CN101733153B - Porous crosslinked polystyrene sulfonic acid resin loaded quinine quaternary ammonium salt and preparation method thereof - Google Patents
Porous crosslinked polystyrene sulfonic acid resin loaded quinine quaternary ammonium salt and preparation method thereof Download PDFInfo
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- CN101733153B CN101733153B CN2009102010863A CN200910201086A CN101733153B CN 101733153 B CN101733153 B CN 101733153B CN 2009102010863 A CN2009102010863 A CN 2009102010863A CN 200910201086 A CN200910201086 A CN 200910201086A CN 101733153 B CN101733153 B CN 101733153B
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Abstract
The invention discloses porous crosslinked polystyrene sulfonic acid resin loaded quinine quaternary ammonium salt. In the salt, porous (macroporous) crosslinked polystyrolsulfon acid resin is used as a carrier; sulfonic ions of the porous (macroporous) crosslinked polystyrolsulfon acid resin are bonded with quinine quaternary ammonium salt through ionic bonds; and the quinine quaternary ammonium salt is preferably quaternary ammonium salt formed by quinine and 9-methylanthracene. The preparation method thereof comprises the following steps: reacting the quinine quaternary ammonium salt serving as a raw material with the porous crosslinked polystyrene sulfonic acid resin or porous crosslinked polystyrene sulfonate resin for 10 to 100 hours at 20 DEG C to reflux temperature in the presence of an organic solvent, and filtering out the resin, wherein the molar ratio of the quinine quaternary ammonium salt to the sulfonic acid groups in the porous crosslinked polystyrene sulfonic acid resin is 0.7-5.0:1. The product can be applied to asymmetric synthesis of chiral compounds serving as a chiral catalyst.
Description
Technical field
The present invention relates to a class many (greatly) resin-carried chiral catalyst and the preparation method in hole, be specifically related to the preparation method of the crosslinked polystyrene sulfonic acid resin loaded quinine quaternary ammonium salt in many (greatly) hole.
Background technology
Chipal compounds is widely used in fields such as medicine, biomedicine, agricultural chemicals, perfume industry and special material.Though the most physicochemical properties of chipal compounds identical (as the chemical reaction of fusing point, solubility, generation same type etc.) also have some different (as optical activity, smell, physiologically actives etc.).The possible physiologically active difference of chipal compounds causes drug development person's special concern, close as the enantiomer pharmacological properties that has in the chipal compounds, the pharmacological properties of the enantiomer that has is opposite, and promptly one is good medicine, and another then is a poison.Present many countries stipulate that all the medicine producer must study enantiomter contained in medicine pharmacological action, toxicity and clinical effectiveness separately, thereby rejects poisonous enantiomter.Worldwide caused the upsurge of chipal compounds research and development thus.At present, chiral drug has accounted for sells the over half of medicine, and this trend is also rising.
Because the different enantiomers of chipal compounds may have different physiologically actives, thereby (remarks: the ee value is an enantiomeric excess, represents an enantiomer excessive to another enantiomer, represents with percentage usually to produce high ee value.) chipal compounds be that organic synthesis researcher and medicine manufacturer are pursued.At occurring in nature, the content of the chipal compounds of high ee value is rare, and a large amount of chipal compounds obtained by artificial synthesizing,
The preparation method of chipal compounds mainly contains fractionation, asymmetric syntheses and biosynthesis etc., along with kind and the quantity of fields such as medical industry, agricultural chemicals, life science and material to chipal compounds constantly increases, the preparation method of traditional chipal compounds has been difficult to satisfy the demands, excites people constantly to seek to develop the technology of synthesizing chiral compound.The asymmetric syntheses technology has become present research focus, the especially asymmetric syntheses of chiral catalyst catalysis.
