JP6732369B2 - Triazine compound and method for producing the same - Google Patents

Description

The present invention relates to a simple and inexpensive method for producing a 4,6-dichlorotriazine compound useful as a synthetic intermediate for a charge transport material used in an organic electroluminescent device.

Triaryltriazine derivatives having two different aromatic groups at the 2-position and 4- and 6-positions of the 1,3,5-triazine ring are reported to be useful as charge transport materials used in organic electroluminescent devices. (For example, see Patent Documents 1 and 2). A 4,6-dichlorotriazine compound having a phenyl group substituted with a halogen atom or the like at the 2-position of the 1,3,5-triazine ring is useful as a synthetic intermediate for the charge transport material.

JP, 2008-280330, A Japanese Patent Publication No. 2010-155826 JP, 2010-95452, A

An object of the present invention is to provide a simple and inexpensive method for producing a 4,6-dichlorotriazine compound useful as a synthetic intermediate for a charge transport material used in an organic electroluminescence device.

As a result of intensive studies to solve the above problems, the present inventors have found that a triazine compound having a phenyl group substituted with a halogen atom or the like is 4,6-dichloro, which is a useful synthetic intermediate for a charge transport material. They have found that they are excellent raw materials for the production of triazine compounds, and that they can be produced inexpensively without using expensive metal catalysts, and have completed the present invention.

That is, the present invention is
(I) General formula (1)

(In the formula, R represents a halogen atom or a phenyl group which may be substituted with a halogen atom. n represents an integer of 1 to 5. When n is 2 to 5, a plurality of Rs are the same or phase. May be different. Z represents a hydroxyl group or a mercapto group.)
A triazine compound represented by:
(Ii) In the general formula (1), R is a halogen atom, the triazine compound according to the above (i);
(Iii) In the general formula (1), n is 2 or 3, and R is a halogen atom, the triazine compound according to the above (i);
(Iv) In the general formula (1), n is 2, and the halogen atom represented by R is a chlorine atom or a bromine atom;
Regarding

Further, the present invention is
(V) General formula (1b)

(In the formula, R represents a halogen atom or a phenyl group which may be substituted with a halogen atom. n represents an integer of 1 to 5. When n is 2 to 5, a plurality of Rs are the same or phase. It may be different.)
A general formula (2), characterized in that a triazine compound represented by

(In the formula, R and n have the same meanings as described above.)
A method for producing a 4,6-dichlorotriazine compound represented by:
(Vi) The production method according to the above (v), wherein R is a halogen atom in the general formula (1b);
(Vii) In the general formula (1b), n is 2 or 3, and R is a halogen atom.
(Viii) In the general formula (1b), n is 2, and the halogen atom represented by R is a chlorine atom or a bromine atom.
(Viii) A method for producing a triazine compound represented by the general formula (1c) described below, which comprises subjecting a thiobiuret compound represented by the general formula (4) described below to an intramolecular cyclization reaction in the presence of a base. ;
It is about.

According to the present invention, a 4,6-dichlorotriazine compound, which is useful as a synthetic intermediate for a charge transport material used in an organic electroluminescence device, can be obtained easily and inexpensively.

The present invention will be described in detail below.

The definitions of R, n, and Z in the triazine compound (1) of the present invention will be described.

Examples of the halogen atom represented by R include a fluorine atom, a chlorine atom, a bromine atom or an iodine atom, and a chlorine atom or a bromine atom is preferable from the viewpoint of low cost and good reactivity.

Examples of the phenyl group which may be substituted with a halogen atom represented by R include a monohalophenyl group, a dihalophenyl group, a trihalophenyl group, a tetrahalophenyl group and a pentahalophenyl group, and 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-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-dibromophenyl 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-difluorophenyl 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-iodo Examples thereof include a phenyl group, a 5-iodo-3-chlorophenyl group, a 3-bromo-5-fluorophenyl group, a 3-chloro-5-fluorophenyl group and the like. A mono-, di- or trihalophenyl group is preferable, or a mono- or dihalophenyl group is more preferable, specifically 2 in view of high versatility in synthesis of a 4,6-dichlorotriazine compound obtained from the triazine compound of the present invention. -Chlorophenyl group, 3-chlorophenyl group, 4-chlorophenyl group, 2-bromophenyl group, 3-bromophenyl group, 4-bromophenyl group, 2-fluorophenyl group, 3-fluorophenyl group, 4-fluorophenyl group, A 3,5-dichlorophenyl group, a 3-bromo-5-chlorophenyl group, or a 3,5-dibromophenyl group is preferable.

