CN104826655A - Alkylamino pyridine catalyst taking active carbon as carrier and preparation method thereof - Google Patents
Alkylamino pyridine catalyst taking active carbon as carrier and preparation method thereof Download PDFInfo
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- CN104826655A CN104826655A CN201510230632.1A CN201510230632A CN104826655A CN 104826655 A CN104826655 A CN 104826655A CN 201510230632 A CN201510230632 A CN 201510230632A CN 104826655 A CN104826655 A CN 104826655A
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Abstract
The invention discloses an alkylamino pyridine catalyst taking active carbon as the carrier and a preparation method thereof. The preparation method comprises the following steps: using benzyl groups to modify active carbon, and then bonding an alkylamino pyridine group to the benzyl modified active carbon to obtain the catalyst. The alkylamino pyridine group and the benzyl modified active carbon are connected by a nitrogen-carbon covalent bond, and the obtained alkylamino pyridine catalyst loaded on active carbon has a high catalytic performance, is capable of solving the problems that micromolecular catalyst cannot be separated out of the reaction system easily and cannot be repeatedly used, thus saves the reaction cost, and can be used to replace the DMAP catalyst in organic reactions such as acylation reaction, and the like.
Description
Technical field
The invention belongs to catalyst field, being specifically related to a kind of take active carbon as the alkylamino radical pyridine type Catalysts and its preparation method of carrier.
Background technology
Since the middle of last century; have and report DMAP(4-N in a large number; N-dimethylamino naphthyridine) and PPY(4-nafoxidine yl pyridines) to organic acylation reaction, there is good catalytic activity; except above two kinds of active materials; it is found that the compound with alkylamino radical pyridine structure type all shows good catalytic activity to organic reactions such as acidylate, esterification, hydrolysis and etherificates; its reaction rate can be made to improve several times, and this type of catalyst has now become one of the most frequently used catalyst of organic synthesis worker.Domestic chemical pharmacy industry is successfully applied to, in the production of the bulk drug such as acetyl spiramycin and lipid-lowering statins, optimize process conditions; On chemical pesticide is produced, it is used in the reaction of isocyanates synthesis of carbamates and chrysanthemum acyl chlorides synthetic pyrethroid also obvious catalytic activity, acts on quite remarkable.These utilize the reaction of alkylamino radical pyridine type catalyst to achieve good economic and social benefit above.But the alkylamino pyridine type compounds such as most of DMAP are all be dissolved in reaction solution, form homogeneous system catalysis, be difficult to after completion of the reaction be separated and reclaim, cause product separation difficulty, increased the weight of again pollution simultaneously.
On the other hand, active carbon is as porous carbon containing porous material, having good chemical stability, mechanical strength and the performance such as alkaline-resisting, acidproof, heat-resisting, except being widely used in the aspects such as purification of air, solution decolouring and water treatment, is also excellent catalyst carrier.Active carbon normally makes catalyst loading on it by impregnating method as carrier, and this method likely can make catalyst come off in the reaction, and impact is active.Its performance as carrier determined by microcellular structure and surface chemical structure in addition, and kind and the quantity of surface functional group usually affect loading, determine the activity of catalyst.The present invention is the bonding reaction method being different from dipping, first adds novel active group at activated carbon surface, then is fixed on absorbent charcoal carrier with the form of covalent bond wanting the catalyst of load by active group.Result shows, like this can effective solid-carried catalyst, improves active, can prevent from again coming off in catalytic reaction, after completion of the reaction catalyst and the easily separated recovery of product.
Summary of the invention
For alkylamino radical pyridine type catalyst Problems existing, the invention provides a kind of take active carbon as the alkylamino radical pyridine type Catalysts and its preparation method of carrier.The present invention, by bonding reaction, by immobilized for catalyst bonding at activated carbon surface, improves the activity of catalyst, can prevent again catalyst from coming off in catalytic reaction, after completion of the reaction catalyst and the easily separated recovery of product.
In order to realize foregoing invention object, the present invention takes following technical scheme:
A kind of take active carbon as the preparation method of the alkylamino radical pyridine type catalyst of carrier: first that active carbon is Benzylation, then 1-(4-pyridine radicals) piperazine bonding is connected on the activated carbon, after reaction terminates, active carbon after filtration, after multiple wash and oven dry, obtained take active carbon as the alkylamino radical pyridine type catalyst of carrier.
