WO2012127425A1 - Process for the preparation of s-triazine compounds - Google Patents

Process for the preparation of s-triazine compounds Download PDF

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Publication number
WO2012127425A1
WO2012127425A1 PCT/IB2012/051344 IB2012051344W WO2012127425A1 WO 2012127425 A1 WO2012127425 A1 WO 2012127425A1 IB 2012051344 W IB2012051344 W IB 2012051344W WO 2012127425 A1 WO2012127425 A1 WO 2012127425A1
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Prior art keywords
process according
reaction
solvent
acid halide
preparation
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PCT/IB2012/051344
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French (fr)
Inventor
Rudi KRÖNER
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BASF China Co Ltd
BASF SE
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BASF China Co Ltd
BASF SE
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Priority to EP12759876.1A priority Critical patent/EP2688875B1/en
Priority to KR1020137027518A priority patent/KR101859249B1/en
Priority to ES12759876.1T priority patent/ES2560019T3/en
Priority to BR112013023786-4A priority patent/BR112013023786B1/en
Priority to JP2014500522A priority patent/JP6066986B2/en
Priority to CN201280014574.3A priority patent/CN103443086B/en
Priority to US14/004,180 priority patent/US8765753B2/en
Publication of WO2012127425A1 publication Critical patent/WO2012127425A1/en
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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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
    • C07D251/54—Three nitrogen atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D253/00—Heterocyclic compounds containing six-membered rings having three nitrogen atoms as the only ring hetero atoms, not provided for by group C07D251/00
    • C07D253/02—Heterocyclic compounds containing six-membered rings having three nitrogen atoms as the only ring hetero atoms, not provided for by group C07D251/00 not condensed with other rings
    • C07D253/06—1,2,4-Triazines

