KR20190136506A - Manufacturing method of triazine-based compound and derivative thereof - Google Patents

Abstract

The present invention relates to a triazine-based compound, and a method for manufacturing derivatives thereof. The method for manufacturing the triazine-based compound according to an embodiment of the present invention can manufacture the triazine-based compound represented by chemical formula 1 by conducting a reaction of cyanuric chloride, anisole, and resorcinol. The method for manufacturing the triazine-based compound according to an embodiment of the present invention can simplify a reaction step.

Description

Manufacturing method of triazine-based compound and derivatives thereof {Manufacturing method of triazine-based compound and derivative thereof}

The present invention relates to a triazine compound and a method for preparing the derivative thereof, and more specifically 2,4-bis (2,4-dihydroxyphenyl) -6- (4-methoxyphenyl) -1,3,5 It relates to a process for preparing triazine compounds and derivatives thereof.

Skin aging is closely related to the increase of wrinkles, sagging and relaxation. Aging caused by environmental factors such as physiological natural aging and UV exposure is mentioned as the cause of this phenomenon.

In particular, most of the causes of skin aging associated with cosmetics are continuous exposure to ultraviolet rays, which causes deep wrinkles, sagging skin, and uneven spots that damage the appearance of the skin. Histologically, this phenomenon shows that the skin's constant UV exposure causes thinning of the epidermis, decreasing the thickness of the dermis, and severe deformation of elastin, a major component of the elastic fibers present in the skin, forming large molecules in the upper and middle layers of the dermis. Elastotic 'accumulates, which inhibits the normal function of elastic fibers, leading to loss of collagen due to the activity of matrix metalloproteinases (MMPs) and wrinkled skin types that lack elasticity.

Therefore, many studies have been conducted on cosmetics for reducing or retarding the above-described skin aging phenomenon. First of all, there is a method of reducing the penetration of ultraviolet light by using a sunscreen. In addition, much research has been conducted on sunscreen compounds for protecting the skin from ultraviolet rays (particularly UV-A, B).

UV blocking components are known as two kinds of inorganic sunscreens and organic sunscreens, when used together, it is known to exhibit a much higher UV protection effect than when used alone. This is because organic sunscreens only have the ability to absorb UV rays, while inorganic sunscreens have the ability to absorb, scatter and reflect UV rays. This is because the path of light until the UV light penetrates the skin increases, increasing the probability of encountering a component that is capable of absorbing UV light.

Korean Patent Publication No. 10-2008-0051830 Korean Patent Publication No. 10-2015-0122820

The present invention relates to a method for producing a triazine compound and derivatives thereof, specifically 2,4-bis (2,4-dihydroxyphenyl) -6- (4-methoxyphenyl) -1,3,5 Provided are methods for preparing triazine compounds and derivatives thereof.

However, the problem to be solved by the present application is not limited to the problem described above, other problems that are not described will be clearly understood by those skilled in the art from the following description.

One aspect of the present invention provides a method for preparing a triazine-based compound represented by the following Chemical Formula 1 by reacting cyanuric chloride (Cyanuric Chloride), anisole (anisole) and resorcinol (Resorcinol).

[Formula 1]

The reaction is a first step of obtaining an intermediate reactant by reacting cyanuric chloride and anisole; And a second step of obtaining the compound represented by Chemical Formula 1 by reacting the intermediate reactant of the first step with resorcinol.

The first step and the second step may be performed for 3 to 6 hours at a temperature of 20 to 80 ℃.

The molar ratio of cyanuric chloride and anisole in the first step is 1: 0.8 to 5, and the molar ratio of resorcinol to the intermediate reactant is 1.8 to 5 in the second step. Can be.

The reaction may be carried out in a one-step reaction performed by adding cyanuric chloride as a starting material and sequentially adding anisole and resorcinol.

The one-step reaction may be performed by reacting cyanuric chloride and anisole at a temperature of 20 to 80 ° C. for 1 to 4 hours, and then adding resorcinol.

The one-step reaction may be performed by reacting cyanuric chloride and resorcinol at a temperature of 20 to 80 ° C. for 1 to 4 hours, and then adding anisole.

The molar ratio of anisole to cyanuric chloride (Cyanuric Chloride) in the first step reaction may be 1.8 to 5, the molar ratio of resorcinol may be 1.8 to 5.

Method for producing a triazine-based compound according to an embodiment of the present invention can be carried out in the presence of aluminum chloride (AlCl ₃ ).

In the method for preparing a triazine compound according to an embodiment of the present invention, the solvent may be acetone, sulfolane, toluene, benzyl chloride, chloroform and nitrobenzyl chloride ( nitro benzyl chloride, dichloroethane, and methylene chloride.

Method for producing a triazine-based compound according to an embodiment of the present invention may further comprise a purification step further comprising the step of neutralizing the reactants with a base after the reaction, and purified using an organic solvent.

