CN104248972B - Immobilized bichiral ligand metal complex and synthetic method and application thereof - Google Patents
Immobilized bichiral ligand metal complex and synthetic method and application thereof Download PDFInfo
- Publication number
- CN104248972B CN104248972B CN201410388810.9A CN201410388810A CN104248972B CN 104248972 B CN104248972 B CN 104248972B CN 201410388810 A CN201410388810 A CN 201410388810A CN 104248972 B CN104248972 B CN 104248972B
- Authority
- CN
- China
- Prior art keywords
- type
- immobilized
- chiral ligand
- resin
- complex
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 239000003446 ligand Substances 0.000 title claims abstract description 109
- 150000004696 coordination complex Chemical class 0.000 title claims description 9
- 238000010189 synthetic method Methods 0.000 title abstract description 5
- 239000011347 resin Substances 0.000 claims description 38
- 229920005989 resin Polymers 0.000 claims description 38
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 38
- 229910052721 tungsten Inorganic materials 0.000 claims description 38
- 239000010937 tungsten Substances 0.000 claims description 38
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 31
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 30
- 229910052750 molybdenum Inorganic materials 0.000 claims description 30
- 239000011733 molybdenum Substances 0.000 claims description 30
- 239000010936 titanium Substances 0.000 claims description 29
- 229910052719 titanium Inorganic materials 0.000 claims description 29
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 27
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 18
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 18
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 16
- 238000006243 chemical reaction Methods 0.000 claims description 15
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical group CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 12
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- 238000006735 epoxidation reaction Methods 0.000 claims description 9
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 7
- 238000003672 processing method Methods 0.000 claims description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 claims description 6
- KPGXUAIFQMJJFB-UHFFFAOYSA-H tungsten hexachloride Chemical compound Cl[W](Cl)(Cl)(Cl)(Cl)Cl KPGXUAIFQMJJFB-UHFFFAOYSA-H 0.000 claims description 6
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 claims description 5
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- 239000008096 xylene Substances 0.000 claims description 4
- 239000011230 binding agent Substances 0.000 claims description 3
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- 239000007809 chemical reaction catalyst Substances 0.000 claims description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 2
- 239000003054 catalyst Substances 0.000 abstract description 13
- 238000000034 method Methods 0.000 abstract description 6
- 238000011914 asymmetric synthesis Methods 0.000 abstract description 4
- 239000007787 solid Substances 0.000 abstract description 3
- 238000004519 manufacturing process Methods 0.000 abstract 1
- 238000002360 preparation method Methods 0.000 description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- -1 TBHP does oxidant Chemical class 0.000 description 6
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 4
- 150000001336 alkenes Chemical class 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 239000007800 oxidant agent Substances 0.000 description 3
- 230000001590 oxidative effect Effects 0.000 description 3
- 230000008929 regeneration Effects 0.000 description 3
- 238000011069 regeneration method Methods 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- MAGPZHKLEZXLNU-SSDOTTSWSA-N (R)-mandelamide Chemical group NC(=O)[C@H](O)C1=CC=CC=C1 MAGPZHKLEZXLNU-SSDOTTSWSA-N 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- 241000790917 Dioxys <bee> Species 0.000 description 2
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 2
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 2
- IWYDHOAUDWTVEP-UHFFFAOYSA-N R-2-phenyl-2-hydroxyacetic acid Natural products OC(=O)C(O)C1=CC=CC=C1 IWYDHOAUDWTVEP-UHFFFAOYSA-N 0.000 description 2
