JPH09151177A - Phenylation of aminotriazine derivative - Google Patents

Abstract

PROBLEM TO BE SOLVED: To introduce phenyl group to an amino group of triazine nucleus to phenylate an aminotriazine derivative by reacting a cyclohexanone derivative and/or a phenol derivative with the amino group in the presence of a catalyst. SOLUTION: 1,3,5-Triazine derivative represented by formula I [at least one among X<1> , X<2> and X<3> is an amino and when the group is not amino, NR<1> R<2> (R<1> and R<2> are each H, a 1-20C alkyl, a 2-10C alkenyl, etc.)] and having at least one or more amino groups is reacted with a cyclohexanone derivative of formula II [R is a 1-20 alkyl, a 1-20C alkoxy or a halogen; (n) is 0-3] and/or a phenol derivative of formula III in the presence of a metal catalyst (e.g. Pd-C) at room temperature to 500 deg.C for 1 to 100hr to provide a phenylamino- substituted, 1,3,5-triazine derivative of formula IV (at least one or more groups among X<4> , X<5> and X<6> are each NHR<3> ; R<3> is a halogen, etc.]. The compound of formula IV is useful as an intermediate for fine chemicals such as agrochemicals, medicines, dyes and coating materials and as a resin material, a flame retardant material, etc.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to the reaction of various 1,3,5-triazines having at least one or more amino groups with a cyclohexanone derivative and / or a phenol derivative in the presence of a catalyst. The present invention relates to a method for phenylating an amino-1,3,5-triazine derivative in which a phenyl group is introduced into the amino group.

Phenylamino-substituted 1,3,5-triazine derivatives obtained by the method of phenylating an amino group on the triazine ring carbon atom of the 1,3,5-triazine derivative of the present invention are pesticides, pharmaceuticals, dyes and paints. It is a useful compound group that is widely used as various fine chemical intermediates, etc., as various resin materials, especially as an aminoplast former component, and also as flame retardant materials.

[0003]

2. Description of the Related Art Various synthetic methods for synthesizing aminotriazines having a phenyl group are known.

[0004]

[Chemical 6]

In the compound represented by the following formula, compounds in which X ⁷ and X ⁸ are amino groups and X ⁹ is a phenyl group are
Reaction of 4-diamino-6-chloro-1,3,5-triazine with aniline (J. Am. Chem. So.
c. ), 73, 2985, 1951), or the reaction of dicyanoguanidine with aniline (US Pat.
92,607), a compound in which X ⁷ , X ⁸ and X ⁹ are phenyl groups similarly reacts with cyanuric chloride and aniline (Journal of American Chemicals).
Society (J. Am. Chem. Soc.), 73
Vol., 2985, 1951), or an example synthesized by the reaction of melamine with aniline hydrochloride (US Pat. No. 2,228,161).

In the above example, a method using a halogenated triazine derivative (J. Am. Chem. So.
c. ), 73, 2985, 1951), the yield is generally good, but the number of manufacturing steps is large or the operation is complicated, and a method using aniline hydrochloride (US Pat.
228,161) is a simple method, but requires a high reaction temperature. Further, in the method of using these halogen-containing compounds as raw materials, a stoichiometric amount of hydrogen halide or its salt (ammonium chloride, sodium chloride, etc.) is by-produced in the reaction, and therefore separation and treatment thereof are required.

The method using dicyanoguanidine is
The synthesis of the intermediate is complicated and the yield is not always high. For details on the synthesis of various aminotriazine derivatives including such phenylamino-substituted triazine derivatives, see the following publications (s-Triazines and Der.
ivatives. The Chemistry of Heterocyclic Compounds.
EM Smolin and L. Rapoport. Interscience Publis
hers Inc., New York. 1959).

[0008]

DISCLOSURE OF THE INVENTION As a result of intensive studies to solve the above problems, the present inventors have found that various industrially inexpensive cyclohexanone derivatives and / or phenol derivatives and amino groups on the triazine nucleus are used. Was reacted in the presence of a catalyst to introduce a phenyl group onto the amino group, and the present invention was completed in which basically only water was used as a by-product.

The phenylamino-substituted triazines obtained by this reaction differ greatly in the basicity, lipophilicity of the compound and the steric effect of the molecule from the starting triazines, so that the reactivity, solubility, etc. change. As a result, the physical properties when applied to resins and the like can be greatly changed. The purpose of the present invention is
The amino group on the ring carbon atom of 1,3,5-triazine is phenylated with a cyclohexanone derivative and / or a phenol derivative, and used as a fine chemical intermediate for various pesticides, pharmaceuticals, dyes, paints, and various resin materials. A phenylamino-substituted-1,3,5-triazine derivative, which is a useful compound group that can be widely used as a flame-retardant material, can be easily produced 1,3,5
-Providing a method for phenylating a triazine derivative.

[0010]

That is, the present invention provides an amino-1,3,5-triazine derivative having at least one amino group on a ring carbon atom of a cyclohexanone derivative and / or a phenol derivative and a metal catalyst. Amino-1,3, which introduces a phenyl group into the amino group on the triazine ring, characterized by reacting in the presence of
The present invention relates to a method for phenylating a 5-triazine derivative.

[0011]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention is described in detail below. The 1,3,5-triazine derivative having at least one amino group, which is the raw material of the present invention, is the 1,3,5-triazine derivative represented by the general formula (I).

[0012]

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[In the formula, at least one of X ¹ , X ² and X ³ independently represents an amino group, and when it is not an amino group, X ¹ , X ² and X ³ are independently NR ¹ R ² groups {in the formula, R ¹ or R ² are each independently a hydrogen atom, C _1-20
An alkyl group of (C _1-6 alkoxy group, aryloxy group, C _2-7 alkoxycarbonyl group, C _2-7 acyloxy group, C _2-7 acyl group, C _2-12
Dialkylamino group, a dialkylamino group of C _2-12, dialkylaminocarbonyl group of C _2-12, a phenyl group (the phenyl group, an alkyl group of C _1-6, alkoxy group of C _1-6 (May be replaced arbitrarily)
Optionally substituted with), a C _2-20 alkenyl group (the alkenyl group is a C _1-6 alkoxy group, an aryloxy group, a C _2-7 alkoxycarbonyl group, a C _2-7 An acyloxy group, a C _2-7 acyl group, a C _2-12 dialkylamino group, a C _2-12 dialkylaminocarbonyl group,
Dialkylaminocarbonyloxy group of C _2-12, a phenyl group (the phenyl group, an alkyl group of C _1-6, C may be optionally substituted by an alkoxy group _1-6) are optionally substituted by Good), C _2-7 alkoxycarbonyl group,
Acyl C _2-7, dialkylaminocarbonyl group of C _2-12, a phenyl group (the phenyl group, an alkyl group of C _1-6, may be optionally substituted by an alkoxy group C _1-6)
And R ¹ and R ² are taken together and the alkylene chain is optionally substituted by 1 or 2 C _1-8 alkyl groups — (CH ₂ ) _2-5 —, —CH ₂ CH ₂ -N (C
_1-8 alkyl) -CH ₂ CH ₂ - or -CH ₂ CH ₂ -O
-CH ₂ CH ₂ - may be formed},

C₁-₂₀An alkyl group of {wherein the alkyl group is C
_1-6An alkoxy group, a carboxyl group, C_2-7Alcoqui
Cicarbonyl group, C_2-10An acyloxy group of C_2-7No
Silyl group, C_2-12Dialkylamino group, C_2-12Gials
Killaminocarbonyl group, C _2-12Dialkylaminoca
Rubonyloxy group, aryl group (the aryl group is C
_1-6Alkyl group of C_1-6Optionally substituted with an alkoxy group of
May be arbitrarily substituted)),

[0015] C ₂ - ₂₀ alkenyl group {said alkenyl group is an alkoxy group of C _1-6, a carboxyl group, an alkoxycarbonyl group having C _2-7, an acyloxy group having C _2-10, C
_2-7 acyl group, C _2-12 dialkylamino group, C _2-12
Dialkylaminocarbonyl group, dialkylaminocarbonyl group of C _2-12, an aryl group (the aryl group, alkyl group of C _1-6, may be optionally substituted by an alkoxy group C _1-6) May be arbitrarily replaced},

Phenyl group (the phenyl group is a C _1-6 alkyl group, a C _1-6 alkoxy group, an aryloxy group, C
_2-10 acyloxy group, C _2-7 acyl group, carboxyl group, C _2-7 alkoxycarbonyl group, C _2-10 acyl group, C _2-12 dialkylamino group, C _2-12 dialkyl Aminocarbonyl group, C _2-12 dialkylaminocarbonyloxy group, aryl group (the aryl group is C _1-6
Optionally substituted with a C _1-6 alkoxy group), and optionally substituted with a C _1-6 alkoxy group}, C
_1-10 alkoxy group (the alkoxy group is a C _1-6 alkoxy group, aryloxy group, carboxyl group, C _2-7
Alkoxycarbonyl group, C _2-10 acyloxy group,
C _2-7 acyl group, C _2-12 dialkylamino group, C
_2-12 dialkylaminocarbonyl group, dialkylaminocarbonyl group of C _2-12, aryl group (the aryl group, alkyl group of C _1-6, be optionally substituted by an alkoxy group C _1-6 It may be optionally substituted with)},

[0017] or an alkylthio group {said alkylthio group C _1-10, the alkoxy group of C _1-6, aryloxy group, a carboxyl group, an alkoxycarbonyl group having C _2-7, an acyloxy group having C _{2-1 0,} C _2-7 acyl group, C
_2-12 dialkylamino group, C _2-12 dialkylaminocarbonyl group, C _2-12 dialkylaminocarbonyloxy group, aryl group (the aryl group is a C _1-6 alkyl group, a C _1-6 It may be optionally substituted with an alkoxy group). ].

In the specification and claims of the present application,
"It may be optionally substituted with the listed substituents."
Means that it may be substituted with one or more substituents of the same type or different types arbitrarily selected from the listed substituents. The 1,3,5-triazine derivative preferably used in the above general formula (I) is the 1,3,5-triazine derivative of the general formula (I) having X ¹ , X ² and X ^2.
At least one of ³ is an amino group, and when it is not an amino group, X ¹ , X ² and X ³ are each independently NR ¹ R
² groups (wherein R ¹ or R ² are each independently a hydrogen atom, a C _1-20 alkyl group (wherein the alkyl group is a C _1-6 alkoxy group, a phenyl group (wherein the phenyl group is C _{1 -6} alkyl group, C _1-6 alkoxy group may be optionally substituted), C _2-20 alkenyl group (the alkenyl group is C _1-6 An alkoxy group of
Phenyl group (the phenyl group is a C _1-6 alkyl group, C
_1-6 may be optionally substituted with an alkoxy group), and may be optionally substituted with),

[0019] or is R ^1, R ² together form an alkylene chain is substituted by an alkyl group having one or two C _1-8 optionally _{- (CH 2) 3-5 -,} - CH 2 CH ₂ -N
(C _{1 -8} alkyl) -CH ₂ CH ₂ - or -CH ₂ CH ₂
-O-CH ₂ CH ₂ - may be formed}, C ₁ - ₂₀ alkyl group {said alkyl group is an alkoxy group, an aryl group (said aryl group C _1-6 is C _1-6 alkyl Group, optionally substituted with a C _1-6 alkoxy group), optionally substituted with)},

Phenyl group (wherein the phenyl group is a C _1-6 alkyl group, a C _1-6 alkoxy group, an aryl group (the aryl group is a C _1-6 alkyl group, a C _1-6 alkoxy group Optionally substituted), optionally substituted}, a C _1-10 alkoxy group {wherein the alkoxy group is C
_1-6 alkoxy group, aryl group (the aryl group is C
_1-6 alkyl group, C _1-6 alkoxy group may be optionally substituted)), and the 1,3,5-triazine derivative.

More preferably, the general formula (I) used for the reaction
The 1,3,5-triazine derivative of is a 1,3,5-triazine derivative of the general formula (I) in which X ¹ , X ² and X
^At least one of ³ is an amino group, and when it is not an amino group, X ¹ , X ² and X ³ are NR ¹ R ² groups (in the formula, R ¹
Or R ² independently represents a hydrogen atom, a C _1-20 alkyl group (the alkyl group may be optionally substituted with a C _1-6 alkoxy group, a phenyl group), or R ¹ , R ² are taken together, and the alkylene chain is optionally 1
Or it is substituted by two alkyl groups of C _1-8 -
_{(CH 2) 4-5 -, -} CH 2 CH 2 -N (C 1 -8 alkyl) -CH ₂ CH ₂ - or _{-CH 2 CH 2 -O-CH 2} CH 2
- may form a}, C ₁ - ₂₀ alkyl group, is either a phenyl group, an alkoxy group of C _1-10 1, 3, 5
A triazine derivative.

