CN102093184A - 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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- CN102093184A CN102093184A CN2010105986269A CN201010598626A CN102093184A CN 102093184 A CN102093184 A CN 102093184A CN 2010105986269 A CN2010105986269 A CN 2010105986269A CN 201010598626 A CN201010598626 A CN 201010598626A CN 102093184 A CN102093184 A CN 102093184A
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- cyclodextrin
- catalyzer
- general formula
- chitosan polymer
- 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 35
- KJPRLNWUNMBNBZ-QPJJXVBHSA-N (E)-cinnamaldehyde Chemical compound O=C\C=C\C1=CC=CC=C1 KJPRLNWUNMBNBZ-QPJJXVBHSA-N 0.000 title claims abstract description 32
- 238000000034 method Methods 0.000 title claims abstract description 20
- 230000003197 catalytic effect Effects 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 16
- 239000003054 catalyst Substances 0.000 title abstract description 11
- 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 53
- 229920000642 polymer Polymers 0.000 claims abstract description 44
- 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 12
- 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 7
- 239000002994 raw material Substances 0.000 claims abstract description 5
- 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 17
- 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 14
- 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 11
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 10
- 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
- 239000011347 resin Substances 0.000 claims description 8
- 229920005989 resin Polymers 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 7
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound 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
- 238000001035 drying Methods 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
- 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
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 3
- 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
- 150000002148 esters Chemical group 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
- 239000012141 concentrate Substances 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
- 238000000746 purification Methods 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
- 239000001116 FEMA 4028 Substances 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
- 235000011175 beta-cyclodextrine Nutrition 0.000 description 2
- 229960004853 betadex Drugs 0.000 description 2
- 230000004071 biological effect Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000002209 hydrophobic effect Effects 0.000 description 2
- 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
- 238000005406 washing Methods 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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- 230000009286 beneficial effect Effects 0.000 description 1
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- 239000000796 flavoring agent 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
- 239000002245 particle Substances 0.000 description 1
- BHTJEPVNHUUIPV-UHFFFAOYSA-N pentanedial;hydrate Chemical compound O.O=CCCCC=O BHTJEPVNHUUIPV-UHFFFAOYSA-N 0.000 description 1
- 229920001282 polysaccharide Polymers 0.000 description 1
- 239000005017 polysaccharide Substances 0.000 description 1
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- MWOOGOJBHIARFG-UHFFFAOYSA-N vanillin Chemical compound COC1=CC(C=O)=CC=C1O MWOOGOJBHIARFG-UHFFFAOYSA-N 0.000 description 1
- FGQOOHJZONJGDT-UHFFFAOYSA-N vanillin Natural products COC1=CC(O)=CC(C=O)=C1 FGQOOHJZONJGDT-UHFFFAOYSA-N 0.000 description 1
- 235000012141 vanillin Nutrition 0.000 description 1
Landscapes
- 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 the 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, all has very widely in industries such as food, healthcare products, makeup and medicine intermediates and uses.According to statistics, at present the whole world once be only be used for food flavor(ing) spices natural benzaldehyde up to more than 7000 tons, and the demand of natural benzaldehyde is also in increase year by year.
What the research of preparation natural benzaldehyde was maximum at present is phenylacrolein alkaline water solution.Because phenylacrolein and water are immiscible, are difficult between the 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 shortcomings such as deleterious phase-transfer catalyst difficulty.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 this method exists the yield of long reaction time, phenyl aldehyde low, defectives such as cyclodextrin cost recovery height.
Alkaline hydrolysis prepares the deficiency that phenyl aldehyde exists based on phenylacrolein, Ji Hongbing etc. propose " method of a kind of cyclodextrin spirit catalytic of cinnamaldehyde or Oleum Cinnamomi preparing benzaldehyde by oxidizing " (2010181273.2) again, this method is made catalyzer with epoxy chloropropane and beta-cyclodextrin cross-linked polymkeric substance, water insoluble and the organic solvent of this catalyzer, solve the recovery problem of cyclodextrin preferably, 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, while reaction conditions gentleness, the yield height.But this catalyzer consumption in reaction process is big, easy water absorption and swelling, and under the effect of oxygenant, easily become tiny particle, and conglomerate has greatly influenced the catalytic activity of this catalyzer.
