CN1235946A - Process for preparing stereo hindered amine nitrogen-oxygen free-radical - Google Patents
Process for preparing stereo hindered amine nitrogen-oxygen free-radical Download PDFInfo
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- CN1235946A CN1235946A CN 99113523 CN99113523A CN1235946A CN 1235946 A CN1235946 A CN 1235946A CN 99113523 CN99113523 CN 99113523 CN 99113523 A CN99113523 A CN 99113523A CN 1235946 A CN1235946 A CN 1235946A
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- hindered amine
- hydrogen peroxide
- metal ion
- exchange resin
- karb
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Abstract
The present invention relates to the field of fine chemical industry. The present invention uses hydrogen peroxide as oxidant and cationic exchange resin carrying Ca2+, Mg2+, Ba2+, Sr2+ and other alkali earth metal ions as well as metallic ions Zn2+ and Sn2+ as catalyst. The reaction has mild condition with high yield and no environmental pollution, and the catalyst may be used repeatedly. The preparation is suitable for industrial production.
Description
The invention belongs to field of fine chemical, relate to a kind of preparation method of stereo hindered amine nitrogen-oxygen free-radical.
As everyone knows, stereo hindered amine nitrogen-oxygen free-radical is the crucial organic compound of a class, and its general structure is:
Stereo hindered amine nitrogen-oxygen free-radical can be used as the photostabilizer of organic polymer, and the spin label in the living things system research also can be used as the catalyst for selective oxidation in the organic synthesis.
Stereo hindered amine nitrogen-oxygen free-radical is to be raw material with the hindered amine, in the presence of catalyzer, obtains through oxidation.At present, existing many patents and document disclose the preparation method of stereo hindered amine nitrogen-oxygen free-radical, comparatively typically have: US4,665,185 disclose that a kind of employing tertbutyl peroxide is made oxygenant, transition metal is made the Preparation of catalysts method, and the major defect that this method exists is that not only catalyzer costs an arm and a leg, and can not reclaim repeated use, also will produce the by product of equivalent simultaneously, be unfavorable for scale operation; Document " J.Org.Chem.1974,39,2356-2360 " has been reported a kind of method that adopts trichlorine peroxidation phenylformic acid to make oxygenant, has above-mentioned defective too; Document " Z.Naturforsch.1976; 31b; 1376 ", " J.Prakt.Chem., 1985,327; 1011 ", " Synthesis; 1971,190 " adopt hydrogen peroxide as oxidant, with sodium wolframate or catalysis of phosphotungstic acid, this method reaction times reaches several days, industrial can't practical application; United States Patent (USP) U.S.5,416,215 and U.S.5,629,426 use hydrogen peroxide as oxidant, make catalyzer with carbonate, vitriol or the volatile salt of basic metal or alkaline-earth metal, though can shorten the reaction times, but employed catalyzer is a homogeneous catalyst, and the purge process of reaction after product is very complicated, and will pollute environment; U.S.5,218,116 propose to make catalyzer with ZSM-5, and the main drawback of this method is that catalyst activity reduction is fast, and it is few, non-renewable to reuse number of times, will pollute environment.
In sum, the present various methods that prepare stereo hindered amine nitrogen-oxygen free-radical are all not ideal enough, need a kind of new method for preparing stereo hindered amine nitrogen-oxygen free-radical of research and development, to satisfy the needs of branch of industry.
The objective of the invention is to disclose a kind of with hydrogen peroxide as oxidant, with load the Zeo-karb of metal ion be the method for Preparation of catalysts stereo hindered amine nitrogen-oxygen free-radical, the existing in prior technology catalyzer costs an arm and a leg to overcome, long reaction time, repeated use number of times are few, non-renewable, will be to shortcomings such as environment pollute.
Design of the present invention is such:
To adopt conventional method to be adsorbed on the ion exchange resin as the metal ion of catalyzer as catalyzer, adopt hydrogen peroxide as oxygenant, after reaction finished, target product was very easy with separating of catalyzer, and catalyzer can be repeatedly used.