- XXROGKLTLUQVRX-UHFFFAOYSA-N allyl alcohol Chemical compound OCC=C XXROGKLTLUQVRX-UHFFFAOYSA-N 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 239000003957 anion exchange resin Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 230000000536 complexating effect Effects 0.000 description 2
- 238000010668 complexation reaction Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 150000002118 epoxides Chemical class 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000004128 high performance liquid chromatography Methods 0.000 description 2
- 229960002510 mandelic acid Drugs 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 235000011121 sodium hydroxide Nutrition 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 description 2
- 150000003657 tungsten Chemical class 0.000 description 2
- QBYIENPQHBMVBV-HFEGYEGKSA-N (2R)-2-hydroxy-2-phenylacetic acid Chemical compound O[C@@H](C(O)=O)c1ccccc1.O[C@@H](C(O)=O)c1ccccc1 QBYIENPQHBMVBV-HFEGYEGKSA-N 0.000 description 1
- IWYDHOAUDWTVEP-SSDOTTSWSA-N (R)-mandelic acid Chemical group OC(=O)[C@H](O)C1=CC=CC=C1 IWYDHOAUDWTVEP-SSDOTTSWSA-N 0.000 description 1
- 0 **1C(CC(N)=O)*1 Chemical compound **1C(CC(N)=O)*1 0.000 description 1
- WBYWAXJHAXSJNI-VOTSOKGWSA-M .beta-Phenylacrylic acid Natural products [O-]C(=O)\C=C\C1=CC=CC=C1 WBYWAXJHAXSJNI-VOTSOKGWSA-M 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- VEUMANXWQDHAJV-UHFFFAOYSA-N 2-[2-[(2-hydroxyphenyl)methylideneamino]ethyliminomethyl]phenol Chemical compound OC1=CC=CC=C1C=NCCN=CC1=CC=CC=C1O VEUMANXWQDHAJV-UHFFFAOYSA-N 0.000 description 1
- CUNYTKVXYZYERK-UHFFFAOYSA-N 6-(2-prop-2-ynoxyphenyl)hexanoic acid Chemical compound OC(=O)CCCCCC1=CC=CC=C1OCC#C CUNYTKVXYZYERK-UHFFFAOYSA-N 0.000 description 1
- WBYWAXJHAXSJNI-SREVYHEPSA-N Cinnamic acid Chemical compound OC(=O)\C=C/C1=CC=CC=C1 WBYWAXJHAXSJNI-SREVYHEPSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- 238000006683 Mannich reaction Methods 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000005708 Sodium hypochlorite Substances 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 238000009876 asymmetric hydrogenation reaction Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 244000309464 bull Species 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 229930016911 cinnamic acid Natural products 0.000 description 1
- 235000013985 cinnamic acid Nutrition 0.000 description 1
- 230000003111 delayed effect Effects 0.000 description 1
- YSAVZVORKRDODB-PHDIDXHHSA-N diethyl (2r,3r)-2,3-dihydroxybutanedioate Chemical compound CCOC(=O)[C@H](O)[C@@H](O)C(=O)OCC YSAVZVORKRDODB-PHDIDXHHSA-N 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- ZHNUHDYFZUAESO-UHFFFAOYSA-N formamide Substances NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 description 1
- 238000007172 homogeneous catalysis Methods 0.000 description 1
- 239000011989 jacobsen's catalyst Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- MAGPZHKLEZXLNU-UHFFFAOYSA-N mandelamide Chemical group NC(=O)C(O)C1=CC=CC=C1 MAGPZHKLEZXLNU-UHFFFAOYSA-N 0.000 description 1
- 238000013507 mapping Methods 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- WBYWAXJHAXSJNI-UHFFFAOYSA-N methyl p-hydroxycinnamate Natural products OC(=O)C=CC1=CC=CC=C1 WBYWAXJHAXSJNI-UHFFFAOYSA-N 0.000 description 1
- 150000001451 organic peroxides Chemical class 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 229920000768 polyamine Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000008213 purified water Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 150000003658 tungsten compounds Chemical class 0.000 description 1
- FZFRVZDLZISPFJ-UHFFFAOYSA-N tungsten(6+) Chemical compound [W+6] FZFRVZDLZISPFJ-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
Abstract
The invention discloses an immobilized chiral ligand for production of a bichiral ligand complex and a synthetic method thereof, and is characterized in that the molecular structural formulas of L type and D type solid supported chiral ligands are shown in the specification; the immobilized chiral ligand has the following advantages: the immobilization method is simple; the immobilized chiral ligand can be applied to a variety of asymmetric synthesis objectives, a produced immobilized chiral ligand complex catalyst is easy to separate, and a disabled immobilized chiral ligand complex catalyst is easy to regenerate.