Definitions

  • the present invention relates to a process for the technically simple and economic preparation of s-triazine compounds, which can be used as photoprotective agents.
  • DE-A 32 05 398 describes s-triazine derivatives which are substituted by radicals of p- aminobenzoic acid esters, which are extraordinarily good photoprotective agents.
  • the compounds are prepared by reacting cyanuric chloride with a p-aminobenzoic acid ester in relatively large amounts of an aliphatic or aromatic hydrocarbon, in particular benzine or xylene, as solvent.
  • the solvent residues remaining in the end product of ca. 20 to 30% by weight have to be completely removed by careful drying under reduced pressure.
  • the present invention therefore relates to a process for the preparation of s-triazine derivatives of the formula
  • R is a Ci-Ci2-alkyl radical, by reacting a cyanuric acid halide with a p-aminobenzoic acid ester, which comprises a CrCi 2 -alkyl radical as radical of the ester alcohol, in a molar ratio of 1 :3 to 1 :5 in a xylene isomer mixture as solvent, characterized in that the solvent is used in amounts of from 0.6 to 2.1 mol/l.
  • the process according to the invention relates to the preparation of the
  • the xylene isomer mixture is recycled in the course of the process. By reducing the amount of solvent, less water and fewer other secondary components are therefore entrained. The energy and time requirements decrease; the mixture is altogether more concentrated. In a particularly preferred embodiment, the reaction is carried out without solvents.
  • the reaction is carried out at a temperature of 85-140°, preferably 105-125°, particularly preferably 1 10-120°C.
  • the reaction can be carried out in this temperature range as a quasi one-stage reaction. Surprisingly, it has been found that during a reaction carried out within this temperature range, the formation of monohydroxytriazine, a secondary component, which is extremely troublesome in comparatively small amounts and reduces the yield, decreases significantly.
  • p-aminobenzoic acid ester is dosed stoichiometrically.
  • the product quality is positively influenced since secondary components are entrained as a function of concentration and temperature during the crystallization.
  • the end temperature of the process of ca. 20-25°C can be fallen below, i.e. it is possible to cool to lower temperatures, which leads to an improved yield.
  • the p-aminobenzoic acid ester is purified by vacuum distillation prior to dosing.
  • the xylene isomer mixture used as reaction solvent is preferably azeotropically dewatered prior to the reaction.
  • the cyanuric acid halide is introduced as initial charge as suspension with the azeotropically dewatered xylene isomer mixture.
  • the solvent is preferably transferred to the receiver at elevated temperature, in particular at a temperature of from 80 to 90°C, in order to prevent the possible formation of monohydroxytriazine upon adding the cyanuric acid halide for the preparation of the suspension at a temperature of > 60°.
  • problems have always arisen with caked cyanuric acid halide on the walls of the reaction vessels.
  • the feed amounts of cyanuric acid halide fluctuated considerably, and an excess of the p-aminobenzoic acid ester was required to ensure the complete conversion of cyanuric acid halide.
  • a particular embodiment of the process according to the invention consists in introducing the p-aminobenzoic acid ester purified by vacuum distillation into the reactor which comprises the dewatered xylene isomer mixture and heating it to ca. 80-1 10°C, preferably 85-95°C, and then metering in the cyanuric acid halide suspension at a temperature of 1 10-120°C.
  • heating is carried out with a ramp to 105-125°C, preferably 1 10-120°C.
  • the post-reaction is carried out at a temperature of 105-125°C, preferably 1 15-120°C from a receiver for 1-5 h, preferably 1 .5-2.5 h.
  • reaction mixture is then cooled, and neutralized with a base, for example NH 3 , alkali metal hydroxide, carbonate or bicarbonate.
  • a base for example NH 3 , alkali metal hydroxide, carbonate or bicarbonate.
  • the process solvent is distilled off, replaced by another solvent, for example an alcohol, and filtered.
  • the mixture is then precipitated by chilled crystallization, and filtered and the product is washed and dried.
  • the sliding ring liquid used in the dryer is preferably 3% strength hydrogen peroxide solution. This can avoid problems with germs. Small amounts of the sliding ring liquid can find their way into the product; however, this has proven unproblematical since the hydrogen peroxide decomposes to harmless components which are removed during drying.
  • palatinol phthalic acid ester
  • 2-ethylhexylhexanol can perform this function.
  • the compounds of the formula (1 ) prepared by the process according to the invention are suitable as photoprotective agents in cosmetic preparations. Examples of the compositions of such cosmetic preparations as photoprotective emulsions, oil-in-water photoprotective creams, water-in-oil photoprotective creams or photoprotective foams can be found in EP 0 087 098.
  • Customary cosmetic oils serving as solvents for compounds of the formula (1 ) in cosmetic preparations are, besides the parent C 6 -Ci 0 -alkanoic acid Ci 0 -C 2 o-alkyl esters such as cetylstearyl 2-ethylhexanoate, described in DE 35 18 670, for example peanut oil, olive oil, isopropyl stearate, isopropyl myristate, coconut fatty acid triglycerides, caprylic/capric triglyceride, triethyl citrate, polyethylene glycol glyceryl cocoate, diisopropyl adipate, propoxylated myristyl alcohol or mixtures thereof.
  • the solubility of the compound of the formula (1 ) in the specified cosmetic oils is sufficiently high.
  • 500 kg of cyanuric chloride are suspended with stirring in a receiver in 1000 I of xylene at elevated temperature (> 60°C).
  • ca. 50 I of xylene are metered into the receiver via a rinsing nozzle in order to rinse any adhering cyanuric chloride from the wall etc. into the suspension.
  • 2000 I of xylene are introduced as initial charge beforehand and dewatered by azeotropic distillation (desired value: ⁇ 250 ppm, determined by Karl- Fischer titration). After checking the water content, 1000 I of the xylene are transferred to the receiver and used for the suspension of the xylene. The transfer preferably takes place at temperatures of 60-80°C.
  • a 750 ml flask 147 g of ethylhexyl p-aminobenzoate are introduced as initial charge with 75 ml of xylene and heated to 120°C. Over the course of one hour, 37.5 g of cyanuric chloride are metered in with stirring at 1 15°-125°C and subsequently rinsed with 37 ml of xylene. At ca. 120°C, the post-reaction takes place over the course of 1 h. After cooling to ca. 90°C, the mixture is neutralized with sodium chloride solution and subsequently stirred for 30 minutes.
  • the organic phase is separated off and analysed by means of HPLC. 90.5 area % main component, 0.5% by weight of secondary components.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Cosmetics (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)

Abstract

A process is described for the preparation of s-triazine derivatives of the formula in which R is a C1-C12-alkyl radical, by reacting a cyanuric acid halide with a p-aminobenzoic acid ester, which comprises a C6-C12-alkyl radical as radical of the ester alcohol, in a molar ratio of 1:3 to 1:5 in a xylene isomer mixture as solvent. 10 The process is characterized in that the solvent is used in amounts of from 0.6 to 2.1mol/l.

