CN103433076B - Immobilized asymmetric catalyst and application thereof in asymmetric hydrogenation reaction - Google Patents
Immobilized asymmetric catalyst and application thereof in asymmetric hydrogenation reaction Download PDFInfo
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- 239000011982 enantioselective catalyst Substances 0.000 title claims abstract description 32
- 238000009876 asymmetric hydrogenation reaction Methods 0.000 title claims abstract description 23
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims abstract description 48
- 238000006243 chemical reaction Methods 0.000 claims abstract description 24
- 229910052763 palladium Inorganic materials 0.000 claims abstract description 18
- 239000002904 solvent Substances 0.000 claims abstract description 9
- 239000002253 acid Substances 0.000 claims abstract description 7
- 230000003197 catalytic effect Effects 0.000 claims abstract description 5
- NEHNMFOYXAPHSD-UHFFFAOYSA-N citronellal Chemical compound O=CCC(C)CCC=C(C)C NEHNMFOYXAPHSD-UHFFFAOYSA-N 0.000 claims description 24
- 229910052739 hydrogen Inorganic materials 0.000 claims description 16
- 239000001257 hydrogen Substances 0.000 claims description 16
- WTEVQBCEXWBHNA-JXMROGBWSA-N geranial Chemical group CC(C)=CCC\C(C)=C\C=O WTEVQBCEXWBHNA-JXMROGBWSA-N 0.000 claims description 15
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 claims description 14
- 150000001299 aldehydes Chemical class 0.000 claims description 13
- WTEVQBCEXWBHNA-UHFFFAOYSA-N Citral Natural products CC(C)=CCCC(C)=CC=O WTEVQBCEXWBHNA-UHFFFAOYSA-N 0.000 claims description 12
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 12
- 229930003633 citronellal Natural products 0.000 claims description 12
- 235000000983 citronellal Nutrition 0.000 claims description 12
- 229910052757 nitrogen Inorganic materials 0.000 claims description 12
- 229940043350 citral Drugs 0.000 claims description 11
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 9
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 6
- -1 methoxyl group Chemical group 0.000 claims description 6
- 125000005843 halogen group Chemical group 0.000 claims description 5
- 125000003119 4-methyl-3-pentenyl group Chemical group [H]\C(=C(/C([H])([H])[H])C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 claims description 4
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 3
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims description 2
- 229910052731 fluorine Inorganic materials 0.000 claims description 2
- 239000011737 fluorine Substances 0.000 claims description 2
- 229910052760 oxygen Inorganic materials 0.000 claims description 2
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims 4
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims 1
- 229910052794 bromium Inorganic materials 0.000 claims 1
- 229910052801 chlorine Inorganic materials 0.000 claims 1
- 239000000460 chlorine Substances 0.000 claims 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims 1
- 238000002360 preparation method Methods 0.000 abstract description 6
- 238000004519 manufacturing process Methods 0.000 abstract description 4
- 238000005516 engineering process Methods 0.000 abstract description 3
- WRYCSMQKUKOKBP-UHFFFAOYSA-N Imidazolidine Chemical compound C1CNCN1 WRYCSMQKUKOKBP-UHFFFAOYSA-N 0.000 abstract description 2
- 238000004064 recycling Methods 0.000 abstract description 2
- RWRDLPDLKQPQOW-UHFFFAOYSA-N Pyrrolidine Chemical compound C1CCNC1 RWRDLPDLKQPQOW-UHFFFAOYSA-N 0.000 abstract 3
- 239000003795 chemical substances by application Substances 0.000 abstract 2
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 abstract 1
- 229920000642 polymer Polymers 0.000 abstract 1
- 239000003054 catalyst Substances 0.000 description 18
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 16
- 239000000047 product Substances 0.000 description 16
- MSXVEPNJUHWQHW-UHFFFAOYSA-N 2-methylbutan-2-ol Chemical compound CCC(C)(C)O MSXVEPNJUHWQHW-UHFFFAOYSA-N 0.000 description 12
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 12
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 8
- 238000006555 catalytic reaction Methods 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 238000005984 hydrogenation reaction Methods 0.000 description 5
