JPH08193071A - Method for alkylating triazine derivative - Google Patents

Abstract

PURPOSE: To readily alkylate a specific triazine derivative into a substituted one useful as an intermediate for medicines, agrochemicals, dyes, etc., in high yield by reacting the triazine derivative with an aldehyde or a ketone in the presence of a specified catalyst and a gas containing hydrogen. CONSTITUTION: (C) A 1,3,5-triazine derivative having a (monosubstituted) amino group on a ring carbon atom [e.g. a compound of the formula one or more of X<1> , X<2> and X<3> are each a group of the formula NHR<1> [R<1> is H, a (halogen, CF3 , etc., -substituted) 1-20C alkyl, a (halogen, CF3 , etc., -substituted) 2-20C alkenyl, etc.] and the rest are each a group of the formula NR<2> R<3> (R<2> and R<3> are each R<1> , etc., except H), a (halogen, OH, etc., -substituted) 1-20C alkyl, etc.}] is reacted with (D) an aldehyde or a ketone in the presence of (A) a group VII or VIII catalyst of the periodic table (e.g. an Ni, an Ru, a Pd, a Pt or an Re catalyst) and (B) a gas containing hydrogen. Thereby, the (monosubstituted) amino group in the component (C) is alkylated.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to Group VII of the Periodic Table and / or
Or in the presence of a Group VIII catalyst and a hydrogen-containing gas, various 1,3,5-triazines having at least one or more amino groups or mono-substituted amino groups are reacted with aldehydes or ketones, and at least 1 The present invention relates to a method for alkylating a 1,3,5-triazine derivative, which comprises alkylating one or more amino groups or mono-substituted amino groups.

Substitutions of 1,3,5-triazine derivatives of the present invention obtained by the method of alkylating an amino group or a mono-substituted amino group on the carbon atom of the triazine ring of the derivative-1,3,5-
-Triazine derivatives are a group of useful compounds that are widely used as flame-retardant materials as various fine chemical intermediates for agricultural chemicals, pharmaceuticals, dyes, paints, etc., and as various resin materials, especially as aminoplast former components. .

[0003]

2. Description of the Related Art Conventionally, various synthetic methods have been known as a synthetic method of substituted triazines.

[0004]

[Chemical 4]

(Wherein X ⁴ and X ⁵ represent a diethylamino group, X ⁶ represents an ethylamino group, or X ⁴ and X ⁵ represent an amino group, and X ⁶ represents an ethylamino group or a diethylamino group). Is 2-chloro-1,3,5-
A synthetic method by the reaction of a triazine derivative and ethylamine has been reported [J.Amer.Chem.Soc.], 73, 298.
P. 4, 1951].

General formula (III) (wherein X ⁴ , X ⁵ and X ⁶
Represents an ethylamino group. ) Compounds, 2,
A synthetic method by the reaction of 4,6-trimethylthio-1,3,5-triazine and ethylamine has been reported [Chem. Ber., Vol. 18, p. 2755, 1].
885]. Formula (III) (wherein X ⁴ is an amino group, X
⁵ represents an amino group or an octylamino group, and X ⁶ represents an octylamino group. ), The compound of 2, 4, 6-
A synthetic method by the reaction of triamino-1,3,5-triazine and octylamine hydrochloride has been reported [US Pat. No. 2,228,161, 1941].

Formula (III) (wherein X ⁴ is a phenyl group,
X ⁵ and X ⁶ represent a butylamino group. ), The compound of 2-phenyl-4,6-diamino 1,3,5-
A synthetic method by the reaction of triazine and butylamine has been reported [US Pat. No. 2,385,766, 1945].
Year〕. In addition, various 2,4 synthesized from cyanuric chloride
Derivatives of 6-substituted-1,3,5-triazines are used as flame retardants for thermoplastic polymers [JP-A-3-2
No. 15564]. Some of the specific examples of the derivatives described in JP-A-3-215564 are shown below.

[0008]

Embedded image

An example of the reaction of aminotriazines with a carbonyl compound such as an aldehyde or a ketone is represented by a reaction example of hydroxymethylation under mild alkaline conditions with an aqueous solution of melamine and formalin [Journal of America.・ Chemical Society (J.Amer.Che
m.Soc.), 69, 599, 1947]. Journal of America Chemical Society (J.Amer.C
Chem. Soc.), 73, 2984, 1954, often requires more than the equivalent amount of condensing agent and produces by-products such as salts which are often industrially problematic. Also,
Hemsche Berichte (Chem.Ber.), Vol. 18, 2755
P., 1885 The synthesis method produces by-products such as sulfur compounds which are often problematic in industry. US Patent 2,228,
161, 1941 and US Patent 2,385,766.
No. 1945 requires a high temperature for the reaction, and the former produces ammonium chloride as a by-product. In any case,
It has a common point that a substitution reaction with a leaving group is carried out using a substituted amine which is not industrially cheap, and this is one reason why the substituted triazines cannot be supplied at a low cost.

The reaction between aminotriazines and carbonyl compounds such as aldehydes or ketones is low due to the low reactivity of the amino group on the triazine ring, so that the Journal of America Chemical Society (J. Amer. Chem. So
c.), 69, 599, 1947, the hydroxymethylation reaction by the reaction of melamine with highly reactive formaldehyde is common, and in the case of reaction with other carbonyl compounds, especially aldehydes. It is known that a polynuclear body can be obtained by providing an equilibrium mixture of a raw material and a hydroxyalkylated product, and the product thereof is unstable or further easily dehydrated and condensed with other aminotriazines.

[0011]

DISCLOSURE OF THE INVENTION As a result of intensive investigations aimed at solving the above problems, the present inventors have found that various industrially inexpensive aldehyde derivatives or ketone derivatives and amino groups or mono groups on the triazine nucleus are used. A substituted amino group is reacted in the presence of a catalyst of Group VIII of the periodic table and a hydrogen-containing gas to introduce an alkyl group onto the amino group or mono-substituted amino group in a high yield, and only water is added. The present invention as a by-product has been completed.

The substitutions 1,3,5 obtained in this reaction are also
-The triazine derivative remarkably inhibits the association of multi-molecules due to the intermolecular hydrogen bond inherent in aminotriazines, so that the solubility in various solvents is improved, and at the same time, the melting point is also lowered. The compatibility with organic compounds is also improved. For example, taking melamine as an example, after reaction,
Most of the unreacted melamine precipitates as crystals in the solvent used for the reaction and is separated by means such as filtration. On the other hand, the product is an excellent method in terms of separation and purification because almost all of the product is dissolved in the solvent.

The object of the present invention is to alkylate an amino group or mono-substituted amino group on a ring carbon atom of 1,3,5-triazine with a carbonyl compound of an aldehyde or a ketone to obtain various agricultural chemicals, pharmaceuticals, dyes, A substituted-1,3,5-triazine derivative, which is a useful compound group that can be widely used as a fine chemical intermediate for paints, various resin materials and flame-retardant materials, can be easily produced in high yield. The present invention provides a method for alkylating a 1,3,5-triazine derivative that can be used.

[0014]

[Means for Solving the Problems] That is, the present invention provides that at least one or more amino groups or mono-substituted amino groups are cyclic in the presence of a catalyst of Group VII and / or Group VIII of the periodic table and a hydrogen-containing gas. A 1,3,5-triazine derivative having a carbon atom, which is reacted with an aldehyde or a ketone to alkylate at least one or more amino groups or mono-substituted amino groups. A method for alkylating a triazine derivative.

Alkylating the amino group or mono-substituted amino group of the present invention means converting the amino group into a mono- or dialkylamino group, or converting the mono-substituted amino group into a further alkylated dialkylamino group. Say. Hereinafter, the present invention will be described in more detail. The 1,3,5-triazine derivative having at least one amino group or mono-substituted amino group, which is the raw material of the present invention, is the 1,3,5-triazine derivative represented by the general formula (I).

[0016]

[Chemical 6]

[Wherein X¹, X²And X³Less of
Both are independently NHR¹Group {in the formula, R¹Is hydrogen
Child, C_1-20An alkyl group (wherein the alkyl group is a halogen source)
Child, trifluoromethyl group, hydroxyl group, C_1-6The Archoki
Shi group, C_1-6A haloalkoxy group, an aryloxy group,
C_2-7Alkoxycarbonyl group of C_2-7Akiruoki
Si group, amino group, C_1-8Monoalkylamino group, C
_2-12Dialkylamino group, phenyl group (the phenyl group
Is a halogen atom, C_1-6Alkyl group, hydroxyl group, C_{1- 6}
It may be optionally substituted with an alkoxy group of
May be replaced), C_2-20Alkenyl group of
Kenyl group is a halogen atom, trifluoromethyl group, water
Acid group, C_1-6Alkoxy group of C_1-6The haloalkoxy
Group, aryloxy group, C_2-7Alkoxycarbonyl
Group, C_2-7Acyloxy group, amino group, C_1-8Things
Alkylamino group, C_2-12The dialkylamino group of
Nyl group (the phenyl group is a halogen atom, C_1-6The archi
Group, hydroxyl group, C_1-6Optionally substituted with an alkoxy group of
May be substituted with)).
Represents the above NHR¹X when not a group¹, X²as well as
X³Each independently NR²R³Group {R², R³Haso
Each independently C_1-20An alkyl group (wherein the alkyl group is
Halogen atom, trifluoromethyl group, hydroxyl group, C_1-6
Alkoxy group of C_1-6Haloalkoxy group, aryl
Oxy group, C_2-7Alkoxycarbonyl group of C _2-7of
Acyloxy group, amino group, C_1-8Monoalkylami
No group, C_2-12Dialkylamino group, phenyl group
A phenyl group is a halogen atom, C_1-6Alkyl group of hydroxy
Group, C_1-6Optionally substituted with an alkoxy group of
Optionally substituted with), C_2-20Alkenyl
A group (the alkenyl group is a halogen atom, trifluorme
Chill group, hydroxyl group, C_1-6Alkoxy group of C_1-6The halo
Alkoxy group, aryloxy group, C_2-7The alkoxy
Carbonyl group, C_2-7Acyloxy group, amino group, C
_1-8Monoalkylamino group, C_2-12Dialkylami
Group, phenyl group (the phenyl group is a halogen atom, C
_1-6Alkyl group, hydroxyl group, C_1-6With the alkoxy group of
May be arbitrarily substituted))
Represents) or R²And R³Together, if desired
C having 1 or 2 alkylene chains_1-8By the alkyl group of
Substituted-(CH₂)_2-5-, -CH ₂CH₂
− (C_1-8Alkyl) N-CH₂CH₂-Or-CH
₂CH₂-O-CH₂CH₂-May be formed}, C
_1-20Alkyl group of {wherein the alkyl group is a halogen atom, hydroxy
Group, C_1-6Alkoxy group, carboxyl group, C_2-7of
Alkoxycarbonyl group, C_2-10Acyloxy group
Mino group, C_1-8Monoalkylamino group, C_2-12Zia
Alkylamino group, aryl group (the aryl group is a halogen
Atom, C_1-6Alkyl group, hydroxyl group, C_1-6The Archoki
Optionally substituted with a Si group)
May be}, C_2-20An alkenyl group of {the alkenyl group is
Halogen atom, hydroxyl group, C_1-6The alkoxy group of carbo
Xyl group, C_2-7Alkoxycarbonyl group of C_2-10of
Acyloxy group, amino group, C_1-8Monoalkylami
No group, C_2-12Dialkylamino group and aryl group of
Reel group is halogen atom, C_1-6Alkyl group of hydroxy
Group, C_1-6Optionally substituted with an alkoxy group of
Optionally substituted with}, a phenyl group
Nyl group is C_1-6Alkyl group, halogen atom, hydroxyl group,
C _1-6Alkoxy group, aryloxy group, C_2-10A
Syloxy group, carboxyl group, C_2-7Alkoxyka
Rubonyl group, C_2-10Acyl group, amino group, C_1-8Mo
Noalkylamino group, C_2-12Dialkylamino group of
Reel group (the aryl group is a halogen atom, C_1-6Al
Kill group, hydroxyl group, C_1-6Optionally substituted with an alkoxy group of
May be substituted)), ha
Rogen atom, C_1-10An alkoxy group of {the alkoxy group is
Halogen atom, hydroxyl group, C_1-6An alkoxy group of
Luoxy group, carboxyl group, C_2-7The alkoxycar
Bonyl group, C_2-10Acyloxy group, amino group, C_1-8
Monoalkylamino group, C _2-12Dialkylamino
Group, an aryl group (the aryl group is a halogen atom, C_1-6
Alkyl group, hydroxyl group, C_1-6Optionally with an alkoxy group of
May be substituted), and may be arbitrarily substituted},
Or C_1-10Alkylthio group of {wherein the alkylthio group is halo
Gen atom, hydroxyl group, C _1-6The alkoxy group of Aryl
Xy group, carboxyl group, C_2-7Alkoxy Carboni
Group, C_2-10Acyloxy group, amino group, C_1-8Mo
Noalkylamino group, C_2-12Dialkylamino group of
Reel group (the aryl group is a halogen atom, C_1-6Al
Kill group, hydroxyl group, C_1-6Optionally substituted with an alkoxy group of
May be substituted) may be arbitrarily substituted}
You. ].

