WO2002060882A2 - Process for the preparation of 2-(disubstituted-amino)-4,6-diaryl triazines - Google Patents
Process for the preparation of 2-(disubstituted-amino)-4,6-diaryl triazines Download PDFInfo
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- WO2002060882A2 WO2002060882A2 PCT/EP2002/000626 EP0200626W WO02060882A2 WO 2002060882 A2 WO2002060882 A2 WO 2002060882A2 EP 0200626 W EP0200626 W EP 0200626W WO 02060882 A2 WO02060882 A2 WO 02060882A2
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D251/00—Heterocyclic compounds containing 1,3,5-triazine rings
- C07D251/02—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings
- C07D251/12—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members
- C07D251/26—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members with only hetero atoms directly attached to ring carbon atoms
- C07D251/40—Nitrogen atoms
- C07D251/42—One nitrogen atom
- C07D251/44—One nitrogen atom with halogen atoms attached to the two other ring carbon atoms
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D251/00—Heterocyclic compounds containing 1,3,5-triazine rings
- C07D251/02—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings
- C07D251/12—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members
- C07D251/14—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members with hydrogen or carbon atoms directly attached to at least one ring carbon atom
- C07D251/22—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members with hydrogen or carbon atoms directly attached to at least one ring carbon atom to two ring carbon atoms
Definitions
- R and R 1 independently are alkyl, hydroxyalkyl, alkenyl, alkynyl, or alkyl ether groups substituted by one or more hydroxy and/or alkoxy groups, and Ar represents one of the residues
- R 2 is hydroxy, alkyl, alkenyl, alkynyl, or an alkyl, alkenyl, alkynyl ether residue, or polyalkyl ether residue optionally substituted by one or more hydroxy and/or alkoxy groups and R 3 is hydrogen or signifies a residue R 2 and in which the hydroxy group is present in the ⁇ -position to the bonding to the triazine nucleus, with the number of C and O atoms present in R and R 1 being a total of 8 to 42, especially 8 to 18, and the number of O atoms corresponding to at most half of the C atoms, are useful as UV-A filters and are disclosed in EP 780,382.
- these compounds can be prepared by a process which comprises reacting cyanuric chloride with an amine NH(R,R') in the presence of an equimolar amount of aqueous sodium hydroxide solution and subsequently submitting the amino- substituted dichloro triazine reaction product of the formula II
- the reaction of the cyanuric chloride with the substituted amine NH(R,R 1 ) can be improved by carrying out the reaction in an anhydrous aromatic hydrocarbon, such as anhydrous benzene, toluene or xylene, preferably anhydrous toluene, first at low temperature to form a mixture of a compound of formula II and the amine hydrochloride, NH(R,R 1 ) • HC1, and unreacted cyanuric chloride, and subsequently heating said mixture to convert the remaining cyanuric chloride and amine hydrochloride to the desired dichloro triazine of formula II. In this manner, the formation of sodium chloride that has to be disposed of as waste is avoided.
- anhydrous aromatic hydrocarbon such as anhydrous benzene, toluene or xylene, preferably anhydrous toluene
- the Friedel-Crafts reaction can be carried out by using methanesulfonic acid as the catalyst which can be recovered thus avoiding the formation of waste which is produced in the work-up procedure of the conventional Friedel-Crafts reaction as disclosed in EP 780,382 where aluminum trichloride is used as a catalyst.
- the product of the Friedel-Crafts reaction i.e. the compound of formula I can be isolated from the Friedel-Crafts reaction mixture as an adduct with solvents that form an adduct with the compounds of formula I such as lower alkyl nitriles or lower alkanoic acid lower alkyl esters. From the adduct, the compound of formula I can be obtained in high purity by heating and/or applying reduced pressure.
- the present invention relates to a process for the preparation of compounds of the general formula II as defined above, which process comprises reacting cyanuric chloride with a substituted amine NH(R,R 1 ) in substantially equimolar amounts in an anhydrous aromatic hydrocarbon first at low temperature to form a mixture of a compound of formula II and the amine hydrochloride, NH(R,R 1 ) • HC1, and unreacted cyanuric chloride, and subsequently heating said mixture to convert the remaining cyanuric chloride and amine hydrochloride to the desired dichloro triazine of formula II.
