CN1315768C - Synthesis method of 2-alkyl anthraquinone - Google Patents
Synthesis method of 2-alkyl anthraquinone Download PDFInfo
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- CN1315768C CN1315768C CNB2004101554735A CN200410155473A CN1315768C CN 1315768 C CN1315768 C CN 1315768C CN B2004101554735 A CNB2004101554735 A CN B2004101554735A CN 200410155473 A CN200410155473 A CN 200410155473A CN 1315768 C CN1315768 C CN 1315768C
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- PYKYMHQGRFAEBM-UHFFFAOYSA-N anthraquinone Natural products CCC(=O)c1c(O)c2C(=O)C3C(C=CC=C3O)C(=O)c2cc1CC(=O)OC PYKYMHQGRFAEBM-UHFFFAOYSA-N 0.000 title abstract description 11
- 238000001308 synthesis method Methods 0.000 title 1
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 claims abstract description 55
- 229910021536 Zeolite Inorganic materials 0.000 claims abstract description 43
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims abstract description 43
- 239000010457 zeolite Substances 0.000 claims abstract description 43
- 239000002808 molecular sieve Substances 0.000 claims abstract description 39
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims abstract description 39
- 238000006243 chemical reaction Methods 0.000 claims abstract description 22
- 239000003054 catalyst Substances 0.000 claims abstract description 17
- 239000011973 solid acid Substances 0.000 claims abstract description 14
- 238000010189 synthetic method Methods 0.000 claims abstract description 11
- 239000007788 liquid Substances 0.000 claims abstract description 4
- 239000002253 acid Substances 0.000 claims description 39
- CFHIDWOYWUOIHU-UHFFFAOYSA-N oxomethyl Chemical compound O=[CH] CFHIDWOYWUOIHU-UHFFFAOYSA-N 0.000 claims description 26
- 239000000243 solution Substances 0.000 claims description 10
- 238000005119 centrifugation Methods 0.000 claims description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 4
- 229910044991 metal oxide Inorganic materials 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 4
- -1 stir Substances 0.000 claims description 4
- JHUUPUMBZGWODW-UHFFFAOYSA-N 3,6-dihydro-1,2-dioxine Chemical compound C1OOCC=C1 JHUUPUMBZGWODW-UHFFFAOYSA-N 0.000 claims description 3
- 239000003929 acidic solution Substances 0.000 claims description 3
- 150000003863 ammonium salts Chemical class 0.000 claims description 3
- 238000004821 distillation Methods 0.000 claims description 3
- ICQOWIXIHDDXDI-UHFFFAOYSA-N 2-(4-methylbenzoyl)benzoic acid Chemical compound C1=CC(C)=CC=C1C(=O)C1=CC=CC=C1C(O)=O ICQOWIXIHDDXDI-UHFFFAOYSA-N 0.000 claims description 2
- 239000007795 chemical reaction product Substances 0.000 claims description 2
- 239000012265 solid product Substances 0.000 claims description 2
- 238000003756 stirring Methods 0.000 claims description 2
- SJEBAWHUJDUKQK-UHFFFAOYSA-N 2-ethylanthraquinone Chemical compound C1=CC=C2C(=O)C3=CC(CC)=CC=C3C(=O)C2=C1 SJEBAWHUJDUKQK-UHFFFAOYSA-N 0.000 abstract description 18
- 238000000034 method Methods 0.000 abstract description 14
- 230000018044 dehydration Effects 0.000 abstract description 3
- 238000006297 dehydration reaction Methods 0.000 abstract description 3
- 238000002360 preparation method Methods 0.000 abstract description 3
- 239000000126 substance Substances 0.000 abstract description 3
- 239000005711 Benzoic acid Substances 0.000 abstract 2
- 235000010233 benzoic acid Nutrition 0.000 abstract 2
- JZFDKGFWNSQAHU-UHFFFAOYSA-N 2-(4-ethylbenzoyl)benzoic acid Chemical compound C1=CC(CC)=CC=C1C(=O)C1=CC=CC=C1C(O)=O JZFDKGFWNSQAHU-UHFFFAOYSA-N 0.000 abstract 1
- 230000002378 acidificating effect Effects 0.000 abstract 1
- 238000003889 chemical engineering Methods 0.000 abstract 1
- 238000006798 ring closing metathesis reaction Methods 0.000 abstract 1
- 230000009466 transformation Effects 0.000 description 15
- 239000000047 product Substances 0.000 description 8
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 239000000843 powder Substances 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 5
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical group OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 description 5
- 150000004056 anthraquinones Chemical class 0.000 description 5
- 238000004587 chromatography analysis Methods 0.000 description 5
- 238000001816 cooling Methods 0.000 description 5