The present invention also is achieved in that
(1) at first adopt conventional method to prepare the ion exchange resin of loaded metal ion, preparation process is as follows:
With H type Zeo-karb after washing transition, freeze-day with constant temperature is 12 hours under the condition of 800Pa and 70 ℃, joining concentration of metal ions then is the mixing solutions (V/V=1: 5) of the second alcohol and water of 0.5～10.0M, add-on is advisable with w/w=0.2～1.0, reflux 12 hours, water and washing with acetone then, 800Pa dry 5 hours down can obtain the ion exchange resin of loaded metal ion.Said metal ion is Ca
2+, Mg
2+, Ba
2+, Sr
2+Deng alkaline-earth metal ions and Zn
2+, Sn
2+A kind of in the ion, preferably Mg
2+Or Zn
2+Said metal ion derives from ZnSO
4, SnCl
2, CaCl
2, MgSO
4Deng water-soluble metal salt.Said H type Zeo-karb is a kind of in styrene type cation exchange resin, acrylic acid type cation exchange resin, metha crylic Zeo-karb or the phenolic type cation exchange resin, and the metal ion charge capacity is good with 2.0～10.0mmol metal ion/gram dried resin on the ion exchange resin.
(2) hydrogen peroxide slowly is added drop-wise in the mixture by the ion exchange resin of hindered amine, catalyzer-loaded metal ion and solvent composition and reacts, and constantly stir, after reaction finishes, from mixture, leach the ion exchange resin of loaded metal ion, the pressure reducing and steaming solvent, can obtain target product-stereo hindered amine nitrogen-oxygen free-radical, the method for recrystallization that in case of necessity can be by routine is carried out purifying, to obtain high-quality stereo hindered amine nitrogen-oxygen free-radical.
Said hindered amine is the compound with one of following general structure:
4-replaces-2,2,6, and 6-tetramethyl piperidine 3-replaces-2,2,4,5,5-pentamethyl-tetramethyleneimine 2,3,3,5,5-pentamethyl-morpholine
Wherein: X is CHOH, CH
2, CHOCH
3, C=O, HCOOCCH
3, CHCl,
CHOSO
3A kind of in H, CHBr or the polystyrene etc.;
Y is CH
3, CHO, CH
2OH or CONH
2Deng in a kind of;
Said solvent is a kind of and composition thereof in water, methyl alcohol, ethanol, acetone, hydrochloric ether such as the methylene dichloride.
Reaction expression is as follows:
The processing condition of reaction are such: temperature is 20～100 ℃, and preferred temperature is 50～95 ℃; Reaction times is 3～16 hours; The hydrogen peroxide dropping time is 2～15 hours; The mol ratio of hydrogen peroxide and hindered amine is: hydrogen peroxide: hindered amine=(4～1): 1, and preferred ratio is: hydrogen peroxide: hindered amine=(1.4～3): 1; The consumption of the ion exchange resin of loaded metal ion is 1～10% of a hindered amine weight, preferably 4～6%.
The ion exchange resin of the loaded metal ion that reaction leaches after finishing is reusable, its active group originally can remain unchanged, through behind tens of secondary responses, when activity descends to some extent, can be once more with adsorption of metal ions in ion exchange resin, recover its catalytic activity.
Reaction yield is slightly different with different catalyzer according to different types of hindered amine, but general equal reaching more than 90%.
Therefore, the said method of the present invention, reaction conditions is very gentle, and catalyzer is reusable, and the reaction yield height does not have environmental pollution, is a kind of preparation method of being convenient to the stereo hindered amine nitrogen-oxygen free-radical of suitability for industrialized production.
Below will do further related content of the present invention by embodiment
Embodiment 1
In being provided with the 250ml four-hole reaction flask of stirring, reflux condensation mode and constant pressure funnel, add 15.7 gram (0.1 mole) 4-hydroxyls-2,2,6,6-tetramethyl piperidine, 0.7 gram load Zn
2+Amberlite200 (Rohm﹠amp; Hass company product), charge capacity is 4.2mmolZn
2+/ g dried resin, the mixture of 20ml water and methyl alcohol (3: 1, volume ratio).Under 70 ℃, slowly drip the hydrogen peroxide of 20.25 grams (0.18 mole) 30% (wt%) in 6 hours continuously, continue reaction 2 hours, leach catalyzer (load Zn
2+Amberlite200).Add the sulfuric acid of 5ml10% in filtrate, use 50ml n-hexane extraction 4 times, extraction liquid merges the back steaming and desolventizes, promptly obtain fusing point and be 71.5 ± 0.5 ℃, the target product-4-hydroxyl-2,2 of orange red needle-like crystal, 6,6-tetramethyl piperidine-1-oxygen 16.8 grams, productive rate is 97.7%.
