AU725423B2 - Process for the preparation of 2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-s- triazine - Google Patents
Process for the preparation of 2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-s- triazine Download PDFInfo
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- AU725423B2 AU725423B2 AU74217/96A AU7421796A AU725423B2 AU 725423 B2 AU725423 B2 AU 725423B2 AU 74217/96 A AU74217/96 A AU 74217/96A AU 7421796 A AU7421796 A AU 7421796A AU 725423 B2 AU725423 B2 AU 725423B2
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- 238000000034 method Methods 0.000 title claims abstract description 48
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- FROCQMFXPIROOK-UHFFFAOYSA-N 4-[4,6-bis(2,4-dimethylphenyl)-1,3,5-triazin-2-yl]benzene-1,3-diol Chemical compound CC1=CC(C)=CC=C1C1=NC(C=2C(=CC(C)=CC=2)C)=NC(C=2C(=CC(O)=CC=2)O)=N1 FROCQMFXPIROOK-UHFFFAOYSA-N 0.000 title claims description 8
- 150000001875 compounds Chemical class 0.000 claims abstract description 42
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 claims abstract description 28
- MGNCLNQXLYJVJD-UHFFFAOYSA-N cyanuric chloride Chemical compound ClC1=NC(Cl)=NC(Cl)=N1 MGNCLNQXLYJVJD-UHFFFAOYSA-N 0.000 claims abstract description 23
- 239000002841 Lewis acid Substances 0.000 claims abstract description 14
- 150000007517 lewis acids Chemical class 0.000 claims abstract description 14
- IVSZLXZYQVIEFR-UHFFFAOYSA-N m-xylene Chemical group CC1=CC=CC(C)=C1 IVSZLXZYQVIEFR-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000000203 mixture Substances 0.000 claims abstract description 9
- 239000003849 aromatic solvent Substances 0.000 claims abstract description 8
- 125000003118 aryl group Chemical group 0.000 claims abstract description 7
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 8
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 claims description 6
- 239000006096 absorbing agent Substances 0.000 claims description 3
- PQLAYKMGZDUDLQ-UHFFFAOYSA-K aluminium bromide Chemical compound Br[Al](Br)Br PQLAYKMGZDUDLQ-UHFFFAOYSA-K 0.000 claims description 3
- OCJBOOLMMGQPQU-UHFFFAOYSA-N 1,4-dichlorobenzene Chemical compound ClC1=CC=C(Cl)C=C1 OCJBOOLMMGQPQU-UHFFFAOYSA-N 0.000 claims description 2
- 229940117389 dichlorobenzene Drugs 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 1
- 239000000126 substance Substances 0.000 claims 1
- -1 2,4-dimethylphenyl Chemical group 0.000 abstract description 6
- 238000006243 chemical reaction Methods 0.000 description 29
- RFFLAFLAYFXFSW-UHFFFAOYSA-N 1,2-dichlorobenzene Chemical compound ClC1=CC=CC=C1Cl RFFLAFLAYFXFSW-UHFFFAOYSA-N 0.000 description 18
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical class CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 11
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 239000002904 solvent Substances 0.000 description 9
- 239000000047 product Substances 0.000 description 8
- 239000000243 solution Substances 0.000 description 6
- 239000000725 suspension Substances 0.000 description 6
- 238000002955 isolation Methods 0.000 description 5
- 239000011541 reaction mixture Substances 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- QGJOPFRUJISHPQ-UHFFFAOYSA-N Carbon disulfide Chemical compound S=C=S QGJOPFRUJISHPQ-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 239000012071 phase Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- LVWOBZPDFCTAOU-UHFFFAOYSA-N 2-chloro-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine Chemical compound CC1=CC(C)=CC=C1C1=NC(Cl)=NC(C=2C(=CC(C)=CC=2)C)=N1 LVWOBZPDFCTAOU-UHFFFAOYSA-N 0.000 description 2
- 238000006418 Brown reaction Methods 0.000 description 2
- 238000005727 Friedel-Crafts reaction Methods 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- RDOXTESZEPMUJZ-UHFFFAOYSA-N anisole Chemical compound COC1=CC=CC=C1 RDOXTESZEPMUJZ-UHFFFAOYSA-N 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 description 2