- 239000007791 liquid phase Substances 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 238000005303 weighing Methods 0.000 description 4
- FGTYTUFKXYPTML-UHFFFAOYSA-N 2-benzoylbenzoic acid Chemical compound OC(=O)C1=CC=CC=C1C(=O)C1=CC=CC=C1 FGTYTUFKXYPTML-UHFFFAOYSA-N 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- NJWGQARXZDRHCD-UHFFFAOYSA-N 2-methylanthraquinone Chemical group C1=CC=C2C(=O)C3=CC(C)=CC=C3C(=O)C2=C1 NJWGQARXZDRHCD-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 229910000287 alkaline earth metal oxide Inorganic materials 0.000 description 2
- 238000007598 dipping method Methods 0.000 description 2
- 238000007323 disproportionation reaction Methods 0.000 description 2
- 239000013067 intermediate product Substances 0.000 description 2
- UEGPKNKPLBYCNK-UHFFFAOYSA-L magnesium acetate Chemical compound [Mg+2].CC([O-])=O.CC([O-])=O UEGPKNKPLBYCNK-UHFFFAOYSA-L 0.000 description 2
- 239000011654 magnesium acetate Substances 0.000 description 2
- 229940069446 magnesium acetate Drugs 0.000 description 2
- 235000011285 magnesium acetate Nutrition 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 229910001404 rare earth metal oxide Inorganic materials 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- IATRAKWUXMZMIY-UHFFFAOYSA-N strontium oxide Chemical compound [O-2].[Sr+2] IATRAKWUXMZMIY-UHFFFAOYSA-N 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- KMOUUZVZFBCRAM-OLQVQODUSA-N (3as,7ar)-3a,4,7,7a-tetrahydro-2-benzofuran-1,3-dione Chemical compound C1C=CC[C@@H]2C(=O)OC(=O)[C@@H]21 KMOUUZVZFBCRAM-OLQVQODUSA-N 0.000 description 1
- MAKLMMYWGTWPQM-UHFFFAOYSA-N 2-butylanthracene-9,10-dione Chemical compound C1=CC=C2C(=O)C3=CC(CCCC)=CC=C3C(=O)C2=C1 MAKLMMYWGTWPQM-UHFFFAOYSA-N 0.000 description 1
- UMWZLYTVXQBTTE-UHFFFAOYSA-N 2-pentylanthracene-9,10-dione Chemical compound C1=CC=C2C(=O)C3=CC(CCCCC)=CC=C3C(=O)C2=C1 UMWZLYTVXQBTTE-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 230000010933 acylation Effects 0.000 description 1
- 238000005917 acylation reaction Methods 0.000 description 1
- 150000004996 alkyl benzenes Chemical class 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 230000029936 alkylation Effects 0.000 description 1
- 238000005804 alkylation reaction Methods 0.000 description 1
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical class Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 1
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 1
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 1
- 235000011130 ammonium sulphate Nutrition 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- 239000000292 calcium oxide Substances 0.000 description 1
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 229910000420 cerium oxide Inorganic materials 0.000 description 1
- 238000004939 coking Methods 0.000 description 1
- RKTYLMNFRDHKIL-UHFFFAOYSA-N copper;5,10,15,20-tetraphenylporphyrin-22,24-diide Chemical compound [Cu+2].C1=CC(C(=C2C=CC([N-]2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3[N-]2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 RKTYLMNFRDHKIL-UHFFFAOYSA-N 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 230000003413 degradative effect Effects 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical group [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 238000003760 magnetic stirring Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The present invention relates to a synthetic method of 2-alkyl anthraquinone, which belongs to the technical field of synthetic chemical engineering and relates to the preparation of 2-alkyl anthraquinone. The present invention discloses a new method which makes 2-(4'-alkyl group benzoyl) benzoic acid produce 2-alkyl anthraquinone by dehydration ring closure under the action of a solid acid catalyst. The liquid 2-(4'-alkyl group benzoyl) benzoic acid is mixed with the solid acid catalyst fully to prepare high-purity 2-alkyl anthraquinone in one step at a certain temperature. The present invention has the advantages of no environment pollution, simple process and high efficiency. An acidic beta zeolite molecular sieve is used as a catalyst, the conversion rate of the reacting substance of 2-(4'-ethyl benzoyl) benzoic acid can reach 96%, and the selectivity of the product of the 2-ethyl anthraquinone can reach 99%.
