JPH08253460A - Monoalkylation of 1,3,5-triazine derivative - Google Patents

Abstract

PURPOSE: To alkylate an amino-substituted 1,3,5-triazine derivative in high selectivity by reducing an amino group-containing triazine derivative and an aldehyde or a ketone in the presence of a metal catalyst supported on zeolite and a hydrogen-containing gas. CONSTITUTION: A compound of formula I [at least one of X<1> to X<3> is NHR (R<1> is H, an alkyl, an alkenyl, etc.) and X<1> and X<3> which are not NHR<1> are each NR<2> R<3> (R<2> and R<3> are each an alkyl, a halogen, etc.)] containing at least one amino group or mono-substituted amino group is reacted with a compound of formula II (R<4> and R<5> are each H, an alkyl, etc.) in the presence of a catalyst of a metal of the group VIII of the periodic table supported on zeolite, especially a metal catalyst supported on zeolite and a hydrogen-containing gas at 50-300 deg.C for 0.1-100 hours to give a compound of formula III [at least one of X<4> to X<6> is a group of the formula NR<6> R<7> (R<6> and R<7> are each H, an alkyl, etc.), an alkyl, etc.]. The compound of formula III useful as an intermediate for agrochemicals, medicines, dyes, coating materials, etc., and a flame-retardant material for resin materials is readily obtained selectively and in high yield by controlling the number of alkyl groups.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a variety of 1, 1 or more amino groups or monosubstituted amino groups.
3,5-triazine and an aldehyde or a ketone are reductively reacted in the presence of a zeolite-supported Group VIII metal catalyst and a hydrogen-containing gas, the at least one or more amino groups or The present invention relates to a method for selectively monoalkylating an amino-substituted 1,3,5-triazine derivative having a mono-substituted amino group.

Substituted amino-1,3,5-obtained by the method of selective alkylation of the amino group on the triazine ring carbon atom of the amino-substituted 1,3,5-triazine derivative of the present invention
5-triazine derivatives are useful compounds 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. is there.

[0003]

2. Description of the Related Art Various synthetic methods for synthesizing substituted aminotriazines have hitherto been known.
V)

[0004]

[Chemical 4]

(Where X is⁷And X⁸Is diethylamino
Group, X⁹Is an ethylamino group, or X ⁷, X⁸Is net
No group, X⁹Is an ethylamino group or a diethylamino group
Represent The compound of) is 2-chloro-1,3,5-tria.
A synthetic method by the reaction of a gin derivative with ethylamine was reported.
Have been. [Journal of America Chemicals
Society (J. Amer. Chem. Soc), 73, 2984,
1951].

The compound of the general formula (IV) (wherein X ⁷ , X ⁸ and X ⁹ represent an ethylamino group) is 2,4,6-trimethylthio-1,3,5-triazine and ethylamine. A synthetic method based on the reaction has been reported. [Chem Rer., 18, 1855, 2785
Year〕. The compound of the general formula (IV) (in the formula, X ⁷ represents an amino group, X ⁸ represents an amino group or an octylamino group, and X ⁹ represents an octylamino group) is 2,4,6-triamino-
A synthetic method by the reaction of 1,3,5-triazine and octylamine hydrochloride has been reported [US Patent 2,228,
No. 161, 1941].

Formula (IV) (wherein X ⁷ is a phenyl group, X
⁸ and X ⁹ represent a butylamino group. ) Is 2
A synthetic method by the reaction of -phenyl-4,6-diamino 1,3,5-triazine and butylamine has been reported [US Pat. No. 2,385,766, 1945]. Further, various 2,4,6-substituted-1,3,5-triazine derivatives synthesized from cyanuric chloride are used as flame retardants for thermoplastic polymers [JP-A-3-215564].
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 ketone is represented by a reaction example of hydroxymethylation with melamine and an aqueous formalin solution under weak alkaline conditions. [Journal of America Chemical Society (J.Ame
r. Chem. Soc), 69, 599, 1947]. Journal of America Chemical Society (J.Am
Chem. Soc), 73, 2984, 1954, often requires an equivalent amount or more of a condensing agent, and produces by-products such as salts which are often industrially problematic. See also Chem Ber., Volume 18, 27.
The synthetic method of page 55, 1885 produces by-products such as sulfur compounds, which are often industrially problematic. US Patent 2,22
8,161, 1941 and US Patent 2,385,7.
No. 66, 1945 synthesis requires high temperature for reaction,
The former produces ammonium chloride as a by-product. Further, in both cases, there is a common point that the substitution reaction with the leaving group is carried out by using the substituted amines which are not industrially cheap, which is one reason why the substituted triazines cannot be inexpensively supplied. Has become.

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 and highly reactive formaldehyde is common, and other carbonyl compounds,
In particular, in the case of reaction with aldehydes, a reaction which gives an equilibrium mixture of a raw material and a hydroxyalkylated product, and the product thereof is unstable, or easily undergoes dehydration condensation reaction with other aminotriazines to obtain a polynuclear compound Is known (ES
molin and Rapoport 1959, "s-Triazines and Derivati
ves "from the series" The Chemistry of Heterocycli
c Compounds. "). Therefore, the reaction of reacting an aminotriazine derivative with an aldehyde or a ketone to highly selectively introduce one alkyl group into an amino group on a triazine ring is not known.

[0011]

DISCLOSURE OF THE INVENTION The inventors of the present invention have made diligent efforts to solve the above-mentioned problems, and as a result, various industrially inexpensive aldehyde derivatives or ketone derivatives and amino groups or mono groups on the triazine nucleus have been investigated. A substituted amino group is reductively reacted with a metal-supported catalyst selected from Group VIII of the Periodic Table, particularly a zeolite-supported metal catalyst, and a hydrogen-containing gas to react on the amino group or the mono-substituted amino group. The present invention has been completed in which the number of one alkyl group is introduced at a high yield and only water is used as a by-product.

As described in the prior art, the only method for selectively synthesizing a derivative having one alkyl group among aminotriazine derivatives is, for example, a method of synthesizing cyanuric chloride as a raw material in several steps. It was a highly practical method. However, according to the method of the present invention, for example, in the case of a triaminotriazine (melamine) derivative, melamine and an industrially inexpensive carbonyl compound are used as raw materials, and an aminotriazine derivative having a desired number of alkyl groups is used as a catalytic reaction. It can be manufactured in one step.

Further, the substituted amino-1, obtained by this reaction,
The 3,5-triazine derivative remarkably inhibits the multimolecular association due to the intermolecular hydrogen bond inherent in aminotriazines, and thus the solubility in various solvents is improved,
At the same time, since the melting point also drops, the compatibility with other organic compounds also improves. For example, taking melamine as an example, after the reaction, most of the unreacted melamine is precipitated as crystals in the solvent used for the reaction, and separated by means such as filtration. On the other hand, the products obtained with high selectivity are excellent in terms of separation and purification because almost all of them are dissolved in the solvent.

An object of the present invention is to carry an amino group or a mono-substituted amino group on a ring carbon atom of 1,3,5-triazine, an aldehyde or a ketone, and a zeolite as a carrier for a metal of Group VIII of the periodic table. Reductively reacting in the presence of a catalyst and hydrogen-containing gas, and can be widely used as a fine chemical intermediate for various agricultural chemicals, pharmaceuticals, dyes, paints, etc., and also as various resin materials and flame-retardant materials. Substituted amino-1,3,5-triazine derivatives, which are various compounds, can be easily produced selectively and in high yield by controlling the number of alkyl groups.
-Providing a method for monoalkylating a triazine derivative.

[0015]

That is, the present invention is directed to a 1,3,5-triazine derivative having at least one or more amino groups or mono-substituted amino groups on a ring carbon atom, an aldehyde or a ketone, and a zeolite as a carrier. Characterized in that the reaction is carried out reductively in the presence of a supported catalyst of a metal of Group VIII of the periodic table and a hydrogen-containing gas, and at least one amino group or monosubstituted amino group Amino-substituted 1,3 to introduce one alkyl group
The present invention relates to a method for monoalkylating a 5-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 amino-substituted 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 represented by the general formula (I). Is.

[0017]

[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, 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)), optionally substituted),
C_2-20An alkenyl group of
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
And may be replaced).
R¹X when not a group¹, X²And X³Are independent
Then NR²R³Group {R², R³Are each independently C
_1-20Alkyl group (wherein the alkyl group is a halogen atom, 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
Optionally)), C _2-20of
An alkenyl group (the alkenyl group is a halogen atom,
Fluoromethyl group, hydroxyl group, C_1-6Alkoxy group of C
_1-6Haloalkoxy group, aryloxy group, C_2-7of
Alkoxycarbonyl group, C_2-7Acyloxy group
Mino group, C _1-8Monoalkylamino group, C_2-12Zia
Alkylamino group, phenyl group (the phenyl group is a halogen
Atom, C_1-6Alkyl group, hydroxyl group, C_1-6The Archoki
Optionally substituted with a Si group)
May be used), and R ²And R³Together,
If desired, C having 1 or 2 alkylene chains_1-8The archi
-(CH₂)_2-5-, -CH
₂CH₂-N (C_1-8Alkyl) -CH₂CH₂-Also
Is -CH₂CH₂-O-CH₂CH₂Good to form
I}, C₁-₂₀Alkyl 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}, C₂-₂₀Alkenyl 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
Optional}, halogen atom, hydroxyl group, C_1-10Arco
Xy group (the alkoxy group is a halogen atom, a hydroxyl group, C
_1-6Alkoxy group, aryloxy group, carboxyl
Group, C_2-7Alkoxycarbonyl group of C_2-10The acyl
Oxy group, amino group, C_1-8A monoalkylamino group of
C _2-12Dialkylamino 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 thiol group, or C_1-10
An alkylthio group of {wherein the alkylthio group is a halogen atom,
Hydroxyl group, C_1-6Alkoxy group, aryloxy group,
Ruboxyl 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_1-6May be optionally substituted with the alkoxy group of
May be optionally substituted}. ].