The integer of 1 to 5 represented by n is preferably 1 to 3, more preferably 2 or 3 and most preferably 2 in terms of high versatility in synthesis of 4,6-dichlorotriazine compound.

The triazine compound of the present invention is not particularly limited, but for example, compounds having the structures shown in 1-1 to 1-69 below can be specifically exemplified.

The triazine compound (1) of the present invention can have a tautomeric structure 1a ^{1 to} 1a ⁴ represented by the following formula.

(Wherein, .Z ^a R and n represent the same meanings as described above represents an oxygen atom or a sulfur atom.)
The present invention includes all of these tautomers, but for convenience, they are described by the structure of the general formula (1).

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

The manufacturing method of the present invention is shown in the following step 1.

(In the formula, R and n have the same meanings as described above.)
In Step 1, the triazine compound (1b) contained in the triazine compound of the present invention (hereinafter referred to as “triazine compound (1b) of the present invention”) is reacted with a chlorinating agent to give a 4,6-dichlorotriazine compound. In the step of producing (2), the target product can be obtained in good yield by applying general conditions for the conversion reaction of a hydroxyl group into a chlorine atom.

As the chlorinating agent used in Step 1, chlorine, N-chlorosuccinimide, N-chlorophthalimide, benzyltrimethylammonium tetrachloroiodide, tert-butyl hypochlorite, chloramine B, chloramine T, cyanuric chloride, dichloramine, Examples thereof include oxalyl chloride, trichloroisocyanuric acid, thionyl chloride, phosphorus oxychloride, phosphorus pentachloride and the like, and these may be appropriately mixed and used. Among them, phosphorus oxychloride, phosphorus pentachloride, or a mixture thereof is preferable because it is inexpensive and the reaction yield of the 4,6-dichlorotriazine compound (2) is good.

The molar equivalent of the chlorinating agent used in Step 1 is not particularly limited, but is preferably 1 to 50 molar equivalents relative to the triazine compound (1b) of the present invention, and the reaction of the 4,6-dichlorotriazine compound (2). From the viewpoint of good yield, 5 to 20 molar equivalents are more preferable. When the chlorinating agent is liquid, it may be used as a reaction solvent.

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 the solvent include hydrocarbons such as pentane, hexane, heptane, octane, decane and decalin, aromatic hydrocarbons such as benzene, toluene and nitrobenzene, dichloromethane, chloroform, 1,2-dichloroethane, 1, Halogenated hydrocarbons such as 1,2,2-tetrachloroethane, dichlorobenzene, chlorobenzene, trichlorobenzene, 1-chloronaphthalene, triethylamine, diisopropylethylamine, tributylamine, N-methylpyrrolidine, N-methylpiperidine, N,N'. -Dimethylpiperazine, N-methylmorpholine, 1,4-diazabicyclo[2.2.2]octane, 1,8-diazabicyclo[5.4.0]-7-undecene, N,N-dimethylaniline, N,N Examples thereof include tertiary amines such as -diethylaniline, N,N-diethyltoluidine, pyridine and picoline, and these may be mixed in any ratio and used. From the viewpoint of good reaction yield of the 4,6-dichlorotriazine compound (2), a tertiary amine is preferable, and diethylaniline is more preferable. The amount of solvent used is not particularly limited.

The reaction temperature for carrying out Step 1 is not particularly limited, but it can be carried out at a temperature appropriately selected from 20 to 180° C., and the reaction yield of the 4,6-dichlorotriazine compound (2) is From a good point, it is preferable to carry out at a temperature appropriately selected from 60 to 120°C.

The 4,6-dichlorotriazine compound (2) can be obtained by performing a usual treatment after the completion of the reaction in step 1. If necessary, it may be purified by recrystallization, column chromatography, sublimation, preparative HPLC or the like.

