylbiphenyl-4-yl group, 2 ', 4', 6'-trimethylbiphenyl-4-yl group, 6-methylbiphenyl-3-yl group, 5-methyl Phenyl-3-yl group, 2′-methylbiphenyl-3-yl group, 4′-methylbiphenyl-3-yl group, 6,2′-dimethylbiphenyl-3-yl group, 2 ′, 4 ′, 6 ′ -Trimethylbiphenyl-3-yl group, 5-methylbiphenyl-2-yl group, 6-methylbiphenyl-2-yl group, 2'-methylbiphenyl-2-yl group, 4'-methylbiphenyl-2-yl group 6,2′-dimethylbiphenyl-2-yl group, 2 ′, 4 ′, 6′-trimethylbiphenyl-2-yl group, 2-trifluoromethylbiphenyl-4-yl group, 3-trifluoromethylbiphenyl- 4-yl group, 2′-trifluoromethylbiphenyl-4-yl group, 4′-trifluoromethylbiphenyl-4-yl group, 6-trifluoromethylbiphenyl-3-yl group, 5-trifluoro Fluoromethylbiphenyl-3-yl group, 2′-trifluoromethylbiphenyl-3-yl group, 4′-trifluoromethylbiphenyl-3-yl group, 5-trifluoromethylbiphenyl-2-yl group, 6- Trifluoromethylbiphenyl-2-yl group, 2′-trifluoromethylbiphenyl-2-yl group, 4′-trifluoromethylbiphenyl-2-yl group, 3-ethylbiphenyl-4-yl group, 4′-ethyl Biphenyl-4-yl group, 2 ′, 4 ′, 6′-triethylbiphenyl-4-yl group, 6-ethylbiphenyl-3-yl group, 4′-ethylbiphenyl-3-yl group, 5-ethylbiphenyl- 2-yl group, 4′-ethylbiphenyl-2-yl group, 2 ′, 4 ′, 6′-triethylbiphenyl-2-yl group, 3-propylbiphenyl-4-yl 4'-propylbiphenyl-4-yl group, 2 ', 4', 6'-tripropylbiphenyl-4-yl group, 6-propylbiphenyl-3-yl group, 4'-propylbiphenyl-3-yl group 5-propylbiphenyl-2-yl group, 4′-propylbiphenyl-2-yl group, 2 ′, 4 ′, 6′-tripropylbiphenyl-2-yl group, 3-isopropylbiphenyl-4-yl group, 4′-isopropylbiphenyl-4-yl group, 2 ′, 4 ′, 6′-triisopropylbiphenyl-4-yl group, 6-isopropylbiphenyl-3-yl group, 4′-isopropylbiphenyl-3-yl group, 5-isopropylbiphenyl-2-yl group, 4′-isopropylbiphenyl-2-yl group, 2 ′, 4 ′, 6′-triisopropylbiphenyl-2-yl group, 3-butyl Rubiphenyl-4-yl group, 4′-butylbiphenyl-4-yl group, 2 ′, 4 ′, 6′-tributylbiphenyl-4-yl group, 6-butylbiphenyl-3-yl group, 4′-butyl Biphenyl-3-yl group, 5-butylbiphenyl-2-yl group, 4′-butylbiphenyl-2-yl group, 2 ′, 4 ′, 6′-tributylbiphenyl-2-yl group, 3-tert-butyl Biphenyl-4-yl group, 4′-tert-butylbiphenyl-4-yl group, 2 ′, 4 ′, 6′-tri-tert-butylbiphenyl-4-yl group, 6-tert-butylbiphenyl-3- Yl group, 4'-tert-butylbiphenyl-3-yl group, 5-tert-butylbiphenyl-2-yl group, 4'-tert-butylbiphenyl-2-yl group, 2 ', 4', 6'- Tri-t An ert-butylbiphenyl-2-yl group and the like can be mentioned. A phenyl group, a p-tolyl group, an m-tolyl group, an o-tolyl group, a 4-butylphenyl group, a 4-tert-butylphenyl group, a p-chlorophenyl group, and an m-chlorophenyl group in that the raw materials are easily available. , O-chlorophenyl group, p-bromophenyl group, m-bromophenyl group, o-bromophenyl group, biphenyl-4-yl group and biphenyl-3-yl group are preferable, and a phenyl group in terms of easy synthesis, More preferred are p-tolyl, m-tolyl, 4-tert-butylphenyl, m-chlorophenyl, biphenyl-4-yl and biphenyl-3-yl.

  Examples of the optionally substituted naphthyl group represented by Ar include 1-naphthyl group, 4-methylnaphthalen-1-yl group, 4-trifluoromethylnaphthalen-1-yl group, 4-ethylnaphthalene- 1-yl group, 4-propylnaphthalen-1-yl group, 4-butylnaphthalen-1-yl group, 4-tert-butylnaphthalen-1-yl group, 5-methylnaphthalen-1-yl group, 5-tri Fluoromethylnaphthalen-1-yl group, 5-ethylnaphthalen-1-yl group, 5-propylnaphthalen-1-yl group, 5-butylnaphthalen-1-yl group, 5-tert-butylnaphthalen-1-yl group 2-naphthyl group, 6-methylnaphthalen-2-yl group, 6-trifluoromethylnaphthalen-2-yl group, 6-ethylnaphthalen-2-yl group, 6- Lopylnaphthalen-2-yl group, 6-butylnaphthalen-2-yl group, 6-tert-butylnaphthalen-2-yl group, 7-methylnaphthalen-2-yl group, 7-trifluoromethylnaphthalene-2- Yl group, 7-ethylnaphthalen-2-yl group, 7-propylnaphthalen-2-yl group, 7-butylnaphthalen-2-yl group, 7-tert-butylnaphthalen-2-yl group and the like. The 1-naphthyl group, 4-methylnaphthalen-1-yl group, 4-tert-butylnaphthalen-1-yl group, 5-methylnaphthalen-1-yl group, 5-tert- Butylnaphthalen-1-yl group, 2-naphthyl group, 6-methylnaphthalen-2-yl group, 6-tert-butylnaphthalen-2-yl group, 7-methylnaphthalen-2-yl group or 7-tert-butyl A naphthalen-2-yl group is preferable, and a 1-naphthyl group and a 2-naphthyl group are more preferable in terms of easy synthesis.

  The optionally substituted anthranyl group, the optionally substituted perylenyl group and the optionally substituted triphenylenyl group represented by Ar include a 1-anthranyl group, a 2-anthranyl group, a 9-anthranyl group, 1 -Perylenyl group, 2-perylenyl group or 1-triphenylenyl group is mentioned.

Examples of the counter anion represented by Y ⁻ include F ⁻ , Cl ⁻ , Br ⁻ , I ⁻ , OTf ⁻ , PF ₆ ⁻ , BF ₄ ⁻ , AlCl ₄ ⁻ , SnCl ₅ ⁻ , FeCl ₄ ⁻ , TiCl ₅ ⁻ , ZrCl ₅ ⁻ , SbCl ₆ ⁻ , ZnCl ₃ ⁻ , MnCl ₃ ^{− and the} like can be exemplified, and AlCl ₄ ⁻ , FeCl ₄ ⁻ and SbCl ₆ ⁻ are preferable in terms of easy availability and good reaction yield.

  Next, the manufacturing method of this invention is demonstrated.

  The 1,3,5-triazine compound having a 3,5-dihalo-substituted phenyl group represented by the general formula (1) of the present invention has the following reaction formula:

(In the formula, R ¹ , R ² , R ³ , X, Ar and Y ⁻ are the same as described above.)
It can manufacture by the method shown by.

  “Step 1” is a step of reacting an acid chloride (3) and an aromatic nitrile (4) in the presence of a Lewis acid to obtain an oxonium salt (2), which is used in a general Friedel-Crafts reaction. By applying the reaction conditions and Lewis acid, the desired product can be obtained with a good reaction yield. The molar ratio between the acid chloride (3) and the aromatic nitrile (4) is preferably 1: 3 to 2: 3 in terms of good selectivity. The acid chloride (3) and the aromatic nitrile (4) can be produced by methods known to those skilled in the art.

