WO2000014076A1

WO2000014076A1 - Process for making 2,4-dihydroxyphenyl and 2-hydroxy-4-alkoxyphenyl substituted triazine compounds

Info

Publication number: WO2000014076A1
Application number: PCT/US1999/020170
Authority: WO
Inventors: Ram B. Gupta; Dennis J. Jakiela; Sampath Venimadhavan; Russell C. Cappadona; Venkatrao K. Pai
Original assignee: Ciba Spezialitaetenchemie Holding AG; Cytec Technology Corp
Current assignee: BASF Schweiz AG; Cytec Technology Corp
Priority date: 1998-09-04
Filing date: 1999-09-02
Publication date: 2000-03-16
Anticipated expiration: 2001-03-04
Also published as: AU5907399A

Abstract

The invention relates to a process of making substituted triazine compounds and mixtures of substituted triazine compounds. The invention particularly relates to a process of making mono- and bis-(2-hydroxy-4-alkoxyphenyl) substituted triazines, mono- and bis-(2,4-bishydroxyphenyl) substituted triazines, and mixtures thereof. The invention further relates to triazine compounds and mixtures of triazine compounds formed by the process.

Description

Process for Making 2,4-Dihydroxyphenyl and 2-Hydroxy- 4-AIkoxyphenyl Substituted Triazine Compounds

1. FIELD OF INVENTION

The invention relates to a process of making substituted triazine compounds and mixtures of substituted triazine compounds. The invention particularly relates to a process of making mono- and bis-(2-hydroxy-4-alkoxyphenyl) substituted triazines, mono- and bis- (2,4-bishydroxyphenyl) substituted triazines, and mixtures thereof. The invention further relates to triazine compounds and mixtures of triazine compounds formed by the process.

2. BACKGROUND OF THE INVENTION

Although exposure to sunlight and other sources of ultraviolet (UV) radiation can cause the embrittlement and yellowing of some polymers, this polymer degradation may be inhibited by mixing or coating susceptible polymers with compounds known as UV stabilizers.

Trisaryltriazine compounds are particularly effective UV stabilizers, especially those of Formula I:

Formula I

wherein Ar, and Ar₂ are aryl or substituted aryl, and R indicates any type of substitution about the 2-hydroxyphenyl ring.

For example, when compared to other classes of UV stabilizers such as benzotriazoles and benzophenones, 2-(2-hydroxyl-4-alkoxyphenyl)-4,6-bisaryl- 1,3,5- triazine compounds exhibit high inherent light stability and permanence. These compounds have the structure shown in Formula II:

wherein Ar, and Ar₂ are aryl or substituted aryl, and R is alkyl or substituted alkyl. Commercially available examples of 2-(2 -hydroxyl-4-alkoxyphenyl)-4,6-bisaryl- 1,3,5- _j Q triazine compounds include Tinuvin® 1577, Cyasorb® UV-1164, Cyasorb® UV-1164L, and Tinuvin® 400.

Other effective trialkyltrizole UV absorbers are 2,4-bis(2-hydroxyl-4-alkoxyphenyl)- 6-aryl-l,3,5-triazine compounds, shown in Formula III:

20 Formula III wherein Ar, is aryl or substituted aryl and R, and R₂ are alkyl or substituted alkyl. These compounds are disclosed, for example, in U.S. Patent Nos. 5,686,233 and 5,489,503.

According to the literature, the synthesis of the 2-(2-hydroxyl-4-alkoxyphenyl)-4,6- bisaryl- 1,3, 5 -triazine compounds of Formula II and the 2,4-bis(2-hydroxyl-4- 25 alkoxyphenyl)-6-aryl-l,3,5-triazine compounds of Formula III may be accomplished in several ways. See, e.g., H. Brunetti and C. E. Luethi, Helvetica ChimicaActa, 55:1566- 1595 (1972); S. Tanimoto and M. Yamagata, Senryo to Yakahin. 40(12):325-339 (1995). For example, U.S. Patent No. 3,268,474 discloses a method of producing potential intermediates, m-xylene substituted mono- and dichlorotriazines, from cyanuric acid, m- 30 xylene and A1C1₃.

U.S. Patent No. 5,726,310 instead discloses a one pot method of making 2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-triazine in which cyanuric chloride is reacted with m-xylene in the presence of a Lewis acid to produce the intermediate 2-chloro-

4,6-bis(2,4-dimethylphenyl)-triazine which is then reacted with resorcinol. 35 U.S. Patent No. 3,244,708 discloses a method of producing ether substituted aryl triazines from resorcinol substituted triazines wherein a base is used to deprotonate the phenolic proton prior to addition of an alklylhalide.