Chiral catalyst mostly is metal complex greatly, catalytic efficiency height, but the central ion of chiral catalyst heavy metal or noble metal often, in course of reaction, may decompose and pollution products, simultaneously the cost of catalyst own is higher, and is difficult to shortcoming such as recovery, is difficult to extensive use.Quinine is a kind of alkaloid, is present in the bark of Peruvian bark tree, and the quaternary ammonium salt of quinine can be used for chiral catalyst.For the metal species chiral catalyst, the quinine stable performance, bought easily, relatively cheap, can be recycled and easily modification etc. a bit be subjected to paying close attention to widely.
The quinine of macromolecule loading or its quaternary ammonium salt have easy separation, can be recycled, advantage such as environmentally friendly.Publication number CN 101168134A has reported with the mesoporous material to be carrier, synthetic a kind of heterogeneous quinine bionic catalyst.The patent report of publication number CN 1523024A immobilized cinchonine Alkaloid part and the synthetic method of macromolecule.Publication number CN 1524835A has reported the preparation method of the dicinchonine Alkaloid part that macromolecule is immobilized.
In patent and other documents, the macromolecule carrier that is used for load quinine or its quaternary ammonium salt mainly contains the Merrifield of linear polystyrene, polyethylene glycol (CN 1523024A) and gel-type
TMResin (Kacprzak, K.;
J.synthesis, 2001,7,961-998; Lv, J.; Wang, X.; Liu, J.Y.; Zhang, L.P.; Wang, Y. M.Tetrahedron:Asymmetry, 2006,17 (3), 330-335) etc.The shortcoming of these carrier maximums shows: on the one hand, need add when catalytic reaction that specific solvent dissolves or these solid-carrying type chiral catalysts of swelling, different carriers need dissolve or swelling in different solvents, needing to add specific precipitating reagent after reaction is finished again separates out carrier, so not only increased the use amount of solvent greatly, and Application of Catalyst also is subjected to the restriction of solvent species, thus the range of application of limiting catalyst; On the other hand, when reclaiming catalyst, cause the loss of catalyst easily.Excessive use solvent also causes the increase of cost and the burden of environment.We are faced with serious environmental now and pollute, and the pollution of volatile solvent is the main source of environmental pollution, develops the trend that environment amenable green catalyst is a current social development.
Therefore, this area press for exploitation separate easily, simple to operate, can be recycled, the preparation method and the chiral catalyst thereof of environment amenable chiral catalyst.
Summary of the invention
The purpose of this invention is to provide a kind of porous crosslinked polystyrene sulfonic acid resin loaded type quinine quaternary ammonium salt.
Another object of the present invention is to provide the preparation method of above-mentioned porous crosslinked polystyrene sulfonic acid resin loaded type quinine quaternary ammonium salt.
Its technical scheme is: a kind of porous crosslinked polystyrene sulfonic acid resin loaded type quinine quaternary ammonium salt, with many (greatly) hole crosslinked polystyrene sulfonic acid resin is carrier, and the azochlorosulfonate acid ion of many (greatly) hole crosslinked polystyrene sulfonic acid resin combines by ionic bond with quinine quaternary ammonium salt.
Described quinine quaternary ammonium salt is preferably the quaternary ammonium salt of quinine and the formation of 9-methyl anthracene, includes but not limited to N-9-anthracene methylene cinchonine quaternary ammonium salt, N-9-anthracene methylene cinchonidine quaternary ammonium salt, N-9-anthracene methylene quinine quaternary ammonium salt and N-9-anthracene methylene chinidine quaternary ammonium salt etc.
The degree of cross linking of described many (greatly) hole crosslinked polystyrene sulfonic acid resin is 6%～50%, and granularity is 20～200 orders, and the aperture is 10～200 nanometers.Better, the granularity of porous crosslinked polystyrene sulfonic acid resin is 30～100 orders, the aperture is 50～150 nanometers.
Can at first be crosslinking agent and many (greatly) hole polystyrene resin carrier of BPO (dibenzoyl peroxide) for the synthetic different degrees of cross linking of initator with the divinylbenzene; obtain the macroporous cross-linked polystyrene (6) of chlorosulfonylation then with the chlorosulfonic acid reaction, hydrolysis generates the crosslinked polystyrene sulfonic acid resin in many (greatly) hole again.By the quaternary ammonium salt of the cinchona alkaloid of the chirality mode with chemical bond (ionic bond) is connected on the carrier, thereby synthesized many
The polystyrene sulfonic acid resin loaded type quinine quaternary ammonium salt that (greatly) hole is crosslinked can be used as the solid phase chiral catalyst.