As described above, it is possible to provide all 1,3,5-triazine derivatives having one or more amino groups and other substituents not directly involved in the reaction in this reaction. However, various melamine derivatives and various guanamine derivatives as industrially available intermediates (these are mainly available as a main agent or modifier of thermosetting resin, a cross-linking agent for baking coating, and the synthesis method is , S-Triazines and
Derivatives. The Chemistry of Heterocyclic Compoun
ds. EM Smolin and L. Rapoport. Interscience Pub
Full details on lishers Inc., New York. 1959. ).

The cyclohexanone derivative which can be used in the present invention has the general formula (II)

[0024]

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[In the formula, R may be the same or different and may be a C _1-20 alkyl group which may be substituted. A carbonyl group, a dialkylamino group, a dialkylaminocarbonyl group, and an optionally substituted C _1-20 alkoxy group (as the substituent, a hydroxyl group, a halogen atom, an alkoxy group,
A haloalkoxy group, an alkoxycarbonyl group, a dialkylamino group, a dialkylaminocarbonyl group) or a halogen atom, and n represents an integer of 0 to 3. } The cyclohexanone derivative shown by these is mentioned.

[0026] Preferably in this, in the general formula (II), R may be the same or different, represent an alkyl group, an alkoxy group of C _1-20 of C _1-20, n is 0-3 The cyclohexanone derivative showing an integer is mentioned. Of these, cyclohexanone, 2-methylcyclohexanone, 3-methylcyclohexanone, 4-methylcyclohexanone, 2-
Ethylcyclohexanone, 3-ethylcyclohexanone, 4-ethylcyclohexanone, 2-normalpropylcyclohexanone, 4-normalpropylcyclohexanone, 2-isopropylcyclohexanone, 3-isopropylcyclohexanone, 4-isopropylcyclohexanone, 2-normalbutylcyclohexanone, 4-
Normal butyl cyclohexanone, 2-secondary butyl cyclohexanone, 4-secondary butyl cyclohexanone, 4-tertiary butyl cyclohexanone, 2-tertiary butyl cyclohexanone,

4-normal pentyl cyclohexanone,
4-cyclopentylcyclohexanone, 4-tert-amylcyclohexanone, 4-normalhexylcyclohexanone, 2-cyclohexylcyclohexanone,
4-cyclohexylcyclohexanone, 2- (2-ethylbutyl) cyclohexanone, 2- (2-methylpentyl) cyclohexanone, 4-normaloctylcyclohexanone, 2- (2-ethylhexyl) cyclohexanone, 4-decylcyclohexanone, 4-dodecylcyclohexanone, 3 -Pentadecylcyclohexanone, 4-
Hexadecylcyclohexanone, 4-octadecylcyclohexanone, 2,4-dimethylcyclohexanone,
3,4-dimethylcyclohexanone, 3,5-dimethylcyclohexanone, 2,6-dimethylcyclohexanone, 2,4,6-trimethylcyclohexanone, 2-methyl-4-isopropylcyclohexanone, menthone,
Isomenthone, tetrahydrocarbon, 2-tert-butyl-4-methylcyclohexanone, 2,6-disecondary-butylcyclohexanone, 2,4- (ditertiary amyl) cyclohexanone, 4-hydroxymethylcyclohexanone,

2-trifluoromethylcyclohexanone, 3-trifluoromethylcyclohexanone, 4-trifluoromethylcyclohexanone, 4-chloromethylcyclohexanone, 4- (2-chloroethyl) cyclohexanone, 4- (2-chloropropyl) cyclohexanone, 4 -Methoxymethylcyclohexanone, 4-ethoxymethylcyclohexanone, 4-methoxyethylcyclohexanone, 4-ethoxyethylcyclohexanone, 4
-Isopropoxymethylcyclohexanone, 4-normalbutoxymethylcyclohexanone, 4-tert-butoxymethylcyclohexanone, 4-chloromethoxymethylcyclohexanone, 4-methoxycarbonylmethylcyclohexanone, 4-ethoxycarbonylmethylcyclohexanone, 4-dimethylaminomethylcyclohexanone, 2 -Dimethylaminomethylcyclohexanone,
4-diethylaminomethylcyclohexanone, 4-dimethylaminocarbonylmethylcyclohexanone, 2-methoxycyclohexanone,

2-ethoxycyclohexanone, 2-chlorocyclohexanone, 3-chlorocyclohexanone, 4
-Chlorocyclohexanone, 2-bromocyclohexanone, 3-bromocyclohexanone, 4-bromocyclohexanone, 2,4-dichlorocyclohexanone, 3,4
-Dichlorocyclohexanone, 3,5-dichlorocyclohexanone and 2,4,6-trichlorocyclohexanone.

The above-mentioned various cyclohexanone derivatives can be used in any range depending on the purpose of the reaction, but when they are generally added, the catalyst amount is 0.001 times the molar amount of the starting aminotriazine compound. To a large excess amount of the solvent, and a range of 0.1 to 50 times mol is effective from the viewpoint of reaction and operability.

The phenol derivative used in the reaction has the general formula (III)

[0032]

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{In the formula, R may be the same or different and may be a C _1-20 alkyl group which may be substituted, (as the substituent, a hydroxyl group, a halogen atom, an alkoxy group,
A haloalkoxy group, an alkoxycarbonyl group, a dialkylamino group, a dialkylaminocarbonyl group, and an optionally substituted C _1-20 alkoxy group (as the substituent, a hydroxyl group, a halogen atom, an alkoxy group,
A haloalkoxy group, an alkoxycarbonyl group, a dialkylamino group, a dialkylaminocarbonyl group) or a halogen atom, and n represents an integer of 0 to 3. } The phenol derivative represented by these is mentioned.

[0034] Preferably in this, in the general formula (III) R may be the same or different, represent an alkyl group, an alkoxy group of C _1-20 of C _1-20, n is an integer of from 0 to 3 A phenol derivative that represents Of these, phenol, 2
-Cresol, 3-cresol, 4-cresol, 2-
Ethylphenol, 3-ethylphenol, 4-ethylphenol, 2-normalpropylphenol, 3-normalpropylphenol, 4-normalpropylphenol, 2-isopropylphenol, 3-isopropylphenol, 4-isopropylphenol, 2-normalbutylphenol , 3-normal butylphenol, 4-normal butylphenol, 2-tert-butylphenol, 3-tert-butylphenol, 4-tert-butylphenol, 4-cyclopentylphenol, 4-normalhexylphenol,
4-cyclohexylphenol, 4-normal octylphenol, 4-decylphenol, 4-dodecylphenol,

4-hexadecylphenol, 4-octadecylphenol, 2,4-dimethylphenol, 3,
4-dimethylphenol, 3,5-dimethylphenol, 2,6-dimethylphenol, 2,4,6-trimethylphenol, 2-methyl-4-isopropylphenol, 4-hydroxymethylphenol, 4-chloromethylphenol, 2 -Trifluoromethylphenol,
3-trifluoromethylphenol, 4-trifluoromethylphenol, 4- (2-chloroethyl) -phenol, 4- (2-chloropropyl) -phenol, 4-
Methoxymethylphenol, 4-ethoxymethylphenol, 4-methoxyethylphenol, 4-ethoxyethylphenol, 4-isopropoxymethylphenol, 4-normalbutoxymethylphenol, 4-tert-butoxymethylphenol, 4-chloromethoxymethylphenol , 4-methoxycarbonylmethylphenol, 4-ethoxycarbonylmethylphenol,
4-dimethylaminomethylphenol, 2-dimethylaminomethylphenol, 4-diethylaminomethylphenol, 4-dimethylaminocarbonylmethylphenol, 2-chlorophenol, 3-chlorophenol, 4
-Chlorophenol, 2-bromophenol, 3-bromophenol, 4-bromophenol, 2,4-dichlorophenol, 3,4-dichlorophenol, 3,5-
Examples include dichlorophenol and 2,4,6-trichlorophenol.

The amount of the above various phenol derivatives used is
It may be in any range depending on the purpose of the reaction, but in general, when added, it may be in a range from 0.01 times mol to the starting amount of the aminotriazine compound to a large excess amount of the solvent. , Preferably 0.1 to 50
A double molar range is effective in terms of reaction and operability.

The above-mentioned various cyclohexanone derivatives and phenol derivatives are independently used for phenylation.
Alternatively, they can be mixed and used. When mixed and used, it is generally more suitable for the production of the intended phenylamino-substituted triazine that the cyclohexanone derivative and the phenol derivative have the same substituents and structures, but in some cases, the cyclohexanone derivative It is also possible to combine the compounds having different substituents in the phenol derivative with each other and use them in this reaction.

This reaction is carried out using a metal catalyst, and as the metal catalyst used, chromium or a metal catalyst of Group VIII of the Periodic Table gives preferable results. Among them, a catalyst containing at least one metal selected from chromium, cobalt, iron, nickel, ruthenium, palladium, platinum, copper, rhodium and iridium is preferable, and particularly chromium, iron, nickel, ruthenium, palladium, Catalysts containing platinum, copper and rhodium are preferred.

When using these catalysts, for example, complex catalysts of these elements, supported catalysts and the like can be used.
More specific examples of the catalyst will be given below. As the iron catalyst, Raney iron, pentacarbonyl iron, dodecacarbonyltriiron, dichlorobis (triphenylphosphine) iron,
Examples thereof include complex catalysts such as tetracarbonyl (triphenylphosphine) iron and tricarbonylbis (triphenylphosphine) iron.

As the nickel catalyst, Raney nickel catalyst, solid silica and supported catalyst such as nickel-supported silica, nickel-supported alumina and nickel-supported carbon, dichlorobis (triphenylphosphine) nickel, tetrakis (triphenylphosphine) nickel, tetrakis (triphenyl) are used. Examples thereof include complex catalysts such as phosphite) nickel, nickel chloride, and nickel oxide.

Examples of the ruthenium catalyst include ruthenium-supported silica, ruthenium-supported alumina, ruthenium-supported carbon, ruthenium-supported zeolite and other supported catalysts, pentacarbonyl ruthenium, dodecacarbonyltriruthenium, tetrahydridododecacarbonyltetraruthenium, and dihydrido (2 nitrogen) tris. (Triphenylphosphine)
Ruthenium, dicarbonyltris (triphenylphosphino) ruthenium, tetracarbonyl (trimethylphosphite) ruthenium, pentakis (trimethylphosphite) ruthenium, tris (acetylacetonato) ruthenium, diacetatodicarbonylbis (triphenylphosphine) ruthenium, Dichlorobis (chlorotricarbonyl) ruthenium, carbonylchlorohydridotris (triphenylphosphine) ruthenium, tetrahydridotris (triphenylphosphine) ruthenium, acetatohydridotris (triphenylphosphine) ruthenium,

Dichlorobis (acetonitrile) bis (triphenylphosphine) ruthenium, ruthenocene, bis (pentamethylcyclopentadienyl) ruthenium, dichloro (pentamethylcyclopentadienyl) ruthenium, chloro (cyclopentadienyl) bis (triphenyl) Phosphine) ruthenium, hydride (cyclopentadienyl) bis (triphenylphosphine) ruthenium,
Chlorocarbonyl (cyclopentadienyl) ruthenium, hydrido (cyclopentadienyl) (1,5-cyclooctadiene) ruthenium, chloro (cyclopentadienyl) (1,5-cyclooctadiene) ruthenium,
Dihydridotetrakis (triphenylphosphine) ruthenium, cyclooctatriene (cyclooctadiene)
Ruthenium, chlorohydrido tris (triphenylphosphine) ruthenium, tricarbonylbis (triphenylphosphine) ruthenium, tricarbonyl (cyclooctatetraene) ruthenium, tricarbonyl (1,5
Examples thereof include complex catalysts such as -cyclooctadiene) ruthenium and dichlorotris (triphenylphosphine) ruthenium, and ruthenium chloride, ruthenium oxide, ruthenium black.

Examples of the palladium catalyst include Raney palladium, palladium-supported silica catalyst, palladium-supported alumina catalyst, palladium-supported carbon catalyst, palladium-supported barium sulfate catalyst, palladium-supported various zeolite catalysts, palladium-supported silica / alumina catalyst, and other solid or supported catalysts. , Dichlorobis (triphenylphosphine) palladium, dichlorobis (trimethylphosphine) palladium, dichlorobis (tributylphosphine) palladium, bis (tricyclohexylphosphine) palladium, tetrakis (triethylphosphite) palladium, bis (cycloocta-1,5-diene) palladium, Tetrakis (triphenylphosphine) palladium, dicarbonylbis (triphenylphosphine) palladium, carbonyltris ( Li triphenylphosphine)
Examples thereof include complex catalysts such as palladium, dichlorobis (benzonitrile) palladium and dichloro (1,5-cyclooctadiene) palladium, and palladium chloride and palladium oxide.

