CN102093184B - Method for preparing benzaldehyde by performing catalytic oxidation on cinnamyl aldehyde or cinnamon oil and special catalyst thereof - Google Patents
Method for preparing benzaldehyde by performing catalytic oxidation on cinnamyl aldehyde or cinnamon oil and special catalyst thereof Download PDFInfo
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- CN102093184B CN102093184B CN 201010598626 CN201010598626A CN102093184B CN 102093184 B CN102093184 B CN 102093184B CN 201010598626 CN201010598626 CN 201010598626 CN 201010598626 A CN201010598626 A CN 201010598626A CN 102093184 B CN102093184 B CN 102093184B
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- cyclodextrin
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- benzaldehyde
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- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 title claims abstract description 37
- KJPRLNWUNMBNBZ-QPJJXVBHSA-N (E)-cinnamaldehyde Chemical compound O=C\C=C\C1=CC=CC=C1 KJPRLNWUNMBNBZ-QPJJXVBHSA-N 0.000 title claims abstract description 33
- 230000003197 catalytic effect Effects 0.000 title claims abstract description 19
- 238000000034 method Methods 0.000 title claims abstract description 19
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 title claims abstract description 17
- 239000003054 catalyst Substances 0.000 title abstract description 10
- 230000003647 oxidation Effects 0.000 title abstract description 5
- 238000007254 oxidation reaction Methods 0.000 title abstract description 5
- 239000010630 cinnamon oil Substances 0.000 title abstract 4
- 229920001661 Chitosan Polymers 0.000 claims abstract description 52
- 229920000642 polymer Polymers 0.000 claims abstract description 43
- 238000006243 chemical reaction Methods 0.000 claims abstract description 34
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 24
- 230000001590 oxidative effect Effects 0.000 claims abstract description 13
- 238000000605 extraction Methods 0.000 claims abstract description 11
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000002904 solvent Substances 0.000 claims abstract description 6
- 239000002994 raw material Substances 0.000 claims abstract description 5
- 238000000746 purification Methods 0.000 claims abstract description 3
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 claims abstract description 3
- -1 phenyl aldehyde Chemical class 0.000 claims description 24
- 229920000858 Cyclodextrin Polymers 0.000 claims description 20
- HFHDHCJBZVLPGP-UHFFFAOYSA-N schardinger α-dextrin Chemical compound O1C(C(C2O)O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC(C(O)C2O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC2C(O)C(O)C1OC2CO HFHDHCJBZVLPGP-UHFFFAOYSA-N 0.000 claims description 15
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 12
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 12
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 12
- WHGYBXFWUBPSRW-FOUAGVGXSA-N beta-cyclodextrin Chemical compound OC[C@H]([C@H]([C@@H]([C@H]1O)O)O[C@H]2O[C@@H]([C@@H](O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O3)[C@H](O)[C@H]2O)CO)O[C@@H]1O[C@H]1[C@H](O)[C@@H](O)[C@@H]3O[C@@H]1CO WHGYBXFWUBPSRW-FOUAGVGXSA-N 0.000 claims description 12
- 229940117916 cinnamic aldehyde Drugs 0.000 claims description 10
- KJPRLNWUNMBNBZ-UHFFFAOYSA-N cinnamic aldehyde Natural products O=CC=CC1=CC=CC=C1 KJPRLNWUNMBNBZ-UHFFFAOYSA-N 0.000 claims description 10
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 9
- 239000011347 resin Substances 0.000 claims description 8
- 229920005989 resin Polymers 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 7
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical group CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- 239000000126 substance Substances 0.000 claims description 6
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 claims description 5
- 239000001116 FEMA 4028 Substances 0.000 claims description 4
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 claims description 4
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 claims description 4
- 235000011175 beta-cyclodextrine Nutrition 0.000 claims description 4
- 229960004853 betadex Drugs 0.000 claims description 4
- SXRSQZLOMIGNAQ-UHFFFAOYSA-N Glutaraldehyde Chemical compound O=CCCCC=O SXRSQZLOMIGNAQ-UHFFFAOYSA-N 0.000 claims description 3