The base is an inorganic base selected from the group consisting of sodium hydroxide, potassium hydroxide, calcium hydroxide, sodium carbonate, potassium carbonate, calcium carbonate, sodium bicarbonate, potassium bicarbonate, sodium phosphate, and sodium hydrogen phosphate, pyridine, trimethylamine, triethyl It may be an organic base selected from the group consisting of amine, diethylamine, dimethylamine, and ammonia water.

The organic solvent may be selected from the group consisting of cyclohexane, toluene, N-methylpyrrolidone, dimethylformamide, methanol, ethanol, isopropanol, butanol, acetone, and ethyl acetate.

The base may be added in a weight ratio of 0.1 to 3 with respect to the reactant, and the organic solvent may be added in a weight ratio of 1 to 10 with respect to the reactant.

The method for preparing a triazine-based compound according to an embodiment of the present invention can simplify the reaction step by selecting an appropriate solvent and adjusting the reaction temperature and reaction time. In addition, by appropriately adjusting the reaction material and the reaction sequence, the reaction step can be reduced, and a higher purity compound can be obtained.

Triazine-based compounds and derivatives thereof according to an embodiment of the present invention can be used as a sunscreen.

The triazine-based compound and derivatives thereof according to the present invention may have the ability to absorb, scatter and reflect ultraviolet rays, and thus may be used to protect human and animal skin as well as substances sensitive to ultraviolet rays from the harmful effects of ultraviolet rays. In addition, the triazine-based compound and derivatives thereof according to the present invention can be used in cosmetic compositions, pharmaceutical compositions and veterinary compositions that require a sunscreen effect.

1 is an NMR spectrum of a triazine-based compound prepared according to an embodiment of the present invention, Figure 2 is an enlarged view of the NMR spectrum.

Hereinafter, with reference to the accompanying drawings will be described in detail the embodiments and embodiments of the present application to be easily carried out by those of ordinary skill in the art.

As those skilled in the art would realize, the described embodiments may be modified in various different ways, all without departing from the spirit or scope of the present invention. In the drawings, parts irrelevant to the description are omitted in order to clearly describe the present invention, and like reference numerals designate like parts throughout the specification.

Throughout this specification, when a member is located "on" another member, this includes not only when one member is in contact with another member but also when another member exists between the two members.

Throughout this specification, when a part is said to "include" a certain component, it means that it can further include other components, without excluding the other components unless specifically stated otherwise. As used throughout this specification, the terms "about", "substantially" and the like are used at, or in the sense of, numerical values when a manufacturing and material tolerance inherent in the stated meanings is indicated, Accurate or absolute figures are used to assist in the prevention of unfair use by unscrupulous infringers. As used throughout this specification, the term "step to" or "step of" does not mean "step for."

Throughout this specification, the term "combination of these" included in the expression of the makushi form means one or more mixtures or combinations selected from the group consisting of constituents described in the expression of the makushi form, wherein the constituents It means to include one or more selected from the group consisting of.

Throughout this specification, the description of "A and / or B" means "A or B, or A and B."

In addition, the same symbol throughout the present specification may have the same meaning unless specifically noted.

The present invention relates to a method for producing a triazine compound, more specifically, a compound represented by the following formula (1), 2,4-bis (2,4-dihydroxyphenyl) -6- (4-methoxyphenyl)- Provided is a method for preparing 1,3,5-triazine (2,4-Bis (2,4-Dihydroxyphenyl) -6- (4-Methoxyphenyl) -1,3,5-Triazine).

[Formula 1]

2,4-bis (2,4-dihydroxyphenyl) -6- (4-methoxyphenyl) -1,3,5-triazine (2,4-Bis (2,4) represented by Chemical Formula 1 -Dihydroxyphenyl) -6- (4-Methoxyphenyl) -1,3,5-Triazine (hereinafter also referred to as 'triazine compound') compounds include cyuric chloride, anisole and resorcinol It can be prepared by reacting (Resorcinol).

The cyanuric chloride (Cyanuric Chloride) may be represented by the following formula A, the anisole (anisole) may be represented by the following formula B, the resorcinol may be represented by the formula (C). .

[Formula A] [Formula B] [Formula C]

According to one embodiment of the present invention, the compound represented by Chemical Formula 1 may be performed through a two-step reaction. More specifically, the first step of obtaining an intermediate reactant by reacting cyanuric chloride and anisole; And reacting the intermediate reactant of the first step with resorcinol to obtain the compound represented by Chemical Formula 1 in the second step.

The first step may be represented as in Scheme 1 below.

Scheme 1

In the first step, as shown in Scheme 1, the compound of Formula A and the compound of Formula B react to form an intermediate reactant (IM), 2,4-dichloro-6- (4-methoxyphenyl) -1,3,5-tri It is possible to produce azine (2,4-Dichloro-6- (4-Methoxyphenyl) -1,3,5-Triazine).