Summary of the invention
The object of the present invention is to provide the 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 a b-cyclodextrin or derivatives thereof, its chemical structural formula shown in general formula (II),
General formula (I)
General formula (II)
In general formula (I) and the general formula (II), R all is selected from H, CH
3Or CH
3CH (OH) CH
2
This catalyzer can prepare as follows:
With acetate dissolved chitosan (deacetylation is 95%) and glutaraldehyde at 40-60
oUnder the condition of C stirring reaction 1-2 hour, filter, obtain chitosan resin after the 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-chitosan polymer catalyzer of different polymerization degree 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, be that raw meat oil of bay or phenylacrolein are carried out catalytic oxidation under the effect of catalyzer and oxygenant thereof, catalyst system therefor is cyclodextrin-chitosan polymer of the present invention, with water is solvent, adding mass concentration is 1%～90%, a kind of oxygenant of doing in preferred 1 ~ 30% hydrogen peroxide, clorox or the 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 after the organic extractant extraction, concentrate and obtain phenyl aldehyde after purifying.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 (1,4)-2-amino-2-deoxidation-β-D-glucose of constituting with β-(1,4) glycosidic link behind the chitin deacetylase base, shows good biological activity and adsorptivity.Cyclodextrin is that a class is passed through α-1 by the D-glucopyranose units, and the macrocylc compound that the 4-glycosidic link joins end to end and forms has hydrophilic outer wall and hydrophobic cavity, 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 characteristics such as excellent mechanical intensity, stability and chemical adjustability.
The envelope recognition performance of cyclodextrin-existing cyclodextrin of chitosan polymer catalyzer that the present invention adopts has the biological activity of chitosan and the dual nature of absorption property again.Therefore this catalyzer is when spirit catalytic of cinnamaldehyde or Oleum Cinnamomi preparing benzaldehyde by oxidizing, catalytic activity is greatly improved, catalyst levels also significantly reduces, and to reducing the production cost of phenyl aldehyde effectively, realizes that the industrialization of phenyl aldehyde has extremely important meaning.Polymkeric substance is degraded easily 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 water insoluble, organic solvent, strong acid and alkaline character, and has excellent mechanical intensity, and is reusable, reduced production cost;
2, cyclodextrin-chitosan polymer of the present invention is degraded easily, 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, catalyst consumption 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, add the glutaraldehyde water solution of 7g, 40 with the chitosan (deacetylation is 95%) of 5% acetate dissolving 4g
oStirring reaction filtered after 1 hour under the C temperature, got chitosan resin, through cleaning, drying.This resin of 2g is placed there-necked flask, add purified water, NaOH solution and the dimethyl sulfoxide (DMSO) of 50mL, fully stir, drip the propylene oxide of 45mL, take out the reaction back, and washing obtains activated resin after washing with acetone, the drying.In the NaOH of 40mL solution, add the b-cyclodextrin of this activated resin of 4g and 4g, 60
oStirring reaction is 4 hours under the C temperature, and product promptly gets b-cyclodextrin-chitosan polymer catalyzer of n=3.6 after pure water rinsing, oven dry.
In the 100mL flask, add 0.6591gb-cyclodextrin-chitosan polymer (n=3.6 in the general formula) and 25mL deionized water respectively, 40
oBeing stirred to b-cyclodextrin-chitosan polymer under the C is uniformly dispersed, the chlorine bleach liquor who adds 0.1362g phenylacrolein and 3mL10% more successively, 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
In the flask of 100mL, add 0.0266g b-cyclodextrin-chitosan polymer (n=2.5 in the general formula) and 25mL deionized water respectively, 30
oBeing stirred to b-cyclodextrin chitosan polymer under the C is uniformly dispersed, the chlorine bleach liquor who adds 0.1362g phenylacrolein and 4mL 4.5% more successively, 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
In the 100mL flask, add 0.2992g b-cyclodextrin-chitosan polymer (n=3 in the general formula) and 25mL deionized water respectively, 70
oBeing stirred to b-cyclodextrin-chitosan polymer under the C is uniformly dispersed, the chlorine bleach liquor who adds 0.1362g phenylacrolein and 4mL 4.5% more successively, 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
In the 100mL flask, add 0.1364g methyl-b-cyclodextrin-chitosan polymer (n=3 in the general formula) and 25mL deionized water respectively, 50
oBeing stirred to methyl b-cyclodextrin-chitosan polymer under the C is uniformly dispersed, the chlorine bleach liquor who adds 0.1362g phenylacrolein and 4mL 10% more successively, 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