Examples of the Lewis acid that can be used in “Step 1” include metal halides exhibiting Lewis acidity, specifically, TiCl ₄ , ZrCl ₄ , MnCl ₂ , MnBr ₂ , FeCl ₃ , FeBr ₃ , ZnCl ₂ , BF ₃ , AlCl ₃ , AlBr ₃ , SnCl ₄ , SbCl ₅ , SbBr _{5 and the} like can be exemplified, and these may be used in appropriate combination. FeCl ₃ , AlCl ₃ , SnCl ₄ and SbCl ₅ are preferable in terms of easy availability, and SbCl ₅ is more preferable in terms of a good reaction yield. The molar ratio of the Lewis acid used in the reaction to the acid chloride (3) is preferably 1: 2 to 2: 1 in terms of good reaction yield.

  Examples of the solvent that can be used in “Step 1” include dichloromethane, chloroform, carbon tetrachloride, chlorobenzene, dichlorobenzene, trichlorobenzene, and nitrobenzene, and these may be used in appropriate combination. It is preferable to use chloroform or chlorobenzene in terms of a good reaction yield.

  The oxonium salt (2) may be isolated by a normal operation after completion of “Step 1”, but may be subjected to “Step 2” without isolation.

  “Step 2” is a step of obtaining the 1,3,5-triazine compound (1) of the present invention by reacting the oxonium salt (2) with an ammonia source.

  Examples of the ammonia source that can be used in “Step 2” include ammonia and ammonium chloride. Ammonia is preferable in that the reaction yield is good. Ammonia can be passed as a gas into the reaction system, but is preferably dissolved in a solvent such as water, methanol, ethanol, diethyl ether, or dichloromethane and used as an ammonia solution in terms of simple operation. An aqueous ammonia solution is more preferable in that the reaction yield is good. There is no restriction | limiting in particular in the density | concentration of ammonia solution, A 1 weight%-saturated solution can be used. The molar ratio between the oxonium salt (2) and the ammonia source is preferably 1: 1 to 1: 100 in terms of good reaction yield.

  Examples of the solvent that can be used in “Step 2” include the solvents exemplified in “Step 1”, and it is preferable to use chloroform or chlorobenzene because the reaction yield is good. An ammonia solution may be used as a solvent.

  “Step 2” is carried out at a reaction temperature appropriately selected from the range of −50 to 50 ° C., preferably −30 to 5 ° C., whereby the target product can be obtained in good yield. There is no particular limitation on the reaction time.

  Compound (1) can be obtained by carrying out a normal treatment after completion of “Step 2”. If necessary, it may be purified by recrystallization, column chromatography or sublimation.

  EXAMPLES Hereinafter, although an Example and a reference example are given and this invention is demonstrated further in detail, this invention is not limited to these.

^For measurement of ¹ H-NMR and ¹³ C-NMR spectra, DPX250 and DPX500 spectrometers manufactured by Bruker were used.

  For HPLC measurement, Waters 2690 (column: GL Science Inertsil ODS-3V, eluent: acetonitrile-tetrahydrofuran, flow rate: 1 mL / min) was used.

  The reagent used in the experiment was Sigma-Aldrich Co. , Ltd., Ltd. , Purchased from Tokyo Chemical Industry Co., Ltd., Wako Pure Chemical Industries, Ltd. and Kanto Chemical Co., Ltd. and purified as necessary.

  For column chromatography, spherical silica gel with a particle size of 63-210 μm manufactured by Kanto Chemical Co., Inc. was used.

Example 1
Synthesis of 2- (3,5-dibromophenyl) -4,6-diphenyl-1,3,5-triazine

  3,5-Dibromobenzoyl chloride (5.97 g) and benzonitrile (4.12 g) were dissolved in chloroform (50 mL), cooled to 0 ° C., and then antimony pentachloride (5.98 g) was added dropwise. The mixture was stirred at room temperature for 10 minutes and then refluxed for 22 hours. After cooling to room temperature, chloroform was distilled off under reduced pressure to obtain 2- (3,5-dibromophenyl) -4,6-diphenyl-1,3,5-oxadiazin-1-ium = hexachloroantimonic acid as a yellow solid. It was.

  The obtained yellow solid was gradually added to 28% aqueous ammonia solution (300 mL) cooled to 0 ° C. to produce a white solid. After stirring at room temperature for 1 hour and filtration, the resulting white solid was washed with water and methanol. The white solid was dried, chloroform (150 mL) was added, and the mixture was filtered with heating. Furthermore, chloroform (100 mL) was added to the insoluble component separated by filtration, and the mixture was heated and filtered three times. All the filtrates were collected, chloroform was distilled off under reduced pressure, and the resulting solid was recrystallized from dichloromethane-methanol to give 2- (3,5-dibromophenyl) -4,6-diphenyl-1,3,5. -A white solid of triazine (yield 6.32 g, yield 68%) was obtained.

¹ H-NMR (CDCl ₃ ): δ 7.56-7.61 (m, 4H), 7.61-7.67 (m, 2H), 7.90 (t, J = 1.8 Hz, 1H), 8.72-8.78 (m, 4H), 8.82 (d, J = 1.8 Hz, 2H).
¹³ C-NMR (CDCl ₃ ): δ 123.4, 128.8, 129.1, 130.6, 133.0, 135.7, 137.6, 139.8, 169.3, 172.0.
Example 2
Synthesis of 2- (3-bromo-5-chlorophenyl) -4,6-diphenyl-1,3,5-triazine

  3-Bromo-5-chlorobenzoic acid chloride (9.10 g) and benzonitrile (7.40 g) were dissolved in chloroform (200 mL) under an argon stream. The resulting solution was cooled to 0 ° C. and antimony pentachloride (10.7 g) was added dropwise. The mixture was stirred at room temperature for 1 hour and then refluxed for 12 hours. After cooling to room temperature, low-boiling components were removed under reduced pressure, and 2- (3-bromo-5-chlorophenyl) -4,6-diphenyl-1,3,5-oxadiazin-1-ium = hexachloroantimonic acid was yellow. Obtained as a solid.

  The obtained yellow solid was pulverized in a stream of argon, and this was slowly added to a 28% aqueous ammonia solution cooled to 0 ° C. The resulting suspension was stirred for an additional hour at room temperature. The precipitated solid was collected by filtration and washed successively with water and methanol. The solid was dried and extracted with a Soxhlet extractor (extraction solvent: tetrahydrofuran). The extract was allowed to cool, and the precipitated solid was collected by filtration and dried to give a white powder of 2- (3-bromo-5-chlorophenyl) -4,6-diphenyl-1,3,5-triazine (yield 5.60 g). Yield 44%).

¹ H-NMR (CDCl ₃ ): δ 7.57-7.70 (m, 6H), 7.75 (dd, J = 1.7 Hz, 1.7 Hz, 1H), 8.66 (brs, 1H), 8.74 (d, J = 7.2 Hz, 4H), 8.76 (brs, 1H).
¹³ C-NMR (CDCl ₃ ): δ 123.2, 127.7, 128.8, 129.1, 130.1, 132.9, 134.9, 135.7, 135.7, 139.5, 169 .3, 172.0.
Example 3
Synthesis of 2- (3,5-dibromophenyl) -4,6-di-p-tolyl-1,3,5-triazine

  Under a stream of argon, take 3,5-dibromobenzoyl chloride (29.8 g) and p-tolylnitrile (23.4 g) in a 500 mL three-necked reaction vessel equipped with a reflux tube and a mechanical stirrer, and add 200 mL of chlorobenzene. Dissolved. The resulting solution was cooled to 0 ° C. and antimony pentachloride (29.9 g) was added dropwise. The mixture was refluxed at room temperature for 1 hour and further at 100 ° C. for 2 hours. The resulting deep red suspension was cooled to −20 ° C. and 28% aqueous ammonia (135 mL) was added. The milky white suspension was stirred at room temperature for 30 minutes and then slowly heated to 140 ° C. using an oil bath to distill off the solvent. Chlorobenzene (100 mL) was added, heated at 130 ° C., and filtered to remove insolubles. The filtrate was allowed to cool, and methanol (100 mL) was added. The precipitated solid was collected by filtration, washed with methanol (30 mL × 2), and dried to give 2- (3,5-dibromophenyl) -4,6-bis (biphenyl-3-yl) -1, A white powder of 3,5-triazine was obtained (yield 21.2 g, yield 43%). From HPLC, the content of 2- (3,5-dibromophenyl) -4,6-bis (biphenyl-3-yl) -1,3,5-triazine was 95.2%.

