JPH08245599A - Monoalkylation of melamines - Google Patents

Abstract

PURPOSE: To obtain readily and selectively an N-substituted melamine derivative which is useful as an intermediate for various kinds of agrochemicals, medicines and coatings in high yield by selective monoalkylation of a melamine in the presence of a base and an inorganic solid. CONSTITUTION: The reaction of (A) a melamine of formula I (R<1> -R<3> are independently from one another H, a 1-20C alkyl, 2-20C alkenyl) with (B) an organic halide of the formula: R<4> -X (R<4> is a 1-20C alkyl, a 2-20C alkenyl; X is a halogen) are carried out in the presence of a base and one or more inorganic compounds selected from alumina, silica, zeolite, cerite and laminar clay minerals to give (C) an N-substituted melamine derivative of formula II. Melamine is preferably used as component A, while methyl chloride, sec.-butyl chloride, n-butyl chloride or the like may be used as component B.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a method for monoalkylating melamines, which comprises reacting melamines with an organic halide in the presence of a base and an inorganic solid. The melamine derivative obtained by the monoalkylation method of the present invention is used as various fine chemical intermediates for agricultural chemicals, medicines, dyes, paints, etc., and as various resin materials, especially as aminoplast former components, and as flame-retardant materials for resins. Is also a widely used group of useful compounds.

[0002]

2. Description of the Related Art Various synthetic methods of N-monosubstituted melamines have been known in the prior art. For example, general formula (I
V)

[0003]

[Chemical 4]

The compound represented by the formula (wherein R ⁵ and R ⁶ are amino groups and R ⁷ is a normal butyl group) is 2,4-diamino-6-chloro-1,3,5-triazine and normal butyl amine. Have been reported [J.Am Chemical Society (J. Am
er. Chem. Soc), 73, 2984, 1951]. The compound of the general formula (IV) (wherein R ⁵ and R ⁶ are amino groups, and R ⁷ is an octylamino group) is 2,4,6-triamino-1,3,5-triazine (melamine). A synthetic method by the reaction of octylamine hydrochloride with octylamine has been reported [US Pat. No. 2,228,161, 1941]. Generally, in order to synthesize N-mono-substituted melamines using a compound having a triazine skeleton as a raw material, a chlorine atom represented by the former, a case of a substitution reaction of an alkoxy group, an alkylthio group and amines, and a latter reaction The most general case is such a synthesis by a substitution reaction of an amino group with a monoalkylamine. Further, it has been reported that undesired production of isomeramine is prioritized in the reaction using an ordinary alkylating agent using melamine as a raw material [US Pat. No. 2,485,983, 1949].

Another typical synthetic method is the general formula (IV) (wherein R ⁵ and R ⁶ are amino groups, and R ⁷
Represents a tertiary butylamino group. It is a conventional method to synthesize the compound by the cyclization reaction of alkylcyanamides with dicyandiamide (US Pat. No. 2,628,234, 1953). In addition, various 2,4,6-substituted-1,3,5 synthesized from cyanuric chloride
-A derivative of triazine is used as a flame retardant for thermoplastic polymers [JP-A-3-215564]. This Japanese Patent Laid-Open No.
Some of the specific examples of the derivative described in -215564 are shown below.

[0006]

Embedded image

Journal of America Chemicals
Society (J. Amer. Chem. Soc), 73, 2984,
In many cases, the synthetic method of 1954 and similar synthetic methods are complicated because the synthesis of raw materials requires several steps until the final product is produced, and when the alkylthio group is substituted, it is often an industrial problem. By-products such as sulfur compounds are formed. US Pat. No. 2,228,161, 194
The one-year synthetic method requires a high temperature for the reaction and generally has a low yield. 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.

The alkylation reaction by reacting melamine with an alkylating agent is described in [US Pat. No. 2,485,983,
1949] As described above, a synthetic method using a compound having a triazine skeleton, which is generally considered to be easy, such as undesired reaction being prioritized, is not necessarily industrially superior. Cyclization reaction of cyanamides with dicyandiamide, which is an alternative method [US Pat. No. 2,628,2]
No. 34, 1953], selective production of the desired cyclized product requires control of the mixing ratio of raw materials, reaction conditions, etc. and is not necessarily an easy production method.

[0009]

DISCLOSURE OF THE INVENTION The inventors of the present invention have made earnest studies to solve the above problems, and as a result, industrially inexpensive melamines as raw materials, bases and inorganic compounds such as alumina, silica, zeolite and the like. The present invention has been completed on a method for monoalkylating melamines, which comprises reacting with an organic halide in the coexistence of

Further, the substituted melamines obtained by this reaction inhibit the association of multi-molecules due to intermolecular hydrogen bonds originally possessed by aminotriazines, and further improve the lipophilicity, so that they are dissolved in various solvents. Property is 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.

