JPH0827128A - Method for alkylating triazine derivative - Google Patents

Abstract

PURPOSE:To provide a method for alkylating a triazine derivative by which a substituted 1,3,5-triazine derivative widely usable even as an intermediate for specialty chemicals or resin materials and flame retardant materials can readily be produced in high yield. CONSTITUTION:This method for alkylating a 1,3,5-triazine derivative having at least one or more amino groups or mono-substituted amino groups on a ring C atom, e.g. a compound of the formula [at least one of X<1> to X<3> is NHR<1> (R<2> is H, a 1-20C alkyl or a 2-20C alkenyl); the rest are NR<2>R<3> (R<2> and R<3> are each a 1-20C alkyl or a 2-20C alkenyl), a 1-20C alkyl, a 2-20C alkenyl, phenyl, a halogen, a 1-10C alkoxy or a 1-10C alkylthio] is to react the 1,3,5-triazine derivative with an alcohol of the formula ROH (R is a 1-20C alkyl or a 2-20C alkenyl) in the presence of a group VII (preferably Mn or Re) and/or a group VIII catalyst (preferably Ru or Rh) of the periodic table and alkylate at least the one or more amino groups or mono-substituted amino groups.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to Group VII of the Periodic Table and / or
Or in the presence of a Group VIII catalyst, various 1,3 having at least one or more amino groups or mono-substituted amino groups
The present invention relates to a method for alkylating a 1,3,5-triazine derivative having at least one amino group or a mono-substituted amino group by reacting 5-triazine with an alcohol.

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

[0003]

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

[0004]

[Chemical 4]

The compound of the formula (wherein X ⁴ and X ⁵ represent an amino group and X ⁶ represents an ethylamino group or a diethylamino group) is obtained by reacting a 2-chloro-1,3,5-triazine derivative with ethylamine. Synthetic methods have been reported. [Journal of America Chemical Society (J.
Amer. Chem. Soc), 73, 2984, 1951].
The compound of the general formula (III) (wherein X ⁴ , X ⁵ and X ⁶ represent an ethylamino group) is prepared by reacting 2,4,6-trimethylthio-1,3,5-triazine with ethylamine. Synthetic methods have been reported. [Hemische Berichte (Ch
em Rer.), 18, 2755, 1885]. General formula
The compound of formula (III) (in the formula, X ⁴ represents an amino group, X ⁵ represents an amino group or an octylamino group, and X ⁶ represents an octylamino group) is 2,4,6-triamino-1,3,3.
A synthetic method by the reaction of 5-triazine and octylamine hydrochloride has been reported. [US Patent 2,228,161
No., 1941]. The compound of the general formula (III) (in the formula, X ⁴ represents a phenyl group, X ⁵ and X ⁶ represent a butylamino group) is 2-phenyl-4,6-diamino-1,3,5-
A synthetic method by the reaction of triazine and butylamine has been reported. [U.S. Pat. No. 2,385,766, 1945
Year〕. In addition, various 2,4 synthesized from cyanuric chloride
A derivative of 6-1,3,5-triazine is used as a flame retardant for thermoplastic polymers [Japanese Patent Application Laid-Open No. 3-215564].
issue〕. Specific examples of the derivatives described in JP-A-3-215564 are shown below.

[0006]

Embedded image

Journal of America Chemicals
Society (J. Amer. Chem. Soc), 73, 2984,
The synthetic method of 1954 often requires an equivalent amount or more of a condensing agent, and produces by-products such as salts which are often industrially problematic. In addition, Hemische Berichte (Chem Be
r.), Vol. 18, p. 2755, 1885, produces by-products such as sulfur compounds which are often industrially problematic. The synthetic methods of U.S. Pat. No. 2,228,161 (1941) and U.S. Pat. No. 2,385,766 (1945) require a high temperature for the reaction, and the former produces by-product ammonium chloride. Further, in both cases, there is a common point that the substitution reaction with the leaving group is carried out using the substituted amines which are not industrially inexpensive, which is one reason why the substituted triazines cannot be supplied at a low price. Has become.

[0008]

DISCLOSURE OF INVENTION Problems to be Solved by the Invention As a result of intensive investigations by the present inventors to solve the above-mentioned problems of the prior art,
Using various industrially inexpensive alcohols, 1, 3,
Finding a novel method for alkylating triazine in which an alkyl group can be introduced on an amino group or a mono-substituted amino group on a ring carbon atom of 5-triazine and only water is used as a by-product, and the present invention has been completed. .

The substitutions 1,3,5 obtained in this reaction are also
-The triazine derivative remarkably inhibits the intrinsic intermolecular association of aminotriazine, so that the solubility in various solvents is improved. 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 product is an excellent method in terms of separation and purification because almost all of the produced amount is dissolved in the solvent.

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

[0011]

That is, the present invention provides at least one amino group or mono-substituted amino group on a ring carbon atom in the presence of a catalyst of Group VII and / or Group VIII of the Periodic Table. A method for alkylating a 1,3,5-triazine derivative for alkylating at least one amino group or mono-substituted amino group, comprising reacting the 1,3,5-triazine derivative having .

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

[0013]

[Chemical 6]

[Wherein X¹, X²And X³Less of
Both are independently NHR¹Group {in the formula, R¹Is hydrogen
Child, C_1-20Alkyl group (the alkyl group is trifluoro
Rumethyl group, C_1-6Alkoxy group of C_1-6The halo al
Coxy group, C_2-7Alkoxycarbonyl group of phenyl
A group (the phenyl group is a halogen atom, C_1-6The alkyl
Group, C_1-6Optionally substituted with an alkoxy group of
Optionally substituted with), C_2-20Alkenyl
A group (the alkenyl group is a trifluoromethyl group, C_{1- 6}
Alkoxy group of C_1-6Haloalkoxy group, C_2-7of
Alkoxycarbonyl group, phenyl group (the phenyl group is
Halogen atom, C_1-6Alkyl group of C_1-6The Archoki
Optionally substituted with a Si group)
The above-mentioned NHR¹Base
If no¹, X²And X³Each independently, NR
²R³Group {R², R³Are each independently C_1-20Al
Kill group (the alkyl group is a trifluoromethyl group, C
_1-6Alkoxy group of C_1-6Haloalkoxy group, C
_2-7Alkoxycarbonyl group, phenyl group (the phenyl group
Group is a halogen atom, C_1-6Alkyl group of C_1-6A
Optionally substituted with a lucoxy group)
May be included), C_2-20Alkenyl group of
Group is a trifluoromethyl group, C_1-6The alkoxy
Group, C_1-6Haloalkoxy group, C_2-7Alkoxyka
Rubonyl group, phenyl group (the phenyl group is a halogen atom
Child, C_1-6Alkyl group of C_1-6Any alkoxy group
May be substituted)) may be optionally substituted)
Or R²And R³Together, if desired
C having 1 or 2 alkylene chains_1-8By the alkyl group of
Substituted-(CH₂) _2-5-, -CH₂CH₂
− (C_1-8Alkyl) N-CH₂CH₂-Or-CH
₂CH₂-O-CH₂CH₂-May be formed}, C₁
~ C₂₀Alkyl group of {wherein the alkyl group is a halogen atom,
Toro group, cyano group, C_1-6Alkoxy group of carboxy
Group, C_2-7Alkoxycarbonyl group of C_2-10Reed
Group, C_2-10Acyloxy group, C_2-12Dialkyla
Mino group, aryl group (the aryl group is a halogen atom, C
_1-6Alkyl group of C_1-6Optionally substituted with the alkoxy group of
Optionally)), C₂
~ C ₂₀Alkenyl group of {the alkenyl group is a halogen source
Child, nitro group, cyano group, C_{1- 6}The alkoxy group of
Boxyl group, C_2-7Alkoxycarbonyl group of C_2-10
Acyl group of C_2-10Acyloxy group, C_2-12The dial
Kiramino group, aryl group (the aryl group is a halogen atom
Child, C_1-6Alkyl group of C_1-6Any alkoxy group
May be replaced with))
I}, phenyl group (the phenyl group is C_1-6The alkyl
Group, halogen atom, nitro group, cyano group, C_1-6Al
Coxy group, aryloxy group, carboxyl group, C_2-7
Alkoxycarbonyl group of C_2-10Acyl group of C_2-10
Acyloxy group, C_{2- 12}The dialkylamino group of ants
Group (the aryl group is a halogen atom, C_1-6The archi
Group, C_1-6Even if it is optionally substituted with an alkoxy group of
Good), optionally substituted}, halogen source
Child, C_1-10Alkoxy group of {wherein the alkoxy group is halogen
Atom, nitro group, cyano group, C_1-6The alkoxy group of
Ruboxyl group, C_2-7Alkoxycarbonyl group of C
_2-10Acyl group of C_2-10Acyloxy group, C_2-12The di
Alkylamino group, aryl group (the aryl group is a halogen
Atom, C_1-6Alkyl group of C_1-6With the alkoxy group of
May be arbitrarily replaced with)
I} or C_1-10Alkylthio group of {the alkylthio
Group is a halogen atom, nitro group, cyano group, C_1-6Al
Coxy group, carboxyl group, C_2-7The alkoxy carbo
Nyl group, C_2-10Acyl group of C_2-10An acyloxy group of
C_2-12Dialkylamino group, aryl group (the aryl
Group is a halogen atom, C_1-6Alkyl group of C_1-6Al
Optionally substituted with a coxyl group) optionally substituted with
May be present}. ].

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 R¹Is a hydrogen atom, C
_1-20An alkyl group of {wherein the alkyl group is C_1-6The Archoki
Si group, phenyl group (the phenyl group is a halogen atom, C
_1-6Alkyl group of C_1-6Optionally substituted with the alkoxy group of
May be substituted)), C_2-20of
Alkenyl group {The alkenyl group is C_1-6The alkoxy
Group, phenyl group (the phenyl group is a halogen atom, C_1-6
Alkyl group of C_1-6Optionally substituted with an alkoxy group of
May be substituted).
The above NHR¹X when not a group¹, X²And X³
, Each independently, NR²R³Group [R², R³Haso
Each independently C_1-20An alkyl group of {the alkyl group is
C_1-6Alkoxy group and phenyl group (the phenyl group is
Rogen atom, C_1-6Alkyl group of C_1-6The alkoxy
Optionally substituted with a group)
Good}, C_2-20An alkenyl group of {the alkenyl group is
C_1-6Alkoxy group and phenyl group (the phenyl group is
Rogen atom, C_1-6Alkyl group of C_1-6The alkoxy
Optionally substituted with a group) optionally substituted with
Represents good or R²And R³Together,
C having 1 or 2 alkylene chains as desired _1-8The alkyl
Substituted by a group-(CH₂)_3-5-, -CH₂
CH₂− (C_1-8Alkyl) N-CH₂CH₂-Or
-CH₂CH₂-O-CH₂CH ₂Good to form
], C₁~ C₂₀Alkyl group of {wherein the alkyl group is halogen
Atom, C_1-6Alkoxy group, aryl group (the aryl
Group is a halogen atom, C_1-6Alkyl group of C_1-6A
Optionally substituted with a lucoxy group)
Phenyl group (wherein the phenyl group is C_1-6
Alkyl group, halogen atom, C_1-6With the alkoxy group of
Optionally substituted), halogen atom, C_1-10
An alkoxy group of {wherein the alkoxy group is a halogen atom, C
_1-6Alkoxy group and aryl group (wherein the aryl group is halo
Gen atom, C_1-6Alkyl group of C_1-6Alkoxy group
May be optionally substituted with)
1,3,5-triazine derivative which is any of
Is.