In the specification and claims of the present application
And the listed substituents "can be arbitrarily substituted.
The expression "i" means a heterologous group selected from the listed substituents.
Or, it may be selected by one or more substituents of the same kind.
It means that Preferred of the above general formula (I)
The 1,3,5-triazine derivative is represented by the formula (I)
NHR in 3,5-triazine derivatives¹Base R¹Base
Is a hydrogen atom, C_1-20An alkyl group of {the alkyl group is
Halogen atom, hydroxyl group, C_1-6The alkoxy group of pheny
Group (the phenyl group is a halogen atom, C_1-6The alkyl
Group, hydroxyl group, C_1-6Optionally substituted with an alkoxy group of
May be optionally substituted), C_2-20A
Lucenyl group (the alkenyl group is a halogen atom, hydroxyl group
Group, C_1-6Alkoxy group, phenyl group (the phenyl group
Is a halogen atom, C_1-6Alkyl group, hydroxyl group, C_1-6
It may be optionally substituted with an alkoxy group of
May be replaced}, and the above NHR
¹X when not a group¹, X²And X³Are each independent
NR²R³Group [R², R³Are each independently C_1-20
Alkyl group (wherein the alkyl group is a halogen atom, hydroxy
Group, C_1-6Alkoxy group, phenyl group (the phenyl group
Is a halogen atom, C_1-6Alkyl group, hydroxyl group, C_1-6
It may be optionally substituted with an alkoxy group of
May be replaced}, C_2-20Alkenyl group of {the al
Kenyl group is a halogen atom, C_1-6The alkoxy group of
Phenyl group (the phenyl group is a halogen atom, C_1-6Al
Kill group, hydroxyl group, C_1-6Optionally substituted with an alkoxy group of
May be substituted), and may be arbitrarily substituted}.
Or R²And R³Together, optionally alkylene
C with 1 or 2 chains_{1- 8}Substituted by an alkyl group of
There- (CH₂)_3-5-, -CH₂CH₂− (C_1-8of
Alkyl) N-CH₂CH₂-Or-CH₂CH₂-O
-CH₂CH₂-May be formed], C_1-20The alkyl
Group {the alkyl group is a halogen atom, a hydroxyl group, C_1-6A
Lucoxy group, aryl group (the aryl group is a halogen atom
Child, C_1-6Alkyl group, hydroxyl group, C_1-6The alkoxy
Optionally substituted with a group) optionally substituted with
Good, phenyl group {wherein the phenyl group is C_1-6The archi
Group, halogen atom, hydroxyl group, C _1-6An alkoxy group of
Aryl group (the aryl group is a halogen atom, C_1-6A
Rukyl group, hydroxyl group, C_1-6Optionally substituted with the alkoxy group of
May be optionally substituted).
Halogen atom, C_1-10Alkoxy group of {the said alkoxy group
Is a halogen atom, hydroxyl group, C_1-6Alkoxy group of
Group (the aryl group is a halogen atom, C_1-6The archi
Group, hydroxyl group, C_1-6Optionally substituted with an alkoxy group of
May be optionally substituted with)}.
Which is a 1,3,5-triazine derivative.

More preferred 1,3,5-of the general formula (I)
The triazine derivative is 1,3,5-tri of the general formula (I).
NHR in azine derivatives¹Base R¹The base is hydrogen
Child, C _1-20Alkyl group (wherein the alkyl group is a hydroxyl group, C
_1-6Optionally substituted with alkoxy or phenyl groups
It may be either), and the above NHR¹Not base
X in case¹, X²And X³Each independently NR²R
³Group {R², R³Are each independently C_1-20The alkyl
Group (the alkyl group is a hydroxyl group, C_1-6An alkoxy group of
Optionally substituted with a phenyl group),
Is R²And R³Together, optionally an alkylene chain
Is 1 or 2 C_1-8Substituted by an alkyl group of
-(CH₂)_4-5-, -CH₂CH₂− (C_1-8A
Rukiru) N-CH₂CH₂-Or-CH₂CH₂-O-
CH₂CH₂-May be formed}, C_1-20The alkyl
Group, phenyl group, C_1-10Any of the alkoxy groups of
1,3,5-triazine derivative.

As described above, it is possible to provide all 1,3,5-triazine derivatives having a substituent not directly involved in the reaction in this reaction, but as an industrially available intermediate, Various melamine derivatives and various guanamine derivatives (these are mainly the main components or modifiers of thermosetting resins,
It is available as a cross-linking agent for baking paint, and the synthetic method is s-Triazines and Derivatives. The Chemistry of
Heterocyclic Compounds. EM Smolin and L. Rapopo
rt. Interscience Publishers Inc., New York. 1959.
Details).

Aldehydes or ketones that can be used in the present invention are represented by the general formula (II)

[0022]

[Chemical 7]

[Wherein R ⁴ and R ⁵ are each independently a hydrogen atom, a C _1-20 alkyl group (wherein the alkyl group is a halogen atom, a hydroxyl group, a C _1-6 alkoxy group, C _{1- 6} haloalkoxy groups, C _2-7 alkoxycarbonyl groups, C _2-7
Optionally substituted with an acyloxy group or a phenyl group (the phenyl group may be optionally substituted with a halogen atom, a C _1-6 alkyl group, a hydroxyl group, or a C _1-6 alkoxy group)} , A C _2-20 alkenyl group (the alkenyl group is a halogen atom, a hydroxyl group, a C _1-6 alkoxy group, C
_1-6 haloalkoxy group, C _2-7 alkoxycarbonyl group, C _2-7 acyloxy group, phenyl group (the phenyl group is a halogen atom, a C _1-6 alkyl group, a hydroxyl group, C
_1-6 optionally substituted with an alkoxy group)), or optionally substituted with an alkoxy group _1-6 ), or R ⁴ and R ⁵ together form an alkylene group — (CH ₂ ) _3-5 -May be formed].

As preferred aldehydes or ketones of the above general formula (II), R ⁴ and R ⁵ are each independently a hydrogen atom or a C _1-20 alkyl group (the alkyl group is a halogen atom or a hydroxyl group). , A C _1-6 alkoxy group, optionally substituted with a phenyl group), or a C _2-20 alkenyl group (the alkenyl group is a halogen atom, a hydroxyl group, a C group).
_1-6 alkoxy group, which may be optionally substituted with a phenyl group), or R ⁴ and R ⁵ are taken together to form an alkylene group — (CH ₂ ) _3-5 —. It is an aldehyde derivative or a ketone derivative represented by "good".

As more preferred aldehydes or ketones of the general formula (II), R ⁴ and R ⁵ are each independently a hydrogen atom, a C _1-20 alkyl group (the alkyl group is a halogen atom, a hydroxyl group, C _1-6 alkoxy group, which may be optionally substituted with a phenyl group), or R ⁴ and R ⁵ are taken together to form an alkylene group — (CH ₂ ) _3-5 —. Is a good aldehyde derivative or ketone derivative.

Among these, as industrially easily available ones, formaldehyde, acetaldehyde, propionaldehyde, n-butyraldehyde, n-pentylaldehyde, n-hexylaldehyde, n-octanal, n-nonanal, 2-ethylhexylaldehyde, Cyclohexyl aldehyde, benzaldehyde, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone,
Examples thereof include cyclohexanone and acetophenone.

Examples of the catalysts of Group VII and / or Group VIII of the periodic table used in this reaction include rhenium, iron, cobalt, nickel, ruthenium, rhodium, palladium, osmium, iridium and platinum catalysts. Examples thereof include complex catalysts of these elements and supported catalysts. Among these elements, nickel, ruthenium, rhodium, palladium and platinum catalysts are preferable, and nickel, ruthenium, palladium and platinum complexes and supported catalysts are particularly preferable.
More specific examples of the catalyst will be given below.

Examples of rhenium catalysts include activated carbon-supported rhenium catalysts, alumina-supported rhenium catalysts, and rhenium heptaoxide. Examples of the iron catalyst include Raney iron, complex catalysts such as pentacarbonyl iron, dodecacarbonyltriiron, dichlorobis (triphenylphosphine) iron, tetracarbonyl (triphenylphosphine) iron, and tricarbonylbis (triphenylphosphine) iron. To be

Examples of the cobalt catalyst include Raney cobalt, and complex catalysts such as octacarbonyldicobalt, dodecacarbonyltricobalt, and chlorotris (triphenylphosphine) cobalt. Examples of the nickel catalyst include Raney nickel catalyst, nickel-supporting silica, nickel-supporting alumina, nickel-supporting carbon and other solid and supported catalysts, dichlorobis (triphenylphosphine) nickel, tetrakis (triphenylphosphine).
Nickel, tetrakis (triphenyl phosphite)
Examples thereof include complex catalysts such as nickel, nickel chloride, nickel oxide and the like.

Examples of the ruthenium catalyst include ruthenium-supported silica, ruthenium-supported alumina, ruthenium-supported carbon and other supported catalysts, pentacarbonyl ruthenium, dodecacarbonyltriruthenium, tetrahydridododecacarbonyltetraruthenium, dihydrido (2 nitrogen) tris (triphenylphosphine). ) Ruthenium, dicarbonyltris (triphenylphosphino) ruthenium, tetracarbonyl (trimethylphosphite) ruthenium, pentakis (trimethylphosphite) ruthenium, tris (acetylacetonato) ruthenium, diacetatodicarbonylbis (triphenylphosphine) ruthenium , Dichlorobis (chlorotricarbonyl) ruthenium, carbonylchlorohydride tris (triphenylphosphine) ruthenium, tetrahydo Ridotorisu (triphenylphosphine) ruthenium, acetate Tato hydride tris (triphenylphosphine) ruthenium, dichlorobis (acetonitrile) bis (triphenylphosphine) ruthenium, ruthenocene, bis (pentamethylcyclopentadienyl)
Ruthenium, dichloro (pentamethylcyclopentadienyl) ruthenium, chloro (cyclopentadienyl) bis (triphenylphosphine) ruthenium, hydride (cyclopentadienyl) bis (triphenylphosphine) ruthenium, chlorocarbonyl (cyclopentadienyl) ) Ruthenium, hydride (cyclopentadienyl)
(1,5-Cyclooctadiene) ruthenium, chloro (cyclopentadienyl) (1,5-cyclooctadiene) ruthenium, dihydridotetrakis (triphenylphosphine) ruthenium, cyclooctatriene (cyclooctadiene) ruthenium, chloro Hydride tris (triphenylphosphine) ruthenium, tricarbonylbis (triphenylphosphine) ruthenium, tricarbonyl (cyclooctatetraene) ruthenium, tricarbonyl (1,5-cyclooctadiene) ruthenium, dichlorotris (triphenylphosphine) ruthenium, etc. And complex catalysts of ruthenium chloride, ruthenium oxide, ruthenium black, and the like.

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 zeolite catalyst, 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, di Examples thereof include complex catalysts such as carbonylbis (triphenylphosphine) palladium, carbonyltris (triphenylphosphine) palladium, dichlorobis (benzonitrile) palladium and dichloro (1,5-cyclooctadiene) palladium, and palladium chloride and palladium oxide.

Examples of rhodium catalysts include rhodium-supported silica catalysts, rhodium-supported alumina catalysts, supported catalysts such as rhodium-supported carbon catalysts, chlorotris (triphenylphosphine) rhodium, hexadecacarbonyl hexarhodium, dodecacarbonyltetrarhodium and 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, rhodium oxide and the like.

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.

The above-mentioned catalysts may be used alone or in combination of two or more, and the following is a list of preferred catalyst groups among the methods of the present invention. (1) A method in which the catalyst of Group VII of the periodic table is a rhenium catalyst, (2) A method of the group (1) in which the rhenium catalyst is a supported catalyst, (3) A catalyst of Group VIII of the periodic table is cobalt or nickel , Ruthenium, rhodium, palladium, osmium,
(4) at least one selected from the group consisting of cobalt, nickel, ruthenium, rhodium, palladium and platinum catalysts, wherein the catalyst of Group VIII of the periodic table is at least one selected from iridium and platinum catalysts The method of group (3) which is a catalyst of (5), the method of group (4) in which the catalyst of group VIII of the periodic table is at least one catalyst selected from nickel, ruthenium, palladium and platinum catalysts,
(6) The method of group (3), (4) or (5) in which the catalyst is a complex catalyst, (7) group (3) in which the catalyst is a supported catalyst,
(4) or (5), and (8) the carrier of the supported catalyst is silica, alumina, zeolite or carbon (2)
Or the method of (7).

The amount of the Group VII and Group VIII catalysts used in the periodic table is usually in the range of 0.00001 to 20 mol%, preferably 0.0001 to 10 mol% based on the triazine derivative of the general formula (I). The range of mol% is good. 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, sodium 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, tris (2,6-dimethylphenyl) phosphite and other phosphites , Triphenylmethylphosphonium iodide, triphenylmethylphosphonium bromide, triphenylmethylphosphonium chloride,
Triphenylallylphosphonium iodide, triphenylallylphosphonium bromide, triphenylallylphosphonium bromide, tetraphenylphosphonium iodide, tetraphenylphosphonium bromide, phosphonium salts such as tetraphenylphosphonium chloride, triphenyl phosphate, trimethyl phosphate, phosphoric acid Examples thereof include phosphoric acid esters such as triethyl and triallyl phosphate, unsaturated hydrocarbons such as cyclooctadiene and cyclopentadiene, nitriles such as benzonitrile and acetonitrile, and acetylacetone.

The amount of the ligand used is as shown in Table VIII of the Periodic Table.
The range is usually from 0.1 to 10,000 mol%, preferably from 10 to 5,000 mol% with respect to the group metal catalyst.
The reaction temperature is usually room temperature to 500 ° C., preferably 50 to
300 ° C is good. The reaction time depends on the reactivity of the triazine derivative of the general formula (I), but is usually 1 to 100 hours, preferably 2 to 50 hours.