The triazine compound (1b) of the present invention used in the production method (step 1) of the present invention can be produced by step 2 shown in the following reaction formula.

(In the formula, R and n have the same meanings as described above.)
In step 2, the triazine compound (1c) contained in the triazine compound of the present invention (hereinafter referred to as “triazine compound (1c) of the present invention”) is reacted with an oxidizing agent in the presence of a base, and It is a step of producing the triazine compound (1b).

Examples of the oxidizing agent used in step 2 include oxygen, ozone, Oxone (registered trademark), hydrogen peroxide, benzoic acid peroxide, m-chlorobenzoic acid peroxide, maleic acid peroxide, phthalic acid peroxide, propionic acid peroxide, and peracetic acid. , Tert-butylhydroperoxide, tert-amylhydroperoxide, cumylhydroperoxide, bis(trimethylsilyl)peroxide and other peroxides, ammonium molybdate, tungstic acid, vanadium oxide, rhenium oxide, osmium oxide and other metal oxides Can be illustrated. Among them, peroxides are preferable in that the yield of the triazine compound (1b) of the present invention is good, and hydrogen peroxide is more preferable in that they are inexpensive.

The base used in Step 2 is not particularly limited, but for example, a metal hydroxide salt such as sodium hydroxide, potassium hydroxide, or calcium hydroxide is preferable, and sodium hydroxide is more preferable because it is inexpensive. preferable. The molar equivalent of the base used is not particularly limited, but is preferably 1 to 100 molar equivalents relative to the triazine compound (1c) of the present invention, and the reaction yield of the triazine compound (1b) of the present invention is good, More preferably, it is 5 to 20 molar equivalents.

Step 2 can be performed 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. Examples of the solvent include water, alcohols such as methanol, ethanol, 2-propanol, butanol, octanol, benzyl alcohol, ethylene glycol, propylene glycol, diethylene glycol, triethylene glycol, 2,2,2-trifluoroethanol, and dichloromethane. , Halogenated hydrocarbons such as chloroform, 1,2-dichloroethane, 1,1,2,2-tetrachloroethane, dichlorobenzene, chlorobenzene, trichlorobenzene, 1-chloronaphthalene, ethylene carbonate, propylene carbonate, dimethyl carbonate, diethyl carbonate Carbonic acid esters such as ethyl methyl carbonate, 4-fluoroethylene carbonate, methyl formate, ethyl formate, propyl formate, methyl acetate, ethyl acetate, butyl acetate, methyl propionate, ethyl propionate, methyl butyrate, γ-lactone, etc. , Diethyl ether, diisopropyl ether, dibutyl ether, cyclopentyl methyl ether (CPME), tetrahydrofuran (THF), 2-methyltetrahydrofuran, 1,4-dioxane, ether such as dimethoxyethane, acetone, methyl ethyl ketone, diethyl ketone, diisopropyl ketone, cyclohexanone , Ketones such as acetophenone, etc., and these may be mixed and used at an arbitrary ratio. From the viewpoint of good reaction yield of the triazine compound (1b) of the present invention, water, alcohol and ketone are preferable, and water, methanol and acetone are more preferable. The amount of solvent used is not particularly limited.

The reaction temperature for carrying out step 2 is not particularly limited, but it can be carried out at a temperature appropriately selected from -20 to 100°C, and the reaction yield of the triazine compound (1b) of the present invention is good. It is preferable to carry out at a temperature appropriately selected from -5 to 40°C.

The triazine compound (1b) of the present invention can be obtained by performing a usual treatment such as neutralization after the completion of the reaction of step 2. If necessary, it may be purified by recrystallization, column chromatography, sublimation, preparative HPLC or the like.

The triazine compound (1c) of the present invention used in Step 2 can be produced by Steps 3 and 4 which are the production methods of the present invention shown in the following reaction formula.

(In the formula, R and n have the same meanings as described above.)
Step 3 is a step of reacting thiobiuret (4) with a base to produce the triazine compound (1c) of the present invention used in Step 2.