The preparation method of described with active carbon the is alkylamino radical pyridine type catalyst of carrier, specifically comprises the following steps:
1) Benzylation reaction:
In flask, add active carbon, chloromethyl ether and zinc chloride back flow reaction, use distilled water and methanol wash active carbon successively after reaction terminates, then dry 12 h under 80 C in vacuum drying chamber, obtain the active carbon being rich in chlorobenzyl;
2) covalence graft of catalytic activity group:
Benzylation active carbon, 1-(4-pyridine radicals) piperazine and triethylamine that step 1) is obtained is added in flask, abundant stirring and refluxing, distilled water and methanol wash active carbon is used successively after reaction terminates, dry 12 h under 80 C in vacuum drying chamber, obtaining take active carbon as the alkylamino radical pyridine type catalyst of carrier.
Active carbon described in step 1) is wooden or ature of coal merchandise active carbon.
The time of Benzylation reaction in step 1) is 8 ~ 10 h.
Step 2) in Benzylation active carbon, 1-(4-pyridine radicals) piperazine mass ratio be 0.2 ~ 1.0:1.0.
Step 2) in Benzylation active carbon, 1-(4-pyridine radicals) piperazine and triethylamine, abundant stirring and refluxing 12 ~ 14h.
The alkylamino radical pyridine type catalyst of what a kind of preparation method as above obtained with active carbon is carrier.
Remarkable result of the present invention is:
1) active carbon is as porous carbon containing porous material, has good chemical stability and mechanical strength; So be that the catalyst of carrier has the scope of application and excellent catalytic activity widely with active carbon, applied widely;
2) the catalytic activity molecule that activated carbon surface increases is fixing with the mode bonding of covalent bond, Heat stability is good, can effective solid-carried catalyst, improves activity, can prevent from again coming off in catalytic reaction;
3) activated carbon surface bonding solid-carried catalyst, simplifies the separation process of post catalyst reaction and product, can repeatedly use, and improves the utilization rate of catalyst, decreases pollution.
Accompanying drawing explanation
Fig. 1 is the synthetic route chart of the alkylamino pyridine type catalyst taking active carbon as carrier;
Fig. 2 is etherification reaction route map;
Fig. 3 is esterification route map.
Detailed description of the invention
Below by several non-limiting example, embodiment of the present invention and products therefrom are described.The embodiment of other examples in the scope of the invention, also can with reference to the corresponding enforcement of these examples.
Embodiment 1
1) in three-necked bottle, 1.0 g active carbons are added, 70 mL chloromethyl ethers and 0.2 g zinc chloride back flow reaction 8 h; Wash successively with distilled water and methyl alcohol, in vacuum drying chamber, dry 12 h at 80 DEG C, namely obtain the active carbon being rich in benzyl chloride;
2) in round-bottomed flask, add 0.5 g benzyl chloride active carbon, 0.5 g 1-(4-pyridine radicals) piperazine, 0.6 g triethylamine, stirring and refluxing 12 h, be able to the alkylamino pyridine catalyst that active carbon is carrier; Use distilled water and methanol wash successively, be placed in vacuum drying chamber 80 DEG C of drying 12 h.
Catalytic effect (etherification reaction):
In round-bottomed flask, add alkylamino pyridine catalyst, 2 mL triethylamines and 20 mL carrene that 0.5 g phenmethylol, 0.025 g take active carbon as carrier, back flow reaction 24 h, obtains trityl methyl phenyl ethers anisole 1.35 g, and conversion ratio is 83%; Reusing five catalytic conversion is 80%.
Embodiment
2
1) in three-necked bottle, 3.0 g active carbons are added, 180 mL chloromethyl ethers and 0.6 g zinc dichloride back flow reaction 10 h; Wash successively with distilled water and methyl alcohol, in vacuum drying chamber, dry 12 h at 80 DEG C, namely obtain the active carbon being rich in benzyl chloride;
2) in round-bottomed flask, add 2 g benzyl chloride active carbons, add 1-(4-pyridine radicals) piperazine of 2 g, 2.4 g triethylamines, stirring and refluxing 14 h; Obtain active carbon alkylamino pyridine catalyst; Use distilled water and methanol wash successively, be placed in vacuum drying chamber 80 DEG C of drying 12 h.
Catalytic effect (esterification):
0.7 g 2 is added in round-bottomed flask, 4,6-pseudocuminol, 1.5 g take active carbon as the alkylamino pyridine catalyst of carrier, 0.78 g acetic anhydride and 30 mL carrene, stirring reaction 6 h, methanol removed by evaporation, residue is successively with hydrochloric acid and potash washing, anhydrous magnesium sulfate drying, filtration drying is to acetic acid-2,4,6-trimethyl phenyl ester 0.90 g, conversion ratio is 96%; Reusing five catalytic conversion is 90%.