- 238000005580 one pot reaction Methods 0.000 description 2
- 239000011368 organic material Substances 0.000 description 2
- 239000012074 organic phase Substances 0.000 description 2
- 238000005191 phase separation Methods 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 239000008096 xylene Substances 0.000 description 2
- RELMFMZEBKVZJC-UHFFFAOYSA-N 1,2,3-trichlorobenzene Chemical compound ClC1=CC=CC(Cl)=C1Cl RELMFMZEBKVZJC-UHFFFAOYSA-N 0.000 description 1
- HTSVYUUXJSMGQC-UHFFFAOYSA-N 2-chloro-1,3,5-triazine Chemical compound ClC1=NC=NC=N1 HTSVYUUXJSMGQC-UHFFFAOYSA-N 0.000 description 1
- 239000007818 Grignard reagent Substances 0.000 description 1
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 1
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 1
- 239000007983 Tris buffer Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000007717 exclusion Effects 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 150000004795 grignard reagents Chemical class 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 239000004922 lacquer Substances 0.000 description 1
- UZKWTJUDCOPSNM-UHFFFAOYSA-N methoxybenzene Substances CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 description 1
- 239000012454 non-polar solvent Substances 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- 229920000307 polymer substrate Polymers 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 229920001059 synthetic polymer Polymers 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 238000004383 yellowing Methods 0.000 description 1
Classifications
-
- 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
- C07D251/24—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 three ring carbon atoms
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Plural Heterocyclic Compounds (AREA)
Abstract
There is described a process for the preparation of 2-(2-4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-s-triazine of the formula I, which comprises (a) reacting cyanuric chloride of the formula II, in the presence of a Lewis acid in a ratio of 2.3 to 3.0 ml of Lewis acid per mole of cyanuric chloride employed in the presence of at least one inert chlorinated aromatic solvent, with 1,3-xylene of the formula III, in a ratio of 2.1 to 2.5 mol of compound of the formula III per mole of cyanuric chloride employed with addition of compound of the formula III in two steps, wherein the addition of 0.5 to 1.1 mol of the compound of the formula III takes place at 60 to 110 DEG C in the course of 2 to 12 hours, then the mixture is cooled to 20 to 50 DEG C in the course of 0 to 3 hours, after which the additional of 2.0 to 1.0 mol of the compound of the formula III takes place in the temperature range from 20 to 50 DEG C in the course of 5 to 15 hours to give the compound of the formula IV and then, (b) without isolating the compound of the formula IV obtained reacting this with resorcinol in a ratio of 0.5 to 1.0 mol of resorcinol per mole of cyanuric chloride employed at a temperature from 0 to 100 DEG C to give the compound of the formula I.
Description
Our Ref: 621746 P/00/OII Regulation 3:2
AUSTRALIA
Patents Act 1990
ORIGINAL
COMPLETE SPECIFICATION STANDARD PATENT a a a a.
*sa.
Applicant(s): Address for Service: Invention Title: Cibft SG 110lditg AG Kylbeckstrasse 141 Basle 4057
SWITZERLAND
DAVIES COLLISON CAVE Patent Trade Mark Attorneys Level 10, 10 Barrack Street SYDNEY NSW 2000 Process for the preparation of 2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-s-triazifle The following statement is a full description of this invention, including the best method of performing it known to me:- 5020 A-20680/A -1- Process for the preparation of 2-(2,4-dihvdroxvphenvl)-4,6-bis(2,4-dimethvlphenyl)-s-triazine The present invention relates to a novel, simplified and thus more economical process for the preparation of 2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-s-triazine from cyanuric chloride.