As the base used in step 3, the same bases as those exemplified in step 2 can be exemplified, and sodium hydroxide is preferable in that it is inexpensive. The molar equivalent of the base to be used is not particularly limited, but is preferably 1 to 100 molar equivalent to the thiobiuret (4), and 5 to 20 in terms of a good reaction yield of the triazine compound (1c) of the present invention. Molar equivalents are even more preferred.

Step 3 can be carried out in a solvent. As the solvent that can be used, the same solvents as those exemplified in Step 3 can be exemplified, and acetone is preferable in that the reaction yield of the triazine compound (1c) of the present invention is good. The amount of solvent used is not particularly limited.

The reaction temperature for carrying out step 3 is not particularly limited, but it can be carried out at a temperature appropriately selected from -10 to 100°C, and the reaction yield of the triazine compound (1c) of the present invention is good. It is preferable to carry out at a temperature appropriately selected from 5 to 40°C.

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

Step 4 is a step of reacting the acid chloride (3) with potassium thiocyanate and urea to produce thiobiuret (4) used in Step 3.

The acid chloride (3) used in Step 4 can be easily produced by a method well known to those skilled in the art, for example, by chlorinating the corresponding carboxylic acid. Moreover, you may use a commercial item.

The molar equivalent of potassium thiocyanate used in Step 4 is not particularly limited, but 0.8 to 10 molar equivalent is preferable with respect to the acid chloride (3), and the reaction yield of thiobiuret (4) is good. , 1 to 3 molar equivalents are more preferable.

The molar equivalent of urea used in Step 4 is not particularly limited, but is preferably 0.8 to 10 molar equivalent with respect to the acid chloride (3), and the reaction yield of thiobiuret (4) is good, and thus 1 ˜3 molar equivalents are even more preferred.

Step 4 can be performed in a solvent. There is no particular limitation on the solvent that can be used, and any solvent that does not inhibit the reaction may be used, but toluene is preferable in terms of easy post-treatment.

The reaction temperature for carrying out step 4 is not particularly limited, but it can be carried out at a temperature appropriately selected from 0 to 150° C., and the reaction yield of thiobiuret (4) is 60 to 60 because it has a good reaction yield. It is preferable to carry out at a temperature appropriately selected from 120°C.

Thiobiuret (4) can be obtained by carrying out a usual treatment after completion of the reaction of step 4, and can be subjected to step 3 without purification. Moreover, you may refine|purify by recrystallization, column chromatography, sublimation, preparative HPLC, etc. as needed.

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

The following analytical method was used for identifying the triazine compound obtained by the production method of the present invention. Bruker ULTRASHIELD AVANCE III (400 MHz) was used for ¹ H-NMR measurement. ¹ H-NMR was measured using deuterated chloroform (CDCl ₃ ) or deuterated DMSO (DMSO-d ₆ ) as a measurement solvent and tetramethylsilane (TMS) as an internal standard substance. In addition, reagents used were commercial products.

Example-1

Under argon, 3,5-dichlorobenzoic acid chloride (50 g, 239 mmol) was dissolved in toluene (300 mL). Potassium thiocyanate (27.8 g, 286 mm) was added to this solution, and the mixture was stirred at 110° C. for 24 hours. After allowing to cool, the reaction solution was filtered, and the filtrate was dried under reduced pressure. The obtained oil was dissolved in acetone (360 mL), urea (17.2 g, 286 mmol) was added thereto, and the mixture was stirred at 60°C for 3 hr. After cooling, low-boiling components were distilled off under reduced pressure from the reaction mixture, and water was added to the resulting residue to suspend it. This suspension was filtered, and the obtained solid was washed with water and dried under reduced pressure to give a crude product of 1-(3,5-dichlorobenzoyl)thiobiuret (67.7 g, 97%). .. This product was used in the next step without purification.

