CN115819289B - Preparation method of anthraquinone-2-sulfonic acid compound - Google Patents
Preparation method of anthraquinone-2-sulfonic acid compound Download PDFInfo
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- CN115819289B CN115819289B CN202211275286.5A CN202211275286A CN115819289B CN 115819289 B CN115819289 B CN 115819289B CN 202211275286 A CN202211275286 A CN 202211275286A CN 115819289 B CN115819289 B CN 115819289B
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- anthraquinone
- ionic liquid
- sulfonic acid
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- acid
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- -1 anthraquinone-2-sulfonic acid compound Chemical class 0.000 title claims abstract description 93
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 claims abstract description 74
- MMNWSHJJPDXKCH-UHFFFAOYSA-N 9,10-dioxoanthracene-2-sulfonic acid Chemical class C1=CC=C2C(=O)C3=CC(S(=O)(=O)O)=CC=C3C(=O)C2=C1 MMNWSHJJPDXKCH-UHFFFAOYSA-N 0.000 claims abstract description 42
- 239000002608 ionic liquid Substances 0.000 claims abstract description 40
- 235000010265 sodium sulphite Nutrition 0.000 claims abstract description 37
- 238000000034 method Methods 0.000 claims abstract description 16
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical group CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 135
- 238000006243 chemical reaction Methods 0.000 claims description 117
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 46
- 125000000217 alkyl group Chemical group 0.000 claims description 15
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims description 15
- 150000007522 mineralic acids Chemical class 0.000 claims description 9
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 8
- 239000000126 substance Substances 0.000 claims description 8
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical group CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 6
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical group [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 claims description 6
- 229910002651 NO3 Inorganic materials 0.000 claims description 6
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical group [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 6
- DTQVDTLACAAQTR-UHFFFAOYSA-M Trifluoroacetate Chemical group [O-]C(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-M 0.000 claims description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 5
- ITMCEJHCFYSIIV-UHFFFAOYSA-M triflate Chemical compound [O-]S(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-M 0.000 claims description 5
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 4
- 239000003960 organic solvent Substances 0.000 claims description 4
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 claims description 4
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 4
- 125000001453 quaternary ammonium group Chemical group 0.000 claims description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 3
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 229910017604 nitric acid Inorganic materials 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- BMYNFMYTOJXKLE-UHFFFAOYSA-N 3-azaniumyl-2-hydroxypropanoate Chemical compound NCC(O)C(O)=O BMYNFMYTOJXKLE-UHFFFAOYSA-N 0.000 claims description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 2
- 238000001816 cooling Methods 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 150000001450 anions Chemical class 0.000 claims 1
- 150000001805 chlorine compounds Chemical group 0.000 claims 1
- ITMCEJHCFYSIIV-UHFFFAOYSA-N triflic acid Chemical group OS(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-N 0.000 claims 1
- 239000002904 solvent Substances 0.000 abstract description 10
- 239000000758 substrate Substances 0.000 abstract description 8
- 238000006277 sulfonation reaction Methods 0.000 abstract description 4
- 230000007613 environmental effect Effects 0.000 abstract description 3
- 238000000926 separation method Methods 0.000 abstract description 3
- 239000003153 chemical reaction reagent Substances 0.000 abstract description 2
- 150000002894 organic compounds Chemical class 0.000 abstract description 2
- 238000004134 energy conservation Methods 0.000 abstract 1
- NIQCNGHVCWTJSM-UHFFFAOYSA-N Dimethyl phthalate Chemical compound COC(=O)C1=CC=CC=C1C(=O)OC NIQCNGHVCWTJSM-UHFFFAOYSA-N 0.000 description 42
- 239000000047 product Substances 0.000 description 27
- FBSAITBEAPNWJG-UHFFFAOYSA-N dimethyl phthalate Natural products CC(=O)OC1=CC=CC=C1OC(C)=O FBSAITBEAPNWJG-UHFFFAOYSA-N 0.000 description 21
- 229960001826 dimethylphthalate Drugs 0.000 description 21
- 238000004817 gas chromatography Methods 0.000 description 21
- QCVMOSGPTRRUQZ-UHFFFAOYSA-N 2-nitroanthracene-9,10-dione Chemical class C1=CC=C2C(=O)C3=CC([N+](=O)[O-])=CC=C3C(=O)C2=C1 QCVMOSGPTRRUQZ-UHFFFAOYSA-N 0.000 description 20
- 230000020477 pH reduction Effects 0.000 description 19
- 230000000052 comparative effect Effects 0.000 description 7
- 230000000694 effects Effects 0.000 description 6
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 6
- 229910052753 mercury Inorganic materials 0.000 description 6
- YCANAXVBJKNANM-UHFFFAOYSA-N 1-nitroanthracene-9,10-dione Chemical compound O=C1C2=CC=CC=C2C(=O)C2=C1C=CC=C2[N+](=O)[O-] YCANAXVBJKNANM-UHFFFAOYSA-N 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 239000002253 acid Substances 0.000 description 4