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 claims description 3
- 230000006196 deacetylation Effects 0.000 claims description 3
- 238000003381 deacetylation reaction Methods 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- 229940043232 butyl acetate Drugs 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- 150000002148 esters Chemical group 0.000 claims description 2
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 claims description 2
- NUKZAGXMHTUAFE-UHFFFAOYSA-N hexanoic acid methyl ester Natural products CCCCCC(=O)OC NUKZAGXMHTUAFE-UHFFFAOYSA-N 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 239000003513 alkali Substances 0.000 claims 1
- 230000007613 environmental effect Effects 0.000 abstract description 2
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 abstract 2
- 239000005708 Sodium hypochlorite Substances 0.000 abstract 1
- 239000007800 oxidant agent Substances 0.000 abstract 1
- 238000000926 separation method Methods 0.000 abstract 1
- 239000012074 organic phase Substances 0.000 description 14
- 239000008367 deionised water Substances 0.000 description 13
- 229910021641 deionized water Inorganic materials 0.000 description 13
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 8
- 239000007844 bleaching agent Substances 0.000 description 8
- 239000000460 chlorine Substances 0.000 description 8
- 229910052801 chlorine Inorganic materials 0.000 description 8
- DKPFZGUDAPQIHT-UHFFFAOYSA-N butyl acetate Chemical compound CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 6
- 238000003810 ethyl acetate extraction Methods 0.000 description 6
- 238000011084 recovery Methods 0.000 description 4
- 235000013305 food Nutrition 0.000 description 3
- 239000003444 phase transfer catalyst Substances 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- YZOUYRAONFXZSI-SBHWVFSVSA-N (1S,3R,5R,6R,8R,10R,11R,13R,15R,16R,18R,20R,21R,23R,25R,26R,28R,30R,31S,33R,35R,36R,37S,38R,39S,40R,41S,42R,43S,44R,45S,46R,47S,48R,49S)-5,10,15,20,25,30,35-heptakis(hydroxymethyl)-37,39,40,41,42,43,44,45,46,47,48,49-dodecamethoxy-2,4,7,9,12,14,17,19,22,24,27,29,32,34-tetradecaoxaoctacyclo[31.2.2.23,6.28,11.213,16.218,21.223,26.228,31]nonatetracontane-36,38-diol Chemical compound O([C@@H]([C@H]([C@@H]1OC)OC)O[C@H]2[C@@H](O)[C@@H]([C@@H](O[C@@H]3[C@@H](CO)O[C@@H]([C@H]([C@@H]3O)OC)O[C@@H]3[C@@H](CO)O[C@@H]([C@H]([C@@H]3OC)OC)O[C@@H]3[C@@H](CO)O[C@@H]([C@H]([C@@H]3OC)OC)O[C@@H]3[C@@H](CO)O[C@@H]([C@H]([C@@H]3OC)OC)O3)O[C@@H]2CO)OC)[C@H](CO)[C@H]1O[C@@H]1[C@@H](OC)[C@H](OC)[C@H]3[C@@H](CO)O1 YZOUYRAONFXZSI-SBHWVFSVSA-N 0.000 description 2
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 238000005904 alkaline hydrolysis reaction Methods 0.000 description 2
- HFHDHCJBZVLPGP-RWMJIURBSA-N alpha-cyclodextrin Chemical compound OC[C@H]([C@H]([C@@H]([C@H]1O)O)O[C@H]2O[C@@H]([C@@H](O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O3)[C@H](O)[C@H]2O)CO)O[C@@H]1O[C@H]1[C@H](O)[C@@H](O)[C@@H]3O[C@@H]1CO HFHDHCJBZVLPGP-RWMJIURBSA-N 0.000 description 2
- 230000004071 biological effect Effects 0.000 description 2
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- 238000004519 manufacturing process Methods 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 235000013599 spices Nutrition 0.000 description 2
- 239000003643 water by type Substances 0.000 description 2
- LRWZZZWJMFNZIK-UHFFFAOYSA-N 2-chloro-3-methyloxirane Chemical compound CC1OC1Cl LRWZZZWJMFNZIK-UHFFFAOYSA-N 0.000 description 1
- 108010054033 Chitin deacetylase Proteins 0.000 description 1
- 125000003535 D-glucopyranosyl group Chemical group [H]OC([H])([H])[C@@]1([H])OC([H])(*)[C@]([H])(O[H])[C@@]([H])(O[H])[C@]1([H])O[H] 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
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- 150000004676 glycans Chemical class 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 238000003808 methanol extraction Methods 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- ODLHGICHYURWBS-FOSILIAISA-N molport-023-220-444 Chemical compound CC(O)COC[C@@H]([C@@H]([C@H]([C@@H]1O)O)O[C@@H]2O[C@H]([C@H](O[C@@H]3O[C@@H](COCC(C)O)[C@@H]([C@H]([C@@H]3O)O)O[C@@H]3O[C@@H](COCC(C)O)[C@@H]([C@H]([C@@H]3O)O)O[C@@H]3O[C@@H](COCC(C)O)[C@@H]([C@H]([C@@H]3O)O)O[C@@H]3O[C@@H](COCC(C)O)[C@@H]([C@H]([C@@H]3O)O)O3)[C@@H](O)[C@@H]2O)COCC(O)C)O[C@H]1O[C@@H]1[C@@H](O)[C@H](O)[C@H]3O[C@H]1COCC(C)O ODLHGICHYURWBS-FOSILIAISA-N 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
