JP6794029B2 - Method for Producing Triazine Compound Using Amidine - Google Patents

Description

The present invention relates to a simple and inexpensive method for producing a triazine compound useful as a synthetic intermediate for a charge transport material used in an organic electroluminescent device.

It has been reported that triaryltriazine compounds having various aromatic groups at the 2,4,6 positions of the 1,3,5-triazine ring are useful as synthetic intermediates for charge transport materials used in organic electroluminescent devices. (See, for example, Patent Documents 1 and 2).

However, in the acid-catalyzed cyclization trimerization reaction of aromatic nitriles (see, for example, Non-Patent Document 1), which is generally known as a method for synthesizing 1,3,5-triazine, two kinds of aromatic groups different from the triazine ring are used. The triaryltriazine compound having is not selectively available.

Patent Document 3 discloses a method for producing the triaryltriazine compound by allowing antimony chloride to act on an aromatic nitrile and an aromatic carboxylated product. In this method, the triaryltriazine is produced. The reaction yield of the compound is not sufficient, and a large amount of sparingly soluble inorganic salt derived from antimony chloride, which is a reaction reagent, is produced during the post-treatment, so that the cost of removing and treating the inorganic salt is high. Is also a problem.

Further, Patent Document 4 and Non-Patent Document 2 disclose a method for producing the triaryltriazine compound from an aromatic aldehyde and an aromatic amidine. However, this method is economical in that it is necessary to convert it to an imine intermediate once in order to activate the aromatic aldehyde, which is inferior in reactivity, and that an oxidizing agent is required in the process of forming the triazine ring. It cannot be said that it is preferable from the viewpoint of the viewpoint.

Japanese Unexamined Patent Publication No. 2008/280330 Special Table 2010/155826 JP-A-2010 / 95452 WO2005 / 085387

Chemistry Letters, 1999, Vol. 7, p. 545 European Journal of Organic Chemistry, 2012, p. 3492

An object of the present invention is to provide a simple, inexpensive and industrially excellent method for producing a triazine compound useful as a synthetic intermediate for a charge transport material used in an organic electroluminescent device.

As a result of diligent studies to solve the above problems, the present inventors have found that a triazine compound can be efficiently produced by the condensation reaction of the acid chloride and the amidine compound described in the present invention. It was also found that a triazine compound can be produced in high yield by a condensation reaction between an acylamidine compound efficiently obtained from an acid chloride and an amidine compound and an amidine compound. Furthermore, they have also found that the yield of the triazine compound is improved by adding the silicon compound to the condensation reaction, and have completed the present invention.

That is, the present invention
[1]
General formula (4)

(In the formula, R represents a halogen atom, an alkyl group having 1 to 18 carbon atoms, a haloalkyl group having 1 to 8 carbon atoms, a phenyl group, or a phenyl halide group. N represents an integer of 0 to 5. When is 2 to 5, a plurality of Rs may be the same or different. Ar ¹ has an aryl group having 6 to 14 carbon atoms, an aryl halide group having 6 to 14 carbon atoms, and 1 to 8 carbon atoms. Represents an aryl group having 6 to 14 carbon atoms substituted with an alkyl group or an aryl group having 6 to 14 carbon atoms substituted with a haloalkyl group having 1 to 8 carbon atoms.
The acylamidine compound represented by and the general formula (3).

(In the formula, Ar ¹ has the same meaning as described above, and represents the same group as Ar ¹ in the general formula (4).)
The general formula (1), which comprises reacting the amidine compound represented by

(In the equation, Ar ¹ , R and n have the same meanings as described above. The two Ar ¹ are the same.)
A method for producing a triazine compound represented by.
[2]
The production method according to [1], which comprises reacting in the presence of a silicon compound.
[3]
The silicon compound has a general formula (5).

(In the formula, R ¹ and R ² each independently represent an alkyl group having 1 to 4 carbon atoms, an alkyloxy group having 1 to 4 carbon atoms, or a phenyl group. X ¹ and X ² independently represent each. , Hydrogen atom, halogen atom, or alkyloxy group having 1 to 4 carbon atoms.)
The production method according to [2], which is the silane compound (5) represented by.
[4]
The production method according to [3], wherein X ¹ is a hydrogen atom.
[5]
The silicon compound has the general formula (6).

(In the formula, R ³ , R ⁴ , R ⁵ and R ⁶ each independently represent an alkyl group or a phenyl group having 1 to 4 carbon atoms. X ³ represents a hydrogen atom.)
The production method according to [2], which is the silazane compound (6) represented by.
[6]
The production method according to [5], wherein R ³ , R ⁴ , R ⁵ and R ⁶ are methyl groups.
[7]
The silicon compound has the general formula (7).

(In the formula, R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ and R ¹² each independently represent an alkyl group or a phenyl group having 1 to 4 carbon atoms.)
The production method according to [2], which is the trisilazane compound (7) represented by.
[8]
The production method according to [7], wherein R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ and R ¹² are methyl groups.
[9]
General formula (2)

(In the formula, R represents a halogen atom, an alkyl group having 1 to 18 carbon atoms, a haloalkyl group having 1 to 8 carbon atoms, a phenyl group, or a phenyl halide group. N represents an integer of 0 to 5. When is 2 to 5, a plurality of Rs may be the same or different.)
The acid chloride represented by and the general formula (3)

(In the formula, Ar ¹ is an aryl group having 6 to 14 carbon atoms, an aryl group having 6 to 14 carbon atoms, an aryl group having 6 to 14 carbon atoms substituted with an alkyl group having 1 to 8 carbon atoms, or an aryl group having 6 to 14 carbon atoms. Represents an aryl group having 6 to 14 carbon atoms substituted with a haloalkyl group having 1 to 8 carbon atoms.
General formula (4) obtained by reacting the amidine compound represented by

(In the formula, Ar ¹ , R and n have the same meanings as described above.)
The production method according to [1], which comprises using the acylamidine compound represented by.
[10]
The production method according to [9], which comprises reacting in the presence of a base.
[11]
General formula (2)

(In the formula, R represents a halogen atom, an alkyl group having 1 to 18 carbon atoms, a haloalkyl group having 1 to 8 carbon atoms, a phenyl group, or a phenyl halide group. N represents an integer of 0 to 5. When is 2 to 5, a plurality of Rs may be the same or different.)
The acid chloride represented by and the general formula (3)

(In the formula, Ar ¹ is an aryl group having 6 to 14 carbon atoms, an aryl group having 6 to 14 carbon atoms, an aryl group having 6 to 14 carbon atoms substituted with an alkyl group having 1 to 8 carbon atoms, or an aryl group having 6 to 14 carbon atoms. Represents an aryl group having 6 to 14 carbon atoms substituted with a haloalkyl group having 1 to 8 carbon atoms.
The general formula (1), which comprises reacting the amidine compound represented by

(In the equation, Ar ¹ , R and n have the same meaning as above. The two Ar ¹ are the same.)
A method for producing a triazine compound represented by.
[12]
The production method according to [11], wherein the reaction is carried out in the presence of a base and a silicon compound.
[13]
The production method according to [11], wherein the reaction is carried out by adding a base and then a silicon compound.
[14]
The silicon compound has a general formula (5).

(In the formula, R ¹ and R ² each independently represent an alkyl group having 1 to 4 carbon atoms, an alkyloxy group having 1 to 4 carbon atoms, or a phenyl group. X ¹ and X ² independently represent each. , Hydrogen atom, halogen atom, or alkyloxy group having 1 to 4 carbon atoms.)
The production method according to [12] or [13], which is the silane compound (5) represented by.
[15]
The production method according to [13], wherein X ¹ is a hydrogen atom.
[16]
The silicon compound has the general formula (6).

(In the formula, R ³ , R ⁴ , R ⁵ and R ⁶ each independently represent an alkyl group or a phenyl group having 1 to 4 carbon atoms. X ³ represents a hydrogen atom.)
The production method according to [12] or [13], which is the silazane compound (6) represented by.
[7]
The production method according to [16], wherein R ³ , R ⁴ , R ⁵ and R ⁶ are methyl groups.
[18]
The silicon compound has the general formula (7).

(In the formula, R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ and R ¹² each independently represent an alkyl group or a phenyl group having 1 to 4 carbon atoms.)
The production method according to [12] or [13], which is the trisilazane compound (7) represented by.
[19]
The production method according to [18], wherein R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ and R ¹² are methyl groups.
It is about.

The present invention will be described in detail below.

The definitions of Ar ¹ , R and n in the triazine compound represented by the general formula (1) obtained by using the production method of the present invention will be described.

Ar ¹ is an aryl group having 6 to 14 carbon atoms, an aryl group having 6 to 14 carbon atoms, an aryl group having 6 to 14 carbon atoms substituted with an alkyl group having 1 to 8 carbon atoms, or an aryl group having 1 to 1 carbon atoms. Represents an aryl group having 6 to 14 carbon atoms substituted with an 8 haloalkyl group.

The aryl group having 6 to 14 carbon atoms represented by Ar ¹ is not particularly limited, and examples thereof include a phenyl group, a naphthyl group, a phenanthrenyl group, and an anthrenyl group. Of these, a phenyl group or a biphenylyl group is preferable because the yield of the triazine compound (1) is good.