A more preferred triazine derivative of the general formula (I) is the 1,3,5-triazine derivative of the general formula (I) in which R ¹ of the NHR ¹ group is either a hydrogen atom or a C _1-20 alkyl group. And X ¹ , X ² and X ^{3 in the} case of not being the above NHR ¹ group are each independently NR
² R ³ group (R ² and R ³ each independently represent a C _1-20 alkyl group, or R ² and R ³ are taken together to form a C _{1- group} having 1 or 2 alkylene chains, if desired. which is substituted by ₈ alkyl group _{- (CH 2) 4-5 -,} - CH 2
CH ₂ - (C _{1- 8} alkyl) N-CH ₂ CH ₂ - or _{-CH 2 CH 2 -O-CH 2} CH 2 - may be formed), an alkyl group of C ₁ -C _20, phenyl group , C _1-10 alkoxy groups, which are 1,3,5-triazine derivatives.

As described above, it is possible to provide all 1,3,5-triazine derivatives having a substituent not directly involved in the reaction in this reaction, but various industrially available intermediates can be used. Melamine derivatives and various guanamine derivatives (These are mainly available as modifiers for thermosetting raw resins, cross-linking agents for baking coatings, and the synthetic method is s-Tria.
zines and derivatives. The Chemistry of Heterocycl
ic Compounds. EMSmolin and L. Rapoport. Intersci
ence Publishers Inc., NEW York 1959.).

Alcohols that can be used in the present invention include those represented by the general formula (II)

[0019]

[Chemical 7]

[Wherein R is a C _1-20 alkyl group (wherein the alkyl group is a hydroxyl group, a trifluoromethyl group, a C _1-6 alkoxy group, a C _1-6 haloalkoxy group, a C _2-7 Optionally substituted with an alkoxycarbonyl group, a phenyl group (the phenyl group may be optionally substituted with a halogen atom, a C _1-6 alkyl group, a C _1-6 alkoxy group)}, Or a C _2-20 alkenyl group (the alkenyl group is a trifluoromethyl group, a C _1-6 alkoxy group, C
_1-6 haloalkoxy group, C _2-7 alkoxycarbonyl group, phenyl group (the phenyl group is a halogen atom, C
_1-6 alkyl group and C _1-6 alkoxy group may be optionally substituted). ] It is an alcohol derivative represented by.

[0021] Preferred alcohol derivatives of the above general formula (II), R is, C ₁ - ₂₀ alkyl group (the alkyl group of the alkoxy group of C _1-6, optionally substituted with a phenyl group Or a C _2-20 alkenyl group (the alkenyl group may be optionally substituted with a C _1-6 alkoxy group or a phenyl group).

[0022] Further preferred formula (II) alcohol derivatives, R is C ₁ - alkyl group of ₁₀ (the alkyl group, alkoxy group C _1-6, may be optionally substituted with a phenyl group) Is an alcohol derivative. Among these, as industrially easily available, methanol,
Ethanol, n-propanol, n-butanol, n-
Examples thereof include alkanols such as hexanol, n-octanol and 2-ethylhexanol, cellosolves such as methoxyethanol, ethoxyethanol and isopropoxyethanol, and substituted or unsubstituted benzyl alcohols.

Examples of the catalyst of Group VII of the periodic table used in the present invention include manganese and / or rhenium catalysts. Examples of the catalyst of Group VIII of the periodic table include iron, cobalt, nickel, ruthenium, rhodium, palladium, osmium, iridium and platinum catalysts, such as complex catalysts of these elements and supported catalysts. Among these elements, nickel, ruthenium, rhodium, palladium and platinum catalysts of Group VIII of the Periodic Table are preferable, and ruthenium or rhodium complex catalysts are particularly preferable. More specific examples of the catalyst will be given below.

Examples of iron catalysts include complex catalysts of pentacarbonyliron, dodecacarbonyltriiron, dichlorobis (triphenylphosphine) iron, tetracarbonyl (triphenylphosphine) iron, tricarbonylbis (triphenylphosphine) iron and the like. . Examples of cobalt catalysts include octacarbonyldicobalt, dodecacarbonyltricobalt, and chlorotris (triphenylphosphine) cobalt complex catalysts.

As the nickel catalyst, supported catalysts of nickel-supported silica, nickel-supported alumina, nickel-supported carbon, etc., dichlorobis (triphenylphosphine) nickel, tetrakis (triphenylphosphine) nickel, tetrakis (triphenylphosphite) nickel, etc. Examples of complex catalysts include nickel chloride and nickel oxide.

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

Preferred among these ruthenium catalysts are:
Ruthenium-supported silica, ruthenium-supported alumina, ruthenium-supported carbon and other supported catalysts, dodecacarbonyltriruthenium, carbonylchlorohydridotris (triphenylphosphine) ruthenium, tetrahydridotris (triphenylphosphine) ruthenium, dichlorobis (acetonitrile) bis (triphenyl) Phosphine) ruthenium, dichlorotris (triphenylphosphine)
Examples thereof include complex catalysts such as ruthenium, ruthenium chloride, ruthenium oxide and the like. More preferred ruthenium catalyst is
Complex catalysts such as dodecacarbonyltriruthenium, dichlorobis (acetonitrile) bis (triphenylphosphine) ruthenium, and dichlorotris (triphenylphosphine) ruthenium, and ruthenium chloride.

As the palladium catalyst, supported catalysts such as palladium-supported silica catalysts, palladium-supported alumina catalysts and palladium-supported carbon catalysts, dichlorobis (triphenylphosphine) palladium, dichlorobis (trimethylphosphine) palladium, dichlorobis (tributylphosphine) palladium, bis (Tricyclohexylphosphine) palladium, tetrakis (triethylphosphite) palladium, bis (cycloocta-1,5-diene) palladium, tetrakis (triphenylphosphine) palladium, dicarbonylbis (triphenylphosphine) palladium, carbonyltris (triphenylphosphine) ) Palladium, dichlorobis (benzonitrile) palladium, dichloro (1,5-cyclooctadiene) palladium, etc. Body catalyst and palladium chloride, and palladium oxide.

Examples of rhodium catalysts are supported catalysts such as rhodium-supported silica catalysts, rhodium-supported alumina catalysts, rhodium-supported carbon catalysts, chlorotris (triphenylphosphine) rhodium, hexadecacarbonylhexorhodium, dodecacarbonyltetrarhodium and dichlorotetracarbonylrhodium. , Hydrido tetracarbonyl rhodium, hydrido carbonyl tris (triphenylphosphine) rhodium, hydrido tetrakis (triphenylphosphine) rhodium, dichlorobis (cyclooctadiene) dirhodium, dicarbonyl (pentamethylcyclopentadienyl) rhodium, cyclopentadienyl Examples include complex catalysts such as bis (triphenylphosphine) rhodium and dichlorotetrakis (allyl) dirhodium, and rhodium chloride, rhodium oxide and the like. Of these, a chlorotris (triphenylphosphine) rhodium complex catalyst is preferable.

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

The above-mentioned catalysts may be used alone or in combination. The amount of the Group VIII catalyst used in the periodic table is usually in the range of 0.0001 to 20 mol% relative to the 1,3,5-triazine derivative of the general formula (I),
The range of 0.001 to 10 mol% is preferable. A ligand may be added to the above catalyst, if necessary. Examples of the ligand include trimethylphosphine, triethylphosphine, tributylphosphine, triphenylphosphine, tris (paratolyl) phosphine, tris (2,6-dimethylphenyl) phosphine, diphenylphosphinobenzene-3-sulfonate, bis ( 3-sulfonatophenyl) phosphinobenzene sodium salt, 1,2-bis (diphenylphosphino) ethane, 1,3-bis (diphenylphosphino) propane,
Monodentate and polydentate tertiary phosphines such as 1,4-bis (diphenylphosphino) butane and tris (3-sulfonatophenyl) phosphine sodium salt, triethylphosphite, tributylphosphite, triphenylphosphite, tris ( Phosphorous esters such as 2,6-dimethylphenyl) phosphite, triphenylmethylphosphonium iodide, triphenylmethylphosphonium bromide, triphenylmethylphosphonium chloride, triphenylallylphosphonium iodide, triphenylallylphosphonium bromide, triphenylmethylphosphonium iodide Phosphonium salts such as phenylallylphosphonium chloride, tetraphenylphosphonium iodide, tetraphenylphosphonium bromide, tetraphenylphosphonium chloride, triphosphoric acid Eniru, trimethyl phosphate, triethyl phosphate, phosphoric acid esters such as triallyl phosphate,
Examples thereof include unsaturated hydrocarbons such as cyclooctadiene and cyclopentadiene, nitriles such as benzonitrile and acetonitrile, and acetylacetone.

Among these ligands, preferred ligands are
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 (diphenyl) Monodentate and polydentate tris, such as phosphino) butane and tris (3-sulfonatophenyl) phosphine sodium salt
Examples thereof include unsaturated phosphines, unsaturated hydrocarbons such as cyclooctadiene and cyclopentadiene, nitriles such as benzonitrile and acetonitrile, and acetylacetone.

Particularly preferred ligands are triphenylphosphine, diphenylphosphinobenzene-3-sulfonic acid sodium salt, bis (3-sulfonatophenyl) phosphinobenzene sodium salt and tris (3-sulfonatophenyl) phosphine sodium salt. Can be mentioned. The amount of the ligand used is usually in the range of 0.1 to 10000 mol% and preferably in the range of 10 to 5000 mol% based on the Group VIII metal catalyst of the periodic table.

The reaction temperature is usually around room temperature to 500 ° C.
It is preferably 50 to 300 ° C. The reaction time depends on the reactivity of the 1,3,5-triazine derivative of the general formula (I), but is usually 1 to 100 hours, preferably 2 to 50 hours. This reaction proceeds even without a solvent, but a solvent can be used if necessary in view of operability and the like.