Its preparation method comprises the steps:
In the presence of organic solvent, with the quinine quaternary ammonium salt is raw material, to reflux temperature, reacted 10～100 hours at 20 ℃ with porous crosslinked polystyrene sulfonic acid resin or porous crosslinked polystyrene sulfonic acid salt resin, leach resin then, obtain porous crosslinked polystyrene sulfonic acid resin loaded quinine quaternary ammonium salt.The mol ratio of sulfonic acid group is 0.7～5.0: 1 in described quinine quaternary ammonium salt and the porous crosslinked polystyrene sulfonic acid resin, preferred mol ratio 1.0～3.0: 1.
Described organic solvent is an aprotic solvent, is preferably nail benzene, benzene, carrene, chloroform, N, aprotic solvent such as dinethylformamide, methyl-sulfoxide.Reflux temperature of the present invention is the reflux temperature of above-mentioned organic solvent.
Described Chinine class quaternary ammonium salt is meant the quaternary ammonium salt that quinine and 9-methyl anthracene form, and includes but not limited to N-9-anthracene methylene cinchonine quaternary ammonium salt, N-9-anthracene methylene cinchonidine quaternary ammonium salt, N-9-anthracene methylene quinine quaternary ammonium salt and N-9-anthracene methylene chinidine quaternary ammonium salt etc.
The degree of cross linking of described many (greatly) hole crosslinked polystyrene sulfonic acid resin is 6%～50%, and granularity is 20～200 orders, and the aperture is 10～200 nanometers.Better, the granularity of porous crosslinked polystyrene sulfonic acid resin is 30～100 orders, the aperture is 50～150 nanometers.
Described porous crosslinked polystyrene sulfonic acid salt resin is porous crosslinked polystyrene sulfonic acid sodium resin or porous crosslinked polystyrene sulfonic acid potassium resin.
Synthesizing of the 9-anthracene methylene quaternary ammonium salt of quinine (cinchonine CN and cinchonidine CD): cinchonine or cinchonidine are dissolved in the toluene, (9-(chloromethyl)-anthracene), refluxing to obtain the 9-anthracene methylene quaternary ammonium salt of cinchonine and the 9-anthracene methylene quaternary ammonium salt of cinchonidine in 4～5 hours to add 9-chloromethyl anthracene again.
Above-mentioned porous crosslinked polystyrene sulfonic acid resin loaded type quinine quaternary ammonium salt is used for the catalysis Chirality Reaction as solid-phase catalyst.
The carrier of the present invention many (greatly) hole crosslinked polystyrene sulfonic acid resin loaded quinine compound is the macroporous cross-linked polystyrene of rigidity, and in solvent and the smooth manhole appendix of substrate energy, this is the total characteristics of macropore carrier.When catalytic reaction, do not need specific dissolution with solvents or swelling, not only reduce the use amount of solvent, environmentally friendly, and be not subjected to the influence of solvent species, catalytic reaction can carried out in the solvent scope widely.In addition, can also have only catalysis asymmetric syntheses under the situation of substrate there not being solvent.
The specific embodiment
Below in conjunction with specific embodiment, further set forth the present invention.Should be understood that these embodiment only are used to illustrate the present invention, limit the scope of the invention and be not used in.
All quote in this application as a reference at all documents that the present invention mentions, just quoted as a reference separately as each piece document.Others of the present invention are because disclosing of the technology of this paper is conspicuous to those skilled in the art.
Should be understood that in addition those skilled in the art can make various changes or modifications the present invention after having read above-mentioned instruction content of the present invention, these equivalent form of values fall within the application's appended claims institute restricted portion equally.