The object of the present invention is to selectively monoalkylate melamines, which are industrially inexpensive, into various agricultural chemicals, pharmaceuticals,
An N-substituted melamine derivative, which is a useful compound group that can be widely used as a fine chemical intermediate for dyes, paints, etc., and as various resin materials and flame-retardant materials, is selectively and easily produced in high yield. The present invention provides a method for monoalkylating melamines that can be used.

[0012]

[Means for Solving the Problems] That is, according to the present invention, a melamine is treated with an organic halide in the presence of a base and one or more inorganic compounds selected from alumina, silica, zeolite, celite or layered clay minerals. The present invention relates to a method for selectively monoalkylating melamines, which comprises reacting and selectively monoalkylating the amino group.

The present invention will be described in more detail below. Melamines, which are the raw materials of the present invention, have the general formula (I)

[0014]

[Chemical 6]

## STR1 ## wherein R ¹ , R ² and R ³ each independently represent a hydrogen atom, a C _1-20 alkyl group and a C _2-20 alkenyl group;
Preferably, R ¹ , R ² and R ³ are melamine which are simultaneously hydrogen atoms. As mentioned above, this reaction can be provided with melamine and N-alkyl or N-alkenyl melamine. Industrially, it is particularly desirable to use melamine, but these are mainly available as the main component or modifier of thermosetting resins, crosslinking agents for baking coatings, and the synthetic method is "s-triazines and derivatives". . "
fromthe series "The Chemistry of Heterocyclic Co
mpounds. "EM Smolin andL. Rapoport. Interscienc
Learn more about e Publishers Inc., New York. 1959.

The organic halide which can be used in the present invention is represented by the general formula (II)

[0017]

[Chemical 7]

[Wherein R ⁴ is a C _1-20 alkyl group (wherein the alkyl group is a hydroxyl group, an alkoxy group, a carboxyl group,
Alkoxycarbonyl group, acyl group, phenyl group, which may be optionally substituted), or C _2-20 alkenyl group (the alkenyl group, hydroxyl group, alkoxy group, carboxyl group, alkoxycarbonyl group, acyl group, phenyl group) Which may be optionally substituted) and X represents a halogen atom. } It is an organic halide represented.

Of these, preferred organic halides are those in which R ⁴ in the general formula (II) is a C _1-20 alkyl group or a C _2-20 alkenyl group. More preferred organic halides are represented by the general formula (I
In I), R ⁴ is an organic halide represented by a C _1-20 alkyl group.

Among them, methyl chloride, methyl bromide, methyl iodide, ethyl chloride, ethyl bromide, ethyl iodide, normal propyl chloride, normal propyl bromide, normal propyl iodide are generally available, including industrial meanings. Dydide, isopropyl chloride, isopropyl bromide, isopropyl iodide, normal butyl chloride, normal butyl bromide, normal butyl iodide, isobutyl chloride, isobutyl bromide, isobutyl iodide, sec-butyl chloride, sec-butyl bromide, tert
-Butyl chloride, tert-butyl bromide, normal amyl chloride, normal amyl bromide,
Isoamyl chloride, isoamyl bromide, neopentyl bromide, normal hexyl chloride, normal hexyl bromide, normal octyl chloride, normal octyl bromide, 2-ethylhexyl chloride, 2-ethylhexyl bromide, normal decyl chloride, normal decyl bromide, normal hexadecyl chloride, Octadecyl chloride, ethylene chlorohydrin, ethylene bromohydrin, chloroethyl methyl ether, monochloroacetic acid, monobromoacetic acid, 2-chloropropionic acid, 2-bromopropionic acid, methyl chloroacetate, methyl bromoacetate, ethyl chloroacetate, bromoacetate Ethyl, chloroacetate-n-butyl, bromoacetate-n-butyl, chloroacetate-
tert-butyl, bromoacetate-tert-butyl, chloroacetone, bromoacetone, benzyl chloride,
Benzyl bromide, benzyl iodide, α-phenethyl chloride, α-phenethyl bromide, β-phenethyl chloride, β-phenethyl bromide, phenacyl chloride, phenacyl bromide, vinyl chloride, vinyl bromide, allyl chloride, allyl bromide, methallyl chloride. , Methallyl bromide, crotyl chloride, crotyl bromide, 3-chloroacrylic acid, methyl 3-chloroacrylate, -tert-butyl 3-chloroacrylate, cinnamyl chloride, cinnamyl bromide and the like.

In this reaction, the organic halide represented by the general formula (II) is selected from a base and alumina, silica, zeolite, celite or layered clay mineral.
The monoalkylation of melamines can be selectively carried out in the presence of one kind or two or more kinds of inorganic compounds. The amount of the organic halide used may be in the range of 0.1 to 20 mol, based on 1 mol of the melamine of the general formula (I).
In order to selectively carry out monoalkylation of the present invention, an organic halide can be highly selectively used on the amino group by using 0.5 to 3.0 mol per mol of the triazine derivative represented by the general formula (I). Monoalkylation is possible.