The solvent is not particularly limited as long as it is inert to the reaction. For example, ethers such as tetrahydrofuran, diethyl ether, diethylene glycol diethyl ether, 1,4-dioxane, benzene, toluene, xylene, tetrahydronaphthalene, etc. Aromatic hydrocarbons, aliphatic hydrocarbons such as n-hexane, cyclohexane, n-octane and n-decane, amides such as N, N-dimethylformamide, N, N-dimethylacetamide and N-methylpyrrolidone And ureas such as 1,3-dimethylimidazolidinone and N, N, N ′, N′-tetramethylurea. Further, an excess of the alcohol derivative represented by the general formula (II) may be used as a solvent.

Preferred solvents are ethers such as tetrahydrofuran, diethyl ether, diethylene glycol diethyl ether, 1,4-dioxane, aromatic hydrocarbons such as benzene, toluene, xylene, tetrahydronaphthalene, n-hexane, cyclohexane, n-octane. , N-decane and other aliphatic hydrocarbons and an excess of the alcohol derivative represented by the general formula (II).

Particularly preferred solvents are ethers such as tetrahydrofuran, diethyl ether, diethylene glycol diethyl ether, 1,4-dioxane and an excess of an alcohol derivative represented by the general formula (II). This reaction can be carried out under various gas atmospheres as long as it does not directly participate in the reaction. For example, nitrogen, argon, helium, etc. are generally used, but carbon dioxide, air, etc. can also be used, and also ammonia, hydrogen, carbon monoxide, etc. for the purpose of stabilizing products and catalysts, etc. used. The gases used in these reaction atmospheres may be used alone or as a mixture.

During the reaction, an autogenous pressure of the solvent of the reaction system is generated, and the reaction pressure as the sum of them and the reaction atmosphere gas pressure is 1 to 500 kg / cm ² , preferably 1 to 200 kg / cm ^2.
You can choose freely within the range of. As a treatment method after completion of the reaction, after removing unreacted triazines by means such as filtration, the solvent is removed by distillation or the like, if necessary, or the product is prepared as a two-phase system of water-organic solvent. After extraction into the organic solvent layer, the reaction product can be purified and isolated by recrystallization, distillation, chromatographic separation and the like.

In the case of a supported catalyst, the catalyst may be filtered, and in the case of an organic metal complex, the solvent and the product may be distilled.
Separation, recovery, and reuse in various forms from the residue removed by recrystallization, or in the case of using a water-soluble ligand, in the water layer as a water-soluble metal complex by extraction. Is. Thus, the substituted triazine derivative obtained by the method for alkylating an amino group on the ring carbon of the 1,3,5-triazine ring of the present invention is a substituted 1,3,5-substituted compound represented by the general formula (III). It is a triazine derivative.

[0040]

Embedded image

[Where X is^Four, X^FiveAnd X⁶Less of
Both are independent NR^FourR^FiveGroup {R ^Four, R^FiveEach
Independently, a hydrogen atom (however, X^Four, X^FiveAnd X⁶R
^Four, R ^FiveExcept when all are hydrogen atoms), C_1-20
An alkyl group of (wherein the alkyl group is a hydroxyl group, trifluoro
Methyl group, C_1-6Alkoxy group of C_1-6The halo arco
Xy group, C_2-7Alkoxycarbonyl group, phenyl group
(The phenyl group is a halogen atom, C_1-6An alkyl group of
C_1-6May be optionally substituted with an alkoxy group of
Optionally substituted), or C_2-20Archeni
Group (the alkenyl group is a trifluoromethyl group, C
_1-6Alkoxy group of C_1-6Haloalkoxy group, C
_2-7Alkoxycarbonyl group, phenyl group (the phenyl group
Group is a halogen atom, C_1-6Alkyl group of C_1-6A
Optionally substituted with a lucoxy group)
May be present) or R^FourAnd R^FiveTogether
And optionally C having 1 or 2 alkylene chains.
_1-8Substituted with an alkyl group of-(CH₂)
_2-5-, -CH₂CH₂− (C_1-8Alkyl) N-C
H₂CH₂-Or-CH₂CH₂-O-CH₂CH₂−
May be formed}, and the above NR^FourR^FiveNon-base
Combined X^Four, X^FiveAnd X⁶Are each independently C ₁~ C
₂₀Alkyl group of {wherein the alkyl group is a halogen atom, nitro
Group, cyano group, C _1-6The alkoxy group of carboxyl
Group, C_2-7Alkoxycarbonyl group of C_{2- Ten}The acyl
Group, C_2-10Acyloxy group, C_2-12Dialkylami
Group, an aryl group (the aryl group is a halogen atom, C
_1-6Alkyl group of C_1-6Optionally substituted with the alkoxy group of
Optionally)), C₂
~ C₂₀Alkenyl group of {the alkenyl group is a halogen source
Child, nitro group, cyano group, C_1-6The alkoxy group of
Boxyl group, C_2-7Alkoxycarbonyl group of C_2-10
Acyl group of C_2-10Acyloxy group, C_2-12The dial
Kiramino group, aryl group (the aryl group is a halogen atom
Child, C_1-6Alkyl group of C_1-6Any alkoxy group
May be replaced with))
I}, phenyl group (the phenyl group is C_1-6The alkyl
Group, halogen atom, nitro group, cyano group, C_1-6Al
Coxy group, aryloxy group, carboxyl group, C_2-7
Alkoxycarbonyl group of C_2-10Acyl group of C_2-10
Acyloxy group, C_{2- 12}The dialkylamino group of ants
Group (the aryl group is a halogen atom, C_1-6The archi
Group, C_1-6Even if it is optionally substituted with an alkoxy group of
Good), optionally substituted}, halogen source
Child, C_1-10Alkoxy group of {wherein the alkoxy group is halogen
Atom, nitro group, cyano group, C_1-6The alkoxy group of
Ruboxyl group, C_2-7Alkoxycarbonyl group of C
_2-10Acyl group of C_2-10Acyloxy group, C_2-12The di
Alkylamino group, aryl group (the aryl group is a halogen
Atom, C_1-6Alkyl group of C_1-6With the alkoxy group of
May be arbitrarily replaced with)
I} or C_1-10Alkylthio group of {the alkylthio
Group is a halogen atom, nitro group, cyano group, C_1-6Al
Coxy group, carboxyl group, C_2-7The alkoxy carbo
Nyl group, C_2-10Acyl group of C_2-10An acyloxy group of
C_2-12Dialkylamino group, aryl group (the aryl
Group is a halogen atom, C_1-6Alkyl group of C_{1- 6}Al
Optionally substituted with a coxyl group) optionally substituted with
May be present}. ].

Preferred Substitutions of Formula (III) -1,3,5
The triazine derivative is NR in the general formula (III)^FourR
^FiveR^Four, R^FiveAre each independently a hydrogen atom (however,
X^Four, X^FiveAnd X⁶R^Four, R^FiveAre all hydrogen atoms
Except case), C_1-20An alkyl group of {the alkyl group is
C_1-6Alkoxy group and phenyl group (the phenyl group is
Rogen atom, C_1-6Alkyl group of C_1-6The alkoxy
Optionally substituted with a group) optionally substituted with
Also good} or C_2-20Alkenyl group of {the alkenyl
The base is C_1-6Alkoxy group, phenyl group (the phenyl
Group is a halogen atom, C_1-6Alkyl group of C_1-6Al
Optionally substituted with a coxyl group) optionally substituted with
May be present, or R^FourAnd R^FiveTogether
And, if desired, C having 1 or 2 alkylene chains _1-8of
-(CH substituted by an alkyl group₂)_3-5-,
-CH₂CH₂− (C_1-8Alkyl) N-CH₂CH
₂-Or-CH₂CH₂-O-CH₂CH ₂Form-
NR above^FourR^FiveX when not a group^Four, X^FiveOver
And X⁶But each independently C ₁~ C₂₀Alkyl group of
{The alkyl group is a halogen atom, C_1-6The alkoxy
Group, an aryl group (the aryl group is a halogen atom, C_1-6
Alkyl group of C_1-6Optionally substituted with an alkoxy group of
Optionally)), phenyl
A group (the phenyl group is C_1-6Alkyl group of halogen source
Child, C_1-6May be optionally substituted with the alkoxy group of
I), halogen atom, C_1-10Alkoxy group of {the alco
The xy group is a halogen atom, C_1-6An alkoxy group of
Group (the aryl group is a halogen atom, C_1-6The alkyl
Group, C_1-6Optionally substituted with an alkoxy group of
May be optionally substituted with}
It is a -1,3,5-triazine derivative.

Further preferred substitution of the general formula (III) -1,
The 3,5-triazine derivative has the following general formula (III):
NR^FourR^FiveR^Four, R^FiveBut each independently a hydrogen atom
(However, X^Four, X^FiveAnd X⁶R^Four, R^FiveIs all water
Except for elementary atoms), C_1-20Represents an alkyl group of
Or R^Four, R^FiveAre bonded to form a carbon atom, nitrogen atom, oxygen
The above NR which may form a 3- to 6-membered ring consisting of atoms
^FourR^FiveX when not a group^Four, X^FiveAnd X⁶But each
Independently C _1-20Alkyl group, phenyl group, C_1-10A
Substituted-1,3,5-tria which is any of the lucoxy groups
It is a gin derivative.

As described above, in the method of the present invention,
Various compounds can be used as the raw material 1,3,5-triazine derivative and alcohol, and the product obtained by the method of the present invention has various substituents depending on the combination of the raw material 1,3,5-triazine derivative and alcohol. Have 1, 3,
A 5-triazine derivative is obtained. As described above, from the viewpoint of availability of raw materials, 1,3,5-triazine derivatives, melamine, various melamine derivatives, and various guanamine derivatives of raw materials, and alcohols include various alkanols, cellosolves, and benzyl alcohols. Are listed as typical products, and combinations of these products give typical products. Further, for example, a substituted triazine derivative obtained by alkylating melamine by the method of the present invention can also be used as long as an amine is present on the ring carbon atom of the triazine ring.
It can also be used as a 3,5-triazine derivative.