As the platinum catalyst, a platinum-supported silica catalyst,
Platinum-supported alumina catalyst, supported catalyst such as platinum-supported carbon catalyst, dichlorobis (triphenylphosphine) platinum,
Dichlorobis (trimethylphosphine) platinum, dichlorobis (tributylphosphine) platinum, tetrakis (triphenylphosphine) platinum, tetrakis (triphenylphosphite) platinum, tris (triphenylphosphine) platinum, dicarbonylbis (triphenylphosphine) platinum, carbonyl Tris (triphenylphosphine) platinum, cis-bis (benzonitrile) dichloroplatinum,
Examples thereof include complex catalysts such as bis (1,5-cyclooctadiene) platinum, platinum chloride, platinum oxide (Adams catalyst), platinum black and the like.

As the rhodium catalyst, a supported catalyst such as a rhodium-supported silica catalyst, a rhodium-supported alumina catalyst, a rhodium-supported carbon catalyst, chlorotris (triphenylphosphine) rhodium, hexadecacarbonyl hexarhodium, dodecacarbonyltetrarhodium, dichlorotetracarbonyl rhodium. , Hydrido tetracarbonyl rhodium, hydrido carbonyl tris (triphenylphosphine) rhodium, hydrido tetrakis (triphenylphosphine) rhodium, dichlorobis (cyclooctadiene) dirhodium, dicarbonyl (pentamethylcyclopentadienyl) rhodium, cyclopentadienyl Examples include complex catalysts such as bis (triphenylphosphine) rhodium and dichlorotetrakis (allyl) dirhodium, and rhodium chloride and rhodium oxide.

As the iridium catalyst, dichlorobis (cyclooct-1,5-diene) diiridium, dichlorobis (cyclooctene) diiridium, chlorocarbonylbis (triphenylphosphine) iridium, hydridotris (triphenylphosphine) iridium,
Examples thereof include bis (cycloocta-1,5-diene) bis (1H-pyrazolate) diiridium, iridium acetylacetonate, iridium chloride, iridium oxide and iridium black.

In addition to the above, simple metals or metal oxides such as chromium, iron, nickel, ruthenium, palladium, rhodium and iridium which can be used in the reaction can be preferably used. Each of the above catalysts may be used alone or in combination. Further, a polynuclear complex catalyst and a multi-element system (iron-chromium, nickel-copper, copper-chromium, copper-chromium-ruthenium, copper-nickel-ruthenium, etc.) metal catalyst in which two or more kinds of the above metals are combined and its alumina, silica, silica. It is also possible to use supported catalysts on alumina, activated carbon, diatomaceous earth and the like.

The amount of the metal catalyst used is represented by the general formula (I)
Usually 0.00001 to 20 with respect to the triazine derivative of
The range of mol% is preferable, and the range of 0.0001 to 10 mol% is preferable. A ligand may be added to the above catalyst, if necessary. Examples of the ligand include trimethylphosphine, triethylphosphine, tributylphosphine, triphenylphosphine, tris (paratolyl) phosphine, tris (2,6-dimethylphenyl) phosphine, diphenylphosphinobenzene-3-sulfonate, bis ( 3-sulfonatophenyl) phosphinobenzene sodium salt, 1,2-bis (diphenylphosphino) ethane, 1,3-bis (diphenylphosphino) propane, 1,4-bis (diphenylphosphino) butane, tris ( 3-sulfonatophenyl) phosphine sodium salt and other monodentate and polydentate tertiary phosphines, triethylphosphite, tributylphosphite, triphenylphosphite, and tris (2,6-dimethylphenyl) phosphite Acid esters,
Triphenylmethylphosphonium iodide, triphenylmethylphosphonium bromide, triphenylmethylphosphonium chloride, triphenylallylphosphonium iodide, triphenylallylphosphonium bromide, triphenylallylphosphonium chloride, tetraphenylphosphonium iodide, tetraphenylphosphonium bromide, tetra Phosphonium salts such as phenylphosphonium chloride, triphenyl phosphate, trimethyl phosphate, triethyl phosphate, phosphate esters such as triallyl phosphate, unsaturated hydrocarbons such as cyclooctadiene and cyclopentadiene, benzonitrile, acetonitrile, etc. And acetylacetone.

The amount of the ligand used is usually in the range of 0.1 to 10000 mol%, preferably 10 to 5000 mol% based on the above metal catalyst. The reaction temperature is
Triazine derivative of general formula (I) used, general formula (II)
Cyclohexanone derivative and / or the general formula (II
Although it depends on the reactivity of the phenol derivative of I), it is usually room temperature to 500 ° C, preferably 50 to 350 ° C.

The reaction time is usually 1 to 100 hours, preferably 2 to 50 hours, depending on the reactivity of the triazine derivative of the general formula (I). This reaction proceeds even without solvent, but a solvent can be used if necessary from the viewpoint of operability and the like. The solvent is not particularly limited as long as it is inert to the reaction, for example, tetrahydrofuran, diethyl ether, diethylene glycol diethyl ether,
Ethers such as 1,4-dioxane, alcohols such as methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, isobutanol, 2-methyl-2-propanol, cyclohexanol and benzyl alcohol. , Benzene, toluene, xylene, mesitylene, cumene, chlorobenzene, o-dichlorobenzene, m-dichlorobenzene, p-dichlorobenzene, aromatic hydrocarbons such as tetrahydronaphthalene, n-
Hexane, cyclohexane, n-octane, aliphatic hydrocarbons such as n-decane, methyl acetate, ethyl acetate, butyl acetate, ethyl propionate, methyl benzoate, esters of ethyl benzoate, etc., acetonitrile, propionitrile, Nitriles such as butyronitrile, N, N-dimethylformamide, N, N-dimethylacetamide, amides such as N-methylpyrrolidone, 1,3-dimethylimidazolidinone, N, N, N ′, N′-tetramethyl Urea such as urea, and water are included. These can be used alone or in combination. It is also possible to use an excessive amount of the cyclohexanone derivative represented by the general formula (II) and the phenol derivative represented by the general formula (III) in combination, or each independently as a solvent. May be used as a solvent.

This reaction is generally carried out in a reaction atmosphere inert to the reaction.
Helium, argon and the like are preferable, but even if air, oxygen, carbon monoxide and the like coexist, no phenomenon that inhibits the reaction is observed. The pressure is preferably 0.1 to 500 kg / cm ² , and more preferably 0.5 to 200 kg / cm ² . In this reaction, due to the transfer of hydrogen during the reaction, in addition to the target phenyl-substituted aminotriazine derivative, a compound in which a part of the aromatic ring is reduced to a cyclohexyl group is by-produced.
Since the amount of by-products varies depending on the substrate used, the type of raw material, the catalyst species, the reaction temperature, the reaction time, the reaction solvent, etc., it is possible to suppress the amount produced by controlling these. It can also be controlled by coexisting a substance having a hydrogen accepting ability in the reaction system.

As a treatment method after completion of the reaction, when the product is soluble in an organic solvent, after removing unreacted triazines by means such as filtration, the solvent may be removed by distillation or the like if necessary. After extracting the product as a water-organic solvent two-phase system, the reaction product can be purified and isolated by recrystallization, distillation, chromatographic separation or the like. The metal catalyst is used in the case of a solid or supported catalyst by filtration, in the case of an organic metal complex, the solvent, the product removed by distillation, recrystallization, etc., and the water-soluble ligand. In the case of presence, in the water layer as a water-soluble metal complex by the extraction operation,
It can be separated, recovered and reused in various forms.

The substituted-1,3,5-triazine derivative obtained by the phenylation method of the amino group on the ring carbon atom of the 1,3,5-triazine ring of the present invention as described above is
It is a 1,3,5-triazine derivative represented by the general formula (IV).

[0054]

Embedded image

[Wherein at least one or more of X ⁴ , X ⁵ and X ⁶ is independently an NHR ³ group (wherein R ³ is a group represented by the general formula (V))

[0056]

Embedded image

(In the formula, R may be the same or different and may be a C _1-20 alkyl group which may be substituted; (the substituents are a hydroxyl group, a halogen atom, an alkoxy group,
A haloalkoxy group, an alkoxycarbonyl group, a dialkylamino group, a dialkylaminocarbonyl group, and an optionally substituted C _1-20 alkoxy group (as the substituent, a hydroxyl group, a halogen atom, an alkoxy group,
A haloalkoxy group, an alkoxycarbonyl group, a dialkylamino group, a dialkylaminocarbonyl group) or a halogen atom, and n represents an integer of 0 to 3).

NR in other cases^FourR_FiveGroup {R^Four, R_FiveHaso
Independently hydrogen atom, C_1-20Alkyl group of
The kill group is C_1-6An alkoxy group, an aryloxy group,
C_2-7An alkoxycarbonyl group of C_2-7Acyloxy
Group, C_2-7Acyl group of C_2-12A dialkylamino group of
C_2-12Dialkylaminocarbonyl group, C_2-12Zia
Alkylaminocarbonyloxy group, phenyl group (the group
The nil group is C_1-6Alkyl group of C_1-6With an alkoxy group of
Optionally substituted))
I), C_2-20An alkenyl group (wherein the alkenyl group is C
_1-6An alkoxy group, an aryloxy group, C_2-7Arco
Xycarbonyl group, C_2-7An acyloxy group of C_2-7No
Silyl group, C_2-12Dialkylamino group, C_2-12Gials
Killaminocarbonyl group, C_2-12Dialkylaminoca
Rubonyloxy group, phenyl group (the phenyl group is C
_1-6Alkyl group of C_1-6Optionally substituted with an alkoxy group of
Optionally)), C)_2-7
An alkoxycarbonyl group of C_2-7Acyl group of C_2-12
Represents a dialkylaminocarbonyl group of^Four, R ^Five
Together, optionally with 1 or 2 alkylene chains
C_1-8-(CH substituted by an alkyl group of_Two)
_2-5-, -CH_TwoCH_Two−N (C_1-8Alkyl) -CH_Two
CH_Two-Or -CH_TwoCH_Two-O-CH_TwoCH_TwoForm-
Good},

C₁-₂₀An alkyl group of {wherein the alkyl group is C
_1-6An alkoxy group, a carboxyl group, C_2-7Alcoqui
Cicarbonyl group, C_2-10An acyloxy group of C_2-7No
Silyl group, C_2-12Dialkylamino group, C_2-12Gials
Killaminocarbonyl group, C _2-12Dialkylaminoca
Rubonyloxy group, aryl group (the aryl group is C
_1-6Alkyl group of C_1-6Optionally substituted with an alkoxy group of
May be arbitrarily substituted)),

[0060] C ₂ - ₂₀ alkenyl group {said alkenyl group is an alkoxy group of C _1-6, a carboxyl group, an alkoxycarbonyl group having C _2-7, an acyloxy group having C _2-10, C
_2-7 acyl group, C _2-12 dialkylamino group, C _2-12
Dialkylaminocarbonyl group, dialkylaminocarbonyl group of C _2-12, an aryl group (the aryl group, alkyl group of C _1-6, may be optionally substituted by an alkoxy group C _1-6) May be arbitrarily replaced},

Phenyl group (the phenyl group is a C _1-6 alkyl group, a C _1-6 alkoxy group, an aryloxy group, C
_2-10 acyloxy group, C _2-7 acyl group, carboxyl group, C _2-7 alkoxycarbonyl group, C _2-10 acyl group, C _2-12 dialkylamino group, C _2-12 dialkyl Aminocarbonyl group, C _2-12 dialkylaminocarbonyloxy group, aryl group (the aryl group is C _1-6
Optionally substituted with an alkyl group of C _1-6 , optionally substituted with a C _1-6 alkoxy group)},

C _1-10 alkoxy group (the alkoxy group is a C _1-6 alkoxy group, aryloxy group, carboxyl group, C _2-7 alkoxycarbonyl group, C _2-10 acyloxy group, C _{2 -7} acyl group, C _2-12 dialkylamino group, C _2-12 dialkylaminocarbonyl group,
Dialkylaminocarbonyloxy group of C _2-12, aryl group (the aryl group, C _1-6 alkyl, may be optionally substituted by an alkoxy group C _1-6) optionally substituted with Good},

[0063] or an alkylthio group {said alkylthio group C _1-10, the alkoxy group of C _1-6, aryloxy group, a carboxyl group, an alkoxycarbonyl group having C _2-7, an acyloxy group having C _{2-1 0,} C _2-7 acyl group, C
_2-12 dialkylamino group, C _2-12 dialkylaminocarbonyl group, C _2-12 dialkylaminocarbonyloxy group, aryl group (the aryl group is a C _1-6 alkyl group, a C _1-6 It may be optionally substituted with an alkoxy group). ].