In the specification and claims of the present application,
"It may be optionally substituted with the listed substituents."
Is a heterologous or homologous 1 selected from the listed substituents.
Meaning that it may be selected by more than one substituent
Is. Preferred 1,3,5-totes of the above general formula (I)
The lyazine derivative is 1,3,5-tria represented by the general formula (I).
NHR in gin derivatives¹Base R¹The group is a hydrogen atom,
C_1-20An alkyl group of {wherein the alkyl group is a halogen atom,
Hydroxyl group, C_1-6Alkoxy group, phenyl group (the phenyl group
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 said
Alkenyl groups include halogen atoms, hydroxyl groups, C_1-6Al
Coxy 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 replaced with)
And the above NHR.¹If not base
X¹, X²And X³Each independently NR²R³Base
[R², R³Are each independently C_1-20Alkyl group of
{The alkyl group is a halogen atom, a hydroxyl group, C_1-6A
Lucoxy group, phenyl group (the phenyl 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}, C_2-20An alkenyl group of {the alkenyl group is
Halogen atom, 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}, or R²
And R³Together with one or more alkylene chains if desired
Is two Cs _1-8Substituted by an alkyl group of
(CH₂)_3-5-, -CH₂CH₂− (C_1-8The archi
Le) N-CH₂CH₂-Or-CH₂CH₂-O-CH
₂CH ₂-May be formed], C₁-₂₀An alkyl group of {the
Alkyl group is 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))
I}, phenyl group (the phenyl group is C_1-6The alkyl
Group, halogen atom, hydroxyl group, C_1-6The alkoxy 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, hydroxyl group, C_1-10Alkoxy group of {the alco
The xy group is a halogen atom, hydroxyl group, C_1-6The alkoxy
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) may be optionally substituted}
It is any one of the 1,3,5-triazine derivatives.

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),
Or R²And R³Together, if desired,
C having 1 or 2 chains _1-8Substituted by the alkyl group of
-(CH₂)_4-5-, -CH₂CH₂− (C_1-8
Alkyl) N-CH₂CH₂-Or-CH₂CH₂−
O-CH₂CH ₂-May be formed}, C₁-₂₀The archi
Group, phenyl group, hydroxyl group, C_1-10The alkoxy group
It is a 1,3,5-triazine derivative which is a lag.

As described above, it is possible to provide all amino-substituted 1,3,5-triazine derivatives having a substituent not directly involved in the reaction in this reaction, but it is industrially available intermediates. Various melamine derivatives and various guanamine derivatives as the body (these are mainly available as the main agent or modifier of thermosetting resin, cross-linking agent for baking coating, and the synthesis method is "s-triazines and derivatives." From
the series "The Chemistry of Heterocyclic Compoun
ds. "EM Smolin and L. Rapoport. Interscience Pu
blishers Inc., New York. 1959.).

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

[0023]

[Chemical 7]

[Wherein R^Four, R^FiveAre each independently hydrogen
Atom, C_1-20Alkyl group of {wherein the alkyl group is halogen
Atom, hydroxyl group, C_1-6Alkoxy group of C_1-6Halo a
Lucoxy group, C_2-7Alkoxycarbonyl group, Holmi
Group, C_2-7Acyl group of C_{2- 7}The acyloxy 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 optionally substituted), or
C_2-20An alkenyl group of {the alkenyl group is a halogen source
Child, hydroxyl group, C _1-6Alkoxy group of C_1-6The halo al
Coxy group, C_2-7Alkoxycarbonyl group of formyl
Group, C_2-7Acyl group of C_2-7The acyloxy 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}.
1 or R^FourAnd R^FiveTogether, an alkylene group (-
(CH₂)_3-5-) May be formed. ] (In the formula,
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
Alkoxy group of C_1-6Haloalkoxy group, C_2-7of
Alkoxycarbonyl group, formyl group, C_2-7The acyl
Group, C_{2- 7}Acyloxy 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 {the alkenyl group is a halogen atom, a hydroxyl group, C_1-6
Alkoxy group of C_1-6Haloalkoxy group, C_2-7of
Alkoxycarbonyl group, formyl group, C_2-7The acyl
Group, C_2-7Acyloxy 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 replaced with}. Or R^FourAnd R^Five
Together with an alkylene group-(CH₂)_3-5Form-
Aldehyde derivative or keto represented by
Derivative.

Preferred aldehydes of general formula (II) above
Or as ketones, R^Four, R ^FiveEach independently,
Hydrogen atom, C_1-20An alkyl group of (wherein the alkyl group is a halo
Gen atom, hydroxyl group, C_1-6Alkoxy group of formyl
Group, C_2-7Optionally substituted with an acyl group or phenyl group
Or C_2-20Alkenyl group of the
Nyl group is a halogen atom, hydroxyl group, C_1-6The alkoxy
Group, formyl group, C_2-7Optional acyl group or phenyl group
R), or R^FourAnd R^FiveTogether
Becomes an alkylene group-(CH₂)_3-5Even if-is formed
Any good aldehyde derivative or ketone derivative
Conductor.

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, formyl group,
C _2-7 acyl group, optionally substituted with phenyl group) or R ⁴ and R ^{5 taken} together may form an alkylene group — (CH ₂ ) _3-5 — It is a derivative or a ketone derivative.

Of these, formaldehyde, acetaldehyde, propionaldehyde, n-butyraldehyde, i-butyraldehyde, n-pentylaldehyde, n-hexylaldehyde, n-octanal, n-nonanal, 2-Ethylhexyl aldehyde, cyclohexyl aldehyde, benzaldehyde, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone, cyclohexanone, acetophenone and other monoaldehydes, monoketones and their acetals or ketals, malondialdehyde, succindialdehyde, glutaraldehyde Dicarbonyl compounds such as 2,5-hexanedione,
Alternatively, aldehyde equivalents such as paraformaldehyde and 1,3,5-trioxane may be mentioned.

In this reaction, these aldehydes or ketones are treated with the amino-1,3,5-triazine derivative of the general formula (I), a metal-supported catalyst of Group VIII of the periodic table, particularly a metal catalyst supported on zeolite and hydrogen. An alkyl-substituted amino-1,3,3 represented by the general formula (III) is prepared by reacting reductively in the presence of a containing gas to selectively introduce one alkyl group.
This is a reaction for highly selectively obtaining a 5-triazine derivative.

The amount of the aldehyde or ketone used can be generally in the range of 0.1 to 1000 moles per 1 mole of the aminotriazine derivative of the general formula (I). Substituted amino-introduced group
In order to obtain the 1,3,5-triazine derivative, it is desirable to use the aldehyde or the ketone in the range of 0.1 to 50 mol based on 1 mol of the triazine derivative of the general formula (I).

Further, in this reaction, although depending on the reactivity of the carbonyl compound, a side reaction in which the starting carbonyl compound itself is reduced also occurs. Therefore, it is also desirable to supply a carbonyl compound according to the progress of the reaction during the reaction, or to adopt a method of suppressing side reactions by the hydrogen supply amount and rate, reaction temperature, reaction time, reaction mode such as batch and continuous. These conditions can be freely selected depending on the desired reaction.

This reaction contains pure hydrogen gas or hydrogen.
The gas pressure is 0.1 to
500 kg / cm², Preferably 0.5 to 200 kg /
cm ²Is preferred. In the case of hydrogen-containing gas,
Various types of release gas as long as they do not directly participate in the reaction
Any gas can be used. Eg nitrogen, argon,
Helium and the like are generally used, but in some cases diacid
Carbon dioxide, air, etc. can also be used, products and catalysts
Ammonia, carbon monoxide, etc. are also used for the purpose of stabilizing etc.
Is done. When using these mixed gases, the water required for the reaction
There is no problem if there is a partial pressure, and the total pressure is 0.5
~ 500kg / cm² , Preferably 1.0 to 300 kg
/ Cm²It is desirable to react in the pressure range of.

As the catalyst of Group VIII of the periodic table used in this reaction, iron, cobalt, nickel, ruthenium,
Rhodium, palladium, osmium, iridium and platinum catalysts are mentioned, and supported catalysts of these elements are used alone or in combination. Among these elements, iron, nickel, ruthenium, rhodium, palladium and platinum catalysts are preferable, and nickel, ruthenium, palladium and platinum complexes and supported catalysts are particularly preferable.

The amount of the Group VIII catalyst used in the periodic table is usually in the range of 0.00001 to 20 mol%, preferably 0, relative to the amino-substituted-1,3,5-triazine derivative of the general formula (I). A range of 0.0001 to 10 mol% is preferable. As the metal carrier, a carrier having a uniform pore structure such as zeolite is particularly preferable in the selective alkylation reaction. The pore size of the zeolite used is not particularly limited, and the correlation between the reaction and the pore size varies depending on the molecular size and reactivity of the starting triazines and the aldehydes and ketones used, but generally 3 to 1
The use of zeolites with a pore size of 2Å, preferably 5-10Å, gives good results.

The zeolite carrier preferably used in this reaction will be illustrated more specifically below. Zeolites are ρ type zeolite, erionite, chabazite, Z
K-5, A type zeolite, SAPO-11, clinoptilolite, ZSM-48, ZSM-22, ZSM-2
3, ZSM-5, ferrilite, ZSM-11, EU-
1, ZSM-12, offretite, mordenite, L-type zeolite, β-type zeolite, EMC-2, X-type faujasite, ZSM-4, ZSM-12, SAPO-
5, Y-type faujasite, AlPO ₄ -8, VPI-
5, various metallosilicates including aluminosilicates having a structure such as Cloverlite.

In the present invention, the aminotriazine derivative and the carbonyl compound such as aldehyde and ketone to be used are introduced on the amino group of the aminotriazine derivative by selecting and combining the pore sizes of the carrier having these pore structures. It is possible to have a high degree of control over the number of alkyl groups carried. In particular, the monoalkyl group-substituted aminotriazine derivative can be highly selectively obtained by selecting these solid carriers.

