JPH08143554A - Production of n,n-alkylene-substituted melamine derivative - Google Patents

Abstract

PURPOSE: To readily obtain an N,N-alkylene-substituted melamine derivative useful as an intermediate for medicines and agrochemicals, dyes, coatings, etc., and a flame retardant material in high yield without producing by-products other than water by reacting a specific melamine derivative with a dicarbonyl compound in the presence of a specific catalyst and H2 -containing gas. CONSTITUTION: The objective compound of formula III (one or more groups are groups of formula IV and the others are groups of the formula NR1 R2 ] is obtained by reacting (C) a compound expressed by formula I one or more groups of X<1> to X<3> are amino groups and the other groups are groups of the formula NR<1> R<2> [R<1> and R<2> are each H or a 1-10C alkyl, with the proviso that these both are not simultaneously H or R<1> and R<2> together form a group of the formula (CH2 )m -Y-(CH2 )n (Y is a single bond, O, etc.; (m) and (n) are each 1-3)]} with (D) a compound of formula II [R<4> and R<5> are each H or a 1-10C alkyl; (k) is 1-4] in the presence of (A) a catalyst of the VIII group of the periodic table [e.g. palladium-supported carbon catalyst, dichlorobis(triphenylphosphine)palladium, platinium-supported carbon catalyst, dichlorobis(triphenylphosphine)platinium] and (B) H2 -containing gas such as H2 .

Description

Detailed Description of the Invention

[0001]

The present invention relates to the reductive alkylation of various melamine derivatives with dicarbonyl compounds in the presence of a catalyst of Group VIII of the Periodic Table and a hydrogen-containing gas,
The present invention relates to a novel method for producing an N, N-alkylene substituted melamine derivative. The substituted melamine derivative of the present invention is a useful compound widely used as a flame-retardant material as various fine chemical intermediates for agricultural chemicals, pharmaceuticals, dyes, paints, etc., and also as various resin materials, particularly as aminoplast former components. It is a group.

[0002]

2. Description of the Related Art Conventionally, various synthetic methods have been known as a synthetic method of substituted melamines, for example, general formula (V)

[0003]

Embedded image

(Wherein X ⁷ and X ⁸ represent a diethylamino group, X ⁹ represents an ethylamino group, or X ⁷ and X ⁸ represent an amino group, and X ⁹ represents an ethylamino group or a diethylamino group). , A 2-chloro-1,3,5-triazine derivative and a reaction method of ethylamine have been reported [J. Amer. Chem. Soc, 73, 2984]. ,
1951].

General formula (V) (wherein X ⁷ , X ⁸ and X
⁹ represents an ethylamino group. ) Compounds are 2, 4, 6
A synthetic method by the reaction of -trimethylthio-1,3,5-triazine and ethylamine has been reported [Hemische.
Berichte (Chem Rer.), 18: 2755, 188.
5 years]. The compound of the general formula (V) (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-1, A synthetic method by the reaction of 3,5-triazine and octylamine hydrochloride has been reported [US Pat.
8, 161, 1941].

The compound of the general formula (V) (in the formula, X ⁷ represents a piperidino group and X ⁸ and X ⁹ represent an amino group):
A synthetic method by the reaction of cyanopiperidine and cyanoguanidine has been reported [German Patent 889,593,
1953]. Further, various 2,4,6-substituted melamine 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.

[0007]

[Chemical 6]

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 under mild alkaline conditions with an aqueous solution of melamine and formalin. [Journal of America Chemical Society (J.Ame
r. Chem. Soc), 69, 599, 1947]. Journal of America Chemical Society (J.
Amer.Chem.Soc), 73, 2984, 1954 often requires more than an equivalent amount of condensing agent.
It produces by-products such as salts, which are often industrially problematic.
Also, Chem Ber., Vol. 18,
The synthetic method of pages 2755 and 1885 produces by-products such as sulfur compounds which are often industrially problematic. US Patent 2,
The synthetic method of 228, 161, 1941 requires high temperature for the reaction, and the former produces ammonium chloride as a by-product. The synthesis methods of German Patents 889,593 and 1953 are excellent methods in a laboratory because they use a compound having a cyano group as a raw material, but are not necessarily industrially suitable methods. Further, in both cases, there is a common point that a substituted amine or a derivative thereof which is not industrially inexpensive is used to carry out a substitution reaction or an addition reaction with a leaving group, which makes substituted triazines inexpensive. Is one of the reasons why we cannot supply it to

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

Therefore, a reaction of reacting a melamine derivative with a dicarbonyl compound having two aldehyde and ketone structures to introduce an N, N-alkylene group forming a cyclic structure on the same amino group is not known at all. .

[0011]

DISCLOSURE OF THE INVENTION As a result of intensive investigations aimed at solving the above problems, the present inventors have found that industrially inexpensive melamine or a derivative thereof is used as a catalyst of Group VIII of the Periodic Table and a hydrogen-containing substance. The present invention has been completed by reacting with a dialdehyde derivative in the presence of gas, introducing an alkylene group onto an amino group in a high yield in one step and cyclizing it, and using only water as a by-product.