- the invention in another aspect relates to a process for the preparation of compounds of the general formula I as defined above, which process comprises submitting a compound of the general formula II as defined above to a Friedel-Crafts reaction with an appropriate aryl hydrocarbon ArH to obtain a reaction mixture containing a compound of the formula I, and working up the reaction mixture by adding water and an organic solvent that is substantially water-immiscible, separating, drying and concentrating the solvent phase, isolating the compound of formula I as an adduct with an appropriate solvent, and decomposing subsequently the adduct to obtain the compound of formula I in pure form.
- the invention relates to the novel adducts of the compounds of formula I, particularly the ethyl acetate and acetonitrile adducts.
- substantially water-immiscible solvents for use in the work-up of the Friedel-Crafts reaction mixture are lower alkanoic acid lower alkyl esters having a boiling point of less than about 120 °C such as methyl acetate, ethyl acetate, propyl acetate, methyl formiate and ethyl formiate. Particularly preferred is ethylacetate.
- Appropriate solvents for forming an adduct with the compounds of formula I are lower alkanoic acid lower alkyl esters having a boiling point of less than about 120 °C, and lower alkyl nitriles. Particularly preferred solvents for adduct formation are ethylacetate and acetonitrile.
- the invention relates to the preparation of compounds of formula I and II, respectively, wherein Ar is 2,4-dihydroxyphenyl and R and R 1 are 2-ethylhexyl.
- the reaction of cyanuric chloride with the amine NH RjR 1 ) is first carried out at low temperature, e.g., at about -20 °C to about 70 °C, preferably at -10 °C to about 20 °C, At low temperature, a mixture of about equimolar amounts of dichloro triazine of formula II, amine hydrohalogenide and unreacted cyanuric chloride is formed as can be readily determined by conventional analytical procedures such as gas chromatography.
- reaction mixture is heated to elevated temperature, e.g., to reflux temperature thus converting unreacted cyanuric chloride and amine hydrohalogenide to the desired compound of formula II.
- the subsequent Friedel-Crafts reaction can be carried out in the same solvent as used in the reaction of the cyanuric chloride with the amine, e.g., in benzene, toluene or xylene.
- the reaction can be carried out with catalysts which are conventional for this particular reaction, i.e. Lewis acids such as aluminum chloride as disclosed in EP 780,382.
- Lewis acids such as aluminum chloride as disclosed in EP 780,382.
- methanesulfonic acid is used as the catalyst in the Friedel-Crafts reaction.
- the hydrocarbon used as the solvent in the preceding amination reaction is removed prior to the Friedel-Crafts reaction and the Friedel-Crafts reaction is suitably carried out at a temperature of about 10 to 30°C. At this temperature, optimal yield and purity of the desired compound of formula I is achieved in a reaction time of about 2 days.
- the amount of catalyst is suitably 2 to 4 g of methanesulfonic acid per mmole of substituted amino dichlorotriazine.
- a Lewis acid such as aluminum chloride the Friedel-Crafts reaction can be carried out at about 70 to 100 °C and using about 1,5 to 3 mole of catalyst per mole of compound of formula II.
- the Friedel-Crafts reaction mixture is worked up by adding water and, if required, an organic solvent to obtain a suspension comprising a solvent phase and an aqueous phase.
- the suspension is filtered and the filter cake resuspended in an organic solvent that is substantially immiscible with water.
- the organic phase is then washed with water until the suspension has dissolved.
- the organic phase obtained after adding water to the Friedel-Crafts reaction is washed with water without prior separating the solids. In either case the organic phase is separated and concentrated. If an appropriate solvent that is capable to form an adduct or solvate was used an adduct or solvate of the compound of formula I is thus obtained.
- the residue is recrystallised from a solvent that is capable to form such adduct or solvate.
- the adduct or solvate of the compound of formula I is converted to the pure compound of formula I by heating, e.g. up to about 80 °C to about 120 °C and/or applying reduced pressure, e.g. 1 to 30 mbar.
- the orange solution was diluted, at 6°-8°C by the dropwise addition of 500 ml of ethyl acetate. To this solution, 1000 ml of water were added at about 8°C to afford a suspension.