The crude product of 1-(3,5-dichlorobenzoyl)thiobiuret (67.2 g, 230 mmol) was suspended in ethanol (690 mL), 4M-sodium hydroxide aqueous solution (690 mL) was added, and the mixture was stirred for 18 hours. After concentrating the volume of the reaction solution to about 1/2 under reduced pressure, water (600 mL) was added and the insoluble material was filtered off. The filtrate was adjusted to pH=4 by adding 6M-sulfuric acid aqueous solution and acetic acid. The resulting precipitate was filtered off, washed with water, and dried under reduced pressure to give the desired 2-(3,5-dichlorophenyl)-4-hydroxy-6-sulfanyl-1,3,5-triazine. A yellow solid (54.6 g, 87% yield) was obtained.
¹ H-NMR (400 MHz, DMSO-d ₆ ): δ 12.87 (s, 1 H), 8.08 (d, J=1.8 Hz, 2 H), 7.95 (t, J=1.8 Hz, 1 H). ).
Example-2

1-M sodium hydroxide aqueous solution (2.0 L) was added to 2-(3,5-dichlorophenyl)-4-hydroxy-6-sulfanyl-1,3,5-triazine (34.0 g, 124 mmol). This mixture was cooled to 0° C., 7%-hydrogen peroxide solution (2.0 L) was added over 6 hours, and the mixture was stirred at room temperature for 18 hours. The reaction solution was neutralized by adding 12M-hydrochloric acid. The precipitate was filtered off, dissolved in a 1M aqueous sodium hydroxide solution (500 mL), and then neutralized with acetic acid water. The resulting solid was filtered off, washed with water, and dried under reduced pressure to obtain the desired 2-(3,5-dichlorophenyl)-4,6-dihydroxy-1,3,5-triazine hydrate as a white solid. (35.0 g, yield 96%) was obtained.
¹ H-NMR (400 MHz, DMSO-d ₆ ): δ 12.53 (brs, 1H), 11.50 (s, 1H), 8.07 (d, J=1.9 Hz, 2H), 7.94 ( t, J=1.9 Hz, 1H).
Example-3

A 1-L flask was charged with 2-(3,5-dichlorophenyl)-4,6-dihydroxy-1,3,5-triazine hydrate (35.0 g, 119 mmol), where phosphorus oxychloride (280 mL) was added. Phosphorus pentachloride (59.3g) was added. A drying tube was attached to the reaction vessel, heated to 100° C., and stirred for 40 hours. After completion of the reaction, low boiling components were distilled off under reduced pressure at 130°C. Ice water (1 L) was added to the obtained residue, and the mixture was neutralized with a saturated aqueous sodium carbonate solution. The generated solid was filtered off, washed with water, and then dried under reduced pressure. This solid was purified by silica gel column chromatography (eluent: hexane/chloroform) to obtain the desired 4,6-dichloro-2-(3,5-dichlorophenyl)-1,3,5-triazine (30 0.5 g, yield 87%).
¹ H-NMR (400 MHz, CDCl ₃ ): δ8.39 (d, J=2.0 Hz, 2H), 7.63 (t, J=2.0 Hz, 1H).
Example-4

Under argon, potassium thiocyanate (546 mg, 5.6 mmOl) was added to a toluene solution (12 mL) of 3,5-dibromobenzoic acid chloride (1.40 g, 4.7 mmOl), and the mixture was stirred at 110°C for 24 hours. After allowing to cool, the reaction solution was filtered, and the filtrate was dried under reduced pressure. The obtained residue was dissolved in acetone (14 mL), urea (337 mg, 5.6 mmol) was added thereto, and the mixture was stirred at 60°C for 3 hr. After cooling, low-boiling components were distilled off under reduced pressure from the reaction mixture, and water was added to the resulting residue to suspend it. The suspension was filtered, and the obtained solid was washed with water and then dried under reduced pressure by heating to obtain a crude product of 1-(3,5-dibromobenzoyl)thiobiuret. This product was used in the next step without purification.

The crude product of 1-(3,5-dibromobenzoyl)thiobiuret was suspended in ethanol (23 mL), 4M-aqueous sodium hydroxide solution (23 mL) was added, and the mixture was stirred for 24 hr. The reaction mixture was adjusted to pH=6 by adding 1M-sulfuric acid aqueous solution. The generated precipitate was filtered off, washed with water, and then dried under reduced pressure. The obtained solid was recrystallized from acetic acid to give the desired 2-(3,5-dibromophenyl)-4-hydroxy-6-sulfanyl-1,3,5-triazine as a yellow solid (645 mg, yield 38%). Got The above filtrate was concentrated under reduced pressure, and the obtained solid was recrystallized in the same manner to give 2-(3,5-dibromophenyl)-4-hydroxy-6-sulfanyl-1,3,5-triazine. (187 mg, yield 11%).
¹ H-NMR (400 MHz, DMSO-d ₆ ): δ 12.84 (s, 1 H), 8.25 (d, J=1.7 Hz, 2 H), 8.18 (t, J=1.7 Hz, 1 H). ).
Example-5