Among these, the phenyl group obtained favorably in production
The substituted 1,3,5-triazine derivative is represented by the above formula (IV)
X^Four, X^FiveAnd X⁶At least one of them is independent
NHR^ThreeIn the formula, R^ThreeIs the above general formula (V) (R is the same as
One or different, C _1-20An alkyl group of
C_1-20Represents an alkoxy group, and n represents an integer of 0 to 3.
Represents)),

Others are independently NR ⁴ R ⁵ groups {R
⁴ , R ⁵ are each independently a hydrogen atom, a C _1-20 alkyl group (the alkyl group is a C _1-6 alkoxy group, a phenyl group (the phenyl group is a C _1-6 alkyl group, C _1-6 alkoxy group may be optionally substituted), C _2-20 alkenyl group (the alkenyl group may be a C _1-6 alkoxy group, a phenyl group ( the phenyl group, C _1-6 alkyl group may be optionally substituted with may also be) optionally substituted by an alkoxy group C _1-6)
Represents

[0066] or is R ^4, R ⁵ are together an alkylene chain is substituted by an alkyl group having one or two C _1-8 optionally _{- (CH 2) 3-5 -,} - CH 2 CH ₂ -N
(C _{1 -8} alkyl) -CH ₂ CH ₂ - or -CH ₂ CH ₂
-O-CH ₂ CH ₂ - represents represents} to the may be formed),
Each independently of the other X ^4, X ^5, X ⁶ is C ₁ - ₂₀ alkyl group {said alkyl group is an alkoxy group of C _1-6, aryl group (the aryl group, the C _1-6 Alkyl group, optionally substituted with C _1-6 alkoxy group)), optionally substituted with},

Phenyl group (the phenyl group is a C _1-6 alkyl group, a C _1-6 alkoxy group, an aryl group (the aryl group is a C _1-6 alkyl group, a C _1-6 alkoxy group Optionally substituted), optionally substituted}, a C _1-10 alkoxy group {wherein the alkoxy group is C
_1-6 alkoxy group, aryl group (the aryl group is C
_1-6 alkyl group, C _1-6 alkoxy group may be optionally substituted)), and the 1,3,5-triazine derivative.

The substituted 1,3,5-triazine derivative of the general formula (IV), which is more preferably produced, is the compound of the general formula (IV) in which at least one of X ⁴ , X ⁵ and X ⁶ is NH.
R ³ group (in the formula, R ³ may be the same as or different from the general formula (V), and R ³ may be the same or different, and is a C _1-20 alkyl group or C _1-20.
Represents an alkoxy group, and n represents an integer of 0 to 3). }, And the others are each independently an NR ⁴ R ⁵ group {R ⁴ and R ⁵ are hydrogen atoms, C _1-20 alkyl groups (the alkyl groups are C _1-6 alkoxy groups, phenyl groups May be replaced with),

[0069] or R ^4, R ⁵ together an alkylene chain is substituted by an alkyl group having one or two C _1-8 optionally _{- (CH 2) 4-5 -,} - CH 2 CH ₂ -N
(C _{1 -8} alkyl) -CH ₂ CH ₂ - or -CH ₂ CH ₂
-O-CH ₂ CH ₂ - may be formed. _１ ，, a 1,3,5-triazine derivative which is any one of a C _1-20 alkyl group, a phenyl group and a C _1-10 alkoxy group.

As described above, various compounds can be used as the raw material 1,3,5-triazine derivative, cyclohexanone derivative and / or phenol derivative in the present invention, and the product obtained by the method of the present invention is ,
1,3,5-triazine derivatives, which have various phenylamino groups, depending on the combination of phenol derivatives
A 3,5-triazine derivative is obtained.

As described above, from the viewpoint of availability of raw materials, melamine, various melamine derivatives and various guanamine derivatives are used as raw materials 1,3,5-, and various basic organic intermediates are used as cyclohexanone derivatives and / or phenol derivatives. And cyclohexanone derivatives and / or phenol derivatives as petroleum products, and combinations of these give representative products.

The range of raw materials applicable to this reaction is not limited by the price and availability of these raw materials, but the following are specific examples of the raw materials in this reaction and the substituents of the products. , Further clarify the scope of this reaction.
In the formula, X ¹ , X ² and X ³ of the general formula (I) of the raw material, and NR ¹ R ^{2 of the} substituents represented by X ⁴ , X ⁵ and X ⁶ of the general formula (IV) of the product, and NR ⁴ R ⁵ includes a methylamino group, an ethylamino group, an isopropylamino group,
n-butylamino group, i-butylamino group, sec-butylamino group, tert-butylamino group, cyclohexylamino group, cyclohexylmethylamino group, n-octylamino group, n-decylamino group, n-dodecylamino group, n-hexadecylamino group, dimethylamino group, diethylamino group, diisopropylamino group, di-n-butylamino group,
Di-i-butylamino group, di-sec-butylamino group, methyl
-tert-butylamino group, methylcyclohexylamino group, cyclohexylmethylamino group, di-n-octylamino group, dicyclohexylmethylamino group, methoxymethylamino group, 1-ethoxymethylamino group, 1-n-propoxymethylamino group , 1-n-butoxymethylamino group, 1-i-butoxymethylamino group, 1-n-pentyloxymethylamino group,

1-methoxyethylamino group, 2-methoxyethylamino group, 1-ethoxyethylamino group, 1-
n-propoxyethylamino group, 1-n-butoxyethylamino group, 1-i-butoxyethylamino group, 1-n-pentyloxyethylamino group, 1-methoxypropylamino group, 1-ethoxypropylamino group, 1 -N-propoxypropylamino group, 1-n-butoxypropylamino group,
1-i-butoxypropylamino group, 1-n-pentyloxypropylamino group, 2-ethoxyethylamino group, 3
-Methoxypropylamino group, 2-pentyloxyethylamino group, 3-cyclohexyloxypropylamino group, phenoxymethyl group, 1-phenoxyethyl group, 2
-Phenoxyethyl group, 2-methoxycarbonylethylamino group,

2-ethoxycarbonylethylamino group,
tert-butoxycarbonylethylamino group, 2-cyclohexyloxycarbonylethylamino group, acetoxymethylamino group, 3-acetoxypropylmethylamino group, cyclohexanoyloxyethylamino group, 2-benzoyloxypropylamino group, 2-acetyl Ethylamino group, 3-benzoylpropylamino group, dimethylaminoethylamino group, diethylaminoethylamino group, dimethylaminocarbonylmethylamino group, diethylaminocarbonylmethylamino group, dimethylaminocarbonyloxymethylamino group, diethylaminocarbonyloxymethylamino group, N-methyl N-phenylamino group, benzylamino group, dibenzylamino group, N-
Benzyl-N-methylamino group, 2-phenylethylamino group, 2- (4-cyclohexylphenyl) -ethylamino group, 4-methoxybenzylamino group, 3,5-dimethylbenzylamino group, 4-cyclopentyloxybenzylamino group Group, vinylamino group, allylamino group, methallylamino group, crotylamino group, 3-cyclopentenylamino group, 3-cyclohexenylamino group, diallylamino group, dimethallylamino group, 3- (1-methoxy) -allyl group, ethoxycarbonylallyl Amino group,
Cinnamylamino group, N- (4-methylcinnamyl)-
Examples thereof include N-methylamino group and 4-methoxycinnamylamino group.

Further, specific examples of the group to which R ¹ and R ² of the NR ¹ R ² group are bonded or R ⁴ and R ⁵ of the NR ⁴ R ⁵ group are bonded include aziridino group, pyrrolidino group, piperidino group, N-
Examples thereof include a methylpiperazino group and a morpholino group.
Examples of the NR ¹ R ² group or NR ⁴ R ⁵ group other than the above include methoxycarbonylamino group, ethoxycarbonylamino group, propoxycarbonylamino group, isopropoxycarbonylamino group, n-butoxycarbonylamino group, is
o-butoxycarbonylamino group, sec-butoxycarbonylamino group, tert-butoxycarbonylamino group, n-pentyloxycarbonylamino group, iso-pentyloxycarbonylamino group, sec-pentyloxycarbonylamino group, neo-pentyloxycarbonyl Amino group, 1,
2-dimethylpropyloxycarbonylamino group, n-hexyloxycarbonylamino group, N-methoxycarbonyl-N-methylamino group,

N-ethoxycarbonyl-N-methylamino group, N-propoxycarbonyl-N-methylamino group, N-isopropoxycarbonyl-N-methylamino group, Nn-butoxycarbonyl-N-methylamino group,
N-iso-butoxycarbonyl-N-methylamino group, N
-Sec-butoxycarbonyl-N-methylamino group, N-
tert-butoxycarbonyl-N-methylamino group, Nn
-Pentyloxycarbonyl-N-methylamino group, N
-Iso-pentyloxycarbonyl-N-methylamino group, N-sec-pentyloxycarbonyl-N-methylamino group, N-neo-pentyloxycarbonyl-N-methylamino group, Nn-hexyloxycarbonyl-N -Methylamino group, N-1,2-dimethylpropyloxycarbonyl-N-methylamino group,

N-methoxycarbonyl-N-ethylamino group, N-ethoxycarbonyl-N-ethylamino group,
N-propoxycarbonyl-N-ethylamino group, N-
Isopropoxycarbonyl-N-ethylamino group, N-
n-butoxycarbonyl-N-ethylamino group, N-iso-
Butoxycarbonyl-N-ethylamino group, N-sec-butoxycarbonyl-N-ethylamino group, N-tert-butoxycarbonyl-N-ethylamino group, Nn-pentyloxycarbonyl-N-ethylamino group, N -Iso-pentyloxycarbonyl-N-ethylamino group, N-se
c-pentyloxycarbonyl-N-ethylamino group, N
-Neo-pentyloxycarbonyl-N-ethylamino group, Nn-hexyloxycarbonyl-N-ethylamino group, N-1,2-dimethylpropyloxycarbonyl-N-ethylamino group,

N-methoxycarbonyl-Nn-propylamino group, N-ethoxycarbonyl-Nn-propylamino group, N-propoxycarbonyl-Nn-propylamino group, N-isopropoxycarbonyl-N- n-propylamino group, Nn-butoxycarbonyl-Nn-propylamino group, N-iso-butoxycarbonyl-Nn-propylamino group, N-sec-butoxycarbonyl-Nn-propylamino group , N-tert-butoxycarbonyl-N-n
-Propylamino group, Nn-pentyloxycarbonyl-Nn-propylamino group, N-iso-pentyloxycarbonyl-Nn-propylamino group, N-sec-pentyloxycarbonyl-Nn-propyl Amino group, N-neo-
Pentyloxycarbonyl-N-n-propylamino group,
Nn-hexyloxycarbonyl-Nn-propylamino group, N-1,2-dimethylpropyloxycarbonyl-Nn-propylamino group,

N-methoxycarbonyl-Nn-butylamino group, N-ethoxycarbonyl-Nn-butylamino group, N-propoxycarbonyl-Nn-butylamino group, N-isopropoxycarbonyl-N- n-butylamino group, Nn-butoxycarbonyl-Nn-butylamino group, N-iso-butoxycarbonyl-Nn-butylamino group, N-sec-butoxycarbonyl-Nn-butylamino group , N-tert-butoxycarbonyl-Nn-butylamino group, Nn-pentyloxycarbonyl-Nn-butylamino group, N-iso-pentyloxycarbonyl-Nn-
Butylamino group, N-sec-pentyloxycarbonyl-
Nn-butylamino group, N-neo-pentyloxycarbonyl-Nn-butylamino group, Nn-hexyloxycarbonyl-Nn-butylamino group, N-1,2-dimethylpropyloxycarbonyl -N-n-butylamino group,

N-methoxycarbonyl-Nn-hexylamino group, N-ethoxycarbonyl-N-ethylamino group, N-propoxycarbonyl-N-ethylamino group,
N-isopropoxycarbonyl-N-ethylamino group,
N-n-butoxycarbonyl-N-ethylamino group, N-
iso-butoxycarbonyl-N-ethylamino group, N-se
c-butoxycarbonyl-N-ethylamino group, N-tert
-Butoxycarbonyl-N-ethylamino group, Nn-pentyloxycarbonyl-N-ethylamino group, N-is
o-pentyloxycarbonyl-N-ethylamino group, N
-Sec-pentyloxycarbonyl-N-ethylamino group, N-neo-pentyloxycarbonyl-N-ethylamino group, Nn-hexyloxycarbonyl-N-ethylamino group,

N-1,2-dimethylpropyloxycarbonyl-N-ethylamino group, N-methoxycarbonyl-N-ethylamino group, N-ethoxycarbonyl-N-
Ethylamino group, N-propoxycarbonyl-N-ethylamino group, N-isopropoxycarbonyl-N-ethylamino group, Nn-butoxycarbonyl-N-ethylamino group, N-iso-butoxycarbonyl-N-ethyl Amino group, N-sec-butoxycarbonyl-N-ethylamino group, N-tert-butoxycarbonyl-N-ethylamino group, Nn-pentyloxycarbonyl-N-ethylamino group, N-iso-pentyloxycarbonyl -N-ethylamino group, N-sec-pentyloxycarbonyl-N-ethylamino group, N-neo-pentyloxycarbonyl-N
-Ethylamino group, N-n-hexyloxycarbonyl-
N-ethylamino group, N-1,2-dimethylpropyloxycarbonyl-N-ethylamino group, N-methoxycarbonyl-N-ethylamino group, N-ethoxycarbonyl-N-ethylamino group,