- 125000001424 substituent group Chemical group 0.000 description 4
- 239000002699 waste material Substances 0.000 description 4
- GSDUKDFFPSGANX-UHFFFAOYSA-N 1-butyl-2H-pyridine hydrobromide Chemical compound Br.CCCCN1CC=CC=C1 GSDUKDFFPSGANX-UHFFFAOYSA-N 0.000 description 3
- 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 description 3
- 150000004056 anthraquinones Chemical class 0.000 description 3
- 125000000020 sulfo group Chemical group O=S(=O)([*])O[H] 0.000 description 3
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 description 3
- CCQSBGJULPBARL-UHFFFAOYSA-N 1,4-dihydroxy-9,10-dioxoanthracene-2-sulfonic acid Chemical compound O=C1C2=CC=CC=C2C(=O)C2=C1C(O)=C(S(O)(=O)=O)C=C2O CCQSBGJULPBARL-UHFFFAOYSA-N 0.000 description 2
- QWVMIYZXMZSUIZ-UHFFFAOYSA-N 2-methyl-3-nitroanthracene-9,10-dione Chemical compound O=C1C2=CC=CC=C2C(=O)C2=C1C=C(C)C([N+]([O-])=O)=C2 QWVMIYZXMZSUIZ-UHFFFAOYSA-N 0.000 description 2
- ITZHIZDBMLUISB-UHFFFAOYSA-N [N+](=O)([O-])C=1C(=CC=2C(C3=CC=CC=C3C(C2C1)=O)=O)CC Chemical compound [N+](=O)([O-])C=1C(=CC=2C(C3=CC=CC=C3C(C2C1)=O)=O)CC ITZHIZDBMLUISB-UHFFFAOYSA-N 0.000 description 2
- 239000012752 auxiliary agent Substances 0.000 description 2
- 239000007810 chemical reaction solvent Substances 0.000 description 2
- HIFJUMGIHIZEPX-UHFFFAOYSA-N sulfuric acid;sulfur trioxide Chemical compound O=S(=O)=O.OS(O)(=O)=O HIFJUMGIHIZEPX-UHFFFAOYSA-N 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- ZDEPXVXEADUOAV-UHFFFAOYSA-N 1-decyl-3-methyl-1,2-dihydroimidazol-1-ium;chloride Chemical compound [Cl-].CCCCCCCCCC[NH+]1CN(C)C=C1 ZDEPXVXEADUOAV-UHFFFAOYSA-N 0.000 description 1
- WREWAMXVXPPKQU-UHFFFAOYSA-N 1-dodecyl-3-methyl-1,2-dihydroimidazol-1-ium;chloride Chemical compound [Cl-].CCCCCCCCCCCC[NH+]1CN(C)C=C1 WREWAMXVXPPKQU-UHFFFAOYSA-N 0.000 description 1
- STESGJHDBJZDRY-UHFFFAOYSA-N 1-hexadecyl-3-methyl-1,2-dihydroimidazol-1-ium;bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[NH+]1CN(C)C=C1 STESGJHDBJZDRY-UHFFFAOYSA-N 0.000 description 1
- OLLYMAMAGXVXBS-UHFFFAOYSA-N 1-methyl-3-tetradecyl-1,2-dihydroimidazol-1-ium;bromide Chemical compound [Br-].CCCCCCCCCCCCCCN1C[NH+](C)C=C1 OLLYMAMAGXVXBS-UHFFFAOYSA-N 0.000 description 1
- SFPTVQNKTCPLAX-UHFFFAOYSA-N 3-ethyl-1-methyl-1,2-dihydroimidazol-1-ium;2,2,2-trifluoroacetate Chemical compound [O-]C(=O)C(F)(F)F.CC[NH+]1CN(C)C=C1 SFPTVQNKTCPLAX-UHFFFAOYSA-N 0.000 description 1
- WIRUFYPSLSFKAU-UHFFFAOYSA-N CCCCCCCCN1C=CC=CC1.Br Chemical compound CCCCCCCCN1C=CC=CC1.Br WIRUFYPSLSFKAU-UHFFFAOYSA-N 0.000 description 1
- QGKOZWJXEMFEOW-UHFFFAOYSA-N CN1CN(C=C1)CC.[N+](=O)(O)[O-] Chemical compound CN1CN(C=C1)CC.[N+](=O)(O)[O-] QGKOZWJXEMFEOW-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 229930013930 alkaloid Natural products 0.000 description 1
- 150000003797 alkaloid derivatives Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- CFAPFDTWIGBCQK-UHFFFAOYSA-N bis(trifluoromethylsulfonyl)azanide;tetrabutylazanium Chemical class FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F.CCCC[N+](CCCC)(CCCC)CCCC CFAPFDTWIGBCQK-UHFFFAOYSA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000003990 capacitor Substances 0.000 description 1
- 239000013064 chemical raw material Substances 0.000 description 1
- 238000007405 data analysis Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000012949 free radical photoinitiator Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000006396 nitration reaction Methods 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- GUEIZVNYDFNHJU-UHFFFAOYSA-N quinizarin Chemical compound O=C1C2=CC=CC=C2C(=O)C2=C1C(O)=CC=C2O GUEIZVNYDFNHJU-UHFFFAOYSA-N 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-L sulfite Chemical compound [O-]S([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-L 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- IPILPUZVTYHGIL-UHFFFAOYSA-M tributyl(methyl)azanium;chloride Chemical compound [Cl-].CCCC[N+](C)(CCCC)CCCC IPILPUZVTYHGIL-UHFFFAOYSA-M 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/54—Improvements relating to the production of bulk chemicals using solvents, e.g. supercritical solvents or ionic liquids
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to the technical field of organic compound preparation, and discloses a preparation method of anthraquinone-2-sulfonic acid compounds. According to the preparation method provided by the invention, the 2-nitroanthraquinone compound is used as a substrate, the sodium sulfite is used as a sulfonation reagent, and the ionic liquid is used as a solvent, so that the anthraquinone-2-sulfonic acid compound can be efficiently prepared under mild conditions, and meanwhile, the method has the advantages of wide application range, simple product separation, energy conservation, environmental protection and the like, and has a good industrial application prospect.
Description
Technical Field
The invention relates to the technical field of organic compound preparation, in particular to a preparation method of anthraquinone-2-sulfonic acid compounds.
Background
The anthraquinone-2-sulfonic acid compound is an important chemical raw material, is mainly applied to the fields of alkaloid analysis, dye synthesis, organic synthesis and the like, and can be used as a free radical photoinitiator, a super capacitor additive, an electrochemical sensor auxiliary agent, an electrode film material auxiliary agent and the like.
