CN101157603B - Environment-friendly method for synthesizing acetylacetone - Google Patents
Environment-friendly method for synthesizing acetylacetone Download PDFInfo
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- CN101157603B CN101157603B CN2007101566331A CN200710156633A CN101157603B CN 101157603 B CN101157603 B CN 101157603B CN 2007101566331 A CN2007101566331 A CN 2007101566331A CN 200710156633 A CN200710156633 A CN 200710156633A CN 101157603 B CN101157603 B CN 101157603B
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- methyl ethyl
- ethyl diketone
- magnetic
- solid base
- base catalyst
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- 238000000034 method Methods 0.000 title claims abstract description 24
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 title abstract description 12
- 230000002194 synthesizing effect Effects 0.000 title abstract description 7
- 239000007787 solid Substances 0.000 claims abstract description 27
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000003054 catalyst Substances 0.000 claims abstract description 22
- 229960001545 hydrotalcite Drugs 0.000 claims abstract description 9
- 229910001701 hydrotalcite Inorganic materials 0.000 claims abstract description 9
- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 claims abstract description 8
- 239000003513 alkali Substances 0.000 claims abstract description 6
- 229910001051 Magnalium Inorganic materials 0.000 claims abstract description 3
- 230000000694 effects Effects 0.000 claims abstract description 3
- TZMFJUDUGYTVRY-UHFFFAOYSA-N pentane-2,3-dione Chemical compound CCC(=O)C(C)=O TZMFJUDUGYTVRY-UHFFFAOYSA-N 0.000 claims description 33
- 238000006243 chemical reaction Methods 0.000 claims description 25
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 24
- 239000002585 base Substances 0.000 claims description 23
- 238000003756 stirring Methods 0.000 claims description 14
- 150000002148 esters Chemical class 0.000 claims description 12
- 239000007788 liquid Substances 0.000 claims description 10
- 238000010189 synthetic method Methods 0.000 claims description 10
- 235000019439 ethyl acetate Nutrition 0.000 claims description 8
- -1 phenyl ester Chemical class 0.000 claims description 8
- 239000000126 substance Substances 0.000 claims description 7
- WRQNANDWMGAFTP-UHFFFAOYSA-N Methylacetoacetic acid Chemical compound COC(=O)CC(C)=O WRQNANDWMGAFTP-UHFFFAOYSA-N 0.000 claims description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 6
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 claims description 4
- 238000002360 preparation method Methods 0.000 claims description 4
- WOFAGNLBCJWEOE-UHFFFAOYSA-N Benzyl acetoacetate Chemical compound CC(=O)CC(=O)OCC1=CC=CC=C1 WOFAGNLBCJWEOE-UHFFFAOYSA-N 0.000 claims description 3
- REIYHFWZISXFKU-UHFFFAOYSA-N Butyl acetoacetate Chemical compound CCCCOC(=O)CC(C)=O REIYHFWZISXFKU-UHFFFAOYSA-N 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 claims description 3
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 claims description 2
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- 238000000975 co-precipitation Methods 0.000 claims description 2
- 239000012153 distilled water Substances 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- 238000010792 warming Methods 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 2
- 125000000590 4-methylphenyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)C([H])([H])[H] 0.000 claims 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims 1
- 125000000636 p-nitrophenyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)[N+]([O-])=O 0.000 claims 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 abstract description 9
- 239000012295 chemical reaction liquid Substances 0.000 abstract 1
- XYIBRDXRRQCHLP-UHFFFAOYSA-N ethyl acetoacetate Chemical compound CCOC(=O)CC(C)=O XYIBRDXRRQCHLP-UHFFFAOYSA-N 0.000 abstract 1
- 238000005516 engineering process Methods 0.000 description 12
- 239000000047 product Substances 0.000 description 10
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 8
- 238000009835 boiling Methods 0.000 description 8
- 238000004821 distillation Methods 0.000 description 8
- 238000003786 synthesis reaction Methods 0.000 description 7
- 230000015572 biosynthetic process Effects 0.000 description 6
- 239000003814 drug Substances 0.000 description 5
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- CCGKOQOJPYTBIH-UHFFFAOYSA-N ethenone Chemical compound C=C=O CCGKOQOJPYTBIH-UHFFFAOYSA-N 0.000 description 3
- JDABVQRGDRXPEV-UHFFFAOYSA-N CC(=O)C.C=C=O Chemical group CC(=O)C.C=C=O JDABVQRGDRXPEV-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 2
- WETWJCDKMRHUPV-UHFFFAOYSA-N acetyl chloride Chemical compound CC(Cl)=O WETWJCDKMRHUPV-UHFFFAOYSA-N 0.000 description 2