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, methanol, ethanol, 1-
Propanol, 2-propanol, 1-butanol, 2
-Alcohols such as butanol, isobutanol, 2-methyl-2-propanol, cyclohexanol, benzyl alcohol, benzene, toluene, xylene, mesitylene, cumene, chlorobenzene, o-dichlorobenzene, m-dichlorobenzene, p -Aromatic hydrocarbons such as dichlorobenzene and tetrahydronaphthalene, n-hexane,
Aliphatic hydrocarbons such as cyclohexane, n-octane and n-decane, esters such as methyl acetate, ethyl acetate, butyl acetate, ethyl propionate, methyl benzoate and ethyl benzoate, N, N-dimethylformamide, N , N-dimethylacetamide, N-methylpyrrolidone and other amides, 1,3-dimethylimidazolidinone, N, N, N '
, N′-tetramethylurea and other ureas, and water. These can be used alone or in combination. Further, an excess amount of the aldehyde or ketone derivative represented by the general formula (II) may be used as a solvent.

This reaction is carried out in a pure hydrogen gas or a gas atmosphere containing hydrogen, and the pressure is 0.1 to 5
A pressure of 00 kg / cm ² , preferably 0.5 to 200 kg / cm ² gives good results. Further, in the case of the hydrogen-containing gas, various gases can be used as the diluent gas as long as they do not directly participate in the reaction. For example, nitrogen, argon, helium, etc. are generally used, but carbon dioxide, air, etc. can also be used, and ammonia, carbon monoxide, etc. are also used for the purpose of stabilizing products and catalysts. It When using these mixed gases, there is no problem as long as there is a hydrogen partial pressure necessary for the reaction, and the total pressure is 0.5 to 500 kg / c.
It is desirable to react at a pressure of m ² , preferably 1.0 to 300 kg / cm ² .

As a treatment method after completion of the reaction, after removing unreacted triazines by means such as filtration, the solvent is removed by distillation or the like, if necessary, or a two-phase system of water-organic solvent is produced. After the product is extracted, the reaction product can be purified and isolated by recrystallization, distillation, chromatographic separation or the like. Further, the metal complex 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, and the water-soluble ligand. When used, it can be separated, recovered, and reused in various forms such as a water-soluble metal complex in the aqueous layer by extraction operation.

The substituted-1,3,5-triazine derivative obtained by the method for alkylating an 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 (III).

[0041]

Embedded image

[Wherein X^Four, X^FiveAnd X⁶Less of
Both are independent NR⁶R⁷Group {R ⁶, R⁷Each
Independently, a hydrogen atom (however, X^Four, X^FiveAnd X⁶of
R⁶, R⁷Except when all are hydrogen atoms), C
_1-20An alkyl group (wherein the alkyl group is a halogen atom,
Rifluoromethyl group, hydroxyl group, C_1-6An alkoxy group of
C_1-6Haloalkoxy group, aryloxy group, C_2-7
Alkoxycarbonyl group of C _2-7An acyloxy group of
Amino group, C_1-8Monoalkylamino group, C_2-12The di
Alkylamino group, phenyl group (the phenyl group is a halogen
Atom, C_1-6Alkyl group, hydroxyl group, C_1-6Arco
Optionally substituted with a xy group) optionally substituted with
Or C_2-20Alkenyl group of
Group is a halogen atom, trifluoromethyl group, hydroxy
Group, C_1-6Alkoxy group of C_1-6The haloalkoxy
Group, aryloxy group, C_2-7Alkoxycarbonyl
Group, C_2-7Acyloxy group, amino group, C_1-8Things
Alkylamino group, C_2-12The dialkylamino group of
Nyl group (the phenyl group is a halogen atom, C_1-6The archi
Group, hydroxyl group, C_1-6Optionally substituted with an alkoxy group of
May be optionally substituted).
Is R⁶And R⁷Together, optionally an alkylene chain
Is 1 or 2 C_1-8Substituted by an alkyl group of
-(CH₂)_2-5-, -CH₂CH₂− (C_1-8A
Rukiru) N-CH₂CH₂-Or-CH₂CH₂-O-
CH₂CH₂-May be formed}, and the above NR⁶
R⁷X when not a group^Four, X^FiveAnd X⁶Are each German
Stand up C _1-20Alkyl group of {the alkyl group is a halogen atom
Child, hydroxyl group, C_1-6Alkoxy group, carboxyl group,
C_2-7Alkoxycarbonyl group of C_2-10Akiruoki
Si group, amino group, C_1-8Monoalkylamino group, C
_2-12Dialkylamino group, aryl group (the aryl group
Is a halogen atom, C_1-6Alkyl group, hydroxyl group, C_{1- 6}
It may be optionally substituted with an alkoxy group of
May be replaced}, C_2-20Alkenyl group of {the al
Kenyl group is a halogen atom, hydroxyl group, C_1-6The alkoxy
Group, carboxyl group, C_2-7Alkoxycarbonyl
Group, C_2-10Acyloxy group, amino group, C_1-8Things
Alkylamino group, C_2-12The dialkylamino group of ants
Group (the aryl group is a halogen atom, C_1-6The archi
Group, hydroxyl group, C_1-6Optionally substituted with an alkoxy group of
Optionally)), phenyl
Group {wherein the phenyl group is C_1-6Alkyl group of halogen source
Child, hydroxyl group, C _1-6Alkoxy group of aryloxy
Group, C_2-10Acyloxy group, carboxyl group, C_2-7
Alkoxycarbonyl group of C_2-10The acyl group, amino
Group, C_1-8Monoalkylamino group, C_2-12The Archi
Ruamino group, aryl group (the aryl group is a halogen atom
Child, C_1-6Alkyl group, hydroxyl group, C_1-6The alkoxy
Optionally substituted with a group) optionally substituted with
May be used}, halogen atom, C_1-10Alkoxy group
{The alkoxy group is a halogen atom, a hydroxyl group, C_1-6A
Lucoxy group, aryloxy group, carboxyl group, C
_2-7Alkoxycarbonyl group of C_2-10Acyloxy
Group, amino group, C_1-8Monoalkylamino group, C _2-12
Dialkylamino group, aryl group (the aryl group is
Rogen atom, C_1-6Alkyl group, hydroxyl group, C_1-6A
Optionally substituted with a lucoxy group)
May be present}, or C_1-10Alkylthio group of
The rukylthio group is a halogen atom, hydroxyl group, C _1-6Arco
Xy, aryloxy, carboxyl, C_2-7of
Alkoxycarbonyl group, C_2-10Acyloxy group
Mino group, C_1-8Monoalkylamino group, C_2-12Zia
Alkylamino group, aryl group (the aryl group is a halogen
Atom, C_1-6Alkyl group, hydroxyl group, C_1-6The Archoki
Optionally substituted with a Si group)
May be used}. ].

Preferred Substitutions of Formula (III) -1,3,5
The triazine derivative is represented by the formula (III)^Four, X
^FiveAnd X⁶NR⁶R⁷Base R⁶, R⁷Are independent
And hydrogen atom (provided that X^Four, X^FiveAnd X⁶of
R⁶, R⁷Except when all are hydrogen atoms), C
_1-20Alkyl group of {wherein the alkyl group is a halogen atom, water
Acid group, C_1-6Alkoxy group, phenyl group (the phenyl
Group is a halogen atom, C_1-6Alkyl group, hydroxyl group, C
_1-6Optionally substituted with an alkoxy group of
May be substituted with}, or C_2-20Alkenyl group of
{The alkenyl group is a halogen atom, a hydroxyl group, C_{1- 6}of
Alkoxy group, phenyl group (the phenyl group is halogen
Atom, C_1-6Alkyl group, hydroxyl group, C_1-6The Archoki
Optionally substituted with a Si group)
May be represented, or R⁶And R⁷Together,
C having 1 or 2 alkylene chains as desired_1-8The alkyl
Substituted by a group-(CH₂) _3-5-, -CH₂
CH₂− (C_1-8Alkyl) N-CH₂CH₂-Or
-CH ₂CH₂-O-CH₂CH₂-May be formed,
NR above^FourR^FiveIf not X^Four, X^FiveAnd X⁶But,
Each independently C_{1- 20}An alkyl group of {the alkyl group is
Halogen atom, hydroxyl group, C_1-6An alkoxy group of
Group (the aryl group is a halogen atom, C_1-6The alkyl
Group, hydroxyl group, C _1-6Optionally substituted with an alkoxy group of
May be optionally substituted}, phenyl group
(The phenyl group is C_1-6Alkyl group, halogen atom,
Hydroxyl group, C _1-6Optionally substituted with an alkoxy group of
Good), halogen atom, C_1-10An alkoxy group of
Lucoxy group is a halogen atom, hydroxyl group, C_1-6The Archoki
Si group, aryl group (the aryl group is a halogen atom, C
_1-6Alkyl group, hydroxyl group, C_1-6With the alkoxy group of
May be arbitrarily substituted))
Substituted 1,3,5-triazine derivative having any of
It is the body.

More preferred substitution of the general formula (III) -1,
The 3,5-triazine derivative is represented by the formula (III)
^Four, X^FiveAnd X⁶NR⁶R⁷Base R⁶, R⁷Each
Independently, a hydrogen atom (however, X^Four, X^FiveAnd X⁶of
R⁶, R⁷Unless all are hydrogen atoms) or C
_1-20Alkyl group (wherein the alkyl group is a hydroxyl group, C_1-6of
May be optionally substituted with an alkoxy group or phenyl group
Represents) or R⁶And R⁷Together, if desired
C having 1 or 2 alkylene chains_1-8By the alkyl group of
Substituted-(CH₂)_4-5-, -CH₂CH₂
− (C_1-8Alkyl) N-CH₂CH₂-Or-CH
₂CH₂-O-CH₂CH₂-May be formed, and
NR⁶R⁷X when not a group^Four, X^FiveAnd X⁶But that
Each independently C _1-20Alkyl group, phenyl group, C_1-10
A substituted 1,3,5-tri which is any of the alkoxy groups of
It is an azine derivative.

As described above, various compounds can be used as the raw material 1,3,5-triazine derivative, aldehydes and ketones in the present invention, and the product obtained by the method of the present invention is The 1,3,5-triazine derivative having various substituents can be obtained by combining the 1,3,5-triazine derivative, aldehydes and ketones.

As described above, in view of availability of raw materials, 1,3,5-triazine derivatives as raw materials include melamine, various melamine derivatives and various guanamine derivatives, and aldehydes and ketones as various petrochemical products. Representative aldehydes and ketones derived from
Representative products are obtained by these combinations. Further, for example, a substituted melamine derivative obtained by alkylating melamine by the method of the present invention also has a part of —NH on its ring carbon atom.
If it has a — group, it can be used as the raw material 1,3,5-triazine derivative of the present invention.

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) as a raw material and NHR ¹ , NR ² among the substituents represented by X ⁴ , X ⁵ and X ⁶ of the general formula (III) of the product R ³ and NR ⁶ R ⁷
As, amino group, methylamino group, ethylamino group, 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-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, chloroethylamino group, 3-chloropropylamino group, hydroxyethylamino group, 4- Hydroxybutylamino group,
5-hydroxypentylamino group, bis (hydroxyethyl) amino group, trifluoroethylamino group, 2-trifluoropropylamino group, 2-ethoxyethylamino group, 3-methoxypropylamino group, 2-pentyloxyethylamino group , 3-cyclohexyloxypropylamino group, 2-chloroethoxyethylamino group, 5-
Monofluoropentyloxypentylamino group, 2-methoxycarbonylethylamino group, 2-ethoxycarbonylethylamino group, tert-butoxycarbonylethylamino group, 2-cyclohexyloxycarbonylethylamino group, acetoxymethylamino group, 3-acetoxy Propylmethylamino group, cyclohexanoyloxyethylamino group, 2-benzoyloxypropylamino group,
2-aminoethylamino group, 6-aminohexylamino group, cyclohexylaminoethylamino group, dimethylaminoethylamino group, diethylaminoethylamino group,
Methylphenylamino group, benzylamino group, dibenzylamino group, N-benzyl-N'-methylamino group, 2
-Phenylethylamino group, 3- (4-chlorophenyl) -propylamino group, 2- (4-cyclohexylphenyl) -ethylamino group, 2- (3-fluorophenyl) -pentylamino group, 4-methoxybenzylamino Group, 2-chloro-4-fluorobenzylamino group, 3,
5-dimethylbenzylamino group, 4-cyclopentyloxybenzylamino group, 2- (2-chloro-4-fluoro-5-isopropylphenyl) -propylamino group,
4-hydroxybenzylamino group, 4-hydroxyphenylethylamino group, allylamino group, methallylamino group, 3-cyclopentenylamino group, 3-cyclohexenylamino group, 3- (6-trifluoromethyl) -cyclohexenylamino group, Diallylamino group, dimethallylamino group, 3- (1-methoxy) -allyl group, crotylamino group, chloromethoxyethylamino group, ethoxycarbonylallylamino group, cinnamylamino group, 4-chlorocinnamylamino group, N- (4 -Methylcinnamyl) -N'-methylamino group, 4-methoxycinnamylamino group and the like.

Further, R ² and R ³ of the NR ² R ³ group are bonded to each other,
Alternatively, specific examples of the group to which R ⁶ and R ⁷ of the NR ⁶ R ⁷ group are bonded include an aziridino group, a pyrrolidino group, a piperidino group, an N-methylpiperazino group, a morpholino group and the like. 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, trifluoromethyl group, 3-chloropropyl group,
2-trifluoromethylethyl group, hydroxymethyl group, 2-hydroxyethyl group, methoxymethyl group, methoxyethyl group, ethoxymethyl group, cyclohexylmethoxyethyl group, 2-carboxyethyl group, 3-carboxypropyl group, methoxycarbonylmethyl group Group, methoxycarbonylethyl group, tert-butoxycarbonylmethyl group, cyclohexyloxycarbonylethyl group, 2-propanoylethyl group, benzoylmethyl group, 2,4,6
-Trimethylphenylbenzoylmethyl group, acetyloxymethyl group, benzoyloxymethyl group, 3- (tert-
Butylcarbonyloxy) -propyl group, 3-aminopropyl group, cyclohexylaminomethyl group, 2-cyclopentylaminoethyl group, dimethylaminomethyl group, diethylaminomethyl group, diisopropylaminomethyl group, di-n-butylaminomethyl group, di- -i-butylaminomethyl group, di-sec-butylaminomethyl group, methyl-ter
t-butylaminomethyl group, methylcyclohexylaminomethyl group, cyclohexylmethylaminomethyl group, benzyl group, 4-methylbenzyl group, 4-methoxybenzyl group, 2-chloro-4-fluorobenzyl group, 3,5-dimethylbenzyl group Group, 4-cyclopentyloxybenzyl group and the like.