The aryl halide group having 6 to 14 carbon atoms represented by Ar ¹ is an aryl group having 6 to 14 carbon atoms to which an atom selected from the group consisting of a fluorine atom, a chlorine atom, a bromine atom and an iodine atom is bonded. It can be paraphrased as a group, and is not particularly limited, for example, 2-chlorophenyl group, 3-chlorophenyl group, 4-chlorophenyl group, 2,3-dichlorophenyl group, 2,4-dichlorophenyl group, 2,5-. Dichlorophenyl group, 2,6-chlorophenyl group, 3,4-dichlorophenyl group, 3,5-dichlorophenyl group, 2,3,5-trichlorophenyl group, 3,4,5-trichlorophenyl group, 2,3,5 6-Tetrachlorophenyl group, 2,3,4,5,6-pentachlorophenyl group, 2-bromophenyl group, 3-bromophenyl group, 4-bromophenyl group, 2,3-dibromophenyl group, 2,4- Dibromophenyl group, 2,5-dibromophenyl group, 2,6-bromophenyl group, 3,4-dibromophenyl group, 3,5-dibromophenyl group, 2,3,5-tribromophenyl group, 3,4 , 5-Tribromophenyl group, 2-iodophenyl group, 3-iodophenyl group, 4-iodophenyl group, 3,4-diiodophenyl group, 3,5-diiodophenyl group, 2-fluorophenyl group, 3-Fluorophenyl group, 4-Fluorophenyl group, 2,3-difluorophenyl group, 2,4-difluorophenyl group, 2,5-difluorophenyl group, 2,6-fluorophenyl group, 3,4-difluorophenyl Group, 3,5-difluorophenyl group, 2,3,5-trifluorophenyl group, 3,4,5-trifluorophenyl group, 2,3,5,6-tetrafluorophenyl group, 2,3,4 , 5,6-Pentafluorophenyl group, 2-bromo-3-chlorophenyl group, 3-bromo-2-chlorophenyl group, 2-bromo-4-chlorophenyl group, 4-bromo-2-chlorophenyl group, 2-bromo- 5-Chlorophenyl group, 5-bromo-2-chlorophenyl group, 2-bromo-6-chlorophenyl group, 3-bromo-4-chlorophenyl group, 4-bromo-3-chlorophenyl group, 3-bromo-5-chlorophenyl group, 4-Bromo-3,5-difluorophenyl group, 3-bromo-5-iodophenyl group, 5-iodo-3-chlorophenyl group, 3-bromo-5-fluorophenyl group, 3-chloro-5-fluorophenyl group , 2-Chloronaphthalene-1- Il group, 3-chloronaphthalen-1-yl group, 4-chloronaphthalene-1-yl group, 5-chloronaphthalene-1-yl group, 8-chloronaphthalene-1-yl group, 2,3-dichloronaphthalene- 1-yl group, 2,6-dichloronaphthalene-1-yl group, 4,8-dichloronaphthalene-1-yl group, 2,4,5-trichloronaphthalene-1-yl group, 5,6,7,8 -Tetrachloronaphthalene-1-yl group, 2,3,4,5,6,7,8-heptachloronaphthalene-1-yl group, 1-chloronaphthalen-2-yl group, 3-chloronaphthalene-2- Il group, 4-chloronaphthalen-2-yl group, 6-chloronaphthalen-2-yl group, 1,3-dichloronaphthalen-2-yl group, 4,5,8-trichloronaphthalen-2-yl group, 2 -Bromonaphthalene-1-yl group, 3-bromonaphthalene-1-yl group, 4-bromonaphthalene-1-yl group, 5-chloronaphthalene-1-yl group, 8-chloronaphthalene-1-yl group, 2 , 3-Dibromonaphthalene-1-yl group, 2,6-dibromonaphthalene-1-yl group, 4,5-dibromonaphthalene-1-yl group, 2,4,5-tribromonaphthalene-1-yl group, 1-Bromonaphthalene-2-yl group, 3-bromonaphthalen-2-yl group, 4-bromonaphthalene-2-yl group, 6-bromonaphthalene-2-yl group, 1,3-dibromonaphthalene-2-yl group Group, 5,6,7,8-Tetrabromonaphthalene-2-yl group, 2-iodonphthalene-1-yl group, 3-iodonaphthalene-1-yl group, 4-iodonaphthalene-1-yl group, 5 -Iodonaphthalen-1-yl group, 8-iodonaphthalene-1-yl group, 1-iodonaphthalene-2-yl group, 3-iodonaphthalene-2-yl group, 4-iodonaphthalene-2-yl group, 6 -Iodonaphthalen-2-yl group, 2,3,4-trifluorochloronaphthalene-1-yl group, 2,4,5-trifluoronaphthalene-1-yl group, 5,6,7,8-tetrafluoro Naphthalene-1-yl group, 2,3,4,5,6,7,8-heptafluoronaphthalene-1-yl group, 1,3,4-trifluoronaphthalene-2-yl group, 3,4,5 , 6-Tetrafluoronaphthalen-2-yl group, 5,6,7,8-tetrafluoronaphthalen-2-yl group, 1,3,4,5,6,7,8-heptafluoronaphthalen-2-yl Group, 4-bromo-2-chloronaphthalene-1- Il group, 3-bromo-5-chloronaphthalene-1-yl group, 4-bromo-5-chloro-7-iodonanthrene-1-yl group, 3-bromo-1-chloronaphthalene-2-yl group, 4 -Bromo-3-chloronaphthalen-2-yl group, 3-bromo-5-chloronaphthalene-2-yl group, 6-bromo-4-chloronaphthalene-2-yl group, 3-bromo-5,6,7 , 8-Tetrafluoronaphthalene-2-yl group, 2-chlorophenanthrene-1-yl group, 3-chlorophenanthrene-1-yl group, 4-chlorophenanthrene-1-yl group, 6-chlorophenanthrene-1-yl group Group, 7-chlorophenanthrene-1-yl group, 9-chlorophenanthrene-1-yl group, 2,7-dichlorophenanthrene-1-yl group, 3,6-dichlorophenanthrene-1-yl group, 3,9- Dichlorophenanthrene-1-yl group, 6,10-dichlorophenanthrene-1-yl group, 9,10-dichlorophenanthrene-1-yl group, 2,4,6-trichlorophenanthrene-1-yl group, 3,9, 10-Trichlorophenanthrene-1-yl group, 3,6,9,10-tetrachlorophenanthrene-1-yl group, 1-chlorophenanthrene-2-yl group, 3-chlorophenanthrene-2-yl group, 6-chloro Phenanthrene-2-yl group, 7-chlorophenanthrene-2-yl group, 9-chlorophenanthrene-2-yl group, 10-chlorophenanthrene-2-yl group, 1,9-dichlorophenanthrene-2-yl group, 3 , 6-Dichlorophenanthrene-2-yl group, 3,9-dichlorophenanthrene-2-yl group, 9,10-dichlorophenanthrene-2-yl group, 3,9,10-trichlorophenanthrene-2-yl group, 7 , 8,9,10-Tetrachlorophenanthrene-2-yl group, 1-chlorophenanthrene-3-yl group, 2-chlorophenanthrene-3-yl group, 6-chlorophenanthrene-3-yl group, 9-chlorophenanthrene -3-yl group, 10-chlorophenanthrene-3-yl group, 2,7-dichlorophenanthrene-3-yl group, 9,10-dichlorophenanthrene-3-yl group, 1-chlorophenanthrene-9-yl group, 2-Chloronaphthalene-9-yl group, 3-chlorophenanthrene-9-yl group, 4-chlorophenanthrene-9-yl group, 5-chlorophenanthrene-9-yl group, 6-chlorophenanthrene-9-yl group , 7-Chlorophenanthrene-9-yl group, 8-chlorophenanthrene-9-yl group, 10-chlorophenanthrene-9-yl group, 2,7-dichlorophenanthrene-9-yl group, 3,6-dichlorophenanthrene- 9-yl group, 1,2,3-trichlorophenanthrene-9-yl group, 2,4,6-trichlorophenanthrene-9-yl group, 2-bromophenanthrene-1-yl group, 3-bromophenanthrene-1- Il group, 4-bromophenanthrene-1-yl group, 5-bromophenanthrene-1-yl group, 6-bromophenanthrene-1-yl group, 7-bromophenanthrene-1-yl group, 8-bromophenanthrene-1-yl group Il group, 9-bromophenanthrene-1-yl group, 10-bromophenanthrene-1-yl group, 2,7-dibromophenanthrene-1-yl group, 3,6-dibromophenanthrene-1-yl group, 3,9 -Dibromophenanthrene-1-yl group, 6,10-dibromophenanthrene-1-yl group, 9,10-dibromophenanthrene-1-yl group, 2,4,6-tribromophenanthrene-1-yl group, 3, 9,10-Tribromophenanthrene-1-yl group, 3,6,9,10-tetrabromophenanthrene-1-yl group, 1-bromophenanthrene-2-yl group, 3-bromophenanthrene-2-yl group, 6-Bromophenanthrene-2-yl group, 7-bromophenanthrene-2-yl group, 9-bromophenanthrene-2-yl group, 10-bromophenanthrene-2-yl group, 1,9-dibromophenanthrene-2-yl group Group, 3,6-dibromophenanthrene-2-yl group, 3,9-dibromophenanthrene-2-yl group, 9,10-dibromophenanthrene-2-yl group, 3,9,10-tribromophenanthrene-2-yl group Il group, 7,8,9,10-tetrabromophenanthrene-2-yl group, 1-bromophenanthrene-3-yl group, 2-bromophenanthrene-3-yl group, 6-bromophenanthrene-3-yl group, 9-Bromophenanthrene-3-yl group, 10-bromophenanthrene-3-yl group, 2,7-dibromophenanthrene-3-yl group, 9,10-dibromophenanthrene-3-yl group, 1-bromophenanthrene-9 -Il group, 2-bromophenanthrene-9-yl group, 3-bromophenanthrene-9-yl group, 4-bromophenanthrene-9-yl group, 5-bromofe Nantren-9-yl group, 6-bromophenanthrene-9-yl group, 7-bromophenanthrene-9-yl group, 8-bromophenanthrene-9-yl group, 10-bromophenanthrene-9-yl group, 2,7 −Dibromophenanthrene-9-yl group, 3,6-dibromophenanthrene-9-yl group, 1,2,3-tribromophenanthrene-9-yl group, 2,4,6-tribromophenanthrene-9-yl group , 7-Iodophenanthrene-1-yl group, 9-iodophenanthrene-1-yl group, 3,6-diiodophenanthrene-1-yl group, 3-iodophenanthrene-2-yl group, 10-iodophenanthrene-2 -Il group, 6,9,10-triiodophenanthrene-2-yl group, 2-iodophenanthrene-9-yl group, 3-iodophenanthrene-9-yl group, 6-iodophenanthrene-9-yl group, 8 -Iodophenanthrene-9-yl group, 3,6-diiodophenanthrene-9-yl group, 9,10-difluorophenanthrene-1-yl group, 2,3,4,5,6,7,8,9, 10-Nonafluorophenanthrene-1-yl group, 3,6-difluorophenanthrene-2-yl group, 1,3,4,5,6,7,8,9,10-nonafluorophenanthrene-2-yl group, 1,2,4,5,6,7,8,9,10-nonafluorophenanthrene-3-yl group, 2,7-difluorophenanthrene-9-yl group, 3,6-difluorophenanthrene-9-yl group , 1,2,3,4,5,6,7,8,10-nonafluorophenanthrene-9-yl group, 2-bromo-7-chlorophenanthrene-1-yl group, 6-bromo-3-chlorophenanthrene -1-yl group, 9-bromo-10-chlorophenanthrene-1-yl group, 3,6-dibromo-8-chlorophenanthrene-1-yl group, 7-bromo-3-chloro-9-iodophenanthrene-1 -Il group, 6-bromo-3-chlorophenanthrene-2-yl group, 9-bromo-10-iodophenanthrene-2-yl group, 6-bromo-3-chlorophenanthrene-9-yl group, 2-bromo- 7-Chlorophenanthrene-9-yl group, 3-bromo-5,6,7,8-tetrafluorophenanthrene-9-yl group, 2-chloroanthrene-1-yl group, 3-chloroanthrene-1-yl group , 4-Chloroanthrene-1-yl group, 5-chloroanthrene-1-yl group, 6- Chloroanthracene-1-yl group, 7-chloroanthracene-1-yl group, 8-chloroanthracene-1-yl group, 9-chloroanthracene-1-yl group, 10-chloroanthracene-1-yl group, 2, 4-Dichloroanthracene-1-yl group, 4,5-dichloroanthracene-1-yl group, 2,6-dichloroanthracene-1-yl group, 6,7-dichloroanthracene-1-yl group, 9,10- Dichloroanthracene-1-yl group, 2,3,4-trichloroanthracene-1-yl group, 4,8,10-trichloroanthracene-1-yl group, 2,9,10-trichloroanthracene-1-yl group, 4,5,9-Trichloroanthracene-1-yl group, 1-chloroanthracene-2-yl group, 3-chloroanthracene-2-yl group, 4-chloroanthracene-2-yl group, 5-chloroanthracene-2 -Il group, 6-chloroanthracene-2-yl group, 7-chloroanthracene-2-yl group, 8-chloroanthracene-2-yl group, 9-chloroanthracene-2-yl group, 10-chloroanthracene-2 -Il group, 1,3-dichloroanthracene-2-yl group, 1,5-dichloroanthracene-2-yl group, 1,8-dichloroanthracene-2-yl group, 6,7-dichloroanthracene-2-yl group Group, 9,10-dichloroanthracene-2-yl group, 1,5,9-trichloroanthracene-2-yl group, 1,8,9-trichloroanthracene-2-yl group, 5,6,7-trichloroanthracene -2-yl group, 1-chloroanthracene-9-yl group, 2-chloroanthracene-9-yl group, 3-chloroanthracene-9-yl group, 4-chloroanthracene-9-yl group, 10-chloroanthracene -9-yl group, 1,8-dichloroanthracene-9-yl group, 4,5-dichloroanthracene-9-yl group, 2,7-dichloroanthracene-9-yl group, 3,6-dichloroanthracene-9 -Il group, 2,3,6,7-tetrachloroanthracene-9-yl group, 2-bromoanthracene-1-yl group, 3-bromoanthracene-1-yl group, 4-bromoanthracene-1-yl group , 5-Bromoanthracene-1-yl group, 6-bromoanthracene-1-yl group, 7-bromoanthracene-1-yl group, 8-bromoanthracene-1-yl group, 9-bromoanthracene-1-yl group 10,-Bromoanthracene-1-yl group, 2 , 4-Dibromoanthracene-1-yl group, 4,5-dibromoanthracene-1-yl group, 2,6-dibromoanthracene-1-yl group, 6,7-dibromoanthracene-1-yl group, 9,10 -Dibromoanthracene-1-yl group, 2,3,4-tribromoanthracene-1-yl group, 4,8,10-tribromoanthracene-1-yl group, 2,9,10-tribromoanthracene-1 -Il group, 4,5,9-tribromoanthracene-1-yl group, 1-bromoanthracene-2-yl group, 3-bromoanthracene-2-yl group, 4-bromoanthracene-2-yl group, 5 -Bromoanthracene-2-yl group, 6-bromoanthracene-2-yl group, 7-bromoanthracene-2-yl group, 8-bromoanthracene-2-yl group, 9-bromoanthracene-2-yl group, 10 -Bromoanthracene-2-yl group, 1,3-dibromoanthracene-2-yl group, 1,5-dibromoanthracene-2-yl group, 1,8-dibromoanthracene-2-yl group, 6,7-dibromo Anthracene-2-yl group, 9,10-dibromoanthracene-2-yl group, 1,5,9-tribromoanthracene-2-yl group, 1,8,9-tribromoanthracene-2-yl group, 5 , 6,7-Tribromoanthracene-2-yl group, 1-bromoanthracene-9-yl group, 2-bromoanthracene-9-yl group, 3-bromoanthracene-9-yl group, 4-bromoanthracene-9 -Il group, 10-bromoanthracene-9-yl group, 1,8-dibromoanthracene-9-yl group, 4,5-dibromoanthracene-9-yl group, 2,7-dibromoanthracene-9-yl group, 3,6-Dibromoanthracene-9-yl group, 3-iodoanthracene-1-yl group, 5-iodoanthracene-1-yl group, 6-iodoanthracene-1-yl group, 10-iodoanthracene-1-yl group Group, 2,6-diiodoanthracene-1-yl group, 9,10-diiodoanthracene-1-yl group, 1-iodoanthracene-2-yl group, 3-iodoanthracene-2-yl group, 6- Iodoanthracene-2-yl group, 10-iodoanthracene-2-yl group, 9,10-diiodoanthracene-2-yl group, 3-iodoanthracene-9-yl group, 10-iodoanthracene-9-yl group , 2,9-diiodoanthracene-9-yl group, 3,6-diiodoanthracene Sen-9-yl group, 2,3,4,5,6,7,8,9,10-nonafluoroanthracene-1-yl group, 1,3,4,5,6,7,8,9, 10-Nonafluoroanthracene-2-yl group, 1,2,3,4,5,6,7,8,10-nonafluoroanthracene-9-yl group, 2-bromo-4-chloroanthracene-1-yl Group, 5-bromo-4-chloroanthracene-1-yl group, 2-bromo-6-iodoanthracene-1-yl group, 7-bromo-6-chloroanthracene-1-yl group, 9-bromo-10- Chloroanthracene-1-yl group and the like can be exemplified.