Embodiment 2-12
Operating process is identical with embodiment 1, and catalyzer is reused 11 times, and its reaction result is as follows:
| Embodiment | The reuse number of times | 4-hydroxyl-2,2,6,6-tetramethyl piperidine transformation efficiency % |
| ????2 | ????0 | ????99.2 |
| ????3 | ????1 | ????99.1 |
| ????4 | ????2 | ????99.1 |
| ????5 | ????3 | ????98.8 |
| ????6 | ????4 | ????98.7 |
| ????7 | ????5 | ????98.7 |
| ????8 | ????6 | ????98.5 |
| ????9 | ????7 | ????98.1 |
| ????10 | ????8 | ????97.6 |
| ????11 | ????9 | ????97.2 |
| ????12 | ????10 | ????97.0 |
Embodiment 13-16
Adopt embodiment 1 identical operations process, catalyzer then adopts the Amberlite200 that has adsorbed different metal ions respectively, and charge capacity is 4.2mmol metal ion/g dried resin, and its result is as follows:
| Embodiment | The ion title | 4-hydroxyl-2,2,6,6-tetramethyl piperidine transformation efficiency % |
| ????13 | ????Ca 2+ | ????98.1 |
| ????14 | ????B a2+ | ????98.4 |
| ????15 | ????Mg 2+ | ????98.8 |
| ????16 | ????Sn 2+ | ????85.4 |
Embodiment 17-19
Adopt embodiment 1 identical operations process, catalyzer then adopts respectively and has adsorbed Zn
2+The ion exchange resin that ionic is different, its result is as follows:
*The HD-1 resin is the Shanghai China scientific and technological trading company of a shake product
| Embodiment | The resin title | Charge capacity mmolZn 2+/ g dried resin | 4-hydroxyl-2,2,6,6-tetramethyl piperidine transformation efficiency % |
| ????17 | ?Amberlite-120 | ????3.9 | ????92.2 |
| ????18 | ?HD-1 | ????4.5 | ????97.5 |
| ????19 | ?Amberlite?IRC-84 | ????7.0 | ????98.9 |
Embodiment 20-23
Adopt and embodiment 1 identical operations process and processing condition, with above-mentioned various hindered amines with different structure is the feedstock production stereo hindered amine nitrogen-oxygen free-radical, the add-on of hindered amine is 0.1 mole, the add-on of hydrogen peroxide is 0.18 mole, solvent is the water-methanol solution of 1: 1 (weight), and its result is as follows: embodiment raw material product yield %20
98.621
91.022
92.323
95.5
Embodiment 24
In the device identical, add 25.3 gram (0.1 mole) 4-sulfate groups-2,2,6,6-tetramethyl piperidine, 2.53 gram load Zn with embodiment 1
2+Amberlite200, charge capacity is 4.2mmolZn
2+/ g dried resin, 20ml water.Under 100 ℃, slowly drip the hydrogen peroxide of 45.3 grams (0.4 mole) 30% (wt%) in 2.5 hours continuously, continue reaction 1 hour, adopt the purification process identical, promptly obtain target product-4-sulfate group-2,2 with embodiment 1,6,6-tetramethyl piperidine-1-oxygen 25.2 grams, productive rate 94.2%.
Claims (10)
1. the preparation method of a stereo hindered amine nitrogen-oxygen free-radical, it is characterized in that mainly comprising following two steps: (1) with the hindered amine be raw material, with hydrogen peroxide as oxidant, with load the Zeo-karb of metal ion be catalyzer, in solvent, reacted under 20～100 ℃ the condition 3～16 hours, the consumption of the Zeo-karb of loaded metal ion is 1～10% of a hindered amine weight; The mol ratio of hydrogen peroxide and hindered amine is: hydrogen peroxide: hindered amine=(4～1): 1; (2) from reaction product, reclaim catalyzer and collect target product-stereo hindered amine nitrogen-oxygen free-radical with conventional method.
2. the method for claim 1, it is characterized in that: said hindered amine is the compound with one of following general structure:
4-replaces-2,2,6, and 6-tetramethyl piperidine 3-replaces-2,2,4,5,5-pentamethyl-tetramethyleneimine 2,3,3,5,5-pentamethyl-morpholine wherein: X is CHOH, CH
2, CHOCH
3, C=O, HCOOCCH
3, CHCl,
CHOSO
3A kind of in H, CHBr or the polystyrene;
Y is CH
3, CHO, CH
2OH or CONH
2In a kind of;
3. the method for claim 1 is characterized in that:
Said metal ion is Ca
2+, Mg
2+, Ba
2+, Sr
2+, Zn
2+Or Sn
2+In the ion one or more;
Said H type Zeo-karb is a kind of in styrene type cation exchange resin, acrylic acid type cation exchange resin, metha crylic Zeo-karb or the phenolic type cation exchange resin, and the metal ion charge capacity is 2.0～10.0mmol metal ion/gram dried resin on the ion exchange resin.