Synthesizing of embodiment 120% degree of cross linking porous crosslinked polystyrene (PS) resin
In the there-necked flask of the 250mL that mechanical agitation and condenser pipe are housed, add gelatin 0.3g, distilled water 150mL, heating and stirring make the gelatin dissolving, add normal heptane 20mL then, styrene 16g, divinylbenzene 4g, BPO 0.2g (being added in the styrene).Start mechanical agitation and control mixing speed, drop is controlled in the suitable scope.Progressively be warming up to 70 ℃, be incubated 2 hours, be warming up to 85 ℃ again, be incubated and rise to 95 ℃ after 4 hours, be incubated after 1 hour, filter, with hot wash for several times, with drying for standby after the acetone extracting.Promptly obtain the degree of cross linking and be 20% porous crosslinked polystyrene resin.
Synthesizing of embodiment 26% degree of cross linking porous crosslinked polystyrene (PS) resin
In the there-necked flask of the 250mL that mechanical agitation and condenser pipe are housed, add gelatin 0.3g, distilled water 150mL, heating and stirring make the gelatin dissolving, add normal heptane 20mL then, styrene 18.8g, divinylbenzene 1.2g, BPO 0.2g (being added in the styrene).Start mechanical agitation and control mixing speed, drop is controlled in the suitable scope.Progressively be warming up to 70 ℃, be incubated 2 hours, be warming up to 85 ℃ again, be incubated and rise to 95 ℃ after 4 hours, be incubated after 1 hour, filter, with hot wash for several times, with drying for standby after the acetone extracting.Promptly obtain the degree of cross linking and be 6% porous crosslinked polystyrene resin.
Synthesizing of embodiment 350% degree of cross linking porous crosslinked polystyrene (PS) resin
In the there-necked flask of the 250mL that mechanical agitation and condenser pipe are housed, add gelatin 0.3g, distilled water 150mL, heating and stirring make the gelatin dissolving, add normal heptane 20mL then, styrene 10g, divinylbenzene 10g, BPO 0.2g (being added in the styrene).Start mechanical agitation and control mixing speed, drop is controlled in the suitable scope.Progressively be warming up to 70 ℃, be incubated 2 hours, be warming up to 85 ℃ again, be incubated and rise to 95 ℃ after 4 hours, be incubated after 1 hour, filter, with hot wash for several times, with drying for standby after the acetone extracting.Promptly obtain the degree of cross linking and be 50% porous crosslinked polystyrene resin.
Porous crosslinked polystyrene sulfonic acid (or sodium sulfonate) the resin SPS's that embodiment 420% is crosslinked is synthetic
Add 20% crosslinked expanded polystyrene resin (representing with formula 1) 5g, the carrene 20mL of embodiment 1 preparation in the there-necked flask of 150mL, ambient temperature overnight adds chlorosulfonic acid 15mL then, and stir after 24 hours and filter, with the acetone washing for several times, drying.Add the sodium hydroxide solution of 50mL1N in the conical flask of 100mL, the resin after the chlorosulfonation (formula 2) is added again, static spending the night filtered, and is washed till neutrality with deionized water, and drying obtains 20% crosslinked expanded polystyrene sodium sulfonate resin (formula 3).Wherein exchanging equivalent is 3.2mmol/g.
Expanded polystyrene sodium sulfonate resin is joined in the hydrochloric acid solution of 50mL1N, and static spending the night filtered, and is washed till neutrality with deionized water, and drying obtains 20% crosslinked macroporous polystyrene sulfonate resin (formula 4).Wherein exchanging equivalent is 3.2mmol/g.
The synthetic method of expanded polystyrene sulfonic acid (or sodium sulfonate) resin of other degrees of cross linking is the same.The degree of cross linking is that exchanging equivalent is respectively 3.6mmol/g and 2.8mmol/g in 6% and 50% the porous crosslinked polystyrene sulfonic acid resin.
Synthesizing of embodiment 5N-9-anthracene methylene cinchonine quaternary ammonium salt (formula 6)
Add 10 gram cinchonines and (represent filling in the 250mL round-bottomed flask of 125mL toluene with CN, formula 1), 9-chloromethyl anthracene 10 grams, under agitation added hot reflux 3 hours, after the cooling reactant liquor is poured in the ether of 450mL, filtration obtains the thick product of solid N-9-anthracene methylene cinchonine salt, with mixed solvent carrene/ether recrystallization purifying, obtain pure product.