Description

Process for the preparation of s-triazine compounds Description The present invention relates to a process for the technically simple and economic preparation of s-triazine compounds, which can be used as photoprotective agents.
DE-A 32 05 398 describes s-triazine derivatives which are substituted by radicals of p- aminobenzoic acid esters, which are extraordinarily good photoprotective agents. According to the preparation examples, the compounds are prepared by reacting cyanuric chloride with a p-aminobenzoic acid ester in relatively large amounts of an aliphatic or aromatic hydrocarbon, in particular benzine or xylene, as solvent. The solvent residues remaining in the end product of ca. 20 to 30% by weight have to be completely removed by careful drying under reduced pressure.
This drying and the solvent exchange on an industrial scale cost energy and are very time-consuming since if the compounds are dried too rapidly at excessively high temperatures, the pure product that is produced has a lower solubility in the oils usually used in cosmetics.
Surprisingly, it has now been found that by using significantly reduced amounts of solvents, products of high purity and large yield can be prepared.
The present invention therefore relates to a process for the preparation of s-triazine derivatives of the formula
Figure imgf000002_0001
in which
R is a Ci-Ci2-alkyl radical, by reacting a cyanuric acid halide with a p-aminobenzoic acid ester, which comprises a CrCi2-alkyl radical as radical of the ester alcohol, in a molar ratio of 1 :3 to 1 :5 in a xylene isomer mixture as solvent, characterized in that the solvent is used in amounts of from 0.6 to 2.1 mol/l.
Starting compounds for the preparation of the s-triazine derivatives according to the invention are, besides cyanuric chloride or bromide, preferably cyanuric chloride, the Ci-Ci2-n- or isoalkyl esters of p-aminobenzoic acid, preferably the C6-Ci0-n- or isoalkyl esters and very particularly preferably the 2-ethylhexyl ester (= ethylhexyltriazone).
Preferably, the process according to the invention relates to the preparation of the
Figure imgf000003_0001
(INCI name: Ethylhexyl Triazone). The xylene isomer mixture is recycled in the course of the process. By reducing the amount of solvent, less water and fewer other secondary components are therefore entrained. The energy and time requirements decrease; the mixture is altogether more concentrated. In a particularly preferred embodiment, the reaction is carried out without solvents.
Preferably, the reaction is carried out at a temperature of 85-140°, preferably 105-125°, particularly preferably 1 10-120°C. The reaction can be carried out in this temperature range as a quasi one-stage reaction. Surprisingly, it has been found that during a reaction carried out within this temperature range, the formation of monohydroxytriazine, a secondary component, which is extremely troublesome in comparatively small amounts and reduces the yield, decreases significantly.
In a preferred embodiment, p-aminobenzoic acid ester is dosed stoichiometrically. Besides the increased number of possibilities for use (the p-aminobenzoic acid ester, in the event of excess, is discharged after the reaction via the bottom during the ethanol recovery), the product quality is positively influenced since secondary components are entrained as a function of concentration and temperature during the crystallization. Additionally, the end temperature of the process of ca. 20-25°C can be fallen below, i.e. it is possible to cool to lower temperatures, which leads to an improved yield.
Preferably, the p-aminobenzoic acid ester is purified by vacuum distillation prior to dosing. The xylene isomer mixture used as reaction solvent is preferably azeotropically dewatered prior to the reaction.
In a further preferred embodiment, the cyanuric acid halide is introduced as initial charge as suspension with the azeotropically dewatered xylene isomer mixture. For this, the solvent is preferably transferred to the receiver at elevated temperature, in particular at a temperature of from 80 to 90°C, in order to prevent the possible formation of monohydroxytriazine upon adding the cyanuric acid halide for the preparation of the suspension at a temperature of > 60°. In the case of the conversion reactions of cyanuric acid halide known hitherto, problems have always arisen with caked cyanuric acid halide on the walls of the reaction vessels. As a result, the feed amounts of cyanuric acid halide fluctuated considerably, and an excess of the p-aminobenzoic acid ester was required to ensure the complete conversion of cyanuric acid halide.