The aryl group having 6 to 14 carbon atoms substituted with the alkyl group having 1 to 18 carbon atoms represented by Ar ¹ was substituted with the above-mentioned aryl group having 6 to 14 carbon atoms by the alkyl group having 1 to 18 carbon atoms. It is a thing. The alkyl group having 1 to 18 carbon atoms may be a linear, branched or cyclic alkyl group, and is not particularly limited, but specifically, a methyl group, a cyclohexylmethyl group, an ethyl group, or 2 -Cyclopentylethyl group, propyl group, 2-methylpropyl group, 2,2-dimethylpropyl group, 3-cyclopropylpropyl group, isopropyl group, cyclopropyl group, butyl group, 2-methylbutyl group, 3-methylbutyl group, 3 -Methylbutane-2-yl group, tert-butyl group, cyclobutyl group, pentyl group, 2-methylpentyl group, 3-ethylpentyl group, 2,4-dimethylpentyl group, 2-pentyl group, 2-methylpentane-2 -Il group, 4,4-dimethylpentane-2-yl group, 3-pentyl group, 3-ethylpentane-3-yl group, cyclopentyl group, 2,5-dimethylcyclopentyl group, 3-ethylcyclopentyl group, hexyl group , 2-Methylhexyl group, 3,3-dimethylhexyl group, 4-ethylhexyl group, 2-hexyl group, 2-methylhexane-2-yl group, 5,5-dimethylhexane-2-yl group, 3-hexyl Group, 2,4-dimethylhexane-3-yl group, cyclohexyl group, 4-ethylcyclohexyl group, 4-propylcyclohexyl group, 4,4-dimethylcyclohexyl group, heptyl group, 2-heptyl group, 3-heptyl group, 4-Heptyl group, bicyclo [2.2.1] heptyl group, octyl group, 2-octyl group, 3-octyl group, 4-octyl group, cyclooctyl group, bicyclo [2.2.2] octyl group, nonyl Examples thereof include a group, a 5-nonyl group, a decyl group, a 2-decyl group, a 5-decyl group, an undecyl group, a dodecyl group, a tetradecyl group, an octadecyl group and the like. Of these, a linear alkyl group having 1 to 4 carbon atoms is preferable because the yield of the triazine compound (1) is good.

The aryl group having 6 to 14 carbon atoms substituted with the haloalkyl group having 1 to 8 carbon atoms represented by Ar ¹ was substituted with the above-mentioned aryl group having 6 to 14 carbon atoms by the haloalkyl group having 1 to 8 carbon atoms. It is a thing. The haloalkyl group having 1 to 8 carbon atoms may be a linear, branched or cyclic haloalkyl group, and is not particularly limited, but specifically, a trifluoromethyl group, a difluoromethyl group or a perfluoroethyl group. Group, 2,2,2-trifluoroethyl group, 1,1-difluoroethyl group, 2,2-difluoroethyl group, perfluoropropyl group, 2,2,3,3,3-pentafluoropropyl group, 2, 2,3,3-Tetrafluoropropyl group, 3,3,3-trifluoropropyl group, 1,1-difluoropropyl group, perfluoroisopropyl group, 2,2,2-trifluoro-1- (trifluoromethyl) Ethyl group, perfluorocyclopropyl group, 2,2,3,3-tetrafluorocyclopropyl group, perfluorobutyl group, 2,2,3,3,4,5,4-heptafluorobutyl group, 3,3,4 , 4,4-Pentafluorobutyl group, 4,4,4-trifluorobutyl group, 1,2,2,3,3,3-hexafluoro-1- (trifluoromethyl) propyl group, 1- (trifluoromethyl) propyl group Fluoromethyl) propyl group, 1-methyl-3,3,3-trifluoropropyl group, perfluorocyclobutyl group, 2,2,3,3,4,4-hexafluorocyclobutyl group, perfluoropentyl group, 2, 2,3,3,4,5,5,5-nonafluoropentyl group, 3,3,4,5,5,5-heptafluoropentyl group, 4,4,5,5,5- Pentafluoropentyl group, 5,5,5-trifluoropentyl group, 1,2,2,3,3,3-hexafluoro-1- (perfluoroethyl) propyl group, 2,2,3,3-3 Pentafluoro-1- (perfluoroethyl) propyl group, perfluorocyclopentyl group, perfluorohexyl group, 2,2,3,3,4,5,5,6,6,6-undecafluorohexyl group, 3, 3,4,4,5,5,6,6-Nonafluorohexyl group, 4,4,5,5,6,6,6-Heptafluorohexyl group, 5,5,6,6-6- Examples thereof include pentafluorohexyl group, 6,6,6-trifluorohexyl group, perfluorocyclohexyl group, chloromethyl group, bromomethyl group, iodomethyl group, 2-chloroethyl group, 3-bromopropyl group and the like.

R represents a halogen atom, an alkyl group having 1 to 18 carbon atoms, a haloalkyl group having 1 to 8 carbon atoms, a phenyl group, or a phenyl halide group.

The halogen atom represented by R is not particularly limited, and examples thereof include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

As the alkyl group having 1 to 18 carbon atoms represented by R, a group similar to the alkyl group having 1 to 18 carbon atoms exemplified in Ar ¹ can be exemplified.