Synthesizing of embodiment 6N-9-anthracene methylene cinchonidine quaternary ammonium salt (formula 8)
Add 10.7 gram cinchonidines and (represent filling in the 250mL round-bottomed flask of 125mL toluene with CD, formula 7), 9-chloromethyl anthracene 10 grams, under agitation added hot reflux 3 hours, after the cooling reactant liquor is poured in the ether of 450mL, filtration obtains the thick product of solid N-9-anthracene methylene cinchonidine salt, with mixed solvent carrene/ether recrystallization purifying, obtain pure product.
Embodiment 7SPS-CN-5's is synthetic
Filling 20mL N, adding 4.86g (9.33mmol) cinchonine quaternary ammonium salt (6) in the 50mL round-bottomed flask of N dimethyl formamide, 20% crosslinked porous sulfonate resin of 2g embodiment 4 preparation, 25 ℃ were stirred 60 hours down, filter, use toluene, acetone and water washing for several times respectively, drying.Promptly obtain porous crosslinked polystyrene sulfonic acid resin loaded type N-9-anthracene methylene cinchonine quaternary ammonium salt (SPS-CN-5).
Embodiment 8SPS-CD-6's is synthetic
Filling 20mL N, add 4.86g (9.33mmol) N-9-anthracene methylene cinchonidine quaternary ammonium salt (formula 8) in the 50mL round-bottomed flask of N dimethyl formamide, 20% crosslinked porous sodium sulfonate resin of 2g embodiment 4 preparation, 25 ℃ were stirred 45 hours down, filter, use toluene, acetone and water washing for several times respectively, drying.Promptly obtain porous crosslinked polystyrene sulfonic acid resin loaded type N-9-anthracene methylene cinchonidine quaternary ammonium salt (SPS-CD-6).
Embodiment 9SPS-CN-5's is synthetic
Filling 20mL N, the quaternary ammonium salt (6) that adds 4.86g (9.33mmol) cinchonine CN in the 50mL round-bottomed flask of N dimethyl formamide, 50% crosslinked expanded polystyrene sulfonate resin of 2g embodiment 4 preparation, 25 ℃ were stirred 50 hours down, filter, use toluene, acetone and water washing for several times respectively, drying.
Embodiment 10SPS-CN-5's is synthetic
Filling 20mL N, the quaternary ammonium salt (formula 6) that adds 4.86g (9.33mmol) cinchonine CN in the 50mL round-bottomed flask of N dimethyl formamide, 6% crosslinked expanded polystyrene sodium sulfonate resin of 2g embodiment 4 preparation, 25 ℃ were stirred 30 hours down, filter, use toluene, acetone and water washing for several times respectively, drying.
Embodiment 11SPS-CN-5's is synthetic
Filling the quaternary ammonium salt (formula 6) that adds 4.86g (9.33mmol) cinchonine CN in the 50mL round-bottomed flask of 20mL toluene, 30% crosslinked expanded polystyrene sodium sulfonate resin (exchanging equivalent is 3.3mmol/g) of 2g embodiment 4 preparation, 25 ℃ were stirred 45 hours down, filter, use toluene, acetone and water washing for several times respectively, drying.
Embodiment 12SPS-CN-5's is synthetic
Filling 20mL N, the quaternary ammonium salt (formula 6) that adds 6.25g (12.0mmol) cinchonine CN in the 50mL round-bottomed flask of N dimethyl formamide, 20% crosslinked expanded polystyrene sodium sulfonate resin of 2g embodiment 4 preparation, 25 ℃ were stirred 45 hours down, filter, use toluene, acetone and water washing for several times respectively, drying.