Further, the substituted melamine derivative obtained by this reaction remarkably inhibits the multimolecular association due to the intermolecular hydrogen bond originally possessed by aminotriazines, and at the same time improves the lipophilicity. The solubility is remarkably improved, and at the same time, the melting point is also lowered, so that the compatibility with other organic compounds is also 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 product is dissolved in the solvent.

An object of the present invention is to introduce and cyclize an amino group on a ring carbon atom of a melamine derivative with a dialdehyde in a single step and cyclize it to obtain fine chemical intermediates for various agricultural chemicals, pharmaceuticals, dyes, paints and the like. Another object of the present invention is to provide a method for easily producing a N, N-alkylene-substituted melamine derivative, which is a useful compound group that can be widely used as various resin materials and flame-retardant materials, in high yield.

[0014]

That is, the present invention provides dicarbonyl substituted melamine derivatives having at least one or more amino groups on a ring carbon atom in the presence of a catalyst of Group VIII of the periodic table and a hydrogen-containing gas. The present invention relates to a novel method for producing an N, N-alkylene-substituted melamine derivative, which comprises reacting a compound.

The present invention will be described in more detail below. The melamine derivative having at least one amino group, which is a raw material of the present invention, is a melamine derivative represented by the following general formula (I). General formula (I)

[0016]

[Chemical 7]

[In the formula, at least one of X ¹ , X ² and X ³ represents an amino group, and the others represent NR ¹ R
² groups (in the formula, R ¹ and R ² are each independently a hydrogen atom (except when they are simultaneously hydrogen atoms), C _1-10
Or the alkyl group of R ¹ and R ² together form-(C
_{H 2) m -Y- (CH 2} ) n - group (wherein, Y is a single bond,
—O— or —NR ³ — (R ³ is a hydrogen atom or C _1-10
In the formula, m and n each independently represent an integer of 1 to 3. ) Represents. ) Represents. } Is represented. The preferable melamine derivative of the above general formula (I) is unsubstituted melamine from the viewpoint of industrial raw materials.

In this reaction, it is possible to provide all melamine derivatives having various substituted amino groups, and the synthetic method is s-triazines and derivatives. The Chemi
stryof Heterocyclic Compounds.EM Smolin and L.
Rapoport. IntersciencePublishers Inc., New York.
Detailed on 1959. The dicarbonyl compound that can be used in the present invention has the general formula (II)

[0019]

Embedded image

(Wherein k represents an integer of 1 to 4), and particularly a compound represented by k = 3 or 4, specifically malonaldehyde, succinaldehyde, glutaraldehyde, adipine aldehyde, 2,5-hexanedione, 2,5-octanedione, 3,4-diisopropyl-2,5-hexanedione and the like are preferable.

Examples of the catalyst of Group VIII of the periodic table used in this reaction include iron, cobalt, nickel, ruthenium, rhodium, palladium, osmium, iridium and platinum catalysts. For example, complex catalysts of these elements and supported catalysts. Etc. Among these elements, iron, ruthenium,
Rhodium, palladium and platinum catalysts are preferred, especially
Palladium, platinum complexes and supported catalysts are preferred. More specific examples of the catalyst will be given below.

As the iron catalyst, Raney iron, or a complex of iron pentacarbonyl, iron dodecacarbonyltriiron, iron dichlorobis (triphenylphosphine), iron tetracarbonyl (triphenylphosphine), iron tricarbonylbis (triphenylphosphine), etc. Examples include catalysts. Examples of the cobalt catalyst include Raney cobalt, and complex catalysts such as octacarbonyldicobalt, dodecacarbonyltricobalt, and chlorotris (triphenylphosphine) cobalt.

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

Examples of the ruthenium catalyst include ruthenium-supported silica, ruthenium-supported alumina, ruthenium-supported carbon 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, ruthenium black and the like.

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

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

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

The above-mentioned catalysts may be used alone or in combination. The amount of the Group VIII catalyst used in the periodic table is usually in the range of 0.00001 to 20 mol%, preferably 0.0001 to 10 mol% based on the melamine derivative of the general formula (I). A ligand may be added to the above catalyst, if necessary. Examples of the ligand include trimethylphosphine, triethylphosphine, tributylphosphine, triphenylphosphine, tris (paratolyl) phosphine, tris (2,6)
-Dimethylphenyl) phosphine, sodium diphenylphosphinobenzene-3-sulfonate, bis (3-sulfonatophenyl) phosphinobenzene sodium salt, 1,2-bis (diphenylphosphino) ethane,
1,3-bis (diphenylphosphino) propane, 1,
4-bis (diphenylphosphino) butane, tris (3
-Sulfonatophenyl) phosphine sodium salt and other monodentate and polydentate tertiary phosphines, triethylphosphite, tributylphosphite, triphenylphosphite, tris (2,6-dimethylphenyl) phosphite and other phosphites , Triphenylmethylphosphonium iodide, triphenylmethylphosphonium bromide, triphenylmethylphosphonium chloride,
Triphenylallylphosphonium iodide, triphenylallylphosphonium bromide, triphenylallylphosphonium bromide, tetraphenylphosphonium iodide, tetraphenylphosphonium bromide, phosphonium salts such as tetraphenylphosphonium chloride, triphenyl phosphate, trimethyl phosphate, phosphoric acid Examples thereof include phosphoric acid esters such as triethyl and triallyl phosphate, unsaturated hydrocarbons such as cyclooctadiene and cyclopentadiene, nitriles such as benzonitrile and acetonitrile, and acetylacetone.

