CN1850809A - Benzotriazole compound containing sulfur, and its preparing method - Google Patents
Benzotriazole compound containing sulfur, and its preparing method Download PDFInfo
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- CN1850809A CN1850809A CN 200610035539 CN200610035539A CN1850809A CN 1850809 A CN1850809 A CN 1850809A CN 200610035539 CN200610035539 CN 200610035539 CN 200610035539 A CN200610035539 A CN 200610035539A CN 1850809 A CN1850809 A CN 1850809A
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- butyl
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Abstract
This invention discloses new ultraviolet absorbent 5, 5'-disulfo-bi[2- (2-hydroxy group -3,5-bi tert-butyl phenyl group)-2H-benzotriazole] and its preparation method. This compound can be made by ortho butyl sulfhydrate reacting with alkali to synthesize ortho butyl sulfhydrate alkali metal salt, then 5-chlorine-2-(2-hydroxy group-3,5- bi tert-butyl phenyl group)-2H-benzotriazole is made in non proton solvent. The compound is high efficient UVA ultraviolet ray absorbent material, it can protect plastic, pain and human skin from this kind ultraciolet damaging, and its preparation method is simple, reaction intermediate doesn't need separating and purification, its yield can reach 60 percent.
Description
Technical field
The present invention relates to the ultraviolet absorbers field, particularly benzotriazole compound of a kind of sulfur-bearing and preparation method thereof.
Background technology
Benzotriazole compound is the important ultraviolet absorbers of a class, has been widely used on polymer industry, coatings industry and the cosmetic industry.People have synthesized the benzotriazole compound of various structure now.The synthetic method of the benzotriazole cpd of sulfur-bearing is disclosed among patent EP0323853, US3766205 and the US5942626; A kind of synthetic method that is used for stablizing 5-methyl-sulphur-2-(2-hydroxyl-3-sec-butyl-5-tert-butyl-phenyl)-2H-benzotriazole cpd of colour film material is disclosed among the patent EP0323853; The synthetic method of 5-sulfydryl-2-(2-hydroxyl-3,5-di-tert-butyl-phenyl)-2H-benzotriazole cpd is disclosed among the patent US3766205; Patent US5942626 then discloses 5 of phenyl ring in the multiple 2H-benzotriazole cpd by the alkyl sulfenyl; the synthetic method of the ultraviolet absorption immunomodulator compounds that artyl sulfo or aromatic alkyl sulfurio replace; and red shift has taken place in the maximum absorption wavelength of pointing out this type of ultraviolet absorption immunomodulator compounds; its maximum absorption wavelength is grown up about 20nm than the maximum absorption wave of general 2H-benzotriazole cpd; therefore this type of ultraviolet absorbers can the long UV-light of absorbing wavelength; can protect plastics; coating and people's skin is avoided the infringement of this type of UV-light (UV-A, wavelength is between 320-400nm).
In sum, though disclose both at home and abroad 5 compounds that replaced by the R-S-group of more benzotriazole cpd, then yet there are no report for 5 compounds that replaced by the R-S-S-group of benzotriazole cpd.
Summary of the invention
The object of the present invention is to provide a kind of new ultraviolet absorbers 5,5 '-two sulphur-two [2-(2-hydroxyl-3,5-di-tert-butyl-phenyl)-2H-benzotriazole].
Another object of the present invention is to provide the preparation method of a kind of above-mentioned 5,5 '-two sulphur-two [2-(2-hydroxyl-3,5-di-tert-butyl-phenyl)-2H-benzotriazole].