- 239000012346 acetyl chloride Substances 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 238000005336 cracking Methods 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 125000003107 substituted aryl group Chemical group 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- POILWHVDKZOXJZ-ARJAWSKDSA-M (z)-4-oxopent-2-en-2-olate Chemical compound C\C([O-])=C\C(C)=O POILWHVDKZOXJZ-ARJAWSKDSA-M 0.000 description 1
- 241000894006 Bacteria Species 0.000 description 1
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 1
- KJAJQAMOPXMFPH-UHFFFAOYSA-N C(C)(=O)OC(C)=O.C(CC(=O)C)(=O)OC Chemical compound C(C)(=O)OC(C)=O.C(CC(=O)C)(=O)OC KJAJQAMOPXMFPH-UHFFFAOYSA-N 0.000 description 1
- 241000224483 Coccidia Species 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- UKHWDRMMMYWSFL-UHFFFAOYSA-N Nicarbazin Chemical compound CC=1C=C(C)NC(=O)N=1.C1=CC([N+](=O)[O-])=CC=C1NC(=O)NC1=CC=C([N+]([O-])=O)C=C1 UKHWDRMMMYWSFL-UHFFFAOYSA-N 0.000 description 1
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 1
- OUUUKJBTGQKJLX-UHFFFAOYSA-N acetic acid (4-nitrophenyl) acetate Chemical compound CC(O)=O.CC(=O)OC1=CC=C([N+]([O-])=O)C=C1 OUUUKJBTGQKJLX-UHFFFAOYSA-N 0.000 description 1
- IPBVNPXQWQGGJP-UHFFFAOYSA-N acetic acid phenyl ester Natural products CC(=O)OC1=CC=CC=C1 IPBVNPXQWQGGJP-UHFFFAOYSA-N 0.000 description 1
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 description 1
- 125000002777 acetyl group Chemical group [H]C([H])([H])C(*)=O 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 239000003674 animal food additive Substances 0.000 description 1
- 239000003443 antiviral agent Substances 0.000 description 1
- 229940043232 butyl acetate Drugs 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000005810 carbonylation reaction Methods 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 229920002301 cellulose acetate Polymers 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 206010012601 diabetes mellitus Diseases 0.000 description 1
- WASQWSOJHCZDFK-UHFFFAOYSA-N diketene Chemical compound C=C1CC(=O)O1 WASQWSOJHCZDFK-UHFFFAOYSA-N 0.000 description 1
- 238000006471 dimerization reaction Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- NBEMQPLNBYYUAZ-UHFFFAOYSA-N ethyl acetate;propan-2-one Chemical compound CC(C)=O.CCOC(C)=O NBEMQPLNBYYUAZ-UHFFFAOYSA-N 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 239000000976 ink Substances 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 238000006317 isomerization reaction Methods 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 238000005120 petroleum cracking Methods 0.000 description 1
- 229940049953 phenylacetate Drugs 0.000 description 1
- WLJVXDMOQOGPHL-UHFFFAOYSA-N phenylacetic acid Chemical compound OC(=O)CC1=CC=CC=C1 WLJVXDMOQOGPHL-UHFFFAOYSA-N 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- VBUBYMVULIMEHR-UHFFFAOYSA-N propa-1,2-diene;prop-1-yne Chemical compound CC#C.C=C=C VBUBYMVULIMEHR-UHFFFAOYSA-N 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- MWWATHDPGQKSAR-UHFFFAOYSA-N propyne Chemical group CC#C MWWATHDPGQKSAR-UHFFFAOYSA-N 0.000 description 1
- BDJXVNRFAQSMAA-UHFFFAOYSA-N quinhydrone Chemical compound OC1=CC=C(O)C=C1.O=C1C=CC(=O)C=C1 BDJXVNRFAQSMAA-UHFFFAOYSA-N 0.000 description 1
- 229940052881 quinhydrone Drugs 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000001632 sodium acetate Substances 0.000 description 1
- 235000017281 sodium acetate Nutrition 0.000 description 1
- 239000012312 sodium hydride Substances 0.000 description 1
- 229910000104 sodium hydride Inorganic materials 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- ASWVTGNCAZCNNR-UHFFFAOYSA-N sulfamethazine Chemical compound CC1=CC(C)=NC(NS(=O)(=O)C=2C=CC(N)=CC=2)=N1 ASWVTGNCAZCNNR-UHFFFAOYSA-N 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 239000000273 veterinary drug Substances 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 239000004246 zinc acetate Substances 0.000 description 1
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The invention discloses a method for synthesizing acetylacetone shown in a formula (2). Under the effect of magnetic solid alkali catalyst made from magnetic magnalium hydrotalcite, the acetoacetic ester shown in the a formula (1) reacts with acetic anhydride at 100 to 180 DEG C for 1 to 20 hours, and then the reaction liquid is processed to obtain the acetylacetone. By utilizing the magnetic solid alkali catalyst for synthesizing acetylacetone, compared with the former art, the invention has the advantages of simple art, easy operation, high yield and small environment pollution, thereby being applicable to the industrialization production with a certain scale, and forming a green and clean synthesizing line.