The amount of the ligand used is as shown in Table VIII of the Periodic Table.
The range is usually from 0.1 to 10,000 mol%, preferably from 10 to 5,000 mol% with respect to the group metal catalyst.
The reaction temperature is usually room temperature to 500 ° C., preferably 50 to
300 ° C is good. The reaction time depends on the reactivity of the melamine derivative of the general formula (I), but is usually 0.1 to 100 hours, preferably 0.5 to 50 hours.

This reaction proceeds even without solvent, but a solvent can be used if necessary from the viewpoint of operability and the like. The solvent is not particularly limited as long as it is inert to the reaction, for example, tetrahydrofuran, diethyl ether,
Diethylene glycol diethyl ether, ethers such as 1,4-dioxane, methanol, ethanol, 1-
Propanol, 2-propanol, 1-butanol, 2
-Alcohols such as butanol, isobutanol, 2-methyl-2-propanol, cyclohexanol, benzyl alcohol, benzene, toluene, xylene, mesitylene, cumene, chlorobenzene, o-dichlorobenzene, m-dichlorobenzene, p -Aromatic hydrocarbons such as dichlorobenzene and tetrahydronaphthalene, n-hexane,
Aliphatic hydrocarbons such as cyclohexane, n-octane and n-decane, esters such as methyl acetate, ethyl acetate, butyl acetate, ethyl propionate, methyl benzoate and ethyl benzoate, N, N-dimethylformamide, N , N-dimethylacetamide, N-methylpyrrolidone and other amides, 1,3-dimethylimidazolidinone, N, N, N '
, N′-tetramethylurea and other ureas, and water. These can be used alone or in combination. Further, an excess amount of the dicarbonyl compound represented by the general formula (II) may be used as a solvent.

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

As the treatment method after the reaction, the reaction solution is cooled, the unreacted melamine derivative is removed by a means such as filtration, and then the solvent is removed by distillation or the like, if necessary.
After extracting the product as a two-phase system of an organic solvent, the reaction product can be purified and isolated by recrystallization, distillation, chromatographic separation or the like. Further, the metal catalyst is a solid or supported catalyst by filtration or the like, and in the case of an organic metal complex catalyst, the solvent and the product are removed by distillation, recrystallization or the like, and the water-soluble ligand. If you use
It is possible to separate, collect, and reuse in various forms such as a water-soluble metal complex in the aqueous layer by the extraction operation.

The N, N-alkylene group-substituted melamine derivative obtained by directly introducing an alkylene group into the amino group of the present invention as described above is represented by the general formula (III).
It is an alkylene-substituted melamine derivative.

[0034]

[Chemical 9]

[Wherein at least one of X ⁴ , X ⁵ and X ⁶ is represented by the following formula (IV):

[0036]

[Chemical 10]

(In the formula, R ⁴ , R ⁵ and k have the same meanings as described above), an amino group substituted with an alkylene group, and the others are independently NR ¹ R ²
Group (in the formula, R ¹ and R ² are each independently a hydrogen atom, C
_1-10 alkyl group, or when R ¹ and R ² together-
_{(CH 2) m -Y- (CH} 2) n - group (wherein, Y represents a single bond, -O- or -NR ³ - (R ³ is a hydrogen atom or a C
1-10 alkyl group, m and n independently represent an integer of 1 to 3. ) Represents. ) Represents. } Is represented. More preferred N, N-alkylene-substituted melamine derivative of the general formula (III) is that in the general formula (III), at least one of X ⁴ , X ⁵ and X ⁶ is a piperidino group (k = 3) or a pyrrolidino group. It is an N, N-alkylene substituted melamine derivative having a cyclic substituent represented by (k = 2).

As described above, in the present invention, various compounds can be used as the raw material melamine derivative and the dicarbonyl compound, and the product of the method of the present invention can be used as the raw material melamine derivative and the dicarbonyl compound. N, N- having various substituents depending on the combination of kind and amount
An alkylene group-substituted melamine derivative is obtained. As described above, from the viewpoint of availability of raw materials, melamine as a raw material, various melamine derivatives, and dicarbonyl compounds as malonaldehyde, succinaldehyde, glutaraldehyde, adipine aldehyde, 2,5
-Hexanedione, 2,5-octanedione, 3,4-
Representative examples include diisopropyl-2,5-hexanedione and the like, and a combination thereof gives a representative product.