In order to overcome this disadvantage, in the present process, use is preferably made of rotating cleaning nozzles which are operated with the process solvent under pressure in order to remove any adhesions of cyanuric acid halide present in the receiver container and in the feed tube for solid cyanuric acid halide. This permits a precise and virtually stoichiometric dosing of the p-aminobenzoic acid ester. A particular embodiment of the process according to the invention consists in introducing the p-aminobenzoic acid ester purified by vacuum distillation into the reactor which comprises the dewatered xylene isomer mixture and heating it to ca. 80-1 10°C, preferably 85-95°C, and then metering in the cyanuric acid halide suspension at a temperature of 1 10-120°C.
When the cyanuric acid halide dosing is complete, heating is carried out with a ramp to 105-125°C, preferably 1 10-120°C. The post-reaction is carried out at a temperature of 105-125°C, preferably 1 15-120°C from a receiver for 1-5 h, preferably 1 .5-2.5 h.
The reaction mixture is then cooled, and neutralized with a base, for example NH3, alkali metal hydroxide, carbonate or bicarbonate. The process solvent is distilled off, replaced by another solvent, for example an alcohol, and filtered. The mixture is then precipitated by chilled crystallization, and filtered and the product is washed and dried.
The sliding ring liquid used in the dryer is preferably 3% strength hydrogen peroxide solution. This can avoid problems with germs. Small amounts of the sliding ring liquid can find their way into the product; however, this has proven unproblematical since the hydrogen peroxide decomposes to harmless components which are removed during drying.
As a result of the fact that the p-aminobenzoic acid ester is dosed stoichiometrically in the process according to the invention, there is a lack of an excess of p-aminobenzoic acid ester in the reaction mixture which can be used as solvent for the column bottom of the distillation column and also for the distillation residue.
According to the invention, palatinol (phthalic acid ester) and/or 2-ethylhexylhexanol can perform this function. The compounds of the formula (1 ) prepared by the process according to the invention are suitable as photoprotective agents in cosmetic preparations. Examples of the compositions of such cosmetic preparations as photoprotective emulsions, oil-in-water photoprotective creams, water-in-oil photoprotective creams or photoprotective foams can be found in EP 0 087 098.
Customary cosmetic oils serving as solvents for compounds of the formula (1 ) in cosmetic preparations are, besides the parent C6-Ci0-alkanoic acid Ci0-C2o-alkyl esters such as cetylstearyl 2-ethylhexanoate, described in DE 35 18 670, for example peanut oil, olive oil, isopropyl stearate, isopropyl myristate, coconut fatty acid triglycerides, caprylic/capric triglyceride, triethyl citrate, polyethylene glycol glyceryl cocoate, diisopropyl adipate, propoxylated myristyl alcohol or mixtures thereof. The solubility of the compound of the formula (1 ) in the specified cosmetic oils is sufficiently high.
The examples below illustrate the invention without limiting it to these.
Examples
Example 1 : Preparation of ethylhexyltriazones
Structural formula:
Figure imgf000006_0001
500 kg of cyanuric chloride are suspended with stirring in a receiver in 1000 I of xylene at elevated temperature (> 60°C). Towards the end of the reaction, ca. 50 I of xylene are metered into the receiver via a rinsing nozzle in order to rinse any adhering cyanuric chloride from the wall etc. into the suspension.
In the reactor, 2000 I of xylene are introduced as initial charge beforehand and dewatered by azeotropic distillation (desired value: < 250 ppm, determined by Karl- Fischer titration). After checking the water content, 1000 I of the xylene are transferred to the receiver and used for the suspension of the xylene. The transfer preferably takes place at temperatures of 60-80°C.
Then, ca. 2020 kg of 2-ethylhexyl p-aminobenzoate, which has been purified beforehand by distillation, are pumped into the xylene in the reactor and heated to ca. 90°C. Over the course of 3 h, the contents are then metered into the receiver in a temperature-controlled manner (evolution of HCI), during which the temperature is kept at 105-120°C. By introducing N2, HCI is stripped out of the reaction mixture as far as possible.
The post-reaction takes place at 1 10-120°C for 1 h. Example 2 (laboratory example)
In a 750 ml flask, 147 g of ethylhexyl p-aminobenzoate are introduced as initial charge with 75 ml of xylene and heated to 120°C. Over the course of one hour, 37.5 g of cyanuric chloride are metered in with stirring at 1 15°-125°C and subsequently rinsed with 37 ml of xylene. At ca. 120°C, the post-reaction takes place over the course of 1 h. After cooling to ca. 90°C, the mixture is neutralized with sodium chloride solution and subsequently stirred for 30 minutes.
The organic phase is separated off and analysed by means of HPLC. 90.5 area % main component, 0.5% by weight of secondary components.
The resulting ethylhexyltriazone (CAS No. 88122-99-0) exhibits the following absorption spectrum:
Figure imgf000007_0001
E (1 .1 ) > 1500; Xmax = 314 nm