As the base used in this reaction, it is desirable to use an inorganic base. In particular, salts of alkali metals or alkaline earth metals are desirable, and potassium hydroxide, for example,
Alkali metal hydroxides such as sodium hydroxide and lithium hydroxide, alkaline earth metal hydroxides such as barium hydroxide, strontium hydroxide, calcium hydroxide, and mabnesium hydroxide, potassium carbonate, sodium carbonate, lithium carbonate, etc. Examples thereof include alkali metal carbonates, alkali hydrogen carbonates such as potassium hydrogen carbonate, sodium hydrogen carbonate and lithium hydrogen carbonate, and alkaline earth metal carbonates such as barium carbonate, strontium carbonate, calcium carbonate and mabnesium carbonate. In the reaction, one kind or two or more kinds selected from these inorganic bases are used, and the amount of the base used is 0. 1 with respect to 1 mol of the melamines of the general formula (I).
It is desirable to use about 1 to 20 mol, preferably 0.5 to 5 mol.

Further, in this reaction, the above-mentioned base and alumina,
One or more inorganic compounds selected from silica, zeolite, celite or layered clay minerals are allowed to coexist. The use of this inorganic compound gives suitable results including dispersion of the base during the reaction and post-treatment after the reaction. As the inorganic compound used in the reaction, various compounds can be used as long as they do not change during the reaction.
SM-5, ferrierite, ZSM-11, ZSM-2
3, ZSM-12, offretite, mordenite, L
Type, β type, various zeolites such as faujasite and VPI-5, kaolinite, dickite, nacrite,
Halloysite, pyrophyllite, montmorillonite,
Layered clay minerals such as muscovite, margarite, antigorite, chrysotile, talc, vermiculite, phlogopite, xanthophyllite, chlorite beidellite, nontronite, saponite, hectorite, sauconite, bentonite, kaolin, silica sand, Alumina, silica, alumina-silica, celite (diatomaceous earth) and the like can be mentioned. In the reaction, one kind or two or more kinds of inorganic solids selected from these are used.

In the reaction, the inorganic solid is represented by the general formula (I)
It is desirable to use 10 to 2000 g, preferably 50 to 1500 g, per 1 mol of the melamine. The reaction may be carried by previously supporting the base and the inorganic solid,
It may be used simply as a mixture during the reaction. In this reaction, the following additives may be added to the above reaction system as needed to accelerate the reaction.

Examples of the additives include iodides such as sodium iodide and potassium iodide, tetramethylammonium chloride, tetramethylammonium bromide, tetramethylammonium iodide, tetraethylammonium chloride, tetraethylammonium bromide, tetraethylammonium iodide, Quaternary ammonium salts such as tetrabutylammonium chloride, tetrabutylammonium bromide, trioctylmethylammonium chloride, benzyltriethylammonium chloride and benzyltriethylammonium bromide, 15-crown-5, 18
-Crown-6,1-aza-15-crown-5,1-
Crown ethers such as aza-18-crown-6 and dibenzo-18-crown-6, triphenylmethylphosphonium iodide, triphenylmethylphosphonium bromide, triphenylmethylphosphonium chloride,
Examples thereof include phosphonium salts such as triphenylallylphosphonium iodide, triphenylallylphosphonium bromide, triphenylallylphosphonium bromide, tetraphenylphosphonium iodide, tetraphenylphosphonium bromide and tetraphenylphosphonium chloride.

The amount of the additive used is usually 0.001 to 50 mol%, preferably 0.1 to 10 mol% based on the melamines of the general formula (I). The reaction temperature of this reaction is usually from room temperature to 200 ° C., but preferably 50 to 150 ° C., there is no particular problem in the reaction, and in order to complete the reaction quickly, the boiling point of the solvent used in the reaction is set to the reaction temperature. It is desirable to set the upper limit.

The reaction time depends on the melamine of the general formula (I),
Depending on the reactivity of the organic halide of the general formula (II), it is usually 0.5 to 100 hours, preferably 1 to 50 hours. Since this reaction is mostly solid, it is carried out as a slurry reaction by using a solvent as 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, 1, 4
-Ethers such as dioxane, benzene, toluene, xylene, mesitylene, cumene, chlorobenzene, o-dichlorobenzene, m-dichlorobenzene, p-dichlorobenzene, aromatic hydrocarbons such as tetrahydronaphthalene, n- Hexane, cyclohexane, n-octane, n
-Aliphatic hydrocarbons such as decane, N, N-dimethylformamide, N, N-dimethylacetamide, amides such as N-methylpyrrolidone, 1,3-dimethylimidazolidinone, N, N, N ', N Examples include ureas such as'-tetramethylurea. These can be used alone or in combination. Further, an excess amount of the organic halide represented by the general formula (II) may be used as a solvent.