- 150000003235 pyrrolidines Chemical class 0.000 description 5
- 238000006073 displacement reaction Methods 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- 150000002431 hydrogen Chemical group 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- NOOLISFMXDJSKH-UTLUCORTSA-N (+)-Neomenthol Chemical compound CC(C)[C@@H]1CC[C@@H](C)C[C@@H]1O NOOLISFMXDJSKH-UTLUCORTSA-N 0.000 description 3
- NOOLISFMXDJSKH-UHFFFAOYSA-N DL-menthol Natural products CC(C)C1CCC(C)CC1O NOOLISFMXDJSKH-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 3
- 239000000706 filtrate Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 229940041616 menthol Drugs 0.000 description 3
- 238000011084 recovery Methods 0.000 description 3
- 238000010189 synthetic method Methods 0.000 description 3
- XDEJHXKVKISANH-SDNWHVSQSA-N (2e)-n,n-diethyl-3,7-dimethylocta-2,6-dien-1-amine Chemical compound CCN(CC)C\C=C(/C)CCC=C(C)C XDEJHXKVKISANH-SDNWHVSQSA-N 0.000 description 2
- HEVGGTGPGPKZHF-UHFFFAOYSA-N 1-(1,2-dimethyl-3-methylidenecyclopentyl)-4-methylbenzene Chemical compound CC1C(=C)CCC1(C)C1=CC=C(C)C=C1 HEVGGTGPGPKZHF-UHFFFAOYSA-N 0.000 description 2
- 241000985905 Candidatus Phytoplasma solani Species 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 2
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 2
- 238000004587 chromatography analysis Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- PHTQWCKDNZKARW-UHFFFAOYSA-N isoamylol Chemical compound CC(C)CCO PHTQWCKDNZKARW-UHFFFAOYSA-N 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- WTEVQBCEXWBHNA-YFHOEESVSA-N neral Chemical compound CC(C)=CCC\C(C)=C/C=O WTEVQBCEXWBHNA-YFHOEESVSA-N 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 238000002103 osmometry Methods 0.000 description 2
- 239000010948 rhodium Substances 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- NEHNMFOYXAPHSD-SNVBAGLBSA-N (+)-Citronellal Chemical compound O=CC[C@H](C)CCC=C(C)C NEHNMFOYXAPHSD-SNVBAGLBSA-N 0.000 description 1
- MYHGOWDLVRDUFA-SECBINFHSA-N (3r)-3-phenylbutanal Chemical compound O=CC[C@@H](C)C1=CC=CC=C1 MYHGOWDLVRDUFA-SECBINFHSA-N 0.000 description 1
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 235000002492 Rungia klossii Nutrition 0.000 description 1
- 244000117054 Rungia klossii Species 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000000160 carbon, hydrogen and nitrogen elemental analysis Methods 0.000 description 1
- 229940126214 compound 3 Drugs 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 125000004177 diethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000012065 filter cake Substances 0.000 description 1
- 239000002815 homogeneous catalyst Substances 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 238000006317 isomerization reaction Methods 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 235000013599 spices Nutrition 0.000 description 1
- 238000010025 steaming Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Abstract
The invention discloses an immobilized asymmetric catalyst. The immobilized asymmetric catalyst comprises a palladium-containing active component and an immobilized chiral assisting agent, wherein the immobilized chiral assisting agent loads chiral pyrrolidine or imidazolidine onto a high polymer, so that recycling can be favourably carried out, and good catalytic activity can be maintained. The invention also discloses an application of the immobilized asymmetric catalyst in an asymmetric hydrogenation reaction. The application of the supported asymmetric catalyst in the asymmetric hydrogenation reaction comprises the following steps of: dispersing alpha, beta-unsaturated aldehyde, the immobilized asymmetric catalyst and a catalytic amount of acid into a solvent for carrying out a reaction, and carrying out post-treatment at the end of the reaction, thus obtaining an asymmetric hydrogenation product. After the immobilized asymmetric catalyst is adopted, reaction selectivity is good, reaction conditions are mild, a preparation technology is simple, production cost is low, and the whole synthetic rout is environment-friendly.
Description
Technical field
The invention belongs to asymmetric syntheses technical field, be specifically related to a kind of solid-carrying type asymmetric catalyst and the application in asymmetric hydrogenation thereof.