  Moreover, 2- (3,5-dibromophenyl) -4,6-bis (biphenyl-3) is obtained by performing the same operation using chlorobenzene (100 mL × 2) on the insoluble matter filtered off in the heat filtration. A white powder (yield 12.9 g, yield 26%) of -yl) -1,3,5-triazine was obtained. From HPLC, the content of 2- (3,5-dibromophenyl) -4,6-bis (biphenyl-3-yl) -1,3,5-triazine was 98.5%.

¹ H-NMR (CDCl ₃ ): δ 2.51 (s, 6H), 7.39 (d, J = 8.1 Hz, 4H), 7.90 (t, J = 1.7 Hz, 1H), 8. 63 (d, J = 8.1 Hz, 4H), 8.80 (d, J = 1.7 Hz, 2H).
¹³ C-NMR (CDCl ₃ ): δ 22.5 (CH ₃ × 2), 123.3 (quart. × 2), 129, 1 (CH × 4), 129.5 (CH × 4), 130.6 (CH × 2), 133.1 (quart. × 2), 137.4 (CH), 140.0 (quart.), 143.6 (quart. × 2), 169.0 (quart.), 171 .8 (quart. × 2).
Example 4
Synthesis of 2- (3,5-dibromophenyl) -4,6-bis (m-tolyl) -1,3,5-triazine

  3,5-Dibromobenzoyl chloride (26.6 g) and 3-methylbenzonitrile (20.9 g) were dissolved in chloroform (200 mL), cooled to 0 ° C., and then antimony pentachloride (26.6 g) was added dropwise. The mixture was stirred at room temperature for 10 minutes and then refluxed for 12 hours. After cooling to room temperature, chloroform was distilled off under reduced pressure. The obtained 2- (3,5-dibromophenyl) -4,6-bis (m-tolyl) -1,3,5-oxadiazin-1-ium = hexachloroantimonic acid was obtained as an orange solid.

  The resulting orange solid was gradually added to 28% aqueous ammonia solution (500 mL) cooled to 0 ° C. to produce a white solid. After stirring at room temperature for 1 hour and filtration, the resulting white solid was washed with water and methanol. The white solid was dried, chloroform (200 mL) was added, and the mixture was filtered with heating. Chloroform (200 mL) was added to the filtered insoluble component, and the mixture was heated and filtered three times. All the filtrates were collected, chloroform was distilled off under reduced pressure, and the resulting solid was recrystallized from dichloromethane-methanol to give 2- (3,5-dibromophenyl) -4,6-bis (m-tolyl)- A white solid of 1,3,5-triazine (yield 26.2 g, yield 60%) was obtained.

¹ H-NMR (CDCl ₃ ): δ 2.54 (s, 6H), 7.42-7.46 (m, 2H), 7.48 (dd, J = 7.5 Hz, 7.5 Hz, 2H), 7.89 (t, J = 1.8 Hz, 1H), 8.52 (s, 2H), 8.54 (d, J = 7.5 Hz, 2H), 8.80 (d, J = 1.8 Hz) , 2H).
¹³ C-NMR (CDCl ₃ ): δ 21.6, 123.3, 126.3, 128.6, 129.4, 130.6, 133.7, 135.6, 137.5, 138.5, 139 .8, 169.2, 172.0.
Example 5
Synthesis of 2- (3,5-dibromophenyl) -4,6-bis (4-tert-butylphenyl) -1,3,5-triazine

  3,5-Dibromobenzoyl chloride (2.98 g) and 4-tert-butylbenzonitrile (3.18 g) were dissolved in chloroform (30 mL), cooled to 0 ° C., and then antimony pentachloride (2.99 g) was added. It was dripped. The mixture was stirred at room temperature for 10 minutes and then refluxed for 17 hours. After cooling to room temperature, chloroform was distilled off under reduced pressure. The obtained 2- (3,5-dibromophenyl) -4,6-bis (4-tert-butylphenyl) -1,3,5-oxadiazin-1-ium = hexachloroantimonic acid was obtained as a red solid.

  The obtained red solid was gradually added to 28% aqueous ammonia solution (200 mL) cooled to 0 ° C. to produce a white solid. After stirring at room temperature for 1 hour and filtration, the resulting white solid was washed with water and methanol. The white solid was dried, chloroform (150 mL) was added, and the mixture was filtered with heating. Chloroform (100 mL) was added to the insoluble component separated by filtration, followed by heating and filtration. All the filtrates were collected, chloroform was distilled off under reduced pressure, and the resulting solid was recrystallized from dichloromethane-methanol to give 2- (3,5-dibromophenyl) -4,6-bis (4-tert-butyl). A white solid of phenyl) -1,3,5-triazine (yield 4.46 g, yield 77%) was obtained.

¹ H-NMR (CDCl ₃ ): δ 1.41 (s, 18H), 7.61 (d, J = 8.5 Hz, 4H), 7.88 (t, J = 1.8 Hz, 1H), 8. 65 (d, J = 8.5 Hz, 4H), 8.80 (d, J = 1.8 Hz, 2H).
¹³ C-NMR (CDCl ₃ ): δ 31.2, 35.1, 123.3, 125.7, 128.9, 130.5, 133.1, 137.4, 140.0, 156.5, 169 0.0, 171.8.
Example 6
Synthesis of 2- (3,5-dibromophenyl) -4,6-di (3-chlorophenyl) -1,3,5-triazine

  3,5-Dibromobenzoic acid chloride (5.00 g) and 3-chlorobenzonitrile (4.60 g) were dissolved in chloroform (200 mL) under an argon stream. The resulting solution was cooled to 0 ° C. and antimony pentachloride (4.70 g) was added dropwise. The mixture was stirred at room temperature for 1 hour and then refluxed for 12 hours. After cooling to room temperature, low-boiling components were removed under reduced pressure, and 2- (3,5-dibromophenyl) -4,6-di (3-chlorophenyl) -1,3,5-oxadiazin-1-ium = hexachloro Antimonic acid was obtained as a red solid.

  The resulting red solid was pulverized in a stream of argon and slowly added to a 28% aqueous ammonia solution cooled to 0 ° C. The resulting suspension was stirred for an additional hour at room temperature. The precipitated solid was collected by filtration and washed successively with water and methanol. The solid was dried and extracted with a Soxhlet extractor (extraction solvent: chloroform). The extract was allowed to cool, and the precipitated solid was collected by filtration and dried to give a white powder of 2- (3,5-dibromophenyl) -4,6-di (3-chlorophenyl) -1,3,5-triazine ( Yield 4.10 g, yield 46%).