Description
(1) technical field
The present invention relates to a kind of synthetic method of methyl ethyl diketone, especially a kind of applied magnetic solid alkali is as the novel process of the green synthesis of acetyl acetone of catalyzer.
(2) background technology
Development highly selective, catalyzer are efficiently simplified reactions steps, reduce disposal of pollutants, develops new clean production technology, realize chemical reaction efficiently, realize " zero release ", and important use value is arranged in the Green Chemistry field.
Methyl ethyl diketone is the bigger organic synthesis intermediate of range of application in a kind of field of medicine and chemical technology.At medicine industry, it is mainly used in synthetic sulphamethazine, the intermediate 3 of antiviral agent WIN5 1711,5-dimethyl isoxazole, the intermediate 3 of treatment diabetes medicament AD-58 etc.In veterinary drug and feed additive industry, be used for the synthesising bacteria anti-reflecting medicine methlacetylquinoxalinediode, the raw material 4 of anti-chicken coccidia medicine nicarbazine, 6-dimethyl-2-ancymidol etc.Aspect catalyzer and promotor, be used to encircle the zinc tetraene, quinhydrones, quinhydrone(s) carbonylation reaction, synthesizing of low molecular compounds such as beta-unsaturated ketone, oxidation promotor, petroleum cracking, shortening and isomerized catalyzer, and the polymerization of light alkene, 1, the macromolecular compounds such as copolymerization of 3-diolefine synthetic.In other field, acetylacetonate can also be made resin cross-linking agent except that making catalyzer, hardening of resin promotor, rubber accelerator, the super formation agent that passes different film, hotline-reflective glass film and nesa coating; It also can be used as gasoline, lubricated oil additives, the siccative of paint, coating and printing inks, the additive of tackiness agent, cellulose acetate solvent, the raw material of metallizing etc.; Methyl ethyl diketone can be used as the analytical reagent of most metal ions again, the extraction agent of rare precious metals, and the treatment agent of inorganic materials.
About synthesizing of methyl ethyl diketone, a lot of countries all research and develop its technology, have integrated following several synthesis route:
1. ethyl acetate-acetone method
This method is with ethyl acetate and sodium Metal 99.5 reaction, adds acetone, generates methyl ethyl diketone, and yield is a kind of synthetic method of classics about 50%.Catalyst metal sodium can use sodium acetate, sodium hydride to replace.This synthesis technique produces a large amount of waste water, and thermal discharge is also big, and heat extraction in the commercial run and temperature control are very difficult, and side reaction is many, and catalyzer has ignition hazard, and suitability for industrialized production has certain danger.
2. acetone and diacetyl oxide (Acetyl Chloride 98Min.) condensation method
The yield of this technology is 80%～85%, but experiment shows the yield instability.More because the BF that adopts
3Amount is big, and cost is higher, and dangerous big, carrying out suitability for industrialized production has certain difficulty.
3. acetylacetic ester-ketene process
This technology at first acetate cracking produces ketene, and dimerization forms diketene, forms methyl aceto acetate with ethanol, forms α-ethanoyl methyl aceto acetate through the ketene acidylate again, and hydrolysis generates methyl ethyl diketone again.This technical process is long, and investment is big.