Examples of the alkenyl group having 2 to 20 carbon atoms which may be substituted include vinyl group, isopropenyl group, 1-
Butenyl group, 3-hexenyl group, allyl group, methallyl group, crotyl group, 2-chloroallyl group, methoxyvinyl group, ethoxyvinyl group, cyclohexylvinyl group, 4-
Phenyl-2-butenyl group, 2-carboxylvinyl group, ethoxycarbonylvinyl group, tert-butoxycarbonylvinyl group, acetylvinyl group, acetylallyl group, 3-benzoylallyl group, acetyloxyvinyl group, cyclohexanoyloxyvinyl group , Dimethylaminovinyl group, 4-diethylaminobutenyl group, dicyclohexylaminovinyl group, cinnamyl group, 4-chlorocinnamyl group, 3,5-dimethoxycinnamyl group, 2,
4,6-trimethylcinnamyl group, styryl group, 2,4
-Dichlorostyryl group, 6-dodecen-1-yl group,
Examples include 1,2-diphenylvinyl group.

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, 2-chlorophenyl group, 2,4-dichlorophenyl group, 2-fluoro-
4-chlorophenyl group, 3,5-dimethoxyphenyl group, 4-cyclopentyloxyphenyl group, m-phenoxyphenyl group, 4- (2-naphthyloxy) -phenyl group, 3-acetoxyphenyl group, 3-benzoyloxyphenyl group Group, 4-carboxyphenyl group, 4-methoxycarbonylphenyl group, 3-cyclohexyloxycarbonylphenyl group, 2-acetylphenyl group, 4-octanoylphenyl group, 4-acetyloxyphenyl group, 3-cyclohexylcarbonyloxyphenyl group Base,
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-cyclohexylmethylaminophenyl group, 4-biphenyl group, 4- (2
Examples include -naphthyl) -phenyl group, 4- (4-chlorophenyl) -phenyl group, 4- (5- (1-methyl-3-chloropyrazolo) -yl) -phenyl group and the like.

Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom. The C _1-10 alkoxy group which may be substituted includes a methoxy group, an ethoxy group, an n-propyloxy group, an i-propyloxy group,
n-butyloxy group, i-butyloxy group, sec-butyloxy 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, trifluoromethyloxy group, 3-chloropropyloxy group, 2-trifluoromethylethyloxy group, methoxymethoxy group, methoxyethoxy Group, ethoxymethoxy group, cyclohexylmethoxyethoxy group, 2-carboxyethoxy group, 3-carboxypropoxy group, methoxycarbonylmethoxy group, methoxycarbonylethoxy group, tert-butoxycarbonylmethoxy group, cyclohexyl Oxycarbonylethoxy group, 2-propanoylethoxy group, benzoylmethoxy group, 2,4,6-trimethylphenylbenzoylmethyloxy 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, cyclohexylmethylaminomethyloxy group, benzyloxy group, 4-methylbenzyloxy group, 4
-Methoxybenzyloxy group, 2-chloro-4-fluorobenzyloxy group, 3,5-dimethylbenzyloxy group, 4-cyclopentyloxybenzyloxy group and the like.

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, trifluoromethylthio group, 3-chloropropylthio group, 2-trifluoromethylethylthio group, methoxymethylthio group, methoxyethylthio group,
Ethoxymethylthio group, cyclohexylmethoxyethylthio group, 2-carboxyethylthio group, 3-carboxypropylthio group, methoxycarbonylmethylthio group, methoxycarbonylethylthio group, tert-butoxycarbonylmethylthio group, cyclohexyloxycarbonylethylthio group, 2 -Propanoylethylthio group, benzoylmethylthio group, 2,4,6-trimethylphenylbenzoylmethylthio 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-t ert-butylaminomethylthio group, methylcyclohexylaminomethylthio group, cyclohexylmethylaminomethylthio group, benzylthio group, 4-methylbenzylthio group, 4-methoxybenzylthio group, 2-chloro-4-fluorobenzylthio group, 3,
Examples thereof include a 5-dimethylbenzylthio group and a 4-cyclopentyloxybenzylthio group.

The aldehydes and ketones used as the other raw material can be used in this reaction as long as they are commonly available. In one example, hydrogen is used as the substituents R ⁴ and R ^5. Atom, 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, trifluoromethyl group, 3-chloropropyl group, 2-trifluoromethylethyl group, hydroxyethyl group, methoxymethyl group, methoxyethyl group Group, ethoxymethyl group, cyclohexylmethoxyethyl group, 2-carboxyethyl group, 3-carboxypropyl group, methoxycarl Nirumechiru group, a methoxycarbonylethyl group, tert- butoxycarbonyl methyl group, cyclohexyloxycarbonylethyl group, 2-propanoyl ethyl, benzoyl methyl group, 2,4,6
-Trimethylphenylbenzoylmethyl group, acetyloxymethyl group, benzoyloxymethyl group, 3- (tert-
(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, 2-chloro-4-fluorobenzyl group, 3,5-dimethylbenzyl group, 4-cyclopentyloxybenzyl group, allyl group, homoallyl group, methallyl group, 3-cyclopentenyl group, 3-cyclohexenyl group, 3- (6 -Trifluoromethyl) -cyclohexenyl group, 3- (1-methoxy) -allyl group, crotylamino group, cinnamyl group, 4-methylcinnamyl group, 4-chlorocinnamyl group, 4-ethoxycinnamyl group, 2,
4,6-trimethylcinnamyl group and the like can be mentioned.

Examples of the case where R ⁴ and R ⁵ are combined to form an alkylene group — (CH ₂ ) _3-5 — include a trimethylene group, a tetramethylene group, a pentamethylene group and the like. The examples of these substituents are very representative examples, and the present invention is not limited thereto.

The amount of the above-mentioned aldehyde or ketone derivative having a substituent can be used in any range depending on the purpose, but it is generally 0.01 to 500 times by mole, preferably 0 to the starting aminotriazine compound. The range of 1 to 50 times mol is effective from the viewpoint of reaction and operability. As a treatment method after completion of the reaction, the unreacted triazine derivative is crystallized and then removed by means such as filtration, and then the solvent is removed by distillation or the like, if necessary, or a two-phase system of water-organic solvent is used. After extracting the product, the reaction product can be purified and isolated by recrystallization, distillation, chromatographic separation, or the like.

Further, in the case of a supported catalyst, the catalyst can be continuously used as it is in the case of a fixed bed, and in the case of a suspension bed (liquid phase reaction), it can be easily separated by filtration or the like. In the case of an organic metal complex catalyst, the solvent and the product are distilled,
When it is made water-soluble by the residue removed by recrystallization or by a ligand, etc., it can be separated and recovered from the production system in various forms, such as in the aqueous layer by extraction with water. Therefore, it is possible to construct a recycling process that can be used industrially.

[0057]

The present invention will be described in more detail below with reference to examples, but the present invention is not limited thereto. In all of the examples, the products were separately synthesized beforehand using the product as a standard product (synthesis method is J. Am. Chem. Soc., 7).
Volume 3, page 2984 (1951), or JP-A-3-2
It was carried out according to No. 15564. Reference example shows an example of synthesis from cyanuric chloride. ), A calibration curve was prepared from the pure product and an internal standard substance, and the amount of each product in the reaction product was accurately determined by the internal standard determination method by high performance liquid chromatography. All the yields in the examples are based on the raw material triazine compound.

The analytical 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 substance; Phthalic acid di-n-butyl ester (Quantification method for some products and raw materials (part of alkylaminotriazine)) Detection method; UV 230 nm column; GL Science Inertsil C ₈ 150 mm x
4.6 mm φ Flow rate; 1.0 ml / min Analytical temperature; 35 ° C Internal standard substance; Phthalic acid di (2-ethylhexyl) ester

Reference Example 1 (Synthesis of 4,6-diamino-2-normal-butylamino-1,3,5-triazine) After dissolving 184.5 g (1.0 mol) of cyanuric chloride in 800 mL of acetonitrile at room temperature, To the solution cooled to 0 ° C., while stirring vigorously, 28% aqueous ammonia solution 30
3.7 g (5.0 mol) was added dropwise over 2 hours so that the reaction temperature was kept below 10 ° C. 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. Filtered product under vacuum at 50 ℃
By drying for 6 hours, 115 g of 2,4-diamino-6-chloro-1,3,5-triazine (yield 79%)
Obtained.

2,4-diamino-6-chloro-obtained
A mixed solution of 14.5 g (0.1 mol) of 1,3,5-triazine, 100 mL of water and 29.2 g (0.4 mol) of butylamine was heated with stirring and finally at a reflux temperature. The reaction was carried out for 6 hours. After cooling the reaction solution, the product was filtered off, washed thoroughly with a large amount of water, and then washed with toluene. The filtered product was dried under vacuum at 70 ° C. for 6 hours to give 17.5 g of 4,6-diamino-2-normal-butylamino-1,3,5-triazine (yield 96
%)Obtained. Melting point; 167 [deg.] C.

Reference Example 2 (Synthesis of 2-amino-4,6-bis (normal butylamino) -1,3,5-triazine) 18.5 g (0.1 mol) of cyanuric chloride was dissolved in 150 mL of acetonitrile, While stirring the solution cooled to 0 ° C., butylamine 7.3 g (0.1 mol) of water 20
The mL solution was added dropwise over 1 hour so that the reaction temperature did not exceed 5 ° C. While continuing to stir, add potassium bicarbonate 1
A solution of 0.0 g (0.1 mol) of 100 mL of water was added dropwise at the same temperature and stirred for 3 hours. After confirming by high performance liquid chromatography that the conversion to 2-butylamino-4,6-dichloro-1,3,5-triazine was completed, 24.3 g (0.4 mol) of 28% aqueous ammonia solution was added. , 50
The temperature was raised to ℃ and reacted for 5 hours. After cooling, the product was filtered off and washed thoroughly with plenty of water. The crude product obtained is treated with water 10
The suspension was suspended in 0 mL, 29.2 g (0.4 mol) of butylamine was added, and the mixture was reacted for 6 hours while heating under reflux. After cooling, after adding 200 mL of toluene and stirring vigorously,
The aqueous layer was separated. Further, the toluene layer is 3 times with 150 mL of water.
After washing twice, toluene is distilled off from the organic layer under heating and reduced pressure to give 2-amino-4,6-bis (normal butylamino) -1,3,5-triazine at 22.
1 g (yield 93%) was obtained. Melting point; 73 [deg.] C.

Reference Example 3 (Synthesis of 2,4,6-tris (normal butylamino) -1,3,5-triazine) 18.5 g (0.1 mol) of cyanuric chloride was dissolved in 150 mL of acetonitrile, and the mixture was dissolved at 0 ° C. While stirring the cooled solution, 14.6 g (0.2 mol) of butylamine in water was added.
The 0 mL solution was added dropwise over 1 hour so that the reaction temperature did not exceed 5 ° C. While continuing stirring, a solution of 20.0 g (0.2 mol) of potassium hydrogen carbonate in 100 mL of water was added dropwise at the same temperature. Then, the reaction temperature was gradually raised and stirring was continued at 45 ° C. for 8 hours. 2,4-bis (butylamino) -6-chloro-1,3 by high performance liquid chromatography
After confirming that the conversion to 5-triazine was completed, it was cooled and the product was filtered. After thoroughly washing the filter cake with a large amount of water, the 2,4-bis (butylamino) -6-
Chlor-1,3,5-triazine was suspended in 100 mL of water, 29.2 g (0.4 mol) of butylamine was added, and the mixture was further reacted under heating under reflux for 6 hours. After cooling, 200 mL of toluene was added and vigorously stirred, and then the aqueous layer was separated. Further, the toluene layer was washed three times with 150 mL of water, and then toluene was distilled off from the organic layer under heating and reduced pressure to obtain 2,4,6-tris (normal butylamino) -1,3,5-triazine. 28.2 g (yield 9
6%) was obtained. Properties; oily substance.

Reference Example 4 (Synthesis of 4,6-diamino-2-cyclohexylamino-1,3,5-triazine) 2,4-diamino-6-chloro-synthesized in Reference Example 1
A mixture of 14.5 g (0.1 mol) of 1,3,5-triazine and 280 mL of water was heated to a temperature of 85 ° C., and 29.7 g (0.3 mol) of cyclohexylamine was added dropwise over 2 hours, and the same temperature was applied. And reacted for 1 hour. Subsequently, a solution of sodium hydroxide (6.0 g) in water (30 mL) was added dropwise at the same temperature over 1 hour, and the reaction was further continued for 1 hour. 200 mL of toluene was added to the reaction solution, and the mixture was stirred at 85 ° C. for 1 hour and cooled to room temperature while continuing stirring. The product is separated from the reaction solution,
Further, 100 mL of toluene twice, followed by 100 mL of water
After being washed twice with water, the filtered product was dried under vacuum at 70 ° C. for 6 hours to give 17.5 g (yield 84%) of 4,6-diamino-2-cyclohexylamino-1,3,5-triazine.
Obtained. Melting point; 151 [deg.] C.