The range of raw materials applicable to this reaction is not limited by the price and availability of these raw materials, but the following are specific examples of the raw materials in this reaction and the substituents of the products. , Further clarify the scope of this reaction.
Of the substituents represented by X ¹ , X ² and X ³ of the general formula (I) of the raw material and the substituents represented by X ⁴ , X ⁵ and X ⁶ of the general formula (III) of the product, NHR ¹ , NR ² R ³ and Specific examples of NR ⁴ R ⁵ include an amino group (when X ¹ , X ² and X ³ are amino groups are melamine), methylamino group, ethylamino group, isopropylamino group, n-butylamino group. , I-butylamino group, sec-butylamino group, tert-butylamino group, cyclohexylamino group, cyclohexylmethylamino group, n-octylamino group, dimethylamino group, diethylamino group, diisopropylamino group, di-n-butyl group Amino group, di-i-butylamino group, di-sec-butylamino group, methyl-tert-butylamino group, methylcyclohexylamino group, cyclohexylmethylamino group, di-n
-Octylamino group, dicyclohexylmethylamino group, hydroxyethylamino group, 4-hydroxybutylamino group, 5-hydroxypentylamino group, trifluoroethylamino group, 2-trifluoropropylamino group, 2-ethoxyethylamino group, 3-methoxypropylamino group, 2-pentyloxyethylamino group, 3-
Cyclohexyloxypropylamino group, 2-chloroethoxyethylamino group, 5-monofluoropentyloxypentylamino group, 2-methoxycarbonylethylamino group, 2-ethoxycarbonylethylamino group, tert
-Butoxycarbonylethylamino group, 2-cyclohexyloxycarbonylethylamino group, methylphenylamino group, benzylamino group, dibenzylamino group, N
-Benzyl-N'-methylamino group, 2-phenylethylamino group, 3- (4-chlorophenyl) -propylamino group, 2- (4-cyclohexylphenyl) -ethylamino group, 2- (3-fluorophenyl) ) -Pentylamino group, 4-methoxybenzylamino group, 2-chloro-
4-fluorobenzylamino group, 3,5-dimethylbenzylamino group, 4-cyclopentyloxybenzylamino group, 2- (2-chloro-4-fluoro-5-isopropylphenyl) -propylamino group, allylamino group,
Methallylamino group, 3-cyclopentenylamino group, 3
-Cyclohexenylamino group, 3- (6-trifluoromethyl) -cyclohexenylamino group, diallylamino group, dimethallylamino group, 3- (1-methoxy) -allyl group, crotylamino group, chloromethoxyethylamino group, ethoxycarbonyl Examples thereof include an allylamino group, a cinnamylamino group, a 4-chlorocinnamylamino group, an N- (4-methylcinnamyl) -N′-methylamino group, and a 4-methoxycinnamylamino group.

[0046] Also, bonded NR ² R ³ of R ^2, R ^3,
Alternatively, specific examples of the group in which R ⁴ and R ⁵ of the NR ⁴ R ⁵ group are bonded include an aziridino group, a pyrrolidino group, a piperidino group, an N-methylpiperazino group, a morpholino group and the like. Of these, a pyrrolidino group, a piperidino group, an N-methylpiperazino group, and a morpholino group are preferable. The C _1-20 alkyl group which may be substituted includes methyl group, ethyl group, n-propyl group, n-butyl group, i-butyl group, sec-butyl group, n-amyl group, i-amyl group. 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, cyanoethyl group, 2 -Trifluoromethylethyl group, nitroethyl group, nitropropyl group, methoxymethyl group, methoxyethyl group, ethoxymethyl group, cyclohexylmethoxyethyl group, 2-carboxyethyl group, 3-carboxypropyl group, methoxycarbonylmethyl group, methoxycarbonyl Ethyl group,
tert-butoxycarbonylmethyl group, cyclohexyloxycarbonylethyl group, 2-propanoylethyl group,
Benzoylmethyl group, 2,4,6-trimethylphenylbenzoylmethyl group, acetyloxymethyl group, benzoyloxymethyl group, 3- (tert-butylcarbonyloxy) -propyl group, dimethylaminomethyl group, diethylaminomethyl group, diisopropylamino Methyl 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 C _2-20 alkenyl group which may be substituted include vinyl group, isopropenyl group, 1-butenyl group, 3-hexenyl group, allyl group, methallyl group, crotyl group, 2-chloroallyl group, 2-cyanovinyl group, methoxyvinyl group, ethoxyvinyl group, cyclohexylvinyl group, 4-nitro-2-butenyl group, 2-carboxylvinyl group, ethoxycarbonylvinyl group, tert-butoxycarbonylvinyl group, acetylvinyl group, acetylariz 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, p-nitrophenyl group, 2- A methyl-4-nitrophenyl group,
2-chlorophenyl group, 2,4-dichlorophenyl group,
2-fluoro-4-chlorophenyl group, p-cyanophenyl group, 3,5-dimethoxyphenyl group, 4-cyclopentyloxyphenyl group, m-phenoxyphenyl group, 4-
(2-naphthyloxy) -phenyl 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-butylaminophenyl group, 3-di-i- Butylaminophenyl group, 2-di-sec-
Butylaminophenyl group, 4-methyl-tert-butylaminophenyl group, 4-methylcyclohexylaminophenyl group, 4-cyclohexylmethylaminophenyl group, 4
-Biphenyl group, 4- (2-naphthyl) -phenyl group,
4- (4-chlorophenyl) -phenyl group, 4- (5-
(1-methyl-3-chloropyrazolo) -yl) -phenyl group and the like.

Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom. The C _1-10 alkoxy group which may be substituted includes a methoxy group, an ethoxy group, an n-propyloxy group, an i-propyloxy group,
n-butyloxy group, i-butyloxy group, sec-butyloxy group, tert-butyloxy group, n-amyloxy group, i-amyloxy group, hexyloxy group, cyclohexyloxy group, cyclohexylmethyloxy group, pentyloxy group, octyloxy group , 2-ethylhexyloxy group, nonyloxy group, decyloxy group, hexadecyloxy group, octadecyloxy group, trifluoromethyloxy group, 3-chloropropyloxy group, cyanoethyloxy group, 2-trifluoromethylethyloxy group, nitroethyl Oxy group, nitropropyloxy group, methoxymethyloxy group, methoxyethyloxy group, ethoxymethyloxy group, cyclohexylmethoxyethyloxy group, 2
-Carboxyethyloxy group, 3-carboxypropyloxy group, methoxycarbonylmethyloxy group, methoxycarbonylethyloxy group, tert-butoxycarbonylmethyloxy group, cyclohexyloxycarbonylethyloxy group, 2-propanoylethyloxy group, benzoylmethyl Oxy group, 2,4,6-trimethylphenylbenzoylmethyloxy group, acetyloxymethyloxy group, benzoyloxymethyloxy group, 3- (tert-
Butylcarbonyloxy) -propyloxy group, dimethylaminomethyloxy group, diethylaminomethyloxy group, diisopropylaminomethyloxy group, di-n-butylaminomethyloxy group, di-i-butylaminomethyloxy group, di-sec- Butylaminomethyloxy group, methyl
-tert-butylaminomethyloxy group, methylcyclohexylaminomethyloxy group, cyclohexylmethylaminomethyloxy group, benzyloxy group, 4-methylbenzyloxy group, 4-methoxybenzyloxy group, 2-chloro-4-fluorobenzyloxy group Group, 3,5-dimethylbenzyloxy group, 4-cyclopentyloxybenzyloxy group and the like.

The C _1-10 alkylthio group which may be substituted includes methylthio group, ethylthio group, n-propylthio group, i-propylthio group, n-butylthio group, i-butylthio group, sec-butylthio group, tert-butylthio group, n-amylthio group, i-amylthio group, hexylthio group, cyclohexylthio group, cyclohexylmethylthio group, pentylthio group, octylthio group, 2-ethylhexylthio group,
Nonylthio group, decylthio group, hexadecylthio group, octadecylthio group, trifluoromethylthio group, 3-chloropropylthio group, cyanoethylthio group, 2-trifluoromethylethylthio group, nitroethylthio group, nitropropylthio group, methoxymethylthio group Group, methoxyethylthio group, ethoxymethylthio group, cyclohexylmethoxyethylthio group, 2-carboxyethylthio group, 3
-Carboxypropylthio group, methoxycarbonylmethylthio group, methoxycarbonylethylthio group, tert-butoxycarbonylmethylthio group, cyclohexyloxycarbonylethylthio group, 2-propanoylethylthio group, benzoylmethylthio group, 2,4,6-trimethyl Phenylbenzoylmethylthio group, acetyloxymethylthio group, benzoyloxymethylthio group, 3- (tert-
(Butylcarbonyloxy) -propylthio group, dimethylaminomethylthio group, diethylaminomethylthio group, diisopropylaminomethylthio group, di-n-butylaminomethylthio group, di-i-butylaminomethylthio group, di-s
ec-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.

As the other raw material alcohol, any alcohol that is usually available can be used in this reaction. As an example, the substituent R is methyl, ethyl, n-propyl or the like. 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, trifluoroethyl group, 3-chloropropyl group, cyanoethyl group, 2-trifluoromethylethyl group, nitroethyl group, nitropropyl Group, methoxymethyl group, methoxyethyl group, ethoxymethyl group, cyclohexylmethoxyethyl group, 2-carboxyethyl group, 3-carboxypropyl group, methoxycarbonylmethyl group, methoxycarbonylethyl group, tert-butoxycarbonylmethyl group, cyclohexyloxy Carbonylethyl group, 2-propanoylethyl group, benzoylmethyl group, 2,4,6-trimethylphenylbenzoylmethyl group, acetyloxymethyl group, benzoyloxymethyl group, 3- (tert-butylcarbonyloxy) -propyl group Ropyl group, dimethylaminomethyl group, diethylaminomethyl group, diisopropylaminomethyl group, di-n-butylaminomethyl group, di-i-butylaminomethyl group, di-sec-butylaminomethyl group, methyl-tert-butylamino group Methyl 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
Examples include-(1-methoxy) -allyl group, crotylamino group, cinnamyl group, 4-methylcinnamyl group, 4-chlorocinnamyl group, 4-ethoxycinnamyl group, and 2,4,6-trimethylcinnamyl group. To be

The examples of these substituents are very representative examples, and the present invention is not limited to these.
As a treatment method after completion of the reaction, after unreacted triazines are crystallized and then removed by means such as filtration, the solvent is removed by distillation or the like, if necessary, or a water-organic solvent two-phase system is used. After extracting the product as, the reaction product is recrystallized, distilled,
It can be purified and isolated by chromatographic separation or the like.

In the case of a supported catalyst, the catalyst is a filter or the like, and in the case of an organic metal complex, the solvent and the product are distilled,
From the residue removed by recrystallization, and in the case of a complex catalyst using a water-soluble ligand, the water-soluble metal complex is extracted, extracted, and separated, recovered and re-regenerated in various forms. It can be used.

[0054]

The present invention will be described in more detail below with reference to examples, but the present invention is not limited thereto.
In addition, in the following Examples 1 to 5, the FD-MASS spectra (JEOL Ltd. J.
The composition was analyzed by MS-SX102 type and its peak intensity and high performance liquid chromatography (Hitachi L
The reaction selectivity was determined from the relative area ratio (-6000 series).