Background technology
Dextrorotation citronellal (CAS:2385-77-5), structure as shown in the formula (I), is the intermediate of a kind of key of field of perfumery, may be used for preparing the multiple spices comprising levorotatory menthol.Dextrorotation citronellal is generally by optionally reducing α, the carbon-carbon double bond of beta-unsaturated aldehyde class is prepared, and wherein, catalytic hydrogenation uses a small amount of homogeneous catalyst to utilize hydrogen to carry out hydrogenation to carbon-carbon double bond, do not need auxiliary agent, thus a large amount of refuse can not be produced.Therefore, people constantly attempt using hydrogen to α all the time, and the carbon-carbon double bond of beta-unsaturated aldehyde carries out asymmetric hydrogenation, to obtain optically active dextrorotation citronellal.
Introduce the dextrorotation citronellal synthetic method of several report below successively:
STOL company of Japan develops industrialized asymmetric syntheses levorotatory menthol route (Tani, a K.; Yamagata, T.; Akutagawa, S.; Kumobayashi, H.; Taketomi, T.; Takaya, H.; Miyashita, A.; Noyori, R.; Otsuka, S.J.Am.Chem.Soc.1984,106,5208.).The first step is that laurene and diethyl amido lithium are obtained by reacting N, N-diethyl geranyl amine.Crucial second step is that N, N-diethyl geranyl amine is at (S)-BINAP-Rh
+carry out asymmetric hydrogen migration under type catalyst and obtain dextrorotation citronellal.This route is Article 1 industrialized asymmetric syntheses levorotatory menthol route, and the product quality of producing is higher; But wherein catalysis asymmetric isomerization catalyst preparation condition harsher and recycle difficulty.Concrete reaction scheme is as follows:
BASF Aktiengesellschaft develops the synthetic route (Heydrich, G et al.US2010/0249467A1,2010.) that take citral as initiation material, this route now successful commercialization produce.First the rectifying of citral cis-trans isomerism mixture is obtained cis citral by this synthetic route, then obtains dextrorotation citronellal through rhodium catalyst catalysis asymmetric hydrogenation.This synthetic route synthesis technique is simple, however rectifying citral cis-trans isomerism mixture to obtain cis-configuration higher to production equipment requirement, the trans citral simultaneously obtained is difficult to re-use.Concrete reaction scheme is as follows:
Also bibliographical information is had to use synthetic route (Mayer, the S. of phosphine catalyst catalysis trans citral; List, B.Angew.Chem.Int.Ed.2006,45,4193).But this route also faces separation and the utilization rate problem of the same positive and negative citral of BASF route.In addition, it is higher that this technique bears hydrogen source cost, is not suitable for industrial applicability.Concrete reaction scheme is as follows:
2012, the citral that Japanese STOL company reports a kind of pyrrolidines and palladium chtalyst prepares the method for dextrorotation citronellal, this method solve the separation of citral and the problem of utilization rate, but due to pyrrolidines catalyst and pin material be dissolved in together with, therefore or the recycling problem of catalyst can not be solved can not therefrom extract, make production cost too high and limit its using value (Shinya, Y etal.WO2012074075A1,2012.), synthetic method is as follows:
Summary of the invention
The invention provides a kind of solid-carrying type asymmetric catalyst, this solid-carrying type asymmetric catalyst catalytic efficiency is high, is convenient to recycle, and after recycled, active maintenance better.
Present invention also offers this application of solid-carrying type asymmetric catalyst in asymmetric hydrogenation, use this solid-carrying type asymmetric catalyst can make the yield of this asymmetric hydrogenation and selective height, the metal residual in hydrogenated products is low.
A kind of solid-carrying type asymmetric catalyst, comprise containing palladium active component and solid-carrying type chiral auxiliaries, the structure of described solid-carrying type chiral auxiliaries is such as formula shown in (II) or formula (III):
In formula (II) or (III): R is hydrogen, C
1~ C
4alkyl, phenyl, halogen atom or N, N-dimethyl amido;
R
1for H, hydroxyl, phenyl, halogen atom, methoxyl group or trimethylsiloxy group;
Wherein R is that meta-substituent or para-orientating group or 3,5-are disubstituted;
M is NH or O;
X:y:z=1:100 ~ 300:0.01 ~ 0.5, the number-average molecular weight of described solid-carrying type chiral auxiliaries is 10000 ~ 3500000.
