CN104857987B - A kind of chiral imidazolidinone functionalization heterogeneous catalyst and preparation method - Google Patents
A kind of chiral imidazolidinone functionalization heterogeneous catalyst and preparation method Download PDFInfo
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- CN104857987B CN104857987B CN201510190080.6A CN201510190080A CN104857987B CN 104857987 B CN104857987 B CN 104857987B CN 201510190080 A CN201510190080 A CN 201510190080A CN 104857987 B CN104857987 B CN 104857987B
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Abstract
The invention discloses a kind of chiral imidazolidinone functionalization heterogeneous catalyst and preparation method.This heterogeneous catalyst is the ordered mesoporous polymer heterogeneous catalysis of chiral imidazolidinone functionalization, has the regular side's ordered mesopore structure of two dimension six, BET specific surface area is 110~150 m2g‑1, catalyst loading is 0.6~0.93 mmolg‑1.The greatest feature of the method provided by the present invention there is provided a kind of preparation method of succinct, efficient chiral organic mesoporous catalyst in order, the difference of this method and the immobilized mode of tradition is to use ionic bond as connection means, so as to avoid the synthetic work of cumbersome catalyst precursor.It is of the invention have the advantages that compared with the technology of preparing of existing heterogeneous chiral catalyst it is brief efficiently, reaction condition is gentle and high income.
Description
Technical field
The present invention relates to a kind of multi-phase chiral organic catalyst and its production and use, particularly a kind of chiral imidazole
Quinoline ketone functionalization heterogeneous catalyst and its production and use.
Background technology
Chiral structure is widely present among bioactive natural product and drug molecule.At present, the most efficiently obtain chiral
The method of compound is asymmetric catalysis.In asymmetric catalysis field, Chiral stationary phase is always to study the most
Universal and most efficient chiral catalyst, and it has been widely used in industrial production.But metallic catalyst is generally present
It is expensive, to air-sensitive and easily remain in the product the shortcomings of.
Since two thousand, chiral organic micromolecule（It is asymmetric）Catalysis is gradually taken seriously and is able to fast development.
Now, organic micromolecule catalyst has been considered to the widely used hand of the 3rd class after Chiral stationary phase and enzyme
Property catalyst.It is compared with metal complex catalyst, the advantages of organic micromolecule catalyst：Organic micromolecule catalyst
Reaction condition is gentle, simple to operate during catalytic reaction, catalyst stabilization, it is environment-friendly, be easy to get and price is relatively cheap.So
And often dosage is larger for organic micromolecule catalyst（10%-30%）, and be not easy to separate from product.These shortcomings limit
The commercial Application of organic micromolecule catalyst.Therefore, the heterogeneouss research of homogeneous micromolecule catalyst gradually causes people in recent years
Extensive concern.Heterogeneouss research currently for organic micromolecule catalyst is also fewer, is mainly catalyzed small molecule
Agent is immobilized on linear polymeric material or inorganic porous material, however, due to by carrier and being loaded into mode and limited, it is most of
Generally existing catalyst loading is low after organic micromolecule catalyst is immobilized, stability is poor, avtive spot skewness etc. lacks
Fall into, so catalytic effect is often significantly worse than homogeneous catalyst.
Ordered mesoporous polymer material is due to spies such as its big specific surface area, orderly duct, the organic backbones easily modified
Property, turn into the study hotspot of field of porous materials in recent years.The FDU class ordered mesoporous polymer materials of the first academician's exploitation in Zhao east
（Such as FDU-14, FDU-15）It is the outstanding representative of this kind of material.It is by the way of easy that organic micromolecule catalyst is immobilized
To among the duct of FDU class ordered mesoporous polymer materials, can there must be the chiral ordered mesoporous polymer material of catalysis.
The regular duct of material itself can so be made full use of, realize catalytic site be uniformly distributed and reactant and catalytic site
Abundant contact, the easy recovery of catalyst can be realized again and recycled.Up to the present, it yet there are no relevant small molecule
The report of the ordered mesoporous polymer material of catalyst function.
The content of the invention
The present invention provides a kind of ordered mesoporous polymer for the chiral imidazolidinone functionalization for overcoming prior art deficiency
Heterogeneous catalysis, with and its production and use.