4. ketene-condensation of acetone conversion method
According to the different production methods of ketene, can be divided into acetone method and acetate method again.The cracking process of two kinds of methods is thermally splitting, and different is catalyzer and hot tearing temperature.The production route of domestic methyl ethyl diketone is ketene-acetone method substantially, and the external Japan that removes adopts etheric acid second fat-ketene process, and other enterprises all adopt ketene-acetone method.
5. the ethanoyl method of methylacetylene-propadiene fraction
This method is the exploitation of USSR (Union of Soviet Socialist Republics) organic synthesis institute, sets out by methylacetylene and acetate, and under certain temperature and pressure, be that catalyzer synthesizes with zinc acetate.From raw material sources, this method has great advantage, but generates in the reaction of the different propylene fat of acetate, and by product is too much, and separation difficulty, and as the not direct isomerization of purifying, then the separation of product methyl acrylate is difficult more.
6. methyl aceto acetate-aceticanhydride (Acetyl Chloride 98Min.) method
This technology is subjected to the restriction of raw material sources and price, the production cost height, and Technology is immature, is not subject to people's attention always.
Therefore, adopt new and effective catalyzer, use the Green Chemistry synthetic technology, the new synthesis process of exploitation methyl ethyl diketone enlarges the products production scale, reduces the discharging of the three wastes, fills up the blank of China in this field and has great significance.
(3) summary of the invention
The technical problem to be solved in the present invention provides a kind of novel process of green synthesis of acetyl acetone, selects magnetic solid base as catalyzer, makes the discharging that has reduced the three wastes, and technology is simple simultaneously, yield is high, and what make methyl ethyl diketone syntheticly is easy to industrialization.
The technical solution used in the present invention is as follows:
A kind of synthetic method suc as formula the methyl ethyl diketone shown in (II), under the magnetic solid base catalyst effect that magnetic mg_al hydrotalcite makes, reacted 1～20 hour at 100～180 ℃ suc as formula acetylacetic ester shown in (I) and diacetyl oxide, reaction solution gets described methyl ethyl diketone through aftertreatment; Reaction equation is as follows:
Wherein, R is alkyl, aryl or the substituted aryl of C1～C12, and described substituted aryl is the aryl that contains electrophilic or push away electron substituent group.
The consumption of described magnetic solid base catalyst be acetylacetic ester and diacetyl oxide total mass 1～10%, preferred 5%.
Described acetylacetic ester is 1: 1～3 with the amount of substance ratio of diacetyl oxide, preferred 1: 1～2, and most preferably 1: 1.
Further, formula (I) compound is preferably one of following: methyl aceto acetate, butyl-acetoacetate, etheric acid phenyl ester, benzyl acetoacetate.
The magnetic solid base that magnetic mg_al hydrotalcite makes is magnesium aluminum-hydrotalcite to be carried out magnetic modify, and makes it have magnetic and catalysis dual-use function, reaches the purpose that improves catalytic activity.Particularly, the preparation method of described magnetic solid base catalyst is as follows: get a certain amount of magnetic colloidal sol and join in the reaction flask, add distilled water again, stirring at room, magnesium nitrate and the aluminum nitrate getting the magnalium ratio and be 1: 2 are mixed with solution, and other joins the sodium hydroxide solution of pH=10～13, two kinds of solution are added in the reaction flask, 110 ℃ of stirrings, washing and drying makes magnetic mg_al hydrotalcite, forms magnetic solid base 450～500 ℃ of high-temperature roastings then.Magnetic colloidal sol is to adopt chemical coprecipitation, with Fe
3+And Fe
2+Vitriol or muriate in excessive alkali, mix to stir in 1: 1 ratio and make.Specifically can be with reference to the 29th volume the 3rd phase (in March, 2002) " preparation of magnetic mg_al hydrotalcite solid alkali and sign " of applicating technology.
Described temperature of reaction is carried out at 100 ℃～180 ℃, is preferably 140 ℃.The described reaction times is 1～20 hour, preferred 10 hours.
Described aftertreatment is: reaction solution distills after removing the acetic ester of generation, and the cut of collecting 132～136 ℃ obtains described methyl ethyl diketone.
The described synthetic method of concrete recommendation is carried out according to following steps: in reactor, according to acetylacetic ester: the amount of substance ratio of diacetyl oxide is 1: 1～2 to add acetylacetic ester and diacetyl oxides, the add-on of magnetic solid base catalyst is 1～10% of acetylacetic ester and a diacetyl oxide total mass, be warming up to 140 ℃, be incubated 10 hours, remove acetic ester after, heat up and to distill, cut between collecting 132～136 ℃ gets colourless transparent liquid, is described methyl ethyl diketone.