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 (II) of the raw material¹, X²And X³Indicated by
NR other than the amino groups among the substituted groups¹R²
A group or X of the general formula (III) of the product^Four, X ^Fiveand
X⁶Of the substituents represented by
Other NR except amino group¹R²As a group, methyl
Amino group, ethylamino group, isopropylamino group, n-
Butylamino group, i-butylamino group, sec-butylamino
Group, tert-butylamino group, cyclohexylamino group,
Cyclohexylmethylamino group, n-octylamino group,
n-decylamino group, dimethylamino group, diethylamino
Group, diisopropylamino group, di-n-butylamino group,
Di-i-butylamino group, di-sec-butylamino group, methyl
Ru-tert-butylamino group, 4-methylcyclohexyl
Mino group, N-cyclohexyl-N-methylamino group, di
-n-octylamino group, dicyclohexylmethylamino
Groups and the like.

R ¹ and R ² together form-(C
H ₂ ) _m -Y- (CH ₂ ) _n-in the case of becoming a group X ¹ ~
Specific examples of X ⁶ , N, N-alkyleneamino group simultaneously produced by reaction with dialdehyde include aziridino group, pyrrolidino group, 2,5-dimethylpyrrolidino group, piperidino group and 2,6-dimethylpiperidyl group. Group, hexamethyleneimino group, N-methylpiperazino group, morpholino group and the like.

As the other raw material, a dicarbonyl compound, malonaldehyde, succinaldehyde, glutaraldehyde, adipine aldehyde, 2,5
-Hexanedione, 2,5-octanedione, 3,4-
Diisopropyl-2,5-hexanedione and the like can be mentioned. The amount of the above-mentioned dicarbonyl compound to be used can be in any range depending on the purpose, but is generally in the range of 0.01 to 500 times mol, preferably 0.1 to 50 times mol to the raw material melamine derivative. Is effective in terms of reaction and operability.

As a treatment method after completion of the reaction, the unreacted melamine 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 solvent 2 After extracting the product as a phase system, the reaction product can be purified and isolated by recrystallization, distillation, chromatographic separation or the like. In the case of a supported catalyst, the catalyst can be continuously used as it is in the case of a fixed bed, and can be easily separated by filtration or the like in the case of a suspension bed (liquid phase reaction). In the case of an organic metal complex complex catalyst, the solvent, the product is distilled from the residue removed by recrystallization or the like, and when it is made water-soluble by a ligand or the like, it is extracted into water into the aqueous layer. Since various forms can be separated from the production system and recovered, a recycling process that can be used industrially sufficiently can be constructed.

[0043]

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. Reference example shows an example of synthesis from cyanuric chloride. ), A calibration curve was prepared from the pure product and an internal standard substance, and the amount of each product in the reaction product was accurately determined by the internal standard determination method by high performance liquid chromatography. The yields described in the examples are based on the starting triazine compound.

The analytical conditions of the high performance liquid chromatography used are as follows.

Quantitative Analysis Conditions for High Performance Liquid Chromatography (Method for Quantifying Raw Material Melamine) Eluent: CH ₃ CN / H ₂ O = 1/1 (v / v) Detection method: UV 240 nm column; GL Science Inertsil Ph 150 mm x
4.6 mmφ Flow rate; 1.0 ml / min Analytical temperature; 40 ° C Internal standard substance; Phthalic acid di-n-butyl ester (quantification method of product) Detection method; UV 230 nm column; GL Science Inertsil C ₈ 150 mm x
4.6 mm φ Flow rate; 1.0 ml / min Analytical temperature; 35 ° C Internal standard substance; Phthalic acid di (2-ethylhexyl) ester

The following is an example of the synthesis of the triazine derivative used as the standard for quantitative analysis in this example. Reference Example 1 (Synthesis of 2,4-diamino-6-chloro-1,3,5-triazine) 184.5 g (1.0 mol) of cyanuric chloride was dissolved in 800 mL of acetonitrile at room temperature, and then 0
To the solution cooled to 0 ° C, 303.7 g (5.0 mol) of 28% aqueous ammonia solution was added at a reaction temperature of 1 with vigorous stirring.
The solution was added dropwise over 2 hours 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 (Synthesis of 2,4-diamino-6-piperidino-1,3,5-triazine) 2,4-Diamino-6-chloro-1,3,5-triazine synthesized in Reference Example 1 14.5g
(0.1 mol), 100 mL of water and 34.
0 g (0.4 mol) of the mixed solution was heated with stirring, and finally reacted at reflux temperature for 5 hours. After cooling the reaction solution, the product was filtered off, washed thoroughly with a large amount of water, and then washed with toluene. B) 70% under vacuum
18.2 g of the indicated compound by drying at 6 ° C for 6 hours.
(Yield 94%) was obtained. Melting point; 210 [deg.] C.