The traditional anthraquinone-2-sulfonic acid production process takes anthraquinone as a raw material, fuming sulfuric acid is used as a sulfonating reagent, and sulfonation reaction is carried out under the positioning effect of mercury, but the mercury is gradually replaced by a non-mercury method due to serious environmental protection problem caused by the use of mercury. The non-mercury method consists of two steps of reactions: (1) the anthraquinone and the concentrated nitric acid are subjected to nitration reaction to generate nitroanthraquinone; (2) nitroanthraquinone and sodium sulfite are subject to sulfo reaction to generate anthraquinone-2-sulfonic acid. However, because of poor intersolubility of the reaction substrates in the two steps, particularly when anthraquinone carries different substituents, the reaction is difficult to react with sodium sulfite, so that the sulfo reaction needs to be carried out at a higher temperature for a longer time to obtain the target product, and the reaction selectivity is not ideal.
The Chinese patent with publication number CN103373944A discloses a synthesis method of 1, 4-dihydroxyl-9, 10-anthraquinone-2-sulfonic acid, in which 1, 4-dihydroxyl anthraquinone and anhydrous sulfate are added into fuming sulfuric acid containing 15-20% SO3 according to a certain proportion, sulfonation reaction is carried out at 120-140 ℃, after the sulfonation reaction is completed, the temperature is reduced to below 60 ℃, water is added and stirred, and then the mixture is naturally cooled and washed to obtain 1, 4-dihydroxyl-9, 10-anthraquinone-2-sulfonic acid. However, the method has a smaller application range, and is only aimed at the preparation of specific anthraquinone-2-sulfonic acid compounds.
Therefore, a method for preparing the 1-nitroanthraquinone compound, which has the advantages of simple process flow, less waste acid generation and high yield, is needed to meet the needs of industrial production.
Disclosure of Invention
In order to solve the technical problems, the invention provides a preparation method of anthraquinone-2-sulfonic acid compounds. The preparation method of the anthraquinone-2-sulfonic acid compound provided by the invention takes the 2-nitroanthraquinone compound and sodium sulfite as raw materials, and takes the ionic liquid as a solvent system to react to prepare the anthraquinone-2-sulfonic acid compound, so that the process flow is simple, the generated waste acid is less, and the yield is high.
The specific technical scheme of the invention is as follows:
the invention provides a preparation method of anthraquinone-2-sulfonic acid compounds, which comprises the following steps:
dissolving 2-nitroanthraquinone compound and sodium sulfite in ionic liquid, reacting, cooling to room temperature, adding inorganic acid, mixing completely, adding organic solvent, and extracting to obtain anthraquinone-2-sulfonic acid compound. The reaction equation of the reaction is:
wherein R is H, C 1 -C 6 Straight chain alkyl and C 1 -C 6 Is a branched alkyl group.
According to the preparation method provided by the invention, 2-nitroanthraquinone compounds and sodium sulfite are used as raw materials, ionic liquid is used as a solvent system to react to prepare anthraquinone-2-sulfonic acid compounds, the reaction is carried out at a higher temperature, after the reaction is finished, the temperature is reduced to room temperature, inorganic acid is added for acidification, and finally, the anthraquinone-2-sulfonic acid compounds are obtained through extraction. The preparation method provided by the invention has the advantages of simple process flow, less waste acid generation and high yield.
In the reaction, the effect of the R substituent on the reaction effect is mainly manifested on the effect on the solubility. If the R substituent is too long, the solubility of the 2-nitroanthraquinone compound in the ionic liquid is reduced, and then the 2-nitroanthraquinone compound and sodium sulfite cannot be well contacted, so that the reaction yield is obviously reduced. In addition, when the R substituent is excessively large, steric hindrance at the 2-position increases, and it is difficult for the sulfite group to replace the nitro group at the 2-position, resulting in a decrease in reaction yield.
Preferably, the ionic liquid is imidazole ionic liquid, and the chemical structural formula is as follows:
wherein R is 1 Selected from C 2 -C 16 Straight-chain or branched alkyl, R 2 Selected from C 1 -C 2 Straight-chain alkyl of X 1 Selected from chloride, bromide, nitrate, acetate, trifluoroacetate, tetrafluoroborate, hexafluorophosphate, trifluoromethanesulfonate, and trifluoromethanesulfonyl imide anions.
Preferably, the ionic liquid can also be pyridine ionic liquid, and the chemical structural formula is as follows:
wherein R is 3 Selected from C 3 -C 8 Linear or branched alkyl, X 2 Selected from chloride, bromide, nitrate, acetate, trifluoroacetate, tetrafluoroborate, hexafluorophosphate, trifluoromethanesulfonate, and trifluoromethanesulfonyl imide anions.
As another preferred, the ionic liquid is a quaternary ammonium ionic liquid, and the chemical structural formula is:
wherein R is 4 Selected from C 3 -C 6 Straight-chain or branched alkyl, R 5 、R 6 、R 7 Independently selected from C 1 -C 6 Linear or branched alkyl, X 3 Selected from chloride, bromide, nitrate, acetate, trifluoroacetate, tetrafluoroborate, hexafluorophosphate, trifluoromethanesulfonate, and trifluoromethanesulfonyl imide anions.
The ionic liquid is low-temperature molten salt (melting point is less than 100 ℃), is basically composed of ions, has the advantages of low vapor pressure, wide liquid state temperature range, good chemical stability, wide electrochemical window, strong designability and the like, is used as a solvent in the preparation method, has good dissolving capacity for inorganic matters, organic matters and polymers, and can promote the contact between the 2-nitroanthraquinone compound and sodium sulfite and promote the reaction in the reaction. In the present reaction, further, the ionic liquid is preferably an imidazole type ionic liquid or a pyridine type ionic liquid.