In the present invention, described solid-carrying type chiral auxiliaries and the palladium generation coordination contained in palladium active component, can be used in catalysis asymmetry hydrogenation reaction, yield and the ee value of the hydrogenated products obtained are high; After having reacted, solid-carrying type chiral auxiliaries be present in reaction system with solid-state form containing palladium active component, just can recovery after filtering.
As preferably, the described mass ratio containing palladium active component and solid-carrying type chiral auxiliaries is 1:0.7 ~ 10.
As preferably, described is the palladium of support type containing palladium active component, and the palladium of support type more effectively can prevent the loss of palladium; As further preferred, described is Pd/BaSO containing palladium active component
4, Pd/Al
2o
3, Pd/C or Pd/BaCO
3, these load type palladiums can be buied easily from the market; As further preferred, described is Pd/BaSO containing palladium active component
4, adopt Pd/BaSO
4described solid-carrying type asymmetric catalyst can be made to be convenient to recycle, improve the number of times of recycled, and the yield of product and ee value are better.
As further preferred, in described solid-carrying type chiral auxiliaries, R is hydrogen, C
1~ C
4alkyl, phenyl, halogen atom or N, N-dimethyl amido;
R
1for H, hydroxyl, fluorine or trimethylsiloxy group.Now, conversion ratio and the stereoselectivity of hydrogenation can be improved; As further preferred, R
1for H, work as R
1during for H, relative to other substituting group, yield and the ee value of product are higher.
As preferably, described solid-carrying type chiral auxiliaries is selected from such as formula the one in (II-1) ~ formula (II-16) and formula (III-1) ~ formula (III-13):
Wherein in formula (II-1) ~ formula (II-16) and formula (III-1) ~ formula (III-13), x:y:z=1:165:3.5, the number-average molecular weight of described solid-carrying type chiral auxiliaries is 10000 ~ 3500000.Wherein, the ratio of x, y, z is determined by the consumption of raw material, and number-average molecular weight adopts osmometry to measure.
As further preferred, described solid-carrying type chiral auxiliaries is selected from such as formula a kind of in (II-1) ~ formula (II-13) and formula (III-1) ~ formula (III-10); As most preferably, described solid-carrying type chiral auxiliaries is the structure shown in formula (II-7), now, the ee value of the hydrogenated products obtained when carrying out hydrogenation and product yield higher.
As preferably, the preparation method of described solid-carrying type chiral auxiliaries is shown below:
concrete synthetic method is shown in document (Kristensen, T.E.; Vestli, K.; Jakobsen, M.G.; Hansen, F.K.Hansen, T.J.Org.Chem.2010,75,1620 – 1629).
A kind of described application of solid-carrying type asymmetric catalyst in asymmetric hydrogenation, comprise the steps: α, the acid of beta-unsaturated aldehyde, described solid-carrying type asymmetric catalyst and catalytic amount is scattered in solvent reacts, and obtains asymmetric hydrogenation product after reacting completely through process later;
Described α, the structure of beta-unsaturated aldehyde is such as formula shown in (IV):
R
2, R
3be hydrogen, C independently
1~ C
5one in alkyl, phenyl, 4-methyl-3-pentenyl;
The structure of described asymmetric hydrogenation product is such as formula shown in (V):
R
2, R
3be hydrogen, C independently
1~ C
5one in alkyl, phenyl, 4-methyl-3-pentenyl.
As preferably, described α, beta-unsaturated aldehyde is citral, and described asymmetric hydrogenation product is dextrorotation citronellal, now, selectively can obtain product dextrorotation citronellal with very high.
As preferably, described acid is trifluoroacetic acid, and described trifluoroacetic acid is used for activating catalyst.
As preferably, described solid-carrying type asymmetric catalyst is described α, 0.1% ~ 10% of beta-unsaturated aldehyde mole; Described acid is described α, 0.1% ~ 10% of the mole of beta-unsaturated aldehyde.
As preferably, described solvent is C
1~ C
5at least one in alkylol, toluene, dimethylbenzene and oxolane.As further preferred, described solvent is at least one in the tert-butyl alcohol, tert-pentyl alcohol, isoamyl alcohol, toluene, dimethylbenzene and oxolane.As most preferably, described solvent is tert-pentyl alcohol, when using tert-pentyl alcohol, the yield of product and ee value can be made all to reach more than 90%.