A ligand may be added to the above-mentioned supported catalyst as needed for the reaction. Examples of the ligand include trimethylphosphine, triethylphosphine, tributylphosphine, triphenylphosphine, tris (paratolyl) phosphine, tris (2,6-dimethylphenyl) phosphine, diphenylphosphinobenzene-3-.
Sodium sulfonate, bis (3-sulfonatophenyl) phosphinobenzene sodium salt, 1,2-bis (diphenylphosphino) ethane, 1,3-bis (diphenylphosphino) propane, 1,4-bis (diphenylphos) Fino) butane, tridentate and polydentate tris (3-sulfonatophenyl) phosphine sodium salts, etc.
Phosphines, triethylphosphite, tributylphosphite, triphenylphosphite, tris (2,6-dimethylphenyl) phosphite and other phosphites, triphenylmethylphosphonium iodide, triphenylmethylphosphonium bromide, triphenylphosphite Phenylmethylphosphonium chloride, triphenylallylphosphonium iodide, triphenylallylphosphonium bromide, triphenylallylphosphonium chloride, tetraphenylphosphonium iodide, tetraphenylphosphonium bromide, phosphonium salts such as tetraphenylphosphonium chloride, triphenyl phosphate, phosphorus Phosphates such as trimethyl acid, triethyl phosphate, triallyl phosphate, cyclooctadiene, cyclopentadiene Unsaturated hydrocarbons, benzonitrile, nitriles such as acetonitrile, acetylacetone, carbon monoxide, and the like.

The amount of the ligand used is as shown in Table VII of the Periodic Table.
Usually 0.1 to 10000 mol% based on Group I metal catalyst
Is preferable, and a range of 10 to 5000 mol% is preferable. This reaction proceeds even without solvent, but it is preferable to use a solvent for the operation. As the solvent, any solvent may be used as long as it is inert to the reaction. For example, listed solvents that can be used are ethers such as tetrahydrofuran, diethyl ether, diethylene glycol diethyl ether, and 1,4-dioxane. , Methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, isobutanol, 2-methyl-2-propanol, 1-pentanol, 1-hexanol, cyclohexanol, 1-octanol, 2 -Ethylhexanol, 1-nonanol,
Alcohols such as benzyl alcohol, ethylene glycol and propylene glycol, aromatics such as benzene, toluene, xylene, mesitylene, cumene, chlorobenzene, o-dichlorobenzene, m-dichlorobenzene, p-dichlorobenzene and tetrahydronaphthalene Hydrocarbons, n
-Hexane, cyclohexane, n-octane, n-decane and other aliphatic hydrocarbons, methyl acetate, ethyl acetate, butyl acetate, ethyl propionate, methyl benzoate, esters such as ethyl benzoate, N, N-dimethyl Formamide, N, N-dimethylacetamide, amides such as N-methylpyrrolidone, 1,3-dimethylimidazolidinone, ureas such as N, N, N ', N'-tetramethylurea, and water, and water. . These can be used alone or in combination.

The reaction temperature for this reaction is usually from 50 ° C to 30 ° C.
It is desirable to set the temperature to 0 ° C, preferably 100 to 200 ° C. The reaction time is represented by the general formula (I) amino-substituted-1,
Depending on the reactivity of the 3,5-triazine derivative and the aldehyde or ketone of the general formula (II), it is usually 0.1-100.
The time is preferably 0.5 to 50 hours.

As a treatment method after the completion of all reactions, the catalyst and unreacted aminotriazines are removed by means such as filtration, and then the solvent is removed by distillation or the like, if necessary.
It is possible to separate by extracting the product as a two-phase system of organic solvent. The product obtained in this reaction has a sufficiently high purity as it is, but when a higher-purity product is required, the reaction product is further purified and isolated by recrystallization, distillation, chromatography separation, etc. can do.

Alkylamino-substituted-1,3,3 obtained by the method for selectively monoalkylating an amino group on the ring carbon atom of the 1,3,5-triazine ring of the present invention as described above.
The 5-triazine derivative is a substituted amino-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
_1-20Alkyl group of {wherein the alkyl group is a halogen atom, water
Acid group, C_1-6Alkoxy group of C_1-6The halo arcoki
Ci, 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
Optionally)}, C_{2- 20}of
Alkenyl group {The alkenyl group is a halogen atom, hydroxide
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}.
Also R⁶And R⁷Together, optionally alkylene
C with 1 or 2 chains_1-8Substituted by an alkyl group of
There- (CH₂)_2-5-, -CH₂CH₂-N (C_1-8
Alkyl) -CH₂CH ₂-Or-CH₂CH₂-O
-CH₂CH₂-May be formed}, C₁~ C₂₀Al
Kill group (the alkyl group is a halogen atom, a hydroxyl group, C_1-6
Alkoxy group, carboxyl group, C_2-7The alkoxy
Carbonyl group, C_2-10Acyloxy group, amino group, C
_1-8Monoalkylamino group, C_2-12Dialkylami
Group, an 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))
I}, C₂~ C₂₀Alkenyl group (the alkenyl group is
Rogen atom, hydroxyl group, C_1-6Alkoxy group of carboxy
Silyl group, C_2-7Alkoxycarbonyl group of C_2-10A
Syloxy group, amino group, C_1-8Monoalkylamino
Group, C_2-12Dialkylamino group, aryl group
Group is a halogen atom, C_1-6Alkyl group, hydroxyl group,
C_1-6May be optionally substituted with an alkoxy group of
Optionally substituted}, phenyl group {the phenyl
The base is C_1-6Alkyl group, halogen atom, hydroxyl group, C
_1-6Alkoxy group, aryloxy group, C_2-10Reed
Luoxy group, carboxyl group, C_2-7The alkoxycar
Bonyl group, C_2-10Acyl 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 substituted), halo
Gen atom, hydroxyl group, C_1-10Alkoxy group of {the said alkoxy
Si group is a halogen atom, hydroxyl group, C_1-6An alkoxy group of
Aryloxy group, carboxyl group, C_2-7The Archoki
Sicarbonyl group, C_2-10An acyloxy group, an amino group,
C_1-8Monoalkylamino group, C _2-12Dialkyla
Mino 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))
}, Thiol group, or C_1-10An alkylthio group of
Alkylthio group is a halogen atom, hydroxyl group, C_1-6Al
Coxy group, aryloxy 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
May be present. ].

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 a hydrogen atom (however, X^Four, X^FiveAnd X⁶R⁶, R⁷
Except when all are hydrogen atoms), C_1-20The archi
Group (the alkyl group is a halogen atom, a hydroxyl group, C_{1- 6}
Alkoxy group and phenyl group (the phenyl group is a halogen
Atom, C_1-6Alkyl group, hydroxyl group, C_1-6The Archoki
Optionally substituted with a Si group)
May} or C_2-20Alkenyl group of {the alkeny
Group is a halogen atom, hydroxyl group, C _1-6The alkoxy
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 arbitrarily replaced}
Representation or R⁶And R⁷Together, if desired
C having 1 or 2 alkylene chains_1-8By the alkyl group of
Substituted- (CH ₂)_3-5-, -CH₂CH₂−
N (C_1-8Alkyl) -CH₂CH₂-Or-CH₂
CH₂-O-CH₂CH₂-May be formed, and N above
R^FourR^FiveIf not X^Four, X^FiveAnd X⁶But each
Independently C_{1 -20}Alkyl group of {wherein the alkyl group is halogen
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_1-6May be optionally substituted with the alkoxy group of
Optionally substituted with), a phenyl group (the
Phenyl group is C_1-6Alkyl group, halogen atom, hydroxy
Group, C _1-6May be optionally substituted with the alkoxy group of
H), halogen atom, hydroxyl group, C_1-10Alkoxy group
{The alkoxy 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
1,3,5-triazine which is any of
It is a derivative.

Further preferred substituted amino-groups of general formula (III)
1,3,5-triazine derivatives have the general formula (III) odor
X^Four, X^FiveAnd X⁶NR⁶R⁷Base R⁶, R⁷Gazo
Each is independently a hydrogen atom (however, X^Four, X^FiveAnd X⁶of
R⁶, R⁷Except when all are hydrogen atoms), 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
I) or R⁶And R⁷Together, if desired,
C with 1 or 2 xylene chains_1-8Substituted by the alkyl group of
Is-(CH₂)_4-5-, -CH₂CH₂-N
(C_1-8Alkyl) -CH₂CH₂-Or-CH₂C
H₂-O-CH₂CH₂-Can be formed, and the above NR
⁶R⁷X when not a group^Four, X^FiveAnd X⁶But each
Independently C ₁-₂₀Alkyl group, phenyl group, hydroxyl group, C
_1-10Substituted by any of the alkoxy groups of 1,3,5-
It is a triazine derivative.

As described above, in the present invention, various compounds can be used as the amino-substituted-1,3,5-triazine derivatives, aldehydes and ketones as the raw materials, and the products obtained by the method of the present invention can be used. Is the amino-substitution of the raw material
Substituted amino having a desired number of various substituents by a combination of 1,3,5-triazine derivative, aldehydes and ketones and by using a supported catalyst of a metal of Group VIII of the periodic table with zeolite as a carrier. The -1,3,5-triazine derivative can be selectively obtained.

As described above, from the viewpoint of availability of raw materials, melamine, various melamine derivatives and various guanamine derivatives are used as the amino-substituted-1,3,5-of the raw materials, and various petrochemicals are used as the aldehydes and ketones. Typical examples are aldehydes and ketones derived from products, and combinations of these produce typical products. Further, for example, a substituted melamine derivative obtained by alkylating melamine by the method of the present invention also has an amino-substituted-1, which is a raw material of the present invention, if it has a part of —NH— group on the ring carbon atom.
It can be used as a 3,5-triazine derivative.