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- BHTJEPVNHUUIPV-UHFFFAOYSA-N pentanedial;hydrate Chemical compound O.O=CCCCC=O BHTJEPVNHUUIPV-UHFFFAOYSA-N 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
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- 229920001282 polysaccharide Polymers 0.000 description 1
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- Polysaccharides And Polysaccharide Derivatives (AREA)
Abstract
The invention discloses a method for preparing benzaldehyde by performing catalytic oxidation on cinnamyl aldehyde or cinnamon oil and a special catalyst thereof. The catalyst is a cyclodextrin-chitosan polymer. The method for preparing the benzaldehyde by performing the catalytic oxidation on the cinnamyl aldehyde or the cinnamon oil comprises the following steps of: adding one of hydrogen peroxide, sodium hypochlorite or tert-butyl hydroperoxide, which serves as an oxidant and has the mass concentration of 1 to 90 percent, into water serving as a solvent; performing the catalytic oxidation on the cinnamyl aldehyde or the cinnamon oil at the temperature of between 30 and 90 DEG C to prepare the benzaldehyde, wherein the mass ratio of the catalyst to raw materials is 1:5-5:1; and after the reaction is finished, performing extraction by using an organic extant and performing concentration and purification to obtain the benzaldehyde. The method has the advantages of simple process, mild reaction condition, low cost and environmental friendliness. The catalyst has the advantages of small using amount, easiness in separation, reusability and the like.
Description
Technical field
The present invention relates to method and the special-purpose catalyst thereof of a kind of spirit catalytic of cinnamaldehyde or Oleum Cinnamomi preparing benzaldehyde by oxidizing.
Background technology
Phenyl aldehyde is only second to vanillin food grade,1000.000000ine mesh, is second largest spices of world's consumption, has very widely in industries such as food, healthcare products, makeup and medicine intermediates and uses.According to statistics, at present the whole world is once being only natural benzaldehyde for food flavor(ing) spices up to more than 7000 tons, and the demand of natural benzaldehyde is also in increase year by year.
Preparation natural benzaldehyde most study is phenylacrolein alkaline water solution at present.Due to phenylacrolein and water immiscible, be difficult between reactant contact and cause the yield of product greatly to reduce.In order to improve the solubleness of phenylacrolein in water, introducing phase-transfer catalyst or tensio-active agent is a kind of effective means, but the side reaction that phase-transfer catalyst exists is many, separates the poisonous shortcomings such as phase-transfer catalyst difficulty.The propositions such as Ji Hongbing utilize cyclodextrin compound, make solubilizing agent (CN101037384) or hydroxypropyl-b-cyclodextrin is promotor (200910192485.8) as beta-cyclodextrin, phenylacrolein alkaline hydrolysis prepares the preparation method of phenyl aldehyde, but the method exists the yield of long reaction time, phenyl aldehyde low, the defectives such as cyclodextrin cost recovery height.
alkaline hydrolysis prepares the deficiency that phenyl aldehyde exists based on phenylacrolein, Ji Hongbing etc. propose again " a kind of method of cyclodextrin spirit catalytic of cinnamaldehyde or Oleum Cinnamomi preparing benzaldehyde by oxidizing " (2010181273.2), the method is made catalyzer with epoxy chloropropane and beta-cyclodextrin cross-linked polymkeric substance, water insoluble and the organic solvent of this catalyzer, solve preferably the recovery problem of cyclodextrin, the molecule inclusion of cyclodextrin and the essential property of recognition capability have been kept simultaneously, can form inclusion complex with guest molecule, has good catalytic activity, also has certain mechanical stability, the simultaneous reactions mild condition, yield is high.But this catalyzer consumption in reaction process is large, easy water absorption and swelling, and under the effect of oxygenant, easily become tiny particle, and conglomerate has greatly affected the catalytic activity of this catalyzer.