U.S. Patent Nos. 5,084,570 and 5,106,972 disclose a process for the preparation of 2-(2,4-dihydroxyphenyl)-4,6-diaryl-triazines from an intermediate 2-methylthio-4,6-diaryl- r triazine.

In light of the above references and difficulties unique to the large scale synthesis of triazine compounds, a few preferred methods of making 2-(2-hydroxyl-4-alkoxyphenyl)- 4,6-bisaryl-l,3,5-triazine compounds have emerged. These methods, which typically culminate with the alkylation of 2-(2,4-dihydroxyphenyl)-4,6-bisaryl-l,3,5-triazine, have I o several limitations.

One limitation stems from the fact that the reaction of cyanuric chloride and an aryl compound in the presence of aluminum chloride is typically used to produce 2-(2,4- dihydroxyphenyl)-4,6-bisaryl-l,3,5-triazine. For some aryl compounds, however, this reaction produces the bisaryl compound in low yield, instead preferring to form either the 15 monoaryl or trisaryl compounds, as shown in Scheme I:

20

AIC1₃; Ar

Scheme I

Under carefully controlled conditions, and for some aryl groups, this reaction can provide sufficient amounts of certain 2-chloro-4,6-aryl-l,3,5-triazine compounds. These 30 may then be reacted with resorcinol in another reaction catalyzed by aluminum chloride to form the corresponding 2-chloro-4,6-bis(2,4-dihydroxyphenyl)-l,3,5-triazine compounds, as shown in Scheme II:

Scheme II

Once the desired 2-(2,4-dihydroxyphenyl)-4,6-bisaryl-l,3,5-triazine compound has been formed, it can then alkylated to yield the final 2-(2-hydroxyl-4-alkoxyphenyl)-4,6-bisaryl- ] Q 1,3, 5 -triazine product, as shown in Scheme III:

4-0-alkylation

R = Alkyl group

Scheme III The commercially available UV stabilizer Cyasorb® UV-1164 has been made this way by 20 reacting 2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-l,3,5-triazine with 1-octyl halide in the presence of base, as shown in Scheme IV:

UV-1164

Scheme IV

30 The synthetic process described above can be effective in some cases, yet it has several disadvantages that can render the production of certain UV stabilizers costly and inefficient. For example, this approach is of little use for the production of mixed aryl 2- (2,4-dihydroxyphenyl)-4,6-bisaryl-l,3,5-triazine compounds (i.e. compounds of Formula II wherein Ar, and Ar₂ are different), since the reaction of cyanuric chloride with a mixture of

35 aryl groups typically forms a mixture of products that are difficult to separate. As was alluded to above, another disadvantage of this process is that the type of aryl group initially reacted with cyanuric chloride can have a dramatic effect on the resulting product mixture. Consequently, variation of the aryl group can lead to unanticipated extraction, separation and purification problems. These problems render the formation of mixed aryl triazine compounds especially difficult. The present invention addresses these problems and provides a more economical, efficient, and straight-forward means of making mixed aryl triazine compounds.

Another problem encountered, for example, in the reaction of chlorotriazines and resorcinol is the formation of two immiscible layers during the reaction, the lower of which contains aluminum chloride complexes of the products, and is typically a thick, tarry, sticky mass that renders the reaction mixture very difficult to stir. Furthermore, the poor solubilities of the resulting products hinders their isolation, and leaves comparatively little material for the third step of the reaction. The present invention solves this problem as well by providing an easy to stir, homogeneous reaction solution of low viscosity. The invention further allows the easy isolation of the triazine products using conventional extraction techniques.

The present invention avoids the problems described above in part by employing the catalyzed reaction of aryl ethers and halogenated triazine compounds. Many of these reactions are heretofor uncharacterized. For example, the present inventors could not find in the literature a description of the reaction of 3-alkoxyphenol and a 2,4-bischloro-6-aryl- 1 ,3,5-triazine. It was consequently unclear what such a reaction would yield, as shown in Scheme V:

C-C linked C-C linked C-0 linked

Scheme V The reaction of an alkoxyphenol and a substituted triazine could form several different products.

It is known that the reaction of cyanuric chloride with resorcinol forms the corresponding C-C linked 2-4-dihydroxyphenyl-triazine derivatives. U.S. Patent No. 3,268,474 discloses the formation of 2,4,6-tris(2-hydroxy-4-alkoxyphenyl)-l,3,5-triazine using this method, as shown in Scheme VI:

Scheme VI

Similarly, the Lewis acid catalyzed reaction of cyanuric chloride with excess 1,3- dimethoxybenzene has been found to form a mixture of the corresponding C-C linked tris and bis-substituted dimethoxybenzene triazine compounds.