As preferably, the temperature of reaction is 40 ~ 100 DEG C, yield and the ee value that all can reduce product too high or too low for temperature.
When adopting solid-carrying type asymmetric catalyst catalysis asymmetry hydrogenation reaction of the present invention, catalyst can recycled 5 ~ 30 times, still can keep conversion ratio and ee value preferably.
Wherein, this solid-carrying type asymmetric catalyst can be adopted and apply mechanically with the following method: at last batch α, after beta-unsaturated aldehyde, ketone catalytic hydrogenation, distill out the solvent in reactant liquor and hydrogenated products step by step, then a certain amount of diluted ethyl acetate is added and stirring at normal temperature 0.5 ~ 1.0 hour not steaming in pin material, filter out pyrrolidines immobilized AlCl_3 catalyst, and priority ethyl acetate and each flush cake of carrene are once, proceed next group catalytic reaction after normal temperature drying under reduced pressure.
Beneficial effect of the present invention is embodied in: the present invention adopts the solid-carrying type pyrrolidines that is easy to get or imidazolidine to be catalyst, catalyst is easy to recovery, and good reaction selectivity, reaction condition is gentle, preparation technology is simple, production cost is low, and whole piece synthetic route environmental friendliness, has wide industrial application value.
Detailed description of the invention
Embodiment 1 ~ 18
According to the pulp furnish of table 1, take citral 2 grams, Pd/BaSO
4, II-7 solid-carrying type chiral auxiliaries, trifluoroacetic acid (42mg), solvent (10mL) in the there-necked flask of 50ml, under nitrogen protection, at a certain temperature stir 1 hour.Then use hydrogen balloon displacement nitrogen continue reaction 20 hours after Filtration of catalyst, by the filtrate of gas chromatographic analysis gained.
The conversion ratio rate of reaction gained citronellal and selective in table 1:
Table 1
Embodiment 19 ~ 47
Take citral 2 grams, Pd/BaSO
4(56mg), solid-carrying type chiral auxiliaries L (160mg), trifluoroacetic acid (42mg), tert-pentyl alcohol (10mL) in the there-necked flask of 50ml, under nitrogen protection, at a certain temperature stir 1 hour.Then hydrogen balloon displacement nitrogen is used to continue reaction 20 hours.Filtration of catalyst afterwards, by the filtrate of gas chromatographic analysis gained.
Table 2
Embodiment 48 ~ 58
Catalyst recovery method is: add 5mL diluted ethyl acetate and stirring at normal temperature 0.5 ~ 1.0 hour, filter out pyrrolidines immobilized AlCl_3 catalyst, and priority ethyl acetate and each flush cake of carrene are once, proceed next group catalytic reaction after normal temperature drying under reduced pressure.Reaction applies mechanically the effect of 10 batches in table 3:
Table 3
In table 3, embodiment 48 ~ 58 reaction condition is: take citral 2 grams, the Pd/BaSO that last consignment of deals
4and II-7 catalyst, trifluoroacetic acid 42mg, tert-pentyl alcohol (10mL), in the there-necked flask of 50ml, under nitrogen protection, stirs 1 hour at 60 DEG C.Then hydrogen balloon displacement nitrogen is used to continue reaction 20 hours.Then be cooled to room temperature, and instill 1mL triethylamine, then substep distills out organic solvent and citronellal.
Embodiment 59
(R) preparation of-3-phenyl butyraldehyde: take 3-phenyl-2-crotonaldehyde 2 grams, Pd/BaSO
460mg and II-7 catalyst 160mg, trifluoroacetic acid 42mg, tert-pentyl alcohol (10mL), in the there-necked flask of 50ml, under nitrogen protection, stirs 1 hour at 60 DEG C.Then hydrogen balloon displacement nitrogen is used to continue reaction 20 hours.Filter out solid, then filtrate substep distills out (R)-3-phenyl butyraldehyde of organic solvent and 1.7 grams, and the ee value of vapor detection product is 95.6%.