2-(3,5-Dibromophenyl)-4-hydroxy-6-sulfanyl-1,3,5-triazine (496 mg, 1.4 mmol) was added with 1M-sodium hydroxide aqueous solution (11 mL). This mixture was cooled to 0° C., and 30%-hydrogen peroxide solution (3 mL) was added. After stirring at the same temperature for 15 minutes, the mixture was further stirred at room temperature for 2 hours. The reaction solution was adjusted to pH=7 by adding 1M-sulfuric acid aqueous solution. The precipitate was filtered off, washed with water, and dried under reduced pressure to give the desired 2-(3,5-dibromophenyl)-4,6-dihydroxy-1,3,5-triazine as a white solid (460 mg, yield Rate of 97%).
¹ H-NMR (400 MHz, DMSO-d ₆ ): δ 12.53 (brs, 1H), 11.48 (s, 1H), 8.24 (d, J=1.7 Hz, 2H), 8.18 ( t, J=1.7 Hz, 1H).
Example-6

Into a 50 mL flask, take 2-(3,5-dibromophenyl)-4,6-dihydroxy-1,3,5-triazine (367 mg, 1.1 mmol), and add phosphorus oxychloride (3.0 mL), then Phosphorus chloride (220 mg, 2.2 mmol) was added. A drying tube was attached to the reaction vessel, heated to 100° C., and stirred for 24 hours. After completion of the reaction, low boiling components were distilled off under reduced pressure at 130°C. The obtained residue was added to ice water (10 mL), neutralized with saturated aqueous sodium carbonate solution, and chloroform was added. After separating the organic layer, the aqueous layer was extracted with chloroform. After drying the organic layer with sodium sulfate, the solvent was removed under reduced pressure. The obtained residue was purified by column chromatography (eluent: hexane/ethyl acetate) to obtain the desired 4,6-dichloro-2-(3,5-dibromophenyl)-1,3,5-triazine (359 mg). , 88%).
¹ H-NMR (400 MHz, CDCl ₃ ): δ 8.58 (d, J=1.8 Hz, 2 H), 7.94 (t, J=1.8 Hz, 1 H).
Example-7

Under argon, potassium thiocyanate (2.33 g, 24 mm) was added to a toluene solution (40 mL) of 3-chlorobenzoic acid chloride (3.50 g, 20 mm) and stirred at 110° C. for 24 hours. After allowing to cool, the reaction solution was filtered, and the filtrate was dried under reduced pressure. The obtained residue was dissolved in acetone (35 mL), urea (1.44 g, 24 mmol) was added thereto, and the mixture was stirred at 60°C for 3 hr. After cooling, low-boiling components were distilled off under reduced pressure from the reaction mixture, and water was added to the resulting residue to suspend it. The suspension was filtered, the obtained solid was washed with water, and then dried under reduced pressure by heating to obtain a crude product of 1-(3-chlorobenzoyl)thiobiuret. This product was used in the next step without purification.

The crude product of 1-(3-chlorobenzoyl)thiobiuret was suspended in ethanol (120 mL), 4M-aqueous sodium hydroxide solution (120 mL) was added, and the mixture was stirred for 24 hr. The reaction mixture was adjusted to pH=6 by adding 1M-sulfuric acid aqueous solution. The generated precipitate was filtered off, washed with water, and then dried under reduced pressure. The obtained solid was recrystallized from acetic acid to obtain the desired yellow solid of 2-(3-chlorophenyl)-4-hydroxy-6-sulfanyl-1,3,5-triazine (2.26 g, yield 47%). Obtained.
¹ H-NMR (400 MHz, DMSO-d ₆ ): δ 13.32 (brs, 1H), 12.84 (s, 1H), 8.13 (dd, J=2.1, 1.8 Hz, 1H), 8.04 (ddd, J=8.0, 1.8, 0.9 Hz, 1H), 7.75 (ddd, J=8.0, 2.1, 0.9 Hz, 1H), 7.59 ( dd, J=8.0, 8.0 Hz, 1H).
Example-8