In this reaction, described magnetic solid base catalyst can recycle after reclaiming, and the rate of recovery reaches 95%.
The magnetic solid base that the present invention utilizes magnetic mg_al hydrotalcite to make carries out the synthetic of methyl ethyl diketone as catalyzer, compared with the prior art, its advantage is embodied in: this magnetic solid base catalyst was applied in synthesizing of methyl ethyl diketone, make the preparation of methyl ethyl diketone with respect in the past technology become simple, easy to operate, reaction yield is high, and environmental pollution is little, the suitability for industrialized production that is suitable for certain scale becomes a green clean synthetic route.
(4) embodiment:
Below with specific embodiment technical scheme of the present invention is described, but protection scope of the present invention is not limited thereto.
Embodiment 1
In 500 milliliters of reactors, add methyl aceto acetate 130 grams (1 mole), diacetyl oxide 102 grams (1 mole), magnetic solid base catalyst 2.32 grams, stir, be heated to 140 ℃, be incubated 10 hours, steam the ethyl acetate that generates in the reaction process after, heat up again and carry out the product distillation, collect the cut of 132～136 ℃ of boiling ranges, getting colourless transparent liquid is methyl ethyl diketone 80 grams, yield 80%.
Embodiment 2
In 500 milliliters of reactors, add etheric acid phenyl ester 178 grams (1 mole), diacetyl oxide 102 grams (1 mole), magnetic solid base catalyst 14 grams, stir, be heated to 180 ℃, be incubated 5 hours, steam the phenylacetate that generates in the reaction process, heat up again and carry out the product distillation, collect the cut of 132～136 ℃ of boiling ranges, getting colourless transparent liquid is methyl ethyl diketone 90 grams, yield 90%.
Embodiment 3
In 500 milliliters of reactors, add benzyl acetoacetate 191 grams (1 mole), diacetyl oxide 102 grams (1 mole), magnetic solid base catalyst 2.9 grams, stir, be heated to 150 ℃, be incubated 20 hours, steam the jasmal that generates in the reaction process, heat up again and carry out the product distillation, collect 132～136 ℃ of cuts of boiling range, getting colourless transparent liquid is methyl ethyl diketone 91 grams, yield 91%.
Embodiment 4
In 500 milliliters of reactors, add methyl aceto acetate 130 grams (1 mole), diacetyl oxide 204g (2 moles), magnetic solid base catalyst 33 grams, stir, be heated to 150 ℃, be incubated 1 hour, steam the ethyl acetate that generates in the reaction process, heat up again and carry out the product distillation, collect the cut of 132～136 ℃ of boiling ranges, getting colourless transparent liquid is methyl ethyl diketone 90 grams, yield 90%.
Embodiment 5
In 500 milliliters of reactors, add methyl aceto acetate 130 grams (1 mole), diacetyl oxide 306g (3 moles), magnetic solid base catalyst 4.36 grams, stir, be heated to 140 ℃, be incubated 10 hours, steam the ethyl acetate that generates in the reaction process, heat up again and carry out the product distillation, collect the cut of 132～136 ℃ of boiling ranges, getting colourless transparent liquid is methyl ethyl diketone 88 grams, yield 88%.
Embodiment 6
In 500 milliliters of reactors, add butyl-acetoacetate 158 grams (1 mole), diacetyl oxide 102 grams (1 mole), magnetic solid base catalyst 26 grams of recovery, stir, be heated to 130 ℃, be incubated 10 hours, steam the butylacetate that generates in the reaction process, heat up again and carry out the product distillation, collect the cut of 132～136 ℃ of boiling ranges, getting colourless transparent liquid is methyl ethyl diketone 90 grams, yield 90%.
Embodiment 7
In 500 milliliters of reactors, add etheric acid to methyl phenyl ester 192 grams (1 mole), diacetyl oxide 102 grams (1 mole), magnetic solid base catalyst 29 grams, stir, be heated to 130 ℃, be incubated 10 hours, steam the acetate methyl phenyl ester that generates in the reaction process, heat up again and carry out the product distillation, collect the cut of 132～136 ℃ of boiling ranges, getting colourless transparent liquid is methyl ethyl diketone 90 grams, yield 90%.