In Examples 6 and later, a calibration curve was prepared using an internal standard substance and a pure triazine derivative separately synthesized as a standard, and the concentration of each component in the reaction system was determined by the internal standard quantification method under the following conditions. The analysis conditions of the high performance liquid chromatography used are as shown below. (Determination method of raw material triazines) _{Eluent; CH 3 CN / H 2 O} = 1/1 (V / V) detection method; UV 240 nm Column; GL Sciences Inc. Inertsil Ph 150 mm ×
4.6 mm φ Flow rate: 1.0 ml / min Temperature: 40 ° C. Internal standard substance: Phthalic acid di-n-butyl ester (quantification method of products and a part of raw materials (alkylaminotriazines)) Eluent: CH ₃ CN / H ₂ O = 40/60 (V / V) 15 minutes later CH ₃ CN / H ₂ O = 100/0 (V / V
V) Hold for 15 minutes (gradient system) Detection method: UV 230 nm column; GL Science Inertsil C8 150 mm ×
4.6 mm φ Flow rate; 1.0 ml / min Temperature; 35 ° C Internal standard substance; Di (2-ethylhexyl) phthalate

Example 1 A magnetic rotor was placed in a stainless steel autoclave with a content of 20 mL equipped with a glass liner, and 0.192 g of dichlorotris (triphenylphosphine) ruthenium was added.
(0.20 mmol), 2.52 g of melamine (20.0
Millimolar) and ethanol (10.0 ml) were added, and the reaction temperature was 180 under argon substitution (initial atmospheric pressure 1 atm).
The reaction was carried out at 0 ° C for 20 hours.

After completion of the reaction, the reaction product was analyzed by high performance liquid chromatography and mass spectrometry (FD-MASS). As a result, the raw material conversion rate was 50%. The following conversion products were obtained with the indicated selectivity. 2-Ethylamino-4,6-diamino-1,3,5-triazine 20%, 2,4-bis (ethylamino) -6-amino-1,3,5-triazine 24%, 2,4,6 -Tris (ethylamino) -1,
3,5-triazine 21%, 2-diethylamino-4,
8.2% 6-bis (ethylamino) -1,3,5-triazine and 10.9% 2-melamino-4-ethylamino-6-amino-1,3,5-triazine.

Example 2 A magnetic rotor was placed in a stainless steel autoclave with a content of 20 mL equipped with a glass liner, and 0.096 g of dichlorotris (triphenylphosphine) ruthenium was added.
(0.10 mmol), 1.26 g of melamine (10.0
Millimolar) and benzyl alcohol (10.0 ml) were added, and the reaction was carried out at a reaction temperature of 180 ° C. for 20 hours under argon substitution (initial pressure: 1 atm).

After completion of the reaction, the reaction product was analyzed by high performance liquid chromatography and mass spectrometry (FD-MASS), and the raw material conversion rate was 43%. The following conversion products were obtained with the indicated selectivity. 2-benzylamino-4,6-diamino-1,3,5-triazine 20.5%, 2,4-
Bis (benzylamino) -6-amino-1,3,5-triazine 29.1%, 2,4,6-tris (benzylamino) -1,3,5-triazine 21.7%, 2-dibenzyl Amino-4,6-bis (benzylamino) -1,
2.0% of 3,5-triazine.

Example 3 A magnetic rotor was placed in a stainless steel autoclave with a content of 20 mL equipped with a glass liner, and 0.096 g of dichlorotris (triphenylphosphine) ruthenium was added.
(0.10 mmol), 1.26 g of melamine (10.0
Mmol), 1-butanol (10.0 milliliters)
Under an argon atmosphere (initial atmospheric pressure: 1 atm), reaction temperature: 1
The reaction was carried out at 80 ° C for 20 hours.

After the reaction was completed, the reaction product was analyzed by high performance liquid chromatography and mass spectrometry (FD-MASS), and the raw material conversion rate was 73%. The following conversion products were obtained with the indicated selectivity. 2-normal butylamino-4,
6-diamino-1,3,5-triazine 12.9%,
2,4-bis (normal butylamino) -6-amino-
21% 1,3,5-triazine, 2,4,6-tris (normal butylamino) -1,3,5-triazine 2
8.6%, 2-dinormal butylamino-4,6-bis (normal butylamino) -1,3,5-triazine 1
3.7%, 2,4-bis (dinormal butylamino)-
6-Normal butylamino-1,3,5-triazine 4.0%.

Example 4 A magnetic rotor was placed in a stainless steel autoclave with a content of 20 mL equipped with a glass liner, and 0.096 g of dichlorotris (triphenylphosphine) ruthenium was added.
(0.10 mmol), 1.26 g of melamine (10.0
Mmol), benzyl alcohol 1.08 g (10.0
Was added, 10 ml of tetrahydronaphthalene was added as a solvent, and the reaction was carried out at a reaction temperature of 180 ° C. for 20 hours under argon substitution (initial pressure: 1 atm).

After completion of the reaction, the reaction product was analyzed by high performance liquid chromatography and mass spectrometry (FD-MASS), and the raw material conversion rate was 75%. The following conversion products were obtained with the indicated selectivity. 2-benzylamino-4,6-diamino-1,3,5-triazine 16.7%, 2,4-
Bis (benzylamino) -6-amino-1,3,5-triazine 20.7%, 2,4,6-Tris (benzylamino) -1,3,5-triazine 12.6%.

Example 5 A magnetic rotor was placed in a stainless steel autoclave having a content volume of 20 mL equipped with a glass liner, and 0.093 g of chlorotris (triphenylphosphine) rhodium was added.
(0.10 mmol), 1.26 g of melamine (10.0
Mmol), 1-butanol (10.0 milliliters)
Under an argon atmosphere (initial atmospheric pressure: 1 atm), reaction temperature: 1
The reaction was carried out at 80 ° C for 20 hours.

After completion of the reaction, the reaction product was analyzed by high performance liquid chromatography and mass spectrometry (FD-MASS). As a result, the raw material conversion rate was 5%. The following conversion products were obtained with the indicated selectivity. 2-Normal butylamino-4,6
-Diamino-1,3,5-triazine 20.9%, 2,
4-bis (normal butylamino) -6-amino-1,
25% 3,5-triazine, 2,4,6-tris (normal butylamino) -1,3,5-triazine 25.2
%, 2-dinormal butylamino-4,6-bis (normal butylamino) -1,3,5-triazine 3.7
%.

Example 6 In a stainless steel autoclave having an internal volume of 100 mL, 5.04 g (40.0 mmol) of melamine, 52.0 mg (0.2 mmol) of ruthenium trichloride hydrate, and diphenylphosphinobenzene-3-sulfone. Acid sodium salt 3
64.0 mg (1 mmol), 1-butanol 30 mL
Was charged, the inside of the system was sufficiently replaced with nitrogen gas, and the initial nitrogen pressure was 30 kg / cm ² , and the reaction temperature was 250 ° C.
The reaction was allowed for 0 hours.

After the completion of the reaction, the crude reaction product thus obtained was quantitatively analyzed by high performance liquid chromatography by the method described first, and as a result, the conversion rate of the raw material melamine was 95%. Also,
The crude reaction product was quantitatively analyzed by high performance liquid chromatography by the method described above, and as a result, the following conversion product was obtained in the yield (based on the raw material melamine). 2-normal butylamino-4,6-diamino-1,3,5-triazine 16.
5%, 2,4-bis (normal butylamino) -6-amino-1,3,5-triazine 35.0%, 2,4,6
-Tris (normal butylamino) -1,3,5-triazine 23.6%, 2-dinormal butylamino-4,
6-bis (normal butylamino) -1,3,5-triazine 15.0%.

Further, after distilling off 1-butanol and water from the reaction solution, toluene was added, and the soluble portion was separated by filtration and quantitatively analyzed by high performance liquid chromatography. As a result, a small amount of 2-normal butylamino- 4,6-Diamino-1,3,5-triazine, and almost all the amount of 2,4-bis (normal butylamino) -6-based on the amount produced.
Amino-1,3,5-triazine, 2,4,6-tris (normal butylamino) -1,3,5-triazine,
2-Dinormal-butylamino-4,6-bis (normal-butylamino) -1,3,5-triazine was extracted.

Further, when the insoluble matter was suspended in water and the soluble portion was extracted and analyzed, 98.0% of the catalyst component and a trace amount of melamine were recovered.

Example 7 5.04 g (40.0 mmol) of melamine, 79.7 mg (0.2 mmol) of tris (acetylacetonato) ruthenium, and 262.0 mg of triphenylphosphine were added to a stainless steel autoclave having an internal volume of 100 mL. (1 mmol) and 1-butanol (30 mL) were charged, the system was sufficiently replaced with nitrogen gas, and then the initial nitrogen pressure was 5 kg / cm.
^As No. ² , the reaction was carried out at a reaction temperature of 230 ° C. for 6 hours.

After the completion of the reaction, the crude reaction product was quantitatively analyzed by the method described above by high performance liquid chromatography. As a result, the conversion rate of the raw material melamine was 79.0%. Further, the crude reaction product was quantitatively analyzed by high performance liquid chromatography by the method described at the beginning, and as a result, the following conversion product was obtained at the yield (based on the raw material melamine). 2-Normal butylamino-
4,6-Diamino-1,3,5-triazine 18.5
%, 2,4-bis (normal butylamino) -6-amino-1,3,5-triazine 21.5%, 2,4,6-
Tris (normal butylamino) -1,3,5-triazine 15.3%, 2-dinormal butylamino-4,6
-Bis (normal butylamino) -1,3,5-triazine 8.7%.

Example 8 2.52 g (20.0 mmol) of melamine, 26.0 mg (0.1 mmol) of ruthenium trichloride and 2101.0 mg (0.5 mmol) of tributylphosphine were placed in a stainless steel autoclave having an internal volume of 100 mL. , 1-Butanol (30 mL) was charged, the system was sufficiently replaced with nitrogen gas, and then the reaction was carried out at a reaction temperature of 230 ° C. for 2 hours under an initial nitrogen pressure of 5 kg / cm ² .

After the completion of the reaction, the crude reaction product was quantitatively analyzed by the method described above by high performance liquid chromatography. As a result, the conversion rate of the raw material melamine was 16.0%. Further, the crude reaction product was quantitatively analyzed by high performance liquid chromatography by the method described in the beginning, and as a result, 2-normal-butylamino-4,
6-diamino-1,3,5-triazine has a selectivity of 98.
The yield was 0% and the yield (based on the raw material melamine) was 15.7%.

Example 9 To a stainless steel autoclave having an internal capacity of 100 mL, 5.04 g (40.0 mmol) of melamine, 127.8 mg (0.2 mmol) of triruthenium dodecacarbonyl and 50 mL of 1-butanol were charged and charged with nitrogen gas. After sufficiently replacing the inside of the system, a mixed gas of hydrogen / carbon monoxide = 1/1 was set at an initial pressure of 80 kg / cm ² and a reaction temperature of 2
The reaction was performed at 10 ° C. for 10 hours.