1-M-sodium hydroxide aqueous solution (70 mL) was added to 2-(3-chlorophenyl)-4-hydroxy-6-sulfanyl-1,3,5-triazine (2.10 g, 8.8 mmol). This mixture was cooled to 0° C., and 30%-hydrogen peroxide solution (18 mL) was added. After stirring at the same temperature for 15 minutes, the mixture was further stirred at room temperature for 2 hours. The reaction solution was adjusted to pH=7 by adding 1M-sulfuric acid aqueous solution. The precipitate was filtered off, washed with water, and dried under reduced pressure to give the desired 2-(3-chlorophenyl)-4,6-dihydroxy-1,3,5-triazine as a white solid (1.76 g, yield). 90%).
¹ H-NMR (400 MHz, DMSO-d ₆ ): δ 12.48 (brs, 1H), 11.45 (s, 1H), 8.12 (dd, J=2.1, 1.6 Hz, 1H), 8.03 (ddd, J=8.0, 1.6, 1.0 Hz, 1H), 7.74 (ddd, J=8.0, 2.1, 1.0 Hz, 1H), 7.59 ( dd, J=8.0, 8.0 Hz, 1H).
Example-9

2-(3-Chlorophenyl)-4,6-dihydroxy-1,3,5-triazine (1.73 g, 7.7 mmol) was placed in a 50 mL flask, and phosphorus oxychloride (14 mL) was added thereto, followed by phosphorus pentachloride ( 3.38 g, 16 mmol) was added. A drying tube was attached to the reaction vessel, heated to 100° C., and stirred for 24 hours. After completion of the reaction, low boiling components were distilled off under reduced pressure at 130°C. The obtained residue was added to ice water (10 mL), neutralized with saturated aqueous sodium carbonate solution, and chloroform was added. After separating the organic layer, the aqueous layer was extracted with chloroform. After drying the organic layer with sodium sulfate, the solvent was removed under reduced pressure. The obtained residue was purified by column chromatography (eluent: hexane/ethyl acetate) and the desired 4,6-dichloro-2-(3-chlorophenyl)-1,3,5-triazine (1.84 g, 91%).
¹ H-NMR (400 MHz, CDCl ₃ ): δ8.50 (s, 1H), 8.41 (d, J=7.9 Hz, 1H), 7.63 (d, J=7.9 Hz, 1H), 7.48 (t, J=7.9 Hz, 1H).
Example-10

Under argon, potassium thiocyanate (2.33 g, 24 mm) was added to a toluene solution (40 mL) of 4-chlorobenzoic acid chloride (2.56 mL, 20 mm) and stirred at 110° C. for 24 hours. After allowing to cool, the reaction solution was filtered, and the filtrate was dried under reduced pressure. The obtained residue was dissolved in acetone (200 mL), urea (1.44 g, 24 mmol) was added thereto, and the mixture was stirred at 60°C for 3 hr. After cooling, low-boiling components were distilled off under reduced pressure from the reaction mixture, and water was added to the resulting residue to suspend it. This suspension was filtered, and the obtained solid was washed with water and then dried under reduced pressure by heating to obtain a crude product of 1-(4-chlorobenzoyl)thiobiuret. This product was used in the next step without purification.

The crude product of 1-(4-chlorobenzoyl)thiobiuret was suspended in ethanol (120 mL), 4M-aqueous sodium hydroxide solution (120 mL) was added, and the mixture was stirred for 24 hr. The reaction mixture was adjusted to pH=6 by adding 1M-sulfuric acid aqueous solution. The generated precipitate was filtered off, washed with water, and then dried under reduced pressure. The obtained solid was recrystallized from acetic acid to give the desired yellow solid of 2-(4-chlorophenyl)-4-hydroxy-6-sulfanyl-1,3,5-triazine (2.67 g, yield 56%). Obtained.
¹ H-NMR (400 MHz, DMSO-d ₆ ): δ 13.28 (brs, 1H), 12.81 (s, 1H), 8.10 (d, J=8.6 Hz, 2H), 7.64 ( d, J=8.6 Hz, 2H).
Example-11