The reaction of cyanuric chloride with 1,3-xylene under Friedel-Crafts conditions to give 2-chloro-4,6-bis(2,4-dimethylphenyl)-s-triazine is known, e.g. from DE-A-1 169 947 and Helv. Chim. Acta 55, 1589 (1972). However, the product can also be obtained using an appropriate Grignard reagent, such as described in Helv. Chim. Acta 33, 1365 (1950) and US-A-4 092 466.
The further reaction of the 2-chloro-4,6-bis(2,4-dimethylphenyl)-s-triazine, which is purified '00*o beforehand by recrystallisation, with resorcinol is described in US-A-3 244 708.
The direct reaction of cyanuric chloride with two equivalents of 1,3-xylene, however, has the Sdisadvantage that mono- and trisubstituted products are additionally formed. In particular, the mono-xylyl derivative is undesirable, as it leads in the subsequent stage with resorcinol to the corresponding bis-resorcinol compound. The latter can lead to yellowing in the use of the UV absorbers prepared from the compound of the formula I in various polymer substrates, e.g. in certain lacquers. The formation of this bis-resorcinol compound was earlier excluded by means of the circuitous dichloroalkoxy-s-triazine route [Helv. Chim. Acta 1575 (1972)].
It has now been found that 2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-s-triazine can be prepared by reaction of cyanuric chloride with 1,3-xylene in the presence of a Lewis acid and of an inert chlorinated aromatic solvent without isolation of the chloro-s-triazine intermediate by subsequent reaction with resorcinol in the so-called one-pot process; in this process, surprisingly without increase in the tris content, virtually no monoaryl-substituted dichloro-s-triazine compound is formed in the first reaction step.
-2- Furthermore, it was possible by means of the reaction procedure to exclude an uncontrolled exothermic reaction, which can occur on the simultaneous introduction of the starting materials and the catalyst [for this see DE-A-1 169 947 or BP 884 802], and the safety risk associated therewith.
As solvent, neither the compound of the formula III itself nor carbon disulfide [Helv. Chim. Acta 55, 1589 (1972)] is used, and the reaction mixture also does not become solid, as is described in DE-A-1 169 947.
The invention therefore provides a process for the preparation of 2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-s-triazine of the formula I o
CH
3 which comprises a) reacting cyanuric chloride of the formula II Cl N" N CI N CI at a temperature of 0 to 110 C in the presence of a Lewis acid in a ratio of 2.3 to 3.0 mol of Lewis acid per mole of cyanuric chloride employed in the presence of at least one inert chlorinated aromatic solvent, with 1,3-xylene of the formula III CH3
H
3
C
*e in a ratio of 2.1 to 2.5 mol of compound of the formula III per mole of cyanuric chloride employed with addition of compound of the formula III in a period of from 5 to 30 hours to give the compound of the formula IV
'CH
3 and then b) without isolating the compound of the formula IV obtained reacting this with resorcinol in a ratio of 0.5 to 1.0 mol of resorcinol per mole of cyanuric chloride employed at a temperature from 0 to 100°C to give the compound of the formula I.
The reaction procedure in process step a) is preferably carried out such that the compound of the formula Ill is added in 2 portions. Expediently, first 0.5 to 1.1 mol and then 2.0 to mol of the compound of the formula III are added. The addition of the first portion is carried out at 60 to 1100C, in particular 75 to 950C, that of the second at 20 to 500C, in particular 30 to 400C. In a particularly expedient manner, first 0.5 to 1.0 mol of the compound of the formula III are added at 60 to 1100C to the compound of the formula II in a period of 2 to 12 hours, while the second portion of the compound of the formula III is 2.0 to mol and is metered in at 20 to 500C in a period of 5 to 15 hours. The cooling phase between the two temperature ranges in this case has a length of time of 3 hours, for example 0.1 to 3 hours, in particular 0.5 to 2.5 hours.