- step b) The suspension obtained in step a) was filtered. The filter cake was then suspended in ethyl acetate. The suspension was extracted several times with water of approx. 45°C until all the suspension had dissolved. The organic phase was concentrated to 150 g. The solution was dried under reflux by azeotropic removal of water. The dry solution was left to crystallise with stirring at 0°C. The yellow suspension was sucked off and washed with ice cold ethyl acetate to yield the ethyl acetate adduct (solvate) of 4,4'-[6-[bis-(2- ethylhexyl)amino]-s-triazine-2,4-diyl]-diresorcinol.
- step a The suspension obtained in Example 2, step a) was extracted several times for 25 minutes with water of approx. 45°C until all the suspension had dissolved.
- the organic phase was evaporated to dryness and crystallised from acetonitrile at 0°C.
- the yellow suspension was sucked off and washed with acetonitrile to yield the acetonitrile adduct (solvate) of 4,4'- [6- [bis-(2-ethylhexyl)amino]-s-triazine-2,4-diyl]-diresorcinol.
- the reaction mixture was poured onto a stirred mixture of 600 ml ethylacetate and 350 ml water.
- the organic phase was separated and washed three times with water.
- the organic phase was evaporated to dryness and crystallised from acetonitrile at 0°C.
- the yellow suspension was sucked off and washed with acetonitrile to yield the acetonitrile adduct (solvate) of 4,4'- [6- [bis- (2- ethylhexyl)amino]-s-triazine-2,4-diyl]-diresorcinol.
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Abstract
A process for the preparation of substituted amino-diaryl triazines comprising reacting cyanuric chloride with a substituted amine NH(R,R1) in substantially equimolar amounts in an anhydrous aromatic hydrocarbon first at low temperature, and subsequently heating the resulting mixture to convert the remaining cyanuric chloride and amine hydrochloride, submitting the resulting compound to a Friedel-Crafts reaction wiht an appropriate aryl hydrocarbon, working up the reaction mixture by adding water and an organic solvent that is substantially water-immiscible, separating, drying and concentrating the solvent phase, isolating the desired compound as an adduct with an appropriate solvent, and decomposing subsequently the adduct to obtain the substituted amino-diaryl triazine in pure form.
Description
Case 20841
Process for the preparation of substituted amino-diaryl triazines
Compounds of the general formula I
wherein R and R1 independently are alkyl, hydroxyalkyl, alkenyl, alkynyl, or alkyl ether groups substituted by one or more hydroxy and/or alkoxy groups, and Ar represents one of the residues
in which R2 is hydroxy, alkyl, alkenyl, alkynyl, or an alkyl, alkenyl, alkynyl ether residue, or polyalkyl ether residue optionally substituted by one or more hydroxy and/or alkoxy groups and R3 is hydrogen or signifies a residue R2 and in which the hydroxy group is present in the α-position to the bonding to the triazine nucleus, with the number of C and O atoms present in R and R1 being a total of 8 to 42, especially 8 to 18, and the number of O atoms corresponding to at most half of the C atoms, are useful as UV-A filters and are disclosed in EP 780,382.
According to EP 780,382 these compounds can be prepared by a process which comprises reacting cyanuric chloride with an amine NH(R,R') in the presence of an equimolar amount of aqueous sodium hydroxide solution and subsequently submitting the amino- substituted dichloro triazine reaction product of the formula II
In accordance with the present invention it has been found that the reaction of the cyanuric chloride with the substituted amine NH(R,R1) can be improved by carrying out the reaction in an anhydrous aromatic hydrocarbon, such as anhydrous benzene, toluene or xylene, preferably anhydrous toluene, first at low temperature to form a mixture of a compound of formula II and the amine hydrochloride, NH(R,R1) • HC1, and unreacted cyanuric chloride, and subsequently heating said mixture to convert the remaining cyanuric chloride and amine hydrochloride to the desired dichloro triazine of formula II. In this manner, the formation of sodium chloride that has to be disposed of as waste is avoided.
Further, it has been found that the Friedel-Crafts reaction can be carried out by using methanesulfonic acid as the catalyst which can be recovered thus avoiding the formation of waste which is produced in the work-up procedure of the conventional Friedel-Crafts reaction as disclosed in EP 780,382 where aluminum trichloride is used as a catalyst. Still further, it has been found that the product of the Friedel-Crafts reaction, i.e. the compound of formula I can be isolated from the Friedel-Crafts reaction mixture as an adduct with solvents that form an adduct with the compounds of formula I such as lower alkyl nitriles or lower alkanoic acid lower alkyl esters. From the adduct, the compound of formula I can be obtained in high purity by heating and/or applying reduced pressure.