¹ H-NMR (CDCl ₃ ): δ 7.49 (t, J = 7.9 Hz, 2H), 7.63 (t, J = 1.9 Hz, 1H), 7.79 (brd, J = 7.9 Hz) , 2H), 8.57 (d, J = 1.9 Hz, 2H), 8.66 (brd, J = 7.9 Hz, 2H), 8.81 (t, J = 1.7 Hz, 2H).
¹³ C-NMR (CDCl ₃ ): δ 123.1 (quart. × 2), 127.3 (CH × 2), 127.7 (CH × 2), 130.4 (CH × 2), 131.9 ( CH × 2), 132.6 (CH), 135.7 (quart. × 2), 136.0 (CH × 2), 137.4 (quart. × 2), 138.6 (quart.), 169 .8 (quart.), 170.9 (quart. × 2).
Example 7
Synthesis of 2- (3,5-dibromophenyl) -4,6-di (3-chlorophenyl) -1,3,5-triazine In a 300 mL three-necked reaction vessel equipped with a reflux tube and a mechanical stirrer under an argon stream, 3,5-Dibromobenzoic acid chloride (20.9 g) and 3-chlorobenzonitrile (36.4 g) were taken, and chlorobenzene (150 mL) was added. The resulting solution was cooled to 0 ° C. and antimony pentachloride (29.9 g) was added dropwise. The mixture was refluxed at room temperature for 1 hour and further at 100 ° C. for 2 hours. The resulting orange suspension was cooled to −20 ° C. and 28% aqueous ammonia (140 mL) was added. The milky white suspension was stirred at room temperature for 30 minutes and then slowly heated to 140 ° C. using an oil bath to distill off the organic solvent (116 mL) and water (60 mL). Chlorobenzene (100 mL) was added, and heated and filtered at 130 ° C. The filtrate was allowed to cool, and methanol (100 mL) was added. The precipitated solid was collected by filtration, washed with methanol (30 mL × 2), and dried to give 2- (3,5-dibromophenyl) -4,6-bis (biphenyl-3-yl) -1, A white powder of 3,5-triazine (yield 12.0 g, yield 23%) was obtained.

  Moreover, 2- (3,5-dibromophenyl) -4,6-bis (biphenyl-3-yl) -1,3,3 is obtained by performing the same extraction operation on the insoluble matter filtered off in the heat filtration. A white powder of 5-triazine (yield 1.30 g, yield 2.5%) was obtained.

Example 8
Synthesis of 2,4-bis (biphenyl-4-yl) -6- (3,5-dibromophenyl) -1,3,5-triazine

  3,5-Dibromobenzoyl chloride (2.98 g) and 4-biphenylcarbonitrile (3.58 g) were dissolved in chloroform (40 mL), cooled to 0 ° C., and then antimony pentachloride (2.99 g) was added dropwise. . The mixture was stirred at room temperature for 10 minutes and then refluxed for 14 hours. After cooling to room temperature, chloroform was distilled off under reduced pressure, and 2,4-bis (biphenyl-4-yl) -6- (3,5-dibromophenyl) -1,3,5-oxadiazin-1-ium = hexachloro Antimonic acid was obtained as a red solid.

  The obtained red solid was gradually added to 28% aqueous ammonia solution (150 mL) cooled to 0 ° C. to produce a white solid. This was stirred at room temperature for 1 hour, and after filtration, the resulting white solid was washed with water and methanol. The white solid was dried, suspended in chloroform (200 mL), and filtered with heating. Moreover, it filtered by heating using chloroform (150 mL * 3) with respect to the insoluble component separated by filtration. All the filtrates were collected, chloroform was distilled off under reduced pressure, and the obtained solid was recrystallized from dichloromethane-methanol to give 2,4-bis (biphenyl-4-yl) -6- (3,5-dibromophenyl). ) -1,3,5-triazine was obtained as a white solid (yield 5.14 g, yield 83%).

¹ H-NMR (CDCl ₃ ): δ 7.40-7.45 (m, 2H), 7.49-7.54 (m, 4H), 7.70-7.75 (m, 4H), 7. 83 (d, J = 8.5 Hz, 4H), 7.91 (t, J = 1.8 Hz, 1H), 8.83 (d, J = 8.5 Hz, 4H), 8.85 (d, J = 1.8 Hz, 2H).
¹³ C-NMR (CDCl ₃ ): δ 123.4, 127.3, 127.5, 128.2, 129.0, 129.7, 130.7, 134.7, 137.6, 139.9, 140 .3, 145.7, 169.3, 171.8.
Example 9
Synthesis of 2- (3,5-dibromophenyl) -4,6-bis (biphenyl-3-yl) -1,3,5-triazine

  3,5-Dibromobenzoic acid chloride (4.10 g) and 3-phenylbenzonitrile (5.00 g) were dissolved in chloroform (100 mL) under an argon stream. The resulting solution was cooled to 0 ° C. and antimony pentachloride (4.20 g) was added dropwise. The mixture was stirred at room temperature for 1 hour and then refluxed for 12 hours. After cooling to room temperature, low-boiling components were removed under reduced pressure, and 2- (3,5-dibromophenyl) -4,6-bis (biphenyl-3-yl) -1,3,5-oxadiazine-1-ium = Hexachloroantimonic acid was obtained as a red solid.

  The resulting red solid was pulverized in a stream of argon and slowly added to a 28% aqueous ammonia solution cooled to 0 ° C. The resulting suspension was stirred for an additional hour at room temperature. The precipitated solid was collected by filtration and washed successively with water and methanol. The solid was dried and extracted with a Soxhlet extractor (extraction solvent: chloroform). The extract was allowed to cool, and the precipitated solid was collected by filtration and dried to give white white 2- (3,5-dibromophenyl) -4,6-bis (biphenyl-3-yl) -1,3,5-triazine. A powder (yield 2.80 g, yield 32%) was obtained.

¹ H-NMR (CDCl ₃ ): δ 7.46 (brt, J = 7.4 Hz, 2H), 7.52-7.58 (m, 4H), 7, 67 (dd, J = 7.8 Hz, 7 .7 Hz, 2H), 7.76 (brd, J = 7.7 Hz, 4H), 7.86 (d, J = 7.7 Hz, 2H), 7.90 (brd, 1H), 8.72 (d , J = 7.8 Hz, 2H), 8.81 (d, J = 1.8 Hz, 2H), 8.95 (s, 2H).
¹³ C-NMR (CDCl ₃ ): δ 123.4, 127.4, 127.7, 127.8, 128.1, 130.7, 131.7, 136.2, 137.7, 139.7, 140 .7, 141.9, 169.4, 172.0.
Example 10
Synthesis of 2- (3,5-dibromophenyl) -4,6-bis (biphenyl-3-yl) -1,3,5-triazine 300 mL three-necked reaction vessel equipped with a reflux tube and a mechanical stirrer under an argon stream 3,5-dibromobenzoic acid chloride (15.0 g) and 3-phenylbenzonitrile (18.0 g) were taken, and chloroform (50 mL) was added. The resulting solution was cooled to 0 ° C. and antimony pentachloride (15.1 g) was added dropwise. The mixture was refluxed at room temperature for 1 hour and at 70 ° C. for 6 hours. The resulting deep red suspension was cooled to 0 ° C. and 28% aqueous ammonia (70 mL) was added. The milky white suspension was stirred at room temperature for 1 hour, chlorobenzene (150 mL) was added, and the mixture was slowly heated to 140 ° C. using an oil bath, and the organic solvent (130 mL) and water (46 mL) were distilled off. Chlorobenzene (50 mL) was added, and heated and filtered at 130 ° C. The filtrate was allowed to cool, methanol (50 mL) was added, the precipitated solid was collected by filtration, washed with methanol (20 mL × 2), and dried to give 2- (3,5-dibromophenyl) -4. , 6-Bis (biphenyl-3-yl) -1,3,5-triazine was obtained as a white powder (yield 13.9 g, yield 43%). From HPLC, the content of 2- (3,5-dibromophenyl) -4,6-bis (biphenyl-3-yl) -1,3,5-triazine was 97.4%.

  2- (3,5-dibromophenyl) -4,6-bis (biphenyl-3-) is obtained by performing the same extraction operation using chlorobenzene (50 mL × 2) on the insoluble matter filtered off in the heat filtration. Yl) -1,3,5-triazine (yield 1.30 g, yield 4.3%) was obtained. From HPLC, the content of 2- (3,5-dibromophenyl) -4,6-bis (biphenyl-3-yl) -1,3,5-triazine was 98.0%.