The range of raw materials applicable to this reaction is
It is not limited by the price of raw materials and availability.
However, the following are specific examples of the substituents of the raw materials and products in this reaction.
The scope of this reaction will be further clarified by giving an example.
In the formula, X of the general formula (I) as a raw material¹, X²And X³,Also
X of the general formula (III) of the product^Four, X^FiveAnd X⁶Indicated by
NHR among substituents¹, NR²R³And NR ⁶R⁷When
Then, an amino group, a methylamino group, an ethylamino group,
Isopropylamino group, n-butylamino group, i-butyl
Ruamino group, sec-butylamino group, tert-butyl group
Luamino group, cyclohexylamino group, cyclohexyl
Methylamino group, n-octylamino group, n-decylurea
Mino group, n-hexadecylamino group, dimethylamino
Group, diethylamino group, diisopropylamino group, di-
n-butylamino group, di-i-butylamino group, di-s
ec-butylamino group, methyl-tert-butylami
Group, methylcyclohexylamino group, cyclohexyl
Methylamino group, di-n-octylamino group, dicyclo
Hexylmethylamino group, chloroethylamino group, 3-
Chloropropylamino group, hydroxyethylamino group,
4-hydroxybutylamino group, 5-hydroxyplier
Lumino group, bis (hydroxyethyl) amino group, tri
Fluoroethylamino group, 2-trifluoropropyl group
Mino group, 2-ethoxyethylamino group, 3-methoxy group
Ropylamino group, 2-pentyloxyethylamino group,
3-cyclohexyloxypropylamino group, 2-chloro
Ruethoxyethylamino group, 5-monofluoropentyl
Oxypentylamino group, 2-methoxycarbonylethyl
Ruamino group, 2-ethoxycarbonylethylamino group,
tert-butoxycarbonylethylamino group, 2-cis
Chlohexyloxycarbonylethylamino group, aceto
Xymethylamino group, 3-acetoxypropylmethylami
Group, cyclohexanoyloxyethylamino group, 2-
Benzoyloxypropylamino group, 2-aminoethyl
Amino group, 6-aminohexylamino group, cyclohexyl
Luminoethylamino group, dimethylaminoethylamino
Group, diethylaminoethylamino group, methylphenyl group
Mino group, benzylamino group, dibenzylamino group, N-
Benzyl-N'-methylamino group, 2-phenylethyl
Amino group, 3- (4-chlorophenyl) -propylami
Group, 2- (4-cyclohexylphenyl) -ethyl group
Mino group, 2- (3-fluorophenyl) -pentylami
Group, 4-methoxybenzylamino group, 2-chloro-4
-Fluorobenzylamino group, 3,5-dimethylbenzyl
Ruamino group, 4-cyclopentyloxybenzylamino
Group, 2- (2-chloro-4-fluoro-5-isopropyi
Ruphenyl) -propylamino group, 4-hydroxyben
Dilamino group, 4-hydroxyphenylethylamino
Group, allylamino group, methallylamino group, 3-cyclope
Intenylamino group, 3-cyclohexenylamino group, 3
-(6-Trifluoromethyl) -cyclohexenylami
Group, diallylamino group, dimethallylamino group, 3-
(1-methoxy) -allyl group, crotylamino group, chloro
Rumethoxyethylamino group, ethoxycarbonyl allyl
Amino group, cinnamyl amino group, 4-chlorocinnamyl
Amino group, N- (4-methylcinnamyl) -N'-methyl
Lumino group, 4-methoxycinnamylamino group, etc.
Can be

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 2,5-dimethylpyrrolidino group, a piperidino group, an N-methylpiperazino group, and a morpholino group. To be 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, methoxycarbonylethyl group, tert-butoxycarbonylmethyl group Group, cyclohexyloxycarbonylethyl group, 2-propanoylethyl group, benzoylmethyl group, 2,4,6
-Trimethylphenylbenzoylmethyl group, acetyloxymethyl group, benzoyloxymethyl group, 3- (te
rt-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-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 and the like can be mentioned.

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-carboxyvinyl 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, 4-carboxyphenyl group, 4-
Methoxycarbonylphenyl group, 3-cyclohexyloxycarbonylphenyl group, 2-acetylphenyl group,
4-octanoylphenyl group, 4-acetyloxyphenyl group, 3-cyclohexylcarbonyloxyphenyl group, 2-dimethylaminophenyl group, 4-diethylaminophenyl group, 4-diisopropylaminophenyl group, 3-di-n-butyl Aminophenyl 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-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. As the C ₁ -C ₁₀ alkoxy group which may be substituted, a methoxy group, an ethoxy group, an n-propyloxy group, an i-propyloxy group, an n-butyloxy group, an 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, cyclohexyloxycarbonylethoxy 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, cyclohexylmethylamino Methyloxy group, benzyloxy group, 4-methylbenzyloxy group,
4-methoxybenzyloxy group, 2-chloro-fluorobenzyloxy group, 3,5-dimethylbenzyloxy group, 4-cyclopentyloxybenzyloxy group and the like can be mentioned.

The C ₁ -C ₁₀ alkylthio group which may be substituted includes methylthio group, ethylthio group, n-propylthio group, i-propylthio group, n-butylthio group, i-butylthio group and sec-butylthio group. , Ter
t-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, methoxycarbonylethyl Thio 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 , A diethylaminomethylthio group, a diisopropylaminomethylthio group, a di-n-butylaminomethylthio group,
Di-i-butylaminomethylthio group, di-sec-butylaminomethylthio group, methyl-tert-butylaminomethylthio group, methylcyclohexylaminomethylthio group, cyclohexylmethylaminomethylthio group, benzylthio group, 4-methylbenzylthio group, 4 -Methoxybenzylthio group, 2-chloro-4-fluorobenzylthio group, 3,5-dimethylbenzylthio group, 4-cyclopentyloxybenzylthio group and the like can be mentioned.

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, s
ec-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, trifluoro group Methyl group, 3-chloropropyl group, 2-trifluoromethylethyl group, hydroxyethyl group, methoxymethyl group, methoxyethyl group, ethoxymethyl group, cyclohexylmethoxyethyl group, 2-carboxyethyl group, 3-carboxypropyl group, Methoxycarbonylmethyl group, methoxycarbonylethyl group, tert-butoxycarbonylmethyl group, cyclohexyloxycarbonylethyl group, 2-propanoylethyl group, benzoylmethyl group, 2,4,6-trimethylphenylbenzoylmethyl group, acetyl Kishimechiru group, benzoyloxy methyl group, 3- (tert-butyl-carbonyloxy)
-Propyl group, dimethylaminomethyl group, diethylaminomethyl group, diisopropylaminomethyl group, di-n-
Butylaminomethyl group, di-i-butylaminomethyl group, di-sec-butylaminomethyl group, methyl-te
rt-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. .

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.

As a treatment method after the reaction, a part of unreacted aminotriazine 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 water-organic. After extracting the product as a two-phase solvent system, the reaction product can be purified and isolated by recrystallization, distillation, chromatographic separation, or the like. However, the desired alkylamino-substituted-1, obtained by the method of the present invention,
Since the 3,5-triazines are obtained at a high selectivity by the reaction, unless they are used in an extremely pure form, unnecessary separation and purification are not required.

Further, the supported 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 and recovered by filtration and reused. it can.

[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-
It was carried out according to No. 215564. ), 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.

The analytical conditions of the high performance liquid chromatography used are as follows. (Method for quantifying raw material aminotriazine 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
x4.6 mmφ flow rate; 1.0 mL / min analysis temperature; 40 ° C. internal standard material; phthalic acid di-n-butyl ester (method of quantifying part of product and raw material (part of alkylaminotriazine)) Detection method; UV 230 nm column; GL Sciences Inertsil C ₈ 150 mm
x 4.6 mmφ Flow rate; 1.0 mL / min Analysis temperature; 35 ° C. Internal standard substance: Phthalic acid di (2-ethylhexyl) ester The following is a typical synthesis example of a standard sample for quantitative analysis synthesized according to the above literature. Refer to the reference example. Other standards were also synthesized by the same synthesis method as in this reference example.

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

[0060]

[Chemical 9]

After dissolving 184.5 g (1.0 mol) of cyanuric chloride in 800 mL of acetonitrile at room temperature, 0
To the solution cooled to 0 ° C, 303.7 g (5.0 mol) of 28% aqueous ammonia solution was added at a reaction temperature of 1 with vigorous stirring.
The solution was added dropwise over 2 hours so as to keep the temperature below 0 ° 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. The filtered product was dried under vacuum at 50 ° C. for 6 hours to obtain 115 g (yield 79%) of the title compound.

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

[0063]

[Chemical 10]

2,4-Diamino-6 synthesized in Reference Example 1
-Chlor-1,3,5-triazine 14.5 g (0.1
Mol), 100 mL of water and 29.2 g of butylamine.
The mixed solution of (0.4 mol) is heated with stirring,
Finally, the reaction was carried out at the reflux temperature for 6 hours. After cooling the reaction solution, the product was separated by filtration, and further washed with a large amount of water,
Then, it was washed with toluene. The filtered product was dried under vacuum at 70 ° C. for 6 hours to obtain 17.5 g (yield 96%) of the title compound. Melting point; 167 [deg.] C.

Reference Example 3 (2-amino-4,6-bis (normal butylamino))
Synthesis of -1,3,5-triazine)

[0066]

[Chemical 11]

18.5 g (0.1 mol) of cyanuric chloride
Was dissolved in 150 mL of acetonitrile, and the solution cooled to 0 ° C. was stirred, and a solution of butylamine 7.3 g (0.1 mol) in 20 mL of water was added dropwise over 1 hour so that the reaction temperature did not exceed 5 ° C. While continuing stirring, a solution of 10.0 g (0.1 mol) of potassium hydrogen carbonate in 100 mL of water was added dropwise at the same temperature, and the mixture was stirred for 3 hours. 2-Butylamino-4,6-dichloro- by high performance liquid chromatography
After confirming that the conversion to 1,3,5-triazine was completed, 24.3 g (0.4 mol) of 28% aqueous ammonia solution was added.
Was added, the temperature was raised to 50 ° C., and the reaction was carried out for 5 hours. After cooling, the product was filtered off and washed thoroughly with plenty of water. The obtained crude product was suspended in 100 mL of water, and butylamine 2
9.2 g (0.4 mol) was added, and the mixture was reacted for 6 hours while heating under reflux. 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 the toluene was distilled off from the organic layer under heating and reduced pressure to give the title compound.
2.1 g (yield 93%) was obtained. Melting point; 73 [deg.] C.