Thus, in one aspect the present invention relates to a process for the preparation of compounds of the general formula II as defined above, which process comprises reacting cyanuric chloride with a substituted amine NH(R,R1) in substantially equimolar amounts in an anhydrous aromatic hydrocarbon first at low temperature to form a mixture of a compound of formula II and the amine hydrochloride, NH(R,R1) • HC1, and unreacted cyanuric chloride, and subsequently heating said mixture to convert the remaining cyanuric chloride and amine hydrochloride to the desired dichloro triazine of formula II.
In another aspect the invention relates to a process for the preparation of compounds of the general formula I as defined above, which process comprises submitting a compound of the general formula II as defined above to a Friedel-Crafts reaction with an appropriate aryl hydrocarbon ArH to obtain a reaction mixture containing a compound of the formula I, and working up the reaction mixture by adding water and an organic solvent that is
substantially water-immiscible, separating, drying and concentrating the solvent phase, isolating the compound of formula I as an adduct with an appropriate solvent, and decomposing subsequently the adduct to obtain the compound of formula I in pure form.
In still another aspect, the invention relates to the novel adducts of the compounds of formula I, particularly the ethyl acetate and acetonitrile adducts.
The term "lower" as used herein denotes groups containing 1 to 5, particularly 1 to 3 carbon atoms. Preferred substantially water-immiscible solvents for use in the work-up of the Friedel-Crafts reaction mixture are lower alkanoic acid lower alkyl esters having a boiling point of less than about 120 °C such as methyl acetate, ethyl acetate, propyl acetate, methyl formiate and ethyl formiate. Particularly preferred is ethylacetate. Appropriate solvents for forming an adduct with the compounds of formula I are lower alkanoic acid lower alkyl esters having a boiling point of less than about 120 °C, and lower alkyl nitriles. Particularly preferred solvents for adduct formation are ethylacetate and acetonitrile.
In a preferred aspect, the invention relates to the preparation of compounds of formula I and II, respectively, wherein Ar is 2,4-dihydroxyphenyl and R and R1 are 2-ethylhexyl.
The reaction of cyanuric chloride with the amine NH RjR1) is first carried out at low temperature, e.g., at about -20 °C to about 70 °C, preferably at -10 °C to about 20 °C, At low temperature, a mixture of about equimolar amounts of dichloro triazine of formula II, amine hydrohalogenide and unreacted cyanuric chloride is formed as can be readily determined by conventional analytical procedures such as gas chromatography.
Thereafter, the so-obtained reaction mixture is heated to elevated temperature, e.g., to reflux temperature thus converting unreacted cyanuric chloride and amine hydrohalogenide to the desired compound of formula II.
The subsequent Friedel-Crafts reaction can be carried out in the same solvent as used in the reaction of the cyanuric chloride with the amine, e.g., in benzene, toluene or xylene. The reaction can be carried out with catalysts which are conventional for this particular reaction, i.e. Lewis acids such as aluminum chloride as disclosed in EP 780,382. However, in a preferred embodiment of the invention, methanesulfonic acid is used as the catalyst in the Friedel-Crafts reaction. When using methanesulfonic acid as the catalyst, the hydrocarbon used as the solvent in the preceding amination reaction is removed prior to the Friedel-Crafts reaction and the Friedel-Crafts reaction is suitably carried out at a temperature of about 10 to 30°C. At this temperature, optimal yield and purity of the desired compound of formula I is achieved in a reaction time of about 2 days. The amount
of catalyst is suitably 2 to 4 g of methanesulfonic acid per mmole of substituted amino dichlorotriazine. When using a Lewis acid such as aluminum chloride the Friedel-Crafts reaction can be carried out at about 70 to 100 °C and using about 1,5 to 3 mole of catalyst per mole of compound of formula II.