Example 11
Synthesis of 2- (3,5-dibromophenyl) -4,6-bis (biphenyl-3-yl) -1,3,5-triazine 300 mL three-necked reaction vessel equipped with a reflux tube and a mechanical stirrer under an argon stream 3,5-dibromobenzoic acid chloride (15.0 g) and 3-phenylbenzonitrile (18.0 g) were taken, and chlorobenzene (100 mL) was added. The obtained solution was cooled to 0 ° C., antimony pentachloride (15.1 g) was added dropwise, and the mixture was refluxed at room temperature for 1 hour and further at 100 ° C. for 2 hours. The resulting deep red suspension was cooled to 0 ° C. and 28% aqueous ammonia (70 mL) was added. After stirring the milky white suspension at room temperature for 30 minutes, chlorobenzene (50 mL) was added, and the mixture was slowly heated to 140 ° C. using an oil bath, and the organic solvent (130 mL) and water (42 mL) were distilled off. Chlorobenzene (80 mL) was added, and heated and filtered at 130 ° C. The filtrate was allowed to cool, and then the same operation as in Example 10 was performed to give 2- (3,5-dibromophenyl) -4,6-bis (biphenyl-3-yl) -1,3,5-triazine. Of white powder (14.6 g, 47% yield). From HPLC, the content of 2- (3,5-dibromophenyl) -4,6-bis (biphenyl-3-yl) -1,3,5-triazine was 97.4%.

  Further, 2- (3,5-dibromophenyl) -4,6-bis (biphenyl-3-yl) -1 is obtained by performing the same operation as in Example 10 on the insoluble matter filtered off in the heat filtration. , 3,5-triazine was obtained as a white powder (yield 1.40 g, yield 4.6%). From HPLC, the content of 2- (3,5-dibromophenyl) -4,6-bis (biphenyl-3-yl) -1,3,5-triazine was 95.6%.

Example 12
Synthesis of 2- (3,5-dibromophenyl) -4,6-bis (biphenyl-3-yl) -1,3,5-triazine A 3 L three-necked reaction vessel equipped with a reflux tube and a mechanical stirrer under an argon stream 3,5-dibromobenzoic acid chloride (150 g) and 3-phenylbenzonitrile (180 g) were taken, and chlorobenzene (1.0 L) was added. The obtained solution was cooled to 0 ° C., antimony pentachloride (151 g) was added dropwise, and the mixture was stirred at room temperature for 1 hour and further at 100 ° C. for 2 hours. The resulting deep red suspension was cooled to 0 ° C. and 28% aqueous ammonia (700 mL) was added. The milky white suspension was stirred at room temperature for 30 minutes, chlorobenzene (500 mL) was added, and the mixture was slowly heated to 140 ° C. using an oil bath, and the organic solvent (1.1 L) and water (400 mL) were distilled off. Chlorobenzene (600 mL) was added, and heated and filtered at 130 ° C. The filtrate was allowed to cool, and methanol (500 mL) was added. The precipitated solid was collected by filtration, washed with methanol (200 mL × 2), and dried to give 2- (3,5-dibromophenyl) -4,6-bis (biphenyl-3-yl) -1, A white powder of 3,5-triazine (yield 103 g, yield 33%) was obtained. From HPLC, the content of 2- (3,5-dibromophenyl) -4,6-bis (biphenyl-3-yl) -1,3,5-triazine was 97.7%.

  Moreover, 2- (3,5-dibromophenyl) -4,6-bis (biphenyl-3-yl) is obtained by performing the same operation using chlorobenzene (500 mL) on the insoluble matter filtered off in the above heat filtration. ) -1,3,5-triazine was obtained as a white powder (yield 17.7 g, yield 5.7%). From HPLC, the content of 2- (3,5-dibromophenyl) -4,6-bis (biphenyl-3-yl) -1,3,5-triazine was 97.7%.

Example 13
Synthesis of 2- (3,5-dibromophenyl) -4,6-bis (biphenyl-3-yl) -1,3,5-triazine A 3 L three-necked reaction vessel equipped with a reflux tube and a mechanical stirrer under an argon stream 3,5-dibromobenzoic acid chloride (225 g) and 3-phenylbenzonitrile (270 g) were taken, and chlorobenzene (1.1 L) was added. The resulting solution was cooled to 0 ° C., antimony pentachloride (227 g) was added dropwise, and the mixture was stirred at room temperature for 1 hour and further at 100 ° C. for 2 hours. The resulting deep red suspension was cooled to −20 ° C. and 28% aqueous ammonia (1.0 L) was added. The milky white suspension was stirred at room temperature for 30 minutes, then slowly heated to 140 ° C. using an oil bath, and the organic solvent (335 mL) and water (165 mL) were distilled off. Chlorobenzene (500 mL) was added, and the organic solvent (665 mL) and water (225 mL) were further distilled off. Chlorobenzene (900 mL) was added, and heated and filtered at 130 ° C. The filtrate was allowed to cool, and methanol (750 mL) was added. The precipitated solid was collected by filtration, washed with methanol (300 mL × 2), and dried to give 2- (3,5-dibromophenyl) -4,6-bis (biphenyl-3-yl) -1, A white powder of 3,5-triazine (yield 218 g, 47% yield) was obtained. From HPLC, the content of 2- (3,5-dibromophenyl) -4,6-bis (biphenyl-3-yl) -1,3,5-triazine was 97.3%.

  Moreover, 2- (3,5-dibromophenyl) -4,6-bis (biphenyl-3-) is obtained by performing a similar extraction operation using chlorobenzene (750 mL) on the insoluble matter filtered off in the heat filtration. Yl) -1,3,5-triazine was obtained as a white powder (yield 34.1 g, yield 7.3%). From HPLC, the content of 2- (3,5-dibromophenyl) -4,6-bis (biphenyl-3-yl) -1,3,5-triazine was 97.8%.

Example 14
Synthesis of 2- (3,5-dibromophenyl) -4,6-bis (biphenyl-3-yl) -1,3,5-triazine A 3 L three-necked reaction vessel equipped with a reflux tube and a mechanical stirrer under an argon stream 3,5-dibromobenzoic acid chloride (225 g) and 3-phenylbenzonitrile (270 g) were taken, and chlorobenzene (1.1 L) was added. The resulting solution was cooled to 0 ° C., antimony pentachloride (227 g) was added dropwise, and the mixture was stirred at room temperature for 1 hour and further at 100 ° C. for 2 hours. The resulting deep red suspension was cooled to −20 ° C. and 28% aqueous ammonia (1.0 L) was added. The milky white suspension was stirred at room temperature for 30 minutes and then slowly heated to 140 ° C. using an oil bath. The organic solvent (1.6 L) and water (560 mL) were distilled off while sequentially adding chlorobenzene (2.0 L), and the mixture was heated and stirred at 100 ° C. for 12 hours in the atmosphere. Chlorobenzene (1.0 L) and water (100 mL) were added, and heated and filtered at 130 ° C. to remove insolubles. The filtrate was allowed to cool, and methanol (750 mL) was added. The precipitated solid was collected by filtration, washed with methanol (300 mL × 2), and dried to give 2- (3,5-dibromophenyl) -4,6-bis (biphenyl-3-yl) -1, A white powder of 3,5-triazine (yield 141 g, yield 30%) was obtained. From HPLC, the content of 2- (3,5-dibromophenyl) -4,6-bis (biphenyl-3-yl) -1,3,5-triazine was 96.5%.

  Moreover, 2- (3,5-dibromophenyl) -4,6-bis (biphenyl-3-) is obtained by performing a similar extraction operation on the insoluble matter filtered off in the heat filtration using chlorobenzene (750 mL). Yl) -1,3,5-triazine was obtained as a white powder (yield 82.2 g, yield 18%). From HPLC, the content of 2- (3,5-dibromophenyl) -4,6-bis (biphenyl-3-yl) -1,3,5-triazine was 97.0%.