N-propoxycarbonyl-N-ethylamino group, N-isopropoxycarbonyl-N-ethylamino group, Nn-butoxycarbonyl-N-ethylamino group, N-iso-butoxycarbonyl-N-ethylamino group Group, N-sec-butoxycarbonyl-N-ethylamino group, N-tert-butoxycarbonyl-N-ethylamino group, Nn-pentyloxycarbonyl-N-ethylamino group, N-iso-pentyloxycarbonyl- N-ethylamino group, N-sec-pentyloxycarbonyl-N-ethylamino group, N-neo-pentyloxycarbonyl-N
-Ethylamino group, N-n-hexyloxycarbonyl-
N-ethylamino group, N-1,2-dimethylpropyloxycarbonyl-N-ethylamino group,

N-acetylamino group, propionylamino group, n-butyrylamino group, i-butyrylamino group, valeroylamino group, isovaleroylamino group, 2-methylbutyrylamino group, pivaloylamino group, caproylamino group, tert-butylacetylamino group, enanthylamino group, n-caprylylamino group, acryloylamino group, 3-butenoylamino group, crotonoylamino group,
Methacryloylamino group, 3-pentenoylamino group, benzoylamino group, N-acetyl-N-methylamino group, N-propionyl-N-methylamino group, N-
n-butyryl-N-methylamino group, Ni-butyryl-N
-Methylamino group, N-valeroyl-N-methylamino group, N-isovaleroyl-N-methylamino group, N-
(2-Methylbutyryl) -N-methylamino group, N-pivaloyl-N-methylamino group, N-caproyl-N-
Methylamino group, N- (tert-butylacetyl) -N-
Methylamino group, N-enanthyl-N-methylamino group, Nn-caprylyl-N-methylamino group, N-crotonoyl-N-methylamino group, N-methacryloyl-N-methylamino group, N- ( 3-pentenoyl) -N
-Methylamino group, N-benzoyl-N-methylamino group, N-acetyl-N-ethylamino group, N-propionyl-N-ethylamino group, N- (n-butyryl) -N-
Ethylamino group, N- (i-butyryl) -N-ethylamino group, N-valeroyl-N-ethylamino group, N-isovaleroyl-N-ethylamino group, N- (2-methylbutyryl) -N-ethylamino Group, N-pivaloyl-N-
Ethylamino group, N-caproyl-N-ethylamino group, N- (tert-butylacetyl) -N-ethylamino group, N-crotonoyl-N-ethylamino group, N-methacryloyl-N-ethylamino group,

N-benzoyl-N-ethylamino group, N
-Acetyl-N- (n-butyl) -amino group, N-propionyl-N- (n-butyl) -amino group, N- (n-butyryl) -N- (n-butyl) -amino group, N- (I-Butyryl) -N- (n-butyl) -amino group, N-valeroyl-
N- (n-butyl) -amino group, N-isovaleroyl-N
-(N-Butyl) -amino group, N- (2-methylbutyryl) -N- (n-butyl) -amino group, N-pivaloyl-
N- (n-butyl) -amino group, N-caproyl-N-
(N-Butyl) -amino group, N- (tert-butylacetyl) -N- (n-butyl) -amino group, N-crotonoyl-N- (n-butyl) -amino group, N-methacryloyl-N -(N-Butyl) -amino group, N- (3-butyne-1)
-Oil) -N- (n-butyl) -amino group, N-benzoyl-N- (n-butyl) -amino group, N-acetyl-N
-(N-hexyl) -amino group, N-propionyl-N-
(N-hexyl) -amino group, N- (n-butyryl) -N-
(N-hexyl) -amino group, N- (i-butyryl) -N-
(N-hexyl) -amino group, N-valeroyl-N- (n-
Hexyl) -amino group, N-isovaleroyl-N- (n-
Hexyl) -amino group, N- (2-methylbutyryl)-
N- (n-hexyl) -amino group, N-pivaloyl-N-
(N-hexyl) -amino group, N-caproyl-N- (n-
Hexyl) -amino group,

N- (tert-butylacetyl-N- (n-hexyl) -amino group, N-acryloyl-N- (n-hexyl) -amino group, N- (3-butenoyl) -N- (n-
Hexyl) -amino group, N-crotonoyl-N- (n-hexyl) -amino group, N-methacryloyl-N- (n-
Hexyl) -amino group, N-benzoyl-N- (n-hexyl) -amino group, N-acetyl-N-cyclohexylamino group, N-propionyl-N-cyclohexylamino group, N- (n-butyryl) -N -Cyclohexylamino group, N- (i-butyryl) -N-cyclohexylamino group, N-valeroyl-N-cyclohexylamino group, N
-Isovaleroyl-N-cyclohexylamino group, N-
(2-Methylbutyryl) -N-cyclohexylamino group, N-pivaloyl-N-cyclohexylamino group, N
-Caproyl-N-cyclohexylamino group, N- (te
rt-butylacetyl) -N-cyclohexylamino group,
N-benzoyl-N-cyclohexylamino group, N-benzoyl-N- (2-ethylhexyl) -amino group, N
-Acetyl-N-methoxymethylamino group, N-propionyl-N-methoxymethylamino group, N- (n-butyryl) -N-methoxymethylamino group, N- (i-butyryl) -N-methoxymethylamino group , N-valeroyl-
N-methoxymethylamino group, N-isovaleroyl-N
-Methoxymethylamino group, N- (2-methylbutyryl) -N-methoxymethylamino group, N-pivaloyl-
N-methoxymethylamino group, N-caproyl-N-methoxymethylamino group, N- (tert-butylacetyl)
-N-methoxymethylamino group,

Dimethylaminocarbonylamino group, diethylaminocarbonylamino group, dipropylaminocarbonylamino group, dibutylaminocarbonylamino group,
Dipentylaminocarbonylamino group, N-methyl-N
-Phenylaminocarbonylamino group, dicyclohexylaminocarbonylamino group, phenylamino group, 4-
Trilylamino group, 3-tolylamino group, 2-tolylamino group, 4-ethylphenylamino group, 4-isopropylphenylamino group, 4-cyclohexylphenylamino group, 2-methoxyphenylamino group, 3-methoxyphenylamino group, 4- Examples thereof include a methoxyphenylamino group.

Examples of the optionally substituted alkyl group having 1 to 20 carbon atoms include methyl group, ethyl group, n-propyl group,
n-butyl group, i-butyl group, sec-butyl group, n-amyl group,
i-amyl group, hexyl group, cyclohexyl group, cyclohexylmethyl group, pentyl group, octyl group, 2-ethylhexyl group, nonyl group, decyl group, hexadecyl group, octadecyl group, methoxymethyl group, methoxyethyl group, ethoxymethyl group, Cyclohexylmethoxyethyl group, methoxycarbonylmethyl group, methoxycarbonylethyl group, tert-butoxycarbonylmethyl group, cyclohexyloxycarbonylethyl group, 2-propanoyloxyethyl group, benzoyloxymethyl group,

2,4,6-trimethylphenylbenzoyloxymethyl group, acetyloxymethyl group, 3- (ter
t-butylcarbonyloxy) -propyl group, dimethylaminomethyl group, diethylaminomethyl group, diisopropylaminomethyl group, di-n-butylaminomethyl group, di-i-
Butylaminomethyl group, di-sec-butylaminomethyl group, methyl-tert-butylaminomethyl group, methylcyclohexylaminomethyl group, cyclohexylmethylaminomethyl group, benzyl group, 4-methylbenzyl group, 4-methoxybenzyl group, 3,5-dimethylbenzyl group and 4-
Examples thereof include a cyclopentyloxybenzyl group.

Examples of the alkenyl group having 2 to 20 carbon atoms which may be substituted include vinyl group, isopropenyl group and 1-
Butenyl group, 3-hexenyl group, allyl group, methallyl group, crotyl group, methoxyvinyl group, ethoxyvinyl group, cyclohexylvinyl group, 4-phenyl-2-butenyl group, ethoxycarbonylvinyl group, tert-butoxycarbonylvinyl group, Acetyloxyvinyl group, cyclohexanoyloxyvinyl group, dimethylaminovinyl group, 4-diethylaminobutenyl group, dicyclohexylaminovinyl group, cinnamyl group, 3,5-dimethoxycinnamyl group, 2,4,6-trimethylcinnamyl group Group, styryl group, 6-dodecen-1-yl group, 1,2-diphenylvinyl group and the like.

As the phenyl group which may be substituted,
Phenyl group, p-toluyl group, m-toluyl group, o-toluyl group, 3,5-dimethylphenyl group, 4-cyclohexylphenyl group, 2,4,6-trimethylphenyl group, 2-
Methyl-4-isopropylphenyl group, 3,5-dimethoxyphenyl group, 4-cyclopentyloxyphenyl group, m-phenoxyphenyl group, 4- (2-naphthyloxy) -phenyl group, 3-acetoxyphenyl group, 3-benzoyl Oxyphenyl group, 4-carboxyphenyl group, 4-methoxycarbonylphenyl group, 3-cyclohexyloxycarbonylphenyl group, 2-acetylphenyl group, 4-octanoylphenyl group, 4-acetyloxyphenyl group, 3-cyclohexylcarbonyl group Oxyphenyl group, 2-dimethylaminophenyl group, 4-diethylaminophenyl group, 4-diisopropylaminophenyl group, 3-di-n-butylaminophenyl group, 3-di-
i-butylaminophenyl group, 2-di-sec-butylaminophenyl group, 4-methyl-tert-butylaminophenyl group, 4-methylcyclohexylaminophenyl group, 4-
Examples thereof include a cyclohexylmethylaminophenyl group, a 4-biphenyl group and a 4- (2-naphthyl) -phenyl group.

The C _1-10 alkoxy group which may be substituted includes methoxy group, ethoxy group, n-propyloxy group, i-propyloxy group, n-butyloxy group, i-butyloxy group and sec-butyloxy group. Group, tert-butyloxy group, n-amyloxy group, i-amyloxy group, hexyloxy group, cyclohexyloxy group, cyclohexylmethyloxy group, pentyloxy group, octyloxy group, 2-
Ethylhexyloxy group, nonyloxy group, decyloxy group, hexadecyloxy group, octadecyloxy group,
Methoxymethoxy group, methoxyethoxy group, ethoxymethoxy group, cyclohexylmethoxyethoxy group, 2-carboxyethoxy group, 3-carboxypropoxy group, methoxycarbonylmethoxy group, methoxycarbonylethoxy group, tert-butoxycarbonylmethoxy group, cyclohexyloxycarbonylethoxy Group, acetyloxymethyloxy group, benzoyloxymethyloxy group, 3
-(Tert-butylcarbonyloxy) -propyloxy group, dimethylaminomethyloxy group, diethylaminomethyloxy group, diisopropylaminomethyloxy group,
Di-n-butylaminomethyloxy group, di-i-butylaminomethyloxy group, di-sec-butylaminomethyloxy group, methyl-tert-butylaminomethyloxy group, methylcyclohexylaminomethyloxy group, cyclohexylmethylamino Examples thereof include a methyloxy group, a benzyloxy group, a 4-methylbenzyloxy group, a 4-methoxybenzyloxy group, a 3,5-dimethylbenzyloxy group and a 4-cyclopentyloxybenzyloxy group.

The C _1-10 alkylthio group which may be substituted includes methylthio group, ethylthio group, n-propylthio group, i-propylthio group, n-butylthio group, i-butylthio group, sec-butylthio group, tert-butylthio group, n-amylthio group, i-amylthio group, hexylthio group, cyclohexylthio group, cyclohexylmethylthio group, pentylthio group, octylthio group, 2-ethylhexylthio group,
Nonylthio group, decylthio group, hexadecylthio group, octadecylthio group, methoxymethylthio group, methoxyethylthio group, ethoxymethylthio group, cyclohexylmethoxyethylthio group, 2-carboxyethylthio group, 3
-Carboxypropylthio group, methoxycarbonylmethylthio group, methoxycarbonylethylthio group, tert-butoxycarbonylmethylthio group, cyclohexyloxycarbonylethylthio group, acetyloxymethylthio group, benzoyloxymethylthio group, 3- (tert-butylcarbonyloxy) -Propylthio group, dimethylaminomethylthio group, diethylaminomethylthio group, diisopropylaminomethylthio group, di-n-butylaminomethylthio group, di-i-butylaminomethylthio group, di-sec-butylaminomethylthio group, methyl-tert-butyl Aminomethylthio group, methylcyclohexylaminomethylthio group,
Examples thereof include a cyclohexylmethylaminomethylthio group, a benzylthio group, a 4-methylbenzylthio group, a 4-methoxybenzylthio group, a 3,5-dimethylbenzylthio group and a 4-cyclopentyloxybenzylthio group.