Reference Example 5 (Synthesis of 2-amino-4,6-bis (cyclohexylamino) -1,3,5-triazine) 18.5 g (0.1 mol) of cyanuric chloride was dissolved in 500 mL of acetonitrile to give 0. While stirring the solution cooled to ℃, cyclohexylamine 9.9g (0.1mol), triethylamine 10.5g (0.104mol)
And a solution of 330 mL of water were added dropwise over 3 hours so that the reaction temperature did not exceed 5 ° C. After continuing stirring at the same temperature for 2 hours, 683 mL of 28% aqueous ammonia solution was added dropwise at the same temperature, and the mixture was added at 5 ° C for 1 hour, 20 ° C for 1 hour, and 50 ° C for 1 hour.
Stir for time. Then cyclohexylamine 5
5.5 g (0.56 mol) was added at a reaction temperature of 60 ° C. or lower, and the mixture was reacted at 70 ° C. for 4 hours. Further, water 16 in the reaction solution
00 mL was added dropwise while maintaining the temperature at 70 ° C, and then gradually cooled to 10 ° C. After cooling, the product was separated from the reaction solution by filtration, washed with 660 mL of water 5 times, and the filtered product was dried under vacuum at 70 ° C. for 6 hours to give 2-amino-4,6-.
16.4 g (yield 56%) of bis (cyclohexylamino) -1,3,5-triazine was obtained. Melting point; 153 [deg.] C.

Reference Example 6 (Synthesis of 2,4,6-tris (cyclohexylamino) -1,3,5-triazine) 18.5 g (0.1 mol) of cyanuric chloride was dissolved in 400 mL of 1,4-dioxane. , 60.2 g of cyclohexylamine (0.
61 mol) was added dropwise over 2 hours so that the reaction temperature did not exceed 50 ° C. While continuing stirring, the temperature was raised to 85 ° C and 60.2 g (0.61 mol) of cyclohexylamine was added.
Was added dropwise while maintaining the temperature. Then, the temperature was raised again and the reaction was carried out at a reaction temperature of 95 ° C. for 6 hours. Water 230 in the reaction solution
g was added so that the temperature did not fall below 90 ° C., and then cooled to room temperature with stirring. The product was separated from the reaction solution by filtration, washed with 150 mL of water four times, and the filtrate was removed under vacuum 70
By drying for 6 hours at 6 ° C., 2,4,6-tris (cyclohexylamino) -1,3,5-triazine was added to 34.
2 g (yield 91%) was obtained. Melting point; 225 [deg.] C.

Example 1 2.52 g (20.0 mmol) of melamine, 52.0 mg (0.2 mmol) of ruthenium trichloride hydrate, and diphenylphosphinobenzene-3-sulfone were placed in a stainless steel autoclave having an internal volume of 100 mL. Acid sodium salt 3
64.0 mg (1 mmol), butyraldehyde 8.6
After charging 4 g (0.12 mol) and 30 mL of diethylene glycol dimethyl ether and thoroughly replacing the inside of the system with nitrogen gas, the synthesis gas (H ₂ / CO = 1/1) was used at an initial pressure of 1
The reaction was carried out at a reaction temperature of 200 ° C. for 10 hours at a pressure of 00 kg / cm ² . After the reaction was completed, the raw material conversion rate was 48% as a result of quantitative analysis of unreacted melamine. As a result of quantitative analysis of the reaction products, each product was obtained in the following yields. 2-Normal butylamino-4,6-diamino-1,3,5-
Triazine was 6.0% and 2,4-bis (normal butylamino) -6-amino-1,3,5-triazine was 7.
7%, 2,4,6-tris (normal butylamino)-
23.3% 1,3,5-triazine, 2-dinormal butylamino-4,6-bis (normal butylamino)
5.3% of -1,3,5-triazine.

Example 2 2.52 g (20.0 mmol) of melamine, 63.9 mg (0.1 mmol) of triruthenium dodecacarbonyl were added to a stainless steel autoclave having an internal volume of 100 mL.
Butyraldehyde 4.32 g (60.0 mmol), diethylene glycol were charged dibutyl ether 30 mL, after thoroughly purging the system with nitrogen gas, synthesis gas _{(H 2 / CO = 1/} 1) the initial pressure 100 kg / cm ² As a result, the reaction was performed at a reaction temperature of 200 ° C. for 10 hours. After the reaction, the unreacted melamine was quantitatively analyzed, and the raw material conversion rate was 95%.
Met. The solvent was distilled off from the reaction solution, and toluene was 100 m.
L was added and dissolved, and unreacted melamine was filtered off. As a result of quantitative analysis of the reaction product, 2-normal butylamino-
4,6-diamino-1,3,5-triazine was 12.5
%, 2,4-bis (normal butylamino) -6-amino-1,3,5-triazine 14.4%, 2,4,6
-Tris (normal butylamino) -1,3,5-triazine 52.1%, 2-dinormal butylamino-
4,6-bis (normal butylamino) -1,3,5-
8.6% triazine, 2,4-bis (dinormal butylamino) -6-normal butylamino-1,3,5-
Triazine was produced in a yield of 3.2%.

Example 3 2.52 g (20.0 mmol) of melamine and 92.5 mg of chlorotris (triphenylphosphine) rhodium were placed in a stainless steel autoclave having an internal volume of 100 mL.
(0.1 mmol), butyraldehyde 4.32 g (6
0.0 mmol) and 30 mL of diethylene glycol dibutyl ether were charged, and the system was sufficiently replaced with argon gas, and then synthetic gas (H ₂ / CO = 1/1) was used at an initial pressure of 1
The reaction was carried out at a reaction temperature of 250 ° C. for 1 hour at a pressure of 00 kg / cm ² . After the reaction was completed, as a result of quantitative analysis of unreacted melamine,
The raw material conversion rate was 28%. The solvent was distilled off from the reaction solution, and 100 mL of toluene was added to dissolve it, and unreacted melamine was filtered off. Toluene was distilled off from the toluene solution and concentrated to a total volume of 10 mL. Crystallized crystals were collected by filtration to give 2-normal-butylamino-4,6-diamino-
0.73 g of 1,3,5-triazine, yield 19.5%
Obtained in.

Example 4 2.52 g (20.0 mmol) of melamine, 63.9 mg (0.1 mmol) of triruthenium dodecacarbonyl were placed in a stainless steel autoclave having an internal volume of 100 mL.
6.36 g (60.0 mmol) of benzaldehyde,
After charging 30 mL of 1,4-dioxane and thoroughly replacing the inside of the system with nitrogen gas, synthesis gas (H ₂ / CO = 1/1)
At an initial pressure of 100 kg / cm ² at a reaction temperature of 200 ° C.
Allowed to react for hours. After the reaction was completed, quantitative analysis of unreacted melamine revealed that the raw material conversion rate was 98%. The solvent was distilled off from the reaction solution, and 100 mL of toluene was added to dissolve it, and unreacted melamine was filtered off. As a result of quantitative analysis of the reaction product, 2-benzylamino-4,6-diamino-1,3,3
5-triazine 10.4%, 2,4-bis (benzylamino) -6-amino-1,3,5-triazine 1
2.0%, 2,4,6-tris (benzylamino)-
58.8% 1,3,5-triazine, 2-dibenzylamino-4,6-bis (benzylamino) -1,3,5
-Triazine was produced in 3.1% yield.

Example 5 1.26 g (10.0 mmol) of melamine, 400 mg of 5% Pd-supporting activated carbon, 3.37 g (30.0 mmol) of cyclohexanecarboxaldehyde, and 1,4 After charging 15 mL of dioxane and thoroughly replacing the inside of the system with nitrogen gas, the initial temperature of hydrogen gas was 50 kg / cm ² , and the reaction temperature was 18
The reaction was performed at 0 ° C. for 6 hours. After the reaction was completed, quantitative analysis of unreacted melamine revealed that the raw material conversion rate was 99.5%. After the catalyst and unreacted melamine were filtered off from the reaction solution, the solvent was distilled off to obtain a crude reaction product. As a result of quantitative analysis of the reaction product, 2,4-diamino-6-cyclohexylmethylamino-1,3,5-triazine was found to be 7.
5%, 2-amino-4,6-bis (cyclohexylmethylamino) -1,3,5-triazine 30.1%,
2,4,6-Tris (cyclohexylmethylamino)-
1,3,5-triazine was produced in a yield of 61.3%.

Example 6 1.26 g (10.0 mmol) of melamine, 205 mg of 5% Rh-supporting activated carbon, 3.37 g (30.0 mmol) of cyclohexanecarboxaldehyde, and 1,4 were added to a stainless steel autoclave having an internal volume of 50 mL. After charging 15 mL of dioxane and thoroughly replacing the inside of the system with nitrogen gas, the initial temperature of hydrogen gas was 70 kg / cm ² , and the reaction temperature was 18
The reaction was carried out at 0 ° C for 10 hours. After the reaction was completed, quantitative analysis of unreacted melamine revealed that the raw material conversion rate was 25.5%. After the catalyst and unreacted melamine were filtered off from the reaction solution, the solvent was distilled off to obtain a crude reaction product. As a result of quantitative analysis of the reaction product, 2,4-diamino-6-cyclohexylmethylamino-1,3,5-triazine was 1
1.2%, 2-amino-4,6-bis (cyclohexylmethylamino) -1,3,5-triazine 3.3%,
2,4,6-Tris (cyclohexylmethylamino)-
1,3,5-triazine was produced in a yield of 3.0%.

Example 7 1.26 g (10.0 mmol) of melamine, 200 mg of 2% Pt-supporting activated carbon, 3.37 g (30.0 mmol) of cyclohexanecarboxaldehyde, 1,4 were placed in a stainless steel autoclave having an internal volume of 50 mL. -After charging 12 mL of dioxane and thoroughly replacing the inside of the system with nitrogen gas, the initial temperature of hydrogen gas was 50 kg / cm ² , while supplying hydrogen so as to maintain the pressure during the reaction, the reaction temperature was 180 ° C.
And reacted for 5 hours. After the reaction was completed, quantitative analysis of unreacted melamine revealed that the raw material conversion rate was 5.9%. After the catalyst and unreacted melamine were filtered off from the reaction solution, the solvent was distilled off to obtain a crude reaction product. As a result of quantitative analysis of the reaction product, 2,4-diamino-6-cyclohexylmethylamino-1,3,5-triazine was found to be 6.6%, 2
-Amino-4,6-bis (cyclohexylmethylamino) -1,3,5-triazine was produced in a yield of 0.8%.

Example 8 1.26 g (10.0 mmol) of melamine, 200 mg of 5% Ru-supported activated carbon, 3.37 g (30.0 mmol) of cyclohexanecarboxaldehyde, 1,4 were placed in a stainless steel autoclave having an internal volume of 50 mL. -After charging 12 mL of dioxane and thoroughly replacing the inside of the system with nitrogen gas, the initial temperature of hydrogen gas was 50 kg / cm ² , while supplying hydrogen so as to maintain the pressure during the reaction, the reaction temperature was 180 ° C.
And reacted for 5 hours. After the reaction was completed, the raw material conversion rate was 19.6% as a result of quantitative analysis of unreacted melamine. After the catalyst and unreacted melamine were filtered off from the reaction solution, the solvent was distilled off to obtain a crude reaction product. As a result of quantitative analysis of the reaction product, 2,4-diamino-6-cyclohexylmethylamino-1,3,5-triazine was found to be 11.5.
%, 2-amino-4,6-bis (cyclohexylmethylamino) -1,3,5-triazine was produced in a yield of 3.1%.

Example 9 1.26 g (10.0 mmol) of melamine, 192 mg of triruthenium dodecacarbonyl, and 5.8 cyclohexanone were placed in a stainless steel autoclave having an internal volume of 60 mL.
8 g (60.0 mmol), 1,4-dioxane 20 m
After L was charged and the inside of the system was sufficiently replaced with nitrogen gas, the reaction was carried out at a reaction temperature of 180 ° C. for 11 hours with a synthesis gas (H ₂ / CO = 1/1) as an initial pressure of 50 kg / cm ² . After the reaction was completed, the raw material conversion rate was 23.3% as a result of quantitative analysis of unreacted melamine. After cooling, unreacted melamine was filtered off from the reaction solution, and then the solvent was distilled off to obtain a crude reaction product. As a result of quantitative analysis of the reaction product, 2,4-diamino-6-cyclohexylamino-1,3,5-triazine was 6.8%, and 2-amino-4,6-bis (cyclohexylamino) -1,3. , 5-triazine 7.8%,
2,4,6-tris (cyclohexylamino) -1,
3,5-triazine was produced in a yield of 4.4%.

Example 10 1.26 g (10.0 mmol) of melamine, 408 mg of 5% Pd-supporting activated carbon and 11.7 g (12) of cyclohexanone were placed in a stainless steel autoclave having an internal volume of 60 mL.
0.0 mmol) and 1,4-dioxane (15 mL) were charged, the system was sufficiently replaced with nitrogen gas, and then the reaction was carried out at a reaction temperature of 180 ° C. for 2.5 hours under an initial pressure of hydrogen gas of 50 kg / cm ² . . After the reaction was completed, quantitative analysis of unreacted melamine revealed that the raw material conversion rate was 69.3%. After cooling
Unreacted melamine was filtered off from the reaction solution, and then the solvent was distilled off to obtain a crude reaction product. As a result of quantitative analysis of the reaction product, 2,4-diamino-6-cyclohexylamino-1,3,5-triazine was 19.8% and 2-amino-
4,6-bis (cyclohexylamino) -1,3,5-
Triazine 31.9%, 2,4,6-tris (cyclohexylamino) -1,3,5-triazine 16.0
It was produced in a yield of%.