Summary of the invention
The object of the present invention is to provide method and the special-purpose effective catalyst thereof of a kind of spirit catalytic of cinnamaldehyde or Oleum Cinnamomi preparing benzaldehyde by oxidizing.
This catalyzer is cyclodextrin-chitosan polymer with general formula (I) structure, n=2.5~4 wherein, described cyclodextrin is b-cyclodextrin or derivatives thereof, its chemical structural formula as shown in general formula (II),
General formula (I)
General formula (II)
In general formula (I) and general formula (II), R all is selected from H, CH
3Or CH
3CH (OH) CH
2
This catalyzer can prepare as follows:
With the chitosan (deacetylation is 95%) of acetic acid dissolving with glutaraldehyde at 40-60
oUnder the condition of C stirring reaction 1-2 hour, filter, obtain chitosan resin after drying, resin and propylene oxide are reacted in the blending agent of NaOH solution and dimethyl sulfoxide (DMSO), and then at alkaline, 60-80
oWith b-cyclodextrin stirring reaction 4-8 hour, wash, be drying to obtain the cyclodextrin of different polymerization degree-chitosan polymer catalyzer under the condition of C, wherein the polymerization degree n value is determined by the mol ratio of chitosan and glutaraldehyde.
The phenyl aldehyde preparation method that the present invention carries out, that raw meat oil of bay or phenylacrolein are carried out catalytic oxidation under the effect of catalyzer and oxygenant thereof, used catalyst is cyclodextrin-chitosan polymer of the present invention, take water as solvent, adding mass concentration is 1%~90%, a kind of oxygenant of doing in preferred 1 ~ 30% hydrogen peroxide, clorox or tertbutyl peroxide, the mass ratio of catalyzer and raw material is 1:5~5:1, is 30 ~ 90 in temperature of reaction
oSpirit catalytic of cinnamaldehyde or Oleum Cinnamomi preparing benzaldehyde by oxidizing under the condition of C, reaction finish by obtaining phenyl aldehyde after organic extractant extraction, the concentrated purification.Reaction equation of the present invention:
In the method for above-mentioned spirit catalytic of cinnamaldehyde or Oleum Cinnamomi preparing benzaldehyde by oxidizing, the mass ratio of preferred catalyzer and raw material is 1:1~2:1, and preferred temperature of reaction is 50 ~ 80
oC, described organic extractant are esters solvent, methyl alcohol, acetone or acetonitrile, and preferred organic extractant is ethyl acetate, methyl acetate and butylacetate.
Chitosan is to couple together the direct-connected polysaccharide of formation (Isosorbide-5-Nitrae)-2-amino-2-deoxidation-β-D-Glucose with β-(Isosorbide-5-Nitrae) glycosidic link after the chitin deacetylase base, shows good biological activity and adsorptivity.Cyclodextrin be a class by the D-glucopyranose units by the macrocylc compound that α-Isosorbide-5-Nitrae-glycosidic link joins end to end and forms, hydrophilic outer wall and hydrophobic cavity are arranged, can form inclusion complex with hydrophobic molecule.With cyclodextrin immobilized to the chitosan resulting polymkeric substance, the envelope recognition performance and the catalytic activity that had both had cyclodextrin, the characteristic such as biological degradability, biocompatibility, nontoxicity of chitosan is arranged again, and have the characteristics such as good physical strength, stability and chemical adjustability.