Description
Technical field
The invention belongs to the synthetic chemistry field of engineering technology.Be particularly related to the preparation method of 2-alkyl-anthraquinone.
Background technology
The 2-alkyl-anthraquinone is mainly used in the carrier of anthraquinone preparation hydrogen peroxide, also can be used as degradative resin, the intermediate of photosensitive polymerization material or dyestuff.Fast development along with industry such as global hydrogen peroxide and synthetic resins.The output of 2-alkyl-anthraquinone can not satisfy growing needs.
The complex technical process of traditional production 2-alkyl-anthraquinone uses the vitriol oil to carry out dehydration closed-loop, produces a large amount of spent acid in the production process, and equipment and environment have been caused serious harm, therefore is badly in need of a kind of new production method and covers the shortage.
The method of traditional production 2-alkyl-anthraquinone mainly is that to adopt Tetra hydro Phthalic anhydride and alkylbenzene be that raw material passes through the acylations method and generates intermediate product 2-(4 '-alkylbenzene formyl radical) phenylformic acid; intermediate product 2-(4 '-alkylbenzene formyl radical) phenylformic acid is again through hydrolysis; closed loop; distillating recovering solvent, redox purification and ethanol distillation abstraction technique finally obtain purpose product 2-alkyl-anthraquinone.The required chemical technology of this method is long, and needs a large amount of aluminum chlorides and the vitriol oil to make catalyzer in the reaction process.It is that the prepared using vitriol oil or oleum are the method for Catalyst Production 2-ethyl-anthraquinone with 2-(4 '-ethylamino benzonitrile acyl group) phenylformic acid mixture that WO96/28410 has related to a kind of.The shortcoming of this method is that the vitriol oil and oleum have stronger corrodibility and environmental hazard, and aftertreatment work is more loaded down with trivial details.Therefore people try hard to prepare 2-ethyl-anthraquinone with a kind of eco-friendly catalyzer.In synthetic anthraquinone process, U.SPatNo4,304,724 utilize 2-(benzoyl) phenylformic acid to cross synthetic anthraquinone under the effect of fluorinated sulfonic resin at catalyzer.This catalyst system environmentally safe, the operational condition gentleness.But shortcoming is that 2-(benzoyl) phenylformic acid transformation efficiency is lower, and the selectivity of anthraquinone is not high.
The Beta zeolite molecular sieve is that the common height of forming of tetragonal system and oblique system is piled up the zeolite acidity molecular sieve of defective, has three-dimensional 12 annulus ducts, and has good hydrothermal stability and anti-coking performance.At present to beta Zeolite molecular sieve catalysis performance, as hydrocarbon cracking and isomery, toluene disproportionation, the alkylation of many toluene is shifted, and extensive studies has been carried out in the aspects such as disproportionation of macromole naphthalene.E.Santacesaria etc. have reported that in CatalysisToday66. (2001) 167-174 with 2-(benzoyl) phenylformic acid be raw material, are catalyzer with the beta zeolite molecular sieve, make the technology of the synthetic anthraquinone of reactant dehydration closed-loop, have obtained effect preferably.But in Synthetic 2-alkyl-anthraquinone process,, therefore to obtain highly purified 2-alkyl-anthraquinone difficulty relatively more owing to have problems such as alkyl comes off in the reaction process.