According to one embodiment of the invention, the solvent in the first stage reaction is acetone (acetone), sulfolane (sulfolane), toluene (toluene), benzyl chloride, chloroform and nitro benzyl chloride (nitro) One or more solvents selected from the group consisting of benzyl chloride, dichloroethane, and methylene chloride can be used. In addition, the solvent may be used 100 to 300mL, specifically 150 to 200mL may be used.

In addition, according to one embodiment of the present invention, the first step reaction may be carried out at a temperature of 20 to 80 ℃, specifically, may be carried out at a temperature of 40 to 50 ℃. In addition, the first step reaction may be performed for 3 to 6 hours, specifically, for 2 to 3 hours.

In addition, according to an embodiment of the present invention, the molar ratio of the cyanuric chloride and anisole may be 1: 0.8 to 5, specifically 1: 0.8 to 3.

In addition, according to an embodiment of the present invention, the first step may be performed by a Friedel-Crafts Reaction.

According to one embodiment of the present invention, the first step reaction may be carried out in the presence of aluminum chloride (AlCl ₃ ), the aluminum chloride in a molar ratio of 0.8 to 2 with respect to cyanuric chloride (Cyanuric Chloride) Can be used.

Upon completion of the first step reaction, the solvent may be removed under reduced pressure to obtain an intermediate reactant (IM).

Thereafter, a second step of obtaining the compound represented by Chemical Formula 1 may be performed by reacting the intermediate reactant (IM) with resorcinol (C) as shown in Scheme 2 below.

Scheme 2

According to one embodiment of the invention, the solvent in the second stage reaction is acetone (acetone), sulfolane (sulfolane), toluene (toluene), benzyl chloride, chloroform and nitro benzyl chloride (nitro) One or more solvents selected from the group consisting of benzyl chloride, dichloroethane, and methylene chloride can be used. In addition, the solvent may be used 10 to 100mL, specifically 20 to 40mL may be used.

In addition, according to one embodiment of the present invention, the second step reaction may be carried out at a temperature of 20 to 80 ℃, specifically, may be carried out at a temperature of 40 to 50 ℃. In addition, the second step reaction may be performed for 3 to 6 hours, specifically, for 4 to 5 hours.

Further, according to one embodiment of the present invention, the molar ratio of Resorcinol to the intermediate reactant may be 1.8 to 5, specifically 1.8 to 2.2.

In addition, according to one embodiment of the present invention, the second step may be carried out in the presence of aluminum chloride (AlCl ₃ ). The aluminum chloride may be used in a molar ratio of 0.5 to 1.2 with respect to the intermediate reactant.

When the second step reaction is completed, a compound represented by Chemical Formula 1 may be obtained.

According to an embodiment of the present invention, a compound represented by Chemical Formula 1 may be obtained by reacting cyanuric chloride, anisole, and resorcinol in one step, which is represented by Reaction Scheme 3 below. It may be indicated by.

Scheme 3

According to one embodiment of the present invention, the one-step reaction may be carried out by adding cyanuric chloride (Cyanuric Chloride) as a starting material and sequentially adding anisole and resorcinol. .

According to one embodiment of the present invention, after reacting cyanuric chloride (Cyanuric Chloride) and anisole (anisole) it can be completed by adding Resorcinol to it.

More specifically, cyanuric chloride (Cyanuric Chloride) and anisole (anisole) may be reacted at a temperature of 20 to 80 ℃, specifically, 50 to 60 ℃. This reaction can be carried out for 1 to 4 hours, specifically 2 to 3 hours.

In addition, according to an embodiment of the present invention, the molar ratio of Resorcinol to Cyanuric Chloride may be 1.8 to 5, more specifically 1.8 to 2.2.

In addition, according to one embodiment of the present invention, the reaction between cyanuric chloride and anisole may be performed in the presence of aluminum chloride (AlCl ₃ ). The aluminum chloride may be used in a molar ratio of 0.5 to 1.2 with respect to the cyanuric chloride.

Resorcinol may then be added. Further, according to one embodiment of the present invention, the molar ratio of resorcinol to cyanuric chloride may be 1.8 to 5, more specifically 1.8 to 2.2.

The reaction after addition of resorcinol can be made to react at the temperature of 20-80 degreeC, specifically, the temperature of 40-50 degreeC. This reaction can be carried out for 2 to 6 hours, specifically for 3 to 4 hours. After the reaction is completed, distilled water (H ₂ O) may be added and stirred at room temperature to obtain the desired triazine compound.

In addition, according to one embodiment of the present invention, after reacting cyanuric chloride (Cyanuric Chloride) and resorcinol (Resorcinol) can be added to the anisole (anisole) to complete the reaction.