After the completion of the reaction, the crude reaction product was quantitatively analyzed by the method described above by high performance liquid chromatography. As a result, the conversion rate of the raw material melamine was 93.5%. Further, the crude reaction product was quantitatively analyzed by high performance liquid chromatography by the method described at the beginning, and as a result, the following conversion product was obtained at the yield (based on the raw material melamine). 2-Normal butylamino-
4,6-diamino-1,3,5-triazine 12.5
%, 2,4-bis (normal butylamino) -6-amino-1,3,5-triazine 19.8%, 2,4,6-
Tris (normal butylamino) -1,3,5-triazine 46.5%, 2-dinormal butylamino-4,6
-Bis (normal butylamino) -1,3,5-triazine 11.6%, 2,4-bis (dinormal butylamino) -6-normal butylamino-1,3,5-triazine 1.8%.

Further, 1-butanol and water were distilled off from the crude reaction product, toluene was added, and the insoluble portion was separated by filtration. As a result, 6.3% of the charged melamine and
2-Normal butylamino-4,6-diamino-1,3,5-triazine was obtained with a yield (based on raw material melamine) of 10.8%.

Example 10 5.04 g (40.0 mmol) of melamine, 52.0 mg (0.2 mmol) of ruthenium chloride hydrate, triphenylmethylphosphonium iodide 404. 0 mg (1.
(0 mmol), 1-butanol (50 mL) was charged, and the system was sufficiently replaced with nitrogen gas.
/ Cm ² , and the reaction was carried out at a reaction temperature of 250 ° C. for 10 hours.

After the completion of the reaction, the crude reaction product was quantitatively analyzed by the method described above by high performance liquid chromatography. As a result, the conversion rate of the raw material melamine was 42.3%. Further, the crude reaction product was quantitatively analyzed by high performance liquid chromatography by the method described at the beginning, and as a result, the following conversion product was obtained at the yield (based on the raw material melamine). 2-Normal butylamino-
4,6-diamino-1,3,5-triazine 6.9%,
2,4-bis (normal butylamino) -6-amino-
1,3,5-triazine 15.7%, 2,4,6-tris (normal butylamino) -1,3,5-triazine 14.4%, 2-dinormal butylamino-4,6-bis ( Normal butylamino) -1,3,5-triazine 2.2%.

Further, 1-butanol and water were distilled off from the crude reaction product, and then toluene was added and the insoluble portion was separated by filtration. 0.8% of 2-normal butylamino-4,6-diamino-1,3,5-triazine was obtained. As a result of quantitative analysis of the other reaction products in the toluene solution by high performance liquid chromatography, it was confirmed that the whole amount was extracted.

Example 11 1.87 g (10.0 mmol) of benzoguanamine, 26.0 mg (0.1 mmol) of ruthenium trichloride hydrate, and diphenylphosphinobenzene-3-sulfone were placed in a stainless steel autoclave having an internal volume of 40 mL. acid sodium salt 182.0mg (0.5 mmol) was charged with 1-butanol 20 mL, after thoroughly purging the system with nitrogen gas, the nitrogen initial pressure 30kg / cm ^2, the reaction temperature 250 ° C.
And reacted for 10 hours.

After the completion of the reaction, the crude reaction product was quantitatively analyzed by the method described above by high performance liquid chromatography, and as a result, the conversion of the raw material triazine was 57.5%. Further, the crude reaction product was quantitatively analyzed by high performance liquid chromatography by the method described at the beginning, and as a result, the following conversion product was obtained in the yield (based on the raw material triazine). 2-Amino-4-normalbutylamino-6-phenyl-1,3,5-triazine 48.0%, 2,4-bis (normal butylamino)-
6.5% of 6-phenyl-1,3,5-triazine.

Further, 1-butanol and water were distilled off from the crude reaction product, and then water was added to extract and analyze the soluble portion. As a result, 98.0% of the catalyst component was recovered.

Example 12 A stainless steel autoclave having an internal volume of 40 mL was charged with 2-
Amino-4-methyl-6-methoxy-1,3,5-triazine 1.40 g (10.0 mmol), dichlorotris (triphenylphosphine) ruthenium 95.8 mg
(0.1 mmol) and 20 mL of 1-hexanol were charged, the system was sufficiently replaced with nitrogen gas, and then the reaction was carried out at a reaction temperature of 230 ° C. for 20 hours under an initial nitrogen pressure of 5 kg / cm ² .

After the completion of the reaction, the crude reaction product was quantitatively analyzed by the method described above by high performance liquid chromatography. As a result, the conversion of the raw material triazine was 53.0%. The crude reaction product was quantitatively analyzed by high performance liquid chromatography by the method described in the beginning, and as a result, 2-normalhexylamino-
4-Methyl-6-methoxy-1,3,5-triazine was obtained in a yield of 44.0% (based on raw material triazine).

Example 13 In a stainless steel autoclave having an internal volume of 100 mL, 2
-N-butyl melamine 3.64 g (20.0 mmol), ruthenium trichloride 26.0 mg (0.1 mmol), diphenylphosphinobenzene-3-sulfonic acid sodium salt 182.0 mg (0.5 mmol), 1 −
After charging 30 mL of butanol and thoroughly replacing the inside of the system with nitrogen gas, the initial temperature of nitrogen was set to 5 kg / cm ² and the reaction temperature was adjusted to 2
The reaction was carried out at 30 ° C for 1.5 hours.

After the completion of the reaction, the crude reaction product was quantitatively analyzed by the method described above by high performance liquid chromatography. As a result, the conversion rate of the raw material triazine was 83.4%. Further, the crude reaction product was quantitatively analyzed by high performance liquid chromatography by the method described at the beginning, and as a result, the following conversion product was obtained in the yield (based on the raw material triazine). 2,4-bis (normal butylamino) -6-amino-1,3,5-triazine 3
6.7%, 2,4,6-Tris (normal butylamino) -1,3,5-triazine 41.5%.

Example 14 In a stainless steel autoclave having an internal volume of 100 mL,
2,4-bis (normal butylamino) -6-amino-
4.76 g (20.0 mmol) of 1,3,5-triazine, 26.0 mg (0.1 mmol) of ruthenium trichloride, and 182.0 mg (0.5 mmol) of sodium salt of diphenylphosphinobenzene-3-sulfonic acid. , 1-
After charging 30 mL of butanol and thoroughly replacing the inside of the system with nitrogen gas, the initial temperature of nitrogen was set to 5 kg / cm ² and the reaction temperature was adjusted to 2
The reaction was carried out at 30 ° C. for 0.5 hours.

After completion of the reaction, the crude reaction product was quantitatively analyzed by high performance liquid chromatography by the method described first, and as a result, the conversion of the raw material triazine was 53.0%. Further, the crude reaction product was quantitatively analyzed by high performance liquid chromatography by the method described at the beginning, and as a result, the following conversion product was obtained in the yield (based on the raw material triazine). 2,4,6-Tris (normal butylamino) -1,3,5-triazine 36.5
%, 2-dibutylamino-4,6-bis (normal butylamino) -1,3,5-triazine 11.2%.

From the crude reaction product of this reaction, n-butanol as a solvent and water produced were distilled off under reduced pressure, 100 mL of toluene and 100 mL of water were added to the residue, and the mixture was thoroughly stirred and then the aqueous layer was formed. separated. The catalyst used is recovered in this water layer. From the analysis results, the Ru derived from the ruthenium chloride used was detected as 99% in the obtained aqueous layer as Ru.

Also, diphenylphosphinobenzene-3
-96% of the amount of sodium sulfonic acid salt used and 2.5% of the amount of sodium diphenylphosphinobenzene-3-sulfonic acid oxide used were detected. Further, the residue obtained by concentrating the toluene layer was separated by silica gel column chromatography (eluent; n-hexane / ethyl acetate = 6/4 (V / V)) to obtain 4
3% was recovered, and the yield of 2,4,6-tris (normal butylamino) -1,3,5-triazine was 33%. 2-dibutylamino-4,6-bis (normal butylamino)
-1,3,5-triazine was isolated with a yield of 8%.

Example 15 In a stainless steel autoclave having an internal volume of 100 mL, 2
-Dibutylamino-4,6-diamino-1,3,5-triazine 4.76 g (20.0 mmol), ruthenium trichloride 26.0 mg (0.1 mmol), sodium diphenylphosphinobenzene-3-sulfonate Salt 18
2.0 mg (0.5 mmol), 1-butanol 30 m
After L was charged and the inside of the system was sufficiently replaced with nitrogen gas, the reaction was carried out at a reaction temperature of 230 ° C. for 3 hours under an initial nitrogen pressure of 5 kg / cm ² .

After the completion of the reaction, the crude reaction product was quantitatively analyzed by the method described above by high performance liquid chromatography, and as a result, the conversion rate of the raw material triazine was 95.4%. Further, the crude reaction product was quantitatively analyzed by high performance liquid chromatography by the method described at the beginning, and as a result, the following conversion product was obtained in the yield (based on the raw material triazine). 2-dinormal butylamino-4-butylamino-6-amino-1,3,5-triazine 37.0%, 2-dinormal butyl-4,6-bis (normal butylamino) -1,3,5 -Triazine yield 33.2%.

Example 16 A stainless steel autoclave having an internal volume of 100 mL was used for 2 times.
-N-butyl melamine 3.64 g (20.0 mmol), triruthenium dodecacarbonyl 63.9 mg
(0.1 mmol) and 1-butanol (30 mL) were charged, the system was sufficiently replaced with carbon monoxide gas, and then the reaction was carried out at a reaction temperature of 230 ° C. for 2 hours.

After the completion of the reaction, the crude reaction product was quantitatively analyzed by the method described above by high performance liquid chromatography. As a result, the conversion of the raw material triazine was 91.2%. Further, the crude reaction product was quantitatively analyzed by high performance liquid chromatography by the method described at the beginning, and as a result, the following conversion product was obtained in the yield (based on the raw material triazine). 2,4-bis (normal butylamino) -6-amino-1,3,5-triazine 3
5.8%, 2,4,6-Tris (normal butylamino) -1,3,5-triazine 32.5%.

Example 17 Into a stainless steel autoclave having an internal volume of 100 mL, 2
-Diethylamino-4,6-diamino-1,3,5-triazine 3.64 g (20.0 mmol), ruthenium trichloride 26.0 mg (0.1 mmol), diphenylphosphinobenzene-3-sulfonic acid sodium salt 18
2.0 mg (0.5 mmol), 1-butanol 30 m
After L was charged and the inside of the system was sufficiently replaced with nitrogen gas, the reaction was carried out at a reaction temperature of 230 ° C. for 2 hours under an initial nitrogen pressure of 5 kg / cm ² .

After the completion of the reaction, the crude reaction product was quantitatively analyzed by the method described above by high performance liquid chromatography. As a result, the conversion rate of the raw material triazine was 67.8%. Further, the crude reaction product was quantitatively analyzed by high performance liquid chromatography by the method described at the beginning, and as a result, the following conversion product was obtained in the yield (based on the raw material triazine). 2-diethylamino-4-
Normal butylamino-6-amino-1,3,5-triazine 28.8%, 2-diethylamino-4,6-bis (normal butylamino) -1,3,5-triazine 2
5.3%.