In the reaction system of the preparation method, the solubility of the ionic liquid to a reaction substrate is mainly considered, when the 2-nitroanthraquinone compound has alkyl substituent, the ionic liquid with an alkyl chain with proper length is selected as a solvent, and in addition, the length of the alkyl chain has obvious influence on the viscosity of the ionic liquid and can influence the mass transfer process of the reaction.
It is further preferred that the imidazole ionic liquid is selected from the group consisting of 1-ethyl-3-methylimidazole tetrafluoroborate, 1-ethyl-3-methylimidazole nitrate, 1-ethyl-3-methylimidazole trifluoroacetate, 1-ethyl-3-methylimidazole trifluoromethanesulfonyl imide salt, 1-propyl-3-methylimidazole tetrafluoroborate, 1-butyl-3-methylimidazole tetrafluoroborate, 1-tert-butyl-3-methylimidazole tetrafluoroborate, 1-pentyl-3-methylimidazole tetrafluoroborate, 1-tert-pentyl-3-methylimidazole tetrafluoroborate, 1-hexyl-3-methylimidazole hexafluorophosphate, 1-octyl-3-methylimidazole hexafluorophosphate, 1-decyl-3-methylimidazole chloride, 1-decyl-3-methylimidazole tetrafluoroborate, 1-dodecyl-3-methylimidazole chloride, 1-tetradecyl-3-methylimidazole bromide, 1-hexadecyl-3-methylimidazole bromide.
Further preferably, the pyridine-type ionic liquid is selected from the group consisting of N-propylpyridine trifluoroacetate, N-butylpyridine bromide, N-butylpyridine tetrafluoroborate, N-hexylpyridine hexafluorophosphate, N-hexylpyridine tetrafluoroborate and N-octylpyridine bromide.
Further preferably, the quaternary ammonium type ionic liquid is selected from tributyl methyl ammonium chloride, tributyl hexyl ammonium tetrafluoroborate, tetrabutyl ammonium bromide, tetrabutyl ammonium bis (trifluoromethanesulfonyl) imide salt.
Specifically, the molar ratio of the 2-nitroanthraquinone compound to the sodium sulfite is 1:5-10.
Since the sulfo reaction is an equilibrium reaction, the sodium sulfite is added in an amount higher than the reaction equivalent to a certain extent in order to ensure the complete conversion of 2-nitroanthraquinone as much as possible. The molar ratio of the 2-nitroanthraquinone compound to the sodium sulfite is 1:5-10, and the optimal conversion effect is achieved.
Specifically, the mass ratio of the 2-nitroanthraquinone compound to the ionic liquid is 1:5-16.
The dosage of the ionic liquid is controlled within a certain range. Too low a substrate concentration can lead to separation difficulties if too much is added. If the addition is too small, the solubility of the substrate and the product reaches the upper limit, which is disadvantageous for the progress of the reaction. Therefore, the ratio of the ionic liquid to be added needs to be controlled in a proper range.
Preferably, the reaction temperature is 50-80 ℃ and the reaction time is 1-5 h.
At the temperature of 50-80 ℃, the 2-nitroanthraquinone compound can react with sodium sulfite at a proper rate, and the reaction is complete within 1-5 h. When the temperature is too low, the reaction is incomplete or the reaction time is prolonged, and when the temperature is too high, the occurrence of by-products is caused.
Specifically, the added inorganic acid is one or more of hydrochloric acid, hydrobromic acid, sulfuric acid, sulfurous acid, nitric acid, phosphoric acid and perchloric acid.
The purpose of the addition of the inorganic acid is to acidify the anthraquinone-2-sulfonic acid product, which is convenient for the subsequent separation process.
Preferably, the molar ratio of anthraquinone-2-sulfonic acid to inorganic acid is 1:1-1.1. In the range of 1:1-1.1 of the molar ratio of the anthraquinone-2-sulfonic acid to the inorganic acid, the anthraquinone-2-sulfonic acid compound can be well acidified.
Specifically, the organic solvent is ethyl acetate. The product is extracted and separated by using ethyl acetate, and the anthraquinone-2-sulfonic acid compound with higher yield is obtained.
Compared with the prior art, the invention has the following technical effects:
(1) The preparation method of the invention takes the ionic liquid as the reaction solvent, greatly enhances the intersolubility of the reaction substrate, improves the reaction efficiency and the reaction yield, and has mild reaction conditions.
(2) The preparation method provided by the invention has wide application range and is suitable for preparing various anthraquinone-2-sulfonic acid compounds.
(3) The preparation method has simple flow, less waste acid production, and the used solvent ionic liquid is easy to recycle, thus being a green and environment-friendly preparation method, and simultaneously avoiding the problem of environmental damage caused by the traditional mercury method.
Detailed Description
The invention is further described below with reference to examples.
Example 1
1.27g (5 mmol) of 2-nitroanthraquinone, 3.78g (30 mmol) of sodium sulfite and 15g of 1-ethyl-3-methylimidazole tetrafluoroborate are put into a 50mL single-neck flask, the flask is placed in an oil bath, heated to 60 ℃ and stirred by using a magnet, the reaction is carried out for 2 hours until the end point of the reaction, the reaction solution is cooled to room temperature, and then 0.54g of 38% hydrochloric acid is added for acidification. The reaction solution was transferred to a separating funnel, extracted with ethyl acetate (10 ml×3), and finally, the ethyl acetate phase was spin-dried to obtain an anthraquinone-2-sulfonic acid product, which was analyzed by gas chromatography, and dimethyl phthalate was used as an internal standard, and the results are shown in table 1.