The structural formula of ultraviolet absorbers 5,5 '-two sulphur-two [2-(2-hydroxyl-3,5-di-tert-butyl-phenyl)-2H-benzotriazole] that the present invention is new is:
The preparation method of described 5,5 '-two sulphur-two [2-(2-hydroxyl-3,5-di-tert-butyl-phenyl)-2H-benzotriazole] comprises the steps:
(1) at first n-butyl mercaptan and alkali are mixed under room temperature, reaction obtains n-butyl mercaptan an alkali metal salt CH
3CH
2CH
2CH
2S
-M
+
(2) then above-mentioned n-butyl mercaptan an alkali metal salt and aprotic solvent are mixed, add 5-chloro-2-(2-hydroxyl-3,5-di-tert-butyl-phenyl)-2H-benzotriazole, be warming up to reflux temperature, reacted 10～24 hours;
(3) be cooled to room temperature again, and add acidifying, thin up is separated out precipitation, filters, and purifies, and obtains 5,5 '-two sulphur-two [2-(2-hydroxyl-3,5-di-tert-butyl-phenyl)-2H-benzotriazole] at last.
In the step 1, the mol ratio of described n-butyl mercaptan and alkali is 1: 1～2, and preferred molar ratio is 1: 1.2.
In the step 1, described n-butyl mercaptan and alkali can heat after mixing slightly, make quickly to react completely.
In the step 1, described alkali can be sodium hydroxide, sodium hydride, potassium hydroxide, sodium tert-butoxide or potassium tert.-butoxide.
In the step 1, also can add the band aqua water that generates in the reaction process is taken out of.The preferred toluene of described band aqua, dimethylbenzene.
In the step 2, the mol ratio of described n-butyl mercaptan an alkali metal salt and 5-chloro-2-(2-hydroxyl-3,5-di-tert-butyl-phenyl)-2H-benzotriazole is 8～1: 1, and preferred molar ratio is 4: 1; The mol ratio of described aprotic solvent and 5-chloro-2-(2-hydroxyl-3,5-di-tert-butyl-phenyl)-2H-benzotriazole is 45～1: 1, and preferred molar ratio is 15: 1.
In the step 2, described aprotic solvent can be N-Methyl pyrrolidone or dimethyl formamide; Be preferably N-Methyl pyrrolidone.
In the step 2, described reflux temperature is 120 ℃～200 ℃, is preferably 160 ℃～190 ℃.
In the step 3, described acid can be hydrochloric acid, sulfuric acid or acetate.
In the step 3, the available petroleum ether of described precipitation.
The present invention compared with prior art has following advantage and effect:
(1) the invention provides a kind of new ultraviolet absorbers 5,5 '-two sulphur-two [2-(2-hydroxyl-3,5-di-tert-butyl-phenyl)-2H-benzotriazole];
(2) 5,5 '-two sulphur provided by the invention-two [2-(2-hydroxyl-3,5-di-tert-butyl-phenyl)-2H-benzotriazole] are a kind of UVA efficiently (wavelength is between 320-400nm) UV light absorber; Can protect plastics, coating and people's skin to exempt from the infringement of this type of UV-light (UV-A, wavelength is between 320-400nm);
(3) preparation method of benzotriazole compound provided by the invention is simple, and reaction intermediate does not need to separate purifies, and productive rate can be up to 60%.
Description of drawings
Fig. 1 is the preparation flow figure of 5,5 '-two sulphur-two [2-(2-hydroxyl-3,5-di-tert-butyl-phenyl)-2H-benzotriazole].
Embodiment
Below in conjunction with embodiment the present invention is done further detailed description, but embodiments of the present invention are not limited thereto.
The four-hole boiling flask of 250ml is installed on the magnetic stirrer that has heating unit, connect the nitrogen access tube, load onto thermometer and water trap prolong, add 3.2 gram sodium hydroxide (0.08mol) and 7.25 gram n-butyl mercaptans (0.08mol).Start stirring, heating makes dissolution of sodium hydroxide slightly.Add 12.5ml toluene again, mixture heating up steams toluene to refluxing with the water (approximately 1.4ml) of taking generation out of.