The Friedel-Crafts reaction mixture is worked up by adding water and, if required, an organic solvent to obtain a suspension comprising a solvent phase and an aqueous phase. The suspension is filtered and the filter cake resuspended in an organic solvent that is substantially immiscible with water. The organic phase is then washed with water until the suspension has dissolved. Alternatively, the organic phase obtained after adding water to the Friedel-Crafts reaction is washed with water without prior separating the solids. In either case the organic phase is separated and concentrated. If an appropriate solvent that is capable to form an adduct or solvate was used an adduct or solvate of the compound of formula I is thus obtained. Otherwise, e.g., to, the residue is recrystallised from a solvent that is capable to form such adduct or solvate. Finally, the adduct or solvate of the compound of formula I is converted to the pure compound of formula I by heating, e.g. up to about 80 °C to about 120 °C and/or applying reduced pressure, e.g. 1 to 30 mbar.
The invention is illustrated further by the Examples which follow.
Example 1
To a solution of 94.1 g of cyanuric chloride (97%; 495 mmole)in 250 ml of toluene under inert atmosphere there were added with stirring at 0-4°C within 60 min 150.2ml of bis- (2- ethylhexyl) amine. The reaction mixture was then stirred under reflux for 3h. The toluene was distilled off and the residue distilled in high vacuum. There were obtained 183.6 g of 2,4-dichloro-[ 1,3,5] -triazin-2-yl-bis-(2-ethylhexyl)amine, bp0.02-0.05mbar = 125-132°C, purity (GC) >99%; yield 95%.
Example 2
a) To 19.01 g of cyanuric chloride (97%, 100 mmole) and 25 ml of toluene there were added with stirring at 0-4°C within 60 min 30.34 ml of bis-(2-ethylhexyl)amine (101 mmole). After the addition was complete the reaction mixture was stirred for 3,5 h under reflux. After 2 h the production of gaseous HC1 had nearly-ceased. The toluene was distilled off under reduced pressure.
To the residue, 33.03 g of resorcinol (300 mmole) were added under inert atmosphere. Then 202.3 ml of methanesulfonic acid (mp > 18.5°C) were added dropwise at 10°C within
approx. 15 min. The resorcinol dissolved within ca.l hour. The reaction solution was warmed within 29h slowly from 10°C to 18°C and subsequently left to react further for 18h at room temperature.
The orange solution was diluted, at 6°-8°C by the dropwise addition of 500 ml of ethyl acetate. To this solution, 1000 ml of water were added at about 8°C to afford a suspension.
b) The suspension obtained in step a) was filtered. The filter cake was then suspended in ethyl acetate. The suspension was extracted several times with water of approx. 45°C until all the suspension had dissolved. The organic phase was concentrated to 150 g. The solution was dried under reflux by azeotropic removal of water. The dry solution was left to crystallise with stirring at 0°C. The yellow suspension was sucked off and washed with ice cold ethyl acetate to yield the ethyl acetate adduct (solvate) of 4,4'-[6-[bis-(2- ethylhexyl)amino]-s-triazine-2,4-diyl]-diresorcinol. After drying the solvate for 8h at 110°C under water jet vacuum there was obtained 41.45 g of4,4'-[6-[bis-(2- ethylhexyl)amino]-s-triazine-2,4-diyl]-diresorcinol, purity (HPLC) 98.9 %. Yield 76 %.
The mother liquor afforded upon crystallisation from ethyl acetate an additional 2.37 g of product of a purity of 97 %. Total yield 80 %.
Example 3
The suspension obtained in Example 2, step a) was extracted several times for 25 minutes with water of approx. 45°C until all the suspension had dissolved. The organic phase was evaporated to dryness and crystallised from acetonitrile at 0°C. The yellow suspension was sucked off and washed with acetonitrile to yield the acetonitrile adduct (solvate) of 4,4'- [6- [bis-(2-ethylhexyl)amino]-s-triazine-2,4-diyl]-diresorcinol. After drying the solvate for 8h at 110°C under vacuum there was obtained 41.9 g of 4,4'-[6-[bis-(2-ethylhexyl)amino]-s- triazine-2,4-diyl]-diresorcinol, purity (HPLC) 98 %. Yield 78 %.