Example 2
1.27g (5 mmol) of 2-nitroanthraquinone, 3.78g (30 mmol) of sodium sulfite and 15g of 1-propyl-3-methylimidazole tetrafluoroborate are put into a 50mL single-neck flask, the flask is placed in an oil bath, heated to 60 ℃ and stirred by using a magnet, the reaction is carried out for 2 hours until the end point of the reaction, the reaction solution is cooled to room temperature, and then 0.54g of 38% hydrochloric acid is added for acidification. The reaction solution was transferred to a separating funnel, extracted with ethyl acetate (10 ml×3), and finally, the ethyl acetate phase was spin-dried to obtain an anthraquinone-2-sulfonic acid product, which was analyzed by gas chromatography, and dimethyl phthalate was used as an internal standard, and the results are shown in table 1.
Example 3
1.27g (5 mmol) of 2-nitroanthraquinone, 3.78g (30 mmol) of sodium sulfite and 15g of 1-butyl-3-methylimidazole tetrafluoroborate are put into a 50mL single-neck flask, the flask is placed in an oil bath, heated to 60 ℃ and stirred by using a magnet, the reaction is carried out for 2 hours until the end point of the reaction, the reaction solution is cooled to room temperature, and then 0.54g of 38% hydrochloric acid is added for acidification. The reaction solution was transferred to a separating funnel, extracted with ethyl acetate (10 ml×3), and finally, the ethyl acetate phase was spin-dried to obtain an anthraquinone-2-sulfonic acid product, which was analyzed by gas chromatography, and dimethyl phthalate was used as an internal standard, and the results are shown in table 1.
Example 4
Into a 50mL single-necked flask, 1.27g (5 mmol) of 2-nitroanthraquinone, 3.78g (30 mmol) of sodium sulfite and 15g of 1-hexyl-3-methylimidazole hexafluorophosphate were charged, the flask was placed in an oil bath, heated to 60℃and stirred with a magnet, the reaction was allowed to reach the end point after 2 hours of reaction, the reaction solution was cooled to room temperature, and then 0.54g of 38% hydrochloric acid was added for acidification. The reaction solution was transferred to a separating funnel, extracted with ethyl acetate (10 ml×3), and finally, the ethyl acetate phase was spin-dried to obtain an anthraquinone-2-sulfonic acid product, which was analyzed by gas chromatography, and dimethyl phthalate was used as an internal standard, and the results are shown in table 1.
Example 5
Into a 50mL single-necked flask, 1.27g (5 mmol) of 2-nitroanthraquinone, 3.78g (30 mmol) of sodium sulfite and 15g of 1-octyl-3-methylimidazole hexafluorophosphate were charged, the flask was placed in an oil bath, heated to 60℃and stirred with a magnet, the reaction was allowed to reach the end point after 2 hours of reaction, the reaction solution was cooled to room temperature, and then 0.54g of 38% hydrochloric acid was added for acidification. The reaction solution was transferred to a separating funnel, extracted with ethyl acetate (10 ml×3), and finally, the ethyl acetate phase was spin-dried to obtain an anthraquinone-2-sulfonic acid product, which was analyzed by gas chromatography, and dimethyl phthalate was used as an internal standard, and the results are shown in table 1.
Example 6
1.27g (5 mmol) of 2-nitroanthraquinone, 3.78g (30 mmol) of sodium sulfite and 15g of N-propylpyridine trifluoroacetate were put into a 50mL single-neck flask, the flask was heated to 60℃in an oil bath and stirred with a magnet, the reaction was completed after 2 hours, the reaction solution was cooled to room temperature, and then 0.54g of 38% hydrochloric acid was added to acidify. The reaction solution was transferred to a separating funnel, extracted with ethyl acetate (10 ml×3), and finally, the ethyl acetate phase was spin-dried to obtain an anthraquinone-2-sulfonic acid product, which was analyzed by gas chromatography, and dimethyl phthalate was used as an internal standard, and the results are shown in table 1.
Example 7
1.27g (5 mmol) of 2-nitroanthraquinone, 3.78g (30 mmol) of sodium sulfite and 15g of N-butylpyridine bromide were added into a 50mL single-neck flask, the flask was placed in an oil bath, heated to 60 ℃ and stirred with a magnet, the reaction was completed after 2 hours, the reaction solution was cooled to room temperature, and then 0.54g of 38% hydrochloric acid was added for acidification. The reaction solution was transferred to a separating funnel, extracted with ethyl acetate (10 ml×3), and finally, the ethyl acetate phase was spin-dried to obtain an anthraquinone-2-sulfonic acid product, which was analyzed by gas chromatography, and dimethyl phthalate was used as an internal standard, and the results are shown in table 1.
Example 8
1.27g (5 mmol) of 2-nitroanthraquinone, 3.78g (30 mmol) of sodium sulfite and 15g of N-butylpyridine tetrafluoroborate are added into a 50mL single-neck flask, the flask is placed in an oil bath, heated to 60 ℃ and stirred by using a magnet, the reaction is carried out for 2 hours until the reaction end point is reached, the reaction solution is cooled to room temperature, and then 0.54g of 38% hydrochloric acid is added for acidification. The reaction solution was transferred to a separating funnel, extracted with ethyl acetate (10 ml×3), and finally, the ethyl acetate phase was spin-dried to obtain an anthraquinone-2-sulfonic acid product, which was analyzed by gas chromatography, and dimethyl phthalate was used as an internal standard, and the results are shown in table 1.
Example 9
To a 50mL single-necked flask, 1.27g (5 mmol) of 2-nitroanthraquinone, 3.78g (30 mmol) of sodium sulfite and 15g of tetrabutylammonium bromide were charged, the flask was placed in an oil bath, heated to 60℃and stirred with a magnet, the reaction was completed after 2 hours, the reaction solution was cooled to room temperature, and then 0.54g of 38% hydrochloric acid was added to acidify. The reaction solution was transferred to a separating funnel, extracted with ethyl acetate (10 ml×3), and finally, the ethyl acetate phase was spin-dried to obtain an anthraquinone-2-sulfonic acid product, which was analyzed by gas chromatography, and dimethyl phthalate was used as an internal standard, and the results are shown in table 1.