As the haloalkyl group having 1 to 8 carbon atoms represented by R, a group similar to the haloalkyl group having 1 to 8 carbon atoms exemplified in Ar ¹ can be exemplified.

Examples of the halogenated phenyl group represented by R include a monohalophenyl group, a dihalophenyl group, a trihalophenyl group, a tetrahalophenyl group, and a pentahalophenyl group, and are not particularly limited, but specifically. 2-Chlorophenyl group, 3-chlorophenyl group, 4-chlorophenyl group, 2,3-dichlorophenyl group, 2,4-dichlorophenyl group, 2,5-dichlorophenyl group, 2,6-dichlorophenyl group, 3,4-dichlorophenyl group, 3,5-Dichlorophenyl group, 2,3,5-trichlorophenyl group, 3,4,5-trichlorophenyl group, 2,3,5,6-tetrachlorophenyl group, 2,3,4,5,6-penta Chlorophenyl group, 2-bromophenyl group, 3-bromophenyl group, 4-bromophenyl group, 2,3-dibromophenyl group, 2,4-dibromophenyl group, 2,5-dibromophenyl group, 2,6-dibromo Phenyl group, 3,4-dibromophenyl group, 3,5-dibromophenyl group, 2,3,5-tribromophenyl group, 3,4,5-tribromophenyl group, 2-iodophenyl group, 3-iodo Phenyl group, 4-iodophenyl group, 3,4-diiodophenyl group, 3,5-diiodophenyl group, 2-fluorophenyl group, 3-fluorophenyl group, 4-fluorophenyl group, 2,3-difluoro Phenyl group, 2,4-difluorophenyl group, 2,5-difluorophenyl group, 2,6-difluorophenyl group, 3,4-difluorophenyl group, 3,5-difluorophenyl group, 2,3,5-tri Fluorophenyl group, 3,4,5-trifluorophenyl group, 2,3,5,6-tetrafluorophenyl group, 2,3,4,5,6-pentafluorophenyl group, 2-bromo-3-chlorophenyl Group, 3-bromo-2-chlorophenyl group, 2-bromo-4-chlorophenyl group, 4-bromo-2-chlorophenyl group, 2-bromo-5-chlorophenyl group, 5-bromo-2-chlorophenyl group, 2-bromo -6-Chlorophenyl group, 3-bromo-4-chlorophenyl group, 4-bromo-3-chlorophenyl group, 3-bromo-5-chlorophenyl group, 4-bromo-3,5-difluorophenyl group, 3-bromo-5 Examples thereof include −iodophenyl group, 5-iodo-3-chlorophenyl group, 3-bromo-5-fluorophenyl group, 3-chloro-5-fluorophenyl group and the like. A mono, di or trihalophenyl group is preferable because the yield of the triazine compound (1) is good.

As an integer of 0 to 5 represented by n, 0, 1, 2 or 3 is preferable because the yield of the obtained triazine compound (1) is good.

When n is 2 to 5, the plurality of Rs may be the same or different from each other.

The triazine compound (1) obtained by the production method of the present invention is not particularly limited, and for example, the compounds having the structures shown in 1-1 to 1-239 below can be specifically shown.

Next, the production method of the present invention will be described.

The production method of the present invention is shown in the following steps 1 and 2.

(In the formula, Ar ¹ , R and n have the same meanings as described above.)
Step 1 is a step of reacting the acid chloride (2) with the amidine compound (3) to produce the acylamidine compound (4) used in step 2, and is a general condition for N-acylation reaction of amines. By applying the above, the acylamidine compound (4) can be obtained in good yield.

The acid chloride (2) used in step 1 can be produced by a general-purpose method familiar to those skilled in the art. For example, the acylamidine compound (4) can be obtained in high yield according to the method disclosed in "4th Edition Experimental Chemistry Course", Vol. 22, pp. 115-127, edited by the Chemical Society of Japan. Moreover, you may use a commercially available product.

The amidine compound (3) used in step 1 can be produced by a general-purpose method well known to those skilled in the art. Med. Chem. , 1990, Vol. 33, pp. 1230-1241, etc., the amidine compound (3) can be obtained in good yield. Moreover, you may use a commercially available product.

Further, the amidine compound (3) used in step 1 may be produced in a reaction system by mixing a chemically acceptable salt and a base thereof. The chemically acceptable salt of the amidin compound (3) may be either an inorganic acid salt or an organic acid salt, and the inorganic acid salt includes hydrochloride, bromide, sulfate, nitrate, perchlorate and phosphorus. Acid salts, silicates, tetrafluoroborates, hexafluorophosphates, etc. can be used as organic acid salts, such as acetates, citrates, fumarates, maleates, p-toluenesulfonates, and trifluo. Examples thereof include lomethanesulfonate and trifluoroacetate. Of these, inorganic acid salts are preferable in terms of low cost, and hydrochlorides are even more preferable.

The molar equivalent of the amidine compound (3) used in step 1 is preferably 1 equivalent or more with respect to the acid chloride (2).

By carrying out the step 1 in the presence of a base, the reaction yield of the acylamidine compound (4) can be improved. The base used may be either an inorganic base or an organic base, and the inorganic base includes metal hydroxides such as sodium hydroxide, potassium hydroxide and calcium hydroxide, and metals such as sodium carbonate, potassium carbonate, lithium carbonate and cesium carbonate. Metal acetates such as carbonates, potassium acetate and sodium acetate, metal phosphates such as potassium phosphate and sodium phosphate, metal hydrides such as sodium hydride, potassium hydride and calcium hydride, sodium methoxydo and potassium. Metallic alkyl oxides such as methoxydo, sodium ethoxide, potassium isopropyl oxide and potassium tert-butoxide, and tertiary alkyl amines such as trimethylamine, triethylamine, diisopropylethylamine and tributylamine as organic bases, pyridine, pyrazine, etc. Cyclic azines such as quinoline, N-methylpyrrolidin, N-methylpiperidin, N, N'-dimethylpiperazin, N-methylmorpholin, diazabicycloundecene, 1,4-diazabicyclo [2.2.2] octane and the like. Examples thereof include tertiary cyclic amines. In terms of good reaction yield of the acylamidine compound (4), an organic base is preferable, a tertiary alkylamine is more preferable, and triethylamine is particularly preferable.

The molar equivalent of the base used in step 1 may be 1 equivalent or more with respect to the acidified compound (2), but when the amidin compound (3) is produced from its chemically acceptable salt in the reaction system. May be added in an amount of 1 equivalent or more to each of the chemically acceptable salts of the acidified compound (2) and the amidin compound (3).

Step 1 can be carried out in a solvent. The solvent that can be used is not particularly limited, and any solvent that does not inhibit the reaction may be used. Specific examples of such a solvent include ethers such as diethyl ether, diisopropyl ether, dibutyl ether, cyclopentyl methyl ether (CPME), tetrahydrofuran (THF), 2-methyl tetrahydrofuran, 1,4-dioxane, and dimethoxyethane. Aromatic hydrocarbons such as benzene, toluene, xylene, mesityrene, nitrobenzene, anisole, or tetralin, dichloromethane, chloroform, 1,2-dichloroethane, 1,1,2,2-tetrachloroethane, dichlorobenzene, chlorobenzene, trichlorobenzene, Halogenized hydrocarbons such as 1-chloronaphthalene, methyl formate, ethyl formate, propyl formate, methyl acetate, ethyl acetate, butyl acetate, methyl propionate, ethyl propionate, methyl butyrate, esters such as γ-lactone, N, N Examples of amides such as −dimethylformamide (DMF), N, N-dimethylacetamide (DMAc), N-methylpyrrolidone (NMP), dimethylsulfoxide (DMSO), etc. can be exemplified, and these are mixed at an arbitrary ratio. You may use it. There is no particular limitation on the amount of solvent used. Of these, ether, aromatic hydrocarbon, halogenated hydrocarbon, or a mixed solvent thereof is preferably used from the viewpoint of good reaction yield in step 1, and diethyl ether or chloroform is more preferable.

The reaction temperature at which step 1 is carried out is not particularly limited, but it can be carried out at an appropriately selected temperature from -20 to 100 ° C., and the reaction yield of the acylamidine compound (4) is good. It is preferable to carry out at a temperature appropriately selected from 0 to 80 ° C.

The acyl amidine compound (4) can be obtained by carrying out a usual treatment after completion of the reaction of step 1. If necessary, it may be purified by recrystallization, column chromatography, sublimation, preparative HPLC or the like. Further, it may be subjected to step 2 without purification.

The acylamidine compound (4) can have tautomeric structures (4), (4a) and (4b) represented by the following formulas.

(In the formula, Ar ¹ , R and n have the same meanings as described above.)
Although the present invention includes all of these tautomers, it is described by the structure of the general formula (4) for convenience.

Step 2 is a step of reacting the acylamidine compound (4) with the amidin compound (3) to produce the triaryltriazine compound (1).

The molar equivalent of the amidine compound (3) used in step 2 is preferably 1 equivalent or more, preferably 1 to 30 equivalents, relative to the acylamidine compound (4), in terms of good yield of the triazine compound (1). It is more preferably in the range.

Further, the amidine compound (3) used in step 2 may be produced in a reaction system by mixing a chemically acceptable salt and a base thereof, as in step 1. At this time, the base used can be the same as the base exemplified in step 1, and in terms of the good yield of the triazine compound (1), a tertiary alkylamine or a metal carbonate is preferable, and triethylamine. Alternatively, sodium hydrogen carbonate is more preferable. The molar equivalent of the base to be used may be 1 equivalent or more added to the chemically acceptable salt of the amidine compound (3).

The yield of the triazine compound (1) can be improved by performing the step 2 in the presence of the silicon compound. The silicon compound is not particularly limited, but is represented by, for example, a silane compound represented by the general formula (5) described later, a silazane compound represented by the general formula (6), or a general formula (7). Trisilazane compounds are preferred.

The silane compound represented by the general formula (5) (hereinafter referred to as silane compound (5)) is represented by the following formula.

(In the formula, R ¹ and R ² each independently represent an alkyl group having 1 to 4 carbon atoms, an alkyloxy group having 1 to 4 carbon atoms, or a phenyl group. X ¹ and X ² independently represent each. , Hydrogen atom, halogen atom, or alkyloxy group having 1 to 4 carbon atoms.)
In the silane compound (5), the alkyl group having 1 to 4 carbon atoms represented by R ¹ or R ² may be a linear, branched or cyclic alkyl group, and is not particularly limited. Specific examples thereof include methyl group, ethyl group, vinyl group, propyl group, isopropyl group, cyclopropyl group, butyl group, 2-butyl group, isobutyl group, tert-butyl group, cyclobutyl group and the like. Of these, a linear alkyl group having 1 to 4 carbon atoms is preferable, and a methyl group is more preferable, because the yield of the triazine compound (1) is good.