As a treatment method after the completion of all reactions, after the reaction is completed, unreacted aminotriazines and inorganic compounds are removed by means such as filtration, and then the solvent is removed by distillation or the like, if necessary. After extracting the product as a water-organic solvent two-phase system, the reaction product can be purified and isolated by recrystallization, distillation, chromatographic separation, or the like.

The N-substituted melamine derivative obtained by the method for selectively monoalkylating melamines of the present invention as described above is an N-substituted melamine derivative represented by the general formula (III).

[0030]

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[In the formula, R ¹ , R ² and R ³ each independently represent a hydrogen atom, a C _1-20 alkyl group and a C _2-20 alkenyl group, and R ⁴ is a C _{1-20 group} . Alkyl group (the alkyl group is a hydroxyl group, an alkoxy group, a carboxyl group,
Alkoxycarbonyl group, acyl group, phenyl group may be optionally substituted), or C _2-20 alkenyl group (the alkenyl group is a hydroxyl group, an alkoxy group, a carboxyl group, an alkoxycarbonyl group, an acyl group, phenyl) Optionally substituted with a group). } In this, the preferred product in N- substituted melamine derivative of the general formula (III) R ^1, R ² and R ³ are hydrogen atom, an alkyl group or a C _2-20 of R ⁴ is C _1-20 It is a melamine derivative which is an alkenyl group of.

Further, among them, preferred products are R ¹ and R ² in the N-substituted melamine derivative of the general formula (III).
And R ³ is a hydrogen atom, and R ⁴ is a C _1-20 alkyl group, which is an N-substituted melamine derivative. As described above, in the present invention, various compounds can be used as the raw material melamines and organic halides, and the products obtained by the method of the present invention are various depending on the combination of the raw material melamines and organic halides. The N-substituted melamine derivative of is selectively obtained.

As described above, from the viewpoint of availability of raw materials, melamine and various melamine derivatives are used as raw materials, and organic halides such as various petrochemical products are used as organic halides. Representative products are obtained by the combination of. The range of raw materials applicable to this reaction is not limited by the price and availability of these raw materials, but examples of substituents of the compound represented by the general formula (III) obtained by the combination of the above raw materials Is specifically shown below to further clarify the scope of this reaction.

In the formula, the substituents R ¹ , R ² and R ^{3 in} the general formula (I) of the raw material and the general formula (III) of the product are as follows:
Hydrogen atom, methyl group, ethyl group, normal propyl group,
Isopropyl group, normal butyl group, isobutyl group, s
ec-butyl group, tert-butyl group, normal amyl group, isoamyl group, neopentyl group, normal hexyl group, cyclohexyl group, cyclohexylmethyl group, normal octyl group, 2-ethylhexyl group, nonyl group, decyl group, hexadecyl group, octadecyl group Group, eicosyl group, vinyl group, allyl group, methallyl group, crotyl group, cinnamyl group and the like.

R ³ is a methyl group, an ethyl group, a normal propyl group, an isopropyl group, a normal butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, a normal amyl group, an isoamyl group, a neopentyl group, a normal hexyl group. Group, normal octyl group, 2-
Ethylhexyl group, normal decyl group, normal dodecyl group, normal hexadecyl group, normal octadecyl group, hydroxyethyl group, methoxymethyl group, carboxymethyl group, 1-carboxyethyl group, methoxycarbonyl group, ethoxycarbonyl group, n-butoxycarbonyl group Group, tert-butoxycarbonyl group, acetylmethyl group, propanoylmethyl group, benzyl group, α-phenethyl group, β-phenethyl group, phenacyl group, vinyl group, allyl group, methallyl group, crotyl group, 2-carboxy-1
-Vinyl group, 2-methoxycarbonylvinyl group, 2-t
Examples thereof include ert-butoxycarbonylvinyl group and cinnamyl group.

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, the unreacted aminotriazine derivative is removed together with the inorganic compound by a means such as filtration, and then the solvent is removed by distillation or the like, if necessary, or as a water-organic solvent two-phase system. After extracting the product, the reaction product can be purified and isolated by recrystallization, distillation, chromatographic separation and the like. However, since the desired N-alkyl-substituted melamine derivative obtained by the method of the present invention can be obtained with a high selectivity by the reaction, it is not necessary to separate or purify more than necessary unless it is used in an extremely pure form.

Further, since the filtered inorganic solids adsorb unreacted raw material melamines, they can be recycled by further adding a raw material and a base. Therefore, this reaction can be said to be an extremely efficient method for producing an N-alkyl-substituted melamine derivative including recycling of raw materials.

[0038]

The present invention will be described in more detail below with reference to examples, but the present invention is not limited thereto. In all of the examples, the products were separately synthesized beforehand using the product as a standard product (synthesis method is J. Am. Chem. Soc., 7).
Volume 3, page 2984 (1951), or JP-A-3-
It was carried out according to No. 215564. ), A calibration curve was prepared from the pure product and an internal standard substance, and the amount of each product in the reaction product was accurately determined by the internal standard determination method by high performance liquid chromatography.