Description
Technical field
The present invention relates to the synthetic method of metal complex and its application in asymmetric synthesis, particularly double in catalysis
Oxygen water carries out the application of asymmetric Epoxidation aspect to alkene.
Background technology
Chiral ligand and its metal complex are widely used in asymmetric synthesis, such as asymmetric oxidation, asymmetric epoxy
Change, asymmetric hydrogenation, asymmetric addition, asymmetric Mannich reaction etc..
In order to realize asymmetric Epoxidation, people's design has synthesized numerous chiral ligands and its metal complex .1980
Year K. Barry Sharpless D/L diethyl tartrate. and titanate esters react prepared catalyst, with organic peroxide such as
TBHP does oxidant, makes 1-propenol-3 that asymmetric Epoxidation to occur, obtains very high ee value.Nineteen ninety Jacobsen has developed a class
Be called the chiral ligand of salen, can be catalyzed after such part and complexing of metal ion non-functional dough alkene carry out not right
Claim epoxidation, with sodium hypochlorite as oxidant, also achieve very high ee value.Tsing-Hua University's prosperous grade of stone letter synthesizes within 2006
Chiral pyridyl alcohol dioxy closes molybdenum (VI) and dioxy closes tungsten (VI) coordination compound, using both coordination compounds as catalyst, realizes
The catalytic asymmetric epoxidation to PPOH (CPPA) in water, enantioselectivity ee value reaches 78%.
Above-mentioned catalyst system and catalyzing all haves the shortcomings that certain：Sharpless catalyst is only effective to 1-propenol-3, and reacts and need
Strictly anhydrous, the synthesis of jacobsen catalyst is complicated, using butyl lithium, high cost in the chiral pyridyl alcohol synthesis of the prosperous grade of Shi Hong
Easily, catch fire.And these are all homogeneous catalysis, all have the shortcomings that catalyst can not reclaim and polluted product.In order to overcome this
Individual shortcoming, people begin one's study solid catalysis.Its method one is will be immobilized for homogeneous chiral ligand catalyst, and two is to join chirality
Body monomer is immobilized, then again and complexing of metal ion, forms solid-supported catalyst.For second method, by chiral ligand
Monomer solid is downloaded to most practical method on polymer.
Korean Park Sang-Woo etc. delivers on Bull. Korean Chem. Soc.2000,21,446.
Article, is used chiral mandelic acid's amide as part, forms chiral peroxo-complex with tungsten and molybdenum, TBHP is used as oxidation
Agent, carries out the epoxidation of alkene in anhydrous conditions, and enantioselectivity ee value reaches the chiral peroxide complexation in 40-81%. Park
Thing structural formula is as follows：
The present invention has carried out to the catalyst of Park dissecting it is believed that only one of which chiral ligand in its structure, can only provide
Two coordinations are although cheap and easy to get, but there is also that catalyst is not water-fast, hydrogen peroxide can not be used as oxidant, and urge
Agent can only be once effective.
Content of the invention
It is an object of the invention to provide immobilized chiral ligand metal complex and synthetic method and application.
The immobilized L-type of D311 resin or D type chiral ligand titanium, molybdenum and tungsten complex,
Immobilized L-type chiral ligand titanium complex structural formula is:
Immobilized D type chiral ligand titanium complex structural formula is:
Immobilized L-type chiral ligand molybdenum complex structural formula is:
Immobilized D type chiral ligand molybdenum complex structural formula is:
Immobilized L-type chiral ligand tungsten complex structural formula is:
Immobilized D type chiral ligand tungsten complex structural formula is:
Above-mentioned formula middle skeleton part
Represent D311 resin, and
Represent D311 resin immobilized L-type chiral ligand,
Represent D311 resin immobilized D- type chiral ligand.