In a particularly preferred manner, the reaction procedure in process step a) is carried out such that the addition of 0.85 to 1.0 mol of the compound of the formula III takes place at S"83 to 870C in the course of 3.5 to 4.5 hours, then the mixture is cooled to 33 to 370C for 1.4 to 1.6 hours, after which the addition of 1.45 to 1.3 mol of the compound of the formula III takes place in the temperature range from 33 to 370C in the course of 5.5 to 6.5 hours.
In reaction stage an aromatic solvent or a mixture is employed. Examples therefor are mono-, di- or trichlorobenzene or mixtures thereof, in particular chlorobenzene or dichlorobenzene, e.g, 1,2-dichlorobenzene.
.i In the second reaction stage a different solvent from the first reaction stage a) can be •used.
Suitable solvents are, for example: nitrobenzene, anisole, chlorobenzene and 1,2-dichlorobenzene or mixtures of these with one another.
If in the second reaction stage b) another solvent is used, the first solvent can be partially or completely removed, e.g. by distilling off.
Preferably, however, a chlorinated aromatic solvent is also employed in reaction stage in particular the same one as in reaction stage a).
In reaction stage the Lewis acid used in the reaction known to the person skilled in the art as a Friedel-Crafts reaction is preferably aluminium chloride or aluminium bromide, where the former is to be particularly preferred. The Lewis acids mentioned are expediently essentially anhydrous.
The Lewis acid is preferably employed in a ratio of 2.4 to 2.6 mol per mole of cyanuric chloride.
Process step b) can expediently follow directly without isolation of the product of the formula IV formed in the first process step i.e. working-up is unnecessary under the reaction conditions mentioned here, as in process step a) virtually no mono-xylyl compound is formed. The relatively high percentage proportion of the tris-xylyl compound does not interfere with the further course of the reaction, as this compound remains in solution during the isolation of the desired product and is therefore recovered in the filtrate.
In process step preferably 0.7 to 0.8 mol of resorcinol are employed per mole of cyanuric chloride and the temperature during the reaction is expediently continuously increased from to 80 0
C.
The isolation of the final product can be carried out by methods which are customary per se.
Expediently the Lewis acid is first hydrolysed.
If, for example, a chlorinated aromatic solvent is used, the compound of the formula I can S. be obtained as a crystalline compound by slow addition of a non-polar solvent and seeding.
The temperature during the crystallization is expediently lowered and the product obtained is preferably isolated using a suction filter.
The product separated off from the solvent is expediently washed on the suction filter and then dried, drying preferably taking place in vacuo at 65 to 70 0
C.
The compound of the formula I is itself already distinguished by its photostabilizing action in organic materials; it can moreover be advantageously employed by substitution of the hydrogen of the p-hydroxy function for the preparation of compounds such as 2-(2-hydroxy-4-alkoxyphenyl)-4,6-bis(2,4-dimethylphenyl)-s-triazines, which are known as photostabilizers for organic material, in particular synthetic polymers. Examples of these uses of compounds similar to the formula I are found, for example, in US-A-3 268 474.
A further subject matter of the instant invention is the use of the compound of the formula I as a UV absorber.
-6- The following Example illustrates the process according to the invention further.
All data in percentages are by weight, unless stated otherwise.
Example: Preparation of 2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-s-triazine Process step a) 200 g (1.50 mol) of aluminium chloride are added to 110.7 g (0.60 mol) of cyanuric chloride, dissolved in 360 g of 1,2-dichlorobenzene, with stirring (about 200 rpm). The readily stirrable suspension is then heated to 84 to 86 0 C in the course of 30 minutes and kept at this temperature for 15 minutes. At about 200 rpm, 67.9 ml (58.6 g, 0.55 mol) of m-xylene are metered in at 84 to 86°C in the course of 4 hours (exothermic reaction!), then the suspension is cooled as evenly as possible to 34 to 36°C in the course of 1.5 hours.