Then reaction mixture is cooled to room temperature, takes down water trap, prolong then directly is connected on the flask ground.Add 30ml N-Methyl pyrrolidone (0.31mol) again in flask, 7.16 gram 2-(2 '-hydroxyl-3 ', 5 '-di-tert-butyl-phenyl)-5-chlorinated benzotriazoles (0.02mol) are heated to 186 ℃, react 18 hours.Solution is cooled to room temperature.Slowly add 7.5ml water and 7.5ml concentrated hydrochloric acid under stirring, cooling promptly has precipitation to separate out, and filters, and precipitation is used petroleum ether, is drying to obtain 5,5 '-two sulphur-two [2-(2-hydroxyl-3,5-di-tert-butyl-phenyl)-2H-benzotriazole].
5,5 '-two sulphur that present embodiment prepares-two [2-(2-hydroxyl-3,5-di-tert-butyl-phenyl)-2H-benzotriazole] are the yellow powder powder.Physicochemical property is as follows:
(1) fusing point 269-270 ℃.
(2)NMR：δ1.35-1.37(s，18H)，δ1.47(s，18H)，δ7.39-7.40(s，2H)，δ7.57-7.59(d，2H)，δ7.88-7.90(d，2H)，δ58.09-8.10(s，2H)，δ8.21(s，2H)，δ11.52(s，2H)，(400MHz，CDCl
3)。
(3) FABMS:709 (M+1,7.3), 355 (6.6), 340 (10.4), 307 (4.5), 219 (5.4), 176 (5.4), 154 (40.8), 136 (36.6), 107 (17.9), 91 (23.4), 57 (100) m/z (% relative abundance).
(4) UV absorption (measuring in the chloroform) characteristic is as follows: λ
Max=364nm; ε
Max=56800.
The four-hole boiling flask of 250ml is installed on the magnetic stirrer that has heating unit, connect the nitrogen access tube, load onto thermometer and prolong, add 7.25 gram n-butyl mercaptans (0.08mol), stir the 2.3 gram sodium hydrides (0.096mol) of adding down.
In reaction flask, add 30ml N-Methyl pyrrolidone (0.31mol) and 7.16 gram 2-(2 '-hydroxyl-3 ', 5 '-di-tert-butyl-phenyl)-5-chlorinated benzotriazoles (0.02mol) again, be heated to 186 ℃, reacted 18 hours.Solution is chilled to room temperature.Slowly add 9.3ml water and 9.3ml concentrated hydrochloric acid under stirring, cooling promptly has precipitation to separate out, and filters, and precipitation is used petroleum ether, is drying to obtain 5,5 '-two sulphur-two [2-(2-hydroxyl-3,5-di-tert-butyl-phenyl)-2H-benzotriazole], productive rate 60%.
Physicochemical property, spectroscopic data and the UV of 5,5 '-two sulphur-two [2-(2-hydroxyl-3,5-di-tert-butyl-phenyl)-2H-benzotriazole] of present embodiment preparation absorbs (measuring in the chloroform) characteristic with embodiment 1.
The four-hole boiling flask of 250ml is installed on the magnetic stirrer that has heating unit, connect the nitrogen access tube, load onto thermometer and prolong, add 7.25 gram n-butyl mercaptans (0.08mol), stir the 1.92 gram sodium hydrides (0.08mol) of adding down.
In reaction flask, add 30ml N-Methyl pyrrolidone (0.31mol) and 7.16 gram 2-(2 '-hydroxyl-3 ', 5 '-di-tert-butyl-phenyl)-5-chlorinated benzotriazoles (0.01mol) again, be heated to 186 ℃, reacted 18 hours.Solution is chilled to room temperature.Slowly add 7.5ml water and 7.5ml concentrated hydrochloric acid under stirring, cooling promptly has precipitation to separate out, and filters, and precipitation is used petroleum ether, is drying to obtain 5,5 '-two sulphur-two [2-(2-hydroxyl-3,5-di-tert-butyl-phenyl)-2H-benzotriazole], productive rate 20%.
Physicochemical property, spectroscopic data and the UV of 5,5 '-two sulphur-two [2-(2-hydroxyl-3,5-di-tert-butyl-phenyl)-2H-benzotriazole] of present embodiment preparation absorbs (measuring in the chloroform) characteristic with embodiment 1.