The NHR ³ group produced by the reaction is
Phenylamino group, 2-tolylamino group, 3-tolylamino group, 4-tolylamino group, 2-ethylphenylamino group, 3-ethylphenylamino group, 4-ethylphenylamino group, 4-normalpropylphenylamino group,
4-isopropylphenylamino group, 4-normal butylphenylamino group, 4-tert-butylphenylamino group, 4-cyclopentylphenylamino group, 4-
Normalhexylphenylamino group, 4-cyclohexylphenylamino group, 4-normaloctylphenylamino group, 4-decylphenylamino group, 4-dodecylphenylamino group, 4-hexadecylphenylamino group,
4-octadecylphenylamino group, 2,4-dimethylphenylamino group, 3,4-dimethylphenylamino group, 3,5-dimethylphenylamino group, 2,6-dimethylphenylamino group, 2,4,6-trimethyl Phenylamino group, 2-methyl-4-isopropylphenylamino group, 4-hydroxymethylphenylamino group, 4-
Chlormethylphenylamino group, 4- (2-chloroethyl) -phenylamino group, 4- (2-chloropropyl)
-Phenylamino group,

4-methoxymethylphenylamino group, 4
-Ethoxymethylphenylamino group, 4-methoxyethylphenylamino group, 4-ethoxyethylphenylamino group, 4-isopropoxymethylphenylamino group, 4
-Normal butoxymethylphenylamino group, 4-tert-butoxymethylphenylamino group, 4-chloromethoxymethylphenylamino group, 4-methoxycarbonylmethylphenylamino group, 4-ethoxycarbonylmethylphenylamino group, 4-dimethylaminomethyl Phenylamino group, 2-dimethylaminomethylphenylamino group, 4-diethylaminomethylphenylamino group,
4-dimethylaminocarbonylmethylphenylamino group, 2-chlorophenylamino group, 3-chlorophenylamino group, 4-chlorophenylamino group, 2-bromophenylamino group, 3-bromophenylamino group, 4-bromophenylamino group Group, 2,4-dichlorophenylamino group, 3,4-dichlorophenylamino group, 3,5-dichlorophenylamino group, 2,4,6-trichlorophenylamino group and the like.

The examples of these substituents are very representative examples, and the present invention is not limited to these.
As a treatment method after completion of the reaction, when the product is soluble in an organic solvent, unreacted triazines are removed by means such as filtration, and then the solvent is removed by distillation or the like, if necessary.
After extracting the product as a two-phase system of an organic solvent, the reaction product can be purified and isolated by recrystallization, distillation, chromatographic separation or the like. When the product is sparingly soluble or insoluble in the organic solvent, the target product can be separated by utilizing the difference in solubility with the raw material in the system using water.

The metal catalyst is a solid or supported catalyst by filtration or the like, and in the case of an organic metal complex, the solvent and the product are removed by distillation, recrystallization or the like, or the water-soluble coordination. When the pups are used, they can be separated, recovered and reused in various forms such as a water-soluble metal complex in the aqueous layer by an extraction operation.

[0097]

EXAMPLES Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited thereto. In all of the examples, the product was separately synthesized in advance as a standard product (synthesis method: Journal of America Chemical Society (J. Amer. Chem. Soc), 6
9, 495, 1947 and 70, 343,
1948, or German Patent Appli
c.) 7432, 1943.
A reference example shows an example of synthesis of a representative standard. ), A calibration curve is created using the pure standard and the internal standard substance.
The amount of each product in the reaction product was accurately determined by the internal standard determination method by high performance liquid chromatography. Hereinafter, the yields described in this example are quantitative yields based on the aminotriazine derivative as a raw material.

The analysis conditions of the high performance liquid chromatography used are as follows. (Method for quantifying raw material triazine such as melamine) Eluent: CH ₃ CN / H ₂ O = 1/1 (v / v) Detection method: UV 240 nm column; GL Science Inertsil Ph 150 mm x
4.6 mmφ Flow rate; 1.0 ml / min Analytical temperature; 40 ° C Internal standard material; Phthalic acid di-n-butyl ester (Gradient analysis) Detection method; UV 230 nm column; GL Science Inertsil C ₈ 150 mm x
4.6 mmφ Flow rate; 1.0 ml / min Analysis temperature; 35 ° C Internal standard substance; Phthalic acid di (2-ethylhexyl) ester

Reference Example 1 (2,4-diamino-6-phenylamino-1,3,5
-Synthesis of triazine)

[0100]

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184.5 g (1.0 mol) of cyanuric chloride was dissolved in 800 mL of acetonitrile at room temperature, and then 0
To the solution cooled to 0 ° C., 303.7 g (5.0 mol) of 28% aqueous ammonia solution was added at a reaction temperature of 1 with vigorous stirring.
The solution was added dropwise over 2 hours to keep the temperature at 0 ° C or lower. After completion of the dropping, cooling was stopped, the mixture was stirred at room temperature for 1 hour, then gradually heated to 45 ° C. and further reacted for 4 hours. After cooling, the product was filtered and washed with a large amount of water. The filtered product is dried under vacuum at 50 ° C. for 6 hours to give 2,4-
Diamino-6-chloro-1,3,5-triazine was used as 11
5 g (yield 79%) was obtained.

5.8 g (0.04 mol) of 2,4-diamino-6-chloro-1,3,5-triazine synthesized above and 3.72-g (0.04 mol) of aniline were added to 1,4-
Dioxane (60 mL) was added, and the mixture was reacted by heating and stirring at a reaction temperature of 95 ° C. for 3 hours. After cooling, the precipitated crystals were collected by filtration, washed with water and dried to give the title compound (7.8).
3 g (yield 97%) was obtained. Melting point; 274 [deg.] C.

Reference Example 2 (2,4,6-tris (phenylamino) -1,3,5
-Synthesis of triazine)

[0104]

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Cyanuric chloride (10 g, 0.054 mol) and aniline (18.6 g, 0.2 mol) were added to 1,4-dioxane (130 g), and the mixture was heated at 60 ° C. for 1 hour and further 90 minutes.
The reaction was carried out while stirring at ℃ for 1 hour, and then 156 g of a 3.8 wt% aqueous solution of sodium hydroxide was added dropwise at the same temperature over 1 hour. After cooling, the precipitated crystals were collected by filtration, washed thoroughly with water, and then dried to obtain 3.36 g of the title compound (isolated yield 17.6%). Melting point;
234 ° C.

Reference Example 3 (Synthesis of 2,4-bis (cyclohexylamino) -6-phenylamino-1,3,5-triazine)

[0107]

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18.4 g (0.1 mol) of cyanuric chloride, 19.8 g (0.2 g) of cyclohexylamine,
A mixture of 180 g of 1,4-dioxane was stirred at 5 ° C. for 1 hour and then at 20 ° C. for 30 minutes, and 68 g of an 11 wt% aqueous solution of sodium hydroxide was further added thereto. The mixture was stirred and reacted for a time. The precipitated crystals were collected by filtration, washed thoroughly with water, 180 g of 1,4-dioxane was added to the obtained crystals, and then 9.3 g (0.1 mol) of aniline was added dropwise, and the reaction temperature was adjusted to 7
The temperature was raised to 0 ° C and stirred for 3 hours.
% Aqueous solution was added and stirred for 1 hour to complete the reaction. The precipitated crystals were collected by filtration, washed thoroughly with water, and dried under reduced pressure to give the title compound (31.2 g, yield 85.2%). Melting point; 211 [deg.] C.

Reference Example 4 (Synthesis of 2-cyclohexylamino-4,6-bis (phenylamino) -1,3,5-triazine)

[0110]

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A mixture of 18.4 g (0.1 mol) of cyanuric chloride, 18.6 g (0.2 g) of aniline and 180 g of 1,4-dioxane was added at 5 ° C. for 0.5 hours, followed by 20 ° C. for 30 minutes. Stir and add 1 part of sodium hydroxide.
After adding 68 g of a 1% by weight aqueous solution, the reaction temperature was 20
The reaction was carried out with stirring for 3 hours while maintaining the temperature. The precipitated crystals were collected by filtration, washed thoroughly with water, 180 g of 1,4-dioxane was added to the obtained crystals, and subsequently 19.6 g (0.2 mol) of cyclohexylamine was added dropwise. The mixture was stirred at 70 ° C. for 2 hours and at 90 ° C. for 2 hours, 204 g of a 2% aqueous solution of sodium hydroxide was further added, and the mixture was stirred for 1 hour to complete the reaction. The precipitated crystals are collected by filtration, washed thoroughly with water, and dried under reduced pressure to give the title compound
2.1 g (yield 61.4%) was obtained. Melting point; 199 [deg.] C.

Example 1 (2-amino-4,6-bis (cyclohexylamino))
Reaction of -1,3,5-triazine with cyclohexanone)

[0113]

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2-amino-4,6-bis (cyclohexylamino) -1,3,5-triazine (2.90 g, 10 mmol) and cyclohexanone (47.3 g, 0.483 mol) were placed in a stainless steel autoclave having an internal volume of 100 mL. 5% Pd-C (0.20 g) was charged, the system was sufficiently replaced with nitrogen gas, the temperature was raised, and the reaction was carried out at a reaction temperature of 250 ° C. for 6 hours. After cooling, the contents of the autoclave were taken out and quantitatively analyzed according to the above-mentioned analysis conditions. The conversion rate of the starting material 2-amino-4,6-bis (cyclohexylamino) -1,3,5-triazine was 9%.
8.3%, 5,4-bis (cyclohexylamino) -6-phenylamino-1,3,5-triazine as a product, 57.3%, 2,4,6-tris (cyclohexylamino)- 25.1% of 1,3,5-triazine
Was produced in a yield of. Example 2 (2-amino-4,6-bis (cyclohexylamino)
Reaction of -1,3,5-triazine with cyclohexanone)

[0115]

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2-amino-4,6-bis (cyclohexylamino) -1,3,5-triazine (2.90 g, 10 mmol) and cyclohexanone (47.3 g, 0.483 mol) were placed in a stainless steel autoclave having an internal volume of 100 mL. 2% Pt-C (0.10 g) was charged, the system was sufficiently replaced with nitrogen gas, the temperature was raised, and the reaction was carried out at a reaction temperature of 250 ° C. for 0.5 hour. After cooling, the contents of the autoclave were taken out and quantitatively analyzed according to the above analysis conditions. The conversion rate of the starting material 2-amino-4,6-bis (cyclohexylamino) -1,3,5-triazine was 4.1. %, 2,4-bis (cyclohexylamino) -6-phenylamino-1,3,5-triazine as a product was 1.8%, and 2,4,6-tris (cyclohexylamino) -1,3. , 5-triazine was produced in a yield of 0.4%.

Example 3 (2-amino-4,6-bis (cyclohexylamino))
Reaction of -1,3,5-triazine with cyclohexanone)

[0118]

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2-amino-4,6-bis (cyclohexylamino) -1,3,5-triazine (2.90 g, 10 mmol) and cyclohexanone (47.3 g, 0.483 mol) were placed in a stainless steel autoclave having an internal volume of 100 mL. 5% Ph-C (0.10 g) was charged, the system was sufficiently replaced with nitrogen gas, the temperature was raised, and the reaction was carried out at a reaction temperature of 250 ° C. for 0.3 hours. After cooling, the contents of the autoclave were taken out and quantitatively analyzed according to the above analysis conditions. The conversion rate of 2-amino-4,6-bis (cyclohexylamino) -1,3,5-triazine as a raw material was 8.1. %, 2,3-bis (cyclohexylamino) -6-phenylamino-1,3,5-triazine as a product 3.3%, 2,4,6-tris (cyclohexylamino) -1,3 , 5-triazine was produced in a yield of 4.2%.

Example 4 (2-amino-4,6-bis (cyclohexylamino))
Reaction of -1,3,5-triazine with phenol)

[0121]

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2-amino-4,6-bis (cyclohexylamino) -1,3,5-triazine (2.90 g, 10 mmol) and phenol 47.0 g (0.5 mol) were placed in a stainless steel autoclave having an internal volume of 100 mL. 5% P
After 0.20 g of d-C was charged and the inside of the system was sufficiently replaced with nitrogen gas, the temperature was raised and the reaction was carried out at a reaction temperature of 250 ° C. for 6 hours. After cooling, take out the contents of the autoclave,
Quantitative analysis was performed according to the above analysis conditions, and it was found that the starting material, 2-amino-4,6-bis (cyclohexylamino)
The conversion of -1,3,5-triazine was 49.8%, and the product, 2,4-bis (cyclohexylamino) -6-phenylamino-1,3,5-triazine was 10.3%, 2,4,6-Tris (cyclohexylamino) -1,3,5-triazine was obtained in a yield of 4.2%.