The envelope recognition performance of the cyclodextrin that the present invention adopts-existing cyclodextrin of chitosan polymer catalyzer has again the biological activity of chitosan and the dual nature of absorption property.Therefore this catalyzer is when spirit catalytic of cinnamaldehyde or Oleum Cinnamomi preparing benzaldehyde by oxidizing, catalytic activity is greatly improved, catalyst levels also greatly reduces, and to effectively reducing the production cost of phenyl aldehyde, realizes that the industrialization of phenyl aldehyde has extremely important meaning.Polymkeric substance is easily degraded simultaneously, and is little to environmental influence, also really realizes the characteristics of green non-pollution.
Compared with prior art, the present invention has following beneficial effect:
1, cyclodextrin of the present invention-chitosan polymer catalyzer has the character of water insoluble, organic solvent, strong acid and highly basic, and has good physical strength, and is reusable, reduced production cost;
2, cyclodextrin-chitosan polymer of the present invention is easily degraded, the problem of environmental pollution of having avoided catalyzer to cause;
3, cyclodextrin of the present invention-chitosan polymer catalyzer is when spirit catalytic of cinnamaldehyde or Oleum Cinnamomi preparing benzaldehyde by oxidizing, has that speed of reaction is fast, the consumption of catalyzer is few, the product yield advantages of higher.
Embodiment
The present invention is described further below in conjunction with embodiment, but protection scope of the present invention is not limited to the scope that embodiment represents.
Example 1
In the solution of 50mL with the chitosan (deacetylation is 95%) of 5% acetic acid dissolving 4g, add the glutaraldehyde water solution of 7g, 40
oAt the C temperature, stirring reaction after 1 hour, filters, and gets chitosan resin, through cleaning, drying.This resin of 2g is placed in there-necked flask, adds purified water, NaOH solution and the dimethyl sulfoxide (DMSO) of 50mL, fully stir, drip the propylene oxide of 45mL, take out after reaction, washing obtains activated resin after washing with acetone, drying.In the NaOH of 40mL solution, add the b-cyclodextrin of this activated resin of 4g and 4g, 60
oAt the C temperature, stirring reaction is 4 hours, and product namely gets the b-cyclodextrin of n=3.6-chitosan polymer catalyzer after pure water rinsing, oven dry.
Add respectively 0.6591gb-cyclodextrin-chitosan polymer (n=3.6 in general formula) and 25mL deionized water in the 100mL flask, 40
oBeing stirred to b-cyclodextrin-chitosan polymer under C is uniformly dispersed, add successively again the chlorine bleach liquor of 0.1362g phenylacrolein and 3mL10%, after reaction finishes, use the 50mL ethyl acetate extraction, it is 63% phenyl aldehyde that the organic phase of gained can obtain yield through concentrating under reduced pressure.
Example 2
Add respectively 0.0266g b-cyclodextrin-chitosan polymer (n=2.5 in general formula) and 25mL deionized water in the flask of 100mL, 30
oBeing stirred to b-cyclodextrin chitosan polymer under C is uniformly dispersed, the chlorine bleach liquor who adds successively again 0.1362g phenylacrolein and 4mL 4.5%, after reaction finishes, use the 50mL n-butyl acetate extraction, it is 52% phenyl aldehyde that the organic phase of gained can obtain yield through concentrating under reduced pressure.
Example 3
Add respectively 0.2992g b-cyclodextrin-chitosan polymer (n=3 in general formula) and 25mL deionized water in the 100mL flask, 70
oBeing stirred to b-cyclodextrin-chitosan polymer under C is uniformly dispersed, the chlorine bleach liquor who adds successively again 0.1362g phenylacrolein and 4mL 4.5%, after reaction finished, with the extraction of 50mL methyl acetate, it was 45% phenyl aldehyde that the organic phase of gained can obtain yield through concentrating under reduced pressure.
Example 4
Add respectively 0.1364g methyl-b-cyclodextrin-chitosan polymer (n=3 in general formula) and 25mL deionized water in the 100mL flask, 50
oBeing stirred to methyl b-cyclodextrin-chitosan polymer under C is uniformly dispersed, the chlorine bleach liquor who adds successively again 0.1362g phenylacrolein and 4mL 10%, after reaction finishes, use the 50mL acetone extract, it is 63% phenyl aldehyde that the organic phase of gained can obtain yield through concentrating under reduced pressure.