Reference Example 3 (Synthesis of 2-amino-4,6-dipiperidino-1,3,5-triazine) 18.5 g (0.1 mol) of cyanuric chloride was dissolved in 150 mL of acetonitrile and cooled to 0 ° C. While stirring the solution, 8.5 g of piperidine (0.1 g
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, 10.0 g (0.1 mol) of potassium hydrogen carbonate in 100 mL of water
The solution was added dropwise at the same temperature and stirred for 3 hours. 2,4-dichloro-6-piperidino-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 piperidine 34.
0 g (0.4 mol) was added, and the mixture was reacted under heating under reflux for 5 hours. After cooling, 200 mL of toluene was added and vigorously stirred, and then the aqueous layer was separated. Furthermore, the toluene layer is mixed with water 1
After washing three times with 50 mL, toluene was distilled off from the organic layer under heating and reduced pressure to give the title compound as 24.
1 g (yield 92%) was obtained. Melting point; 200 ° C.

Reference Example 4 (Synthesis of 2,4,6-tripiperidino-1,3,5-triazine) 18.5 g (0.1 mol) of cyanuric chloride was dissolved in 150 mL of acetonitrile, and the solution was cooled to 0 ° C. With stirring, a solution of 17.0 g (0.2 mol) of piperidine 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 20.0 g (0.2 mol) of potassium hydrogen carbonate in 100 mL of water was added dropwise at the same temperature. Then, the reaction temperature was gradually raised and stirring was continued at 45 ° C. for 8 hours. 2-chloro-4,6-dipiperidino-1,3 by high performance liquid chromatography
After confirming that the conversion to 5-triazine was completed, it was cooled and the product was filtered. After thoroughly washing the filter cake with a large amount of water, the 2-chloro-4,6-dipiperidino-
1,3,5-Triazine was suspended in 100 mL of water, 34.0 g (0.4 mol) of piperidine was added, and the mixture was further reacted under heating under reflux for 6 hours. After cooling, toluene 200
After adding mL and stirring vigorously, the aqueous layer was separated. Furthermore, after washing the toluene layer three times with 150 mL of water,
Toluene was distilled off from the organic layer under heating and reduced pressure to obtain 31.7 g (yield 96%) of the title compound. Melting point; 219 [deg.] C.

Reference Example 5 (4,6-diamino-2-cyclohexylamino-1,
Synthesis of 3,5-triazine) 2, synthesized in Reference Example 1
4-diamino-6-chloro-1,3,5-triazine 1
A mixture of 4.5 g (0.1 mol) and 280 mL of water was heated to a temperature of 85 ° C. to give 29.7 g of cyclohexylamine.
(0.3 mol) was added dropwise over 2 hours and further reacted at the same temperature for 1 hour. Continuously 6.0 g of sodium hydroxide in water 3
The 0 mL solution was added dropwise at the same temperature over 1 hour, and the reaction was continued for 1 hour. Add 200 mL of toluene to the reaction mixture, and add 8
The mixture was stirred at 5 ° C for 1 hour and cooled to room temperature while continuing stirring. The product was separated from the reaction solution by filtration and toluene 100 was added.
The product was washed twice with mL and twice with 100 mL of water, and the filtered product was dried under vacuum at 70 ° C. for 6 hours to obtain 17.5 g (yield 84%) of the title compound. Melting point; 151 [deg.] C.

Reference Example 6 (2-amino-4,6-bis (cyclohexylamino))
Synthesis of -1,3,5-triazine) Cyanuric chloride 1
8.5 g (0.1 mol) of acetonitrile was dissolved in 500 mL of acetonitrile, and while stirring the solution cooled to 0 ° C., cyclohexylamine 9.9 g (0.1 mol), triethylamine 10.5 g (0.104 mol) and A solution of 330 mL of water was added dropwise over 3 hours so that the reaction temperature did not exceed 5 ° C. After continuing stirring at the same temperature for 2 hours, 683 mL of 28% ammonia aqueous solution was added dropwise at the same temperature, and stirring was performed at 5 ° C for 1 hour, 20 ° C for 1 hour, and 50 ° C for 1 hour.
Subsequently, 55.5 g (0.56 mol) of cyclohexylamine was added at a reaction temperature of 60 ° C or lower, and the mixture was reacted at 70 ° C for 4 hours. Further, add 1600 mL of water to the reaction solution at a temperature of 70
The solution was added dropwise while maintaining the temperature at 0 ° C, and then gradually cooled to 10 ° C. After cooling, the product was separated from the reaction solution by filtration, and the water was 660 m.
After washing 5 times with L, the filtered product was dried under vacuum at 70 ° C. for 6 hours to obtain 16.4 g (yield 56%) of the title compound. Melting point; 153 [deg.] C.

Reference Example 7 (2,4,6-tris (cyclohexylamino) -1,
Synthesis of 3,5-triazine) 18.5 g of cyanuric chloride
(0.1 mol) was dissolved in 400 mL of 1,4-dioxane, and 60.2 g (0.61 mol) of cyclohexylamine was added at a reaction temperature of 5 while stirring the solution heated to 50 ° C.
The solution was added dropwise over 2 hours so that the temperature did not exceed 0 ° C. While continuing stirring, the temperature was raised to 85 ° C. and 60.2 g (0.61 mol) of cyclohexylamine was added dropwise while maintaining the temperature. Then, the temperature was raised again and the reaction was carried out at a reaction temperature of 95 ° C. for 6 hours. 230 g of water was added to the reaction solution so that the temperature did not fall below 90 ° C., and then cooled to room temperature with stirring. The product was separated from the reaction solution by filtration, washed with 150 mL of water four times, and the filtered product was dried under vacuum at 70 ° C. for 6 hours to obtain 34.2 g (yield 91%) of the title compound. Melting point; 225 [deg.] C.