The analytical conditions of the high performance liquid chromatography used are as shown below. (Determination method of the raw material melamines) _{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 mmφ flow rate; 1.0 mL / min analysis temperature; 40 ° C. internal standard substance; phthalic acid di-n-butyl ester Detection method; UV 230 nm column; GL Sciences Inertsil C ₈ 150 mm
× 4.6 mmφ flow rate; 1.0 mL / min analysis temperature; 35 ° C. internal standard substance: phthalic acid di (2-ethylhexyl) ester A synthesis example of a standard sample for quantitative analysis synthesized according to the above literature is as follows. This is shown in the reference example. Other standards were also synthesized by the same synthesis method as in this reference example.

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

[0041]

[Chemical 9]

After dissolving 184.5 g (1.0 mol) of cyanuric chloride in 800 mL of acetonitrile at room temperature, 0
To the solution cooled to 0 ° C, 303.7 g (5.0 mol) of 28% aqueous ammonia solution was added at a reaction temperature of 1 with vigorous stirring.
The solution was added dropwise over 2 hours so as to keep the temperature below 0 ° C. After completion of the dropping, cooling was stopped, the mixture was stirred at room temperature for 1 hour, then gradually heated to 45 ° C. and further reacted for 4 hours. After cooling, the product was filtered and washed with a large amount of water. The filtered product was dried under vacuum at 50 ° C. for 6 hours to obtain 115 g (yield 79%) of the title compound.

Reference Example 2 (2.4,6-diamino-2-normal butylamino-
Synthesis of 1,3,5-triazine)

[0044]

[Chemical 10]

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

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

[0047]

[Chemical 11]

18.5 g (0.1 mol) of cyanuric chloride
Was dissolved in 150 mL of acetonitrile, and the solution cooled to 0 ° C. was stirred, and a solution of butylamine 7.3 g (0.1 mol) in 20 mL of water was added dropwise over 1 hour so that the reaction temperature did not exceed 5 ° C. While continuing stirring, a solution of 10.0 g (0.1 mol) of potassium hydrogen carbonate in 100 mL of water was added dropwise at the same temperature, and the mixture was stirred for 3 hours. 2-Butylamino-4,6-dichloro- by high performance liquid chromatography
After confirming that the conversion to 1,3,5-triazine was completed, 24.3 g (0.4 mol) of 28% aqueous ammonia solution was added.
Was added, the temperature was raised to 50 ° C., and the reaction was carried out for 5 hours. After cooling, the product was filtered off and washed thoroughly with plenty of water. The obtained crude product was suspended in 100 mL of water, and butylamine 2
9.2 g (0.4 mol) was added, and the mixture was reacted for 6 hours while heating under reflux. After cooling, 200 mL of toluene was added and vigorously stirred, and then the aqueous layer was separated. Further, the toluene layer was washed three times with 150 mL of water, and then the toluene was distilled off from the organic layer under heating and reduced pressure to give the title compound.
2.1 g (yield 93%) was obtained. Melting point; 73 [deg.] C.

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

[0050]

[Chemical 12]

2,4-Diamino-6 synthesized in Reference Example 1
-Chlor-1,3,5-triazine 14.5 g (0.1
Mol), 50 mL of water, 50 mL of 1,4-dioxane, and 12.9 g (0.1 mol) of normal octylamine were heated with stirring, and finally reacted at reflux temperature for 2 hours. . Then sodium hydroxide 4.0
A 20 mL solution of g (0.1 mol) in water was added dropwise over 1 hour while continuing the reflux, and the reaction was further continued for 2 hours. After cooling the reaction solution, 100 mL of toluene and 100 mL of water were added to extract the product, and the obtained organic layer was sufficiently washed with water. By concentrating the obtained toluene solution under reduced pressure,
23.1 g (yield 97%) of the title compound was obtained. Melting point;
108 ° C.

Examples of the method of the present invention will be listed below.

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

[0054]

[Chemical 13]