Embodiment 4
The four-hole boiling flask of 250ml is installed on the magnetic stirrer that has heating unit, connect the nitrogen access tube, load onto thermometer and prolong, add 7.25 gram n-butyl mercaptans (0.08mol).Stir and add 3.12 gram sodium hydrides (0.13mol) down.
In reaction flask, add 30ml N-Methyl pyrrolidone (0.31mol) and 7.16 gram 2-(2 '-hydroxyl-3 ', 5 '-di-tert-butyl-phenyl)-5-chlorinated benzotriazoles (0.08mol) again, be heated to 186 ℃ of reactions 18 hours.Solution is chilled to room temperature.Slowly add 12ml water and 12ml concentrated hydrochloric acid under stirring, cooling promptly has precipitation to separate out, and filters, and precipitation is used petroleum ether, is drying to obtain 5,5 '-two sulphur-two [2-(2-hydroxyl-3,5-di-tert-butyl-phenyl)-2H-benzotriazole], productive rate 50%.
Physicochemical property, spectroscopic data and the UV of 5,5 '-two sulphur-two [2-(2-hydroxyl-3,5-di-tert-butyl-phenyl)-2H-benzotriazole] of present embodiment preparation absorbs (measuring in the chloroform) characteristic with embodiment 1.
Embodiment 5,6, Comparative Examples 1,2
The component and the consumption that provide by table 1 prepare four kinds of transparent polychloroethylene compositions.Wherein, in embodiment 5 and 6, new ultraviolet absorbers 5,5 '-two sulphur provided by the invention-two [2-(2-hydroxyl-3,5-di-tert-butyl-phenyl)-2H-benzotriazole] have been added; In Comparative Examples 1 and 2, then do not add new ultraviolet absorbers provided by the invention.
Table 1 unit: gram
| Component | PHR | |||
| Embodiment 5 | Comparative Examples 1 | Embodiment 6 | Comparative Examples 2 | |
| Polyvinyl chloride resin (LS080s) | 100.0 | 100.0 | 100.0 | 100.0 |
| Processing aid (ACR401, industrial goods) | 2.0 | 2.0 | 2.0 | 2.0 |
| Calcium stearate (industrial goods) | 0.5 | 0.5 | 0.5 | 0.5 |
| Three (isooctyl mercaptoacetate) antimony thermo-stabilizer (STH) | 2.0 | 2.0 | 2.0 | 2.0 |
| Dimixo-octyl phthalate (industrial goods) | - | - | 40.0 | 40.0 |
| 5,5 '-two sulphur provided by the invention-two [2-(2-hydroxyl-3,5-di-tert-butyl-phenyl)-2H-benzotriazole] | 0.2 | - | 0.2 | - |
Above-mentioned four kinds of polychloroethylene compositions are made plate, be placed on and two 40W (centre wavelength 365nm) be housed in the accelerated deterioration experimental machine of colour filter quartz burner, its stability of test under UV-light to light, a colour-change result is as follows in observation in per 24 hours:
The composition of embodiment 5 1200 hours still was little yellow transparent;
The composition of embodiment 6 720 hours still was little yellow transparent;
The composition of Comparative Examples 1 promptly became yellow in 360 hours;
The composition of Comparative Examples 2 promptly became yellow in 72 hours;
The above results shows, in adopting the stable polychloroethylene composition of mercaptan antimony organic, use new ultraviolet absorbers 5 provided by the invention, 5 '-two sulphur-two [2-(2-hydroxyl-3,5-di-tert-butyl-phenyl)-2H-benzotriazole] can obviously improve the anti-ultraviolet ageing stability of polychloroethylene composition.