Heterogeneous catalysis provided by the invention, which is that the ordered mesoporous polymer of chiral imidazolidinone functionalization is heterogeneous, urges
Agent, there is the regular side's ordered mesopore structure of two dimension six, BET specific surface area is 110~150 m2g-1, catalyst loading is
0.60~0.93 mmolg-1。
The preparation method of chiral imidazolidinone functionalization heterogeneous catalyst of the present invention is：
1）The sulfonation of ordered mesoporous polymer material
2.0~2.5 g FDU-15 are scattered in dichloromethane, at a temperature of 273K~298K, add 35~45 g chlorine sulphurs
Solid is isolated after acid, fully reaction and carries out drying process, such as：Rear naturally dry or vacuum drying is washed with deionized,
Obtain the FDU-15 ordered mesoporous polymer materials of sulfonic functional；
2）The load of catalyst
The FDU-15 ordered mesoporous polymer materials of sulfonic functional obtained by step on 1.0~1.2 g are scattered in two
In chloromethanes, homogeneous chiral imidazolidinone catalyst is added, is fully reacted at a temperature of 298~308K, isolated after solid with two
Chloromethanes fully washs, and processing is dried, such as 333~353K vacuum drying treatments or naturally dry, obtains chiral imidazole quinoline
The ordered mesoporous polymer heterogeneous catalysis of ketone functionalization.
Chiral imidazolidinone functionalization heterogeneous catalyst provided by the present invention can be used for spirit catalytic of cinnamaldehyde derivative and ring
Asymmetric D iels-Alder the reactions of pentadiene.
Beneficial effects of the present invention：
1st, chiral imidazolidinone functionalization heterogeneous catalyst preparation method provided by the invention, is order mesoporous with FDU-15
High polymer material is carrier, by sulfonation and with homogeneous chiral imidazolidinone catalyst by ion key connection, obtains chirality
The ordered mesoporous polymer heterogeneous catalysis of imidazolone functionalization.The greatest feature of this route there is provided it is a kind of succinct,
The difference of the preparation method of efficient chiral order mesoporous heterogeneous catalysis, this method and the immobilized mode of tradition be use from
Sub-key is as connection means, so as to avoid the synthesis of cumbersome catalyst precursor.It is of the invention to be urged with existing heterogeneous chirality
The technology of preparing of agent compared to have the advantages that it is brief efficiently, reaction condition gently and high income.
2nd, raw material sources of the invention are extensive, cheap, and preparation process reaction condition is gentle, easily controllable and operation.
3rd, the ordered mesoporous polymer heterogeneous catalysis Mac-MP prepared in the present invention derives available for spirit catalytic of cinnamaldehyde
Asymmetric D iels-the Alder of thing and cyclopentadiene react.Compared with the such heterogeneous catalysis reported, Mac-MP has
The advantages that stability is good, high catalytic efficiency and enantioselectivity are good.
Brief description of the drawings
Fig. 1 is the PXRD figures of ordered mesoporous polymer heterogeneous catalysis Mac-MP in the present invention；
Fig. 2 is the HPLC figures of Diels-Alder reaction products racemization sample in the present invention；
Fig. 3 is the HPLC figures of Diels-Alder reaction products chirality sample in the present invention.
Embodiment
Below in conjunction with the particular preferred embodiment technical characterstic that the present invention is furture elucidated.
Embodiment 1：
A kind of preparation method of the ordered mesoporous polymer heterogeneous catalysis of chiral imidazolidinone functionalization, including it is as follows
Step：
1）2.0 g FDU-15 ordered mesoporous polymer materials are scattered in dichloromethane, at a temperature of 273 K, add chlorine
Sulfonic acid, react 24 hours.Filter, a large amount of deionized water washings, 333 K are dried in vacuo 10 hours, obtain sulfonic functional
FDU-15 ordered mesoporous polymer materials.
2）The FDU-15 ordered mesoporous polymer materials of sulfonic functional obtained by 1.0 g step 1 are scattered in dichloromethane
In alkane, homogeneous chiral imidazolidinone catalyst is added, is reacted 24 hours at a temperature of 298 K.Filter, dichloromethane washing, Soxhlet
Extraction, 333 K vacuum drying, obtains the ordered mesoporous polymer heterogeneous catalysis Mac-MP of chiral imidazolidinone functionalization.
After measured, BET specific surface area is 113 m2g-1, catalyst loading is 0.60 mmolg-1。
Embodiment 2：
1）2.4 g FDU-15 ordered mesoporous polymer materials are scattered in dichloromethane, at a temperature of 278 K, add chlorine
Sulfonic acid, react 24 hours.Filter, a large amount of deionized water washings, 333 K are dried in vacuo 10 hours, obtain sulfonic functional
FDU-15 ordered mesoporous polymer materials.
2）The FDU-15 ordered mesoporous polymer materials of sulfonic functional obtained by 1.1 g step 1 are scattered in dichloromethane
In alkane, homogeneous chiral imidazolidinone catalyst is added, is reacted 16 hours at a temperature of 308 K.Filter, dichloromethane washing, Soxhlet
Extraction, 343 K vacuum drying, obtains the ordered mesoporous polymer heterogeneous catalysis Mac-MP of chiral imidazolidinone functionalization.