To 2-(4-chlorophenyl)-4-hydroxy-6-sulfanyl-1,3,5-triazine (2.63 g, 11 mmol) was added 1M-sodium hydroxide aqueous solution (22 mL). This mixture was cooled to 0° C., and 30%-hydrogen peroxide solution (88 mL) was added. After stirring at the same temperature for 15 minutes, the mixture was further stirred at room temperature for 2 hours. The reaction solution was adjusted to pH=7 by adding 1M-sulfuric acid aqueous solution. The precipitate was filtered off, washed with water, and dried under reduced pressure to give the desired 2-(4-chlorophenyl)-4,6-dihydroxy-1,3,5-triazine as a white solid (2.20 g, yield). 89%).
¹ H-NMR (400 MHz, DMSO-d ₆ ): δ 12.46 (brs, 1H), 11.42 (s, 1H), 8.09 (d, J=8.6 Hz, 2H), 7.64 ( d, J=8.6 Hz, 2H).
Example-12

2-(4-Chlorophenyl)-4,6-dihydroxy-1,3,5-triazine (2.20 g, 9.8 mmol) was placed in a 50 mL flask, and phosphorus oxychloride (18 mL) was added thereto, followed by phosphorus pentachloride ( 4.30 g, 21 mmol) was added. A drying tube was attached to the reaction vessel, heated to 100° C., and stirred for 24 hours. After completion of the reaction, low boiling components were distilled off under reduced pressure at 130°C. The obtained residue was added to ice water (10 mL), neutralized with saturated aqueous sodium carbonate solution, and chloroform was added. After separating the organic layer, the aqueous layer was extracted with chloroform. After drying the organic layer with sodium sulfate, the solvent was removed under reduced pressure. The obtained residue was purified by column chromatography (eluent: hexane/ethyl acetate), and the target 4,6-dichloro-2-(4-chlorophenyl)-1,3,5-triazine (2.46 g, 96%).
¹ H-NMR (400 MHz, CDCl ₃ ): δ8.46 (d, J=8.8 Hz, 2H), 7.51 (d, J=8.8 Hz, 2H).

Claims (7)

General formula ( 11 )

(Wherein, R is a halogen atom, or be substituted with a halogen atom represent also a phenyl group. R in multiple may be the same or different .Z, one hydroxyl group and the other is a mercapto group A material for an organic electroluminescence device represented by. General formula (12)

(In the formula, R represents a halogen atom or a phenyl group which may be substituted with a halogen atom. A plurality of R may be the same or different. Z is a hydroxyl group on one side and a mercapto group on the other side. The material for an organic electroluminescence device represented by General formula (13)

(In the formula, R represents a halogen atom or a phenyl group which may be substituted with a halogen atom. A plurality of R may be the same or different. Z is a hydroxyl group on one side and a mercapto group on the other side. The material for an organic electroluminescence device represented by General formula (14)

(In the formula, R represents a halogen atom or a phenyl group which may be substituted with a halogen atom. A plurality of R may be the same or different. Z is a hydroxyl group on one side and a mercapto group on the other side. The material for an organic electroluminescence device represented by General formula (15)

(In the formula, R represents a halogen atom or a phenyl group which may be substituted with a halogen atom. A plurality of R may be the same or different. Z is a hydroxyl group on one side and a mercapto group on the other side. The material for an organic electroluminescence device represented by General formula (1)

(In the formula, R represents a halogen atom or a phenyl group which may be substituted with a halogen atom. n represents 3 and a plurality of Rs may be the same or different. Z is a hydroxyl group on one side. , The other of which represents a mercapto group). A method of fabricating an organic light emitting device material according to any one of claims 1 to 6
A method for producing an organic electroluminescent device material represented by the following general formula (1c) by subjecting a thiobiuret compound represented by the general formula (4) to an intramolecular cyclization reaction in the presence of a base.

(In the formula, R represents a halogen atom or a phenyl group which may be substituted with a halogen atom. n represents 2 or 3, and a plurality of Rs may be the same or different.)