By contrast, it has been reported that the reaction of cyanuric chloride with phenols can yield both C-C and C-O linked products. See, e.g., Y. Horikoshi et al., Nippon Kagaku Kaishi, 3:530-535 (1974); CA 81 :152177. There have been no reports, however, of the reaction of alkoxyphenols and cyanuric chloride. Recently, Japanese Patent 09059263-A [CA 126:277502] described the formation of C-O linked products from the reaction of cyanuric chloride and substituted phenols in the presence of a Lewis acid, as shown in Scheme VII:

Scheme VII wherein R, and R₂ are H, C,.,₀ alkyl, alkoxy, alkenyl, halo or nitro. No example was provided, however, wherein the reaction cyanuric chloride and an alkoxyphenol was described. In light of these references, and as shown in Scheme V above, until now it was unclear whether the reaction of a monoaryl-bishalogenated triazine and 3 -alkoxyphenol would yield C-C or C-O linked products. Furthermore, the regiochemistry of the preferred products of the reaction were also unknown, as was whether the reaction would allow the selective monosubstitution of a chlorotriazine. By studying this reaction, the present r inventors have surprisingly found a particularly effective means of synthesizing triazine compounds suitable as UV stabilizers.

3. SUMMARY OF THE INVENTION

The present invention encompasses a process for preparing compositions comprising _j 0 triazine compounds. The invention further encompasses specific triazine compounds especially useful as UV inhibitors.

A first embodiment of the present invention encompasses a process of making a composition comprising at least one triazine compound of Formula A:

Formula A wherein Ar₂ is Ar, or a radical of a compound of Formula B:

Formula B 30 and Ar, is a radical of a compound of Formula C:

35

wherein R,, R₂, R₃, R₄, R₅, Rg, R₇, R₈, R , and R,₀ are the same or different and each is hydrogen, alkyl of 1 to 24 carbons atoms, cycloalkyl of 5 to 24 carbon atoms, aralkyl of 7 to 10 24 carbon atoms, alkoxy, amine, or thiol, and R_t and R₇ taken together, R₇ and R₈ taken together, R₈ and R, taken together, or R_> and R,₀ taken together may be part of a fused carbocyclic ring optionally containing O, N or S atoms. This process has two steps. In step one, a suitable amount of a compound of Formula D:

Formula D 20 wherein X is halogen is reacted in the presence of a catalyst with a compound of Formula B.

This reaction is conducted at a suitable temperature and pressure and for a time sufficient to produce a first reaction mixture.

In step two of this embodiment, the first reaction mixture is reacted with a suitable 25 amount of a compound of Formula C in the presence of a second catalyst. This reaction is conducted at a suitable temperature and pressure and for a time sufficient to produce a second reaction mixture comprising the composition.

A second embodiment of the present invention also encompasses a process for making compositions comprising compounds of Formula A. In this second embodiment, a 3 compound of Formula F:

35

Formula F

is isolated from the first reaction mixture. A suitable amount of this compound of Formula E is then reacted with a compound of Formula B at a suitable temperature and pressure and for a time sufficient to produce a second reaction mixture comprising the composition. The present invention also encompasses triazine compounds of Formula G:

Formula G

wherein Z is a chemical group of Formula H. Formula I or Formula J:

Formula H Formula I Formula J

wherein R,, R₂, R₃, R₄, R₅, R^, R', and R" are the same or different and are each hydrogen, cycloalkyl, aralkyl or aryl, X is CH₂, O, NRs or S, Y is halogen, and n is 0, 1 or 2. These compounds are particularly effective UV stabilizers.

4. DETAILED DESCRIPTION OF THE INVENTION

This invention relates to a new process of making substituted triazine compounds wherein a di-halogenated triazine compound is reacted with one or more aromatic compounds. This process solves a variety of the synthetic difficulties characteristic of prior art processes. In particular, the present invention encompasses a process of making a composition comprising at least one triazine compound of Formula A:

Formula A wherein Ar₂ is Ar, or a radical of a compound of Formula B:

and Ar, is a radical of a compound of Formula C:

Formula C

wherein R,, R₂, R₃, R₄, R₅, Rg, R₇, R_g, R,, and R,₀ are the same or different and each is hydrogen, alkyl of 1 to 24 carbons atoms, cycloalkyl of 5 to 24 carbon atoms, aralkyl of 7 to 24 carbon atoms, alkoxy, amine, or thiol, and Rg and R₇ taken together, R₇ and R₈ taken together, R₈ and , taken together, or R, and R,₀ taken together may be part of a fused carbocyclic ring optionally containing O, N or S atoms.