The described immobilized L-type of D311 resin or D type chiral ligand titanium, molybdenum and tungsten complex are it is characterised in that it is processed
Method is：
Isopropyl titanate, acetyl acetone or tungsten hexachloride and immobilized L-type or D type chiral ligand are added in solvent
Row reaction, then filters, washs, dries, obtain immobilized L-type or D type chiral ligand metal complex.
The described immobilized L-type of D311 resin or D type chiral ligand titanium, molybdenum and tungsten complex are it is characterised in that it is immobilized
Change L-type or D type chiral ligand titanium complex processing method is：
Immobilized for D311 resin L-type or D type chiral ligand and isopropyl titanate are added second benzene,toluene,xylene or chlorine
In benzene, 80-90 DEG C of reaction 1.5-2.5 hour, it is cooled to room temperature, filter, washed with methanol, 60-80 DEG C of drying 4-6 hour, obtain
To the immobilized L-type of D311 resin or D type chiral ligand titanium complex.
The described immobilized L-type of D311 resin or D type chiral ligand titanium, molybdenum and tungsten complex are it is characterised in that its D311
The immobilized L-type of resin or D type chiral ligand molybdenum complex processing method are：
Immobilized for D311 resin L-type or D type chiral ligand and acetyl acetone are added second benzene,toluene,xylene or chlorine
In benzene, 110-130 DEG C of reaction 1.5-2.5 hour, it is cooled to room temperature, filter, washed with methanol, 60-80 DEG C of drying 4-6 hour,
Obtain the immobilized L-type of D311 resin or D type chiral ligand molybdenum complex.
The described immobilized L-type of D311 resin or D type chiral ligand titanium, molybdenum and tungsten complex are it is characterised in that D311 tree
The immobilized L-type of fat or D type chiral ligand tungsten complex processing method are：
Immobilized for D311 resin L-type or D type chiral ligand are added in acid binding agent and solvent isopropanol, methanol or ethanol,
Acid binding agent is triethylamine and pyridine, is cooled to 0 DEG C, Deca tungsten hexachloride and chloroformic solution, controls 10-15 DEG C of dropping temperature, drips
Add to finish and be slowly warmed up to 40-50 DEG C of reaction 1.5-2.5 hour, be cooled to room temperature, add water, stirring, filter, washed with isopropanol
Wash, 40-60 DEG C of drying 6-9 hour, obtain the immobilized L-type of D311 resin or D type chiral ligand tungsten complex.
The described immobilized L-type of D311 resin or D type chiral ligand titanium, molybdenum and tungsten complex are it is characterised in that D311 tree
The immobilized L-type of fat or D type chiral ligand titanium, molybdenum and tungsten complex are used as asymmetric epoxidation reaction catalyst.
The invention has the advantages that：
Advantage one, immobilized method are simple；
Advantage two, immobilized chiral ligand can be applicable to multiple asymmetric synthesis purposes；
Advantage three, the immobilized chiral ligand complex catalyst being produced are easily isolated；
Advantage four, the immobilized chiral ligand complex catalyst losing efficacy are easy to regenerate.
Specific embodiment
The reaction mechanism of the present invention:D311 macroreticular weakly base acrylic acid type anion exchange resin, containing polyethylene polyamine
Unit, has numerous free ammonias（Amine）Base, makes these free ammonias（Amine）Base and L-type or D- mandelic acid form amide, just make L-type or
D type mandelic acid acyl unit obtains immobilized, obtains immobilized chiral ligand, then titanium, molybdenum, tungsten compound and immobilized chirality are joined
Body complexation, just obtains D311 resin supported chiral ligand titanium, molybdenum, tungsten complex.
The implementation steps of the present invention are as follows：
One. the preparation of immobilized chiral ligand
The preparation of example immobilized pair of chiral ligand of 1.L type
By 50 grams of D311 macroporous anion exchange resins 500ml 1mol/L NaOH soaked overnight, filter, use purification
Water fully washs PH7.5, dries 5 hours for 80 DEG C, takes 1 gram of dry resin, measures its exchanging equivalent and is 7.5mmol/ gram.