Example 15
Synthesis of 2- (3,5-dibromophenyl) -4,6-bis (biphenyl-3-yl) -1,3,5-triazine 500 mL three-necked reaction vessel equipped with a reflux tube and a mechanical stirrer under an argon stream 3,5-dibromobenzoic acid chloride (22.5 g) and 3-phenylbenzonitrile (27.0 g) were taken, and chlorobenzene (200 mL) was added. The resulting solution was cooled to 0 ° C., and antimony pentachloride (22.7 g) was added dropwise thereto, followed by stirring at room temperature for 1 hour and further at 100 ° C. for 2 hours. The resulting deep red suspension was cooled to −20 ° C., and 28% aqueous ammonia solution (100 mL) cooled to −20 ° C. was added dropwise over 20 minutes. After stirring the milky white suspension at room temperature for 30 minutes, chlorobenzene (70 mL) was added, and the mixture was slowly heated to 140 ° C. using an oil bath, and the organic solvent (80 mL) and water (40 mL) were distilled off. The mixture was heated and filtered at 130 ° C. The filtrate was allowed to cool, and methanol (100 mL) was added. The precipitated solid was collected by filtration, washed with methanol (30 mL × 2), and dried to give 2- (3,5-dibromophenyl) -4,6-bis (biphenyl-3-yl) -1, A white powder of 3,5-triazine was obtained (yield 23.9 g, yield 51%). From HPLC, the content of 2- (3,5-dibromophenyl) -4,6-bis (biphenyl-3-yl) -1,3,5-triazine was 96.7%.

  2- (3,5-dibromophenyl) -4,6-bis (biphenyl-3-yl) is obtained by performing the same extraction operation using chlorobenzene (75 mL) on the insoluble matter filtered off in the heat filtration. A white powder of -1,3,5-triazine (yield 800 mg, yield 2.0%) was obtained. From HPLC, the content of 2- (3,5-dibromophenyl) -4,6-bis (biphenyl-3-yl) -1,3,5-triazine was 95.9%.

Example 16
Synthesis of 2- (3,5-dibromophenyl) -4,6-bis (biphenyl-3-yl) -1,3,5-triazine 500 mL three-necked reaction vessel equipped with a reflux tube and a mechanical stirrer under an argon stream 3,5-dibromobenzoic acid chloride (22.5 g) and 3-phenylbenzonitrile (27.0 g) were taken, and chlorobenzene (200 mL) was added. The resulting solution was cooled to 0 ° C., antimony pentachloride (22.7 g) was added dropwise, and the mixture was stirred at room temperature for 1 hour and further at 100 ° C. for 2 hours. The resulting deep red suspension was cooled to 0 ° C. and added dropwise over 30 minutes to a 28% aqueous ammonia solution (100 mL) cooled to −20 ° C. The reaction vessel was washed with chlorobenzene (60 mL), and the washing was similarly added dropwise to the aqueous ammonia solution. The milky white suspension was stirred at room temperature for 30 minutes, then slowly heated to 140 ° C. using an oil bath, and the organic solvent (110 mL) and water (36 mL) were distilled off. The mixture was heated and filtered at 130 ° C. The filtrate was allowed to cool, and methanol (100 mL) was added. The precipitated solid was collected by filtration, washed with methanol (30 mL × 2), and dried to give 2- (3,5-dibromophenyl) -4,6-bis (biphenyl-3-yl) -1, A white powder of 3,5-triazine was obtained (yield 23.8 g, yield 51%). From HPLC, the content of 2- (3,5-dibromophenyl) -4,6-bis (biphenyl-3-yl) -1,3,5-triazine was 95.6%.

  Moreover, 2- (3,5-dibromophenyl) -4,6-bis (biphenyl-3-) is obtained by performing a similar extraction operation using chlorobenzene (75 mL) on the insoluble matter filtered off in the heat filtration. Yl) -1,3,5-triazine (yield 1.30 g, yield 2.8%). From HPLC, the content of 2- (3,5-dibromophenyl) -4,6-bis (biphenyl-3-yl) -1,3,5-triazine was 94.8%.

Example 17
Synthesis of 2- (3,5-dibromo-4-methylphenyl) -4,6-bis (biphenyl-3-yl) -1,3,5-triazine

  Under a stream of argon, 3,5-dibromo-p-toluic acid chloride (15.6 g) and 3-phenylbenzonitrile (18.0 g) were taken in a 300 mL three-necked reaction vessel equipped with a reflux tube and a mechanical stirrer, and chlorobenzene (100 mL) was added. The resulting solution was cooled to 0 ° C., antimony pentachloride (15.0 g) was added dropwise, and the mixture was stirred at room temperature for 30 minutes and further at 100 ° C. for 2 hours. The resulting deep red suspension was cooled to −20 ° C. and 28% aqueous ammonia (80 mL) was added. After stirring the milky white suspension at room temperature for 1 hour, chlorobenzene (100 mL) was added, and the mixture was slowly heated to 140 ° C. using an oil bath, and the organic solvent (126 mL) and water (50 mL) were distilled off. Chlorobenzene (50 mL) was added, and heated and filtered at 130 ° C. The filtrate was allowed to cool, and methanol (100 mL) was added. The precipitated solid was collected by filtration, washed with methanol (30 mL × 2), and dried to give 2- (3,5-dibromophenyl) -4,6-bis (biphenyl-3-yl) -1, A white powder of 3,5-triazine (yield 9.90 g, yield 31%) was obtained.

  Moreover, 2- (3,5-dibromophenyl) -4,6-bis (biphenyl-3-) is obtained by performing a similar extraction operation using chlorobenzene (100 mL) on the insoluble matter separated in the heat filtration. Yl) -1,3,5-triazine white powder (yield 3.50 g, yield 11%) was obtained.

¹ H-NMR (CDCl ₃ ): δ 2.73 (S, 3H), 7.47 (t, J = 7.4 Hz, 2H), 7.57 (m, 4H), 7.71 (t, J = 7.7 Hz, 2H), 7.79 (d, J = 7.2 Hz, 4H), 7.89 (d, J = 7.7 Hz, 2H), 8.78 (brd, J = 7.7 Hz, 2H) ), 8.91 (s, 2H), 9.00 (brs, 2H).
¹³ C-NMR (CDCl ₃ ): δ 24.0 (CH ₃ ), 125.6 (quart. × 2), 127.4 (CH × 4), 127.7 (CH × 4), 128.0 (CH × 2), 129.0 (CH × 4), 129.2 (CH × 2), 131.6 (CH × 2), 132.2 (CH × 2), 136.5 (quart. × 2), 139.8 (quart.) 140.7 (quart. X2), 141.8 (quart. X2), 141.9 (quart.), 169.9 (quart.) 172.0 (quart. X2) ).
Example 18
Synthesis of 2- (3,5-dibromophenyl) -4,6-bis (1-naphthyl) -1,3,5-triazine

  3,5-Dibromobenzoyl chloride (2.98 g) and 1-naphthonitrile (3.06 g) were dissolved in chloroform (30 mL), cooled to 0 ° C., and then antimony pentachloride (2.99 g) was added dropwise. The mixture was stirred at room temperature for 10 minutes and then refluxed for 22 hours. After cooling to room temperature, chloroform was distilled off under reduced pressure, and 2- (3,5-dibromophenyl) -4,6-bis (1-naphthyl) -1,3,5-oxadiazin-1-ium = hexachloroantimonic acid. Was obtained as a red solid.

  The resulting red solid was gradually added to 28% aqueous ammonia solution (100 mL) cooled to 0 ° C. to produce a white solid. This was stirred at room temperature for 1 hour, and after filtration, the resulting white solid was washed with water and methanol. The white solid was dried, purified by silica gel column chromatography (eluent hexane: chloroform = 3: 1 to 1: 1), recrystallized from dichloromethane-methanol, 2- (3,5-dibromophenyl) -4, A white solid (yield 1.73 g, yield 29%) of 6-bis (1-naphthyl) -1,3,5-triazine was obtained.