The addition of a further 101.8 ml (87.95 g, 0.83 mol) of m-xylene is carried out at 34 to 36°C (exothermic reaction!) in a period of 6 hours. Shortly before the end of addition, a little HCI gas is released, which is neutralized by means of NaOH After addition of xylene is complete, the readily stirrable dark-brown reaction mixture is additionally stirred at 34 to 36°C for a further 15 minutes.
S
*9* (the next page is 8) -7- The process measures and the preferred process embodiments correspond to those described above for reaction stage a) of the one-pot process according to the invention.
The isolation of the compound of the formula IV is carried out by processes known to the person skilled in the art, such as distillation of the solvent, crystallization by addition of a suitable solvent etc.
The following Example illustrates the process according to the invention further.
All data in percentages are by weight, unless stated otherwise.
Example: Preparation of 2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-s-triazine Process step a) 200 g (1.50 mol) of aluminium chloride are added to 110.7 g (0.60 mol) of cyanuric chloride, dissolved in 360 g of 1,2-dichlorobenzene, with stirring (about 200 rpm). The readily stirrable suspension is then heated to 84 to 860C in the course of 30 minutes and kept at this temperature for 15 minutes. At about 200 rpm, 67.9 ml (58.6 g, 0.55 mol) of m-xylene are metered in at 84 to 860C in the course of 4 hours (exothermic reaction!), then the suspension is cooled as evenly as possible to 34 to 36°C in the course of 1.5 hours.
The addition of a further 101.8 ml (87.95 g, 0.83 mol) of m-xylene is carried out at 34 to 36°C (exothermic reaction!) in a period of 6 hours. Shortly before the end of addition, a little HCI gas is released, which is neutralized by means of NaOH After addition of xylene is complete, the readily stirrable dark-brown reaction mixture is additionally stirred at 34 to 36°C for a further 15 minutes.
Process step b) 9.9 g (0.09 mol) of resorcinol are metered into the above reaction solution in the course of 1 hour; the temperature is furthermore 34 to 36°C. The next 9.9 g of resorcinol are likewise added in the course of 1 hour; during the course of this the temperature is increased from to 480C. A further 29.7 g of resorcinol (0.45 mol) are added at 480C in the course of 3 hours.
The reaction mixture is then heated to 79 to 81 C in a period of 3 hours and additionally stirred at this temperature for 1 hour. The HCI gas released over the entire reaction period is neutralized by means of 40% sodium hydroxide solution.
For working-up, the above warm reaction solution is added to a solution stirred at 300 to 350 rpm, of 750 g of water and 750 g of methyl isobutyl ketone or methyl ethyl ketone which is at room temperature, in the course of 10 to 15 minutes. The product is extracted by stirring at 68 to 700C for 10 minutes. After phase separation, the lower (aqueous) phase is separated off and the upper organic phase is treated with 375 g of 3% hydrochloric acid.
SThe mixture is again stirred at 68 to 70°C for 10 minutes and after phase separation has taken place the lower (aqueous) phase is removed.
The solvents are removed from the organic phase at temperatures from about 104 to 1300C and initial normal pressure up to 150 155 mbar at the end. 400 g of 1,2-dichlorobenzene are added to the distillation residue such that the temperature does not fall below 1200C. 580 g of heptane isomer mixture are then metered in in the course of 1 hour such that a distinct reflux always takes place. After about 200 g of heptane have been added, the solution is continuously seeded [1 g of 2-(2,4dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-s-triazine in 20 g of heptane]. After approximately of the heptane has been metered in, the product slowly begins to crystallize in fine needles. After addition of heptane is complete, the viscous, but readily stirrable suspension is kept under reflux (110 to 1120C) for a further hour.
After the suspension has cooled to 20 to 22°C, it is filtered off with suction and the suction filter material is washed first with 500 g of 1,2-dichlorobenzene/heptane and then with 400 g of methanol.