Example 5
Add respectively 0.2724g hydroxypropyl-b-cyclodextrin-chitosan polymer (n=4 in general formula) and 25mL deionized water in the 100mL flask, 90
oBeing stirred to hydroxypropyl-b-cyclodextrin-chitosan polymer under C is uniformly dispersed, add successively again the chlorine bleach liquor of 0.1362g Oleum Cinnamomi and 20mL1.0%, after reaction finishes, use the 50mL n-butyl acetate extraction, it is 68% phenyl aldehyde that the organic phase of gained can obtain yield through concentrating under reduced pressure.
Example 6
Add respectively 0.6591g methyl-b-cyclodextrin-chitosan polymer (n=3.6 in general formula) and 25mL deionized water in the 100mL flask, 60
oBeing stirred to methyl-b-cyclodextrin-chitosan polymer under C is uniformly dispersed, add successively again the chlorine bleach liquor of 0.1362g phenylacrolein and 3mL10%, after reaction finished, with the extraction of 50mL acetonitrile, it was 73% phenyl aldehyde that the organic phase of gained can obtain yield through concentrating under reduced pressure.
Example 7
Add respectively 0.1464g b-cyclodextrin-chitosan polymer (n=3.75 in general formula) and 25mL deionized water in the 100mL flask, 80
oBeing stirred to b-cyclodextrin-chitosan polymer under C is uniformly dispersed, the chlorine bleach liquor who adds successively again 0.1362g phenylacrolein and 5mL 3%, after reaction finishes, use the 50mL ethyl acetate extraction, it is 74% phenyl aldehyde that the organic phase of gained can obtain yield through concentrating under reduced pressure.
Example 8
Add respectively 0.1212g methyl-b-cyclodextrin chitosan polymer (n=2.7 in general formula) and 25mL deionized water in the 100mL flask, 30
oBeing stirred to methyl-b-cyclodextrin chitosan polymer under C is uniformly dispersed, the hydrogen peroxide solution that adds successively again 0.6053g phenylacrolein and 6mL 20%, after reaction finishes, use the 50mL methanol extraction, it is 48% phenyl aldehyde that the organic phase of gained can obtain yield through concentrating under reduced pressure.
Example 9
Add respectively 0.2642g b-cyclodextrin-chitosan polymer (n=4 in general formula) and 25mL deionized water in the 100mL flask, 60
oBe stirred to b-cyclodextrin-chitosan polymer under C and be uniformly dispersed, then add successively the hydrogen peroxide solution of 0.5285g Oleum Cinnamomi and 5mL 30%, after reaction finished, with the extraction of 50mL acetonitrile, it was 68% phenyl aldehyde that the organic phase of gained can obtain yield through concentrating under reduced pressure.
Example 10
Add respectively 0.1286g hydroxypropyl-b-cyclodextrin-chitosan polymer (n=3.25 in general formula) and 25mL deionized water in the 100mL flask, 60
oC is stirred to hydroxypropyl-b-cyclodextrin-chitosan polymer and is uniformly dispersed, the hydrogen peroxide solution that adds successively again 0.1286g Oleum Cinnamomi and 4mL 30%, after reaction finished, with the extraction of 50mL methyl acetate, it was 80% phenyl aldehyde that the organic phase of gained can obtain yield through concentrating under reduced pressure.
Example 11
Add respectively 3.258g a-cyclodextrin epichlorohydrin polymer (n=2.5 in general formula) and 25mL deionized water in the 100mL flask, 60
oBeing stirred to a-cyclodextrin epichlorohydrin polymer under C is uniformly dispersed, the hydrogen peroxide solution that adds successively again 0.1322g phenylacrolein and 4mL 30%, after reaction finishes, use the 50mL ethyl acetate extraction, it is 78% phenyl aldehyde that the organic phase of gained can obtain yield through concentrating under reduced pressure.
Example 12
Add respectively 0.5480g b-cyclodextrin-chitosan polymer (n=2.5 in general formula) and 25mL deionized water in the 100mL flask, 50
oBeing stirred to b-cyclodextrin-chitosan polymer under C is uniformly dispersed, the tertbutyl peroxide that adds successively again 0.274g phenylacrolein and 8mL 90%, after reaction finishes, use the 50mL n-butyl acetate extraction, it is 72% phenyl aldehyde that the organic phase of gained can obtain yield through concentrating under reduced pressure.