In the 100mL flask, add 0.2724g hydroxypropyl-b-cyclodextrin-chitosan polymer (n=4 in the general formula) and 25mL deionized water respectively, 90
oBeing stirred to hydroxypropyl-b-cyclodextrin-chitosan polymer under the C is uniformly dispersed, the chlorine bleach liquor who adds 0.1362g Oleum Cinnamomi and 20mL1.0% more successively, 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
In the 100mL flask, add 0.6591g methyl-b-cyclodextrin-chitosan polymer (n=3.6 in the general formula) and 25mL deionized water respectively, 60
oBeing stirred to methyl-b-cyclodextrin-chitosan polymer under the C is uniformly dispersed, the chlorine bleach liquor who adds 0.1362g phenylacrolein and 3mL10% more successively, 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
In the 100mL flask, add 0.1464g b-cyclodextrin-chitosan polymer (n=3.75 in the general formula) and 25mL deionized water respectively, 80
oBeing stirred to b-cyclodextrin-chitosan polymer under the C is uniformly dispersed, the chlorine bleach liquor who adds 0.1362g phenylacrolein and 5mL 3% more successively, 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
In the 100mL flask, add 0.1212g methyl-b-cyclodextrin chitosan polymer (n=2.7 in the general formula) and 25mL deionized water respectively, 30
oBeing stirred to methyl-b-cyclodextrin chitosan polymer under the C is uniformly dispersed, the hydrogen peroxide solution that adds 0.6053g phenylacrolein and 6mL 20% more successively, 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
In the 100mL flask, add 0.2642g b-cyclodextrin-chitosan polymer (n=4 in the general formula) and 25mL deionized water respectively, 60
oBe stirred to b-cyclodextrin-chitosan polymer under the C and be uniformly dispersed, add the hydrogen peroxide solution of 0.5285g Oleum Cinnamomi and 5mL 30% more successively, 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
In the 100mL flask, add 0.1286g hydroxypropyl-b-cyclodextrin-chitosan polymer (n=3.25 in the general formula) and 25mL deionized water respectively, 60
oC is stirred to hydroxypropyl-b-cyclodextrin-chitosan polymer and is uniformly dispersed, the hydrogen peroxide solution that adds 0.1286g Oleum Cinnamomi and 4mL 30% more successively, 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
In the 100mL flask, add 3.258g a-cyclodextrin epichlorohydrin polymer (n=2.5 in the general formula) and 25mL deionized water respectively, 60
oBeing stirred to a-cyclodextrin epichlorohydrin polymer under the C is uniformly dispersed, the hydrogen peroxide solution that adds 0.1322g phenylacrolein and 4mL 30% more successively, 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
In the 100mL flask, add 0.5480g b-cyclodextrin-chitosan polymer (n=2.5 in the general formula) and 25mL deionized water respectively, 50
oBeing stirred to b-cyclodextrin-chitosan polymer under the C is uniformly dispersed, the tertbutyl peroxide that adds 0.274g phenylacrolein and 8mL 90% more successively, 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
In 100 mL flasks, add 0.5204g b-cyclodextrin-chitosan polymer (n=2.5 in the general formula) and 25 mL deionized waters respectively, 40
oBeing stirred to b-cyclodextrin-chitosan polymer under the C is uniformly dispersed, the tertbutyl peroxide that adds 0.1040g phenylacrolein and 8 mL 60% more successively, 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
In 100 mL flasks, add 0.5204g b-cyclodextrin-chitosan polymer (n=2.5 in the general formula) and 25 mL deionized waters respectively, 60
oBeing stirred to b-cyclodextrin-chitosan polymer under the C is uniformly dispersed, the tertbutyl peroxide that adds 0.1223g Oleum Cinnamomi and 8 mL 30% more successively, 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:, in the 100mL flask, add 0.0266g b-cyclodextrin chitosan polymer (n=2.5 in the general formula) and 25mL deionized water respectively, 30 according to example 2
oBe stirred to b-cyclodextrin chitosan polymer under the C and be uniformly dispersed, add the chlorine bleach liquor of 0.1362g phenylacrolein and 4mL 4.5% more successively, reaction is used the 50mL ethyl acetate extraction after finishing, the extraction after-filtration, and filter residue is 105
oC dry 5 hours down 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, described catalyzer is cyclodextrin-chitosan polymer with general formula (I) structure, n=2.5～4 wherein, and described cyclodextrin is a b-cyclodextrin or derivatives thereof, its chemical structural formula is shown in general formula (II)
General formula (I)
General formula (II)
In general formula (I) and the general formula (II), R all is selected from H, CH
3Or CH
3CH (OH) CH
2
2. method for preparing the described cyclodextrin of claim 1-chitosan polymer catalyzer is characterized in that preparing as follows: with acetate dissolved chitosan (deacetylation is 95%) and glutaraldehyde at 40-60
oUnder the condition of C stirring reaction 1-2 hour, filter, obtain chitosan resin after the drying, resin and propylene oxide are reacted in the blending agent of alkali lye and dimethyl sulfoxide (DMSO), and then at alkaline, 60-80
oWith b-cyclodextrin stirring reaction 4-8 hour, wash, be drying to obtain cyclodextrin-chitosan polymer catalyzer under the condition of C.