Add in reaction bulb, 10 grams of above-mentioned dry D311 resins, 50ml toluene, 90mmol L-type methyl mandelates（14.9
Gram）, 110 DEG C of heating flows back 10 hours, is cooled to room temperature, filters, and 150ml toluene washs, and dries 5 hours for 80 DEG C, obtains 20 grams
Immobilized pair of chiral ligand of L-type, its L-type mandelic acid amide units content is 3.85mmol/ gram.Immobilized L-type chiral ligand
Structural formula is:
.
The preparation of the immobilized D type chiral ligand of example 2.
Add in reaction bulb, 10 grams of above-mentioned dry D311 resins, 50ml dimethylbenzene, 80mmol D- methyl mandelates（13.3
Gram）, 120 DEG C of heating flows back 5 hours, is cooled to room temperature, filters, and 150ml dimethylbenzene washs, and dries 5 hours for 90 DEG C, obtains 20 grams
Immobilized D type chiral ligand, its D- mandelic acid amide units content is 3.85mmol/ gram.The structure of immobilized D type chiral ligand
Formula is:
.
Two. the preparation of immobilized chiral ligand metal complex
Example 1:Immobilized L-type or the preparation of D type chiral ligand titanium complex
20 grams of immobilized L-types or D type chiral ligand, chlorobenzene 100ml, isopropyl titanate 38.5mmol is added in reaction bulb
（10.9 grams）, 85 DEG C are reacted 2 hours, are cooled to room temperature, filter, and 50ml methanol washs, and dry 5 hours for 70 DEG C, obtain 26.3
Gram immobilized L-type or D type chiral ligand titanium complex.
Immobilized L-type chiral ligand titanium complex structural formula is:
Immobilized D type chiral ligand titanium complex structural formula is:
The preparation of example 2, immobilized L-type or D type chiral ligand molybdenum complex
20 grams of immobilized L-types or D type chiral ligand, ethylbenzene 100ml, acetyl acetone 38.5mmol is added in reaction bulb
（12.6 grams）, 120 DEG C are reacted 2 hours, are cooled to room temperature, filter, and 50ml methanol washs, and dry 5 hours for 70 DEG C, obtain immobilized
Change 24.8 grams of L-types or D type chiral ligand molybdenum complex.
Immobilized L-type chiral ligand molybdenum complex structural formula is:
Immobilized D type chiral ligand molybdenum complex structural formula is:
The preparation of example 3, immobilized L-type or D type chiral ligand tungsten complex
Add 20 grams of immobilized L-types or D type chiral ligand, isopropanol 100ml, 3 grams of triethylamine in reaction bulb, be cooled to 0
DEG C, Deca tungsten hexachloride 38.5mmol（14.6 grams）Chloroformic solution（50ml）Control 10-15 DEG C of dropping temperature, completion of dropping is delayed
Slowly it is warmed up to 45 DEG C to react 2 hours, is cooled to room temperature, add 5ml water, stir half an hour, filter, 50ml isopropanol washs, 50
DEG C dry 8 hours, obtain 28.2 grams of immobilized L-types or D type chiral ligand tungsten complex.
Immobilized L-type chiral ligand tungsten complex structural formula is:
Immobilized D type chiral ligand tungsten complex structural formula is:
Chiral ligand unit on described immobilized chiral ligand（L-type or D- mandelic acid amide units）Formed with titanium, molybdenum, tungsten
Mol ratio 2:1 complex.
Three. Application Example
Example 1, L-type immobilized chiral ligand tungsten complex catalyzing expoxidation of olefines
Add in reaction bulb, 14.8 grams of cis acrylic phosphonic acids（0.1mol）, 60ml water, Deca 30% liquid caustic soda adjusts PH6-
6.5, plus 2 grams of immobilized L-type chiral ligand tungsten complexes, it is cooled to 0 DEG C, add 13.6 grams of 30% hydrogen peroxide（0.15mol）,
Then 0-5 DEG C is reacted 12 hours, and sampling carries out HPLC analysis, and cinnamic acid converts completely, and the content of epoxide reaches 98%, right
Reflect selection
The equal ee value of property reaches 47%.Immobilized L-type chiral ligand tungsten complex is recovered by filtration.