Example 10
1.27g (5 mmol) of 2-nitroanthraquinone, 3.78g (30 mmol) of sodium sulfite and 15g of 1-ethyl-3-methylimidazole tetrafluoroborate are put into a 50mL single-neck flask, the flask is placed in an oil bath, heated to 50 ℃ and stirred by using a magnet, the reaction is carried out for 2 hours until the end point of the reaction, the reaction solution is cooled to room temperature, and then 0.54g of 38% hydrochloric acid is added for acidification. The reaction solution was transferred to a separating funnel, extracted with ethyl acetate (10 ml×3), and finally, the ethyl acetate phase was spin-dried to obtain an anthraquinone-2-sulfonic acid product, which was analyzed by gas chromatography, and dimethyl phthalate was used as an internal standard, and the results are shown in table 2.
Example 11
1.27g (5 mmol) of 2-nitroanthraquinone, 3.78g (30 mmol) of sodium sulfite and 15g of 1-ethyl-3-methylimidazole tetrafluoroborate are put into a 50mL single-neck flask, the flask is placed in an oil bath, heated to 80 ℃ and stirred by using a magnet, the reaction is carried out for 2 hours until the end point of the reaction, the reaction solution is cooled to room temperature, and then 0.54g of 38% hydrochloric acid is added for acidification. The reaction solution was transferred to a separating funnel, extracted with ethyl acetate (10 ml×3), and finally, the ethyl acetate phase was spin-dried to obtain an anthraquinone-2-sulfonic acid product, which was analyzed by gas chromatography, and dimethyl phthalate was used as an internal standard, and the results are shown in table 2.
Example 12
1.27g (5 mmol) of 2-nitroanthraquinone, 2.52g (20 mmol) of sodium sulfite and 15g of 1-ethyl-3-methylimidazole tetrafluoroborate are put into a 50mL single-neck flask, the flask is placed in an oil bath, heated to 60 ℃ and stirred by using a magnet, the reaction is carried out for 2 hours until the end point of the reaction, the reaction solution is cooled to room temperature, and then 0.54g of 38% hydrochloric acid is added for acidification. The reaction solution was transferred to a separating funnel, extracted with ethyl acetate (10 ml×3), and finally, the ethyl acetate phase was spin-dried to obtain an anthraquinone-2-sulfonic acid product, which was analyzed by gas chromatography, and dimethyl phthalate was used as an internal standard, and the results are shown in table 2.
Example 13
1.27g (5 mmol) of 2-nitroanthraquinone, 5.04g (40 mmol) of sodium sulfite and 15g of 1-ethyl-3-methylimidazole tetrafluoroborate are put into a 50mL single-neck flask, the flask is placed in an oil bath, heated to 60 ℃ and stirred by using a magnet, the reaction is carried out for 2 hours until the end point of the reaction, the reaction solution is cooled to room temperature, and then 0.54g of 38% hydrochloric acid is added for acidification. The reaction solution was transferred to a separating funnel, extracted with ethyl acetate (10 ml×3), and finally, the ethyl acetate phase was spin-dried to obtain an anthraquinone-2-sulfonic acid product, which was analyzed by gas chromatography, and dimethyl phthalate was used as an internal standard, and the results are shown in table 2.
Example 14
Into a 50mL single-necked flask, 1.27g (5 mmol) of 2-nitroanthraquinone, 3.78g (30 mmol) of sodium sulfite and 8g of 1-ethyl-3-methylimidazole tetrafluoroborate were charged, the flask was placed in an oil bath, heated to 60℃and stirred with a magnet, the reaction was allowed to reach the end point after 2 hours of reaction, the reaction solution was cooled to room temperature, and then 0.54g of 38% hydrochloric acid was added for acidification. The reaction solution was transferred to a separating funnel, extracted with ethyl acetate (10 ml×3), and finally, the ethyl acetate phase was spin-dried to obtain an anthraquinone-2-sulfonic acid product, which was analyzed by gas chromatography, and dimethyl phthalate was used as an internal standard, and the results are shown in table 2.
Example 15
Into a 50mL single-necked flask, 1.27g (5 mmol) of 2-nitroanthraquinone, 3.78g (30 mmol) of sodium sulfite and 20g of 1-ethyl-3-methylimidazole tetrafluoroborate were charged, the flask was placed in an oil bath, heated to 60℃and stirred with a magnet, the reaction was allowed to reach the end point after 2 hours of reaction, the reaction solution was cooled to room temperature, and then 0.54g of 38% hydrochloric acid was added to acidify. The reaction solution was transferred to a separating funnel, extracted with ethyl acetate (10 ml×3), and finally, the ethyl acetate phase was spin-dried to obtain an anthraquinone-2-sulfonic acid product, which was analyzed by gas chromatography, and dimethyl phthalate was used as an internal standard, and the results are shown in table 2.
Example 16
1.34g (5 mmol) of 2-nitro-3-methylanthraquinone, 3.78g (30 mmol) of sodium sulfite and 15g of 1-butyl-3-methylimidazolium tetrafluoroborate are put into a 50mL single-neck flask, the flask is placed in an oil bath, heated to 60 ℃ and stirred by using a magnet, the reaction is completed after 2 hours, the reaction solution is cooled to room temperature, and then 0.54g of 38% hydrochloric acid is added for acidification. The reaction solution was transferred to a separating funnel, extracted with ethyl acetate (10 ml×3), and finally, the ethyl acetate phase was spin-dried to obtain an anthraquinone-2-sulfonic acid product, which was analyzed by gas chromatography, and dimethyl phthalate was used as an internal standard, and the results are shown in table 3.