3.30 g of potassium hydroxide (85% product,
Alumina (manufactured by Merck & Co., trade name Art 1077 (neutral), 70
˜230 mesh) 10.0 g, and then heated to dryness under reduced pressure. Furthermore, 1.26 g of melamine (0.
01 mol), 1.51 g of normal butyl bromide
(0.011 mol) and 1,4-dioxane 20 mL
Was added and reacted at a temperature of 60 ° C. for 3 hours. After the reaction, insoluble solids were removed by filtration, and the product in the obtained solution was quantified. As a result, the target 2,4-diamino-6-normal butylamino-1,3,5-triazine was obtained in a yield of 31. .5%
Then, 2-amino-4,6-bis (normal butylamino) -1,3,5-triazine was produced in a yield of 1.3%. Moreover, as a result of quantitatively analyzing the melamine derivative in the filter cake, the raw material melamine was 60.5% (conversion rate 3
9.5%), and 2,4-diamino-6-normal butylamino-1,3,5-triazine was included in a yield of 2.3%. The selectivity of monoalkylation in this reaction is
It was 96.3%. Example 2 (2,4-diamino-6-normal butylamino-1,
Synthesis of 3,5-triazine) Sodium hydroxide 2.15
g (93% product, 0.05 mol), alumina (manufactured by Merck & Co., trade name Art1077 (neutral), 70 to 230 mesh) 10.0 g, melamine 1.26 g (0.01 mol), normal butyl bromide 1 0.51 g (0.01
A mixture of 1 mol) and 20 mL of 1,4-dioxane was reacted at a temperature of 60 ° C. for 5 hours. After the reaction, the insoluble solid content was removed by filtration, and the product in the obtained solution was quantified. As a result, the target 2,4-diamino-6-normal butylamino-1,3,5-triazine was obtained in a yield of 26. 2% at 0.5%
-Amino-4,6-bis (normal butylamino)-
1,3,5-triazine was produced in a yield of 1.1%. As a result of quantitative analysis of the melamine derivative in the filter cake, the raw material melamine was 68.6% (conversion rate 31.4%).
%), And 2,4-diamino-6-n-butylamino-1,3,5-triazine was contained in a yield of 3.1%. The selectivity of monoalkylation in this reaction is 96.
4%. Example 3 (2,4-diamino-6-normaloctylamino-
Synthesis of 1,3,5-triazine)

[0056]

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3.30 g of potassium hydroxide (58% product,
Alumina (manufactured by Merck & Co., trade name: Art1097, 70-230) in a solution of 0.05 mol of methanol in 50 mL.
After adding 10.0 g of (mesh), it was heated to dryness under reduced pressure. Furthermore, 1.26 g (0.01 mol) of melamine and 2.42 g (0.0 mol) of normal octyl bromide.
(12 mol) and 1,4-dioxane (20 mL) were added, and the mixture was reacted at a temperature of 80 ° C. for 10 hours. After the reaction, the insoluble solid matter was removed by filtration, and the product in the obtained solution was quantified. As a result, the target 2,4-diamino-6-normaloctylamino-1,3,5-triazine was obtained in a yield of 41. .4%
Then, 2-amino-4,6-bis (normal octylamino) -1,3,5-triazine was produced in a yield of 0.8%. As a result of quantitative analysis of the melamine derivative in the filter cake, the raw material melamine was 56.0% (conversion rate 4
4.0%), and the yield of 2,4-diamino-6-normaloctylamino-1,3,5-triazine is 0.8%.
Was included in. The selectivity of monoalkylation in this reaction was 98.1%. Example 4 (2,4-diamino-6-allylamino-1,3,5-
Synthesis of triazine)

[0058]

[Chemical 15]

3.30 g of potassium hydroxide (85% product,
Zeolum A in 50 mL of methanol (0.05 mol)
-3 (manufactured by Tosoh Corporation, trade name: Zeolite-based adsorbent)
After adding 10.0 g, it was heated under reduced pressure to dryness. Further, 1.26 g (0.01 mol) of melamine, 1.45 g (0.012 mol) of allyl bromide and 20 mL of tetrahydrofuran were added, and the reaction was carried out at a temperature of 70 ° C. for 8 hours. After the reaction, insoluble solids were removed by filtration, and the product in the obtained solution was quantified. As a result, the target 2,4-diamino-6-allylamino-1,3,5-triazine was obtained in a yield of 52.1. %, 2-amino-4,6-bis (allylamino) -1,3,5-triazine was produced in a yield of 1.8%. As a result of quantitative analysis of the melamine derivative in the filter cake, the raw material melamine was 44.2% (conversion rate 55.8%), and 2,4-diamino-6-allylamino-1,3,5-triazine was found to be It was contained in a yield of 2.1%. The selectivity of monoallylation in this reaction is 96.8.
%Met. Example 5 (2,4-diamino-6-normal butylamino-1,
Synthesis of 3,5-triazine)

[0060]

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2.92 g of magnesium hydroxide (0.05
Mol), alumina (manufactured by Merck, trade name Art107)
7, 70-230 mesh) 10.0, melamine 1.2
6 g (0.01 mol), n-butyl iodide 2.21 g (0.012 mol) and 1,4-dioxane 20 mL were added and the reaction was carried out at a temperature of 60 ° C. for 3 hours.
After the reaction, insoluble solid matter was removed by filtration, and the product in the obtained solution was quantified. As a result, the desired 2,4-diamino-6-
Normal butylamino-1,3,5-triazine was obtained in a yield of 47.1%, and 2-amino-4,6-bis (normal butylamino) -1,3,5-triazine was obtained in a yield of 1.6%. Was generated by. As a result of quantitative analysis of the melamine derivative in the filter cake, the raw material melamine was 48.4% (conversion rate 51.6%), and 2,4-diamino-6-normal butylamino-1,3,5- Yield of triazine 2.
It was included at 1%. The selectivity of monoalkylation in this reaction was 96.9%. Example 6 (2,4-diamino-6-benzylamino-1,3,5
-Synthesis of triazine)