Immobilized pair of chiral ligand tungsten complex of example 2, L-type circulates catalyzing expoxidation of olefines
Repeat example 6, difference is that, using the immobilized pair of chiral ligand tungsten complex of L-type reclaiming, result is as follows
Table:
Example 3, immobilized pair of chiral ligand tungsten complex of inefficacy L-type bring back to life activation
Continuously recycled 6 times and the immobilized L-type chiral ligand tungsten complex purified water of partial failure is abundant
Washing, is then washed with methanol, dries 8 hours for 50 DEG C.
Then immobilized for the recovery of above-mentioned drying L-type chiral ligand tungsten complex is added reaction bulb, add isopropanol
100ml, 0.3 gram of triethylamine, it is cooled to 0 DEG C, Deca tungsten hexachloride 3.85mmol
（1.46 gram）Chloroformic solution（10ml）, control 10-15 DEG C of dropping temperature, completion of dropping is slowly warmed up to 45 DEG C instead
Answer 2 hours, be cooled to room temperature, add 5ml water, stir half an hour, filter, first 50ml purification water washing, then 50ml isopropanol
Washing, dries 8 hours for 50 DEG C, obtains 28.3 grams of immobilized L-type chiral ligand tungsten complexes bringing back to life regeneration.
Example 4, the immobilized L-type chiral ligand tungsten complex catalysis epoxidation of regeneration
Repeat example 6, difference is the immobilized pair of chiral ligand tungsten complex of L-type using regeneration,
HPLC analysis result shows, acrylic phosphonic acids converts completely, and the content of epoxide reaches 98.2%, and mapping selects
The equal ee value of property reaches 47.5%.
Claims (6)
1. the immobilized L-type of D311 resin or D type chiral ligand titanium, molybdenum and tungsten complex it is characterised in that
Immobilized L-type chiral ligand titanium complex structural formula is:
Immobilized D type chiral ligand titanium complex structural formula is:
Immobilized L-type chiral ligand molybdenum complex structural formula is:
Immobilized D type chiral ligand molybdenum complex structural formula is:
Immobilized L-type chiral ligand tungsten complex structural formula is:
Immobilized D type chiral ligand tungsten complex structural formula is:
Above-mentioned formula middle skeleton part
Represent D311 resin, and
Represent D311 resin immobilized L-type chiral ligand,
Represent D311 resin immobilized D- type chiral ligand.
2. the immobilized L-type of D311 resin according to claim 1 or D type chiral ligand titanium, molybdenum and tungsten complex, its feature
It is that its processing method is：
Isopropyl titanate, acetyl acetone or tungsten hexachloride and immobilized L-type or D type chiral ligand are added in solvent and carries out instead
Should, then filter, wash, dry, obtain immobilized L-type or D type chiral ligand metal complex.
3. the immobilized L-type of D311 resin according to claim 1 and 2 or D type chiral ligand titanium, molybdenum and tungsten complex, its
It is characterised by that its immobilized L-type or D type chiral ligand titanium complex processing method are：
Immobilized for D311 resin L-type or D type chiral ligand and isopropyl titanate are added second benzene,toluene,xylene or chlorobenzene
In, 80-90 DEG C of reaction 1.5-2.5 hour, it is cooled to room temperature, filter, washed with methanol, 60-80 DEG C of drying 4-6 hour, obtain
The immobilized L-type of D311 resin or D type chiral ligand titanium complex.
4. the immobilized L-type of D311 resin according to claim 1 and 2 or D type chiral ligand titanium, molybdenum and tungsten complex, its
It is characterised by that its immobilized L-type of D311 resin or D type chiral ligand molybdenum complex processing method are：
Immobilized for D311 resin L-type or D type chiral ligand and acetyl acetone are added in second benzene,toluene,xylene or chlorobenzene,
110-130 DEG C of reaction 1.5-2.5 hour, is cooled to room temperature, filters, washed with methanol, 60-80 DEG C of drying 4-6 hour, obtains
The immobilized L-type of D311 resin or D type chiral ligand molybdenum complex.