Example 17
1.41g (5 mmol) of 2-nitro-3-ethylanthraquinone, 3.78g (30 mmol) of sodium sulfite and 15g of 1-butyl-3-methylimidazolium tetrafluoroborate are put into a 50mL single-neck flask, the flask is placed in an oil bath, heated to 60 ℃ and stirred by using a magnet, the reaction is completed after 2 hours, the reaction solution is cooled to room temperature, and then 0.54g of 38% hydrochloric acid is added for acidification. The reaction solution was transferred to a separating funnel, extracted with ethyl acetate (10 ml×3), and finally, the ethyl acetate phase was spin-dried to obtain an anthraquinone-2-sulfonic acid product, which was analyzed by gas chromatography, and dimethyl phthalate was used as an internal standard, and the results are shown in table 3.
Example 18
1.62g (5 mmol) of 2-nitro-3-t-amylanthraquinone, 3.78g (30 mmol) of sodium sulfite and 15g of 1-butyl-3-methylimidazole tetrafluoroborate are added into a 50mL single-neck flask, the flask is placed in an oil bath, heated to 60 ℃ and stirred by using a magnet, the reaction is carried out for 2 hours until the end point of the reaction, the reaction solution is cooled to room temperature, and then 0.54g of 38% hydrochloric acid is added for acidification. The reaction solution was transferred to a separating funnel, extracted with ethyl acetate (10 ml×3), and finally, the ethyl acetate phase was spin-dried to obtain an anthraquinone-2-sulfonic acid product, which was analyzed by gas chromatography, and dimethyl phthalate was used as an internal standard, and the results are shown in table 3.
Example 19
Into a 50mL single-necked flask, 1.69g (5 mmol) of 2-nitro-3-hexylanthraquinone, 3.78g (30 mmol) of sodium sulfite and 15g of 1-butyl-3-methylimidazole tetrafluoroborate were charged, the flask was placed in an oil bath, heated to 60℃and stirred with a magnet, the reaction was terminated after 2 hours, the reaction solution was cooled to room temperature, and then 0.54g of 38% hydrochloric acid was added for acidification. The reaction solution was transferred to a separating funnel, extracted with ethyl acetate (10 ml×3), and finally, the ethyl acetate phase was spin-dried to obtain an anthraquinone-2-sulfonic acid product, which was analyzed by gas chromatography, and dimethyl phthalate was used as an internal standard, and the results are shown in table 3.
Comparative example 1 (the main difference from example 1 is that water is used as solvent.)
1.27g (5 mmol) of 2-nitroanthraquinone, 3.78g (30 mmol) of sodium sulfite and 15g of water are added into a 50mL single-neck flask, the flask is placed in an oil bath, heated to 60 ℃ and stirred by using a magnet, the reaction is carried out for 2 hours until the reaction end point is reached, the reaction solution is cooled to room temperature, and then 0.54g of 38% hydrochloric acid is added for acidification. The reaction solution was transferred to a separating funnel, extracted with ethyl acetate (10 ml×3), and finally, the ethyl acetate phase was spin-dried to obtain an anthraquinone-2-sulfonic acid product, which was analyzed by gas chromatography, and dimethyl phthalate was used as an internal standard, and the results are shown in table 1.
Comparative example 2 (the main difference from example 1 is that the reaction temperature is 40 ℃)
1.27g (5 mmol) of 2-nitroanthraquinone, 3.78g (30 mmol) of sodium sulfite and 15g of 1-ethyl-3-methylimidazole tetrafluoroborate are put into a 50mL single-neck flask, the flask is placed in an oil bath, heated to 40 ℃ and stirred by using a magnet, the reaction is carried out for 2 hours until the end point of the reaction, the reaction solution is cooled to room temperature, and then 0.54g of 38% hydrochloric acid is added for acidification. The reaction solution was transferred to a separating funnel, extracted with ethyl acetate (10 ml×3), and finally, the ethyl acetate phase was spin-dried to obtain an anthraquinone-2-sulfonic acid product, which was analyzed by gas chromatography, and dimethyl phthalate was used as an internal standard, and the results are shown in table 2.
The results of examples 1 to 9 and comparative example 1 are shown in Table 1.
TABLE 1
| Numbering device | Solvent(s) | Anthraquinone-2-sulfonic acid yield (%) |
| Example 1 | 1-ethyl-3-methylimidazole tetrafluoroborate | 98 |
| Example 2 | 1-propyl-3-methylimidazole tetrafluoroborate | 95 |
| Example 3 | 1-butyl-3-methylimidazole tetrafluoroborate | 93 |
| Example 4 | 1-hexyl-3-methylimidazole hexafluorophosphate salt | 90 |
| Example 5 | 1-octyl-3-methylimidazole hexafluorophosphate | 89 |
| Example 6 | N-propylpyridine trifluoroacetate salt | 91 |
| Example 7 | N-butylpyridine bromide | 84 |
| Example 8 | N-butylpyridine tetrafluoroborate | 85 |
| Example 9 | Tetrabutylammonium bromide | 78 |
| Comparative example 1 | Water and its preparation method | 3 |
The results of example 1, examples 10 to 15 and comparative example 2 are shown in Table 2. Wherein the sodium sulfite amount is the molar ratio of sodium sulfite to 2-nitroanthraquinone compound, and the solvent amount is the mass ratio of ionic liquid to 2-nitroanthraquinone compound.
TABLE 2
The results of examples 16 to 19 are shown in Table 3.
TABLE 3 Table 3
| Numbering device | Substrate(s) | Product yield (%) |
| Example 16 | 2-nitro-3-methylanthraquinone | 93 |
| Example 17 | 2-nitro-3-ethyl anthraquinone | 93 |
| Example 18 | 2-nitro-3-tert-amylanthraquinone | 95 |
| Example 19 | 2-nitro-3-hexylanthraquinone | 94 |
Data analysis and discussion
(1) As shown in Table 1, comparative example 1 uses water as a solvent, and its yield of anthraquinone-2-sulfonic acid is greatly reduced, compared with example 1, indicating that ionic liquid as a reaction solvent is advantageous for improving the yield of anthraquinone-2-sulfonic acid.