More specifically, Cyanuric Chloride and Resorcinol may be reacted at a temperature of 20 to 80 ° C., specifically, at a temperature of 50 to 60 ° C. This reaction can be carried out for 1 to 4 hours, specifically 2 to 3 hours.

In addition, according to an embodiment of the present invention, the molar ratio of Resorcinol to Cyanuric Chloride may be 1.8 to 5, more specifically 1.8 to 2.2.

In addition, according to one embodiment of the present invention, the reaction of cyanuric chloride and resorcinol may be performed in the presence of aluminum chloride (AlCl ₃ ). The aluminum chloride may be used in a molar ratio of 0.5 to 1.2 with respect to the cyanuric chloride.

Anisole can then be added. In addition, according to one embodiment of the present invention, the molar ratio of the anisole to the cyanuric chloride (Cyanuric Chloride) may be 1.8 to 5, more specifically 1.8 to 2.2.

The reaction after addition of anisole can be reacted at a temperature of 20 to 80 ° C, specifically 40 to 50 ° C. This reaction can be carried out for 2 to 6 hours, specifically for 3 to 4 hours. After the reaction is completed, distilled water (H ₂ O) may be added and stirred at room temperature to obtain the desired triazine compound.

According to one embodiment of the invention, the solvent in the reaction is acetone (acetone), sulfolane (sulfolane), toluene (benzyl chloride), chloroform (chloroform) and nitro benzyl chloride (nitro benzyl chloride) At least one solvent selected from the group consisting of dichloroethane and methylene chloride may be used. In addition, the solvent may be used 100 to 500mL, specifically 200 to 300mL may be used.

In addition, according to one embodiment of the present invention, the step of purifying the triazine-based compound which is the desired compound obtained in the reaction can be performed. When the reaction is completed, a crude compound may be obtained and purification may be performed.

According to one embodiment of the invention, the purification step may be carried out by neutralizing the crude compound (crude compound) obtained after the reaction with a base, using an organic solvent.

According to one embodiment of the present invention, the base may be used an inorganic base such as sodium hydroxide, potassium hydroxide, calcium hydroxide, sodium carbonate, potassium carbonate, calcium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, sodium phosphate, sodium hydrogen phosphate and the like. . Or organic bases such as pyridine, trimethylamine, triethylamine, diethylamine, dimethylamine, and ammonia water. The base may be added in a weight ratio of 0.1 to 3 relative to the crude compound. More specifically, it may be added in a weight ratio of 1 to 2.

In addition, according to one embodiment of the present invention, the organic solvent may be cyclohexane, toluene, N-methylpyrrolidone, dimethylformamide, methanol, ethanol, isopropanol, butanol, acetone, and ethyl acetate. The organic solvent may be added in a 1 to 10 weight ratio based on the crude compound. More specifically, it may be added in a weight ratio of 2 to 4.

According to one embodiment of the present invention, a triazine-based compound having a purity of 90% or more, specifically 95% or more can be obtained.

The method for preparing a triazine-based compound according to an embodiment of the present invention can simplify the reaction step by selecting an appropriate solvent and adjusting the reaction temperature and reaction time. In addition, by appropriately adjusting the reaction material and the reaction sequence, the reaction step can be reduced, and a higher purity compound can be obtained.

In addition, another embodiment of the present invention provides a derivative of the triazine-based compound. More specifically, the derivative of the triazine-based compound is 2,4-bis {[4- (2-ethylhexyloxy) -2-hydroxy] phenyl} -6- (4-methoxyphenyl represented by the following formula (2): ) -1,3,5-triazine (2,4-Bis {[4- (2-Ethylhexyloxy) -2-Hydroxy] phenyl} -6- (4-Methoxyphenyl) -1,3,5-Triazine) yl Can be.

[Formula 2]

The triazine-based compound derivative represented by Chemical Formula 2 may be obtained by reacting the compound represented by Chemical Formula 1 with 3- (bromoethyl) heptane (3- (bromomethyl) heptane).

This may be represented as in Scheme 4 below, wherein 3- (bromoethyl) heptane may be represented by Formula D of Scheme 4.

Scheme 4

More specifically, the solvent of the reaction may be dimethylformamide (Dimethylformamide, DMF), but is not limited thereto, the solvent may be used 50 to 1000mL, specifically 600 to 700mL may be used.

In addition, according to one embodiment of the present invention, the reaction may be carried out at a temperature of 100 to 140 ℃, specifically, may be carried out at a temperature of 110 to 130 ℃.

In addition, according to one embodiment of the invention, the reaction may also be carried out in the presence of sodium hydroxide or sodium carbonate, potassium carbonate. The sodium hydroxide or sodium carbonate, potassium carbonate may be used in a molar ratio of 1 to 4 with respect to the compound represented by the formula (1).