In the silane compound (5), the alkyloxy group having 1 to 4 carbon atoms represented by R ¹ or R ² may be a linear, branched or cyclic alkyloxy group, and is not particularly limited. , Specifically, methoxy group, ethoxy group, 1-methylethyloxy group, 1,1-dimethylethyloxy group, propyloxy group, 1-methylpropyloxy group, cyclopropyloxy group, butyloxy group, or cyclobutyl. An oxy group and the like can be exemplified. Of these, a linear alkyloxy group having 1 to 4 carbon atoms is preferable, and an ethoxy group is more preferable, because the yield of the triazine compound (1) is good.

In the silane compound (5), the halogen atom represented by X ¹ or X ² is not particularly limited, and examples thereof include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. A chlorine atom is preferable because it is inexpensive and has good reactivity.

In the silane compound (5), examples of the alkyloxy group having 1 to 4 carbon atoms represented by X ¹ or X ² are the same as those of the alkyloxy group having 1 to 4 carbon atoms exemplified by R ¹ or R ^2. Of these, a linear alkyloxy group having 1 to 4 carbon atoms is preferable, and an ethoxy group is more preferable, because the yield of the triazine compound (1) is good.

In the silane compound (5), a hydrogen atom is preferable as X ¹ or X ² .

The silane compound (5) preferably used in the step 2 is not particularly limited, but for example, the compounds having the structures shown in 5-1 to 5-75 below can be specifically shown.

Of the silane compounds (5) shown in 5-1 to 5-75, 5-2, 5-9 and 5-12 are preferable.

The silazane compound represented by the general formula (6) (hereinafter, referred to as the silazane compound (6)) is represented by the following formula.

(In the formula, R ³ , R ⁴ , R ⁵ and R ⁶ each independently represent an alkyl group or a phenyl group having 1 to 4 carbon atoms. X ³ represents a hydrogen atom.)
In the silazane compound (6), the alkyl group having 1 to 4 carbon atoms represented by R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ or R ⁸ has 1 carbon atom as exemplified by R ¹ or R ^2. Examples of alkyl groups of ~ 4 can be exemplified, and among them, a linear alkyl group having 1 to 4 carbon atoms is preferable, and a methyl group is more preferable, in terms of good yield of the triazine compound (1).

The silazane compound (6) preferably used in the step 2 is not particularly limited, but for example, the compounds having the structures shown in 6-1 to 6-39 below can be specifically exemplified.

Of the silazane compounds (6) shown in 6-1 to 6-39, 6-1 is preferable.

The trisilazane compound represented by the general formula (7) (hereinafter, referred to as tricillazan compound (7)) is represented by the following formula.

(In the formula, R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ and R ¹² each independently represent an alkyl group or a phenyl group having 1 to 4 carbon atoms.)
In the trisilazane compound (7), the alkyl group having 1 to 4 carbon atoms represented by R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ and R ¹² has 1 carbon atom as exemplified by R ¹ or R ^2. Examples of alkyl groups of ~ 4 can be exemplified, and among them, a linear alkyl group having 1 to 4 carbon atoms is preferable, and a methyl group is more preferable, in terms of good yield of the triazine compound (1).

The trisilazane compound (7) preferably used in the step 2 is not particularly limited, but for example, the compounds having the structures shown in 7-1 to 7-18 below can be specifically exemplified.

Of the trisilazane compounds (7) shown in 7-1 to 7-18, 7-2 is preferable.

The molar equivalent of the silicon compound used in step 2 is preferably in the range of 0.1 to 100 equivalents, more preferably in the range of 1 to 10 equivalents, relative to the acylamidine compound (4).

Step 2 can be carried out in a solvent. The solvent that can be used is not particularly limited, and any solvent that does not inhibit the reaction may be used. Specific examples of such a solvent include ethers such as diisopropyl ether, dibutyl ether, CPME, THF, 2-methylhydrocarbon, 1,4-dioxane and dimethoxyethane, benzene, toluene, xylene, mesityrene, nitrobenzene and anisole. , Or aromatic hydrocarbons such as tetralin, dichloromethane, chloroform, 1,2-dichloroethane, 1,1,2,2-tetrachloroethane, dichlorobenzene, chlorobenzene, trichlorobenzene, halogenated hydrocarbons such as 1-chloronaphthalene, Examples of amides such as DMF, DMAc and NMP, benzonitrile, DMSO and the like can be exemplified, and these may be mixed and used in any ratio. There is no particular limitation on the amount of solvent used. Of these, benzonitrile, DMSO, aromatic hydrocarbons, halogenated hydrocarbons, or a mixed solvent thereof is preferably used, and xylene is more preferable, because the reaction yield in step 2 is good.

Step 2 can be carried out at a temperature appropriately selected from 60 to 200 ° C., and can be carried out at a temperature appropriately selected from 100 to 160 ° C. because the yield of the triazine compound (1) is good. preferable.

The triazine compound (1) can be obtained by carrying out a usual treatment after completion of the reaction in step 2. If necessary, it may be purified by recrystallization, column chromatography, sublimation, preparative HPLC or the like.

The production method of the present invention is shown in the next step 3.

(In the formula, Ar ¹ , R and n have the same meanings as described above.)
Step 3 is a step of reacting the acid chloride (2) with the amidine compound (3) to produce the triazine compound (1).

The molar equivalent of the amidine compound (3) used in step 3 is preferably 1 equivalent or more with respect to the acid chloride (2).

By carrying out the step 3 in the presence of a base, the reaction yield of the triazine compound (1) can be improved. As the base to be used, the same bases as those exemplified in step 1 can be exemplified. Among them, a tertiary alkylamine or a metal carbonate is preferable, and triethylamine is more preferable, because the reaction yield of the triazine compound (1) is good. The molar equivalent of the base to be used may be 1 equivalent or more with respect to the acidified compound (2), but when the amidin compound (3) is produced from the chemically acceptable salt thereof in the reaction system, it may be used. One equivalent or more may be added to each of the chemically acceptable salts of the acidified compound (2) and the amidin compound (3).

The reaction yield of the triazine compound (1) can be improved by performing the step 3 in the presence of the silicon compound. Examples of the silicon compound include the silane compound (5) shown in steps 5-1 to 5-47 and the silazane compound (6) shown in 6-1 to 6-57, among others. The silazane compound (6) is preferable, and 6-1 is particularly preferable, because the reaction yield of the triazine compound (1) is good. The molar equivalent of the silicon compound used is preferably in the range of 0.1 to 100 equivalents with respect to the acid chloride (2), and more preferably in the range of 1 to 10 equivalents.

Step 3 can be carried out in a solvent. The solvent that can be used is not particularly limited, and any solvent that does not inhibit the reaction may be used. As such a solvent, the solvent exemplified in Step 2 can be exemplified, and benzonitrile, DMSO, aromatic hydrocarbons, halogenated hydrocarbons, or a mixed solvent thereof can be used because the yield of triazine is good. It is preferable to use, and xylene is more preferable.

Step 3 can be carried out at a temperature appropriately selected from -20 to 200 ° C. and a reaction time appropriately selected from 1 to 24 hours. In terms of the good yield of the triazine compound (1), the reaction was carried out at a temperature appropriately selected from 0 to 80 ° C. for 0.5 to 5 hours, and then 0 at an appropriately selected temperature from 100 to 160 ° C. It is preferable to carry out the reaction for 5 to 10 hours.

When a base and a silicon compound are used in step 3, they may be added to the reaction system in advance to carry out the reaction, but first the base is added and then the temperature is appropriately selected from 0 to 80 ° C. The reaction yield of the triazine compound (1) can be increased by carrying out the reaction for 5 to 5 hours, then adding a silicon compound, and carrying out the reaction at an appropriately selected temperature from 100 to 160 ° C. for 0.5 to 10 hours. It is preferable in terms of good points.

The triazine compound (1) can be obtained by carrying out a usual treatment after completion of the reaction in step 3. If necessary, it may be purified by recrystallization, column chromatography, sublimation, preparative HPLC or the like.

By using the production method of the present invention, a triazine compound useful as a synthetic intermediate for a charge transport material used in an organic electroluminescent device can be easily and inexpensively obtained.

Hereinafter, the present invention will be described in more detail with reference to Examples and Reference Examples, but the present invention is not construed as being limited thereto.

The following analytical methods were used to identify the triazine compound and the 4,6-dichlorotriazine compound obtained by the production method of the present invention. Bruker ASCEND 400 (400 MHz and 376 MHz) was used for ¹ H-NMR and ¹⁹ F-NMR measurements. ^{1 1} H-NMR was measured using deuterated chloroform (CDCl ₃ ) and heavy toluene (Toluene-d ₈ ) as measurement solvents and tetramethylsilane (TMS) as an internal standard substance. In addition, commercially available reagents were used.