Embodiment 8
In 500 milliliters of reactors, add etheric acid p-nitrophenyl ester 223 grams (1 mole), diacetyl oxide 102 grams (1 mole), magnetic solid base catalyst 16 grams, stir, be heated to 130 ℃, be incubated 10 hours, steam the acetic acid p-nitrophenyl acetate that generates in the reaction process, heat up again and carry out the product distillation, collect the cut of 132～136 ℃ of boiling ranges, getting colourless transparent liquid is methyl ethyl diketone 90 grams, yield 90%.
Claims (5)
1. synthetic method suc as formula the methyl ethyl diketone shown in (II), it is characterized in that described method is under the magnetic solid base catalyst effect that magnetic mg_al hydrotalcite makes, reacted 1～20 hour at 100～180 ℃ suc as formula acetylacetic ester shown in (I) and diacetyl oxide, reaction solution gets described methyl ethyl diketone through aftertreatment;
Wherein, R is alkyl, benzyl, phenyl, p-methylphenyl or the p-nitrophenyl of C1～C12;
The preparation method of described magnetic solid base catalyst is as follows: get a certain amount of magnetic colloidal sol and join in the reaction flask, add distilled water again, stirring at room, magnesium nitrate and the aluminum nitrate getting the magnalium ratio and be 1: 2 are mixed with solution, other joins the sodium hydroxide solution of pH=10～13, and two kinds of solution are added in the reaction flask, 110 ℃ of stirrings, washing and drying makes magnetic mg_al hydrotalcite, forms magnetic solid base catalyst 450～500 ℃ of high-temperature roastings then; Described magnetic colloidal sol is to adopt chemical coprecipitation, with Fe
3+And Fe
2+Vitriol or muriate in excessive alkali, mix to stir in 1: 1 ratio and make.
2. the synthetic method of methyl ethyl diketone as claimed in claim 1, the consumption that it is characterized in that described magnetic solid base catalyst be acetylacetic ester and diacetyl oxide total mass 1～10%, described acetylacetic ester is 1: 1～3 with the amount of substance ratio of diacetyl oxide.
3. the synthetic method of methyl ethyl diketone as claimed in claim 1 is characterized in that described formula (I) compound is one of following: methyl aceto acetate, butyl-acetoacetate, etheric acid phenyl ester, benzyl acetoacetate.
4. as the synthetic method of the described methyl ethyl diketone of one of claim 1～3, it is characterized in that described aftertreatment is: reaction solution distills after removing the acetic ester of generation, and the cut of collecting 132～136 ℃ obtains described methyl ethyl diketone.
5. the synthetic method of methyl ethyl diketone as claimed in claim 1, it is characterized in that described synthetic method carries out according to following steps: in reactor, according to acetylacetic ester: the amount of substance ratio of diacetyl oxide is 1: 1～2 to add acetylacetic ester and diacetyl oxides, the add-on of magnetic solid base catalyst is 1～10% of acetylacetic ester and a diacetyl oxide total mass, be warming up to 140 ℃, be incubated 10 hours, after removing acetic ester, intensification is distilled, cut between collecting 132～136 ℃ gets colourless transparent liquid, is described methyl ethyl diketone.
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| CN101659620B (en) * | 2009-09-04 | 2012-12-12 | 浙江工业大学 | Green synthetic method of 2,5-diaminotoluene |
| CN102260151A (en) * | 2011-06-28 | 2011-11-30 | 西安彩晶光电科技股份有限公司 | Preparation method of 1,1,1,5,5,5-hexafluoro acetylacetone |
| CN102321044B (en) * | 2011-07-20 | 2013-08-07 | 江西华邦药业有限公司 | Preparation method of 3-(2-bromo propionyl)-spiro[2H-1,3-benzoxazine-2,1'-cyclohexane]-4(3H)-one |
| CN105294581B (en) * | 2015-11-19 | 2018-01-12 | 浙江工业大学 | A kind of preparation method of quinocetone |
| CN109824499A (en) * | 2019-03-08 | 2019-05-31 | 合肥工业大学 | A kind of method that microwave reinforced photocatalysis continuously prepares acetylacetone metallic compound |
| CN111423383B (en) * | 2020-06-15 | 2020-09-11 | 湖南速博生物技术有限公司 | Continuous synthesis method of hydroxypyrimidine compounds |
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