Claims (6)
1. porous crosslinked polystyrene sulfonic acid resin loaded type quinine quaternary ammonium salt, it is characterized in that, with the porous crosslinked polystyrene sulfonic acid resin is carrier, and the azochlorosulfonate acid ion of porous crosslinked polystyrene sulfonic acid resin combines by ionic bond with quinine quaternary ammonium salt;
Described quinine quaternary ammonium salt is selected from N-9-anthracene methylene cinchonine quaternary ammonium salt, N-9-anthracene methylene cinchonidine quaternary ammonium salt, N-9-anthracene methylene quinine quaternary ammonium salt and N-9-anthracene methylene chinidine quaternary ammonium salt;
The degree of cross linking of described porous crosslinked polystyrene sulfonic acid resin is 6%～50%, and granularity is 20～200 orders, and the aperture is 10～200 nanometers.
2. the described a kind of porous crosslinked polystyrene sulfonic acid resin loaded type quinine quaternary ammonium salt of claim 1 is characterized in that the granularity of porous crosslinked polystyrene sulfonic acid resin is 30～100 orders, and the aperture is 50～150 nanometers.
3. the preparation method of claim 1 or 2 described a kind of porous crosslinked polystyrene sulfonic acid resin loaded type quinine quaternary ammonium salts is characterized in that, comprises the steps:
In the presence of organic solvent, with the quinine quaternary ammonium salt is raw material, to reflux temperature, reacted 10～100 hours at 20 ℃ with porous crosslinked polystyrene sulfonic acid resin or porous crosslinked polystyrene sulfonic acid salt resin, leach resin then, obtain porous crosslinked polystyrene sulfonic acid resin loaded quinine quaternary ammonium salt;
Described organic solvent is an aprotic solvent;
The mol ratio of sulfonic acid group is 0.7～5.0: 1 in described quinine quaternary ammonium salt and the porous crosslinked polystyrene sulfonic acid resin.
4. the preparation method of the described a kind of porous crosslinked polystyrene sulfonic acid resin loaded type quinine quaternary ammonium salt of claim 3, it is characterized in that the mol ratio of sulfonic acid group is 1.0～3.0: 1 in described quinine quaternary ammonium salt and the porous crosslinked polystyrene sulfonic acid resin.
5. the preparation method of the described a kind of porous crosslinked polystyrene sulfonic acid resin loaded type quinine quaternary ammonium salt of claim 3 is characterized in that, described organic solvent is selected from toluene, benzene, carrene, chloroform, N, dinethylformamide or methyl-sulfoxide.
6. the preparation method of the described a kind of porous crosslinked polystyrene sulfonic acid resin loaded type quinine quaternary ammonium salt of claim 3, it is characterized in that described porous crosslinked polystyrene sulfonic acid salt resin is porous crosslinked polystyrene sulfonic acid sodium resin or porous crosslinked polystyrene sulfonic acid potassium resin.
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| CN1868595A (en) * | 2005-05-26 | 2006-11-29 | 中国科学院大连化学物理研究所 | Chiral schiff base-metal heterogeneous epoxidation catalyst and its prepn. method |
| CN101411996A (en) * | 2008-11-28 | 2009-04-22 | 上海第二工业大学 | Macromolecule supported Cinchona bases compound, production method and application |
| CN101417241A (en) * | 2008-11-28 | 2009-04-29 | 上海第二工业大学 | Preparation method of macromolecule loaded quinine type compound |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1868595A (en) * | 2005-05-26 | 2006-11-29 | 中国科学院大连化学物理研究所 | Chiral schiff base-metal heterogeneous epoxidation catalyst and its prepn. method |
| CN101411996A (en) * | 2008-11-28 | 2009-04-22 | 上海第二工业大学 | Macromolecule supported Cinchona bases compound, production method and application |
| CN101417241A (en) * | 2008-11-28 | 2009-04-29 | 上海第二工业大学 | Preparation method of macromolecule loaded quinine type compound |
Non-Patent Citations (1)
| Title |
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| 李全莲.聚合物负载手性季铵盐相转移催化剂的合成及其在不对称催化反应中的性能研究.《中国优秀硕士论文数据库》.2005,1-67. * |
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