¹ H-NMR (CDCl ₃ ): δ 7.60 (ddd, J = 8.0 Hz, 6.8 Hz, 1.2 Hz, 2H), 7.65 (ddd, J = 8.6 Hz, 6.8 Hz, 1. 5 Hz, 2H), 7.69 (dd, J = 8.1 Hz, 7.4 Hz, 2H), 7.92 (t, J = 1.8 Hz, 1H), 7.99 (brd, J = 8.0 Hz) , 2H), 8.11 (brd, J = 8.1 Hz, 2H), 8.58 (dd, J = 7.4 Hz, 1.3 Hz, 2H), 8.84 (d, J = 1.8 Hz, 2H), 9.16 (brd, J = 8.6 Hz, 2H).
¹³ C-NMR (CDCl ₃ ): δ 123.6, 125.2, 125.9, 126.3, 127.5, 128.8, 130.7, 131.1, 131.3, 132.8, 133 3, 134.3, 137.8, 139.7, 168.9, 174.5.
Example 19
Synthesis of 2- (3,5-dibromophenyl) -4,6-bis (2-naphthyl) -1,3,5-triazine

  Under an argon stream, 3,5-dibromo-p-toluic acid chloride (19.9 g) and 2-cyanonaphthalene (20.4 g) were taken in a 300 mL three-necked reaction vessel equipped with a reflux tube and a mechanical stirrer, and chlorobenzene ( 180 mL) was added. The resulting solution was cooled to 0 ° C., antimony pentachloride (19.9 g) was added dropwise, and the mixture was stirred at room temperature for 30 minutes and further at 100 ° C. for 2 hours. The resulting dark red suspension was cooled to −20 ° C. and 28% aqueous ammonia (100 mL) was added. The milky white suspension was stirred at room temperature for 1 hour, then slowly heated to 140 ° C. using an oil bath, and the organic solvent (70 mL) and water (30 mL) were distilled off. After allowing to cool, the mixture was filtered, and the resulting solid was suspended in chlorobenzene (100 mL). The suspension was heated and filtered at 130 ° C. to remove insoluble matters. The same extraction operation was repeated three more times using chlorobenzene (100 mL). After allowing to cool, the filtrates were combined and methanol (400 mL) was added. The precipitated solid was collected by filtration, washed with methanol (30 mL × 2), and dried to give 2- (3,5-dibromophenyl) -4,6-bis (2-naphthyl) -1,3. A white powder of 5-triazine (yield 7.90 g, 14% yield) was obtained. Furthermore, 2- (3,5-dibromophenyl) -4,6-bis (2-naphthyl) -1,3 is extracted by extracting the insoluble matter obtained by heating filtration with a Soxhlet extractor (solvent: chloroform). , 5-triazine (yield 5.40 g, 9.5% yield).

¹ H-NMR (CDCl ₃ ): δ 7.60-7.69 (m, 4H), 7.94 (s, 1H), 7.98 (d, J = 7.8 Hz, 2H), 8.06 ( d, J = 8.6 Hz, 2H), 8.17 (d, J = 7.8 Hz, 2H), 8.83 (d, J = 8.6 Hz, 2H), 8.90 (s, 2H), 9.34 (s, 2H).
Reference example 1
Synthesis of 2- [5-chloro-4 ′-(2-pyridyl) -1,1′-biphenyl-3-yl] -4,6-diphenyl-1,3,5-triazine

  Under an argon stream, 2- (4-bromophenyl) pyridine (350 mg) was dissolved in tetrahydrofuran (20 mL) and cooled to -78 ° C. A hexane solution (1.04 mL) containing butyllithium (1.65 mmol) was slowly added thereto, and the mixture was stirred at this temperature for 30 minutes. Dichloro (tetramethylethylenediamine) zinc (454 mg) was added, and the mixture was stirred at −78 ° C. for 10 minutes and then stirred at room temperature for 1.5 hours. To this was added 2- (3-bromo-5-chlorophenyl) -4,6-diphenyl-1,3,5-triazine (350 mg), tetrakis (triphenylphosphine) palladium (46 mg) obtained in Example 2, Heated to reflux for 18 hours. After allowing to cool, the reaction solution was concentrated under reduced pressure, and the resulting solid was recrystallized from dichloromethane-methanol. The obtained crude product was purified by silica gel column chromatography (developing solvent hexane: chloroform = 50: 50 to 0: 100), recrystallized again with dichloromethane-methanol, and 2- [5-chloro-4 ′-( A white solid (yield 339 mg, yield 68%) of 2-pyridyl) -1,1′-biphenyl-3-yl] -4,6-diphenyl-1,3,5-triazine was obtained.

¹ H-NMR (CDCl ₃ ): δ 7.28-7.32 (m, 1H), 7.59-7.67 (m, 2H), 7.62 (d, J = 7.6 Hz, 4H), 7.81-7.87 (m, 2H), 7.85 (d, J = 8.3 Hz, 2H), 7.88 (brs, 1H), 8.20 (d, J = 8.3 Hz, 2H) ), 8.74 (brs, 1H), 8.75-8.80 (m, 1H), 8.80 (d, J = 7.6 Hz, 4H), 8.94 (brs, 1H).
¹³ C-NMR (CDCl ₃ ): δ 120.6, 122.4, 125.9, 127.6, 127.7, 127.8, 128.8, 129.1, 130.9, 132.8, 135 4, 136.0, 136.9, 138.6, 139.3, 140.0, 142.4, 149.9, 156.8, 171.5, 172.0.
Reference example 2
Synthesis of 2- {4- (2-pyridyl)-[1,1 ′: 3 ′, 1 ″]-terphenyl-5′-yl} -4,6-diphenyl-1,3,5-triazine

  Under an argon stream, phenylboronic acid (73 mg), tris (dibenzalacetone) dipalladium complex (5.8 mg) and 2-dicyclohexylphosphino-2 ′, 4 ′, 6′-triisopropylbiphenyl (12 mg) , 4-dioxane (15 mL), 3N aqueous potassium phosphate solution (0.6 mL) was added, and the mixture was stirred at room temperature for 10 min. To this mixture, 2- [5-chloro-4 ′-(2-pyridyl) -1,1′-biphenyl-3-yl] -4,6-diphenyl-1,3,5- obtained in Reference Example 1 was added. Triazine (149 mg) was added, and the mixture was heated to reflux at 110 ° C. for 48 hours. After allowing to cool, the reaction solution was concentrated under reduced pressure, and the resulting solid was purified by silica gel column chromatography (developing solvent hexane: chloroform = 50: 50 to 0: 100), recrystallized from dichloromethane-methanol, 2- { White solid of 4- (2-pyridyl)-[1,1 ′: 3 ′, 1 ″]-terphenyl-5′-yl} -4,6-diphenyl-1,3,5-triazine (yield 162 mg) Yield> 99%).

¹ H-NMR (CDCl ₃ ): δ 7.28-7.32 (m, 1H), 7.49 (brt, J = 7.4 Hz, 1H), 7.56-7.72 (m, 8H), 7.80-7.89 (m, 2H), 7.85 (d, J = 8.5 Hz, 2H), 7.95 (d, J = 8.3 Hz, 2H), 8.12 (brs, 1H) ), 8.22 (d, J = 8.3 Hz, 2H), 8.79 (brd, J = 4.5 Hz, 1H), 8.83 (d, J = 8.2 Hz, 4H), 9.02. (Brs, 1H), 9.06 (brs, 1H).
¹³ C-NMR (CDCl ₃ ): δ 120.5, 122.3, 126.7, 126.9, 127.5, 127.6, 127.8, 128.7, 129.0, 129.1, 130 1, 132.6, 136.2, 136.9, 137.5, 138.8, 140.9, 141.4, 141.7, 142.5, 149.9, 157.0, 171.6 171.8.
Reference example 3
2- [4,4 ″ ″-bis (2-pyridyl)-[1,1 ′: 4 ′, 1 ″: 3 ″, 1 ″ ′: 4 ′ ″, 1 ″ ″ ] -Kinkphenyl-5 ''-yl] -4,6-bis (m-tolyl) -1,3,5-triazine