Example 13
Add respectively 0.5204g b-cyclodextrin-chitosan polymer (n=2.5 in general formula) and 25 mL deionized waters in 100 mL flasks, 40
oBeing stirred to b-cyclodextrin-chitosan polymer under C is uniformly dispersed, the tertbutyl peroxide that adds successively again 0.1040g phenylacrolein and 8 mL 60%, after reaction finished, with 50 mL ethyl acetate extractions, it was 58% phenyl aldehyde that the organic phase of gained can obtain yield through concentrating under reduced pressure.
Example 14
Add respectively 0.5204g b-cyclodextrin-chitosan polymer (n=2.5 in general formula) and 25 mL deionized waters in 100 mL flasks, 60
oBeing stirred to b-cyclodextrin-chitosan polymer under C is uniformly dispersed, the tertbutyl peroxide that adds successively again 0.1223g Oleum Cinnamomi and 8 mL 30%, after reaction finished, with 50 mL ethyl acetate extractions, it was 58% phenyl aldehyde that the organic phase of gained can obtain yield through concentrating under reduced pressure.
Example 15
The recovery of cyclodextrin: according to example 2, add respectively 0.0266g b-cyclodextrin chitosan polymer (n=2.5 in general formula) and 25mL deionized water in the 100mL flask, 30
oBe stirred to b-cyclodextrin chitosan polymer under C and be uniformly dispersed, then add successively the chlorine bleach liquor of 0.1362g phenylacrolein and 4mL 4.5%, reaction is used the 50mL ethyl acetate extraction after finishing, and filters after extraction, and filter residue is 105
oUnder C, drying is 5 hours, obtains solid 0.0262g, and the rate of recovery of b-cyclodextrin chitosan polymer is 98.5%.
Claims (9)
1. catalyzer that is used for phenylacrolein or Oleum Cinnamomi preparing benzaldehyde by oxidizing, cyclodextrin-the chitosan polymer of described catalyzer for having general formula (I) structure, n=2.5~4 wherein, described cyclodextrin is the beta-cyclodextrin or derivatives thereof, its chemical structural formula is as shown in general formula (II)
General formula (I)
General formula (II)
In general formula (I) and general formula (II), R all is selected from H, CH
3Or CH
3CH (OH) CH
2
2. a kind of catalyzer for phenylacrolein or Oleum Cinnamomi preparing benzaldehyde by oxidizing according to claim 1, it is characterized in that preparing as follows: be that 95% chitosan dissolves with acetic acid with deacetylation, and with this solution and glutaraldehyde under the condition of 40-60 ° of C stirring reaction 1-2 hour, filter, obtain chitosan resin after drying, resin and propylene oxide are reacted in the blending agent of alkali lye and dimethyl sulfoxide (DMSO), and then in alkalescence, under the condition of 60-80 ° of C with beta-cyclodextrin stirring reaction 4-8 hour, washing, be drying to obtain cyclodextrin-chitosan polymer catalyzer.
3. the method for a spirit catalytic of cinnamaldehyde or Oleum Cinnamomi preparing benzaldehyde by oxidizing, it is characterized in that: catalyzer is cyclodextrin-chitosan polymer claimed in claim 1, take water as solvent, adding mass concentration is a kind of oxygenant of doing in 1%~90% hydrogen peroxide, clorox or tertbutyl peroxide, be spirit catalytic of cinnamaldehyde or Oleum Cinnamomi preparing benzaldehyde by oxidizing under the condition of 30~90 ° of C in temperature of reaction, after reaction finishes with obtaining phenyl aldehyde after organic extractant extraction, the concentrated purification.
4. method according to claim 3, the mass ratio that it is characterized in that described catalyzer and raw material is 1:5~5:1.
5. method according to claim 3, the mass ratio that it is characterized in that described catalyzer and raw material is 1:1~2:1.
6. method according to claim 3, is characterized in that described temperature of reaction is preferably 50~80 ° of C.
7. method according to claim 3, is characterized in that described organic extractant is esters solvent, methyl alcohol, acetone or acetonitrile.
8. according to claim 3 or 7 described methods, is characterized in that described organic extractant is ethyl acetate, methyl acetate and butylacetate.
9. method according to claim 3, is characterized in that the mass concentration of described oxygenant is preferably 1~30%.
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