Example 4
To 19.01 g of cyanuric chloride (97%, 100 mmole) and 25 ml of toluene there were added with stirring at 0-4°C within 60 min 30.34 ml of bis-(2-ethylhexyl)amine (101 mmole). After the addition was complete the reaction mixture was stirred for 3,5 h under reflux. After 2 h the production of gaseous HC1 had nearly ceased. The solution was cooled to 70°C and there was added 28.6g aluminiumchloride, 20.2g sulfolane and 23.6g resocinol. The mixture was stirred for 3 days at 90°C. The reaction mixture was poured onto a stirred mixture of 600 ml ethylacetate and 350 ml water. The organic phase was separated and
washed three times with water. The organic phase was evaporated to dryness and crystallised from acetonitrile at 0°C. The yellow suspension was sucked off and washed with acetonitrile to yield the acetonitrile adduct (solvate) of 4,4'- [6- [bis- (2- ethylhexyl)amino]-s-triazine-2,4-diyl]-diresorcinol. After drying the solvate at 100°C under vacuum there was obtained 42.6 g of 4,4'-[6-[bis-(2-ethylhexyl)amino]-s-triazine- 2,4-diyl]-diresorcinol, purity (HPLC) 97 %. Yield 77 %.
Claims
1. A process for the preparation of a compound of formula II
wherein R and R1 independently are alkyl, hydroxyalkyl, alkenyl, alkynyl, or alkyl ether groups substituted by one or more hydroxy and/or alkoxy groups; which comprises reacting cyanuric chloride with a substituted amine NH(R,R!) in substantially equimolar amounts in an anhydrous aromatic hydrocarbon first at low temperature to form a mixture of a compound of formula II and the amine hydrochloride, NH(R,R') • HCl, and unreacted cyanuric chloride, and subsequently heating said mixture to convert the remaining cyanuric chloride and amine hydrochloride to the desired dichloro triazine of formula II.
2. The process according to claim 1 wherein the aromatic hydrocarbon is toluene or xylene.
3. The process according to claim 1 or 2 wherein the reaction is first carried out at a temperature in the range of from -10 °C to 20 °C and subsequently at elevated temperature.
4. The process according to any one of claims 1 to 3, wherein R and R1 are 2-efhylhexyl.
5. A process for the preparation of compounds of the general formula I
wherein R and R1 are alkyl, hydroxyalkyl, alkenyl, alkynyl, or alkyl ether groups substituted by one or more hydroxy and/or alkoxy groups, and Ar represents one of the residues
wherein R and R1 are as above, to a Friedel-Crafts reaction with an appropriate aryl hydrocarbon ArH to obtain a reaction mixture containing a compound of the formula I, and working up the reaction mixture by adding water and an organic solvent that is substantially water-immiscible, separating, drying and concentrating the solvent phase, isolating the compound of formula I as an adduct with an appropriate solvent, and decomposing subsequently the adduct to obtain the compound of formula I in pure form.
6. The process according to claim 5 wherein the Friedel-Crafts reaction is carried out in the presence of methanesulfonic acid.
7. The process according to claims 5 wherein the solvent is a lower alkanoic acid lower alkyl ester having a boiling point of less than about 120°C.
8. The process according to claim 7 wherein the lower alkanoic acid lower alkyl ester is ethyl acetate.
9. The process according to claim 7 wherein the residue, obtained after concentrating the solvent phase, is crystallised from acetonitrile.
10. The process according to any one claims 5 to 9 wherein R and R are 2-ethylhexyl and Ar is 2,4-dihydroxyphenyl.
11. A process for the preparation of a compound of the general formula I 
wherein R and R1 are alkyl, hydroxyalkyl, alkenyl, alkynyl, or alkyl ether groups substituted by one or more hydroxy and/or alkoxy groups, and Ar represents one of the residues
in which R2 is hydroxy, alkyl, alkenyl, alkynyl, or an alkyl, alkenyl, alkynyl ether residue or polyalkyl ether residue optionally substituted by one or more hydroxy and/or alkoxy groups and R is hydrogen or signifies a residue R and in which the hydroxy group is present in the α-position to the bonding to the triazine nucleus, with the number of C and O atoms present in R and R' being a total of 8 to 42, especially 8 to 18, and the number of O atoms corresponding to at most half of the C atoms, which comprises reacting cyanuric chloride with a substituted amine NH(R,R1) in substantially equimolar amounts in an anhydrous aromatic hydrocarbon first at low temperature to form a mixture of a compound of formula II
wherein R and R1 are as above, and the amine hydrochloride, NH(R,R1) • HCl, and unreacted cyanuric chloride, and subsequently heating said mixture to convert the remaining cyanuric chloride and amine hydrochloride to the compound of formula II, submitting the compound of formula II to a Friedel-Crafts reaction with an appropriate aryl hydrocarbon ArH to obtain a reaction mixture containing a compound of the formula I, and working up the reaction mixture by adding water and an organic solvent that is substantially water-immiscible, separating, drying and concentrating the solvent phase, isolating the compound of formula I as an adduct with an appropriate solvent, and decomposing subsequently the adduct to obtain the compound of formula I in pure form.