Example 5 (2-amino-4,6-bis (cyclohexylamino))
Reaction of -1,3,5-triazine with cyclohexanone and phenol)

[0124]

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2-amino-4,6-bis (cyclohexylamino) -1,3,5-triazine (2.90 g, 10 mmol) and cyclohexanone (24.5 g, 0.25 mol) were placed in a stainless steel autoclave having an internal volume of 100 mL. , Phenol 23.5 g (0.25 mol), 5% P
After 0.20 g of d-C was charged and the inside of the system was sufficiently replaced with nitrogen gas, the temperature was raised and the reaction was carried out at a reaction temperature of 250 ° C. for 6 hours. After cooling, take out the contents of the autoclave,
Quantitative analysis was performed according to the above analysis conditions, and it was found that the starting material, 2-amino-4,6-bis (cyclohexylamino)
The conversion rate of -1,3,5-triazine is 69.0%, and 2,4-bis (cyclohexylamino) -6-phenylamino-1,3,5-triazine is 28.4% as a product. 2,4,6-Tris (cyclohexylamino) -1,3,5-triazine was obtained in a yield of 15.9%.

Example 6 (Reaction of melamine with cyclohexanone)

[0127]

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Melamine (2,4,6-triamino-1,3,3) was placed in a stainless steel autoclave having an internal volume of 100 mL.
5-triazine) 1.26 g (10 mmol), cyclohexanone 50.0 g (0.51 mol), 5% Pd-C
After 0.10 g was charged and the system was sufficiently replaced with nitrogen gas, the temperature was raised and the reaction was carried out at a reaction temperature of 250 ° C. for 6 hours. After cooling, the contents of the autoclave were taken out and quantitatively analyzed according to the above-mentioned analysis conditions. As a result, the conversion rate of the raw material melamine was 98.0% and the product was 2,4
12.0% of -diamino-6-phenylamino-1,3,5-triazine, 3.0% of 2,4-diamino-6-cyclohexylamino-1,3,5-triazine, 2-
Amino-4,6-bis (cyclohexylamino) -1,
2.0% 3,5-triazine, 2,4-bis (cyclohexylamino) -6-phenylamino-1,3,5-
Triazine 18.4%, 2-cyclohexylamino-
4,6-bis (phenylamino) -1,3,5-triazine 5.0%, 2,4,6-tris (cyclohexylamino) -1,3,5-triazine 22.0% 2,
4,6-Tris (phenylamino) -1,3,5-triazine was obtained in a yield of 15.9%.

Example 7 (Reaction of benzoguanamine with cyclohexanone)

[0130]

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1.87 g (10 mmol) of benzoguanamine (2,4-diamino-6-phenyl-1,3,5-triazine), 49.0 g (0.5 mol) of cyclohexanone were placed in a stainless steel autoclave having an internal volume of 100 mL. 5% Pd-C (0.10 g) was charged, the system was sufficiently replaced with nitrogen gas, the temperature was raised, and the reaction was carried out at a reaction temperature of 260 ° C. for 5 hours. After cooling, the contents of the autoclave were taken out and quantitatively analyzed according to the above-mentioned analysis conditions. The conversion rate of benzoguanamine as a raw material was 91.4%.
And 2-amino-4-cyclohexylamino-6-phenyl-1,3,5-triazine as a product.
1%, 2-amino-4-phenyl-6-phenylamino-1,3,5-triazine 8.4%, 2,4-bis (cyclohexylamino) -6-phenyl-1,3,5
-Triazine 16.3%, 2-cyclohexylamino-4-phenyl-6-phenylamino-1,3,5-triazine 20.4%, 2-phenyl-4,6-bis (phenylamino) -1 , 3,5-triazine is 18.
It was obtained in a yield of 0%.

Example 8 (Reaction of acetoguanamine with cyclohexanone)

[0133]

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1.25 g (10 mmol) of acetoguanamine (2,4-diamino-6-methyl-1,3,5-triazine) and 49.0 g (0.5 mol) of cyclohexanone were placed in a stainless steel autoclave having an internal volume of 100 mL. ,
After 5% Pd-C (0.10 g) was charged and the system was sufficiently replaced with nitrogen gas, the temperature was raised and the reaction was carried out at a reaction temperature of 250 ° C. for 4 hours. After cooling, the contents of the autoclave were taken out and subjected to a quantitative analysis according to the above analysis conditions. The conversion rate of acetoguanamine as a raw material was 62.7%, and 2-amino-4-cyclohexylamino-6-methyl as a product. -1,3,5-triazine is 4.4%,
2-amino-4-methyl-6-phenylamino-1,
3,5-triazine is 9.3%, 2,4-bis (cyclohexylamino) -6-methyl-1,3,5-triazine is 13.3%, 2-cyclohexylamino-4-methyl-6-phenyl. Amino-1,3,5-triazine is 1
5.5% and 2-methyl-4,6-bis (phenylamino) -1,3,5-triazine were obtained in a yield of 11.0%, respectively.

[0135]

INDUSTRIAL APPLICABILITY According to the method of the present invention, aminotriazines of the general formula (I) can be used as various fine chemical intermediates for various agricultural chemicals, pharmaceuticals, dyes, paints, etc. under relatively mild reaction conditions, and variously. The phenylamino-1,3,5-triazine derivative of the general formula (IV), which is a useful compound group widely used as the resin material and the flame retardant material, can be easily produced.

The various phenylated substituted-1,3,5-triazine derivatives of the products obtained according to the invention are generally obtained as a mixture of triazine derivatives having different numbers of phenyl groups, but these products are It can be separated in a pure form by a general method for separating an organic compound, and can be used for the above various uses. In addition, depending on the field of use (especially in the case of flame retardants for resins, modifying additives as plasticizers, etc.), the reaction mixture can be used as it is without any particular separation.

Further, many of the phenyl group-substituted triazines obtained by this reaction have hitherto been relatively difficult or expensive to synthesize, and also in terms of physical properties, their solubility in water and various organic solvents, and high temperature Many compounds are interesting in terms of stability, melting point, boiling point, acidity / basicity, etc., and their applications are expected to expand more than before.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI Technical indication location // C07B 61/00 300 C07B 61/00 300 (72) Inventor Yasuo Fukue Tsuboi Town, Funabashi City, Chiba Prefecture 722 Address 1 Central Research Laboratory, Nissan Chemical Industries, Ltd.

Claims (16)