The foregoing is only preferred embodiment of the present invention, all equalizations done according to the present patent application the scope of the claims change and modify, and all should belong to covering scope of the present invention.
Claims (7)
1. one kind take active carbon as the preparation method of the alkylamino radical pyridine type catalyst of carrier, it is characterized in that: first that active carbon is Benzylation, then 1-(4-pyridine radicals) piperazine bonding is connected on the activated carbon, after reaction terminates, active carbon after filtration, after multiple wash and oven dry, obtained take active carbon as the alkylamino radical pyridine type catalyst of carrier.
2. according to claim 1 take active carbon as the preparation method of the alkylamino radical pyridine type catalyst of carrier, it is characterized in that: specifically comprise the following steps:
1) Benzylation reaction:
In flask, add active carbon, chloromethyl ether and zinc chloride back flow reaction, use distilled water and methanol wash active carbon successively after reaction terminates, then dry 12 h under 80 C in vacuum drying chamber, obtain the active carbon being rich in chlorobenzyl;
2) covalence graft of catalytic activity group:
Benzylation active carbon, 1-(4-pyridine radicals) piperazine and triethylamine that step 1) is obtained is added in flask, abundant stirring and refluxing, distilled water and methanol wash active carbon is used successively after reaction terminates, dry 12 h under 80 C in vacuum drying chamber, obtaining take active carbon as the alkylamino radical pyridine type catalyst of carrier.
3. according to claim 2 take active carbon as the preparation method of the alkylamino radical pyridine type catalyst of carrier, it is characterized in that: the active carbon described in step 1) is wooden or ature of coal merchandise active carbon.
4. according to claim 2 take active carbon as the preparation method of the alkylamino radical pyridine type catalyst of carrier, it is characterized in that: the time of Benzylation reaction in step 1) is 8 ~ 10 h.
5. according to claim 2 take active carbon as the preparation method of the alkylamino radical pyridine type catalyst of carrier, it is characterized in that: step 2) in Benzylation active carbon, 1-(4-pyridine radicals) piperazine mass ratio be 0.2 ~ 1.0:1.0.
6. according to claim 2 take active carbon as the preparation method of the alkylamino radical pyridine type catalyst of carrier, it is characterized in that: step 2) in Benzylation active carbon, 1-(4-pyridine radicals) piperazine and triethylamine, abundant stirring and refluxing 12 ~ 14h.
7. the alkylamino radical pyridine type catalyst of what a preparation method as claimed in claim 1 or 2 obtained with active carbon is carrier.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4540743A (en) * | 1983-06-25 | 1985-09-10 | Basf Aktiengesellschaft | Acylation of polyvinyl alcohols, and photopolymerizable and/or photocrosslinkable mixtures containing products thus acylated |
| CN1141217A (en) * | 1996-01-30 | 1997-01-29 | 天津理工学院 | Alkylamino pyridine high molecular catalyst and prepn. method thereof |
| CN1400055A (en) * | 2002-05-14 | 2003-03-05 | 厦门中坤化学有限公司 | Preparation method of acylation reaction catalyst on which 4-N,N-dimethylaminopyridine is loaded |
-
2015
- 2015-05-08 CN CN201510230632.1A patent/CN104826655A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4540743A (en) * | 1983-06-25 | 1985-09-10 | Basf Aktiengesellschaft | Acylation of polyvinyl alcohols, and photopolymerizable and/or photocrosslinkable mixtures containing products thus acylated |
| CN1141217A (en) * | 1996-01-30 | 1997-01-29 | 天津理工学院 | Alkylamino pyridine high molecular catalyst and prepn. method thereof |
| CN1400055A (en) * | 2002-05-14 | 2003-03-05 | 厦门中坤化学有限公司 | Preparation method of acylation reaction catalyst on which 4-N,N-dimethylaminopyridine is loaded |
Non-Patent Citations (3)
| Title |
|---|
| 朱声逾等: "《配位化学简明教程》", 30 June 1990 * |
| 林晨等: "高分子(纤维)负载-N-(4-吡啶)哌嗪的合成及其催化性能", 《合成化学》 * |
| 翁玉攀等: "《固体催化剂》", 31 December 1983 * |
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