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

[0069]

[Chemical 12]

18.5 g (0.1 mol) of cyanuric chloride
Was dissolved in 150 mL of acetonitrile, and 14.6 g (0.2
A 20 mL solution of (mol) in water was added dropwise over 1 hour so that the reaction temperature did not exceed 5 ° C. While continuing stirring, 100 mL of water containing 20.0 g (0.2 mol) of potassium hydrogen carbonate.
The solution was added dropwise at the same temperature. Then, the reaction temperature was gradually raised and stirring was continued at 45 ° C. for 8 hours. After confirming by high performance liquid chromatography that the conversion to 2,4-bis (butylamino) -6-chloro-1,3,5-triazine was completed, it was cooled and the product was separated by filtration. After thoroughly washing the filter cake with a large amount of water, the 2,4-bis (butylamino) -6-chloro-1,3,5-triazine was washed with 100 parts of water.
The mixture was suspended in mL, 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 is 150 mL of water.
After being washed three times with, the toluene was distilled off from the organic layer under heating and reduced pressure to obtain 28.2 g (yield 96%) of the title compound. Properties; oily substance.

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

[0072]

[Chemical 13]

14.6 g of the intermediate 2,4-diamino-6-chloro-1,3,5-triazine synthesized in Reference Example 1
(0.1 mol) was suspended in 50 mL of 1,4-dioxane, 11.8 g (0.20 mol) of isopropylamine and 20 mL of water were added, and then the mixture was stirred at reflux temperature for 4 hours. Thereafter, 4.0 g of sodium hydroxide (0.
1 mL of a 15 mL aqueous solution was added dropwise over 1 hour, and the reflux was continued for 4 hours. After the reaction, the reaction solution was concentrated under reduced pressure, 100 mL of ethanol was added, the salt was filtered, and the soluble portion was separated. The solvent was distilled off from the obtained solution under reduced pressure, and the obtained crystals were filtered, washed with 100 mL of hexane and a small amount of water, and dried to give the desired 2,4-diamino-6-isopropylamino-1. 1,3,5-triazine was obtained (15.5 g, yield 92%). Melting point; 21
6 ° C. Reference Example 6 (Synthesis of 2,4-diamino-6-piperidino-1,3,5-triazine)

[0074]

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14.6 g of the intermediate 2,4-diamino-6-chloro-1,3,5-triazine synthesized in Reference Example 1
(0.1 mol) was suspended in 30 mL of 1,4-dioxane, and 9.4 g (0.11 mol) of piperidine and 20 parts of water were added.
After adding mL, the mixture was stirred at reflux temperature for 2 hours. Then, a 15 mL aqueous solution of sodium hydroxide 4.4 g (0.11 mol) was added dropwise over 1 hour, and the reflux was further continued for 3 hours. After the reaction, the reaction mixture was cooled and the precipitated crystals were collected by filtration. This crystal is further added with toluene 50m
It was recrystallized from L and 30 mL of acetone. The crystals obtained here were collected by filtration and dried under reduced pressure to give the desired 2,4
16.5 g (yield 85%) of -diamino-6-piperidino-1,3,5-triazine was obtained. Melting point; 210
° C.

The examples according to the method of the present invention will be listed below.

Example 1 (2,4-diamino-6-normal butylamino-1,
Synthesis of 3,5-triazine)

[0078]

[Chemical 15]

To a stainless steel autoclave having an internal volume of 100 mL, 1.26 g (10 mmol) of melamine, 1.44 g (20 mmol) of normal butyraldehyde, 40 mL of methanol and 200 mg of 5% Pd loaded with ZSM-5 (manufactured by NE Chemcat) were added. After the system was sufficiently replaced with nitrogen gas, hydrogen gas was introduced at 50 kg / cm ² . The temperature was raised with stirring and the reaction was carried out at a temperature of 150 ° C. for 10 hours. After the reaction, the catalyst and unreacted melamine were separated by filtration, and the melamine in the crystals and the filtrate was quantified. The conversion of melamine was 85.5%. The obtained homogeneous reaction solution was quantitatively analyzed by the above high performance liquid chromatography. As a result, 2,4-diamino-6-n-butylamino-1,3,5-triazine was obtained in a yield of 68.1%, 2-
Amino-4,6-bis (normal butylamino) -1,
3,5-triazine was obtained in a yield of 16.2%. The selectivity of monoalkylation in this reaction was 80.8%.

Example 2 (2,4-diamino-6-normal butylamino-1,
Synthesis of 3,5-triazine) 1.26 g (10 mmol) of melamine, 0.72 g (10 mmol) of normal butyraldehyde, 40 mL of methanol and the same Z as in Example 1 were placed in a stainless steel autoclave having an internal capacity of 100 mL.
After adding 200 mg of 5% Pd supporting SM-5 and thoroughly replacing the inside of the system with nitrogen gas, hydrogen gas was added at 50 kg / cm.
Introduced in ² . The temperature was raised with stirring and the reaction was carried out at a temperature of 150 ° C. for 10 hours. After the reaction, the catalyst and unreacted melamine were separated by filtration, and the melamine in the crystals and the filtrate was quantified. The conversion rate of melamine was 56.0%. The obtained homogeneous reaction liquid was quantitatively analyzed by the above high performance liquid chromatography, and as a result, 2,4-diamino-6-normal butylamino-1,3,5-triazine was obtained in a yield of 48.8.
%, 2-amino-4,6-bis (normal butylamino) -1,3,5-triazine were obtained at a yield of 5.8%. The selectivity of monoalkylation in this reaction is 8
It was 9.4%.

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

[0082]

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To a stainless steel autoclave having an internal volume of 100 mL, 1.26 g (10 mmol) of melamine, 11.70 g (120 mmol) of cyclohexanone, 40 mL of ethanol and 408 mg of 5% Pd supporting L-type zeolite (manufactured by NE Chemcat) were added, After the system was sufficiently replaced with nitrogen gas, hydrogen gas was introduced at 50 kg / cm ² . The temperature is raised with stirring to a temperature of 180 ° C for 10
Allowed to react for hours. After the reaction, the catalyst was filtered off, and the resulting reaction solution was quantitatively analyzed by the high performance liquid chromatography described above. As a result, the conversion rate of the raw material melamine was 16.8%.
The yield of 2,4-diamino-6-cyclohexylamino-1,3,5-triazine was 15.5%,
2-amino-4,6-bis (cyclohexylamino)-
1,3,5-triazine was obtained in a yield of 0.4%. The selectivity of monoalkylation in this reaction is 97.5%.
Met.

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

[0085]

[Chemical 17]

1.26 g (10 mmol) of melamine, 6.96 g (120 mmol) of acetone and 20 mL of ethanol were placed in a stainless steel autoclave having an internal volume of 100 mL.
408 mg of ZSM-5-supported 5% Pd (manufactured by NE Chemcat) was added, and the system was sufficiently replaced with nitrogen gas, and then hydrogen gas was introduced at 50 kg / cm ² . The temperature was raised with stirring and the reaction was carried out at a temperature of 180 ° C. for 6 hours. After the reaction, the catalyst and unreacted melamine were separated by filtration, and the melamine in the crystals and in the filtrate was quantified. Further, the obtained reaction liquid was quantitatively analyzed by the above high performance liquid chromatography. As a result, 2,4-diamino-6-isopropyl-1,3,5-triazine was obtained as a product in a yield of 12.1% and 2-amino -4,6-bis (isopropylamino) -1,3,5
-Triazine was obtained at a yield of 0.8%, and 2,4,6-tris (isopropylamino) -1,3,5-triazine was obtained at a yield of 0.6%. The selectivity of monoalkylation in this reaction was 90.0%.

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

[0088]

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1.26 g (10 mmol) of melamine, 8.01 g (40 mmol) of glutaraldehyde (50% aqueous solution), 10 mL of 1,4-dioxane and 5% Pd loaded with ZSM-5 were placed in a stainless steel autoclave having an internal volume of 50 mL. 200 mg (manufactured by NE Chemcat) was added, and the inside of the system was sufficiently replaced with nitrogen gas, and then hydrogen gas was introduced at 100 kg / cm ² . The temperature was raised with stirring and the reaction was carried out at a temperature of 200 ° C. for 18 hours. After the reaction, the catalyst and unreacted melamine were filtered off, and the melamine in the crystals and in the reaction solution was analyzed. As a result, the raw material conversion rate was 81.8%. In addition, as a result of quantitative analysis of this reaction liquid by the above high performance liquid chromatography, the yield of 2,4-diamino-6-piperidino-1,3,5-triazine was 65.3%,
The yield of 2-amino-4,6-dipiperidino-1,3,5-triazine was 3.8%, and 2,4,6-tripiperidino-
1,3,5-triazine was obtained at a yield of 2.9%. The selectivity of monoalkylation in this reaction is 90.7.
%Met.

Example 6 (2,4-diamino-6-normal butylamino-1,
Synthesis of 3,5-triazine) Stainless steel with an internal capacity of 100 mL
1.26 g of melamine (10 mm
Mol), normal butyraldehyde 0.72 g (10 m
Limol), 40 mL of methanol and Y-type zeolite
Possess 5% Pd (made by NE Chemcat) 200 mg
Well, after thoroughly replacing the system with nitrogen gas, add hydrogen gas.
50 kg / cm ²Introduced in. Raise the temperature while stirring,
The reaction was carried out at a temperature of 150 ° C. for 10 hours. After the reaction,
The melamine in the reaction was filtered off, and the melamine in the crystals and filtrate was filtered.
The melamine conversion rate was 52.0%.
Was. In addition, the obtained uniform reaction solution was used as the above-mentioned high-performance liquid chromatograph.
As a result of quantitative analysis by topography, 2,4-diamino-
6-normal butylamino-1,3,5-triazine
Yield 41.8%, 2-amino-4,6-bis (normal
Butylamino) -1,3,5-triazine yield 7.8
% Were obtained respectively. Selection of monoalkylation in this reaction
The selectivity was 84.3%.