After the reaction is completed, the solid may be filtered to obtain a triazine derivative represented by Chemical Formula 2.

According to one embodiment of the invention, the triazine-based compound and derivatives thereof may be used as a sunscreen. The triazine-based compound and derivatives thereof according to the present invention may have the ability to absorb, scatter and reflect ultraviolet rays, and thus may be used to protect human and animal skin as well as substances sensitive to ultraviolet rays from the harmful effects of ultraviolet rays. In addition, the triazine-based compound and derivatives thereof according to the present invention can be used in cosmetic compositions, pharmaceutical compositions and veterinary compositions that require a sunscreen effect.

Hereinafter, the embodiments of the present application will be described in more detail, and the scope of the present application is not limited by the present embodiment.

EXAMPLE

Preparation Example 1

To prepare the compound represented by Formula 1, the intermediate reactant was synthesized as follows to obtain the desired compound.

Synthesis of Intermediate Reactant IM (2,4-Dichloro-6- (4-Methoxyphenyl) -1,3,5-Triazine)

Synthesis Example 1

100 g (542 mmol) of cyanuric chloride and 77 g (542 mmol) of anisole were added to 200 mL of sulfolane in a 2 L reactor, and 72 g (542 mmol) of AlCl ₃ (aluminium chloride) was added little by little. The mixture was added separately and then reacted at 40 to 60 ° C. for 2 to 3 hours.

When the reaction was completed, sulfolane was removed under reduced pressure, cooled, and 300 mL of IPA was added to form a solid. The resulting solid was filtered to give the desired 2,4-dichloro-6- (4-methoxyphenyl) -1,3,5-triazine (2,4-Dichloro-6- (4-Methoxyphenyl) -1,3, 5-Triazine) 109 g were obtained. mp 131-134 ° C., ¹ H NMR (δ, DMSO-d ₆ ): 7.96-7.97 (d, 2H), 6.88-6.89 (m, 2H), 3.80-3.82 (s, 3H), m / z [M +1] 256

Synthesis Example 2

Using the same method as in Example 1, using benzyl chloride instead of sulfolane, 2,4-dichloro-6- (4-methoxyphenyl) -1,3,5-triazine 105 g of (2,4-Dichloro-6- (4-Methoxyphenyl) -1,3,5-Triazine) were obtained.

Synthesis Example 3

2,4-dichloro-6- (4-methoxyphenyl) -1,3,5-tri using the same method as in Example 1, but using nitrobenzyl choride instead of sulfolane 102 g of azine (2,4-Dichloro-6- (4-Methoxyphenyl) -1,3,5-Triazine) was obtained.

Synthesis Example 4

Using the same method as in Example 1, using 1,2-Dichloroethane (1,2-Dichloroethane) instead of sulfolane (2,4-dichloro-6- (4-methoxyphenyl) -1, 107 g of 3,5-triazine (2,4-Dichloro-6- (4-Methoxyphenyl) -1,3,5-Triazine) was obtained.

Synthesis Example 5

Use the same method as in Example 1, except using 2,4-dichloro-6- (4-methoxyphenyl) -1,3,5-triazine using methylene chloride instead of sulfolane. 106 g of (2,4-Dichloro-6- (4-Methoxyphenyl) -1,3,5-Triazine) was obtained.

Synthesis Example 6

Using the same method as in Example 1, 2,4-Dichloro-6- (4-Methoxyphenyl) -1,3,5-Triazine 107 g was obtained using toluene instead of sulfolane.

Synthesis Example 7

Use the same method as in Example 1, except using 2,4-dichloro-6- (4-methoxyphenyl) -1,3,5-triazine (2) by using chloroform instead of sulfolane. 108 g of, 4-Dichloro-6- (4-Methoxyphenyl) -1,3,5-Triazine) was obtained.

Example 1

Synthesis of 2,4-Bis (2,4-Dihydroxyphenyl) -6- (4-Methoxyphenyl) -1,3,5-Triazine

2,4-dichloro-6- (4-methoxyphenyl) -1,3,5-triazine synthesized in Synthesis Example 1 (2,4-Dichloro-6- (4-Methoxyphenyl) -1,3, 30 g (76.7 mmol) of 5-Triazine) and 16.88 g (153.4 mmol) of Resorcinol were added to 30 mL of Sulfolane, and 7.16 g (53.7 mmol) of AlCl ₃ was added little by little at 40 ° C to 50 ° C. It reacted for 5 hours. When the reaction was completed, 300 mL of H ₂ O was slowly added thereto, followed by stirring for 2 hours, and the resulting solid was filtered to give the desired 2,4-bis (2,4-dihydroxyphenyl) -6- (4-methoxyphenyl)- 48 g of 1,3,5-triazine (2,4-Bis (2,4-Dihydroxyphenyl) -6- (4-Methoxyphenyl) -1,3,5-Triazine) was obtained. mp> 300 ° C., ¹ H NMR (δ, DMSO-d ₆ ): 10.45 (bs, -OH), 8.15 to 8.16 (dm, 2H), 8.13 to 8.14 (m, 2H), 7.00 to 7.01 (m, 2H ), 6.44 ~ 6.46 (m, 2H), 6.13 ~ 6.14 (s, 2H), 3.80 ~ 3.85 (s, 3H), m / z [M + 1] 404