The moist suction filter material (about 300 g) is dried at 65 to 70°C in vacuo.
Yield: 146.5 g [about 98.5% 144.3 g [100 60.5 of theory, P:\WPDOCS\CRN\SPECI\621746.SPE- 31/5/00 -9based on cyanuric chloride.
Throughout this specification and the claims which follow, unless the context requires otherwise, the word "comprise", or variations such as "comprises" or "comprising", will be understood to imply the inclusion of a stated integer or group of integers or steps butnot the exclusion of any other integer or group of integers or steps.
*4
S
t* o **2
Claims (12)
1. A process for the preparation of 2-(2,4-dihydroxyphenyl)-4,6-bis- (2,4-dimethylphenyl)-s-triazine of the formula I .i S S. which comprises a) reacting cyanuric chloride of the formula 11 CI NkN at a temperature of 0 to 110 0 OC in the presence of a Lewis acid in a ratio of 2.3 to 3.0 mol of Lewis acid per mole of cyanuric chloride employed in the presence of at least one inert chlorinated aromatic solvent, with 1 ,3-xylene of the formula III 11 CH: 1-3C, in a ratio of 2.1 to 2.5 mol of compound of the formula III per mole of cyanuric chloride employed with addition of compound of the formula III in a period of from 5 to 30 hours to give the compound of the formula IV CH 3 and then b) without isolating the compound of the formula IV obtained reacting this with resorcinol in a ratio of 0.5 to 1.0 mol of resorcinol per mole of cyanuric chloride employed at a temperature from 0 to 100°OC to give the compound of the formula 1. -12-
2. A process according to claim 1, wherein in process step a) the compound of the formula III is added in 2 portions.
3. A process according to claim 2, wherein first 0.5 to 1.1 mol and then 2.0 to 1.0 mol of the compound of the formula III are added.
4. A process according to claim 2, wherein the addition of the first portion is carried out at 60 to 110°C, that of the second at 20 to 500C. A process according to claim 1, wherein in process step a) the addition of 0.5 to 1.1 mol of the compound of the formula III at 60 to 110°C in the course of 2 to 12 hours, then the mixture is cooled to 20 to 50°C in the course of 0 to 3 hours, after which the addition of 2.0 to 1.0 mol of the compound of the formula III takes place in the temperature range from 20 to 50°C in the course of 5 to 15 hours.
6. A process according to claim 1, wherein in process step a) the addition of 0.85 to 1.0 mol of the compound of the formula III takes place at 83 to 87°C in the course of 3.5 to hours, then the mixture is cooled to 33 to 37°C in the course of 1.4 to 1.6 hours, after which the addition of 1.45 to 1.3 mol of the compound of the formula III takes place in the o temperature range from 33 to 37°C in the course of 5.5 to 6.5 hours.
7. A process according to claim 1, wherein in process steps a) and b) the same chlorinated aromatic solvent is employed.
8. A process according to claim 7, wherein in process steps a) and b) chlorobenzene or dichlorobenzene are employed.
9. A process according to claim 1, wherein in process step a) the Lewis acid is employed in a ratio of 2.4 to 2.6 mol per mole of cyanuric chloride. A process according to claim 9, wherein the Lewis acid is aluminium trichloride or aluminium tribromide. -13-
11. A process according to claim 10, wherein the Lewis acid is aluminium trichloride.
12. A process according to claim 1, wherein in process step b) 0.7 to 0.8 mol of resorcinol are employed per mole of cyanuric chloride.