Summary of the invention
The object of the present invention is to provide a kind of environmental friendliness, process simply, the synthetic method of 2-alkyl-anthraquinone efficiently.
Technical solution of the present invention is; a kind of synthetic method of 2-alkyl-anthraquinone; be at the 0.5-1.1MP normal atmosphere; under temperature 200-350 ℃; 2-(4 '-alkylbenzene formyl radical) phenylformic acid is added in the reactor; after the liquefaction; press 2-(4 '-alkylbenzene formyl radical) phenylformic acid and solid acid catalyst mass ratio 3.0-50.0 and add solid acid catalyst; stir; liquid 2-(4;-alkylbenzene formyl radical) phenylformic acid mixes with solid acid catalyst, reacts 0.5-5.0 hour, is cooled to 30-60 ℃; in reactor, add 1; 4-dioxane, ratio are that 1 gram reaction product adds 25-150ml 1,4-dioxane; centrifugation reaction solution then, reaction solution distillation oven dry obtains solid product 2-alkyl-anthraquinone.
2-(4 '-alkylbenzene formyl radical) phenylformic acid is 2-(4 '-methyl benzoyl) phenylformic acid, and product is a 2-methylanthraquinone.
2-(4 '-alkylbenzene formyl radical) phenylformic acid is 2-(4 '-ethylamino benzonitrile acyl group) phenylformic acid, and product is a 2-ethyl-anthraquinone.
2-(4 '-alkylbenzene formyl radical) phenylformic acid is 2-(4 '-propylbenzene formyl radical) phenylformic acid, and product is a 2-propyl group anthraquinone.
2-(4 '-alkylbenzene formyl radical) phenylformic acid is 2-(4 '-butylbenzene formyl radical) phenylformic acid, and product is the 2-butyl anthraquinone.
2-(4 '-alkylbenzene formyl radical) phenylformic acid is 2-(4 '-amylbenzene formyl radical) phenylformic acid, and product is the 2-amyl anthraquinone.
Solid acid catalyst is acid beta zeolite molecular sieve, acid Y zeolite molecular sieve, acid ZSM-5 zeolite molecular sieve or acid diatomite.
Acid beta zeolite molecular sieve, acid Y zeolite molecular sieve, acid ZSM-5 zeolite molecular sieve and acid diatomite exchange with acidic solution or ammonium salt.
Acidic solution is citric acid, nitric acid, hydrochloric acid, sulfuric acid.
Ammonium salt is ammonium nitrate, ammonium sulfate.
Acid beta zeolite molecular sieve, acid Y zeolite molecular sieve, acid ZSM-5 zeolite molecular sieve and acid diatomite metal oxide modified.
Metal oxide is an alkaline earth metal oxide.
Alkaline earth metal oxide is magnesium oxide, calcium oxide, strontium oxide.
Metal oxide is a rare-earth oxide.
Rare-earth oxide is a lanthanum trioxide, cerium oxide.
Temperature of reaction is 230-300 ℃.
Reaction times is 1.0-2.5 hour.
The mass ratio of 2-(4 '-alkylbenzene formyl radical) phenylformic acid and solid acid catalyst is 3.5-5.0.
The beneficial effect that the present invention reached is; environmental friendliness, process are simply, efficiently; utilize acid beta zeolite molecular sieve to be catalyzer; wherein in the synthesis technique of 2-ethyl-anthraquinone; the benzoic transformation efficiency of reactant 2-(4 '-ethylamino benzonitrile acyl group) can reach 96%, and the selectivity of product 2-ethyl-anthraquinone can reach 99%.
Embodiment
The present invention is further illustrated below in conjunction with embodiment.
Synthesizing of acid beta zeolite molecular sieve: under 80 ℃, the ammonium nitrate exchange with 0.4mol/L makes acid beta zeolite molecular sieve with the beta zeolite powder.
Synthesizing of acid Y zeolite molecular sieve: the Y zeolite molecular screen primary powder is provided by Chang Ling chemical industry company limited, and under 80 ℃, the ammonium nitrate exchange with 0.4mol/L makes acid Y zeolite molecular sieve.