Example 11 1.26 g (10.0 mmol) of melamine, 408 mg of 5% Pd-supporting activated carbon and 11.7 g (12) of cyclohexanone were placed in a stainless steel autoclave having an internal volume of 100 mL.
(0.0 mmol) and 40 mL of ethanol were charged, and the inside of the system was sufficiently replaced with nitrogen gas.
The reaction was carried out at a reaction temperature of 180 ° C. for 8.5 hours at 0 kg / cm ² . After the reaction was completed, the unreacted melamine was quantitatively analyzed, and as a result, the raw material conversion rate was 98.3%. After cooling, unreacted melamine was filtered off from the reaction solution, and then the solvent was distilled off to obtain a crude reaction product. As a result of quantitative analysis of the reaction product, 2,4-diamino-6-cyclohexylamino-
4.5% 1,3,5-triazine, 2-amino-4,
6-bis (cyclohexylamino) -1,3,5-triazine was produced in a yield of 27.6% and 2,4,6-tris (cyclohexylamino) -1,3,5-triazine was produced in a yield of 60.0%. Was.

Example 12 1.87 g (10.0 mmol) of benzoguanamine and 5% P in a stainless steel autoclave having an internal volume of 40 mL.
d-Supported activated carbon (408 mg), normal butyraldehyde (2.16 g, 30 mmol), and ethanol (15 mL) were charged, the system was sufficiently replaced with nitrogen gas, and the initial hydrogen pressure was 50 kg / cm ² , and the reaction was carried out at a reaction temperature of 180 ° C. for 10 hours. Let After the reaction, the result of quantitative analysis of unreacted raw materials,
The raw material conversion rate was 92.5%. As a result of quantitative analysis of the reaction product, 2-amino-4-normal-butylamino-
6-phenyl-1,3,5-triazine is 37.0%,
2,4-bis (normal butylamino) -6-phenyl-1,3,5-triazine was obtained with a yield of 51.5%.

Example 13 A stainless steel autoclave having an internal volume of 38 mL was charged with 2-
Amino-4-methyl-6-methoxy-1,3,5-triazine 1.40 g (10.0 mmol), 5% Pd-supported activated carbon 204 mg, 1-hexanal 2.00 g (2
0.0 mmol) and 15 mL of 1-hexanol were charged, and the system was sufficiently replaced with nitrogen gas, and then the reaction was carried out at a reaction temperature of 200 ° C. for 20 hours under an initial hydrogen pressure of 50 kg / cm ² . After the reaction was completed, the unreacted raw material was quantitatively analyzed, and as a result, the raw material conversion rate was 88.0%. As a result of quantitative analysis of the reaction product, 2-normalhexylamino-4-methyl-
6-Methoxy-1,3,5-triazine was obtained in a yield of 67.0%.

Example 14 Into a stainless steel autoclave having an internal volume of 100 mL, 2
-N-butyl melamine 3.64 g (20.0 mmol), 5% Pd-supporting activated carbon 408 mg, normal butyraldehyde 4.32 g (60.0 mmol), 1-butanol 30 mL were charged, and the system was thoroughly filled with nitrogen gas. After replacement, the initial hydrogen pressure was 50 kg / cm ² and the reaction temperature was 18
The reaction was carried out at 0 ° C for 6.5 hours. After the reaction was completed, the unreacted raw material was quantitatively analyzed, and as a result, the raw material conversion rate was 96.5%. As a result of quantitative analysis of the reaction product, 2,4-bis (normal butylamino) -6-amino-1,3,5-triazine was obtained in a yield of 14.7% and 2,4,6-tris (normal butylamino). ) -1,3,5-triazine yield 7
It was produced at 7.0%.

Example 15 In a stainless steel autoclave having an internal volume of 100 mL,
2,4-bis (normal butylamino) -6-amino-
1.76 g (20.0 mmol) of 1,3,5-triazine, 408 mg of 5% Pd-supporting activated carbon, 2.16 g (30 mmol) of normal butyraldehyde and 30 mL of 1-butanol were charged, and the system was thoroughly filled with nitrogen gas. After the replacement, the initial hydrogen pressure was 50 kg / cm ² , and hydrogen was supplied so as to maintain the pressure, and the reaction was carried out at a reaction temperature of 180 ° C. for 2 hours. After the reaction was completed, the unreacted raw material was quantitatively analyzed, and as a result, the raw material conversion rate was 96.0%. As a result of quantitative analysis of the reaction product, 2,4,6-tris (normal butylamino) -1,3,5-triazine was produced at a yield of 87.5%.

Example 16 Into a stainless steel autoclave having an internal volume of 100 mL, 2
-Dibutylamino-4,6-diamino-1,3,5-triazine 4.76 g (20.0 mmol), 5% Pd-supporting activated carbon 408 mg (0.1 mmol), normal butyraldehyde 4.32 g (60.0 mmol) was charged with 1-butanol 30 mL, after thoroughly purging the system with nitrogen gas, as a hydrogen initial pressure 50 kg / cm ^2, the reaction temperature 1
The reaction was carried out at 90 ° C for 1.5 hours. After the reaction was completed, the unreacted raw material was quantitatively analyzed, and as a result, the raw material conversion rate was 92.6%. As a result of quantitative analysis of the reaction product, 2-dinormal butylamino-4-butylamino-6-amino-1,3,3
The yield of 5-triazine was 16.0%, 2-dinormal butyl-4,6-bis (normal butylamino) -1,3.
5-Triazine was produced in a yield of 69.4%.

Example 17 Into a stainless steel autoclave having an internal volume of 100 mL, 2
-N-butyl melamine 3.64 g (20.0 mmol), triruthenium dodecacarbonyl 63.9 mg
(0.1 mmol), normal butyraldehyde 2.1
After charging 6 g (30.0 mmol) and 30 mL of 1-butanol and thoroughly replacing the inside of the system with nitrogen gas, a synthetic gas (H ₂ / CO = 2/1) was introduced at an initial pressure of 100 kg / cm ² to carry out the reaction. After the temperature was raised to 200 ° C., the reaction was performed for 2 hours while supplying hydrogen gas so as to maintain the pressure. After the reaction was completed, quantitative analysis of unreacted raw materials revealed that the raw material conversion rate was 4
It was 5.3%. As a result of quantitative analysis of the reaction product,
2,4-bis (normal butylamino) -6-amino-
Yield of 12,3% of 1,3,5-triazine was 2,4,6
-Tris (normal butylamino) -1,3,5-triazine was produced in a yield of 25.4%.

Example 18 In a stainless steel autoclave having an internal volume of 100 mL, 2
-Diethylamino-4,6-diamino-1,3,5-triazine 3.64 g (20.0 mmol), 5% Pd-supporting activated carbon 408 mg, normal butyraldehyde 4.3
2 g (60.0 mmol) and 1-butanol (30 mL) were charged, the system was sufficiently replaced with nitrogen gas, and then the reaction was carried out at a reaction temperature of 200 ° C. for 2 hours under an initial hydrogen pressure of 30 kg / cm ² . After the reaction, the result of quantitative analysis of unreacted raw materials,
The raw material conversion rate was 91.9%. As a result of quantitative analysis of the reaction product, 2-diethylamino-4-normal-butylamino-6-amino-1,3,5-triazine was obtained in a yield of 1
3.8%, 2-diethylamino-4,6-bis (normal butylamino) -1,3,5-triazine yield 6
It was produced at 8.5%.

Example 19 A stainless steel autoclave having an internal volume of 40 mL was charged with 2-
Morpholino-4,6-diamino-1,3,5-triazine 1.96 g (10.0 mmol), 5% Pd-supporting activated carbon 204 mg, 1-hexanal 3.00 (30.0 mmol), 1-hexanol 20 mL After charging and thoroughly replacing the system with nitrogen gas, the initial hydrogen pressure was 50 kg / cm ²
As a result, the reaction was performed at a reaction temperature of 200 ° C. for 10 hours. After the reaction was completed, the unreacted raw material was quantitatively analyzed, and as a result, the raw material conversion rate was 95.4%. As a result of quantitative analysis of the reaction product,
9.8% of 2-morpholino-4-normalbutylamino-6-amino-1,3,5-triazine, 2-morpholino-4,6-bis (normal butylamino) -1,3,3
5-Triazine was obtained with a yield of 81.4%.

Example 20 1.26 g (10.0 mmol) of melamine, 200 mg of activated carbon carrying 5% Pd, and 0.72 g of normal butyraldehyde were placed in a stainless steel autoclave having an internal volume of 60 mL.
(10.0 mmol) and 1,4-dioxane (20 mL) were charged, the system was sufficiently replaced with nitrogen gas, and then the reaction was carried out at a reaction temperature of 180 ° C. for 6 hours under an initial pressure of hydrogen gas of 40 kg / cm ² . After the reaction was completed, the raw material conversion rate was 47.7% as a result of quantitative analysis of unreacted melamine. After the catalyst and unreacted melamine were filtered off from the reaction solution, the solvent was distilled off to obtain a crude reaction product. As a result of quantitative analysis of the reaction product, 2,4-diamino-6-normal butylamino-1,3,5-triazine was 23.2% and 2-amino-4,6-bis (normal butylamino) -1. , 3, 5
-Triazine 18.5%, 2,4,6-tris (normal butylamino) -1,3,5-triazine 10.
It was produced in a yield of 0%.

Example 21 1.26 g (10.0 mmol) of melamine, 200 mg of 5% Pd-supporting activated carbon and 1.44 g of normal butyraldehyde were placed in a stainless steel autoclave having an internal volume of 60 mL.
(20.0 mmol) and 1,4-dioxane (20 mL) were charged, the system was sufficiently replaced with nitrogen gas, and then the reaction was carried out at a reaction temperature of 180 ° C. for 6 hours under an initial pressure of hydrogen gas of 40 kg / cm ² . After the reaction was completed, the raw material conversion rate was 82.7% as a result of quantitative analysis of unreacted melamine. After the catalyst and unreacted melamine were filtered off from the reaction solution, the solvent was distilled off to obtain a crude reaction product. As a result of quantitative analysis of the reaction product, 2,4-diamino-6-normal butylamino-1,3,5-triazine was 25.8% and 2-amino-4,6-bis (normal butylamino) -1. , 3, 5
-Triazine 32.4%, 2,4,6-tris (normal butylamino) -1,3,5-triazine 21.
It was produced in a yield of 6%.

Example 22 1.26 g (10.0 mmol) of melamine, 200 mg of 5% Pd-supporting activated carbon, and 2.16 g of normal butyraldehyde were placed in a stainless steel autoclave having an internal volume of 60 mL.
(30.0 mmol) and 1,4-dioxane (20 mL) were charged, the system was sufficiently replaced with nitrogen gas, and then the reaction was carried out at a reaction temperature of 180 ° C. for 6 hours under an initial pressure of hydrogen gas of 40 kg / cm ² . After the reaction was completed, quantitative analysis of unreacted melamine revealed that the raw material conversion rate was 98.8%. After the catalyst and unreacted melamine were filtered off from the reaction solution, the solvent was distilled off to obtain a crude reaction product. As a result of quantitative analysis of the reaction product, 2,4-diamino-6-normal butylamino-1,3,5-triazine was 8.6% and 2-amino-
4,6-bis (normal butylamino) -1,3,5-
33.4% of triazine and 51.3 of 2,4,6-tris (normal butylamino) -1,3,5-triazine.
It was produced in a yield of%.

Example 23 1.26 g (10.0 mmol) of melamine, 200 mg of 5% Pd-supported activated carbon and 4.32 g of normal butyraldehyde were placed in a stainless steel autoclave having an internal volume of 60 mL.
(60.0 mmol) and 1,4-dioxane (20 mL) were charged, the system was sufficiently replaced with nitrogen gas, and then the reaction was carried out at a reaction temperature of 180 ° C. for 6 hours under an initial pressure of hydrogen gas of 40 kg / cm ² . After the reaction was completed, the unreacted melamine was quantitatively analyzed, and as a result, the raw material conversion rate was 99.9%. After the catalyst and unreacted melamine were filtered off from the reaction solution, the solvent was distilled off to obtain a crude reaction product. As a result of quantitative analysis of the reaction product, 2,4-diamino-6-normal butylamino-1,3,5-triazine was 0.1% and 2-amino-
4,6-bis (normal butylamino) -1,3,5-
Triazine is 0.9% and 2,4,6-tris (normal butylamino) -1,3,5-triazine is 75.6.
%, 2,4-bis (normal butylamino) -6-dinormal butylamino-1,3,5-triazine was 21.
6%, 2,4-bis (dinormal butylamino) -6-
Normal butylamino-1,3,5-triazine is 1.
It was produced in a yield of 1%.

Example 24 In a stainless steel autoclave having an internal volume of 60 mL, 1.26 g (10.0 mmol) of melamine, 200 mg of 5% Pd-supporting activated carbon and 7.20 g of normal butyraldehyde.
(100.0 mmol), 20 ml of 1,4-dioxane
Was charged and the inside of the system was sufficiently replaced with nitrogen gas. Then, the initial pressure of hydrogen gas was 40 kg / cm ² , and the reaction temperature was 180 ° C. at 6 ° C.
Allowed to react for hours. After the reaction was completed, the raw material conversion rate was 100% as a result of quantitative analysis of unreacted melamine. After the catalyst and unreacted melamine were filtered off from the reaction solution, the solvent was distilled off to obtain a crude reaction product. As a result of quantitative analysis of the reaction product, 2,4,6-tris (normal butylamino) -1,3,5-triazine was 67.0% and 2,4-
Bis (normal butylamino) -6-dinormal butylamino-1,3,5-triazine 29.3%, 2,4
-Bis (dinormal butylamino) -6-normal butylamino-1,3,5-triazine was produced in a yield of 2.7%.