[0062]

[Chemical 17]

After adding 10.0 g of alumina (manufactured by Merck & Co., trade name Art1077 (neutral), 70 to 230 mesh) to a solution of 3.30 g (0.05 mol) of potassium hydroxide in 50 mL of methanol, the mixture was placed under reduced pressure. Heat to dryness. Further, 1.26 g (0.01 mol) of melamine, 2.05 g (0.012 mol) of benzyl bromide and 20 mL of 1,4-dioxane were added, and the mixture was reacted at a temperature of 90 ° C for 2 hours. After the reaction, the insoluble solid content was removed by filtration, and the product in the obtained solution was quantified. As a result, the desired 2,4-diamino-6-benzylamino-1,3,3 was obtained.
The yield of 2-triazine was 23.6%, and 2-amino-4,
6-bis (benzylamino) -1,3,5-triazine was produced in a yield of 1.0%. As a result of quantitative analysis of the melamine derivative in the filter cake, the raw material melamine was 73.1% (conversion rate 26.9%), and 2,4-diamino-6-benzylamino-1,3,5-triazine was obtained. Was contained in a yield of 1.2%. The selectivity of monobenzylation in this reaction was 96.1%. Example 7 (2,4-diamino-6-normal butylamino-1,
Synthesis of 3,5-triazine) 3.30 g of potassium hydroxide
After adding 10.0 g of alumina (manufactured by Merck & Co., trade name: Art1077 (neutral), 70 to 230 mesh) to 50 mL of methanol (85% product, 0.05 mol), heated under reduced pressure to dryness. Let Furthermore, melamine 1.
26 g (0.01 mol), normal butyl bromide 1.51 g (0.011 mol), potassium iodide 0.1
7 g (0.001 mol) and 1,4-dioxane 30
mL was added and the reaction was carried out at a temperature of 60 ° C. for 6 hours. After the reaction, insoluble solids were removed by filtration, and the product in the obtained solution was quantified. As a result, the target 2,4-diamino-6-normal butylamino-1,3,5-triazine was obtained in a yield of 4
At 4.1%, 2-amino-4,6-bis (normal butylamino) -1,3,5-triazine was produced in a yield of 1.8%. As a result of quantitative analysis of the melamine derivative in the filter cake, the raw material melamine had a residual rate of 51.7%.
(Conversion rate 48.3%) and 2,4-diamino-6-
Normal butylamino-1,3,5-triazine was contained in a yield of 2.1%. The selectivity of monoalkylation in this reaction was 96.3%. Example 8 (2-amino-4,6-bis (normal butylamino))
Synthesis of -1,3,5-triazine)

[0064]

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3.30 g of potassium hydroxide (85% product,
Alumina (manufactured by Merck & Co., trade name Art 1077 (neutral), 70
˜230 mesh) 10.0 g, and then heated to dryness under reduced pressure. Further, 2,4-diamino-6-normal butylamino-1,3,5-triazine 1.82
g (0.01 mol), normal butyl bromide 1.5
1 g (0.011 mol) and 1,4-dioxane 20
mL was added and the reaction was carried out at a temperature of 60 ° C. for 8 hours. After the reaction, insoluble solids were removed by filtration, and the melamine derivative in the obtained solution was quantified. As a result, the desired 2-amino-4,6
-Bis (normal butylamino) -1,3,5-triazine in a yield of 23.8%, 2,4-diamino- of the raw material
6-Normal butylamino-1,3,5-triazine remained at 72.2%. As a result of quantitative analysis of the melamine derivative in the filter cake, the raw material 2,4-diamino-6-normal butylamino-1,3,5-triazine was 2.1% (conversion rate 25.7%), and 2 of the target
Amino-4,6-bis (normal butylamino) -1,
3,5-triazine was contained in a yield of 0.3%. Selectivity of production of target product in this reaction ((Production yield of target product) /
(Conversion rate of raw material) was 93.8%. Comparative Example 1 (Reaction of melamine and normal butyl bromide) 3.30 g of potassium hydroxide (85% product, 0.05 mol), 1.26 g (0.01 mol) of melamine, 1.51 g (0.011) of normal butyl bromide Mol), 0.17 g (0.001 mol) of potassium iodide and 30 mL of 1,4-dioxane were added, and the mixture was reacted at a temperature of 60 ° C. for 6 hours.
After the reaction, the melamine derivative in the reaction solution was quantified, and as a result, the raw material melamine had a residual rate of 98.5% (conversion rate 1.5%).
The target 2,4-diamino-6-normal butylamino-1,3,5-triazine was obtained in a yield of 0.3%. Comparative Example 2 (Reaction of melamine and normal octyl bromide) 3.30 g of potassium hydroxide (85% product, 0.05 mol), 1.26 g (0.01 mol) of melamine, 2.42 g of normal octyl bromide (0.011) Mol) and 1,4
-Adding 20 mL of dioxane, it was made to react at the temperature of 80 degreeC for 10 hours. After the reaction, the melamine derivative in the reaction solution was quantified. As a result, the raw material melamine had a residual ratio of 99.0% (conversion rate 1.0%), and the target 2,4-diamino-6-normaloctylamino-1 was obtained. , 3,5-Triazine was obtained in a yield of 0.4%.