Formula B in the present disclosure is understood to include substituted phenol wherein the substitution group may be in any position on the ring. The alkoxy group includes but is not limited to an ether of formula -OR, wherein the R group comprises an alkyl group such as methyl, ethyl, propyl, butyl, pentyl, hexyl, septyl, octyl, nonyl, decyl, saturated or unsaturated, in straight chain, branched, or cyclic form. Furthermore, the R group may be substituted with at least one additional group, such group including hydroxy, alkyl saturated or unsaturated, in straight chain, branched, or cyclic form, alkoxy (e.g. methoxy, n-butoxy, 2-ethylhexyloxy and n-octyloxy), sulfonic, halide (e.g., iodo, bromo, chloro, fluoro), haloalkyl (e.g. dicholoromethyl and trifiuoromethyl). The list is not intended to be all encompassing, simply demonstrative.

Similarly, the aryl groups indicated by Ar, may be substituted or unsubstituted aryl groups, including but not limited to phenyl, alkylphenyl, alkoxyphenyl, halophenyl, alkoxyhalophenyl, aminophenyl, biphenyl, substituted biphenyl, naphthalene, teralin, substituted naphthalenes and tetralins, or any oxy, alkoxy, nitro, amide, amine. thiol, alkylthiol, or halogen derivatives thereof. The process of the present invention is based in part upon the inventors' unexpected discovery that under certain conditions, specific reactions such as the catalyzed reaction of monoaryl-bishalogenated triazines and 3-alkoxyphenol, yield mono- and bis(2-hydroxy-4- alkoxy)-l,3,5-triazine compounds with good selectivity. This reaction may be a single-pot reaction. It has further been discovered that under certain conditions the reaction of monoaryl-bishalogenated triazines and trialkoxyphenyl or dialkoxyphenyl compounds, such as 1,3-dialkoxyphenyl, causes the selective dealkylation of the alkoxypheny compounds. Consequently, the reaction of monoaryl-bishalogenated triazines and 1,3-dialkoxyphenyl also yields the corresponding mono- and bis(2-hydroxy-4-alkoxy)-l,3,5-triazine compounds with good selectivity. These compounds also can be formed in a one-pot process. This invention offers numerous advantages over the synthetic processes of the prior art, including homogeneous reaction mixtures that are easy to stir and that allow easy isolation of the desired products by the use of conventional solvent extraction means employing common organic solvents.

The process of the present invention has at least two steps. In the first, a triazine compound of Formula D :

Formula D

wherein X is halogen, and preferably chlorine, is reacted with a compound of Formula B to form a reaction mixture that contains compound F, as shown in Scheme VIII:

Scheme VIII

The compound of Formula B preferably is in sufficient amount to react with the dihalogenated triazine compound of Formula D to produce a compound of Formula F in as high a yield as possible. Preferably the amount should be between about 0.8 to 2 mol equivalents based on the amount of halogens present in the triazine compound of Formula D.

This reaction is facilitated by a catalyst, and more preferably by a Lewis acid catalyst. The catalyst should be present in a sufficient amount to react with the number of halogens being substituted. Suitable Lewis acid catalysts may be, for example. A1C1₃, AlBr₃, or any other Lewis acid suitable for a Friedels-Craft reaction. The preferred Lewis acid is aluminum chloride. Based on the amount of 2,4-chloro-6-bisaryl-l,3,5-triazine, the preferred amount of Lewis acid is between about 0.25 to 7.0 mol equivalents to each chloride present in the precursor chlorotriazine compound.

The reaction shown in Scheme VIII is conducted in a solvent, which may be any of those known by those skilled in the art to be suitable for Friedels-Craft reactions. It is preferred, however, that the solvent be a halogenated benzene such as chlorobenzene, dichlorobenzene, trichlorobenzene, 1,1,2,2-tetrachloroethane, bromobenzene, dibromobenzene, tribromobenzene, etc., toluene, dimethylbenzene, trimethylbenzene, in any substitution pattern, nitrobenzene, anisole, or mixtures of these with one another. The temperature range for the reaction shown in Scheme VIII is between 0°C to about 120°C, more preferably between about 10°C to 80°C. Precise temperatures are varied, however, depending upon the type of catalyst used, the pressure under which the reaction occurs, and the exact identities of the compounds of Formulas B and D. Similarly, the time required for the reaction to go to completion will vary with catalyst and reactants, as well as with temperature and pressure. The present processes are preferably performed at about atmospheric pressure, however, and so the preferred reaction time is between about 0.5 hours and about 40 hours, more preferably between about 2.5 hours and about 20 hours.