(2) As shown in Table 2, the reaction temperatures of comparative example 2, example 10, example 1 and example 11 were 40 ℃, 50 ℃, 60 ℃ and 80 ℃ respectively, and the yields of anthraquinone-2-sulfonic acid were 62%, 90%, 98% and 98% respectively, which indicates that the reaction was carried out at a temperature of 50℃to 80 ℃ and that the yields of anthraquinone-2-sulfonic acid were high.
(3) As shown in Table 3, examples 16 to 19, which use different 2-nitroanthraquinone compounds as substrates, have a product yield of 93% or more, and demonstrate that the preparation method of the present invention can be applied to the preparation of different anthraquinone-2-sulfonic acid compounds, and have a higher yield.
The raw materials and equipment used in the invention are common raw materials and equipment in the field unless specified otherwise; the methods used in the present invention are conventional in the art unless otherwise specified.
The foregoing description is only a preferred embodiment of the present invention, and is not intended to limit the present invention, and any simple modification, variation and equivalent transformation of the above embodiment according to the technical substance of the present invention still fall within the scope of the technical solution of the present invention.
Claims (6)
1. A preparation method of anthraquinone-2-sulfonic acid compounds is characterized in that: the method comprises the following steps:
dissolving a 2-nitroanthraquinone compound and sodium sulfite in ionic liquid, reacting, cooling to room temperature, adding inorganic acid, mixing completely, adding an organic solvent, and extracting to obtain an anthraquinone-2-sulfonic acid compound; the ionic liquid is imidazole type ionic liquid, pyridine type ionic liquid or quaternary ammonium type ionic liquid; the reaction temperature is 50-80 ℃, and the reaction time is 1-5 h;
the reaction formula of the reaction is as follows:
；
wherein R is H, C 1 -C 6 Straight chain alkyl and C 1 -C 6 One of the branched alkyl groups of (a);
the ionic liquid is imidazole ionic liquid, and the chemical structural formula is as follows:
wherein R is 1 Selected from C 2 -C 16 Is a straight chain of (2)Or branched alkyl, R2 is selected from C 1 -C 2 X1 is selected from chloride, bromide, nitrate, acetate, trifluoroacetate, tetrafluoroborate, hexafluorophosphate, trifluoromethylsulfonate, trifluoromethylsulfonimide anion;
the ionic liquid is pyridine type ionic liquid, and the chemical structural formula is as follows:
wherein R is 3 Selected from C 3 -C 8 Linear or branched alkyl, X 2 Selected from chloride, bromide, nitrate, acetate, trifluoroacetate, tetrafluoroborate, hexafluorophosphate, trifluoromethanesulfonate, trifluoromethanesulfonyl imide anions;
the ionic liquid is quaternary ammonium ionic liquid, and the chemical structural formula is as follows:
wherein R is 4 Selected from C 3 -C 6 Straight-chain or branched alkyl, R 5 、R 6 、R 7 Independently selected from C 1 -C 6 Linear or branched alkyl, X 3 Selected from chloride, bromide, nitrate, acetate, trifluoroacetate, tetrafluoroborate, hexafluorophosphate, trifluoromethanesulfonate, and trifluoromethanesulfonyl imide anions.
2. The method for preparing anthraquinone-2-sulfonic acid compound according to claim 1, wherein: the molar ratio of the 2-nitroanthraquinone compound to the sodium sulfite is 1:5-10.
3. The method for preparing anthraquinone-2-sulfonic acid compound according to claim 1, wherein: the mass ratio of the 2-nitroanthraquinone compound to the ionic liquid is 1:5-16.
4. The method for preparing anthraquinone-2-sulfonic acid compound according to claim 1, wherein: the inorganic acid is one or more of hydrochloric acid, hydrobromic acid, sulfuric acid, sulfurous acid, nitric acid, phosphoric acid and perchloric acid.
5. The method for producing an anthraquinone-2-sulfonic acid compound according to claim 1 or 4, characterized in that: the molar ratio of the anthraquinone-2-sulfonic acid to the inorganic acid is 1:1-1.1.
6. The method for preparing anthraquinone-2-sulfonic acid compound according to claim 1, wherein: the organic solvent is ethyl acetate.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4942251A (en) * | 1988-01-15 | 1990-07-17 | China Technical Consultants, Inc. | Process for producing α-anthraquinonesulfonic acids and recovering the catalyst used therein |
| JPH10204053A (en) * | 1997-01-24 | 1998-08-04 | Taiyo Yuden Co Ltd | Production of dicyanobenzenesulfonic acids |
| CN101838204A (en) * | 2010-04-28 | 2010-09-22 | 盐城市瓯华化学工业有限公司 | Novel process for controlling waste residue and recycling resources in 1-anthraquinone production |
| CN104892426A (en) * | 2015-05-29 | 2015-09-09 | 江苏亚邦染料股份有限公司 | Method for preparing 1-nitroanthraquinone by using pyrrolidinone ionic liquid as catalyst |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4942251A (en) * | 1988-01-15 | 1990-07-17 | China Technical Consultants, Inc. | Process for producing α-anthraquinonesulfonic acids and recovering the catalyst used therein |
| JPH10204053A (en) * | 1997-01-24 | 1998-08-04 | Taiyo Yuden Co Ltd | Production of dicyanobenzenesulfonic acids |
| CN101838204A (en) * | 2010-04-28 | 2010-09-22 | 盐城市瓯华化学工业有限公司 | Novel process for controlling waste residue and recycling resources in 1-anthraquinone production |
| CN104892426A (en) * | 2015-05-29 | 2015-09-09 | 江苏亚邦染料股份有限公司 | Method for preparing 1-nitroanthraquinone by using pyrrolidinone ionic liquid as catalyst |
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