After measured, BET specific surface area is 130 m2g-1, catalyst loading is 0.71 mmolg-1。
Embodiment 3：
1）2.2 g FDU-15 ordered mesoporous polymer materials are scattered in dichloromethane, at a temperature of 283 K, add chlorine
Sulfonic acid, react 20 hours.Filter, a large amount of deionized water washings, 353 K are dried in vacuo 6 hours, obtain the FDU- of sulfonic functional
15 ordered mesoporous polymer materials.
2）The FDU-15 ordered mesoporous polymer materials of sulfonic functional obtained by 1.2 g step 1 are scattered in dichloromethane
In alkane, homogeneous chiral imidazolidinone catalyst is added, is reacted 20 hours at a temperature of 300 K.Filter, dichloromethane washing, Soxhlet
Extraction, 353 K vacuum drying, obtains the ordered mesoporous polymer heterogeneous catalysis Mac-MP of chiral imidazolidinone functionalization.
After measured, BET specific surface area is 150 m2g-1, catalyst loading is 0.79 mmolg-1。
Embodiment 4：
1）2.3 g FDU-15 ordered mesoporous polymer materials are scattered in dichloromethane, at a temperature of 298 K, add chlorine
Sulfonic acid, react 20 hours.Filter, a large amount of deionized water washings, 353 K are dried in vacuo 6 hours, obtain the FDU- of sulfonic functional
15 ordered mesoporous polymer materials.
2）The FDU-15 ordered mesoporous polymer materials of sulfonic functional obtained by 1.05 g step 1 are scattered in dichloro
In methane, homogeneous chiral imidazolidinone catalyst is added, is reacted 20 hours at a temperature of 303 K.Filter, dichloromethane washing, rope
Family name extracts, and 353 K vacuum drying, obtains the ordered mesoporous polymer heterogeneous catalysis Mac- of chiral imidazolidinone functionalization
MP.After measured, BET specific surface area is 118 m2g-1, catalyst loading is 0.93 mmolg-1
Catalyst applications example
Mac-MP catalysis asymmetric D iels-Alder reaction reaction equation be：
Acetonitrile/water is added in raw material cinnamic acid and cyclopentadiene（95/5, v/v）Mixed solvent and catalyst, room temperature are anti-
Should, after TLC detection raw materials disappear, ethyl acetate being added, centrifugation, pours out supernatant liquor, catalyst is washed 3 times with ethyl acetate,
Vacuum drying 2 hours, for recycling.Merge organic liquor, remove solvent under reduced pressure, column chromatography obtains product.
Product separation yield is 92%.Products therefrom is dissolved in methanol, adds NaBH4Reduction, by reduzate with efficient liquid
Facies analysis.Product ee values are 86% and 76%.Reusable 3 times of the catalyst, yield has without significant change, enantioselectivity
Decline.
Catalytic effect is often significantly worse than homogeneous catalyst after most of organic micromolecule catalysts are immobilized.In the present invention
In, under identical reaction conditions, Mac-MP have and homogeneous chiral imidazolidinone catalyst similar in catalytic activity and slightly lower
Enantioselectivity.
Claims (4)
- A kind of 1. chiral imidazolidinone for the asymmetric D iels-Alder of spirit catalytic of cinnamaldehyde derivative and cyclopentadiene reactions The heterogeneous catalyst preparation method of functionalization, it is characterised in that：1）The sulfonation of ordered mesoporous polymer material2.0~2.5 g FDU-15 ordered mesoporous polymer materials are scattered in dichloromethane, at a temperature of 273K~298K, added Enter 35~45 g chlorosulfonic acids, fully isolate solid after reaction and carry out drying process after being washed with deionized, obtain sulfonic group The FDU-15 ordered mesoporous polymer materials of functionalization；2）The load of catalystThe FDU-15 ordered mesoporous polymer materials of sulfonic functional obtained by step on 1.0~1.2 g are scattered in dichloromethane In alkane, homogeneous chiral imidazolidinone catalyst is added, is fully reacted at a temperature of 298~308K, dichloromethane is used after isolating solid Alkane fully washs, and processing is dried, obtains target product.
- 2. method for preparing catalyst according to claim 1, it is characterised in that BET specific surface area is 110~150 m2g-1, Catalyst loading is 0.6~0.93 mmolg-1。
- 3. the heterogeneous catalyst of chiral imidazolidinone functionalization prepared by the preparation method described in claim 1 or 2.
- 4. the catalyst described in claim 3 is used for the asymmetric D iels-Alder of spirit catalytic of cinnamaldehyde derivative and cyclopentadiene Reaction.
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