  Under an argon stream, 4-bromo-4 ′-(2-pyridyl) biphenyl (1.32 g) was dissolved in tetrahydrofuran (120 mL) cooled to −78 ° C., and a hexane solution containing butyllithium (4.5 mmol) (2 .9 mL) was added slowly. After stirring at −78 ° C. for 20 minutes, dichloro (tetramethylethylenediamine) zinc (1.29 g) was added, and the mixture was stirred at −78 ° C. for 10 minutes and then at room temperature for 2 hours. To this solution, 2- (3,5-dibromophenyl) -4,6-bis (m-tolyl) -1,3,5-triazine (700 mg) and tetrakis (triphenylphosphine) palladium obtained in Example 4 were added. (35 mg) was added, and the mixture was stirred for 14 hours while heating under reflux. The reaction solution was concentrated under reduced pressure, and the resulting solid was recrystallized from dichloromethane-methanol. The resulting crude product was purified by silica gel column chromatography (eluent hexane: chloroform = 1: 1-chloroform) and recrystallized from toluene to obtain the desired 2- [4,4 ″ ″-bis (2 -Pyridyl)-[1,1 ': 4', 1 '': 3 '', 1 '' ': 4' '', 1 '' '']-kinkphenyl-5 ''-yl] -4, A white solid (yield: 970 mg, yield: 86%) of 6-bis (m-tolyl) -1,3,5-triazine was obtained.

¹ H-NMR (CDCl ₃ ): δ 2.55 (s, 6H), 7.24-7.29 (m, 2H), 7.43-7.47 (m, 2H), 7.50 (dd, J = 7.5 Hz, 7.5 Hz, 2H), 7.76-7.84 (m, 4H), 7.84 (d, J = 8.3 Hz, 4H), 7.87 (d, J = 8 .3 Hz, 4H), 7.93 (d, = 8.3 Hz, 4H), 8.12-8.17 (m, 1H), 8.15 (d, J = 8.3 Hz, 4H), 8. 61 (s, 2H), 8.63 (d, J = 7.5 Hz, 2H), 8.74 (brd, J = 4.6 Hz, 2H), 9.04 (d, J = 1.7 Hz, 2H) ).
¹³ C-NMR (CDCl ₃ ): δ 21.7, 120.5, 122.2, 126.4, 126.7, 127.5, 127.7, 128.0, 128.7, 129.5, 129 .9, 133.5, 136.3, 136.8, 137.7, 138.4, 138.6, 140.0, 140.1, 141.1, 141.9, 149.8, 157.1 171.6, 172.0.
Reference example 4
2,4-Bis (biphenyl-3-yl) -6- [4,4 ″ -bis (2-pyridyl)-[1,1 ′: 3 ′, 1 ″]-terphenyl-5′-yl Synthesis of 1,3,5-triazine

  Under an argon stream, 2- (4-bromophenyl) pyridine (1.38 g) was dissolved in tetrahydrofuran (100 mL) and cooled to -78 ° C. A hexane solution (3.99 mL) containing butyl lithium (6.30 mmol) was slowly added thereto, and the mixture was stirred at this temperature for 30 minutes. Dichloro (tetramethylethylenediamine) zinc (1.82 g) was added, and the mixture was stirred at −78 ° C. for 10 minutes and then at room temperature for 1.5 hours. Here, 2- (3,5-dibromophenyl) -4,6-bis (biphenyl-3-yl) -1,3,5-triazine (1.24 g) obtained in Example 9, tetrakis (triphenylphosphine) ) Palladium (185 mg) was added and heated to reflux for 18 hours. After allowing to cool, the reaction solution was concentrated under reduced pressure, and the resulting solid was recrystallized from dichloromethane-methanol. The obtained crude product was purified by silica gel column chromatography (developing solvent hexane: chloroform = 50: 50 to 0: 100), recrystallized from hot toluene, and 2,4-bis (biphenyl-3-yl)- 6- [4,4 ″ -bis (2-pyridyl)-[1,1 ′: 3 ′, 1 ″]-terphenyl-5′-yl] -1,3,5-triazine white solid ( Yield 1.08 g, yield 70%).

¹ H-NMR (CDCl ₃ ): δ 7.30-7.35 (m, 2H), 7.43-7.49 (m, 2H), 7.56 (dd, J = 7.8 Hz, 7.6 Hz) 4H), 7.72 (dd, J = 7.7 Hz, 7.7 Hz, 2H), 7.80 (d, J = 7.8 Hz, 4H), 7.82-7.93 (m, 6H) , 7.98 (d, J = 8.3 Hz, 4H), 8.21 (t, J = 1.7 Hz, 1H), 8.23 (d, J = 8.3 Hz, 4H), 8.79 ( d, J = 4.9 Hz, 2H), 8.83 (d, J = 7.7 Hz, 2H), 9.09 (s, 2H), 9.10 (d, J = 1.7 Hz, 2H).
¹³ C-NMR (CDCl ₃ ): δ 120.6, 122.3, 126.9, 127.4, 127.6, 127.7, 127.8, 127.8, 128.1, 129.0, 129 3, 130.1, 131.4, 136.8, 136.9, 137.6, 138.9, 140.8, 141.3, 141.8, 141.9, 149.9, 157.0 , 171.7, 171.9.

Claims (9)

General formula (1)

(In the formula, R ¹ , R ² and R ³ each independently represent a hydrogen atom or a methyl group. X represents a chlorine atom or a bromine atom. Ar represents an optionally substituted aromatic carbonization. Represents a hydrogen group.)
A 1,3,5-triazine compound having a 3,5-dihalo-substituted phenyl group represented by the formula: The 1,3,5-triazine compound according to claim 1, wherein R ¹ and R ³ are hydrogen atoms. The 1,3,5-triazine compound according to claim 1 or 2, wherein Ar is a phenyl group which may be substituted or a naphthyl group which may be substituted. General formula (2)

(Wherein, R ^1, R ² and R ³ are the .X representing each independently a hydrogen atom or a methyl group, a chlorine atom, or .Ar is an aromatic substituted representing a bromine atom .Y representing a hydrocarbon group ^- represents a counter anion).
Wherein the oxonium salt represented by the general formula (1) is reacted with an ammonia source

(Wherein R ¹ , R ² , R ³ , X and Ar are the same as described above.)
A method for producing a 1,3,5-triazine compound having a 3,5-dihalo-substituted phenyl group represented by the formula: General formula (3)

^(Wherein, R 1, ^{R 2} and ^{R 3} are the .X representing each independently a hydrogen atom or a methyl group, a chlorine atom, or bromine atom.)
Acid chloride represented by the general formula (4)

(In the formula, Ar represents an optionally substituted aromatic hydrocarbon group.)
Is reacted with an aromatic nitrile represented by the general formula (2)

(In the formula, R ¹ , R ² , R ³ , X and Ar are the same as described above. Y ⁻ represents a counter anion.)
The oxonium salt represented by the general formula (1) is obtained and then reacted with an ammonia source.

(Wherein R ¹ , R ² , R ³ , X and Ar are the same as described above.)
A method for producing a 1,3,5-triazine compound having a 3,5-dihalo-substituted phenyl group represented by the formula: The method for producing a 1,3,5-triazine compound according to claim 4 or 5, wherein the ammonia source is an aqueous ammonia solution. The method for producing a 1,3,5-triazine compound according to claim 5, wherein the Lewis acid is aluminum chloride, ferric chloride, tin chloride or antimony chloride. General formula (3)

^(Wherein, R 1, ^{R 2} and ^{R 3} are the .X representing each independently a hydrogen atom or a methyl group, a chlorine atom, or bromine atom.)
Acid chloride represented by the general formula (4)

(In the formula, Ar represents an optionally substituted aromatic hydrocarbon group.)
Wherein the aromatic nitrile represented by the general formula (2) is reacted in the presence of a Lewis acid.

(In the formula, R ¹ , R ² , R ³ , X and Ar are the same as described above. Y ⁻ represents a counter anion.)
The manufacturing method of the oxonium salt shown by these. The method for producing an oxonium salt according to claim 8, wherein the Lewis acid is aluminum chloride, ferric chloride, tin chloride or antimony chloride.