Example-1

N- (3-Bromo-5-chlorobenzoyl) benzamidine (68 mg, 0.2 mmol) and benzamidine (48 mg, 0.4 mmol) were suspended in xylene (1.5 mL) under an argon stream. To this suspension was added 2,2,4,4,6,6-hexamethylcyclotrisilazane (475 μL, 2.0 mmol), and the mixture was stirred at 150 ° C. for 6 hours. After allowing to cool, methanol was added to the reaction mixture and the solid was filtered off. The solid was washed with methanol and then hexane. The obtained solid was dried under reduced pressure to give the desired 2- (3-bromo-5-chlorophenyl) -4,6-diphenyl-1,3,5-triazine as a white solid (73 mg, 86%).
^{1 1} H-NMR (400 MHz, CDCl ₃ ): δ8.79 (dd, J = 1.6 Hz, 1.8 Hz, 1H), δ8.74-8.79 (m, 4H), 8.68 (dd, J) = 1.6, 2.0Hz, 1H), 7.75 (dd, J = 1.8Hz, 2.0Hz, 1H), 7.58-7.67 (m, 6H).
Example-2
The same operation as in Example 1 was carried out except that the amount of 2,2,4,4,6,6-hexamethylcyclotrisilazane was changed to 0.6 mmоl (145 μL), and the desired 2- (3-bromo) was performed. 65 mg (77%) of -5-chlorophenyl) -4,6-diphenyl-1,3,5-triazine was obtained.
Example-3
The same operation as in Example 1 was carried out except that the amount of 2,2,4,4,6,6-hexamethylcyclotrisilazane was changed to 0.2 mmоl (48 μL), and the desired 2- (3-bromo) was performed. -5-Chlorophenyl) -4,6-diphenyl-1,3,5-triazine was obtained in 47 mg (56%).
Example-4
Same as Example-1 except that 1,1,3,3-tetramethyldisilazane (350 μL, 2.0 mmol) was used instead of 2,2,4,4,6,6-hexamethylcyclotrisilazan. To obtain the desired 2- (3-bromo-5-chlorophenyl) -4,6-diphenyl-1,3,5-triazine in 69 mg (82%).
Example-5
The same operation as in Example-1 was carried out except that diphenylsilane (111 μL, 0.6 mmol) was used instead of 2,2,4,4,6,6-hexamethylcyclotrisilazan, and the desired 2- ( 3-Bromo-5-chlorophenyl) -4,6-diphenyl-1,3,5-triazine was obtained in 54 mg (64%).
Example-6
The same operation as in Example-1 was carried out except that chlorodimethylsilane (111 μL, 1.0 mmol) was used instead of 2,2,4,4,6,6-hexamethylcyclotrisilazan, and the desired 2- (3-Bromo-5-chlorophenyl) -4,6-diphenyl-1,3,5-triazine was obtained in 56 mg (66%).
Example-7
The same operation as in Example-1 was carried out except that triethoxysilane (111 μL, 0.6 mmol) was used instead of 2,2,4,4,6,6-hexamethylcyclotrisilazane, and the desired 2- 32 mg (38%) of (3-bromo-5-chlorophenyl) -4,6-diphenyl-1,3,5-triazine was obtained.
Example-8
N- (3-Bromo-5-chlorobenzoyl) benzamidine (68 mg, 0.2 mmol) and benzamidine (481 mg, 4.0 mmol) were suspended in xylene (0.2 mL) under an argon stream. The suspension was stirred at 150 ° C. for 6 hours. After allowing to cool, methanol was added to the reaction mixture and the solid was filtered off. The solid was washed with methanol. The obtained solid was dried under reduced pressure to give the desired 2- (3-bromo-5-chlorophenyl) -4,6-diphenyl-1,3,5-triazine as a white solid (54 mg, 63%).
Example-9
The same procedure as in Example-8 was carried out except that benzonitrile (1.5 mL) was used instead of xylene, and the desired 2- (3-bromo-5-chlorophenyl) -4,6-diphenyl-1,3 was performed. , 5-Triazine was obtained in 54 mg (64%).
Example-10
N- (3-Bromo-5-chlorobenzoyl) benzamidine (170 mg, 0.5 mmol) and benzamidine (120 mg, 1.0 mmol) were suspended in dibutyl ether (1.5 mL) under an argon stream. The suspension was stirred at 150 ° C. for 6 hours. After allowing to cool, methanol was added to the reaction mixture and the solid was filtered off. The solid was washed with methanol. The obtained solid was dried under reduced pressure to give the desired 2- (3-bromo-5-chlorophenyl) -4,6-diphenyl-1,3,5-triazine as a white solid (55 mg, 26%).
Example-11
Benzamidine hydrochloride (63 mg, 0.4 mmol) was suspended in xylene (1.5 mL) under an argon stream. Sodium bicarbonate (34 mg, 0.4 mmol), N- (3-bromo-5-chlorobenzoyl) benzamidine (68 mg, 0.2 mmol) and 2,2,4,4,6,6-hexa in this suspension Methylcyclotrisilazane (145 μL, 0.6 mmol) was added, and the mixture was stirred at 150 ° C. for 6 hours. After allowing to cool, the low boiling point was distilled off from the reaction mixture under reduced pressure, water was added to the obtained residue, and the solid was filtered off. The obtained solid was dried under reduced pressure to give the desired 2- (3-bromo-5-chlorophenyl) -4,6-diphenyl-1,3,5-triazine as a white solid (75 mg, 89%).
Example-12
The same procedure as in Example-11 was carried out except that sodium hydrogen carbonate was not added, and 54 mg of the target 2- (3-bromo-5-chlorophenyl) -4,6-diphenyl-1,3,5-triazine was added ( 64%) obtained.
Example-13
Same as Example-12 except that 1,1,3,3-tetramethyldisilazane (105 μL, 0.6 mmol) was used instead of 2,2,4,4,6,6-hexamethylcyclotrisilazan. To obtain 53 mg (62%) of the desired 2- (3-bromo-5-chlorophenyl) -4,6-diphenyl-1,3,5-triazine.
Example-14
The same procedure as in Example-13 was carried out except that the amount of 1,1,3,3-tetramethyldisilazane was changed to 2.0 mmоl (351 μL), and the desired 2- (3-bromo-5-chlorophenyl) was obtained. 64 mg (76%) of -4,6-diphenyl-1,3,5-triazine was obtained.
Example-15
3-Bromo-5-chlorobenzoyl chloride (51 mg, 0.2 mmol) and benzamidine (481 mg, 4.0 mmol) were suspended in xylene (0.2 mL) under an argon stream. The suspension was stirred at 150 ° C. for 6 hours. After allowing to cool, water was added to the reaction mixture and the solid was filtered off. The solid was washed with water and methanol. The obtained solid was dried under reduced pressure to give the desired 2- (3-bromo-5-chlorophenyl) -4,6-diphenyl-1,3,5-triazine as a white solid (32 mg, 37%).
Example-16
Benzamidine hydrochloride (940 mg, 6.0 mmol) was suspended in xylene (15.0 mL) under an argon stream. The suspension is cooled to 0 ° C., triethylamine (840 μL, 6.0 mmol) and 3-bromo-5-chlorobenzoyl chloride (508 mg, 2.0 mmol) are added, 0 ° C. for 30 minutes, and 60 ° C. for 3 Stirred for hours. After allowing to cool, 1,1,3,3-tetramethyldisilazane (1.04 mL, 6.0 mmol) was added to the reaction mixture, and the mixture was stirred at 150 ° C. for 5 hours. After allowing to cool, the low boiling point was distilled off from the reaction mixture under reduced pressure, water was added to the obtained residue, and the solid was filtered off. The solid was washed with water, methanol and then hexane. The obtained solid was dried under reduced pressure to give the desired 2- (3-bromo-5-chlorophenyl) -4,6-diphenyl-1,3,5-triazine as a white solid (624 mg, 74%).
Example-17
The same procedure as in Example-16 was carried out except that the amount of 1,1,3,3-tetramethyldisilazane was changed to 4.0 mmоl (700 μL), and the desired 2- (3-bromo-5-chlorophenyl) was used. 611 mg (70%) of -4,6-diphenyl-1,3,5-triazine was obtained.
Example-18
The same procedure as in Example-16 was carried out except that the amount of triethylamine was changed to 10 mmоl (1.40 mL), and the desired 2- (3-bromo-5-chlorophenyl) -4,6-diphenyl-1,3 was performed. 579 mg (69%) of 5-triazine was obtained.
Example-19
The same procedure as in Example-16 was carried out except that diisopropylethylamine (1.05 mL, 6.0 mmol) was used instead of triethylamine, and the desired 2- (3-bromo-5-chlorophenyl) -4,6-diphenyl was performed. 410 mg (48%) of -1,3,5-triazine was obtained.
Example-20
The same procedure as in Example-16 was carried out except that tributylamine (1.45 mL, 6.0 mmol) was used instead of triethylamine, and the desired 2- (3-bromo-5-chlorophenyl) -4,6-diphenyl was performed. 494 mg (58%) of -1,3,5-triazine was obtained.
Example-21
The same procedure as in Example-16 was carried out except that N-methylmorpholine (660 μL, 6.0 mmol) was used instead of triethylamine, and the desired 2- (3-bromo-5-chlorophenyl) -4,6-diphenyl was performed. 454 mg (54%) of -1,3,5-triazine was obtained.
Example-22
Benzamidine hydrochloride (188 mg, 1.2 mmol) was suspended in xylene (3.0 mL) under an argon stream. The suspension is cooled to 0 ° C., triethylamine (275 μL, 2.0 mmol) and 3-bromo-5-chlorobenzoyl chloride (102 mg, 0.4 mmol) are added, 0 ° C. for 30 minutes, and 60 ° C. for 3 Stirred for hours. After allowing to cool, 1,1,3,3-tetramethyldisilazane (210 μL, 1.2 mmol) was added to the reaction mixture, and the mixture was stirred at 100 ° C. for 8 hours. After allowing to cool, the low boiling point was distilled off from the reaction mixture under reduced pressure, water was added to the obtained residue, and the solid was filtered off. The solid was washed with water, methanol and then hexane. The obtained solid was dried under reduced pressure to give the desired 2- (3-bromo-5-chlorophenyl) -4,6-diphenyl-1,3,5-triazine as a white solid (89 mg, 53%).
Example-23
Benzamidine hydrochloride (188 mg, 1.2 mmol) was suspended in xylene (3.0 mL) under an argon stream. The suspension is cooled to 0 ° C., triethylamine (165 μL, 1.2 mmol) and 1,1,3,3-tetramethyldisilazane (210 μL, 1.2 mmol) are added, and at 0 ° C. for 30 minutes for an additional 60. The mixture was stirred at ° C. for 30 minutes. After stirring, 3-bromo-5-chlorobenzoyl chloride (102 mg, 0.4 mmol) was added to the reaction mixture, and the mixture was further stirred at 60 ° C. for 30 minutes and further at 150 ° C. for 5 hours and 30 minutes. After allowing to cool, water was added to the reaction mixture and the solid was filtered off. The solid was washed with methanol, water and then hexane. The obtained solid was dried under reduced pressure to give the desired 2- (3-bromo-5-chlorophenyl) -4,6-diphenyl-1,3,5-triazine as a white solid (92 mg, 55%).
Example-24

4-Methylbenzamidine hydrochloride (512 mg, 3.0 mmol) was suspended in xylene (7.5 mL) under an argon stream. The suspension is cooled to 0 ° C., triethylamine (420 μL, 3.0 mmol) and 3-bromo-5-chlorobenzoyl chloride (254 mg, 1.0 mmol) are added, 0 ° C. for 30 minutes, and 60 ° C. for 3 Stirred for hours. After allowing to cool, 1,1,3,3-tetramethyldisilazane (520 μL, 3.0 mmol) was added to the reaction mixture, and the mixture was stirred at 150 ° C. for 5 hours. After allowing to cool, the low boiling point was distilled off from the reaction mixture under reduced pressure, water was added to the obtained residue, and the solid was filtered off. The solid was washed with water, methanol and then hexane. The obtained solid was dried under reduced pressure to give the desired 2- (3-bromo-5-chlorophenyl) -4,6-bis (4-methylphenyl) -1,3,5-triazine as a white solid ( 323 mg, 72%).
^{1 1} H-NMR (400 MHz, CDCl ₃ ): 8.74 (m, 1H: coalcing to d, J = 1.1 Hz by irr. At 8.63 ppm), 8.63 (dd, J = 1.8, 1) .6Hz, 1H), 8.61 (d, J = 8.1Hz, 4H), 7.72 (m, 1H: coalcing to d, J = 1.1Hz by irr. At 8.63ppm), 7.37 (D, J = 8.1Hz, 4H), 2.48 (s, 6H).
Example-25