3. the method for spirit catalytic of cinnamaldehyde or Oleum Cinnamomi preparing benzaldehyde by oxidizing, it is characterized in that: catalyzer is the described cyclodextrin-chitosan polymer of claim 1, with water is solvent, adding mass concentration and be a kind of oxygenant of doing in 1%～90% hydrogen peroxide, clorox or the tertbutyl peroxide, 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 the back with the organic extractant extraction, concentrate and obtain phenyl aldehyde after purifying.
4. require described method according to right 3, the mass ratio that it is characterized in that described catalyzer and raw material is 1:5～5:1.
5. according to right 3 described methods, the mass ratio that it is characterized in that described catalyzer and raw material is 1:1～2:1.
6. according to right 3 described methods, it is characterized in that described temperature of reaction is preferably 50 ~ 80
oC.
7. according to right 3 described methods, it is characterized in that described organic extractant is esters solvent, methyl alcohol, acetone or acetonitrile.
8. according to right 3 or 7 described methods, it is characterized in that described organic extractant is esters solvents such as ethyl acetate, methyl acetate and butylacetate.
9. according to right 3 described methods, it is characterized in that the mass concentration of described oxygenant is preferably 1～30%.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104820005A (en) * | 2015-04-23 | 2015-08-05 | 常州大学 | Chiral sensor based on chitosan/cyclodextrin dinuclear copper and manufacturing method of chiral sensor |
| CN105016996A (en) * | 2014-04-25 | 2015-11-04 | 浙江工业大学 | Green preparing method of p-tert-butylcyclohexanone |
| CN105085210A (en) * | 2015-09-07 | 2015-11-25 | 广西民族大学 | Method for enriching and recovering benzaldehyde from benzaldehyde-containing aqueous solution |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101037384A (en) * | 2007-04-26 | 2007-09-19 | 华南理工大学 | Preparation method of benzaldehyde |
| CN101250096A (en) * | 2008-04-11 | 2008-08-27 | 中山大学 | Preparation method of benzaldehyde |
| CN101648853A (en) * | 2009-09-18 | 2010-02-17 | 中山大学 | Method for preparing benzaldehyde by taking hydroxypropyl-beta-cyclodextrin as accelerating agent |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101037384A (en) * | 2007-04-26 | 2007-09-19 | 华南理工大学 | Preparation method of benzaldehyde |
| CN101250096A (en) * | 2008-04-11 | 2008-08-27 | 中山大学 | Preparation method of benzaldehyde |
| CN101648853A (en) * | 2009-09-18 | 2010-02-17 | 中山大学 | Method for preparing benzaldehyde by taking hydroxypropyl-beta-cyclodextrin as accelerating agent |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105016996A (en) * | 2014-04-25 | 2015-11-04 | 浙江工业大学 | Green preparing method of p-tert-butylcyclohexanone |
| CN104820005A (en) * | 2015-04-23 | 2015-08-05 | 常州大学 | Chiral sensor based on chitosan/cyclodextrin dinuclear copper and manufacturing method of chiral sensor |
| CN105085210A (en) * | 2015-09-07 | 2015-11-25 | 广西民族大学 | Method for enriching and recovering benzaldehyde from benzaldehyde-containing aqueous solution |
| CN105085210B (en) * | 2015-09-07 | 2017-01-25 | 广西民族大学 | Method for enriching and recovering benzaldehyde from benzaldehyde-containing aqueous solution |
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