Example 1 (Synthesis of piperidinotriazine derivative from melamine)

[0054]

[Chemical 11]

In a stainless steel autoclave with an internal volume of 40 mL, 1.26 g (10 mmol) of melamine, 3.00 g (15 mmol) of glutaraldehyde (50% aqueous solution), 5% Pd-C408 mg, 1,4-dioxane 1
After 0 mL was charged and the inside of the reactor was sufficiently replaced with nitrogen, hydrogen gas was introduced at 100 kg / cm ² , the temperature was raised to 180 ° C., and the mixture was reacted for 6 hours while stirring. After cooling, the catalyst and unreacted melamine were separated from the reaction solution, and unreacted melamine in the crystals and in the solution was quantified by high performance liquid chromatography. As a result, the raw material conversion rate was 73.5%. The product in the solution was quantified by high performance liquid chromatography using a standard product. As a result, 2,4-diamino-6-piperidino-1,3,5-triazine was 26.3%, 2-amino-4, 28.8% of 6-dipiperidino-1,3,5-triazine, 2,4,6-tripiperidino-1,3,5
-Triazine was produced in a yield of 14.8%, respectively.
The reaction solution was concentrated under reduced pressure and then subjected to silica gel column chromatography (eluent; ethyl acetate: hexane =
When separated and purified with 1: 1), 2,4-diamino-6
-434 mg of piperidino-1,3,5-triazine
(Colorless crystals, melting point 210 ° C.), 2-amino-4,6-dipiperidino-1,3,5-triazine 694 mg (colorless crystals, melting point 200 ° C.), 2,4,6-tripiperidino-1,3,5 -444 mg (colorless crystals, melting point 219 ° C) of triazine, each isolated as pure product.

Example 2 (Synthesis of piperidinotriazine derivative from melamine) 1.26 g (10 mmol) of melamine, 1.40 g (7 mmol) of glutaraldehyde (50% aqueous solution) were placed in a stainless steel autoclave having an internal volume of 40 mL. 5% Pd
-C 408 mg and 1,4-dioxane 10 mL were charged, the inside of the reactor was sufficiently replaced with nitrogen, and then hydrogen gas was introduced at 100 kg / cm ² , and the temperature was raised to 180 ° C, and the reaction was carried out for 6 hours while stirring. It was After cooling, the catalyst and unreacted melamine were separated from the reaction solution and the unreacted melamine in the crystals and in the solution was quantified by high performance liquid chromatography. As a result, the raw material conversion rate was 36.2%. The product in the solution was quantified by high performance liquid chromatography using a standard product. As a result, 2,4-diamino-6-piperidino-1,
3,5-triazine 18.6%, 2-amino-4,6
-Dipiperidino-1,3,5-triazine is 11.4
%, 2,4,6-tripiperidino-1,3,5-triazine was produced in a yield of 5.0%.

Example 3 (Synthesis of piperidinotriazine from melamine) Content 4
Melamine 1. was added to a 0 mL autoclave made of stainless steel.
26 g (10 mmol), glutaraldehyde (50%
Aqueous solution) 8.01 g (40 mmol), 5% Pd-C2
After charging 00 mg and 10 mL of 1,4-dioxane and thoroughly replacing the inside of the reactor with nitrogen, 100 kg of hydrogen gas was added.
introduced at / cm ^2, after raising the temperature to a temperature 180 ° C., stirring 1
The reaction was carried out for 8 hours. After cooling, the catalyst and the unreacted melamine were separated from the reaction solution, and the unreacted melamine in the crystals and in the solution was quantified by high performance liquid chromatography. As a result, the raw material conversion rate was 99.2%. The product in the solution was quantified by high performance liquid chromatography using a standard product. As a result, 2,4-diamino-6-piperidino-1,3,5-
Triazine 27.0%, 2-amino-4,6-dipiperidino-1,3,5-triazine 40.5% 2,
2,6-Tripiperidino-1,3,5-triazine is 2
It was produced in a yield of 9.3%.