4-Chlorobenzamidine hydrochloride (574 mg, 3.0 mmol) was suspended in xylene (7.5 mL) under an argon stream. The suspension is cooled to 0 ° C., triethylamine (420 μL, 3.0 mmol) and 3-bromo-5-chlorobenzoyl chloride (254 mg, 1.0 mmol) are added, 0 ° C. for 30 minutes, and 60 ° C. for 3 Stirred for hours. After allowing to cool, 1,1,3,3-tetramethyldisilazane (520 μL, 3.0 mmol) was added to the reaction mixture, and the mixture was stirred at 150 ° C. for 5 hours. After allowing to cool, the low boiling point was distilled off from the reaction mixture under reduced pressure, water was added to the obtained residue, and the solid was filtered off. The solid was washed with water, methanol and then hexane. The obtained solid was dried under reduced pressure to give the desired 2- (3-bromo-5-chlorophenyl) -4,6-bis (4-chlorophenyl) -1,3,5-triazine as a white solid (374 mg). , 76%).
^{1 1} H-NMR (400 MHz, CDCl ₃ ): 8.74 (m, 1H: coalcing to d, J = 1.2 Hz by irr. At 8.64 ppm), 8.68 (d, J = 8.7 Hz, 4H) ), 8.64 (dd, J = 1.9, 1.5Hz, 1H), 7.77 (m, 1H: coalcing to d, J = 1.2Hz by irr. At 8.64ppm), 7.57 (D, J = 8.7Hz, 4H).
Example-26

4-Bromobenzamidine hydrochloride (707 mg, 3.0 mmol) was suspended in xylene (7.5 mL) under an argon stream. The suspension is cooled to 0 ° C., triethylamine (420 μL, 3.0 mmol) and 3-bromo-5-chlorobenzoyl chloride (254 mg, 1.0 mmol) are added, 0 ° C. for 30 minutes, and 60 ° C. for 3 Stirred for hours. After allowing to cool, 1,1,3,3-tetramethyldisilazane (520 μL, 3.0 mmol) was added to the reaction mixture, and the mixture was stirred at 150 ° C. for 5 hours. After allowing to cool, the low boiling point was distilled off from the reaction mixture under reduced pressure, water was added to the obtained residue, and the solid was filtered off. The solid was washed with water, methanol and then hexane. The obtained solid was dried under reduced pressure to give the desired 2- (3-bromo-5-chlorophenyl) -4,6-bis (4-bromophenyl) -1,3,5-triazine as a white solid ( 443 mg, 76%).
^{1 1} H-NMR (400 MHz, CDCl ₃ ): 8.74 (m, 1H: coalcing to d, J = 1.3 Hz by irr. At 8.64 ppm), 8.64 (dd, J = 1.7, 1) .6Hz, 1H), 8.60 (d, J = 8.6Hz, 4H), 7.77 (m, 1H: coalcing to d, J = 1.3Hz by irr. At 8.64ppm), 7.73 (D, J = 8.6Hz, 4H).
Example-27

Benzamidine hydrochloride (470 mg, 3.0 mmol) was suspended in xylene (7.5 mL) under an argon stream. The suspension was cooled to 0 ° C., triethylamine (420 μL, 3.0 mmol) and 3-bromobenzoyl chloride (130 μL, 1.0 mmol) were added, and the mixture was stirred at 0 ° C. for 30 minutes and further at 60 ° C. for 3 hours. After allowing to cool, 1,1,3,3-tetramethyldisilazane (520 μL, 3.0 mmol) was added to the reaction mixture, and the mixture was stirred at 150 ° C. for 5 hours. After allowing to cool, the low boiling point was distilled off from the reaction mixture under reduced pressure, water was added to the obtained residue, and the solid was filtered off. The solid was washed with water, methanol and then hexane. The obtained solid was dried under reduced pressure to give the desired 2- (3-bromophenyl) -4,6-diphenyl-1,3,5-triazine as a white solid (278 mg, 72%).
^{1 1} H-NMR (400 MHz, CDCl ₃ ): 8.91 (brs, 1H), 8.75-8.81 (m, 4H), 8.72 (ddd, J = 7.9, 1.4, 1) .1Hz, 1H), 7.74 (ddd, J = 7.9, 2.0, 1.1Hz, 1H), 7.56-7.67 (m, 6H), 7.46 (dd, J = 7.9, 7.9Hz, 1H).
Example-28

4-Fluorobenzamidine hydrochloride hydrate (524 mg, 3.0 mmol) was suspended in chloroform, triethylamine (420 μL, 3.0 mmol) was added, and the mixture was stirred at room temperature for 3 hours. A small amount of methanol and sodium sulfate were added to the reaction mixture, and the mixture was stirred at room temperature for 30 minutes. The desiccant was separated by filtration, the low boiling point was distilled off from the reaction mixture under reduced pressure, and the mixture was dried under reduced pressure to obtain a white solid of 4-fluorobenzamidine. This product was used in the next step without purification.

The obtained 4-fluorobenzamidine (531 mg) was suspended in xylene (7.5 mL) under an argon stream. The suspension is cooled to 0 ° C., triethylamine (140 μL, 1.0 mmol) and 3-bromo-5-chlorobenzoyl chloride (254 mg, 1.0 mmol) are added, 0 ° C. for 30 minutes, and 60 ° C. for 3 Stirred for hours. After allowing to cool, 1,1,3,3-tetramethyldisilazane (520 μL, 3.0 mmol) was added to the reaction mixture, and the mixture was stirred at 150 ° C. for 5 hours. After allowing to cool, the low boiling point was distilled off from the reaction mixture under reduced pressure, water was added to the obtained residue, and the solid was filtered off. The solid was washed with water, methanol and then hexane. The obtained solid was dried under reduced pressure to give the desired 2- (3-bromo-5-chlorophenyl) -4,6-bis (4-fluorophenyl) -1,3,5-triazine as a white solid ( 210 mg, 46%).
^{1 1} H-NMR (400 MHz, Toluene-d ₈ ): 8.72 (m, 1H: coalescing to d, J = 1.1 Hz by irr. At 8.65 ppm), 8.59 (dd, J = 1.8) , 1.5Hz, 1H), 8.50 (dd, J = 8.9, 5.6Hz, 4H), 7.41 (m, 1H: coalcing to d, J = 1.1Hz by irr. At 8. 65 ppm), 6.84-6.90 (m, 4H).
¹⁹ F-NMR (376 MHz, CDCl ₃ ): −106.04 (s, 2F).
Example-29

3-Iodobenzamidine hydrochloride (845 mg, 3.0 mmol) was suspended in xylene (7.5 mL) under an argon stream. The suspension is cooled to 0 ° C., triethylamine (420 μL, 3.0 mmol) and 3-bromo-5-chlorobenzoyl chloride (254 mg, 1.0 mmol) are added, 0 ° C. for 30 minutes, and 60 ° C. for 3 Stirred for hours. After allowing to cool, 1,1,3,3-tetramethyldisilazane (520 μL, 3.0 mmol) was added to the reaction mixture, and the mixture was stirred at 150 ° C. for 5 hours. After allowing to cool, the low boiling point was distilled off from the reaction mixture under reduced pressure, water was added to the obtained residue, and the solid was filtered off. The solid was washed with water, methanol and then hexane. The obtained solid was dried under reduced pressure to give the desired 2- (3-bromo-5-chlorophenyl) -4,6-bis (3-iodophenyl) -1,3,5-triazine as a white solid ( 508 mg, 75%).
^{1 1} H-NMR (400 MHz, CDCl ₃ ): 9.02 (dd, J = 1.6, 1.5 Hz, 2H), 8.73 (m, 1H: coalcing to d, J = 1.4 Hz by irr. at 8.63ppm), 8.70 (brd, J = 7.9Hz, 2H), 8.63 (dd, J = 1.8, 1.5Hz, 1H), 7.98 (ddd, J = 7. 8,1.6,1.1Hz, 2H), 7.77 (m, 1H: coalescating to d, J = 1.4Hz by irr. At 8.63ppm), 7.34 (dd, J = 7.9) , 7.8Hz, 2H).
Example-30

3-Biphenylamidine hydrochloride (698 mg, 3.0 mmol) was suspended in xylene (7.5 mL) under an argon stream. The suspension is cooled to 0 ° C., triethylamine (420 μL, 3.0 mmol) and 3,5-dibromobenzoyl chloride (298 mg, 1.0 mmol) are added, and the mixture is stirred at 0 ° C. for 30 minutes and further at 60 ° C. for 3 hours. did. After allowing to cool, 1,1,3,3-tetramethyldisilazane (520 μL, 3.0 mmol) was added to the reaction mixture, and the mixture was stirred at 150 ° C. for 5 hours. After allowing to cool, the low boiling point was distilled off from the reaction mixture under reduced pressure, water was added to the obtained residue, and the solid was filtered off. The solid was washed with water, methanol and then hexane. The obtained solid was dried under reduced pressure to give the desired 2- (3,5-dibromophenyl) -4,6-bis (3-biphenyl) -1,3,5-triazine as a white solid (396 mg, 64%).
^{1 1} H-NMR (400 MHz, CDCl ₃ ): 8.97 (brs, 2H), 8.83 (d, J = 1.8 Hz, 2H), 8.74 (ddd, J = 7.8, 1.5) , 1.2Hz, 2H), 7.91 (t, J = 1.8Hz, 1H), 7.87 (ddd, J = 7.7, 1.8, 1.2Hz, 2H), 7.74- 7.76 (m, 4H), 7.68 (dd, J = 7.8, 7.7Hz, 2H), 7.54 (dd, J = 7.8, 7.3Hz, 4H), 7.42 -7.46 (m, 2H).
Example-31