Reaction completion may be determined by conventional means known to those of skill in the art, including, for example, 'H NMR, visible, UV and IR optical spectroscopy, and chromatography.

Upon the completion of the reaction, the compound of Formula F:

Formula F may be isolated from the product mixture if so desired. An advantage of the process of the present invention is that isolation of the compound of Formula F may be accomplished with conventional extraction techniques employing conventional solvents. As used herein, the term "completion" means the formation of a desired amount of product, and so does not necessarily mean the formation of the maximum possible amount of a desired product. Step two of the process of this invention may commence immediately following the completion of step one. If step one does not entail the isolation of a compound of Formula F from the first reaction mixture, then step two may also commence after the reaction mixture has cooled down. It has been found that the duration of cooling depends upon several factors, such as the temperature at which the reaction of step two is to be conducted, and the stability of reaction intermediates. It is preferred, however, that if cooling is allowed, that it be done for a period of time of between about 0.25 hours and about 5 hours.

Step two involves the reaction of the product or product mixture of step one with a compound of Formula C:

wherein R,, R₂, R₃, R₄, R₅, R^, R₇, R₈, R<_>, and R,₀ are the same or different and each is hydrogen, alkyl of 1 to 24 carbons atoms, cycloalkyl of 5 to 24 carbon atoms, aralkyl of 7 to 24 carbon atoms, , alkoxy, amine, or thiol, and R^ and R₇ taken together, R₇ and R₈ taken together, R₈ and R, taken together, or R, and R,₀ taken together may be part of a fused carbocyclic ring optionally containing O, N or S atoms. Consequently, the compound of Formula C may be substituted or unsubstituted aryl groups, including but not limited to phenyl, alkylphenyl, alkoxyphenyl, halophenyl, alkoxy halophenyl, aminophenyl, biphenyl, substituted biphenyl, naphthalene, teralin, substituted naphthalenes and tetralins, or any oxy, alkoxy, nitro, amide, amine, thiol, alkylthiol, or halogen derivatives thereof.

Whether the reaction of step two of the process utilizes the crude reaction mixture formed in step one or the isolated compound of Formula F, the fundamental reaction of step two is shown in Scheme IX:

Scheme IX

The compound of Formula C should be in sufficient amount to react with the halogenated triazine compound of Formula F to produce the desired final composition. Preferably the amount should be between about 0.8 to 2 mol equivalents of the triazine compound of Formula F. This reaction, like the first, is facilitated by a catalyst, and more preferably a Lewis acid catalyst. The catalyst should be present in a sufficient amount to react with the number of halogens being substituted. Suitable Lewis acid catalysts may be, for example, A1C1₃, AlBr₃, or any other Lewis acid suitable for a Friedels-Craft reaction. The list is not intended to be all encompassing, simply demonstrative. The preferred Lewis acid is aluminum chloride. Based on the amount of 2,4-chloro-6-bisaryl-l,3,5-triazine, the preferred amount of Lewis acid is between about 0.25 to 7.0 mol equivalents to each chloride present in the precursor chlorotriazine compound.

The reaction shown in Scheme IX is also conducted in a solvent, which may be any of those known to those skilled in the art to be suitable for Friedels-Craft reactions. It is preferred, however, that the solvent be a halogenated benzene such as chlorobenzene, dichlorobenzene, trichlorobenzene, 1,1,2,2-tetrachloroethane, bromobenzene, dibromobenzene, tribromobenzene, etc., toluene, dimethylbenzene, trimethylbenzene. in any substitution pattern, nitrobenzene, anisole, or mixtures of these with one another.

Alternatively, the compound of Formula C may also be the solvent. The usefulness of this approach clearly depends upon the melting point of the compound of Formula C. as those of skill in the art will recognize. In this case, the exact molar ratio of the reactants is of little concern. Another, more significant advantage of this approach is that the solvent in which the first reaction (Scheme VIII) is conducted can be the reactant of Formula C in the second reaction. This allows the efficient, economical two step process described above to be treated as a single step process. A further advantage of using the compound of Formula C as both a solvent and a reactant is that it avoids the need to use halogenated solvents, and so avoids the environmental and health concerns associated with halogenated solvents.