2-(4 '-alkylbenzene formyl radical) phenylformic acid adopts commercially available 2-(4 '-alkylbenzene formyl radical) phenylformic acid solid particulate.
Take by weighing a certain amount of 2-(4 '-alkylbenzene formyl radical) phenylformic acid, it is added in reactor.Treat its liquefaction, add solid acid catalyst.Under the effect of magnetic stirring apparatus, make liquid 2-(4 '-alkylbenzene formyl radical) phenylformic acid and solid acid catalyst thorough mixing.Added afterreaction 0.5-5.0 hour.After reaction was finished, cooling added solvent in reactor.Centrifugation reaction solution then.Form with the liquid-phase chromatographic analysis product.
Embodiment one
The former powder of beta zeolite molecular sieve is exchanged into acid beta zeolite molecular sieve.Take by weighing the former powder of 40g beta zeolite molecular sieve and pack in the there-necked flask, add the ammonium nitrate of 200ml 0.4mol/L again, 80 ℃ of exchanges two hours down.550 ℃ of roastings of retort furnace 4 hours are put in the oven dry of exchange back then, obtain acid beta zeolite molecular sieve.
Embodiment two
At 230 ℃, adding 3.5g 2-in reaction vessel (4 '-the ethylamino benzonitrile acyl group) phenylformic acid, treat its liquefaction, to wherein adding the acid beta zeolite molecular sieve of 1.0g.After adding, reacted 1.5 hours, slightly after the cooling, to wherein adding 1,4-dioxane solvent.The centrifugation catalyzer, the gained reaction solution is with its composition of liquid-phase chromatographic analysis.The benzoic transformation efficiency of 2-(4 '-ethylamino benzonitrile acyl group) is 41%, and the 2-ethyl-anthraquinone selectivity is 89%.
Embodiment three
To change 1.0 hours the reaction times into, other condition is with embodiment two, and the benzoic transformation efficiency of 2-(4 '-ethylamino benzonitrile acyl group) is 28.7%, and the 2-ethyl-anthraquinone selectivity is 89%.
Embodiment four
To change 2.0 hours the reaction times into, other condition is with embodiment two, and the benzoic transformation efficiency of 2-(4 '-ethylamino benzonitrile acyl group) is 52%, and the 2-ethyl-anthraquinone selectivity is 92%.
Embodiment five
Change temperature of reaction into 250 ℃, other conditions are with embodiment two, and the benzoic transformation efficiency of 2-(4 '-ethylamino benzonitrile acyl group) is 88.1%, and selectivity is 93%.
Embodiment six
Change temperature of reaction into 270 ℃, other conditions are with embodiment two, and the benzoic transformation efficiency of 2-(4 '-ethylamino benzonitrile acyl group) is 96%, and the 2-ethyl-anthraquinone selectivity is 99%.
Embodiment seven
Change temperature of reaction into 300 ℃, other conditions are with embodiment two, and the benzoic transformation efficiency of 2-(4 '-ethylamino benzonitrile acyl group) is 75.2%, and the 2-ethyl-anthraquinone selectivity is 91.7%.
Embodiment eight
Change the benzoic add-on of 2-(4 '-ethylamino benzonitrile acyl group) into 3.0g, other is with embodiment two, and the benzoic transformation efficiency of 2-(4 '-ethylamino benzonitrile acyl group) is 22.4%, and the 2-ethyl-anthraquinone selectivity is 85.9%.
Embodiment nine
Change the benzoic add-on of 2-(4 '-ethylamino benzonitrile acyl group) into 4.0g, other is with embodiment two, and the benzoic transformation efficiency of 2-(4 '-ethylamino benzonitrile acyl group) is 26.7%, and the 2-ethyl-anthraquinone selectivity is 84.2%.
Embodiment ten
Change the benzoic add-on of 2-(4 '-ethylamino benzonitrile acyl group) into 4.0g, other is with embodiment two, and the benzoic transformation efficiency of 2-(4 '-ethylamino benzonitrile acyl group) is 26.7%, and the 2-ethyl-anthraquinone selectivity is 84.2%.