Example 4 (Synthesis of piperidinotriazine derivative from 2-N-diethylmelamine)

[0059]

[Chemical 12]

1.82 g (10 mmol) of 2-N-diethylmelamine and 6.0% of glutaraldehyde (50% aqueous solution) were placed in a stainless steel autoclave having an internal volume of 40 mL.
0 g (30 mmol), 5% Pd-C 408 mg, 1,
After charging 10 mL of 4-dioxane and sufficiently replacing the inside of the reactor with nitrogen, hydrogen gas was introduced at 100 kg / cm ² ,
After the temperature was raised to 180 ° C., the reaction was carried out for 12 hours while stirring. After cooling, the catalyst was separated from the reaction solution by filtration, and the unreacted raw materials in the solution were quantified by high performance liquid chromatography. As a result, the raw material conversion rate was 98.5%. The product in the solution was quantified by high performance liquid chromatography using a standard product, and as a result, 2-amino-4-diethylamino-6-piperidino-1,3,5-triazine was 59.6% and 2-diethylamino- 4,6-dipiperidino-1,3,5-triazine was produced in a yield of 32.9%.

Example 5 (Synthesis of piperidinotriazine derivative from butylaminotriazine)

[0062]

[Chemical 13]

2-amino-4,6-bis (dibutylamino) was placed in a stainless steel autoclave having an internal volume of 40 mL.
-1,3,5-triazine 1.75 g (5 mmol),
Glutaraldehyde (50% aqueous solution) 3.00 g (15
Mmol), 5% Pd-C 408 mg, and 1,4-dioxane 10 mL were charged, the inside of the reactor was sufficiently replaced with nitrogen, and then hydrogen gas was introduced at 100 kg / cm ² , and the temperature was 180
After the temperature was raised to ° C, the reaction was carried out for 12 hours while stirring. After cooling, the catalyst was separated from the reaction solution, and each component in the solution was quantitatively analyzed by high performance liquid chromatography.
Amino-4,6-bis (dibutylamino) -1,3,5
-0.6% of triazine remained, and 2,4-bis (dibutylamino) -6-piperidino-1,3,5-triazine was produced in a yield of 96.3%.

Example 6 (Synthesis of di- and tri-piperidinomelamine from monopiperidinotriazine)

[0065]

Embedded image

2,4-Diamino-6-piperidino-1,3,4 was placed in a stainless steel autoclave having an internal volume of 40 mL.
5-triazine 1.94 g (10 mmol), glutaraldehyde (50% aqueous solution) 6.00 g (30 mmol), 5% Pd-C 408 mg, 1,4-dioxane 1
After 0 mL was charged and the inside of the reactor was sufficiently replaced with nitrogen, hydrogen gas was introduced at 100 kg / cm ² , the temperature was raised to 170 ° C., and the reaction was carried out for 10 hours while stirring. After cooling, the catalyst was separated from the reaction solution, and the composition of each component in the solution was quantitatively analyzed by high performance liquid chromatography.
12.1% of diamino-6-piperidino-1,3,5-triazine remained, and 2-amino-as a product.
4,6-dipiperidino-1,3,5-triazine is 5
3.4%, 2,4,6-tripiperidino-1,3,5-
Triazine was produced in a yield of 29.5%.

Example 7. Synthesis of pyrrolidinotriazine derivatives from melamine

[0068]

[Chemical 15]

1.26 g (10 mmol) of melamine, 2,5
-Hexanedione 6.84 g (60 mmol), 5% P
After charging d-C 408 mg and 1,4-dioxane 50 mL and thoroughly replacing the inside of the reactor with nitrogen, hydrogen gas was introduced at 50 kg / cm ² , and the temperature was raised to 180 ° C., and the reaction was continued for 12 hours while stirring. Let After cooling, the catalyst and unreacted melamine were separated from the reaction solution, and unreacted melamine in the crystals and in the solution was quantified by high performance liquid chromatography. As a result, the raw material conversion rate was 31.5%. The product in the solution was quantified by high performance liquid chromatography using a standard product. As a result, 2,4-diamino-6- (2,5-dimethylpyrrolidin-1-yl) -piperidino-1,3,5- Triazine 12.9%, 2-amino-4,6-bis (2,5-dimethylpyrrolidin-1-yl) -piperidino-1,3,5-triazine 14.2% 2,4,6
-Tris (2,5-dimethylpyrrolidin-1-yl)-
Piperidino-1,3,5-triazine was produced in a yield of 3.5%.

Example 8. Synthesis of pyrrolidinotriazine derivative from melamine 1.26 g (10 mmol) of melamine, 11.4 g (100 mmol) of 2,5-hexanedione, and 5% Pd-C40 were added to a stainless steel autoclave having an internal volume of 40 mL.
After charging 8 mg and 1,4-dioxane 50 mL and thoroughly replacing the inside of the reactor with nitrogen, hydrogen gas was added at 100 kg / c.
After introducing m ² and raising the temperature to 200 ° C., the reaction was stirred for 24 hours while maintaining the hydrogen pressure. After cooling, the catalyst and unreacted melamine were separated from the reaction solution, and unreacted melamine in the crystals and in the solution was quantified by high performance liquid chromatography. As a result, the raw material conversion rate was 62.8%. The product in the solution was quantified by high performance liquid chromatography using a standard product. As a result, 2,4-diamino-6- (2,5-dimethylpyrrolidin-1-yl) -piperidino-1,3,5 was obtained.
23.1% of triazine, 24.8% of 2-amino-4,6-bis (2,5-dimethylpyrrolidin-1-yl) -piperidino-1,3,5-triazine, 2,4,6
-Tris (2,5-dimethylpyrrolidin-1-yl)-
Piperidino-1,3,5-triazine was produced in a yield of 13.2%.