The temperature range for the reaction shown in Scheme IX is between 0°C to about 120°C, more preferably between about 10°C to 80°C. Precise temperatures are varied, however, depending upon the type of catalyst used, the pressure under which the reaction occurs, and the exact identities of the compounds of Formulas F and C. Similarly, the time required for the reaction to go to completion will vary with catalyst and reactants, as well as with temperature and pressure. The present processes are preferably performed at about atmospheric pressure, however, and so the preferred reaction time is between about 0.5 hours and about 40 hours, more preferably between about 2.5 hours and about 20 hours. Reaction completion may be determined by conventional means known to those of skill in the art, including, for example, 'H NMR, visible, UV and IR optical spectroscopy, and chromatography.

It has been found that the compositions formed during step two of the reaction of the present invention are particularly useful as UV stabilizers. Furthermore, it has been found that the individual compounds isolated from the product compositions are themselves efficient and stable UV absorbers.

Additional features and advantages of the invention will be apparent from the claims and nonlimiting demonstrative examples.

EXAMPLES

Examples and reaction schemes for producing specific examples of substituted triazines in accordance with the invention are provided below. While the following examples illustrate preparations with one or more substituted aryl ring, one of ordinary skill will understand that these reactions may also be carried out with any of a variety of other substituted aryl rings, where when necessary, reactive substituents on such other substituted aryl rings are protected in accordance with procedures and reagents well known and understood by those of ordinary skill. Example 1 : Reaction of Compound 1 with resorcinol in chlorobenzene

To a stirring mixture of triazine 1 (2.8 g) and resorcinol (1 g) in 25 mL chlorobenzene cooled in an ice-bath was added aluminum chloride (1.34 g). The reaction was warmed to about 15°C and stirred for 3 hr. The reaction mixture was then allowed to warm to room temperature and stirred for an additional 20 hr. The reaction mixture was added into 2% ice-cold aqueous HC1. A precipitate formed, was collected by filtration, washed with water, and dried. The product obtained was analyzed by TLC (thin layer chromatography), HPLC, and LCMS and shown to contain 2 as the major product and compound 3 as the minor product.

The 4 hydroxyl groups of compounds 2 and 3 can be alkylated by one of ordinary skill in the art using well known procedures.

Example 2: Reaction of compound 1 with resorcinol in m-xylene

To a stirring mixture of triazine 1 (2.8 g) and resorcinol (1 g) in 25 mL m-xylene cooled in an ice-bath was added aluminum chloride for 3 hr. The TLC and HPLC analysis of the reaction mixture showed the formation of compounds 2 an 3 but no compound with m-xylene incorporation. The reaction mixture was then allowed to warm to room temperature and was stirred for an additional 20 hr. To the reaction mixture was added additional aluminum chloride (1.34 g) and the reaction mixture was stirred at room temperature for another 24 hr. The reaction mixture after usual work-up was analyzed by TLC (thin layer chromatography), HPLC, and LCMS and shown to contain compounds 3 and 4.

The hydroxyl groups of compounds 3 and 4 can be alkylated by one of ordinary skill in the art using well known procedures.

- 1! Example 3 : Reaction of compound 1 with 4-hexylresorcinol followed by reaction with tetralin

To a stirring mixture of triazine 1 (2.8 g) and 4-hexylresorcinol (1.94 g) in 25 mL chlorobenzene cooled in an ice-bath was added aluminum chloride (1.34 g). The reaction mixture was warmed to room temperature and stirred for 4 hr. The reaction mixture was then heated to 40°C for 2 hr. Analysis of the reaction mixture at this stage by TLC, HPLC, and LCMS, showed the disappearance of 4-hexylresorcinol and the formation of two new compounds identified as compounds 6 and 7. To the reaction mixture was then added 2 mL of tetralin and additional aluminum chloride (1.94 g) and the mixture was heated to 40 °C for 2 hr. Analysis of the product mixture by TLC, HPLC, and LCMS after work-up yielded compounds 7 and 8.

The hydroxyl groups of compounds 7 and 8 can be alkylated by one of ordinary skill in the art using well known procedures.

Example 4: Reaction of Compound 9 with resorcinol in chlorobenzene followed by reaction with m-xylene

To a stirring mixture of triazine 9 (1.27 g) and resorcinol (0.55 g) in 15 mL chlorobenzene cooled in an ice-bath was added aluminum chloride (0.7 g). The reaction mixture was stirred at about 10°C for 8 hr, and then stirred at room temperature for 14 hr. Analysis of the reaction mixture at this stage by TLC, HPLC, and LCMS, showed the formation of compound 10 and 11 roughly in a ratio of 2:1. To the reaction mixture was then added 5 mL of m-xylene and aluminum chloride (0.7 g). The reaction mixture was stirred at room temperature for 2r hr. The reaction mixture was then quenched with 2% ice-cold aqueous HCl and extracted with ethyl acetate. The organic layer was analyzed by by HPLC and shown to contain compounds 12 and 11 in roughly a 2:1 ratio.