Embodiment 60
The preparation of solid-carrying type chiral auxiliaries II-7: add KI(60mg in the there-necked flask of 250mL), K
2cO
3(185mg) with containing polyvinyl alcohol (molecular weight the is approximately 205000) aqueous solution (130mL) of 0.5% weight.Then compound 3(wherein R
1for H, R is the tert-butyl group) (6.0g, 10.4mmol) be dissolved in methyl methacrylate (16.55g, 165.5mmol), add ethylene glycol bis methyl acrylate (0.712g again, 3.5mmol), azodiisobutyronitrile (220mg, 1.2mmol) and toluene (20mL).Under agitation, join in there-necked flask in nitrogen atmosphere, reaction temperature is elevated to 70 DEG C of reactions 16 hours.Then cool to room temperature pour in the cold methanol containing 300mL, the filter cake 300mL methyl alcohol of filtration and the water of 1500mL are respectively washed once, and normal temperature dries and to obtain quantitatively white powder product II-7, and number-average molecular weight is 257760, and measuring method is osmometry.CHN-Analysis(%):N0.48,C60.74,H7.61(catalyst loading:0.35mmol/g).IR(KBr):3437,2998,2954,2846,1734,1630cm
-1。
Claims (10)
1. a solid-carrying type asymmetric catalyst, is characterized in that, comprises containing palladium active component and solid-carrying type chiral auxiliaries, and the structure of described solid-carrying type chiral auxiliaries is such as formula shown in (II) or formula (III):
In formula (II) or (III): R is hydrogen, C
1~ C
4alkyl, phenyl, halogen atom or N, N-dimethyl amido;
R
1for H, hydroxyl, phenyl, halogen atom, methoxyl group or trimethylsiloxy group;
Wherein R is that meta-substituent or para-orientating group or 3,5-are disubstituted;
M is NH or O;
X:y:z=1:100 ~ 300:0.01 ~ 0.5, the number-average molecular weight of described solid-carrying type chiral auxiliaries is 10000 ~ 3500000.
2. solid-carrying type asymmetric catalyst according to claim 1, is characterized in that, the described mass ratio containing palladium active component and solid-carrying type chiral auxiliaries is 1:0.7 ~ 10.
3. solid-carrying type asymmetric catalyst according to claim 1, is characterized in that, described is Pd/BaSO containing palladium active component
4, Pd/Al
2o
3, Pd/C or Pd/BaCO
3.
4. solid-carrying type asymmetric catalyst according to claim 1, is characterized in that, in described solid-carrying type chiral auxiliaries, R is hydrogen, methyl, ethyl, isopropyl, the tert-butyl group, bromine, chlorine, N, N-dimethyl amido or phenyl;
R
1for H, phenyl, hydroxyl, fluorine or trimethylsiloxy group.
5. the application of solid-carrying type asymmetric catalyst in asymmetric hydrogenation as described in any one of Claims 1 to 4, it is characterized in that, comprise the steps: α, the acid of beta-unsaturated aldehyde, described solid-carrying type asymmetric catalyst and catalytic amount is scattered in solvent reacts, and obtains asymmetric hydrogenation product after reacting completely through process later;
Described α, the structure of beta-unsaturated aldehyde is such as formula shown in (IV):
R
2, R
3be hydrogen, C independently
1~ C
5one in alkyl, phenyl, 4-methyl-3-pentenyl;
The structure of described asymmetric hydrogenation product is such as formula shown in (V):
R
2, R
3be hydrogen, C independently
1~ C
5one in alkyl, phenyl, 4-methyl-3-pentenyl.
6. the application of solid-carrying type asymmetric catalyst according to claim 5 in asymmetric hydrogenation, it is characterized in that, described α, beta-unsaturated aldehyde is citral, described asymmetric hydrogenation product is dextrorotation citronellal.
7. the application of solid-carrying type asymmetric catalyst according to claim 5 in asymmetric hydrogenation, is characterized in that, described acid is trifluoroacetic acid.
8. the application of solid-carrying type asymmetric catalyst according to claim 5 in asymmetric hydrogenation, is characterized in that, described solid-carrying type asymmetric catalyst is described α, 0.1% ~ 10% of beta-unsaturated aldehyde mole; Described acid is described α, 0.1% ~ 10% of the mole of beta-unsaturated aldehyde.
9. the application of solid-carrying type asymmetric catalyst according to claim 5 in asymmetric hydrogenation, is characterized in that, described solvent is C
1~ C
5alkylol, toluene, dimethylbenzene or oxolane.
10. the application of solid-carrying type asymmetric catalyst according to claim 5 in asymmetric hydrogenation, is characterized in that, the temperature of reaction is 40 ~ 100 DEG C.
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