12. The process according to claim 11 wherein the Friedel-Crafts reaction is carried out in the presence of methanesulfonic acid as the catalyst and the aromatic hydrocarbon used in the preceeding reaction step is removed prior to the Friedel-Crafts reaction.
13. The process according to claim 11 wherein the Friedel-Crafts reaction is carried out in the presence of aluminum trichloride as the catalyst.
14. The process according to any one of claims 11 to 13 wherein R and R1 are 2-ethylhexyl and Ar is 2,4-dihydroxyphenyl.
15. Adducts of the compounds of formula I, particularly the ethyl acetate and acetonitrile adducts.
16. The invention substantially as described hereinbefore, especially with reference to the Examples.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| AU2002247649A AU2002247649A1 (en) | 2001-01-31 | 2002-01-23 | Process for the preparation of 2-(disubstituted-amino)-4,6-diaryl triazines |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP01102216 | 2001-01-31 | ||
| EP01102216.7 | 2001-01-31 |
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| Publication Number | Publication Date |
|---|---|
| WO2002060882A2 true WO2002060882A2 (en) | 2002-08-08 |
| WO2002060882A3 WO2002060882A3 (en) | 2002-11-28 |
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PCT/EP2002/000626 WO2002060882A2 (en) | 2001-01-31 | 2002-01-23 | Process for the preparation of 2-(disubstituted-amino)-4,6-diaryl triazines |
Country Status (2)
| Country | Link |
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| AU (1) | AU2002247649A1 (en) |
| WO (1) | WO2002060882A2 (en) |
Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US468308A (en) * | 1892-02-02 | Victor seidel | ||
| GB1018107A (en) * | 1963-01-25 | 1966-01-26 | Ciba Ltd | New aryl-1,3,5-triazines,process for their preparation and their use |
| EP0029522A1 (en) * | 1979-11-06 | 1981-06-03 | Hoechst Aktiengesellschaft | s-Triazine derivatives, processes for their preparation from halotriazinylamines and polyamines, and their use as stabilizers |
| US5059689A (en) * | 1988-02-08 | 1991-10-22 | Ciba-Geigy Corporation | Tetramethylpiperidino-s-triazines |
| EP0775698A1 (en) * | 1995-11-23 | 1997-05-28 | Ciba SC Holding AG | Bis-resorcinol-triazines as UV absorber triazine |
| EP0790243A1 (en) * | 1996-02-12 | 1997-08-20 | L'oreal | Derivatives of s-triazine as UV filters |
| FR2757163A1 (en) * | 1996-12-13 | 1998-06-19 | Oreal | NOVEL INSOLUBLE DERIVATIVES OF S-TRIAZINE, PROCESS FOR THEIR PREPARATION, COMPOSITIONS CONTAINING SAME, AND USES THEREOF |
| EP0878469A1 (en) * | 1997-05-16 | 1998-11-18 | Ciba SC Holding AG | Resorcinyl-triazines |
| US5874576A (en) * | 1995-12-19 | 1999-02-23 | Givaudan-Roure (International) Sa | Light screening agents |
| EP0949251A1 (en) * | 1998-04-09 | 1999-10-13 | Ciba SC Holding AG | Diresorcinyltriazines as sunscreen agents |
-
2002
- 2002-01-23 WO PCT/EP2002/000626 patent/WO2002060882A2/en not_active Application Discontinuation
- 2002-01-23 AU AU2002247649A patent/AU2002247649A1/en not_active Abandoned
Patent Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US468308A (en) * | 1892-02-02 | Victor seidel | ||
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Also Published As
| Publication number | Publication date |
|---|---|
| AU2002247649A1 (en) | 2002-08-12 |
| WO2002060882A3 (en) | 2002-11-28 |
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