Example 7 (2,4-diamino-6-normal butylamino-1,
Synthesis of 3,5-triazine) 1.26 g (10 mmol) of melamine, 0.72 g (10 mmol) of normal butyraldehyde, 40 mL of methanol and 5% Pd loaded with L-type zeolite (NE Chemcat Co., Ltd.) were placed in a stainless steel autoclave having an internal capacity of 100 mL. (Manufactured by Mitsui Chemical Co., Ltd.) was added, and the inside of the system was sufficiently replaced with nitrogen gas, and then hydrogen gas was introduced at 50 kg / cm ² . Raise the temperature while stirring,
The reaction was carried out at a temperature of 150 ° C. for 10 hours. After the reaction, the catalyst and unreacted melamine were separated by filtration, and the melamine in the crystals and the filtrate was quantified. The conversion of melamine was 58.3%. The obtained homogeneous reaction solution was quantitatively analyzed by the above high performance liquid chromatography, and as a result, 2,4-diamino-
The yield of 6-normal butylamino-1,3,5-triazine was 48.2%, and the yield of 2-amino-4,6-bis (normal butylamino) -1,3,5-triazine was 9.6.
% Were obtained respectively. The selectivity of monoalkylation in this reaction was 83.4%.

Example 8 (2,4-diamino-6-normaloctylamino-
Synthesis of 1,3,5-triazine)

[0093]

[Chemical 19]

To a stainless steel autoclave having an internal volume of 100 mL, 1.26 g (10 mmol) of melamine, 1.42 g (10 mmol) of normal octyl aldehyde, 40 mL of methanol and 200 mg of the same Y-type zeolite-supported 5% Pd as in Example 6 were added. After the system was sufficiently replaced with nitrogen gas, hydrogen gas was introduced at 40 kg / cm ² . The temperature was raised with stirring and the reaction was carried out at a temperature of 150 ° C. for 6 hours. After the reaction, the catalyst and unreacted melamine are filtered off,
When the melamine in the crystals and the filtrate was quantified, the conversion rate of melamine was 24.0%. The obtained homogeneous reaction solution was quantitatively analyzed by the above high performance liquid chromatography. As a result, 2,4-diamino-6-normaloctylamino-1,3,5-triazine was obtained in a yield of 20.6%, 2- Amino-4,6-bis (normal octylamino) -1,
3,5-triazine was obtained in a yield of 2.1%. The selectivity of monoalkylation in this reaction was 90.7%.

Example 9 (Synthesis of 2-amino-4-normalbutylamino-6-methylamino-1,3,5-triazine)

[0096]

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In a stainless steel autoclave having an internal volume of 100 mL, 1.40 g (10 mmol) of 2-N-methylmelamine, 1.44 g (20 mmol) of normal butyraldehyde, 40 mL of methanol and the same Z as in Example 1 were used.
After adding 200 mg of 5% Pd supporting SM-5 and thoroughly replacing the inside of the system with nitrogen gas, hydrogen gas was added at 50 kg / cm.
Introduced in ² . The temperature was raised with stirring and the reaction was carried out at a temperature of 150 ° C. for 10 hours. After the reaction, the catalyst was filtered off and the solid content was thoroughly washed with ethanol and water. When each component in the obtained filtrate was quantified by the above high performance liquid chromatography, the conversion rate of 2-N-methylmelamine was 92.5%, and 2-amino-4-normal-butylamino-6.
-Methylamino-1,3,5-triazine yield 79.
5% and 2,4-bis (normal butylamino) -6-methylamino-1,3,5-triazine were obtained at a yield of 4.1%, respectively. The selectivity of monobutylation in this reaction was 95.1%.

Example 10 (Synthesis of 2-amino-4-normaloctylamino-6-methylamino-1,3,5-triazine)

[0099]

[Chemical 21]

1.40 g (10 mmol) of 2-N-methylmelamine and 2.84 g (20 ml) of normal octyl aldehyde were placed in a stainless steel autoclave having an internal volume of 100 mL.
Mmol), 40 mL of methanol and 200 mg of the same L-type zeolite-supported 5% Pd as in Example 7 were added, and the system was sufficiently replaced with nitrogen gas, and then 50 kg of hydrogen gas was added.
/ Cm ^{2 It} was introduced. The temperature is raised to 16 with stirring.
The reaction was carried out at 0 ° C for 10 hours. After the reaction, the catalyst was filtered off and the solid content was thoroughly washed with ethanol and water. When each component in the obtained filtrate was quantified by the above high performance liquid chromatography, the conversion rate of 2-N-methylmelamine was 81.
5%, and 2-amino-4-normaloctylamino-6-methylamino-1,3,5-triazine in a yield of 72.4%, 2,4-bis (normaloctylamino) -6-methyl. Amino-1,3,5-triazine was obtained in a yield of 5.2%. The selectivity of monobutylation in this reaction was 93.3%.

Example 11 (2-amino-4,6-bis (normal butylamino))
Synthesis of -1,3,5-triazine)

[0102]

[Chemical formula 22]

1.82 g of 2-N-normal butyl melamine was placed in a stainless steel autoclave having an internal volume of 100 mL.
(10 mmol), normal butyraldehyde 1.44
g (20 mmol), 40 mL of methanol and 200 mg of the same Y-type zeolite-supported 5% Pd as in Example 6 were added, the system was sufficiently replaced with nitrogen gas, and then hydrogen gas was introduced at 50 kg / cm ² . Raise the temperature while stirring,
The reaction was carried out at a temperature of 150 ° C. for 10 hours. After the reaction, the catalyst was filtered off, and the raw materials in the filtrate were quantified. The conversion rate was 89.0.
%Met. The obtained homogeneous reaction solution was quantitatively analyzed by the above high performance liquid chromatography, and as a result, 2-amino-4,6-bis (normal butylamino) -1,3,5
-Triazine was obtained at a yield of 84.5% and 2,4,6-tris (normal butylamino) -1,3,5-triazine was obtained at a yield of 1.2%. The selectivity of monoalkylation in this reaction was 98.6%.

Example 12 (Synthesis of 2-amino-4-normalbutylamino-6-methyl-1,3,5-triazine)

[0105]

[Chemical formula 23]

To a stainless steel autoclave having an internal volume of 100 mL, 1.25 g (10 mmol) of acetoguanamine, 1.44 g (20 mmol) of normal butyraldehyde, 40 mL of methanol and 200 mg of the same L-type zeolite-supported 5% Pd as in Example 7 were added, After thoroughly replacing the system with nitrogen gas, add 50 kg / cm of hydrogen gas.
Introduced in ² . The temperature was raised with stirring and the reaction was carried out at a temperature of 150 ° C. for 10 hours. After the reaction, the catalyst and unreacted raw materials were filtered off, and the raw materials in the crystals and in the filtrate were quantified, and the conversion was 63.0%. The obtained homogeneous reaction solution was quantitatively analyzed by the above high performance liquid chromatography. As a result, 2-amino-4-normalbutylamino-6-methyl-1,3,5-triazine was obtained in a yield of 55.7%. Two
4-bis (normal butylamino) -6-methyl-1,
3,5-triazine was obtained in a yield of 4.2%. The selectivity of monoalkylation in this reaction was 93.0%.

Example 13 (2,4-diamino-6-normal butylamino-1,
Synthesis of 3,5-triazine) 1.26 g (10 mmol) of melamine, 40 mL of methanol and 5% of ZSM-5 supported in a stainless steel autoclave having an internal volume of 100 mL.
After adding 200 mg of Pd and thoroughly replacing the inside of the system with nitrogen gas, hydrogen gas was introduced at 50 kg / cm ² . The temperature was raised with stirring, and when the temperature reached 150 ° C., 0.72 g (10 mmol) of normal butyraldehyde was obtained.
5 mL of methanol solution was continuously introduced with a micropump for 4 hours, and then reacted for 6 hours.
After the reaction, the catalyst and unreacted melamine were separated by filtration, and the melamine in the crystals and the filtrate was quantified. The conversion of melamine was 83.1%. As a result of quantitative analysis of the obtained homogeneous reaction liquid by the high performance liquid chromatography,
2,4-diamino-6-normal butylamino-1,
3,5-triazine yield 73.8%, 2-amino-
4,6-bis (normal butylamino) -1,3,5-
Triazine was obtained in a yield of 7.2%. The selectivity of monoalkylation in this reaction was 91.1%.

Example 14 (2,4-diamino-6-normal butylamino-1,
Synthesis of 3,5-triazine) In a stainless steel autoclave with an internal volume of 100 mL, ethylene glycol 20 mL
And 200 mg of 5% Pd supporting ZSM-5 was added, and the system was sufficiently replaced with nitrogen gas, and then hydrogen gas was added to 50 k
It was introduced at g / cm ² . The temperature is raised to 1 with stirring.
From the point where the temperature reached 50 ° C, 1.26 g of melamine (10
Mmol), n-butyraldehyde 0.72 g (1
(0 mmol) and ethylene glycol (30 mL) were preheated to 120 ° C., continuously introduced by a microslurry pump over 8 hours, and then reacted for further 4 hours. After the reaction, the catalyst and unreacted melamine were filtered off, and the melamine in the crystals and the filtrate was quantified. The conversion of melamine was 71.2%. The obtained homogeneous reaction liquid was quantitatively analyzed by the above high performance liquid chromatography, and as a result, 2,4-diamino-6-normal butylamino-1,3,5-triazine was obtained in a yield of 63.1%, 2-
Amino-4,6-bis (normal butylamino) -1,
3,5-triazine was obtained in a yield of 7.2%. The selectivity of monoalkylation in this reaction was 89.8%.

Example 15 (2,4-diamino-6-normaloctylamino-
Synthesis of 1,3,5-triazine) 1.26 g of melamine (10
Mmol), 40 mL of methanol and 200 mg of the same Y-type zeolite-supported 5% Pd as in Example 6 were added, and the system was sufficiently replaced with nitrogen gas, and then 60 kg of hydrogen gas was added.
/ Cm ^{2 It} was introduced. The temperature is raised to 15 with stirring.
After reaching 0 ° C., a solution of 1.42 g (10 mmol) of normal octyl aldehyde in 5 mL of methanol was continuously introduced by a micro pump over 6 hours, and the reaction was further continued for 4 hours. After the reaction, the catalyst and unreacted melamine were filtered off, and the melamine in the crystals and the filtrate was quantified. The conversion of melamine was 57.2%. The obtained homogeneous reaction liquid was quantitatively analyzed by the above high performance liquid chromatography, and as a result, 2,4-diamino-6-normal octylamino-1,3,5-triazine was obtained in a yield of 51.
8% and 2-amino-4,6-bis (normal octylamino) -1,3,5-triazine were obtained at a yield of 5.0%, respectively. The selectivity of monoalkylation in this reaction is 9
It was 1.2%.