3-Fluorobenzamidine hydrochloride (524 mg, 3.0 mmol) was suspended in xylene (7.5 mL) under an argon stream. The suspension is cooled to 0 ° C., triethylamine (420 μL, 3.0 mmol) and 2,5-dichlorobenzoyl chloride (210 mg, 1.0 mmol) are added, and the mixture is stirred at 0 ° C. for 30 minutes and further at 60 ° C. for 3 hours. did. After allowing to cool, 1,1,3,3-tetramethyldisilazane (520 μL, 3.0 mmol) was added to the reaction mixture, and the mixture was stirred at 150 ° C. for 5 hours. After allowing to cool, the low boiling point was distilled off from the reaction mixture under reduced pressure, water was added to the obtained residue, and the solid was filtered off. The solid was washed with water, methanol and then hexane. The obtained solid was dried under reduced pressure to give the desired 2- (2,5-dichlorophenyl) -4,6-bis (3-fluorophenyl) -1,3,5-triazine as a white solid (200 mg, 48%).
^{1 1} H-NMR (400 MHz, CDCl ₃ ): 8.53 (ddd, J = 7.8, 1.4, 1.1 Hz, 2H), 8.41 (ddd, J = 9.9 Hz, J = 2. 7Hz, J = 1.4Hz, 2H), 8.15 (d, J = 2.6Hz, 1H), 7.56 (ddd, J = 8.2,7.8,5.6Hz, 2H), 7 .54 (d, J = 8.6Hz, 1H), 7.47 (dd, J = 8.6, 2.6Hz, 1H), 7.33 (dddd, J = 8.3,8.2,2) , 7, 1.1Hz, 2H).
¹⁹ F-NMR (376 MHz, CDCl ₃ ): -112.22 (s, 2F).
Example-32

3-Bromo-5-chlorobenzamidine hydrochloride (810 mg, 3.0 mmol) was suspended in xylene (7.5 mL) under an argon stream. The suspension was cooled to 0 ° C., triethylamine (420 μL, 3.0 mmol) and 4-iodobenzoyl chloride (267 mg, 1.0 mmol) were added, and the mixture was stirred at 0 ° C. for 30 minutes and further at 60 ° C. for 3 hours. After allowing to cool, 1,1,3,3-tetramethyldisilazane (520 μL, 3.0 mmol) was added to the reaction mixture, and the mixture was stirred at 150 ° C. for 5 hours. After allowing to cool, the low boiling point was distilled off from the reaction mixture under reduced pressure, water was added to the obtained residue, and the solid was filtered off. The solid was washed with water, methanol and then hexane. The obtained solid was dried under reduced pressure, and then the desired 2,4-bis (3-bromo-5-chlorophenyl) -6- (4-iodophenyl) -1,3,5-triazine was subjected to preparative HPLC. Was obtained as a white solid (293 mg, 44%).
^{1 1} H-NMR (400 MHz, CDCl ₃ ): 8.73 (dd, J = 1.6, 1.5 Hz, 2H), 8.63 (dd, J = 1.7, 1.5 Hz, 2H), 8 .44 (d, J = 8.6Hz, 2H), 7.96 (d, J = 8.6Hz, 2H), 7.78 (brs, 2H).
Example-33

Benzamidine hydrochloride (470 mg, 3.0 mmol) was suspended in xylene (7.5 mL) under an argon stream. The suspension is cooled to 0 ° C., triethylamine (420 μL, 3.0 mmol) and 2,3,4,5-tetrachlorobenzoyl chloride (279 mg, 1.0 mmol) are added, and at 0 ° C. for 30 minutes for an additional 60. The mixture was stirred at ° C. for 3 hours. After allowing to cool, 1,1,3,3-tetramethyldisilazane (520 μL, 3.0 mmol) was added to the reaction mixture, and the mixture was stirred at 150 ° C. for 5 hours. After allowing to cool, the low boiling point was distilled off from the reaction mixture under reduced pressure, water was added to the obtained residue, and the solid was filtered off. The solid was washed with water, methanol and then hexane. The obtained solid was dried under reduced pressure to give the desired 4,6-diphenyl-2- (2,3,4,5-tetrachlorophenyl) -1,3,5-triazine as a white solid (294 mg, 66). %).
^{1 1} H-NMR (400 MHz, CDCl ₃ ): 8.70-8.73 (m, 4H), 8.11 (s, 1H), 7.56-7.66 (m, 6H).
Reference example-1

Benzamidine hydrochloride (156 mg, 1.0 mmol) was suspended in chloroform (5.0 mL) under an argon stream. The solution is cooled to 0 ° C., triethylamine (420 μL, 3.0 mmol) and 3-bromo-5-chlorobenzoyl chloride (5.0 M, 1.0 mL, 5.0 mmol) are added, and at 0 ° C. for 30 minutes, further. The mixture was stirred at 60 ° C. for 3 hours. After allowing to cool, the low boiling point was distilled off from the reaction mixture under reduced pressure, water was added to the obtained residue, and the solid was filtered off. The solid was washed with water, methanol and then hexane. The obtained solid was dried under reduced pressure to give the desired N- (3-bromo-5-chlorobenzoyl) benzamidine as a white solid (305 mg, 90%).
^{1 1} H-NMR (400 MHz, CDCl ₃ ): δ10.78 (brs, 1H), 8.39 (dd, J = 1.6, 1.5 Hz, 1H), 8.28 (dd, J = 1.8) , 1.5Hz, 1H), 8.02-8.05 (m, 2H), 7.61-7.65 (m, 2H), 7.55 (dd, J = 7.8, 7.1Hz, 2H), 6.74 (brs, 1H).

Claims (19)

General formula (4)

(In the formula, R represents a halogen atom, an alkyl group having 1 to 18 carbon atoms, a haloalkyl group having 1 to 8 carbon atoms, a phenyl group, or a phenyl halide group. N represents an integer of 0 to 5. When is 2 to 5, a plurality of Rs may be the same or different. Ar ¹ has an aryl group having 6 to 14 carbon atoms, an aryl halide group having 6 to 14 carbon atoms, and 1 to 8 carbon atoms. Represents an aryl group having 6 to 14 carbon atoms substituted with an alkyl group or an aryl group having 6 to 14 carbon atoms substituted with a haloalkyl group having 1 to 8 carbon atoms.
The acylamidine compound represented by and the general formula (3).

(In the formula, Ar ¹ has the same meaning as described above, and represents the same group as Ar ¹ in the general formula (4).)
The general formula (1), which comprises reacting the amidine compound represented by

(In the equation, Ar ¹ , R and n have the same meanings as described above. The two Ar ¹ are the same.)
A method for producing a triazine compound represented by. The production method according to claim 1, wherein the reaction is carried out in the presence of a silicon compound. The silicon compound has a general formula (5).

(In the formula, R ¹ and R ² each independently represent an alkyl group having 1 to 4 carbon atoms, an alkyloxy group having 1 to 4 carbon atoms, or a phenyl group. X ¹ and X ² independently represent each. , Hydrogen atom, halogen atom, or alkyloxy group having 1 to 4 carbon atoms.)
The production method according to claim 2, wherein the silane compound (5) is represented by. The production method according to claim 3, wherein X ¹ is a hydrogen atom. The silicon compound has the general formula (6).

(In the formula, R ³ , R ⁴ , R ⁵ and R ⁶ each independently represent an alkyl group or a phenyl group having 1 to 4 carbon atoms. X ³ represents a hydrogen atom.)
The production method according to claim 2, wherein the silazane compound (6) is represented by. The production method according to claim 5, wherein R ³ , R ⁴ , R ⁵ and R ⁶ are methyl groups. The silicon compound has the general formula (7).

(In the formula, R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ and R ¹² each independently represent an alkyl group or a phenyl group having 1 to 4 carbon atoms.)
The production method according to claim 2, which is the trisilazane compound (7) represented by. The production method according to claim ⁷ , wherein R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ and R ¹² are methyl groups. General formula (2)

(In the formula, R represents a halogen atom, an alkyl group having 1 to 18 carbon atoms, a haloalkyl group having 1 to 8 carbon atoms, a phenyl group, or a phenyl halide group. N represents an integer of 0 to 5. When is 2 to 5, a plurality of Rs may be the same or different.)
The acid chloride represented by and the general formula (3)

(In the formula, Ar ¹ is an aryl group having 6 to 14 carbon atoms, an aryl group having 6 to 14 carbon atoms, an aryl group having 6 to 14 carbon atoms substituted with an alkyl group having 1 to 8 carbon atoms, or an aryl group having 6 to 14 carbon atoms. Represents an aryl group having 6 to 14 carbon atoms substituted with a haloalkyl group having 1 to 8 carbon atoms.
General formula (4) obtained by reacting the amidine compound represented by

(In the formula, Ar ¹ , R and n have the same meanings as described above.)
The production method according to claim 1, wherein the acylamidine compound represented by is used. The production method according to claim 9, wherein the reaction is carried out in the presence of a base. General formula (2)

(In the formula, R represents a halogen atom, an alkyl group having 1 to 18 carbon atoms, a haloalkyl group having 1 to 8 carbon atoms, a phenyl group, or a phenyl halide group. N represents an integer of 0 to 5. When is 2 to 5, a plurality of Rs may be the same or different.)
The acid chloride represented by and the general formula (3)

(In the formula, Ar ¹ is an aryl group having 6 to 14 carbon atoms, an aryl group having 6 to 14 carbon atoms, an aryl group having 6 to 14 carbon atoms substituted with an alkyl group having 1 to 8 carbon atoms, or an aryl group having 6 to 14 carbon atoms. Represents an aryl group having 6 to 14 carbon atoms substituted with a haloalkyl group having 1 to 8 carbon atoms.
The general formula (1) is characterized in that the amidine compound represented by is reacted in the presence of a silicon compound.

(In the equation, Ar ¹ , R and n have the same meaning as above. The two Ar ¹ are the same.)
A method for producing a triazine compound represented by. Which comprises carrying out the reaction in the presence of a salt group, the manufacturing method according to claim 11. The production method according to claim 11, wherein the reaction is carried out by adding a base and then a silicon compound. The silicon compound has a general formula (5).

(In the formula, R ¹ and R ² each independently represent an alkyl group having 1 to 4 carbon atoms, an alkyloxy group having 1 to 4 carbon atoms, or a phenyl group. X ¹ and X ² independently represent each. , Hydrogen atom, halogen atom, or alkyloxy group having 1 to 4 carbon atoms.)
The production method according to any one of claims 11 to 13, which is the silane compound (5) represented by. The production method according to claim 14, wherein X ¹ is a hydrogen atom. The silicon compound has the general formula (6).

(In the formula, R ³ , R ⁴ , R ⁵ and R ⁶ each independently represent an alkyl group or a phenyl group having 1 to 4 carbon atoms. X ³ represents a hydrogen atom.)
The production method according to any one of claims 11 to 13, which is the silazane compound (6) represented by. The production method according to claim 16, wherein R ³ , R ⁴ , R ⁵ , and R ⁶ are methyl groups. The silicon compound has the general formula (7).

(In the formula, R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ and R ¹² each independently represent an alkyl group or a phenyl group having 1 to 4 carbon atoms.)
The production method according to any one of claims 11 to 13, which is the trisilazane compound (7) represented by. The production method according to claim 18, wherein R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ and R ¹² are methyl groups.