Example 25 1.26 g (10.0 mmol) of melamine, 200 mg of 5% Pd-supported activated carbon and 2.16 g of normal butyraldehyde were placed in a stainless steel autoclave having an internal volume of 60 mL.
(30.0 mmol), 20 mL of ethanol was charged,
After the system was sufficiently replaced with nitrogen gas, hydrogen gas was reacted at an initial pressure of 40 kg / cm ² at a reaction temperature of 180 ° C. for 6 hours. After the reaction was completed, quantitative analysis of unreacted melamine revealed that the raw material conversion rate was 97.2%. After the catalyst and unreacted melamine were filtered off from the reaction solution, the solvent was distilled off to obtain a crude reaction product. As a result of quantitative analysis of the reaction product, 2,4-diamino-6-normal butylamino-
1,3,5-triazine is 9.6%, 2-amino-4,
6-bis (normal butylamino) -1,3,5-triazine 24.5%, 2,4,6-tris (normal butylamino) -1,3,5-triazine 53.9%,
2,4-bis (normal butylamino) -6-dinormal butylamino-1,3,5-triazine was produced in a yield of 7.0%.

Example 26 1.26 g (10.0 mmol) of melamine, 200 mg of 5% Pd-supporting activated carbon and 4.32 g of normal butyraldehyde were placed in a stainless steel autoclave having an internal volume of 60 mL.
(60.0 mmol) and ethanol (20 mL) were charged,
After the system was sufficiently replaced with nitrogen gas, hydrogen gas was reacted at an initial pressure of 40 kg / cm ² at a reaction temperature of 180 ° C. for 6 hours. After the reaction was completed, quantitative analysis of unreacted melamine revealed that the raw material conversion rate was 99.5%. After the catalyst and unreacted melamine were filtered off from the reaction solution, the solvent was distilled off to obtain a crude reaction product. As a result of quantitative analysis of the reaction product, 2,4,6-tris (normal butylamino)-
1,3,5-triazine is 56.5%, 2,4-bis (normal butylamino) -6-dinormal butylamino-1,3,5-triazine is 31.1%, 2,4-bis ( Dinormal butylamino) -6-normal butylamino-1,3,5-triazine was produced in a yield of 10.0%.

Example 27 1.26 g (10.0 mmol) of melamine, 148 mg of Raney nickel catalyst, and 2.16 g of normal butyraldehyde were placed in a stainless steel autoclave having an internal volume of 60 mL.
(30.0 mmol) and 20 mL of methanol were charged,
After the system was sufficiently replaced with nitrogen gas, hydrogen gas was reacted at an initial pressure of 50 kg / cm ² at a reaction temperature of 200 ° C. for 1 hour. After the reaction was completed, quantitative analysis of unreacted melamine revealed that the raw material conversion rate was 25.4%. After cooling the reaction solution, the catalyst and unreacted melamine were filtered off, and then the solvent was distilled off to obtain a crude reaction product. As a result of quantitative analysis of the reaction product, 2,4-diamino-6-n-butylamino-1,3,5-triazine was 15.6% and 2-amino-4,6-bis (n-butylamino) -1. , 3,
5-triazine was produced in a yield of 3.1%.

Example 28 1.26 g (10.0 mmol) of melamine, 25.0 mg of nickel diatomaceous earth catalyst, and normal butyraldehyde were placed in a stainless steel autoclave having an internal volume of 60 mL.
After 16 g (30.0 mmol) and 20 mL of methanol were charged and the inside of the system was sufficiently replaced with nitrogen gas, hydrogen gas was reacted at an initial pressure of 50 kg / cm ² at a reaction temperature of 200 ° C. for 6 hours. After the reaction was completed, the raw material conversion rate was 78.2% as a result of quantitative analysis of unreacted melamine. After the catalyst and unreacted melamine were filtered off from the reaction solution, the solvent was distilled off to obtain a crude reaction product. As a result of quantitative analysis of the reaction product, 2,4-diamino-6-normal butylamino-1,3,5-triazine was 27.8% and 2-amino-
4,6-bis (normal butylamino) -1,3,5-
Triazine 6.9%, 2,4,6-tris (normal butylamino) -1,3,5-triazine 2.5%,
2,4-bis (normal butylamino) -6-dinormal butylamino-1,3,5-triazine was produced in a yield of 1.0%.

Example 29 A stainless autoclave having an internal capacity of 60 mL was charged with 1.26 g (10.0 mmol) of melamine, 408.0 mg of 5% Pd-supporting activated carbon, 6.96 g of acetone (0.12 mol) and 20 mL of ethanol. After sufficiently replacing the inside of the system with nitrogen gas, hydrogen gas was reacted at an initial pressure of 50 kg / cm ² at a reaction temperature of 180 ° C. for 6 hours. After the reaction was completed, the unreacted melamine was quantitatively analyzed, and as a result, the raw material conversion rate was 98.0%. After the catalyst and unreacted melamine were filtered off from the reaction solution, the solvent was distilled off to obtain a crude reaction product. As a result of quantitative analysis of the reaction product, 2,4-diamino-6-isopropylamino-1,3,5-triazine was 31.9% and 2-amino-4,6-bis (isopropylamino) -1,3. , 5-triazine 42.0%,
2,4,6-Tris (isopropylamino) -1,3
5-triazine 13.6%, 2,4-bis (isopropylamino) -6-diisopropylamino-1,3,5
-Triazine was produced in a yield of 1.3%.

[0095]

INDUSTRIAL APPLICABILITY According to the method of the present invention, aminotriazines represented by 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. Substitutes-1,3,5, which is a useful compound group widely used as resin materials and flame-retardant materials,
-The triazine derivative can be easily produced in high yield.

The various alkylated, substituted-1,3,5-triazine derivatives of the products obtained according to the invention are generally obtained as mixtures, which products are pure by common organic compound separation methods. It can be separated in the form and used for the various applications described above. Further, 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 without being particularly separated.

Further, many substituted triazines obtained by this reaction have been relatively difficult or expensive to synthesize conventionally, and also in terms of physical properties, solubility in water and various organic solvents, and high temperature Many compounds are interesting in terms of stability, melting point, boiling point, basicity, etc., and it is considered that their applications will be expanded more than ever before.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Office reference number FI Technical display location B01J 23/44 X 23/46 301 X 311 X 23/70 X 23/755 25/02 X 27 / 13 X 31/22 X 31/24 X C07D 251/14 251/16 B 251/70 B // C07B 37/04 Z 7419-4H 61/00 300 (72) Inventor Yasuo Fukue 722 Tsuboi-cho, Funabashi, Chiba Prefecture Address 1 Nissan Chemical Industry Co., Ltd. Central Research Institute (72) Inventor Isao Hashiba 722 Tsuboi-cho, Funabashi, Chiba Prefecture Address 1 Nissan Chemical Industry Co., Ltd. Central Research Institute (72) Inventor Yoshihisa Watanabe 64-9 Terada Fukaya, Joyo City, Kyoto Prefecture

Claims (18)