Embodiment 11
Change the benzoic add-on of 2-(4 '-ethylamino benzonitrile acyl group) into 5.0g, other is with embodiment two, and the benzoic transformation efficiency of 2-(4 '-ethylamino benzonitrile acyl group) is 26.5%, and the 2-ethyl-anthraquinone selectivity is 82.9%.
Embodiment 12
The Y zeolite molecular screen primary powder is exchanged into acid Y zeolite molecular sieve.Take by weighing 40g Y zeolite molecular screen primary powder and pack in the there-necked flask, add the ammonium nitrate of 200ml 0.4mol/L again, 80 ℃ of exchanges two hours down.550 ℃ of roastings of retort furnace 4 hours are put in the oven dry of exchange back then, obtain acid Y zeolite molecular sieve.
Embodiment 13
At 250 ℃, in reaction vessel, add 3.5g2-(4 '-ethylamino benzonitrile acyl group) phenylformic acid, treat its liquefaction, to wherein adding the acid Y zeolite molecular sieve of 1.0g.Added afterreaction 1.5 hours, slightly after the cooling, to wherein adding 1,4-dioxane solvent.The centrifugation catalyzer, the gained reaction solution is with its composition of liquid-phase chromatographic analysis.The benzoic transformation efficiency of 2-(4 '-ethylamino benzonitrile acyl group) is 8.8%, and the 2-ethyl-anthraquinone selectivity is 6.8%.
Embodiment 14
At 260 ℃, in reaction vessel, add 3.5g2-(4 '-ethylamino benzonitrile acyl group) phenylformic acid, treat its liquefaction, to wherein adding the acid Y zeolite molecular sieve of 1.0g.Added afterreaction 1.5 hours, slightly after the cooling, to wherein adding 1,4-dioxane solvent.The centrifugation catalyzer, the gained reaction solution is with its composition of liquid-phase chromatographic analysis.The benzoic transformation efficiency of 2-(4 '-ethylamino benzonitrile acyl group) is 17.2%, and the 2-ethyl-anthraquinone selectivity is 4.6%.
Embodiment 15
Take by weighing the acid beta zeolite molecular sieve of 2g and put into beaker, with the magnesium acetate dipping modification of 40ml 0.5mol/L, dipping spends the night.After the oven dry, put into 550 ℃ of roastings of retort furnace 4 hours.
Embodiment 16
At 250 ℃, add 3.5g2-(4 '-ethylamino benzonitrile acyl group) phenylformic acid in the reaction vessel, treat its liquefaction, to the acid beta zeolite molecular sieve that wherein adds the modification of 1.0g magnesium acetate.Added afterreaction 1.5 hours, slightly after the cooling, to wherein adding 1,4-dioxane solvent.The centrifugation catalyzer, the gained reaction solution is with its composition of liquid-phase chromatographic analysis.The benzoic transformation efficiency of 2-(4 '-ethylamino benzonitrile acyl group) is 5%, and the 2-ethyl-anthraquinone selectivity is 32.6%.
Claims (7)
1. the synthetic method of a 2-alkyl-anthraquinone, it is characterized in that, at the 0.5-1.1MP normal atmosphere, under temperature 200-350 ℃, 2-(4 '-alkylbenzene formyl radical) phenylformic acid is added in the reactor, after the liquefaction, press 2-(4 '-alkylbenzene formyl radical) phenylformic acid and solid acid catalyst mass ratio 3.0-50.0 and add solid acid catalyst, stir, liquid 2-(4 '-alkylbenzene formyl radical) phenylformic acid mixes with solid acid catalyst, reacted 0.5-5.0 hour, be cooled to 30-60 ℃, in reactor, add 1, the 4-dioxane, ratio is that 1 gram reaction product adds 25-150ml1, the 4-dioxane, centrifugation reaction solution then, reaction solution distillation oven dry obtains solid product 2-alkyl-anthraquinone; Wherein, solid acid catalyst is acid beta zeolite molecular sieve, acid Y zeolite molecular sieve, acid ZSM-5 zeolite molecular sieve or acid diatomite.