Claims

THE CLAIMS What is claimed is:

1. A process for preparing a composition comprising at least one triazine

_<- compound of Formula A:

Formula A , ^ wherein Ar₂ is Ar, or a radical of a compound of Formula B:

20

Formula B and Ar, is a radical of a compound of Formula C:

Formula C

30 wherein R,, R₂, R₃, R₄, R₅, Rg, R₇, R₈, R,, and R,₀ are the same or different and each is hydrogen, alkyl of 1 to 24 carbons atoms, cycloalkyl of 5 to 24 carbon atoms, aralkyl of 7 to 24 carbon atoms, , alkoxy, amine, or thiol, and R_<, and R₇ taken together, R₇ and R₈ taken together, R₈ and R, taken together, or R, and R_I0 taken together may be part of a fused ., , carbocyclic ring optionally containing O, N or S atoms, which process comprises: i) reacting in the presence of a solvent and a first catalyst sufficient amounts of a compound of Formula D:

Formula D

wherein X is halogen and a compound of Formula B at a suitable temperature and pressure , _Λ and for a time sufficient to produce a first reaction mixture; and ii) reacting the first reaction mixture and a compound of Formula C in the presence of a second catalyst and at a suitable temperature and pressure and for a time sufficient to produce a second reaction mixture comprising the composition.

1 2. The process of claim 1 wherein the composition further comprises a compound of Formula E:

Formula E

25

3. The process of claim 1 wherein the reaction of the compounds of Formulas D and B produces an intermediate of Formula F:

Formula F prior to the reaction of the first reaction mixture and the compound of Formula C.

4. The process according to claim 1 wherein the compound of Formula C is selected from the group consisting of benzene, toluene, m-xylene, o-xylene, p-xylene, mesitylene, biphenyl, naphthalene, tetralin, and substituted naphthalenes and substituted tetralins.

5. The process according to claim 1 wherein the first catalyst is a Lewis acid and X is chlorine.

10 6. The process according to claim 5 wherein the Lewis acid is selected from the group consisting of aluminum tribromide, zinc chloride, boron trichloride, titanium tetrachloride. aluminum trichloride, and a mixture thereof.

7. The process according to claim 1 wherein the second catalyst is a Lewis acid

15 and X is chlorine.

8. The process according to claim 7 wherein the Lewis acid is selected from the group consisting of aluminum tribromide, zinc chloride, boron trichloride, titanium tetrachloride, aluminum trichloride, and a mixture thereof.

20

9. The process of claims 6 or 8 wherein the combined amount of first catalyst and of second catalyst is about 0.25 to about 7 equivalents based upon the amount of the compound of Formula D.

~ _- 10. The process of claim 9 wherein the combined amount of first catalyst and of second catalyst is from about 1 to about 4 equivalents based upon the amount of the compound of Formula D.

11. The process of claim 1 wherein the amount of the compound of Formula B is -, from about 0.5 to about 2.5 equivalents based upon the amount of the compound of Formula

D.

12. The process of claim 1 1 wherein the amount of the compound of Formula B is between about 1.0 to about 1.5 equivalents based upon the amount of the compound of

.,_<- Formula D.

13. The process of claim 1 wherein the amount of the compound of Formula C is between about 0.5 to about 2.5 equivalents based upon the amount of the compound of Formula D.

14. The process of claim 13 wherein the amount of the compound of Formula C _<- is between about 1.0 to about 1.5 equivalents based upon the amount of the compound of

Formula D.

15. The process of claim 1 wherein the compounds of Formulas D and B are reacted at a temperature of between about 0 °C and about 120 °C.

10

16. The process of claim 15 wherein the compound of Formulas D and B are reacted at a temperature of between about 10 °C and about 80 °C.

17. The process of claim 1 wherein the first reaction mixture and the compound , ,. of Formula C are reacted at a temperature of between about 0 °C and about 120 °C.

18. The process of claim 17 wherein the first reaction mixture and the compound of Formula C are reacted at a temperature of between about 10 °C and about 80 °C.

2 19. The process of claim 1 wherein the compounds of Formulas D and B are reacted for a time of between about 0.5 hours and about 40 hours.