[0066]

According to the method of the present invention, melamines 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 An N-substituted melamine derivative, which is a useful compound group widely used as a resin material and a flame-retardant material, can be easily produced with high selectivity.

The various N-substituted melamine derivatives of the product obtained in the present invention can be obtained in a highly selective manner in the reaction, and therefore, unless they are used in an extremely pure form, unnecessary separation and purification operations are required. Not. Flame retardants, especially for resins,
In the case of a modifying additive such as a plasticizer, the reaction mixture containing a very small amount of impurities can be used as it is without being particularly separated and purified.

Further, many N-substituted melamine derivatives obtained by this reaction have conventionally been relatively difficult or expensive to synthesize, and their physical properties include solubility in water and various organic solvents, and high temperature. Stability, melting point, boiling point,
Since there are many compounds that are interesting in terms of basicity and the like, their applications are expected to expand more than before.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI Technical display location B01J 29/04 B01J 29/04 X C07B 61/00 300 C07B 61/00 300 (72) Inventor Fukue Yasuo 1 722, Tsuboi-cho, Funabashi, Chiba, Central Research Laboratory, Nissan Chemical Industries, Ltd. (72) Inventor Isao Hashiba, 722, Tsuboi-cho, Funabashi, Chiba Central Research Laboratory, Nissan Chemical Industries, Ltd.

Claims (7)

[Claims] 1. A compound of the general formula (I) (In the formula, R ¹ , R ² and R ³ each independently represent a hydrogen atom, a C _1-20 alkyl group and a C _2-20 alkenyl group.) And a general formula (II ) [Chemical 2] {In the formula, R ⁴ is a C _1-20 alkyl group (wherein the alkyl group is
A hydroxyl group, an alkoxy group, a carboxyl group, an alkoxycarbonyl group, an acyl group or a phenyl group, which may be optionally substituted), or a C _2-20 alkenyl group (the alkenyl group is a hydroxyl group, an alkoxy group, a carboxyl group, Optionally substituted with an alkoxycarbonyl group, an acyl group or a phenyl group), and X represents a halogen atom. } The general formula (III) characterized by reacting an organic halide represented by the following with a base in the presence of one or more inorganic compounds selected from alumina, silica, zeolite, celite or layered clay minerals. ) [Chemical 3] {In the formula, R ¹ , R ² and R ³ each independently represent a hydrogen atom, a C _1-20 alkyl group and a C _2-20 alkenyl group, and R ⁴ is a C _1-20 alkyl group ( The alkyl group is
A hydroxyl group, an alkoxy group, a carboxyl group, an alkoxycarbonyl group, an acyl group or a phenyl group, which may be optionally substituted), or a C _2-20 alkenyl group (the alkenyl group is a hydroxyl group, an alkoxy group, a carboxyl group, Optionally substituted with an alkoxycarbonyl group, an acyl group or a phenyl group). } N-
A method for monoalkylating melamines to obtain a substituted melamine derivative. 2. The method for monoalkylating melamines according to claim 1, wherein the melamines of the general formula (I) are melamines. 3. The monoalkylated melamine according to claim 1, wherein R ⁴ in the organic halide used in the reaction is an organic halide represented by a C _1-20 alkyl group or a C _2-20 alkenyl group. Law. 4. The method for monoalkylating melamines according to claim 3, wherein R ⁴ in the organic halide used in the reaction is an organic halide represented by a C _1-20 alkyl group. 5. In the melamine derivative of the general formula (III) obtained by the reaction, R ¹ , R ² and R ³ are hydrogen atoms, and R ⁴ is a C _1-20 alkyl group or a C _2-20 alkenyl group. The method for monoalkylating melamines according to claim 1, wherein the melamine derivative is 6. A melamine derivative of the general formula (III) obtained by the reaction, wherein R ¹ , R ² and R ³ are hydrogen atoms and R ⁴ is a C _1-20 alkyl group. 5. The method for monoalkylating melamines according to 5. 7. The method for monoalkylating melamines according to claim 1, wherein the base used in the reaction is one or more inorganic bases selected from salts of alkali metals or alkaline earth metals.