2. the synthetic method of a kind of 2-alkyl-anthraquinone according to claim 1; it is characterized in that 2-(4 '-alkylbenzene formyl radical) phenylformic acid is 2-(4 '-methyl benzoyl) phenylformic acid, 2-(4 '-ethylamino benzonitrile acyl group) phenylformic acid, 2-(4 '-propylbenzene formyl radical) phenylformic acid, 2-(4 '-butylbenzene formyl radical) phenylformic acid or 2-(4 '-amylbenzene formyl radical) phenylformic acid.
3. the synthetic method of a kind of 2-alkyl-anthraquinone according to claim 1 is characterized in that, acid beta zeolite molecular sieve, acid Y zeolite molecular sieve, acid ZSM-5 zeolite molecular sieve and acid diatomite exchange with acidic solution or ammonium salt.
4. according to the synthetic method of claim 1 or 3 described a kind of 2-alkyl-anthraquinones, it is characterized in that acid beta zeolite molecular sieve, acid Y zeolite molecular sieve, acid ZSM-5 zeolite molecular sieve and acid diatomite metal oxide modified.
5. the synthetic method of a kind of 2-alkyl-anthraquinone according to claim 1 is characterized in that, temperature of reaction is 230-300 ℃.
6. the synthetic method of a kind of 2-alkyl-anthraquinone according to claim 1 is characterized in that, the reaction times is 1.0-2.5 hour.
7. the synthetic method of a kind of 2-alkyl-anthraquinone according to claim 1 is characterized in that, the mass ratio of 2-(4 '-alkylbenzene formyl radical) phenylformic acid and solid acid catalyst is 3.5-5.0.
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| CN104588087B (en) * | 2013-11-03 | 2017-02-01 | 中国石油化工股份有限公司 | Catalyst for preparing 2-alkyl anthraquinone, and preparation method and application thereof |
| CN104588088B (en) * | 2013-11-03 | 2017-03-01 | 中国石油化工股份有限公司 | For preparing catalyst of 2 alkyl-anthraquinones and its preparation method and application |
| CN104725204B (en) * | 2015-02-14 | 2017-02-01 | 嘉兴润博化工科技有限公司 | Method for producing 2-alkylanthraquinone with sulfonated graphene catalyst |
| CN106040290B (en) * | 2016-05-20 | 2018-11-16 | 大连理工大学 | Prepare HBeta catalyst composite modifying method and the catalyst application of 2- ethyl hydrazine |
| CN106866398A (en) * | 2017-02-27 | 2017-06-20 | 天津大学 | A kind of method of 2 EAQs of industrial continuous production |
| CN107098802B (en) * | 2017-04-13 | 2020-08-14 | 大连理工大学 | Beta zeolite based 2-alkyl anthraquinone preparation method |
| CN108191620A (en) * | 2018-01-10 | 2018-06-22 | 河南中医药大学 | A kind of method that amitriptyline intermediate is prepared using solid acid catalyst |
| CN112007689B (en) * | 2019-05-31 | 2021-10-19 | 大连理工大学 | Catalyst and preparation method and application thereof |
| CN111348997B (en) * | 2020-04-21 | 2022-03-25 | 青岛科技大学 | Preparation method of 2-alkyl anthraquinone |
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| US4304724A (en) * | 1980-12-22 | 1981-12-08 | The Dow Chemical Company | Process for the manufacture of anthraquinone |
| CN1177954A (en) * | 1995-03-15 | 1998-04-01 | 埃勒夫阿托化学有限公司 | Method for synthesising 2 -ethyl -anthraquinone |
| CN1189484A (en) * | 1997-01-27 | 1998-08-05 | 东南大学 | Method of synthetizing anthraquinone by microwave heating |
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| US4304724A (en) * | 1980-12-22 | 1981-12-08 | The Dow Chemical Company | Process for the manufacture of anthraquinone |
| CN1177954A (en) * | 1995-03-15 | 1998-04-01 | 埃勒夫阿托化学有限公司 | Method for synthesising 2 -ethyl -anthraquinone |
| CN1189484A (en) * | 1997-01-27 | 1998-08-05 | 东南大学 | Method of synthetizing anthraquinone by microwave heating |
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| 2-乙基蒽醌的合成工艺研究 董研等，广州化学，第1期 1997 * |
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