Example 2

Using the same method as Example 1, 2,4-dichloro-6- (4-methoxyphenyl) -1,3,5-triazine synthesized in Synthesis Example 2 (2,4-Dichloro-6- (4-Methoxyphenyl) -1,3,5-Triazine) and benzyl chloride instead of Sulfolane to the desired 2,4-Bis (2,4-Dihydroxyphenyl) -6- 43 g of (4-Methoxyphenyl) -1,3,5-Triazine were obtained.

Example 3

Using the same method as Example 1, 2,4-dichloro-6- (4-methoxyphenyl) -1,3,5-triazine synthesized in Synthesis Example 3 (2,4-Dichloro-6- 2,4-bis (2,4-dihydroxyphenyl) by using (4-Methoxyphenyl) -1,3,5-Triazine, and nitrobenzyl chloride instead of Sulfolane ) -6- (4-methoxyphenyl) -1,3,5-triazine (2,4-Bis (2,4-Dihydroxyphenyl) -6- (4-Methoxyphenyl) -1,3,5-Triazine) 41 g was obtained.

Example 4

Using the same method as Example 1, 2,4-dichloro-6- (4-methoxyphenyl) -1,3,5-triazine synthesized in Synthesis Example 4 (2,4-Dichloro-6- 2,4-bis (2,4-dihydroxyphenyl)-using (4-Methoxyphenyl) -1,3,5-Triazine) and 1,2-Dichloroethane instead of Sulfolane. 46 g of 6- (4-methoxyphenyl) -1,3,5-triazine (2,4-Bis (2,4-Dihydroxyphenyl) -6- (4-Methoxyphenyl) -1,3,5-Triazine) Got it.

Example 5

Using the same method as Example 1, 2,4-dichloro-6- (4-methoxyphenyl) -1,3,5-triazine synthesized in Synthesis Example 5 (2,4-Dichloro-6- 2,4-bis (2,4-dihydroxyphenyl) by using (4-Methoxyphenyl) -1,3,5-Triazine and using methylene chloride instead of Sulfolane 43 g of -6- (4-methoxyphenyl) -1,3,5-triazine (2,4-Bis (2,4-Dihydroxyphenyl) -6- (4-Methoxyphenyl) -1,3,5-Triazine) Got.

Example 6

Using the same method as Example 1, 2,4-dichloro-6- (4-methoxyphenyl) -1,3,5-triazine synthesized in Synthesis Example 6 (2,4-Dichloro-6- 2,4-bis (2,4-dihydroxyphenyl) -6 by using (4-Methoxyphenyl) -1,3,5-Triazine, and toluene instead of Sulfolane. 41 g of-(4-methoxyphenyl) -1,3,5-triazine (2,4-Bis (2,4-Dihydroxyphenyl) -6- (4-Methoxyphenyl) -1,3,5-Triazine) was obtained .

Example 7

Using the same method as Example 1, 2,4-dichloro-6- (4-methoxyphenyl) -1,3,5-triazine synthesized in Synthesis Example 7 (2,4-Dichloro-6- 2,4-bis (2,4-dihydroxyphenyl) -6 by using (4-Methoxyphenyl) -1,3,5-Triazine, and chloroform instead of Sulfolane. 43 g of-(4-methoxyphenyl) -1,3,5-triazine (2,4-Bis (2,4-Dihydroxyphenyl) -6- (4-Methoxyphenyl) -1,3,5-Triazine) was obtained .

Preparation Example 2

To prepare the compound represented by Formula 1, the target compound was obtained through a one-step reaction as follows.

Example 8

Synthesis of 2,4-Bis (2,4-Dihydroxyphenyl) -6- (4-Methoxyphenyl) -1,3,5-Triazine

100 g (542 mmol) of cyanuric chloride, 70 mL (650 mmol) of anisole and 300 mL of sulfolane were added to a 2 L reactor, and 72 g (542 mmol) of AlCl _{3 was} slowly added in portions. The reaction was carried out at 50 ° C. to 60 ° C. for 2 hours, and immediately after adding 119 g (1084 mmol) of Resorcinol, the reaction was performed at 40 to 50 ° C. for 4 hours. After completion of the reaction, 600 mL of H ₂ O was slowly added, stirred at room temperature for about 12 hours, and filtered to obtain 320 g of crude compound.