[Claims] 1. In the presence of a catalyst of group VII and / or group VIII of the periodic table and a hydrogen-containing gas, 1,3,3 having at least one or more amino group or mono-substituted amino group on a ring carbon atom. A 5-triazine derivative is reacted with an aldehyde or a ketone to alkylate the at least one or more amino groups or mono-substituted amino groups,
Method for alkylating 3,5-triazine derivative. 2. At least one or more amino groups or mono
1,3,5-triazine derivative having a substituted amino group
1,3,5-triazine derivative represented by the general formula (I)
The 1,3,5-triazine derivative according to claim 1, which is a body
Alkylation method of;[In the formula, X¹, X²And X³At least one of them is German
Stand up NHR¹Group {in the formula, R¹Is a hydrogen atom, C_1-20A
Alkyl group (the alkyl group is a halogen atom, trifluoro group
Rumethyl group, hydroxyl group, C_1-6Alkoxy group of C_1-6of
Haloalkoxy group, aryloxy group, C_2-7Arco
Xycarbonyl group, C_2-7Acyloxy group, amino
Group, C_1-8Monoalkylamino group, C_2-12The Archi
Luamino group, phenyl group (the phenyl group is a halogen source
Child, C_1-6Alkyl group, hydroxyl group, C_{1- 6}The alkoxy
Optionally substituted with a group) optionally substituted with
Good), C_2-20An alkenyl group of
Halogen atom, trifluoromethyl group, hydroxyl group, C_1-6
Alkoxy group of C_1-6Haloalkoxy group, aryl
Oxy group, C_2-7Alkoxycarbonyl group of C_2-7of
Acyloxy group, amino group, C_1-8Monoalkylami
No group, C_2-12Dialkylamino group, phenyl group
A phenyl group is a halogen atom, C_1-6Alkyl group of hydroxy
Group, C_1-6Optionally substituted with an alkoxy group of
Which may be optionally substituted with¹X when not a group¹, X²And X³Haso
NR independently²R³Group {R², R³Each is German
Stand up C_1-20Alkyl group (wherein the alkyl group is a halogen
Atom, trifluoromethyl group, hydroxyl group, C_1-6Arco
Xy group, C_1-6Haloalkoxy group, aryloxy
Group, C_2-7Alkoxycarbonyl group of C _2-7The acyl
Oxy group, amino group, C_1-8A monoalkylamino group of
C_2-12Dialkylamino group, phenyl group (the phenyl
Group is a halogen atom, C_1-6Alkyl group, hydroxyl group, C
_1-6Optionally substituted with an alkoxy group of
May be substituted with), C_2-20Alkenyl group of
The alkenyl group is a halogen atom, trifluoromethyl
Group, hydroxyl group, C_1-6Alkoxy group of C_1-6The halo al
Coxy group, aryloxy group, C_2-7The alkoxycar
Bonyl group, C_2-7Acyloxy group, amino group, C_1-8
Monoalkylamino group, C_2-12Dialkylamino
Group, phenyl group (the phenyl group is a halogen atom, C_1-6
Alkyl group, hydroxyl group, C_1-6Optionally with an alkoxy group of
May be replaced) may be optionally replaced)
Represents, or R²And R³Together, optionally alkylene
C with 1 or 2 chains_{1- 8}Substituted by an alkyl group of
There- (CH₂)_2-5-, -CH₂CH₂− (C_1-8of
Alkyl) N-CH₂CH₂-Or-CH₂CH₂-O
-CH₂CH₂-May be formed}, C_1-20Alkyl group of {wherein the alkyl group is a halogen atom, water
Acid group, C_1-6Alkoxy group, carboxyl group, C_2-7
Alkoxycarbonyl group of C_2-10An acyloxy group of
Amino group, C_1-8Monoalkylamino group, C_2-12The di
Alkylamino group, aryl group (the aryl group is a halogen
Atom, C_1-6Alkyl group, hydroxyl group, C_1-6Arco
Optionally substituted with a xy group) optionally substituted with
You may stay}, C_2-20Alkenyl group of {the alkenyl group is a halogen source
Child, hydroxyl group, C_1-6Alkoxy group, carboxyl group,
C_2-7Alkoxycarbonyl group of C_2-10Akiruoki
Si group, amino group, C_1-8Monoalkylamino group, C
_2-12Dialkylamino group, aryl group (the aryl group
Is a halogen atom, C_1-6Alkyl group, hydroxyl group, C_1-6
It may be optionally substituted with an alkoxy group of
May be substituted}, a phenyl group (the phenyl group is C_1-6Alkyl group of halo
Gen atom, hydroxyl group, C _1-6The alkoxy group of Aryl
Xy group, C_2-10Acyloxy group, carboxyl group, C
_2-7Alkoxycarbonyl group of C_2-10The acyl group of
Mino group, C_1-8Monoalkylamino group, C_2-12Zia
Alkylamino group, aryl group (the aryl group is a halogen
Atom, C_1-6Alkyl group, hydroxyl group, C_1-6The Archoki
Optionally substituted with a Si group)
May be present}, halogen atom, C_1-10An alkoxy group of {the said alkoxy group is a halogen source
Child, hydroxyl group, C_1-6Alkoxy group of aryloxy
Group, carboxyl group, C_2-7Alkoxycarbonyl
Group, C_2-10Acyloxy group, amino group, C_1-8Things
Alkylamino group, C _2-12The dialkylamino group of ants
Group (the aryl group is a halogen atom, C_1-6The archi
Group, hydroxyl group, C_1-6Optionally substituted with an alkoxy group of
Optionally)), or C_1-10Alkylthio group of {wherein the alkylthio group is halo
Gen atom, hydroxyl group, C _1-6The alkoxy group of Aryl
Xy group, carboxyl group, C_2-7Alkoxy Carboni
Group, C_2-10Acyloxy group, amino group, C_1-8Mo
Noalkylamino group, C_2-12Dialkylamino group of
Reel group (the aryl group is a halogen atom, C_1-6Al
Kill group, hydroxyl group, C_1-6Optionally substituted with an alkoxy group of
May be substituted) may be arbitrarily substituted}
You. ]. 3. A 1,3,5-triazine of general formula (I)
NHR in derivatives¹Base R¹The group is a hydrogen atom, C
_1-20Alkyl group of {wherein the alkyl group is a halogen atom, water
Acid group, C_1-6Alkoxy group, phenyl group (the phenyl
Group is a halogen atom, C_1-6Alkyl group, hydroxyl group, C
_1-6Optionally substituted with an alkoxy group of
May be substituted with}, C_2-20An alkenyl group of {the alkenyl group is a halogen source
Child, hydroxyl group, C_1-6Alkoxy group and phenyl group
A phenyl group is a halogen atom, C_1-6Alkyl group of hydroxy
Group, C_1-6Optionally substituted with an alkoxy group of
, Which may be optionally substituted with the above}.¹X when not a group¹, X²And X³Haso
NR independently²R³Group [R², R³Each is German
Stand up C_1-20Alkyl group of {wherein the alkyl group is halogen
Atom, hydroxyl group, C_1-6Alkoxy group, phenyl group (the
Phenyl group is a halogen atom, C_1-6Alkyl group of hydroxy
Group, C_1-6Optionally substituted with an alkoxy group of
Optionally substituted with}, C_2-20An alkenyl group of {the alkenyl group is a halogen source
Child, C_1-6Alkoxy group, phenyl group (the phenyl group
Is a halogen atom, C_1-6Alkyl group, hydroxyl group, C_1-6
It may be optionally substituted with an alkoxy group of
May be replaced}, or R²And R³Together, optionally alkylene
C with 1 or 2 chains_{1- 8}Substituted by an alkyl group of
There- (CH₂)_3-5-, -CH₂CH₂− (C_1-8of
Alkyl) N-CH₂CH₂-Or-CH₂CH₂-O
-CH₂CH₂-May be formed], C_1-20Alkyl group of {wherein the alkyl group is a halogen atom, water
Acid group, C_1-6Alkoxy group, aryl group (the aryl
Group is a halogen atom, C_1-6Alkyl group, hydroxyl 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 halo
Gen atom, hydroxyl group, C _1-6Alkoxy group and aryl group
(The aryl group is a halogen atom, C_1-6An alkyl group of
Hydroxyl group, C_1-6Optionally substituted with an alkoxy group of
May be optionally substituted}, halogen atom, C_1-10An alkoxy group of {the said alkoxy group is a halogen source
Child, hydroxyl group, C_1-6Alkoxy group and aryl group of
Reel group is halogen atom, C_1-6Alkyl group of hydroxy
Group, C_1-6Optionally substituted with an alkoxy group of
May be arbitrarily replaced with}
Item 1. Alkylation of 1,3,5-triazine derivative according to item 2.
Method. Wherein the general formula R ¹ group of NHR ¹ group in 1,3,5-triazine derivative (I) is a hydrogen atom, C
_1-20 alkyl group (wherein the alkyl group may be optionally substituted with a hydroxyl group, a C _1-6 alkoxy group, or a phenyl group), and X ¹ when it is not the above NHR ¹ group , X ² and X ³ are each independently an NR ² R ³ group {R ² , R ³ are each independently a C _1-20 alkyl group (the alkyl group is a hydroxyl group,
Alkoxy C _1-6, represents optionally may be substituted) phenyl group, or R ² and R ³ together optionally alkylene chain of one or two C _1-8 It is substituted with an alkyl group _{- (CH 2) 4-5 -,} - 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}, a C _1-20 alkyl group, a phenyl group or a C _1-10 alkoxy group. Alkylation method. 5. The aldehyde or ketone used in the reaction is represented by the general formula (II): [In the formula, R ⁴ and R ⁵ are each independently a hydrogen atom, C _1-20
Alkyl group (wherein the alkyl group is a halogen atom, a hydroxyl group, a C _1-6 alkoxy group, a C _1-6 haloalkoxy group, a C _2-7 alkoxycarbonyl group, a C _2-7 acyloxy group, a phenyl group) (The phenyl group is a halogen atom,
C _1-6 alkyl group, hydroxyl group, optionally substituted with C _1-6 alkoxy group)), C _2-20 alkenyl group (the alkenyl group is Halogen atom, hydroxyl group, C _1-6 alkoxy group, C _1-6 haloalkoxy group, C _2-7 alkoxycarbonyl group, C _2-7 acyloxy group, phenyl group (the phenyl group is a halogen atom, C _1-6 alkyl group, hydroxyl group, C _1-6 alkoxy group may be optionally substituted)), or R ⁴ and R ⁵ are taken together, Alkylene group- (CH
₂ ) _3-5 -may be formed], 1, 3, 5 according to claim 1, which is an aldehyde derivative or a ketone derivative.
-Method for alkylating triazine derivatives. 6. An aldehyde or ketone of the general formula (II)
R^Four, R^FiveAre each independently a hydrogen atom, C_1-20The archi
Group (the alkyl group is a halogen atom, a hydroxyl group, C_1-6
Even if optionally substituted with an alkoxy group or a phenyl group
Good) or C _2-20An alkenyl group of
Halogen atom, hydroxyl group, C_1-6The alkoxy group of pheny
Optionally substituted with a group), or R^FourAnd R^FiveTogether with an alkylene group-(CH
₂)_3-5-Aldehi, which may either form
A derivative of claim 1 or a ketone derivative,
Method for alkylating 3,5-triazine derivative. 7. An aldehyde or ketone of the general formula (II), wherein R ⁴ and R ⁵ are each independently a hydrogen atom or a C _1-20 alkyl group (wherein the alkyl group is a halogen atom, a hydroxyl group, C
_1-6 alkoxy group, which may be optionally substituted with a phenyl group), or R ⁴ and R ⁵ are taken together to form an alkylene group — (CH ₂ ) _3-5 —. 7. A good aldehyde derivative or ketone derivative according to claim 1,
Method for alkylating 3,5-triazine derivative. 8. By the alkylation method according to claim 1.
The resulting substituted 1,3,5-triazine derivative has the general formula (I
A substituted 1,3,5-triazine derivative represented by II)
A method for alkylating a certain 1,3,5-triazine derivative;[In the formula, X^Four, X^FiveAnd X⁶At least one of them is German
Stand up and NR⁶R⁷Group {R ⁶, R⁷Each independently water
Elementary atom (however, X^Four, X^FiveAnd X⁶R⁶, R⁷All
Is a hydrogen atom), C_1-20Alkyl group of
(The alkyl group is a halogen atom, trifluoromethyl
Group, hydroxyl group, C_1-6Alkoxy group of C_1-6The halo al
Coxy group, aryloxy group, C_2-7The alkoxycar
Bonyl group, C _2-7Acyloxy group, amino group, C_1-8
Monoalkylamino group, C_2-12Dialkylamino
Group, phenyl group (the phenyl group is a halogen atom, C_1-6
Alkyl group, hydroxyl group, C_1-6Optionally with an alkoxy group of
Optionally substituted), optionally substituted), or C_2-20An alkenyl group (wherein the alkenyl group is a halogen
Atom, trifluoromethyl group, hydroxyl group, C_1-6Al
Coxy group, C_1-6Haloalkoxy group, aryloxy
Group, C_2-7Alkoxycarbonyl group of C_2-7The acyl
Oxy group, amino group, C_1-8A monoalkylamino group of
C_2-12Dialkylamino group, phenyl group (the phenyl
Group is a halogen atom, C_1-6Alkyl group, hydroxyl group, C
_1-6Optionally substituted with an alkoxy group of
R), or R⁶And R⁷Is one
And optionally C having 1 or 2 alkylene chains.
_{1- 8}Substituted with an alkyl group of-(CH₂)
_2-5-, -CH₂CH₂− (C_1-8Alkyl) N-C
H₂CH₂-Or-CH₂CH₂-O-CH₂CH₂−
Can be formed}, and the above NR⁶R⁷X when not a group^Four, X^FiveAnd X
⁶Are each independently C _1-20Alkyl group of {the alky
Group is a halogen atom, hydroxyl group, C_1-6An alkoxy group of
Carboxyl group, C_2-7Alkoxycarbonyl group of C
_2-10Acyloxy group, amino group, C_1-8The monoarch
Luamino group, C_2-12Dialkylamino group, aryl group
(The aryl group is a halogen atom, C_1-6An alkyl group of
Hydroxyl group, C_{1- 6}May be optionally substituted with the alkoxy group of
Optional) may be substituted}, C_2-20Alkenyl group of {the alkenyl group is a halogen source
Child, hydroxyl group, C_1-6Alkoxy group, carboxyl group,
C_2-7Alkoxycarbonyl group of C_2-10Akiruoki
Si group, amino group, C_1-8Monoalkylamino group, C
_2-12Dialkylamino group, aryl group (the aryl group
Is a halogen atom, C_1-6Alkyl group, hydroxyl group, C_1-6
It may be optionally substituted with an alkoxy group of
May be substituted}, a phenyl group (the phenyl group is C_1-6Alkyl group of halo
Gen atom, hydroxyl group, C _1-6The alkoxy group of Aryl
Xy group, C_2-10Acyloxy group, carboxyl group, C
_2-7Alkoxycarbonyl group of C_2-10The acyl group of
Mino group, C_1-8Monoalkylamino group, C_2-12Zia
Alkylamino group, aryl group (the aryl group is a halogen
Atom, C_1-6Alkyl group, hydroxyl group, C_1-6The Archoki
Optionally substituted with a Si group)
May be present}, halogen atom, C_1-10An alkoxy group of {the said alkoxy group is a halogen source
Child, hydroxyl group, C_1-6Alkoxy group of aryloxy
Group, carboxyl group, C_2-7Alkoxycarbonyl
Group, C_2-10Acyloxy group, amino group, C_1-8Things
Alkylamino group, C _2-12The dialkylamino group of ants
Group (the aryl group is a halogen atom, C_1-6The archi
Group, hydroxyl group, C_1-6Optionally substituted with an alkoxy group of
Optionally)), or C_1-10Alkylthio group of {wherein the alkylthio group is halo
Gen atom, hydroxyl group, C _1-6The alkoxy group of Aryl
Xy group, carboxyl group, C_2-7Alkoxy Carboni
Group, C_2-10Acyloxy group, amino group, C_1-8Mo
Noalkylamino group, C_2-12Dialkylamino group of
Reel group (the aryl group is a halogen atom, C_1-6Al
Kill group, hydroxyl group, C_1-6Optionally substituted with an alkoxy group of
May be substituted) may be arbitrarily substituted}
You. ]. 9. A substituted 1,3,5-tria of the general formula (III)
X in gin derivative^Four, X^FiveAnd X⁶NR⁶R⁷Base
R⁶, R⁷Are each independently a hydrogen atom (however,
X^Four, X^FiveAnd X⁶R⁶, R⁷Are all hydrogen atoms
Except when_1-20Alkyl group of {the alkyl group
Is a halogen atom, hydroxyl group, C_1-6The alkoxy group of
Phenyl group (the phenyl group is a halogen atom, C_1-6Al
Kill group, hydroxyl group, C_1-6Optionally substituted with an alkoxy group of
Optionally)), or C_2-20An alkenyl group of {the alkenyl group is a halogen
Atom, hydroxyl group, C_{1- 6}Alkoxy group ,, phenyl group
(The phenyl group is a halogen atom, C_1-6An alkyl group of
Hydroxyl group, C_1-6May be optionally substituted with the alkoxy group of
R), which may be optionally substituted}, or R⁶And R⁷Together, optionally alkylene
C with 1 or 2 chains_{1- 8}Substituted by an alkyl group of
There- (CH₂)_3-5-, -CH₂CH₂− (C_1-8of
Alkyl) N-CH₂CH₂-Or-CH₂CH₂-O
-CH₂CH₂-May be formed, and the above NR^FourR^FiveIf not X^Four, X^FiveAnd X⁶But,
Each independently C_{1- 20}An alkyl group of {the alkyl group is
Halogen atom, hydroxyl group, C_1-6An alkoxy group of
Group (the aryl group is a halogen atom, C_1-6The alkyl
Group, hydroxyl 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 halo
Gen atom, hydroxyl group, C _1-6Optionally substituted with the alkoxy group of
May be included), halogen atom, C_1-10An alkoxy group of {the said alkoxy group is a halogen source
Child, hydroxyl group, C_1-6Alkoxy group and aryl group of
Reel group is halogen atom, C_1-6Alkyl group of hydroxy
Group, C_1-6Optionally substituted with an alkoxy group of
May be optionally substituted with}
10. The 1,3,5-triazine derivative according to claim 9.
A method for alkylating a 1,3,5-triazine derivative. 10. A substituted 1,3,5-tri of the general formula (III)
X in azine derivatives^Four, X^FiveAnd X⁶NR⁶R⁷
Base R⁶, R⁷Are each independently a hydrogen atom (provided that X
^Four, X^FiveAnd X⁶R⁶, R⁷Are all hydrogen atoms
Except case) or C_1-20Alkyl group of (the alkyl group
Is a hydroxyl group, C_1-6Alkoxy and phenyl groups are optional
Or R), or R⁶And R⁷Together, optionally alkylene
C with 1 or 2 chains_{1- 8}Substituted by an alkyl group of
There- (CH₂)_4-5-, -CH₂CH₂− (C_1-8of
Alkyl) N-CH₂CH₂-Or-CH₂CH₂-O
-CH₂CH₂-May be formed, and the above NR⁶R⁷X when not a group^Four, X^FiveAnd X
⁶But each independently C _1-20Alkyl group of phenyl
Group, C_1-10A substituted 1, which is any of the alkoxy groups of
The 1,5-triazine derivative according to claim 9,
Method for alkylating 3,5-triazine derivative. 11. The method for alkylating a 1,3,5-triazine derivative according to claim 1, wherein the catalyst of Group VII of the periodic table is a rhenium catalyst. 12. The method for alkylating a 1,3,5-triazine derivative according to claim 11, wherein the rhenium catalyst is a supported catalyst. 13. The catalyst according to claim 1, wherein the catalyst of Group VIII of the periodic table is at least one catalyst selected from iron, cobalt, nickel, ruthenium, rhodium, palladium, osmium, iridium and platinum catalysts. , 3,5-
Method for alkylating triazine derivative. 14. A catalyst of Group VIII of the periodic table is cobalt,
The method for alkylating a 1,3,5-triazine derivative according to claim 13, which is at least one catalyst selected from nickel, ruthenium, rhodium, palladium and platinum catalysts. 15. A catalyst of Group VIII of the periodic table is nickel,
15. The catalyst according to claim 14, which is at least one catalyst selected from ruthenium, palladium and platinum catalysts.
Method for alkylating 5-triazine derivatives. 16. The method for alkylating a 1,3,5-triazine derivative according to claim 13, wherein the catalyst is a complex catalyst. 17. The method for alkylating a 1,3,5-triazine derivative according to claim 13, wherein the catalyst is a supported catalyst. 18. The carrier of the supported catalyst is silica, alumina,
The method for alkylating a 1,3,5-triazine derivative according to claim 12 or 17, which is zeolite or carbon.