4. method as claimed in claim 3 is characterized in that: preferred metal ion is Mg
2+Or Zn
2+
5. as the described method of claim 1-4, it is characterized in that: hydrogen peroxide was added drop-wise in the reactant in 3～16 hours continuously lentamente.
6. as the described method of claim 1-4, it is characterized in that: the mol ratio of preferred hydrogen peroxide and hindered amine is:
Hydrogen peroxide: hindered amine=(1.4～3): 1.
7. as the described method of claim 1-3, it is characterized in that: the consumption of the ion exchange resin of preferred loaded metal ion is 4～6% of a hindered amine weight.
8. as the described method of claim 1-3, it is characterized in that: preferred temperature of reaction is 50～95 ℃.
9. as the described method of claim 1-3, it is characterized in that: preferred H type Zeo-karb is a styrene type cation exchange resin.
10. as the described method of claim 1-3, it is characterized in that: said solvent is a kind of and composition thereof in water, methyl alcohol, ethanol, acetone, the hydrochloric ether.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN99113523A CN1086686C (en) | 1999-03-12 | 1999-03-12 | Process for preparing stereo hindered amine nitrogen-oxygen free-radical |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN99113523A CN1086686C (en) | 1999-03-12 | 1999-03-12 | Process for preparing stereo hindered amine nitrogen-oxygen free-radical |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1235946A true CN1235946A (en) | 1999-11-24 |
| CN1086686C CN1086686C (en) | 2002-06-26 |
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ID=5276703
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN99113523A Expired - Fee Related CN1086686C (en) | 1999-03-12 | 1999-03-12 | Process for preparing stereo hindered amine nitrogen-oxygen free-radical |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101108338B (en) * | 2006-07-20 | 2011-01-12 | 北京化工大学 | Resin carrier solid alkali catalyst and method for synthesizing biological diesel oil with animal vegetable oil |
| CN102049248A (en) * | 2010-11-23 | 2011-05-11 | 南京林业大学 | Catalyst for synthesizing piperidine nitroxide radical and preparation method thereof |
| CN107849458A (en) * | 2015-09-04 | 2018-03-27 | Dic株式会社 | Liquid-crystal composition and use its liquid crystal display cells |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4665185A (en) * | 1984-03-22 | 1987-05-12 | Ciba-Geigy Corporation | Process for preparing nitroxyls of sterically hindered amines |
| DE4219459A1 (en) * | 1992-06-13 | 1993-12-16 | Huels Chemische Werke Ag | Process for the preparation of 2,2,6,6-tetramethylpiperidine-N-oxyl and its derivatives substituted in the 4-position |
| US5629426A (en) * | 1995-11-09 | 1997-05-13 | Ciba-Geigy Corporation | Carbonate-mediated hydrogen peroxide oxidations of 4-hydroxy-2,2,6,6-tetramethylpiperidine |
-
1999
- 1999-03-12 CN CN99113523A patent/CN1086686C/en not_active Expired - Fee Related
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101108338B (en) * | 2006-07-20 | 2011-01-12 | 北京化工大学 | Resin carrier solid alkali catalyst and method for synthesizing biological diesel oil with animal vegetable oil |
| CN102049248A (en) * | 2010-11-23 | 2011-05-11 | 南京林业大学 | Catalyst for synthesizing piperidine nitroxide radical and preparation method thereof |
| CN102049248B (en) * | 2010-11-23 | 2012-12-19 | 南京林业大学 | Catalyst for synthesizing piperidine nitroxide radical and preparation method thereof |
| CN107849458A (en) * | 2015-09-04 | 2018-03-27 | Dic株式会社 | Liquid-crystal composition and use its liquid crystal display cells |
| CN107849458B (en) * | 2015-09-04 | 2021-07-27 | Dic株式会社 | Liquid crystal composition and liquid crystal display element using same |
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| Publication number | Publication date |
|---|---|
| CN1086686C (en) | 2002-06-26 |
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