Example 9

Synthesis of 2,4-Bis (2,4-Dihydroxyphenyl) -6- (4-Methoxyphenyl) -1,3,5-Triazine

100 g (542 mmol) of Cyanuric Chloride, 119 g (1084 mmol) of Resorcinol and 300 mL of Sulfolane were added to a 2 L reactor, and 72 g (542 mmol) of AlCl ₃ were slowly added in portions. The reaction inside temperature was 50 ℃ ~ 60 ℃ and reacted for 2 hours, immediately after adding 70mL (650 mmol) of anisole (Anisole) was reacted for 4 hours at 40 ~ 50 ℃. After completion of the reaction, 600 mL of H ₂ O was slowly added, stirred at room temperature for about 12 hours, and filtered to obtain 318 g of crude compound.

Example 10

Using the same method as Example 8, but using Benzyl Chloride instead of Sulfolane, the desired compound 2,4-Bis (2,4-Dihydroxyphenyl) -6- (4-Methoxyphenyl) -1 3,3,5-Triazine was obtained by 312 g of a crude compound.

Example 11

Using the same method as Example 8, but using Nitrobenzyl Chloride instead of Sulfolane, the desired compound 2,4-Bis (2,4-Dihydroxyphenyl) -6- (4-Methoxyphenyl)- 309 g of 1,3,5-Triazine was obtained as crude.

Example 12

Using the same method as Example 8, but using 1,2-dichloroethane (1,2-Dichloroethane) instead of Sulfolane (2,4-Bis (2,4-Dihydroxyphenyl) -6- 319 g of (4-Methoxyphenyl) -1,3,5-Triazine was obtained as crude.

Example 13

Using the same method as Example 9, but using methylene chloride (Methylene Chloride) instead of Sulfolane (2,4-Bis (2,4-Dihydroxyphenyl) -6- (4-Methoxyphenyl) -1 310 g of, 3,5-Triazine was obtained as crude.

Example 14

Using the same method as Example 9, but using toluene instead of Sulfolane (Toluene) to the desired compound 2,4-Bis (2,4-Dihydroxyphenyl) -6- (4-Methoxyphenyl) -1,3 310g of, 5-Triazine was obtained as crude.

Example 15

Using the same method as Example 9, but using chloroform (Chloroform) instead of Sulfolane (2,4-Bis (2,4-Dihydroxyphenyl) -6- (4-Methoxyphenyl) -1,3 311 g of, 5-Triazine was obtained as crude.

[Tablet 1]

300 g of the crude compound obtained in Examples 8 and 15 was added to 1800 mL of methanol, dissolved by heating, and then, 100 mL of a 10% sodium hydroxide aqueous solution was added thereto, followed by stirring at room temperature for 12 hours. The resulting solid was filtered to obtain 142 g of 2,4-Bis (2,4-Dihydroxyphenyl) -6- (4-Methoxyphenyl) -1,3,5-Triazine having a purity of 95% or more.

[Tablet 2]

300 g of the crude compound obtained in Examples 8 and 15 was added to 1800 mL of isopropanol, and dissolved by heating. Then, 100 mL of 10% sodium carbonate aqueous solution was added thereto and stirred at room temperature for 12 hours. The resulting solid was filtered to obtain 142 g of 2,4-Bis (2,4-Dihydroxyphenyl) -6- (4-Methoxyphenyl) -1,3,5-Triazine having a purity of 95% or more.

[Tablet 3]

300 g of the crude compound obtained in Examples 8 and 15 was added to 1800 mL of methanol and N-methylpyrrolidone 1: 1 mixed solution, dissolved by heating, and then ammonia 100 mL was added and stirred at room temperature for 12 hours. The resulting solid was filtered to obtain 142 g of 2,4-Bis (2,4-Dihydroxyphenyl) -6- (4-Methoxyphenyl) -1,3,5-Triazine having a purity of 95% or more. mp> 300 ° C., ¹ H NMR (δ, DMSO-d ₆ ): 10.45 (bs, -OH), 8.15 to 8.16 (dm, 2H), 8.13 to 8.14 (m, 2H), 7.00 to 7.01 (m, 2H ), 6.44 ~ 6.46 (m, 2H), 6.13 ~ 6.14 (s, 2H), 3.80 ~ 3.85 (s, 3H), m / z [M + 1] 404

1 is an NMR spectrum of a compound obtained after the crude compound obtained in Example 8 was purified by the method of Purification 3, and FIG. 2 is an enlarged view of the NMR spectrum.