Example 18 In a stainless steel autoclave having an internal volume of 100 mL,
2,4-bis (normal butylamino) -6-amino-
4.76 g (20.0 mmol) of 1,3,5-triazine, 26.0 mg (0.1 mmol) of ruthenium trichloride, and 182.0 mg (0.5 mmol) of sodium salt of diphenylphosphinobenzene-3-sulfonic acid. , 1-
After charging 30 mL of butanol and thoroughly replacing the inside of the system with nitrogen gas, the initial temperature of nitrogen was set to 5 kg / cm ² and the reaction temperature was adjusted to 2
The reaction was carried out at 50 ° C for 30 minutes.

After the completion of the reaction, the crude reaction product was quantitatively analyzed by the method described above by high performance liquid chromatography. As a result, the conversion of the raw material triazine was 93.4%. To the residue obtained by distilling off 1-butanol and the produced water from the crude reaction product, 100 mL of toluene and 100 mL of water were added and an extraction operation was performed. As a result of analyzing the obtained aqueous layer, 97.5% of the catalyst component was recovered. The product was separated by silica gel column chromatography (ethyl acetate: n-hexane = 1: 1) after concentrating the toluene layer.
2,4,6-tris (normal butylamino) -1,
The yield of 3,5-triazine was 63.2%, 2-dibutylamino-4,6-bis (normal butylamino) -1,
3,5-triazine was obtained with a yield of 8.8%.

Example 19 A stainless steel autoclave having an internal volume of 40 mL was charged with 2-
Morpholino-4,6-diamino-1,3,5-triazine 1.96 g (10.0 mmol), dichlorotris (triphenylphosphine) ruthenium 95.8 mg
(0.1 mmol) and 20 mL of 1-hexanol were charged, the system was sufficiently replaced with nitrogen gas, and then the reaction was carried out at a reaction temperature of 200 ° C. for 20 hours under an initial nitrogen pressure of 5 kg / cm ² .

After completion of the reaction, the crude reaction product was quantitatively analyzed by high performance liquid chromatography by the method described at the beginning, and as a result, the conversion of the raw material triazine was 47.0%. The crude reaction product was quantitatively analyzed by high performance liquid chromatography by the method described in the beginning, and as a result, 2-morpholino-4-normalbutylamino-6-amino-1,3,5-triazine was obtained in a yield of 23.0%. Obtained at a rate.

[0101]

INDUSTRIAL APPLICABILITY According to the method of the present invention, 1,3,5-triazine represented by the general formula (I) can be used in various mild chemicals under relatively mild reaction conditions to produce various fine chemical intermediates such as pesticides, pharmaceuticals, dyes and paints. Substitution, which is a useful group of compounds widely used as various resin materials and flame-retardant materials,
The 1,3,5-triazine derivative can be easily produced in high yield.

The products obtained by the process of the present invention are various alkylated substituted-1,3,5-triazine derivatives
Generally, they are obtained as a mixture, but these products can be separated in a pure form by the method shown in the examples or the like, and can be used for the above various uses. Further, depending on the field of use (especially in the case of flame retardants for resins, modifying additives as plasticizers, etc.), the reaction mixture can be used without being particularly separated.

Further, many substituted triazines obtained by this reaction have been relatively difficult to synthesize in the past, and also in terms of physical properties, their solubility in water and various organic solvents and their stability at high temperatures are high. Many compounds are interesting in terms of melting point, boiling point, basicity, etc., and it is thought that their applications will expand more than ever before.

Continuation of front page (51) Int.Cl. ⁶ Identification number Office reference number FI Technical indication location B01J 23/44 23/46 301 311 23/755 31/20 31/24 X C07D 251/18 E 251/44 B 251/46 AB // C07B 61/00 300 (72) Inventor Masataka Hatanaka 6903 Onoda, Onoda City, Yamaguchi Prefecture 1903, Onoda Plant, Nissan Chemical Industries, Ltd. (72) Isao Hashiba, Tsuboi Town, Funabashi City, Chiba Prefecture 722 Address 1 Central Research Laboratory, Nissan Chemical Industries, Ltd. (72) Inventor Yoshihisa Watanabe 64-9 Terada Fukaya, Joyo City, Kyoto Prefecture

Claims (19)