13. A process according to claim 1, wherein the temperature in process step b) is 35 to 800C.
14. Use of the compound prepared according to claims 1 to 13 as a UV absorber. A process for the production of compounds of the formula substantially as hereinbefore described with reference to the examples. 0* 0 DATED this 31st day of May, 2000 CIBA SPECIALTY CHEMICALS HOLDING INC S By its Patent Attorneys DAVIES COLLISON CAVE 0* sees C t sees 0
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CH3541/95 | 1995-12-14 | ||
| CH354195 | 1995-12-14 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| AU7421796A AU7421796A (en) | 1997-06-19 |
| AU725423B2 true AU725423B2 (en) | 2000-10-12 |
Family
ID=4258215
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| AU74217/96A Ceased AU725423B2 (en) | 1995-12-14 | 1996-12-06 | Process for the preparation of 2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-s- triazine |
Country Status (7)
| Country | Link |
|---|---|
| KR (1) | KR100484265B1 (en) |
| CN (1) | CN1070187C (en) |
| AT (1) | ATE213732T1 (en) |
| AU (1) | AU725423B2 (en) |
| BR (1) | BR9605986A (en) |
| DE (1) | DE59608792D1 (en) |
| TW (1) | TW366340B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TWI259182B (en) * | 1998-11-17 | 2006-08-01 | Cytec Tech Corp | Process for preparing triazines using a combination of Lewis acids with reaction promoters |
| CN118561772A (en) * | 2024-07-31 | 2024-08-30 | 山东法恩新材料科技有限公司 | Synthesis process for preparing bis-resorcinol methoxyphenyl triazine by one-pot method |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE1169947B (en) * | 1958-12-24 | 1964-05-14 | Ciba Geigy | Process for the preparation of 2- (2 ', 4'-dimethylphenyl) -4, 6-dichloro-1, 3, 5-triazine or 2, 4-di- (2', 4'-dimethylphenyl) -6-chloro- 1, 3, 5-triazine |
| US3244708A (en) * | 1963-02-07 | 1966-04-05 | Ciba Ltd | Hydroxyphenyl-1, 3, 5-triazines |
| US4092466A (en) * | 1976-07-19 | 1978-05-30 | Nasa | Heat resistant polymers of oxidized styrylphosphine |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| NL275368A (en) * | 1961-03-06 |
-
1996
- 1996-12-03 AT AT96810845T patent/ATE213732T1/en not_active IP Right Cessation
- 1996-12-03 DE DE59608792T patent/DE59608792D1/en not_active Expired - Fee Related
- 1996-12-04 TW TW085114935A patent/TW366340B/en active
- 1996-12-06 AU AU74217/96A patent/AU725423B2/en not_active Ceased
- 1996-12-12 CN CN96121532A patent/CN1070187C/en not_active Expired - Fee Related
- 1996-12-13 BR BR9605986A patent/BR9605986A/en not_active IP Right Cessation
- 1996-12-13 KR KR1019960067059A patent/KR100484265B1/en not_active IP Right Cessation
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE1169947B (en) * | 1958-12-24 | 1964-05-14 | Ciba Geigy | Process for the preparation of 2- (2 ', 4'-dimethylphenyl) -4, 6-dichloro-1, 3, 5-triazine or 2, 4-di- (2', 4'-dimethylphenyl) -6-chloro- 1, 3, 5-triazine |
| US3244708A (en) * | 1963-02-07 | 1966-04-05 | Ciba Ltd | Hydroxyphenyl-1, 3, 5-triazines |
| US4092466A (en) * | 1976-07-19 | 1978-05-30 | Nasa | Heat resistant polymers of oxidized styrylphosphine |
Also Published As
| Publication number | Publication date |
|---|---|
| KR100484265B1 (en) | 2005-08-10 |
| KR970042521A (en) | 1997-07-24 |
| CN1070187C (en) | 2001-08-29 |
| DE59608792D1 (en) | 2002-04-04 |
| AU7421796A (en) | 1997-06-19 |
| CN1161331A (en) | 1997-10-08 |
| TW366340B (en) | 1999-08-11 |
| MX9606261A (en) | 1997-10-31 |
| ATE213732T1 (en) | 2002-03-15 |
| BR9605986A (en) | 1998-09-01 |
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| FGA | Letters patent sealed or granted (standard patent) |