Claims (8)
1, a kind of benzotriazole compound of sulfur-bearing, its name is called ultraviolet absorbers 5,5 '-two sulphur-two [2-(2-hydroxyl-3,5-di-tert-butyl-phenyl)-2H-benzotriazole], its structural formula is:
2, the preparation method of a kind of 5,5 '-two sulphur-two [2-(2-hydroxyl-3,5-di-tert-butyl-phenyl)-2H-benzotriazole] is characterized in that comprising the steps:
(1) at first n-butyl mercaptan and alkali are mixed under room temperature, reaction obtains the n-butyl mercaptan an alkali metal salt;
(2) then above-mentioned n-butyl mercaptan an alkali metal salt and aprotic solvent are mixed, add 5-chloro-2-(2-hydroxyl-3,5-di-tert-butyl-phenyl)-2H-benzotriazole, be warming up to reflux temperature, reacted 10～24 hours;
(3) be cooled to room temperature again, and add acidifying, thin up is separated out precipitation, filters, and purifies, and obtains 5,5 '-two sulphur-two [2-(2-hydroxyl-3,5-di-tert-butyl-phenyl)-2H-benzotriazole] at last.
3, the preparation method of 5,5 '-two sulphur according to claim 2-two [2-(2-hydroxyl-3,5-di-tert-butyl-phenyl)-2H-benzotriazole], it is characterized in that: in the step 1, the mol ratio of described n-butyl mercaptan and alkali is 1: 1～2.
4, according to claim 25,5 '-two sulphur-two [2-(2-hydroxyl-3, the 5-di-tert-butyl-phenyl)-the 2H-benzotriazole] the preparation method, it is characterized in that: in the step 1, described alkali is sodium hydroxide, sodium hydride, potassium hydroxide, sodium tert-butoxide or potassium tert.-butoxide.
5, the preparation method of 5,5 '-two sulphur according to claim 2-two [2-(2-hydroxyl-3,5-di-tert-butyl-phenyl)-2H-benzotriazole] is characterized in that: in the step 1, add toluene or dimethylbenzene the water that generates in the reaction process is taken out of.
6, according to claim 25,5 '-two sulphur-two [2-(2-hydroxyl-3, the 5-di-tert-butyl-phenyl)-the 2H-benzotriazole] the preparation method, it is characterized in that: the mol ratio of described n-butyl mercaptan an alkali metal salt and 5-chloro-2-(2-hydroxyl-3,5-di-tert-butyl-phenyl)-2H-benzotriazole is 8～1: 1.
7, the preparation method of 5,5 '-two sulphur according to claim 2-two [2-(2-hydroxyl-3,5-di-tert-butyl-phenyl)-2H-benzotriazole], it is characterized in that: in the step 2, described aprotic solvent is N-Methyl pyrrolidone or dimethyl formamide.
8, the preparation method of 5,5 '-two sulphur according to claim 2-two [2-(2-hydroxyl-3,5-di-tert-butyl-phenyl)-2H-benzotriazole], it is characterized in that: in the step 3, described acid is hydrochloric acid, sulfuric acid or acetate.
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| US5278314A (en) * | 1991-02-12 | 1994-01-11 | Ciba-Geigy Corporation | 5-thio-substituted benzotriazole UV-absorbers |
| US5298380A (en) * | 1991-09-05 | 1994-03-29 | Ciba-Geigy Corporation | Photographic material which contains a UV absober |
| US6846929B2 (en) * | 2001-04-02 | 2005-01-25 | Ciba Specialty Chemicals Corporation | Benzotriazole/hals molecular combinations and compositions stabilized therewith |
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| CN102619108B (en) * | 2011-04-01 | 2014-10-01 | 浙江理工大学 | Protein reactive ultraviolet absorber and preparation method thereof |
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| CN103289317A (en) * | 2013-01-29 | 2013-09-11 | 中科院广州化学有限公司 | LED packaging material, its preparation method and application |
| CN103224758B (en) * | 2013-01-29 | 2015-04-22 | 中科院广州化学有限公司 | EVA adhesive film for solar cell packaging and preparation method thereof |
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Assignee: Sihui City Zechariah Chemical Co. Ltd. Assignor: Guangzhou Inst. of Chemistry, Chinese Academy of Sciences Contract record no.: 2010440001304 Denomination of invention: Benzotriazole compound containing sulfur, and its preparing method Granted publication date: 20080716 License type: Exclusive License Open date: 20061025 Record date: 20100825 |
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