Comparative Example 1 (Comparison with Example 1; Reaction of Melamine with Normal Butyraldehyde) 1.26 g (10 mmol) of melamine and 1.44 g (20 mmol) of normal butyraldehyde were placed in a stainless steel autoclave having an internal volume of 100 mL. , Methanol 40mL and activated carbon supported 5% Pd 216m
After adding g, the inside of the system was sufficiently replaced with nitrogen gas, and then hydrogen gas was introduced at 50 kg / cm ² . The temperature was raised with stirring and the reaction was carried out at a temperature of 150 ° C. for 2 hours. After the reaction, the catalyst and unreacted melamine were separated by filtration, and the melamine in the crystals and the solution was quantified. The conversion of melamine was 84.5.
%Met. The obtained homogeneous reaction liquid was quantitatively analyzed by the above high performance liquid chromatography, and as a result, 2,4-diamino-6-normal butylamino-1,3,5-triazine was obtained in a yield of 23.6%, 2- Amino-4,6-bis (normal butylamino) -1,3,5-triazine yield 23.9%, 2,4,6-tris (normal butylamino) -1,3,5-triazine Rate 29.4%,
The yield of 2,4-bis (normal butylamino) -6-dinormal butylamino-1,3,5-triazine was 2.5.
% Were obtained respectively. The selectivity of monoalkylation in this reaction was 29.7%.

Comparative Example 2 (Comparison with Examples 2, 6 and 7; Reaction of Melamine with Normal Butyraldehyde) 1.26 g (10 mmol) of melamine and 0.72 g of normal butyraldehyde were placed in a stainless steel autoclave having an internal volume of 100 mL. (10 mmol), 40 mL of methanol and 5% P supported on activated carbon
After 216 mg of d was added and the system was sufficiently replaced with nitrogen gas, hydrogen gas was introduced at 50 kg / cm ² . The temperature was raised with stirring and the reaction was carried out at a temperature of 150 ° C. for 2 hours.
After the reaction, the catalyst and unreacted melamine were separated by filtration, and the melamine in the crystals and the solution was quantified. The conversion rate of melamine was 52.2%. The obtained homogeneous reaction solution was quantitatively analyzed by the above high performance liquid chromatography. As a result, 2,4-diamino-6-normal butylamino-
The yield of 1,3,5-triazine was 20.1%, and 2-amino-4,6-bis (normal butylamino) -1,3,5.
-Triazine yield 13.2%, 2,4,6-tris (normal butylamino) -1,3,5-triazine yield 11.2%, 2,4-bis (normal butylamino) -6 -Dinormal butylamino-1,3,5-triazine was obtained in a yield of 0.6%. The selectivity of monoalkylation in this reaction was 44.6%.

Comparative Example 3 (Comparison with Example 3; Reaction of Melamine and Cyclohexanone) 1.26 g (10 mmol) of melamine, 11.70 g (120 mmol) of cyclohexanone, and 1,4 in an autoclave made of stainless steel having an inner volume of 60 mL. -Dioxane (15 mL) and activated carbon-supported 5% Pd (408 mg) were added, the system was sufficiently replaced with nitrogen gas, and then hydrogen gas was introduced at 50 kg / cm ² . Raise the temperature while stirring,
The reaction was carried out at a temperature of 180 ° C. for 2.5 hours. After the reaction, the catalyst was filtered off, and the resulting reaction solution was quantitatively analyzed by the above high performance liquid chromatography. As a result, the conversion rate of the raw material melamine was 69.3%. The yield of 2,4-diamino-6-cyclohexylamino-1,3,5-triazine was 19.8%, and 2-amino-4,6-bis (cyclohexylamino) -1,3,5- was obtained as a product. Triazine yield 3
1.9% and 2,4,6-tris (cyclohexylamino) -1,3,5-triazine were obtained at a yield of 16.0%, respectively. The selectivity of monoalkylation in this reaction is
It was 29.2%.

Comparative Example 4 (Comparison with Example 4; Reaction of Melamine with Acetone) 1.26 g (10 mmol) of melamine and 6.96 g of acetone were placed in a stainless steel autoclave having an internal volume of 100 mL.
(120 mmol), ethanol (20 mL) and activated carbon-supported 5% Pd (408 mg) were added, and the system was sufficiently replaced with nitrogen gas, and then hydrogen gas was introduced at 50 kg / cm ² . The temperature was raised with stirring and the reaction was carried out at a temperature of 180 ° C. for 6 hours. After the reaction, the catalyst and unreacted melamine were separated by filtration, and the melamine in the crystals and in the filtrate was quantified. As a result, the conversion rate of melamine was 98.0%. The obtained reaction solution was quantitatively analyzed by the above high performance liquid chromatography, and as a result, 2,4-diamino-6-isopropyl-1,3,5-triazine was obtained as a product in a yield of 31.9%, 2-
Amino-4,6-bis (isopropylamino) -1,
3,5-triazine yield 42.0%, 2,4,6-tris (isopropylamino) -1,3,5-triazine yield 13.6%, 2,4-bis (isopropylamino)- 6-Diisopropylamino-1,3,5-triazine was obtained in a yield of 1.3%. The selectivity of monoalkylation in this reaction was 35.9%.

Comparative Example 5 (Comparison with Example 5; Reaction of Melamine with Glutaraldehyde) 1.26 g (10 mmol) of melamine and 8.01 g (50% aqueous solution) of melamine were placed in a stainless steel autoclave having an internal volume of 50 mL. 40 mmol),
10 mL of 1,4-dioxane and 5% Pd supported on activated carbon
Was added thereto, the inside of the system was sufficiently replaced with nitrogen gas, and then hydrogen gas was introduced at 100 kg / cm ² . The temperature was raised with stirring and the reaction was carried out at a temperature of 180 ° C. for 18 hours. After the reaction, the catalyst and unreacted melamine were filtered off, and the melamine in the crystals and in the reaction solution was analyzed. As a result, the raw material conversion rate was 99.2%. In addition, as a result of quantitative analysis of this reaction solution by the high performance liquid chromatography, 2,4-
Diamino-6-piperidino-1,3,5-triazine yield 27.0%, 2-amino-4,6-dipiperidino-
1,3,5-triazine yield 40.5%, 2,4,6
-Tripiperidino-1,3,5-triazine yield 2
It was obtained at 9.3% respectively. The selectivity of monoalkylation in this reaction was 27.9%.

[0115]

INDUSTRIAL APPLICABILITY According to the method of the present invention, aminotriazines of the general formula (I) can be used as various fine chemical intermediates for various agricultural chemicals, pharmaceuticals, dyes, paints, etc. under relatively mild reaction conditions, and variously. To produce alkylamino-substituted-1,3,5-triazine derivatives, which is a useful compound group widely used as resin materials and flame-retardant materials, by a highly selective monoalkylation reaction in a high yield You can

The various alkylamino-substituted-1,3,5-triazine derivatives of the products obtained by the present invention can be obtained in a highly selective manner in the reaction, so unless they are used in an extremely pure form, they are more than necessary. No need for separation and purification procedures. Particularly in the case of modifying additives such as flame retardants, plasticizers and stabilizers for resins, the reaction mixture containing a very small amount of impurities can be used as it is without any particular separation / purification.

Furthermore, the substituted amino-1,3,5-triazines obtained by this reaction are mostly compounds that have been relatively difficult or expensive to synthesize, and also in terms of physical properties, water and various organic solvents are used. Since many compounds are interesting in terms of their solubility in water, stability at high temperature, melting point, boiling point, basicity, etc., their applications are expected to expand beyond conventional ones.

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁶ Identification number Internal reference number FI Technical display location C07D 251/70 C07D 251/70 B (72) Inventor Yasuo Fukue 722-1, Tsuboi-cho, Funabashi, Chiba Prefecture (72) Inventor, Isao Hashiba, 722, Tsuboi-cho, Funabashi-shi, Chiba Nissan Chemical Co., Ltd. Central Research Laboratory

Claims (14)