5. the immobilized L-type of D311 resin according to claim 1 and 2 or D type chiral ligand titanium, molybdenum and tungsten complex, its
It is characterised by that the immobilized L-type of D311 resin or D type chiral ligand tungsten complex processing method are：
Immobilized for D311 resin L-type or D type chiral ligand are added in acid binding agent and solvent isopropanol, methanol or ethanol, ties up acid
Agent is triethylamine and pyridine, is cooled to 0 DEG C, Deca tungsten hexachloride and chloroformic solution, controls 10-15 DEG C of dropping temperature, drips
Finish and be slowly warmed up to 40-50 DEG C of reaction 1.5-2.5 hour, be cooled to room temperature, add water, stirring, filter, washed with isopropanol,
40-60 DEG C of drying 6-9 hour, obtains the immobilized L-type of D311 resin or D type chiral ligand tungsten complex.
6. the immobilized L-type of D311 resin according to claim 1 or D type chiral ligand titanium, molybdenum and tungsten complex, its feature
It is the immobilized L-type of D311 resin or D type chiral ligand titanium, molybdenum and tungsten complex as asymmetric epoxidation reaction catalyst
With.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410388810.9A CN104248972B (en) | 2014-08-11 | 2014-08-11 | Immobilized bichiral ligand metal complex and synthetic method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410388810.9A CN104248972B (en) | 2014-08-11 | 2014-08-11 | Immobilized bichiral ligand metal complex and synthetic method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104248972A CN104248972A (en) | 2014-12-31 |
| CN104248972B true CN104248972B (en) | 2017-02-22 |
Family
ID=52184430
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410388810.9A Active CN104248972B (en) | 2014-08-11 | 2014-08-11 | Immobilized bichiral ligand metal complex and synthetic method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104248972B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107552090B (en) * | 2017-09-12 | 2019-12-03 | 石家庄学院 | A kind of quinine catalyst and its preparation method and application that pentaerythrite is immobilized |
| CN107715909B (en) * | 2017-09-13 | 2020-02-14 | 石家庄学院 | Pentaerythritol-supported proline catalyst and preparation method and application thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1944381A (en) * | 2006-10-25 | 2007-04-11 | 福州大学 | Method for preparing mandelic acid by macroporous adsorptive resin |
| CN101090770A (en) * | 2004-12-27 | 2007-12-19 | Dsm精细化学奥地利Nfg两合公司 | Process for transition metal-catalyzed asymmetric hydrogenation of acrylic acid derivatives, and a novel catalyst system for asymmetric transition metal catalysis |
| CN103249484A (en) * | 2010-11-29 | 2013-08-14 | 高砂香料工业株式会社 | Catalyst for asymmetric hydrogenation and method for manufacturing optically active carbonyl compound using the same |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6897332B2 (en) * | 2000-08-02 | 2005-05-24 | Nesmeyanov Institute Of Organoelement Compounds | Process for the cyanation of aldehydes |
-
2014
- 2014-08-11 CN CN201410388810.9A patent/CN104248972B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101090770A (en) * | 2004-12-27 | 2007-12-19 | Dsm精细化学奥地利Nfg两合公司 | Process for transition metal-catalyzed asymmetric hydrogenation of acrylic acid derivatives, and a novel catalyst system for asymmetric transition metal catalysis |
| CN1944381A (en) * | 2006-10-25 | 2007-04-11 | 福州大学 | Method for preparing mandelic acid by macroporous adsorptive resin |
| CN103249484A (en) * | 2010-11-29 | 2013-08-14 | 高砂香料工业株式会社 | Catalyst for asymmetric hydrogenation and method for manufacturing optically active carbonyl compound using the same |
Non-Patent Citations (1)
| Title |
|---|