[Claims] 1. A 1,3,5-triazine derivative having at least one amino group or mono-substituted amino group on a ring carbon atom in the presence of a catalyst of Group VII and / or Group VIII of the periodic table. Is reacted with alcohol to alkylate the 1,3,5-triazine derivative for alkylating at least one or more amino groups or mono-substituted amino groups. 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.
Body alkylation method;[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 trifluoromethyl group, C
_1-6Alkoxy group of C_1-6Haloalkoxy group, C
_2-7Alkoxycarbonyl group, phenyl group (the phenyl group
Group is a halogen atom, C_1-6Alkyl group of C_1-6A
Optionally substituted with a lucoxy group)
May be included), C_2-20Alkenyl group of
Group is a trifluoromethyl group, C_{1- 6}The alkoxy
Group, C_1-6Haloalkoxy group, C_2-7Alkoxyka
Rubonyl group, phenyl group (the phenyl group is a halogen atom
Child, C_1-6Alkyl group of C_1-6Any alkoxy group
May be substituted)) may be optionally substituted)
The above-mentioned NHR¹X when not a group¹, X²And X³Haso
Each independently, NR ²R³Group {R², R³Are each
Independently C_1-20Alkyl group (wherein the alkyl group is
Luormethyl group, C_1-6Alkoxy group of C_1-6The halo
Alkoxy group, C_2-7The alkoxycarbonyl group of
Nyl group (the phenyl group is a halogen atom, C_1-6The archi
Group, C_1-6Optionally substituted with an alkoxy group of
C) may be optionally substituted with)), C_2-20Arche
Nyl group (the alkenyl group is a trifluoromethyl group, C
_1-6Alkoxy group of C_1-6Haloalkoxy group, C
_2-7Alkoxycarbonyl group, phenyl group (the phenyl group
Group is a halogen atom, C_1-6Alkyl group of C_1-6A
Optionally substituted with a lucoxy group)
May be present) or R², R³Together
And, if desired, C having 1 or 2 alkylene chains_1-8
Substituted with an alkyl group of-(CH₂)
_2-5-, -CH₂CH₂− (C_1-8Alkyl) N-C
H₂CH₂-Or-CH ₂CH₂-O-CH₂CH₂−
May be formed}, C₁~ C₂₀Alkyl group of {the alkyl group is a halogen atom
Child, nitro group, cyano group, C_1-6The alkoxy group of
Boxyl group, C_2-7Alkoxycarbonyl group of C_2-10
Acyl group of C_2-10Acyloxy group, C_2-12The dial
Kiramino group, aryl group (the aryl group is a halogen atom
Child, C_1-6Alkyl group of C_1-6Any alkoxy group
May be replaced with))
I}, C₂~ C₂₀An alkenyl group of {the alkenyl group is a halogen
Atom, nitro group, cyano group, C_1-6The alkoxy group of
Ruboxyl group, C_2-7Alkoxycarbonyl group of C
_2-10Acyl group of C_2-10Acyloxy group, C_2-12The di
Alkylamino group, aryl group (the aryl group is a halogen
Atom, C_1-6Alkyl group of C_1-6With the alkoxy group of
May be arbitrarily replaced with)
}, A phenyl group (the phenyl group is C_1-6Alkyl group of halo
Gen atom, nitro group, cyano group, C_1-6The alkoxy
Group, aryloxy group, carboxyl group, C_2-7Al
Coxycarbonyl group, C_2-10Acyl group of C_2-10Reed
Luoxy group, C_{2- 12}Dialkylamino group, aryl group
(The aryl group is a halogen atom, C_1-6An alkyl group of
C_1-6Optionally substituted with an alkoxy group of
Optionally substituted with}, halogen atom, C_1-10Alkoxy group of {the said alkoxy group
Is a halogen atom, nitro group, cyano group, C_1-6Arco
Xy group, carboxyl group, C_2-7Alkoxy Carboni
Group, C_2-10Acyl group of C_2-10Acyloxy group, C
_2-12Dialkylamino group, aryl group (the aryl group
Is a halogen atom, C_1-6Alkyl group of C_1-6Arco
Optionally substituted with a xy group) optionally substituted with
Or C_1-10Alkylthio group of
Rogen atom, nitro group, cyano group, C_1-6The alkoxy
Group, carboxyl group, C_2-7Alkoxycarbonyl
Group, C_2-10Acyl group of C_2-10Acyloxy group, C
_2-12Dialkylamino group, aryl group (the aryl group
Is a halogen atom, C_1-6Alkyl group of C_{1- 6}Arco
Optionally substituted with a xy group) optionally substituted with
May be present. ]. 3. A 1,3,5-triazine of general formula (I)
NHR in derivatives¹Base R¹Is a hydrogen atom, C_1-20
An alkyl group of {wherein the alkyl group is C_1-6The alkoxy
Group, phenyl group (the phenyl group is a halogen atom, C_1-6
Alkyl group of C_1-6Optionally substituted with an alkoxy group of
May be optionally substituted}, C_2-20An alkenyl group of {the alkenyl group is C_1-6A
Lucoxy group, phenyl group (the phenyl group is a halogen atom
Child, C_1-6Alkyl group of C_1-6Any alkoxy group
Can be replaced with))
It is a gap, and the above NHR¹X when not a group¹, X
²And X³, Each independently, NR²R³Base
[R², R³Are each independently C_1-20Alkyl group of
{The alkyl group is C_1-6Alkoxy group, phenyl group
(The phenyl group is a halogen atom, C_1-6An alkyl group of
C_1-6Optionally substituted with an alkoxy group of
It may be substituted at will}, C_2-20An alkenyl group of {the alkenyl group is C_1-6A
Lucoxy group, phenyl group (the phenyl group is a halogen atom
Child, C_1-6Alkyl group of C_1-6Any alkoxy group
May be replaced with))
Or R², R³Together, if desired,
C having 1 or 2 chains _1-8Substituted by the alkyl group of
-(CH₂)_3-5-, -CH₂CH₂− (C_1-8
Alkyl) N-CH₂CH₂-Or-CH₂CH₂−
O-CH₂CH ₂-May be formed], C₁~ C₂₀Alkyl group of {the alkyl group is a halogen atom
Child, C_1-6Alkoxy group, aryl group (the aryl group
Is a halogen atom, C_1-6Alkyl group of C_1-6Arco
Optionally substituted with a xy group) optionally substituted with
), A phenyl group (wherein the phenyl group is C_1-6Alkyl group of halo
Gen atom, C_1-6Optionally substituted with an alkoxy group of
May be used), halogen atom, C_1-10An alkoxy group of {the
The alkoxy group is a halogen atom, C_1-6An alkoxy group of
Aryl group (the aryl group is a halogen atom, C_1-6A
Rukiru group, C_1-6Optionally substituted with an alkoxy group of
Good) and may be optionally substituted}.
3. The 1,3,5-triazine derivative according to claim 2,
A method for alkylating a 1,3,5-triazine derivative. 4. A 1,3,5-triazine of general formula (I)
NHR in derivatives¹Base R¹Is a hydrogen atom or C
_1-20Any of the alkyl groups of¹X when not a group¹, X²And X³But,
Each independently, NR²R³Group (R², R³Each
Independently C_1-20Represents an alkyl group of, 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~ C₂₀Alkyl group, phenyl group, C_1-10Arco
1,3,5-triazine derivative having any of xy groups
The 1,3,5-triazine derivative according to claim 3, wherein
Alkylation method. 5. The alcohol is represented by the general formula (II): [Wherein R is a C _1-20 alkyl group (wherein the alkyl group is a hydroxyl group, a trifluoromethyl group, a C _1-6 alkoxy group,
C _1-6 haloalkoxy group, C _2-7 alkoxycarbonyl group, phenyl group (the phenyl group is a halogen atom, C
_1-6 alkyl group, optionally substituted by C _1-6 alkoxy group), or optionally C _2-20 alkenyl group (the alkenyl group is trifluoro Methyl group, C _1-6 alkoxy group, C _1-6 haloalkoxy group, C _2-7 alkoxycarbonyl group, phenyl group (wherein the phenyl group is a halogen atom, a C _1-6 alkyl group, C _{1- (} Optionally substituted with ₆ alkoxy groups)
May be optionally substituted}. ] 1,3,5- according to claim 1, which is an alcohol derivative represented by
Method for alkylating triazine derivative. 6. The R of the alcohol derivative of the general formula (II)
Is a C _1-20 alkyl group (the alkyl group may be optionally substituted with a C _1-6 alkoxy group or a phenyl group), or a C _2-20 alkenyl group (the alkenyl group is The method for alkylating a 1,3,5-triazine derivative according to claim 5, which is an alcohol derivative which is either a C _1-6 alkoxy group or a phenyl group). 7. The R of the alcohol derivative of the general formula (II)
Is an alcohol derivative which is a C _1-10 alkyl group (the alkyl group may be optionally substituted with a C _1-6 alkoxy group or a phenyl group).
Method for alkylating 3,5-triazine derivative. 8. By the alkylation method according to claim 1.
The resulting substituted-1,3,5-triazine derivative has the general formula
Substitution of 1,3,5-triazine represented by (III)
To alkylate 1,3,5-triazine derivatives
Law;[In the formula, X^Four, X^FiveAnd X⁶At least one of them is German
Stand up and NR^FourR^FiveGroup {R ^Four, R^FiveEach independently water
Elementary atom (however, X^Four, X^FiveAnd X⁶R^Four, R ^FiveGasp
All except hydrogen atom), C_1-20Alkyl group of
(The alkyl group is a hydroxyl group, trifluoromethyl group, C
_1-6Alkoxy group of C_1-6Haloalkoxy group, C
_2-7Alkoxycarbonyl group, phenyl group (the phenyl group
Group is a halogen atom, C_1-6Alkyl group of C_1-6A
Optionally substituted with a lucoxy group)
May be included), or C_2-20Alkenyl group of
The lukenyl group is a trifluoromethyl group, C_1-6Arco
Xy group, C_1-6Haloalkoxy group, C_2-7The Archoki
Sicarbonyl group, phenyl group (the phenyl group is halogen
Atom, C_1-6Alkyl group of C_1-6With the alkoxy group of
May be arbitrarily substituted))
Represents R) or R^FourAnd R^FiveWanted together
Is an alkylene chain having 1 or 2 C_1-8Alkyl group of
Is replaced by-(CH₂)_2-5-, -CH₂C
H₂− (C_1-8Alkyl) N-CH₂CH ₂-Or-
CH₂CH₂-O-CH₂CH₂-May be formed}
Represents the above NR^FourR^FiveX when not a group^Four, X^FiveAnd X
⁶Are each independently C ₁~ C₂₀Alkyl group of
The alkyl group is a halogen atom, nitro group, cyano group, C _1-6
Alkoxy group, carboxyl group, C_2-7The alkoxy
Carbonyl group, C_{2- Ten}Acyl group of C_2-10Akiruoki
Shi group, C_2-12Dialkylamino group and aryl group of
Reel group is halogen atom, C_1-6Alkyl group of C_1-6
It may be optionally substituted with an alkoxy group of
May be replaced}, C₂~ C₂₀An alkenyl group of {the alkenyl group is a halogen
Atom, nitro group, cyano group, C_1-6The alkoxy group of
Ruboxyl group, C_2-7Alkoxycarbonyl group of C
_2-10Acyl group of C_2-10Acyloxy group, C_2-12The di
Alkylamino group, aryl group (the aryl group is a halogen
Atom, C_1-6Alkyl group of C_1-6With the alkoxy group of
May be arbitrarily replaced with)
}, A phenyl group (the phenyl group is C_1-6Alkyl group of halo
Gen atom, nitro group, cyano group, C_1-6The alkoxy
Group, aryloxy group, carboxyl group, C_2-7Al
Coxycarbonyl group, C_2-10Acyl group of C_2-10Reed
Luoxy group, C_{2- 12}Dialkylamino group, aryl group
(The aryl group is a halogen atom, C_1-6An alkyl group of
C_1-6Optionally substituted with an alkoxy group of
Optionally substituted with}, halogen atom, C_1-10An alkoxy group of {the said alkoxy group is a halogen source
Child, nitro group, cyano group, C_1-6The alkoxy group of
Boxyl group, C_2-7Alkoxycarbonyl group of C_2-10
Acyl group of C_2-10Acyloxy group, C_2-12The dial
Kiramino group, aryl group (the aryl group is a halogen atom
Child, C_1-6Alkyl group of C_1-6Any alkoxy group
May be replaced with))
I} or C_1-10Alkylthio group of
Rogen atom, nitro group, cyano group, C_1-6The alkoxy
Group, carboxyl group, C_2-7Alkoxycarbonyl
Group, C_2-10Acyl group of C_2-10Acyloxy group, C
_2-12Dialkylamino group, aryl group (the aryl group
Is a halogen atom, C_1-6Alkyl group of C_{1- 6}Arco
Optionally substituted with a xy group) optionally substituted with
May be present. ]. 9. Substitution of general formula (III) -1,3,5-tri
NR in azine derivatives^FourR^FiveR^Four, R^FiveBut that
Each independently a hydrogen atom (however, X^Four, X^FiveAnd X⁶of
R^Four, R^FiveExcept when all are hydrogen atoms), C
_1-20An alkyl group of {wherein the alkyl group is C_1-6The Archoki
Si group, phenyl group (the phenyl group is a halogen atom, C
_1-6Alkyl group of C_1-6Optionally substituted with the alkoxy group of
Optionally)), or C_2-20An alkenyl group of {the alkenyl group is C
_1-6Alkoxy group, phenyl group (the phenyl group is a halo
Gen atom, C_1-6Alkyl group of C_1-6Alkoxy group
May be optionally substituted with)
Represents good, or R^FourAnd R^FiveTogether,
C having 1 or 2 alkylene chains as desired_{1- 8}The alkyl
Substituted by a group-(CH₂)_3-5-, -CH₂
CH₂− (C_1-8Alkyl) N-CH₂CH₂-Or
-CH₂CH₂-O-CH₂CH₂-May be formed, and the above NR^FourR^FiveX when not a group^Four, X^FiveAnd X
⁶But each independently C ₁~ C₂₀Alkyl group of
The alkyl group is a halogen atom, C_1-6Alkoxy group of
Group (the aryl group is a halogen atom, C_1-6The archi
Group, C_1-6May be optionally substituted with the alkoxy group of
Optionally substituted with)}, a phenyl group (wherein the phenyl group is C_1-6Alkyl group of halo
Gen atom, C_1-6Optionally substituted with an alkoxy group of
May be used), halogen atom, C_1-10An alkoxy group of {the said alkoxy group is a halogen source
Child, C_1-6Alkoxy group, aryl group (the aryl group
Is a halogen atom, C_1-6Alkyl group of C_1-6Arco
Optionally substituted with a xy group) optionally substituted with
May be present} Substitution-1,3,5-tri
The 1,3,5-tria according to claim 8, which is an azine derivative.
Method for alkylating gin derivative. 10. Substitution of the general formula (III) -1,3,5-to
NR in lysine derivatives^FourR^FiveR^Four, R^FiveBut that
Each is independently a hydrogen atom (however, X^Four, X^FiveAnd X⁶
R^Four, R^FiveExcept when all are hydrogen atoms), C
_1-20Represents an alkyl group of R, or R^FourAnd R^FiveTogether
And, if desired, C having 1 or 2 alkylene chains_1-8
Substituted with an alkyl group of-(CH₂)
_4-5-, -CH₂CH₂− (C_1-8Alkyl) N-C
H₂CH₂-Or-CH₂CH₂-O-CH₂CH₂−
To form the above NR^FourR^FiveX when not a group^Four, X^FiveAnd X
⁶But each independently C _1-20Alkyl group of phenyl
Group, C_1-10A substituted-1, which is any of the alkoxy groups of
The 1,5-triazine derivative according to claim 9,
Method for alkylating 3,5-triazine derivative. 11. The method according to claim 1, wherein the catalyst of Group VII of the periodic table is a manganese and / or rhenium catalyst.
Method for alkylating 5-triazine derivatives. 12. The manganese and / or rhenium catalyst as claimed in claim 11, which is a complex catalyst of each element.
Method for alkylating 5-triazine derivatives. 13. The catalyst according to claim 1, wherein the catalyst of Group VIII of the periodic table is at least one catalyst selected from iron, cobalt, nickel, ruthenium, rhodium, palladium, osmium, iridium and platinum catalysts. Of alkylating 3,3,5-triazine derivatives. 14. A catalyst of Group VIII of the periodic table is nickel,
The method for alkylating a 1,3,5-triazine derivative according to claim 13, which is at least one catalyst selected from ruthenium, rhodium, palladium and platinum catalysts. 15. The method for alkylating a 1,3,5-triazine derivative according to claim 14, wherein the catalyst of Group VIII of the periodic table is at least one catalyst selected from ruthenium and rhodium catalysts. 16. The method for alkylating a 1,3,5-triazine derivative according to claim 13, wherein the catalyst is a complex catalyst. 17. The method for alkylating a 1,3,5-triazine derivative according to claim 16, wherein the complex catalyst has a tertiary phosphine as a ligand. 18. The method for alkylating a 1,3,5-triazine derivative according to claim 13, wherein the catalyst is a supported catalyst. 19. The method for alkylating a 1,3,5-triazine derivative according to claim 18, wherein the carrier of the supported catalyst is silica, alumina and carbon.