[Claims] 1. A 1,3,5-triazine derivative having at least one or more amino group or mono-substituted amino group on a ring carbon atom and an aldehyde or a ketone are used as a carrier in a periodic table of Group VIII. Amino-substitution 1 for selectively introducing one alkyl group into at least one or more amino groups or mono-substituted amino groups, which is characterized by reacting reductively in the presence of a metal-supported catalyst and a hydrogen-containing gas. Method for Monoalkylation of 3,3,5-Triazine Derivatives. 2. At least one or more amino groups or molybdenum
1,3,5-triazine derivative having non-substituted amino group
Is a 1,3,5-triazine derivative represented by the general formula (I)
The 1,3,5-triazine derivative according to claim 1, which is a conductor.
Method for monoalkylation of body;[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, a hydroxyl group, C
_1-6Alkoxy group of C_1-6Haloalkoxy group, ant
Group, C _2-7Alkoxycarbonyl group of C
_2-7Acyloxy group, amino group, C_1-8The monoarch
Luamino group, C_2-12Dialkylamino 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
C) may be optionally substituted with)), C_2-20Arche
Nyl group (the alkenyl group is a halogen atom, trifluoro
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_1-6The alkoxy
Optionally substituted with a group) optionally substituted with
The above-mentioned NHR¹X 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, hydroxyl group, C_1-6Alkoxy group of C_1-6Halo a
Lucoxy group, aryloxy group, C_2-7Alkoxyka
Rubonyl 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))
I), C _2-20An alkenyl group of
Gen atom, trifluoromethyl group, hydroxyl group, C_1-6A
Lucoxy group, C_1-6Haloalkoxy group, aryloxy
Shi group, C_2-7Alkoxycarbonyl group of C_2-7Reed
Luoxy group, amino group, C _1-8Monoalkylamino
Group, C_2-12Dialkylamino group, phenyl group
Nyl group is a halogen atom, C_1-6Alkyl group, hydroxyl group,
C_1-6May be optionally substituted with an alkoxy group of
R may be optionally substituted), and R ²And R³
Together, optionally with 1 or 2 alkylene chains
C_1-8Substituted by an alkyl group of-(C
H₂)_2-5-, -CH₂CH₂-N (C_1-8The archi
) -CH₂CH₂-Or-CH₂CH₂-O-CH₂
CH₂-May be formed}, C₁-₂₀Alkyl 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}, C₂-₂₀Alkenyl 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)
}, Halogen atom, hydroxyl group, 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
May optionally be substituted), thiol group, or C_1-10Alkylthio group of
Rogen atom, hydroxyl group, C_1-6The alkoxy group of aryl
Oxy group, carboxyl group, C_2-7The alkoxy carbo
Nyl group, C_2-10Acyloxy group, amino group, C_1-8of
Monoalkylamino group, C_2-12A dialkylamino 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 replaced) may be arbitrarily substituted}
You ]. 3. Amino-substituted 1,3,5-of general formula (I)
NHR in triazine derivatives¹Base R¹Group is hydrogen
Atom, 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, 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 {the alkyl group is a halogen atom
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
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, if desired,
C having 1 or 2 chains _1-8Substituted by the alkyl group of
-(CH₂)_3-5-, -CH₂CH₂-N (C
_1-8Alkyl) -CH₂CH₂-Or-CH₂CH₂
-O-CH₂CH ₂-May be formed], C₁-₂₀Alkyl 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
Optionally)), halogen atom, hydroxyl group, 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 2. An amino-substituted 1,3,5-triazine derivative according to item 2.
Monoalkylation method. 4. Amino-substituted 1,3,5-of the general formula (I)
NHR in triazine derivatives¹Base R¹Group is hydrogen
Atom, C_1-20An alkyl group of (the alkyl group is a hydroxyl group,
C_1-6Optionally substituted with an alkoxy group or phenyl group
It may be any), and the above NHR¹X when not a group¹, X²And X³Haso
NR independently²R³Group {R², R³Each is German
Stand up C_1-20An alkyl group of (the alkyl group is a hydroxyl group,
C_1-6Optionally substituted with an alkoxy group or phenyl group
May be present), or R²And R³Together, if desired,
C having 1 or 2 chains _1-8Substituted by the alkyl group of
-(CH₂)_4-5-, -CH₂CH₂-N (C
_1-8Alkyl) -CH₂CH₂-Or-CH₂CH₂
-O-CH₂CH ₂-May be formed}, C₁-₂₀Alkyl group, phenyl group, hydroxyl group, C_1-10A
4. An amino-substitution according to claim 3, which is either a lucoxy group.
Method for monoalkylating 1,3,5-triazine derivative. 5. The aldehyde or ketone used in the reaction is
General formula (II)[In the formula, R^Four, R^FiveAre each independently a hydrogen atom, C_1-20
Alkyl group of {wherein the alkyl group is a halogen atom, hydroxy
Group, C_1-6Alkoxy group of C_1-6The haloalkoxy
Group, C_2-7Alkoxycarbonyl group, formyl group, C
_2-7Acyl group of C_{2- 7}Acyloxy 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
Optional) may be substituted}, or C_2-20An alkenyl group of {the alkenyl group is a halo
Gen atom, hydroxyl group, C _1-6Alkoxy group of C_1-6Ha
Ralkoxy group, C_2-7Alkoxycarbonyl group of
Lumil group, C_2-7Acyl group of C_2-7Acyloxy
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 arbitrarily replaced}
Representation or R^FourAnd R^FiveTogether, an alkylene group (-
(CH₂)_3-5-) May be formed. ] Represented by
A aldehyde derivative or a ketone derivative.
Of amino-substituted 1,3,5-triazine derivatives of
Killing method. 6. The aldehyde or ketone of the general formula (II), wherein 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, a C group).
_1-6 alkoxy group, formyl group, C _2-7 acyl group,
Optionally substituted with a phenyl group), or C
_2-20 alkenyl groups (the alkenyl groups include halogen atom, hydroxyl group, C _1-6 alkoxy group, formyl group, C
_2-7 acyl group, optionally substituted by phenyl group), or R ⁴ and R ⁵ together form an alkylene group (-
The method for monoalkylating an amino-substituted 1,3,5-triazine derivative according to claim 5, which is an aldehyde derivative or a ketone derivative which may form (CH ₂ ) _3-5- ). 7. An aldehyde or ketone of the general formula (II), wherein 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, a C group).
_1-6 alkoxy group, formyl group, C _2-7 acyl group,
Optionally substituted with a phenyl group), or R ⁴ and R ⁵ together form an alkylene group (-
7. The method for monoalkylating an amino-substituted 1,3,5-triazine derivative according to claim 6, which is an aldehyde derivative or a ketone derivative which may form (CH ₂ ) _3-5 −). 8. The method for monoalkylation according to claim 1.
Substituted amino 1,3,5-triazine derivative obtained by
Is a substituted amino 1,3,5-tol represented by the general formula (III)
Amino-Substituted 1,3,5-Triazide, a Riazine Derivative
Method for mono-alkylation of benzene 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, a hydroxyl group, C_1-6A
Lucoxy group, C_1-6Haloalkoxy group, aryloxy
Shi group, C_2-7Alkoxycarbonyl group of C_2-7Reed
Luoxy group, amino group, C_1-8Monoalkylamino
Group, C_2-12Dialkylamino group, phenyl group
Nyl group is a halogen atom, C_1-6Alkyl group, hydroxyl group,
C_1-6May be optionally substituted with an alkoxy group of
Optionally substituted}, or C_2-20An alkenyl group of
Gen atom, hydroxyl group, C _1-6Alkoxy group of C_1-6Ha
Low alkoxy group, aryloxy group, C_2-7The Archoki
Sicarbonyl group, C_2-7An acyloxy group, an amino group,
C_1-8Monoalkylamino group, C_2-12Dialkyla
Mino 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))
R), and R⁶And R⁷Together, optionally alkylene
C with 1 or 2 chains_{1- 8}Substituted by an alkyl group of
There- (CH₂)_2-5-, -CH₂CH₂-N (C_1-8
Alkyl) -CH₂CH₂-Or-CH₂CH₂-O
-CH₂CH₂-May 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)
}, Halogen atom, hydroxyl group, 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
May optionally be substituted), thiol group, or C_1-10Alkylthio group of
Rogen atom, hydroxyl group, C_1-6The alkoxy group of aryl
Oxy group, carboxyl group, C_2-7The alkoxy carbo
Nyl group, C_2-10Acyloxy group, amino group, C_1-8of
Monoalkylamino group, C_2-12A dialkylamino 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 replaced) may be arbitrarily substituted}
You ]. 9. A substituted amino 1,3,5-of general formula (III)
X in triazine derivatives^Four, X^FiveAnd X⁶NR⁶
R⁷Base R⁶, R⁷Are each independently a hydrogen atom (however
Then X^Four, X^FiveAnd X⁶R⁶, R⁷Are all hydrogen atoms
Except when), C_1-20Alkyl group of {the alkyl
The group is a halogen atom, hydroxyl group, C_1-6An alkoxy group of
Phenyl group (the phenyl group is a halogen atom, C_1-6A
Rukyl group, hydroxyl group, C_1-6Optionally substituted with the alkoxy group of
Optionally)), or C_2-20An alkenyl group of {the alkenyl group is a halo
Gen atom, hydroxyl group, C _1-6The alkoxy group of ,, phenyl
A group (the phenyl group is a halogen atom, C_1-6The alkyl
Group, hydroxyl group, C_1-6Optionally substituted with an alkoxy group of
, Which may be optionally substituted}.
Or R⁶And R⁷Together, optionally alkylene
C with 1 or 2 chains_1-8Substituted by an alkyl group of
There- (CH₂)_3-5-, -CH₂CH₂-N (C_1-8
Alkyl) -CH₂CH₂-Or-CH₂CH₂-O
-CH₂CH₂-May be formed, and the above NR^FourR^FiveIf not X^Four, X^FiveAnd X⁶But,
Each independently C₁- ₂₀An 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 present), halogen atom, hydroxyl group, 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}
The amino 1,3,5-triazine derivative according to claim 8.
Monomers of the listed amino-substituted 1,3,5-triazine derivatives
How to make rukill. 10. A substituted amino 1,3,5 of the general formula (III)
-In triazine derivatives X^Four, X^FiveAnd X⁶NR
⁶R⁷Base R⁶, R⁷Are each independently a hydrogen atom (however
Then X^Four, X^FiveAnd X⁶R⁶, R⁷Are all hydrogen atoms
Except when), C_1-20Alkyl group of (the alkyl
The group is a hydroxyl group, C_1-6Alkoxy and phenyl groups
Optionally substituted), or R⁶And R⁷Together
And optionally C having 1 or 2 alkylene chains.
_1-8Substituted with an alkyl group of-(CH₂)
_4-5-, -CH₂CH₂-N (C_1-8Alkyl) -C
H₂CH₂-Or-CH₂CH₂-O-CH₂CH₂−
To form the above NR⁶R⁷X when not a group^Four, X^FiveAnd X
⁶But each independently C ₁-₂₀Alkyl group of phenyl
Group, hydroxyl group, C_1-10Any of the alkoxy groups of
A modified 1,3,5-triazine derivative according to claim 9.
Monoalkyl of amino-substituted 1,3,5-triazine derivative
Method. 11. A catalyst of Group VIII of the Periodic Table is iron, cobalt, nickel, ruthenium, rhodium, palladium,
The method for selectively monoalkylating an amino-substituted 1,3,5-triazine derivative according to claim 1, which is at least one catalyst selected from osmium, iridium and platinum catalysts. 12. A catalyst of Group VIII of the periodic table is iron, cobalt, nickel, ruthenium, rhodium, palladium,
The method for monoalkylating an amino-substituted 1,3,5-triazine derivative according to claim 11, which is at least one catalyst selected from platinum catalysts. 13. The amino-substituted 1,3,5-triazine derivative according to claim 12, wherein the catalyst of Group VIII of the periodic table is at least one catalyst selected from nickel, ruthenium, palladium and platinum catalysts. Selective monoalkylation method. 14. A monoalkylated amino-substituted 1,3,5-triazine derivative according to claim 11, wherein in the supported catalyst of Group VIII of the periodic table, the carrier is a zeolite having a selected pore size. Method.