20. The process of claim 19 wherein the compounds of Formulas D and B are reacted for a time of between about 2.5 hours and about 20 hours.

25

21. The process of claim 1 wherein the first reaction mixture and the compound of Formula C are reacted for a time of between about 0.5 hours and about 40 hours.

22. The process of claim 21 wherein the first reaction mixture and the compound of Formula C are reacted for a time of between about 2.5 hours and about 20 hours.

30

23. The process of claim 1 further comprising the cooling of the first reaction mixture for a time of between about 0.25 hours and about 5 hours prior to its reaction with the compound of Formula C.

35

24. The process of claim 1 wherein the reaction of the compounds of Formulas D and B is conducted in an inert solvent.

25. The process of claim 1 wherein the inert solvent is a halogenated solvent.

r 26. The process of claim 25 wherein the halogenated solvent is selected from the group consisting of chlorobenzene, dichlorobenzene, 1,1,2,2-tetrachloroethane, and mixtures thereof.

27. The process of claim 1 wherein the reaction of the first reaction mixture and _{1 Λ} the compound of Formula C is conducted in a halogenated solvent.

28. The process of claim 27 wherein the halogenated solvent is selected from the group consisting of chlorobenzene, dichlorobenzene, 1,1,2,2-tetrachloroethane, and mixtures thereof.

15

29. The process of claim 1 further comprising using the compound of Formula C as a solvent in the reaction of the compounds of Formulas D and B to form a compound of Formula F.

2 30. The process of claim 29 further comprising the step of reacting said solvent with said compound F to form a compound of Formula A.

31. The process of claim 30 wherein the compound of Formula C is selected from the group consisting of benzene, toluene, m-xylene, o-xylene, p-xylene, mesitylene, 2_- biphenyl, naphthalene, tetralin, and substituted naphthalenes and substituted tetralins.

30

35

32. A process for preparing a composition comprising at least one triazine compound of Formula A:

Formula A

10 wherein Ar₂ is Ar, or a radical of a compound of Formula B:

Formula B and Ar, is a radical of a compound of Formula C:

wherein R,, R₂, R₃, R₄, R₅, R^ R₇, R₈, ,, and R₁₀ are the same or different and each is hydrogen, alkyl of 1 to 24 carbons atoms, cycloalkyl of 5 to 24 carbon atoms, aralkyl of 7 to 24 carbon atoms, alkoxy, amine, or thiol, and R^ and R₇ taken together, R₇ and R₈ taken ,_n together, R₈ and Rg taken together, or R, and R,₀ taken together may be part of a fused carbocyclic ring optionally containing O, N or S atoms, which process comprises: i) reacting in the presence of a first catalyst sufficient amounts of a compound of Formula D:

35

Formula D

wherein X is halogen and a compound of Formula B at a suitable temperature and pressure and for a time sufficient to produce a first reaction mixture; 0 ii) isolating from the first reaction mixture a compound of Formula F:

Formula F 0 and iii) reacting a suitable amount of the compound of Formula F and a compound of Formula C in the presence of a second catalyst and optionally an inert solvent at a suitable temperature and pressure and for a time sufficient to produce a second reaction mixture ^ comprising the composition.

33. The composition formed by the processes of claims 1 or 32.

0

5

34. A composition comprising a compound of Formula F:

Formula F

wherein X is a halogen, Ar, is a radical of a compound of Formula B:

Formula B or Ar, is a radical of a compound of Formula C:

wherein R,, R₂, R₃, R₄, R₅, R^, R₇, R₈, Rg, and R,₀ are the same or different and each is hydrogen, alkyl of 1 to 24 carbons atoms, cycloalkyl of 5 to 24 carbon atoms, aralkyl of 7 to 24 carbon atoms, , alkoxy, amine, or thiol, and R^ and R₇ taken together, R₇ and R₈ taken together, R₈ and Rg taken together, or R, and R₁₀ taken together may be part of a fused carbocyclic ring optionally containing O, N or S atoms.

35. A composition comprising a compound of Formula G:

Formula G , _n wherein Z is a chemical group of Formula H, Formula I or Formula J:

Formula H Formula I Formula J

20 wherein R,, R₂, R₃, R₄, R₅, Rg, R', and R" are the same or different and are each hydrogen, cycloalkyl, aralkyl or aryl, X is CH₂, O, NRg or S, Y is halogen, and n is 0, 1 or 2.

25

30

35

6. The composition of claim 35 wherein Z is a chemical group of Formula J:

Formula J