Example 16

2,4-bis (2,4-dihydroxyphenyl) -6- (4-methoxyphenyl) -1,3,5-triazine (2,4-Bis (2,4-Dihydroxyphenyl) -6- (4-Methoxyphenyl) -1,3,5-Triazine) Derivative Synthesis

In a 2 L reactor, 140 g (347.1 mmol) of 2,4-bis (2,4-dihydroxyphenyl) -6- (4-methoxyphenyl) -1,3,5-triazine were added to 700 mL of DMF, followed by Na ₂ 91.96 g (798.2 mmol) of CO ₃ was added thereto, and then 137 mL (763.6 mmol) of 3- (bromomethyl) heptane was added thereto, followed by heating to 125 ° C. After reaction by TLC until the reaction disappeared, the solid was filtered and the filtered filtrate was concentrated to remove DMF. Then, 700 mL of ethyl acetate and 700 mL of isopropyl alcohol were added to the concentrated residue for 12 hours. Stirred at ambient temperature. The solid obtained was filtered to afford the desired compound 2,4-bis {[4- (2-ethylhexyloxy) -2-hydroxy] phenyl} -6- (4-methoxyphenyl) -1,3,5- 160 g of triazine (2,4-Bis {[4- (2-Ethylhexyloxy) -2-Hydroxy] phenyl} -6- (4-Methoxyphenyl) -1,3,5-Triazine) was obtained.

The above description of the present application is intended for illustration, and it will be understood by those skilled in the art that the present invention may be easily modified in other specific forms without changing the technical spirit or essential features of the present application. Therefore, it should be understood that the embodiments described above are exemplary in all respects and not restrictive. For example, each component described as a single type may be implemented in a distributed manner, and similarly, components described as distributed may be implemented in a combined form.

The scope of the present application is indicated by the following claims rather than the above description, and it should be construed that all changes or modifications derived from the meaning and scope of the claims and their equivalents are included in the scope of the present application. .

Claims (14)

Cyanuric chloride (Cyanuric Chloride), anisole (anisole) and resorcinol (Resorcinol) reaction method for producing a triazine compound represented by the formula (1).
[Formula 1]

The method of claim 1,
The reaction is a first step of obtaining an intermediate reactant by reacting cyanuric chloride and anisole; And a second step of obtaining the compound represented by Chemical Formula 1 by reacting the intermediate reactant of the first step with resorcinol.
The method of claim 2,
The first step and the second step is a method for producing a triazine-based compound is carried out for 3 to 6 hours at a temperature of 20 to 80 ℃.
The method of claim 2,
The molar ratio of cyanuric chloride and anisole in the first step is 1: 0.8 to 5, and the molar ratio of resorcinol to the intermediate reactant is 1.5 to 3 in the second step. Method for producing a phosphorus triazine compound.
The method of claim 1,
The reaction is a triazine-based compound of the present invention proceeds in a one-step reaction is carried out by adding ayanur chloride (Cyanuric Chloride) as a starting material, sequentially anisole (anisole) and resorcinol (Resorcinol).
The method of claim 5,
The cyanuric chloride (Cyanuric Chloride) and anisole (anisole) is reacted at a temperature of 20 to 80 ℃ 1 to 4 hours after the resorcinol (Resorcinol) method for producing a triazine compound.
The method of claim 5,
The cyanur chloride (Cyanuric Chloride) and Resorcinol (Resorcinol) for 1 to 4 hours at a temperature of 20 to 80 ℃ reaction method for producing a triazine-based compound to add anisole (anisole).
The method of claim 5,
The molar ratio of the anisole to the cyanuric chloride (Cyanuric Chloride) is 1.8 to 5, the molar ratio of resorcinol (1.5) to a triazine compound of 1.5.
The method of claim 1,
The reaction is carried out in the presence of aluminum chloride (AlCl ₃ ) method for producing a triazine compound.
The method of claim 1,
The solvent of the reaction is acetone, sulfolane, toluene, toluene, benzyl chloride, chloroform and nitro benzyl chloride, dichloroethane, and methylene A method for producing at least one triazine-based compound selected from the group consisting of chloride (methylene chloride).
The method of claim 1,
A method for producing a triazine-based compound further comprising a purification step further comprising the step of neutralizing a crude compound obtained after the reaction with a base and purifying with an organic solvent.
The method of claim 11,
The base is an inorganic base selected from the group consisting of sodium hydroxide, potassium hydroxide, calcium hydroxide, sodium carbonate, potassium carbonate, calcium carbonate, sodium bicarbonate, potassium bicarbonate, sodium phosphate, and sodium hydrogen phosphate, pyridine, trimethylamine, triethyl A method for producing a triazine compound, which is an organic base selected from the group consisting of amine, diethylamine, dimethylamine, and ammonia water.
The method of claim 11,
Wherein said organic solvent is selected from the group consisting of cyclohexane, toluene, N-methylpyrrolidone, dimethylformamide, methanol, ethanol, isopropanol, butanol, acetone, and ethyl acetate.
The method of claim 11,
The base is added in a weight ratio of 0.1 to 3 with respect to the reactant, the organic solvent is added in a weight ratio of 1 to 10 with respect to the reactant.

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