| Studies on Enantioselective Epoxidation of Styrene Derivatives with Transition Metal(W, Mo and Re)-Peroxo Complexes;Sang-Woo Park,et al;《Bulletin of the Korean Chemical Society》;20001231;第21卷(第4期);第446-448页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN104248972A (en) | 2014-12-31 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Li et al. | Development of isostructural porphyrin–salen chiral metal–organic frameworks through postsynthetic metalation based on single-crystal to single-crystal transformation | |
| Liu et al. | Engineering homochiral metal‐organic frameworks for heterogeneous asymmetric catalysis and enantioselective separation | |
| Cao et al. | Catalysis through dynamic spacer installation of multivariate functionalities in metal–organic frameworks | |
| Xia et al. | Advances in homogeneous and heterogeneous catalytic asymmetric epoxidation | |
| Štefane et al. | Metal-catalysed transfer hydrogenation of ketones | |
| Abd El Sater et al. | Chiral salen complexes for asymmetric heterogeneous catalysis: Recent examples for recycling and cooperativity | |
| Broicher et al. | A bipyridine-based conjugated microporous polymer for the Ir-catalyzed dehydrogenation of formic acid | |
| Zulauf et al. | Recoverable chiral salen complexes for asymmetric catalysis: recent progress | |
| Demmans et al. | From imine to amine: an unexpected left turn. Cis-β iron (ii) PNNP′ precatalysts for the asymmetric transfer hydrogenation of acetophenone | |
| KR20130079319A (en) | Ruthenium complex and method for preparing optically active alcohol compound | |
| Franconetti et al. | Recent Developments on Supported Hydrogen‐bond Organocatalysts | |
| CN104248972B (en) | Immobilized bichiral ligand metal complex and synthetic method and application thereof | |
| Izák et al. | Catalytic Ionic‐Liquid Membranes: The Convergence of Ionic‐Liquid Catalysis and Ionic‐Liquid Membrane Separation Technologies | |
| Chakraborty et al. | Efficient and Highly Selective CO2 Capture, Separation, and Chemical Conversion under Ambient Conditions by a Polar-Group-Appended Copper (II) Metal–Organic Framework | |
| Song et al. | Dual-linker metal-organic frameworks as efficient carbon dioxide conversion catalysts | |
| CN113457736B (en) | Application of chitosan/cellulose composite microsphere immobilized copper in catalyzing silicon addition reaction of alpha, beta-unsaturated carbonyl compound | |
| Roy et al. | A versatile and microporous Zn-based MOFs as a recyclable and sustainable heterogeneous catalyst for various organic transformations: A review (2015-present) | |
| Zhou et al. | Asymmetric epoxidation of alkenes catalysed by chromium binaphthyl Schiff base complex supported on MCM-41 | |
| Zhu et al. | The multifunctional design of metal–organic framework by applying linker desymmetrization strategy: synergistic catalysis for high CO 2-epoxide conversion | |
| Hu et al. | A novel layered organic polymer-inorganic hybrid zinc poly (styrene-phenylvinylphosphonate)-phosphate immobilized chiral salen Mn (III) catalyst large-scale asymmetric epoxidation of unfunctionalized olefins | |
| JP5642148B2 (en) | Method for producing a porous organometallic framework material based on magnesium formate without solvent | |
| Li et al. | Design catalytic space engineering of Ag-Ag bond-based metal organic framework for carbon dioxide fixation reactions | |
| CN103193808B (en) | Chirality zinc complex | |
| CN102380417B (en) | Preparation of self-immobilization type catalyst and catalytic olefin epoxidation method | |
| CN106475058A (en) | A kind of preparation method of double-core adsorbent and method of modifying and application |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| PE01 | Entry into force of the registration of the contract for pledge of patent right |
Denomination of invention: Fixed supported chiral ligand metal complexes and their synthesis methods and applications Granted publication date: 20170222 Pledgee: Agricultural Bank of China Limited Shayang County Branch Pledgor: SHAYANG QINJIANG CHEMICAL Co.,Ltd. Registration number: Y2024980002499 |
|
| PE01 | Entry into force of the registration of the contract for pledge of patent right |