[0071]

According to the method of the present invention, the melamine derivative 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 various The N, N-alkylene-substituted melamine derivative, which is a useful compound group widely used as a resin material and a flame-retardant material, can be easily produced in high yield.

The various N, N-of the products obtained according to the invention
The alkylene-substituted melamine derivative is generally obtained as a mixture, and these products can be separated in a pure form by a general organic compound separation method, and can be used for the various applications described above. Further, depending on the field of use (especially in the case of flame retardants for resins, modifying additives as plasticizers, etc.), the reaction mixture can be used without being particularly separated.

Furthermore, many N, N-alkylene-substituted melamine derivatives obtained by this reaction have conventionally been relatively difficult or expensive to synthesize, and are physically soluble in water and various organic solvents. In addition, many compounds are interesting in terms of stability at high temperature, melting point, boiling point, basicity, etc., and it is considered that their applications will expand more than ever before.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification number Reference number within the agency FI Technical indication location // C07B 61/00 300 (72) Inventor Yasuo Fukue 722 Tsuboi-cho, Funabashi-shi, Chiba 1 Nissan Chemical Central Research Institute of Industry Co., Ltd. (72) Inventor Akio Kitagawa 3-7-1 Kandanishikicho, Chiyoda-ku, Tokyo Nissan Chemical Industry Co., Ltd.

Claims (9)

[Claims] 1. A compound of the general formula (I) [In the formula, at least one or more of X ¹ , X ² and X ³ represents an amino group, and the others represent an NR ¹ R ² group {in the formula,
R ¹ and R ² are each independently a hydrogen atom (except when they are simultaneously hydrogen atoms), a C _1-10 alkyl group,
Or R ¹ and R ² together form-(CH ₂ ) _m -Y-
(CH _{2) n} - group (wherein, Y represents a single bond, -O- or -
NR ³ — (R ³ represents a hydrogen atom or a C _1-10 alkyl group, and m and n independently represent an integer of 1 to 3.)
Represents ) Represents. } Is represented. ] In the presence of a catalyst of Group VIII of the periodic table and a hydrogen-containing gas, a melamine derivative represented by the general formula (II) (Wherein R ⁴ and R ⁵ represent a hydrogen atom or a C _1-10 alkyl group, and k represents an integer of 1 to 4), and a dicarbonyl compound represented by the formula: General formula (III): [Wherein at least one of X ⁴ , X ⁵ and X ⁶ is represented by the following formula (IV): (In the formula, R ⁴ , R ⁵ and k have the same meanings as described above.) Represents an amino group substituted with an alkylene group, and the others independently represent an NR ¹ R ² group (in the formula: , R ¹ and R ² are each independently a hydrogen atom, a C _1-10 alkyl group, or R ¹ and R ² are taken together to form-(CH
_{2) m -Y- (CH 2)} n - group (wherein, Y is a single bond, -
O- or -NR ³ - (R ³ represents a hydrogen atom or an alkyl group having C _1-10, m and n is an integer of from 1 independently 3.) Represents the. ) Represents. } Is represented. ] The manufacturing method of the N, N-alkylene substitution melamine derivative represented by these. 2. The method for producing an N, N-alkylene-substituted melamine derivative according to claim 1, wherein the melamine derivative represented by the general formula (I) is an unsubstituted melamine. 3. A dicarbonylation represented by the general formula (II)
R in compound^Four, R ^FiveIs a hydrogen atom or C_1-4Al
A kyl group is represented, and k is an integer of 2 or 3.
Method for producing N, N-alkylene substituted melamine derivative
Law. 4. An N, N-alkylene substituted melamine derivative represented by the general formula (III), wherein an alkylene group and N
The method for producing an N, N-alkylene-substituted melamine derivative according to claim 1, wherein the ring composed of atoms is pyrrolidine (k = 2) or piperidine (k = 3). 5. The N 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. , N-Alkylene-substituted melamine derivative manufacturing method. 6. The N, N-alkylene substituted melamine derivative according to claim 5, wherein the catalyst of Group VIII of the periodic table is at least one catalyst selected from iron, ruthenium, rhodium, palladium and platinum catalysts. Production method. 7. The method for producing an N, N-alkylene-substituted melamine derivative according to claim 6, wherein the catalyst of Group VIII of the periodic table is at least one catalyst selected from palladium and platinum catalysts. 8. Iron, cobalt, nickel, ruthenium,
2. The N according to claim 1, wherein the rhodium, palladium, osmium, iridium and platinum catalysts are complex catalysts of the respective elements.
A method for producing an N-alkylene-substituted melamine derivative. 9. Iron, cobalt, nickel, ruthenium,
9. The N according to claim 8, wherein the rhodium, palladium, osmium, iridium, platinum catalyst is a supported catalyst for each of the elements.
A method for producing an N-alkylene-substituted melamine derivative.