Claims

Claims
1 . Process for the preparation of s-triazine derivatives of the formula
Figure imgf000008_0001
in which
R is a Ci-Ci2-alkyl radical,
by reacting a cyanuric acid halide with a p-aminobenzoic acid ester, which comprises a C6-Ci2-alkyl radical as radical of the ester alcohol, in a molar ratio of 1 :3 to 1 :5 in a xylene isomer mixture as solvent, characterized in that the solvent is used in amounts of from 0.6 to 2.1 mol/l.
2. Process according to Claim 1 , characterized in that it relates to the preparation of the
Figure imgf000008_0002
3. Process according to Claim 1 or 2, characterized in that the xylene isomer mixture is azeotropically dewatered prior to the start of the reaction.
4. Process according to one of Claims 1 to 3, characterized in that the reaction is carried out without solvents.
5. Process according to one of Claims 1 to 4, characterized in that the reaction is carried out at a temperature of 85-140°C.
6. Process according to one of Claims 1 to 5, characterized in that the p-aminobenzoic acid ester is dosed stoichiometrically.
7. Process according to one of Claims 1 to 6, characterized in that the cyanuric acid halide is used as suspension with the azeotropically dewatered xylene isomer mixture.
8. Process according to Claim 7, characterized in that cyanuric acid halide adhering to the reaction vessel is removed using rotating cleaning nozzles which are operated with the solvent under pressure.
9. Process according to one of Claims 1 to 8, characterized in that the p-aminobenzoic acid ester purified by vacuum distillation is introduced into the reactor which comprises the dewatered xylene isomer mixture and heated to 80-1 10°C, and then the cyanuric acid halide suspension is metered in at a temperature of 1 10-120°C.
PCT/IB2012/051344 2011-03-23 2012-03-21 Process for the preparation of s-triazine compounds Ceased WO2012127425A1 (en)

Priority Applications (7)

Application Number Priority Date Filing Date Title
EP12759876.1A EP2688875B1 (en) 2011-03-23 2012-03-21 Process for the preparation of s-triazine compounds
KR1020137027518A KR101859249B1 (en) 2011-03-23 2012-03-21 Process for the preparation of s-triazine compounds
ES12759876.1T ES2560019T3 (en) 2011-03-23 2012-03-21 Procedure for the preparation of s-triazine compounds
BR112013023786-4A BR112013023786B1 (en) 2011-03-23 2012-03-21 PROCESS FOR PREPARING S-TRIAZINE DERIVATIVES
JP2014500522A JP6066986B2 (en) 2011-03-23 2012-03-21 Method for preparing s-triazine compound
CN201280014574.3A CN103443086B (en) 2011-03-23 2012-03-21 Prepare the method for s-triaizine compounds
US14/004,180 US8765753B2 (en) 2011-03-23 2012-03-21 Process for the preparation of s-triazine compounds

Applications Claiming Priority (4)

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US201161466481P 2011-03-23 2011-03-23
EP11159352.1 2011-03-23
US61/466481 2011-03-23
EP11159352 2011-03-23

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BR (1) BR112013023786B1 (en)
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US10569075B2 (en) * 2014-09-19 2020-02-25 Children's Medical Center Corporation Apparatuses for cleaning catheter ports
CN104860893B (en) * 2015-04-13 2017-07-11 三峡大学 A kind of synthetic method of ultra-violet absorber octyl triazone
US10472594B2 (en) * 2017-04-11 2019-11-12 Itaconix Corporation Sulfonated copolymers for detergent composition
CN106986839B (en) * 2017-04-28 2018-02-27 湖北师范大学 A kind of ultra-violet absorber UVT 150 preparation method
CN112321522B (en) * 2020-09-09 2022-06-28 马鞍山科思化学有限公司 Preparation method of sunscreen octyl triazone
WO2024046956A1 (en) 2022-08-29 2024-03-07 Basf Se Improved process for preparing s-triazine derivatives
CN117327025A (en) * 2023-09-22 2024-01-02 利安隆（中卫）新材料有限公司 Preparation method of octyl triazinone

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DE3205398A1 (en) 1981-02-18 1982-10-07 Chemcut Corp., State College, Pa. METHOD FOR TREATING A FLAT OBJECT AND DEVICE FOR CARRYING OUT THE METHOD
EP0087098A2 (en) 1982-02-23 1983-08-31 BASF Aktiengesellschaft s-Triazine derivatives and their use as sunscreen agents
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US20140005387A1 (en) 2014-01-02
KR101859249B1 (en) 2018-06-28
KR20140016945A (en) 2014-02-10
EP2688875A4 (en) 2014-09-17
BR112013023786A2 (en) 2016-08-09
EP2688875A1 (en) 2014-01-29
CN103443086B (en) 2016-04-13
ES2560019T3 (en) 2016-02-17
CN103443086A (en) 2013-12-11
EP2688875B1 (en) 2015-12-30
JP6066986B2 (en) 2017-01-25
US8765753B2 (en) 2014-07-01
JP2014512346A (en) 2014-05-22

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