[Claims] 1. A 1,3,5-triazine derivative having at least one or more amino groups on a ring carbon atom is reacted with a cyclohexanone derivative and / or a phenol derivative in the presence of a metal catalyst. A method for phenylating an amino-1,3,5-triazine derivative, which comprises introducing a phenyl group into an amino group or a mono-substituted amino group on a triazine ring. 2. Having at least one or more amino groups
1,3,5-triazine derivative is represented by the general formula (I)
A 1,3,5-triazine derivative
Of amino-1,3,5-triazine derivative of phenyl
Method of conversion;[Where X¹, X^TwoAnd X^ThreeAt least one of them is independent
Represents an amino group, and X when it is not an amino group¹, X^TwoOver
And X^ThreeAre independently NR¹R^TwoIn the formula, R¹Or
R^TwoIs independently a hydrogen atom, C_1-20Alkyl group
(The alkyl group is C_1-6An alkoxy group, arylo
Xy group, C_2-7An alkoxycarbonyl group of C_2-7Reed
Luoxy group, C_2-7Acyl group of C_2-12The dialkyl a
Mino group, C_{2- 12}Dialkylaminocarbonyl group, C
_2-12Dialkylaminocarbonyloxy group, phenyl
Group (the phenyl group is C_1-6Alkyl group of C_1-6Al
Optionally substituted with a cooxy group)
), C_2-20Alkenyl group (the alkenyl
The group is C_1-6An alkoxy group, an aryloxy group, C_2-7
An alkoxycarbonyl group of C_2-7An acyloxy group of
C_2-7Acyl group of C_2-12Dialkylamino group, C
_2-12Dialkylaminocarbonyl group, C_2-12Gials
Killaminocarbonyloxy group, phenyl group (the phenyl group
The radical is C_1-6Alkyl group of C_1-6With the alkoxy group of
May be arbitrarily substituted).
I), C_2-7An alkoxycarbonyl group of C_2-7The acyl
Group, C_2-12Dialkylaminocarbonyl group of phenyl
Group (the phenyl group is C_1-6Alkyl group of C_1-6Al
Optionally substituted with a coxy group),
R¹, R^TwoTogether, optionally with an alkylene chain of 1
Or two C_1-8Substituted by an alkyl group of
(CH_Two)_2-5-, -CH_TwoCH_Two− (C_1-8Alkyl)
N-CH_TwoCH_Two-Or -CH_TwoCH_Two-O-CH_TwoCH_Two−
May be formed}, C_1-20An alkyl group of {wherein the alkyl group is C_1-6Arco
Xy group, carboxyl group, C_2-7Alkoxy Carboni
Group, C_2-10An acyloxy group of C_2-7Acyl group of C
_2-12Dialkylamino group, C_2-12Dialkylamino
Carbonyl group, C _2-12Dialkylaminocarbonyl
An oxy group, an aryl group (the aryl group is C _1-6Archi
Group, C_1-6Optionally substituted with an alkoxy group of
Optional) may be substituted}, C_2-20An alkenyl group of {the alkenyl group is C_1-6No
Lucoxy group, carboxyl group, C_2-7The alkoxycar
Bonyl group, C_2-10An acyloxy group of C_2-7The acyl
Group, C_2-12Dialkylamino group, C_2-12Dialkyl
Aminocarbonyl group, C_2-12Dialkylaminocarbo
Nyloxy group, aryl group (the aryl group is C_1-6of
Alkyl group, C_1-6Optionally substituted with an alkoxy group of
Optionally substituted with)}, a phenyl group {wherein the phenyl group is C_1-6Alkyl group of C_1-6
An alkoxy group, an aryloxy group, C_2-10The acylo
Xy group, C_2-7Acyl group, carboxyl group, C_2-7No
Alkoxycarbonyl group, C_2-10Acyl group of C_2-12No
Alkylamino group, C_2-12Dialkylaminocarboni
Group, C_2-12A dialkylaminocarbonyloxy group of
Aryl group (the aryl group is C_1-6Alkyl group of C
_1-6Optionally substituted with an alkoxy group of
Optionally substituted}, C_1-10An alkoxy group of {wherein the alkoxy group is C_1-6No
Lucoxy group, aryloxy group, carboxyl group, C
_2-7An alkoxycarbonyl group of C_2-10Acyloxy
Group, C_2-7Acyl group of C_2-12A dialkylamino group of
C_2-12Dialkylaminocarbonyl group, C_2-12Zia
Rukylaminocarbonyloxy group, aryl group (the ari
Group is C_1-6Alkyl group of C_1-6With an alkoxy group of
Optionally substituted))
I} or C_1-10An alkylthio group of {the alkylthio group is
C_1-6Alkoxy group, aryloxy group, carboxy
Group, C_2-7An alkoxycarbonyl group of C_{2-1 0}Reed
Luoxy group, C_2-7Acyl group of C_2-12The dialkyl a
Mino group, C_2-12Dialkylaminocarbonyl group, C
_2-12Dialkylaminocarbonyloxy group, aryl
A group (the aryl group is C_1-6Alkyl group of C_1-6Al
Optionally substituted with a cooxy group)
Represents｝. ]. 3. In the 1,3,5-triazine derivative of the general formula (I), at least one of X ¹ , X ² and X ³ is an amino group, and when it is not an amino group, X ¹ , X ² and X ³ are each independently an NR ¹ R ² group (in the formula, R ¹ or R
² are each independently a hydrogen atom, a C _1-20 alkyl group (the alkyl group is a C _1-6 alkoxy group, a phenyl group (the phenyl group is a C _1-6 alkyl group, a C _1-6 Optionally substituted with an alkoxy group of), a C _2-20 alkenyl group (the alkenyl group is a C _1-6 alkoxy group, a phenyl group (the phenyl group). Represents optionally substituted with a C _1-6 alkyl group or a C _1-6 alkoxy group)), or R ¹ and R ² are the same as each other. And optionally the alkylene chain is substituted with one or two C _1-8 alkyl groups — (CH ₂ ) _3-5 —, —CH ₂ CH ₂ —
(Alkyl _{C 1-8) N-CH 2 CH} 2 - or -CH ₂ CH
₂ -O-CH ₂ CH ₂ - may be formed}, C ₁ - ₂₀ alkyl group {said alkyl group is an alkoxy group of C _1-6, aryl group (the aryl group, C _1-6 Optionally substituted with a C _1-6 alkoxy group, optionally substituted with a C _1-6 alkoxy group)}, phenyl group (wherein the phenyl group is a C _1-6 alkyl group, C _1-6
An alkoxy group or an aryl group (the aryl group is C _1-6
An alkyl group, optionally substituted with a C _1-6 alkoxy group)), a C _1-10 alkoxy group {wherein the alkoxy group is a C _1-6 alkoxy group). alkoxy group, an aryl group (the aryl group, C _1-6 alkyl groups, may also be optionally substituted by an alkoxy group C _1-6) is either may be optionally substituted with} The method for phenylating an amino-1,3,5-triazine derivative according to claim 2. 4. In the 1,3,5-triazine derivative of the general formula (I), at least one of X ¹ , X ² and X ³ is an amino group, and when it is not an amino group, X ¹ , X ² and X ³ is an NR ¹ R ² group (wherein R ¹ or R ² are each independently a hydrogen atom, a C _1-20 alkyl group (the alkyl group is a C _1-6 alkoxy group, a phenyl group, Or optionally substituted), or R ¹ and R ² are taken together, and the alkylene chain is optionally substituted by 1 or 2 C _1-8 alkyl _groups- (CH ₂ ) _4-5 −, −C
H ₂ CH ₂ - (C _1-8 alkyl) N-CH ₂ CH ₂ - or _{-CH 2 CH 2 -O-CH 2} CH 2 - may be formed}, alkyl C _1-20, The amino-1, according to claim 3, which is either a phenyl group or a C _1-10 alkoxy group.
A method for phenylating a 3,5-triazine derivative. 5. The cyclohexanone derivative used in the reaction is represented by the general formula (II): {In the formula, R may be the same or different and may be a C _1-20 alkyl group which may be substituted;
A hydroxyl group, a halogen atom, an alkoxy group, a haloalkoxy group, an alkoxycarbonyl group, a dialkylamino group, a dialkylaminocarbonyl group, and an optionally substituted C _1-20 alkoxy group (the substituent is a hydroxyl group, And a halogen atom, an alkoxy group, a haloalkoxy group, an alkoxycarbonyl group, a dialkylamino group and a dialkylaminocarbonyl group.) Or a halogen atom. n represents the integer of 0-3. } The method for phenylating an amino-1,3,5-triazine derivative according to claim 1, which is a cyclohexanone derivative represented by the following formula. 6. In the cyclohexanone derivative represented by the general formula (II), R may be the same or different,
Alkyl C _1-20, an alkoxy group of C _1-20, n
Is a cyclohexanone derivative which represents an integer of 0 to 3. The method for phenylating an amino-1,3,5-triazine derivative according to claim 5. 7. The phenol derivative used in the reaction is represented by the general formula (III): {In the formula, R may be the same or different and may be a C _1-20 alkyl group which may be substituted;
Examples thereof include a hydroxyl group, a halogen atom, an alkoxy group, a haloalkoxy group, an alkoxycarbonyl group, a dialkylamino group and a dialkylaminocarbonyl group. ), An optionally substituted C _1-20 alkoxy group (as the substituent, a hydroxyl group, a halogen atom, an alkoxy group, a haloalkoxy group, an alkoxycarbonyl group, a dialkylamino group,
A dialkylamino carbonyl group is mentioned. ) Or a halogen atom. n represents the integer of 0-3. } Amino derivative according to claim 1, which is a phenol derivative represented by
A method for phenylating a 1,3,5-triazine derivative. 8. In the phenol derivative represented by the general formula (III), R may be the same or different, and C
_The method for phenylating an amino-1,3,5-triazine derivative according to claim 7, wherein the amino-1,3,5-triazine derivative is a phenol derivative which represents a _1-20 alkyl group or a _C1-20 alkoxy group, and n is an integer of 0-3. 9. By the phenylation method according to claim 1.
The resulting substituted 1,3,5-triazine derivative has the general formula
Substituted 1,3,5-triazine derivative represented by (IV)
Of the amino-1,3,5-triazine derivative
Method;[Where X^Four, X^FiveAnd X⁶At least one or more of
NHR independently^ThreeIn the formula, R^ThreeIs the general formula (V)(In the formula, R may be the same or different and
May be C_1-20An alkyl group of (as this substituent,
Hydroxyl group, halogen atom, alkoxy group, haloalkoxy
Group, alkoxycarbonyl group, dialkylamino group, di
Alkylaminocarbonyl groups), substituted
C that can be_1-20Alkoxy group of (as this substituent
Hydroxyl group, halogen atom, alkoxy group, haloalkoxy
Group, alkoxycarbonyl group, dialkylamino group, di
Alkylaminocarbonyl groups) or halo
Represents a gen atom, and n represents an integer of 0 to 3)}
Represents, otherwise NR^FourR^FiveIn the formula, R^Four, R^FiveAre each
Independently hydrogen atom, C _1-20Alkyl group of (the alkyl group
Is C_1-6An alkoxy group, an aryloxy group, C_2-7of
Alkoxycarbonyl group, C_2-7An acyloxy group of C
_2-7Acyl group of C_2-12Dialkylamino group, C_2-12
Dialkylaminocarbonyl group, C_{2- 12}Dialkyl
Aminocarbonyloxy group, phenyl group (the phenyl group
Is C_{1- 6}Alkyl group of C_1-6Optionally with an alkoxy group of
May be substituted) may be optionally substituted),
C_2-20An alkenyl group (wherein the alkenyl group is C_1-6No
Lucoxy group, aryloxy group, C_2-7Alkoxyka
Rubonyl group, C_2-7An acyloxy group of C_2-7The acyl
Group, C_2-12Dialkylamino group, C_2-12Dialkyl
Aminocarbonyl group, C_2-12Dialkylaminocarbo
Nyloxy group, phenyl group (the phenyl group is C_1-6of
Alkyl group, C_1-6Optionally substituted with an alkoxy group of
Optionally)), C_2-7No
Alkoxycarbonyl group, C_2-7Acyl group of C_2-12No
Represents an alkylaminocarbonyl group, and R^Four, R^FiveIs one
And optionally C having 1 or 2 alkylene chains.
_1-8-(CH substituted by an alkyl group of_Two)_2-5
-, -CH_TwoCH_Two−N (C_1-8Alkyl) -CH_TwoCH
_Two-Or -CH_TwoCH_Two-O-CH_TwoCH_TwoGood to form
I}, C₁-₂₀An alkyl group of {wherein the alkyl group is C_1-6Arco
Xy group, carboxyl group, C_2-7Alkoxy Carboni
Group, C_2-10An acyloxy group of C_2-7Acyl group of C
_2-12Dialkylamino group, C_2-12Dialkylamino
Carbonyl group, C _2-12Dialkylaminocarbonyl
An oxy group, an aryl group (the aryl group is C _1-6Archi
Group, C_1-6Optionally substituted with an alkoxy group of
Optional) may be substituted}, C_Two-₂₀An alkenyl group of {the alkenyl group is C_1-6No
Lucoxy group, carboxyl group, C_2-7The alkoxycar
Bonyl group, C_2-10An acyloxy group of C_2-7The acyl
Group, C_2-12Dialkylamino group, C_2-12Dialkyl
Aminocarbonyl group, C_2-12Dialkylaminocarbo
Nyloxy group, aryl group (the aryl group is C_1-6of
Alkyl group, C_1-6Optionally substituted with an alkoxy group of
Optionally substituted with)}, a phenyl group {wherein the phenyl group is C_1-6Alkyl group of C_1-6
An alkoxy group, an aryloxy group, C_2-10The acylo
Xy group, C_2-7Acyl group, carboxyl group, C_2-7No
Alkoxycarbonyl group, C_2-10Acyl group of C_2-12No
Alkylamino group, C_2-12Dialkylaminocarboni
Group, C_2-12A dialkylaminocarbonyloxy group of
Aryl group (the aryl group is C_1-6Alkyl group of C
_1-6Optionally substituted with an alkoxy group of
Optionally substituted}, C_1-10An alkoxy group of {wherein the alkoxy group is C_1-6No
Lucoxy group, aryloxy group, carboxyl group, C
_2-7An alkoxycarbonyl group of C_2-10Acyloxy
Group, C_2-7Acyl group of C_2-12A dialkylamino group of
C_2-12Dialkylaminocarbonyl group, C_2-12Zia
Rukylaminocarbonyloxy group, aryl group (the ari
Group is C_1-6Alkyl group of C_1-6With an alkoxy group of
Optionally substituted))
I} or C_1-10An alkylthio group of {the alkylthio group is
C_1-6Alkoxy group, aryloxy group, carboxy
Group, C_2-7An alkoxycarbonyl group of C_{2-1 0}Reed
Luoxy group, C_2-7Acyl group of C_2-12The dialkyl a
Mino group, C_2-12Dialkylaminocarbonyl group, C
_2-12Dialkylaminocarbonyloxy group, aryl
A group (the aryl group is C_1-6Alkyl group of C_1-6Al
Optionally substituted with a cooxy group)
Represents｝. ]. 10. In the substituted 1,3,5-triazine derivative represented by the general formula (IV), at least one of X ⁴ , X ⁵ and X ⁶ is independently an NHR ³ group (wherein R ³ is the above general formula). formula (V) (R, which may be the same or different, represents an alkoxy group of the alkyl group or C _1-20 of C _1-20, n is 0
Represents an integer of 3 to 3), and the others independently represent NR ⁴ R ⁵ groups (in the formula, R ⁴ and R ⁵
_Are each independently a hydrogen atom, a C _1-20 alkyl group (the alkyl group is a C _1-6 alkoxy group, a phenyl group (the phenyl group is a C _1-6 alkyl group, a C _1-6 Optionally substituted with an alkoxy group) and optionally substituted with a C _2-20 alkenyl group (wherein the alkenyl group is
C _1-6 alkoxy group, phenyl group (the phenyl group is
C _1-6 alkyl group, C _1-6 alkoxy group may be optionally substituted)), or R ⁴ and R ⁵ are taken together to form a desired group. alkylene chain is substituted by an alkyl group having one or two C _1-8 by _{- (CH 2) 3-5 -,} - CH 2 CH 2 -N (C 1- 8
Alkyl) -CH ₂ CH ₂ - or -CH ₂ CH ₂ -O-C
H ₂ CH ₂ - may be a form) represents a}, C ₁ - ₂₀ alkyl group {said alkyl group is an alkoxy group, an aryl group (said aryl group C _1-6 is C _1-6 alkyl Group, optionally substituted with a C _1-6 alkoxy group)), phenyl group {wherein the phenyl group is a C _1-6 alkyl group, C _1-6
An alkoxy group or an aryl group (the aryl group is C _1-6
An alkyl group, optionally substituted with a C _1-6 alkoxy group)), a C _1-10 alkoxy group {wherein the alkoxy group is a C _1-6 alkoxy group). alkoxy group, an aryl group (the aryl group, C _1-6 alkyl groups, may also be optionally substituted by an alkoxy group C _1-6) is either may be optionally substituted with} A method for phenylating an amino-1,3,5-triazine derivative according to claim 9. 11. A substituted 1,3,5-tode of the general formula (III)
X in lysine derivatives^Four, X^FiveAnd X⁶Few of
At least one is NHR^ThreeIn the formula, R^ThreeIs the general formula (V)
(R may be the same or different, and C_1-20Archi
Group or C _1-20Represents an alkoxy group, and n is 0 to 3
Represents an integer), and the others independently represent NR.^FourR_FiveIn the formula, R^Four, R_Five
Is independently a hydrogen atom, C_1-20Alkyl group
(The alkyl group is C_1-6Alkoxy group, phenyl group
Optionally substituted with), or R^Four, R^FiveTogether, optionally alkylene
C with 1 or 2 chains_{1- 8}Substituted by an alkyl group of
There- (CH_Two)_4-5-, -CH_TwoCH_Two−N (C_{1 -8}No
Rukiru) -CH_TwoCH_Two-Or -CH_TwoCH_Two-O-CH_Two
CH_Two-May be formed), C₁-₂₀Alkyl group, phenyl group, C_1-10The alkoxy of
A 1,3,5-triazine derivative which is one of the groups
Amino-1,3,5-triazine derivative according to claim 10,
Method for phenylating conductors. 12. A 1,3,5-triazine derivative having at least one or more amino groups on a ring carbon atom is reacted with a cyclohexanone derivative and / or a phenol derivative by heating in the presence of a catalyst. ,
The method for phenylating an amino-1,3,5-triazine derivative according to claim 1, wherein a phenyl group is introduced into the amino group on the triazine ring. 13. The amino according to claim 1, wherein the metal catalyst is a catalyst containing at least one metal selected from chromium, cobalt, iron, nickel, ruthenium, palladium, platinum, copper, rhodium and iridium. -1,
A method for phenylating a 3,5-triazine derivative. 14. The metal catalyst is chromium, iron, nickel,
The method for phenylating an amino-1,3,5-triazine derivative according to claim 13, which is a catalyst containing at least one metal selected from ruthenium, palladium, platinum, copper and rhodium. 15. The metal catalyst is a complex catalyst.
Or a method for phenylating an amino-1,3,5-triazine derivative according to item 14. 16. The metal catalyst is a supported catalyst according to claim 13.
Or a method for phenylating an amino-1,3,5-triazine derivative according to item 14.