CN113831237A - Synthesis method of 9-anthracenecarboxylic acid - Google Patents
Synthesis method of 9-anthracenecarboxylic acid Download PDFInfo
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- CN113831237A CN113831237A CN202110879538.4A CN202110879538A CN113831237A CN 113831237 A CN113831237 A CN 113831237A CN 202110879538 A CN202110879538 A CN 202110879538A CN 113831237 A CN113831237 A CN 113831237A
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- XGWFJBFNAQHLEF-UHFFFAOYSA-N 9-anthroic acid Chemical compound C1=CC=C2C(C(=O)O)=C(C=CC=C3)C3=CC2=C1 XGWFJBFNAQHLEF-UHFFFAOYSA-N 0.000 title claims abstract description 28
- 238000001308 synthesis method Methods 0.000 title claims abstract description 8
- 238000006243 chemical reaction Methods 0.000 claims abstract description 32
- 239000002904 solvent Substances 0.000 claims abstract description 14
- 239000012074 organic phase Substances 0.000 claims abstract description 12
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 9
- 239000002994 raw material Substances 0.000 claims abstract description 9
- 239000007800 oxidant agent Substances 0.000 claims abstract description 7
- 230000001590 oxidative effect Effects 0.000 claims abstract description 7
- 239000006179 pH buffering agent Substances 0.000 claims abstract description 7
- 230000009471 action Effects 0.000 claims abstract description 5
- BKOOMYPCSUNDGP-UHFFFAOYSA-N 2-methylbut-2-ene Chemical group CC=C(C)C BKOOMYPCSUNDGP-UHFFFAOYSA-N 0.000 claims description 22
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 22
- 238000000034 method Methods 0.000 claims description 14
- 230000002194 synthesizing effect Effects 0.000 claims description 10
- YMNKUHIVVMFOFO-UHFFFAOYSA-N anthracene-9-carbaldehyde Chemical compound C1=CC=C2C(C=O)=C(C=CC=C3)C3=CC2=C1 YMNKUHIVVMFOFO-UHFFFAOYSA-N 0.000 claims description 8
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 6
- 229910000403 monosodium phosphate Inorganic materials 0.000 claims description 6
- 235000019799 monosodium phosphate Nutrition 0.000 claims description 6
- UKLNMMHNWFDKNT-UHFFFAOYSA-M sodium chlorite Chemical group [Na+].[O-]Cl=O UKLNMMHNWFDKNT-UHFFFAOYSA-M 0.000 claims description 6
- 229960002218 sodium chlorite Drugs 0.000 claims description 6
- AJPJDKMHJJGVTQ-UHFFFAOYSA-M sodium dihydrogen phosphate Chemical group [Na+].OP(O)([O-])=O AJPJDKMHJJGVTQ-UHFFFAOYSA-M 0.000 claims description 6
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 claims description 5
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 4
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 claims description 4
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 2
- MHNNAWXXUZQSNM-UHFFFAOYSA-N 2-methylbut-1-ene Chemical compound CCC(C)=C MHNNAWXXUZQSNM-UHFFFAOYSA-N 0.000 claims description 2
- QXIKMJLSPJFYOI-UHFFFAOYSA-L calcium;dichlorite Chemical compound [Ca+2].[O-]Cl=O.[O-]Cl=O QXIKMJLSPJFYOI-UHFFFAOYSA-L 0.000 claims description 2
- QBWCMBCROVPCKQ-UHFFFAOYSA-M chlorite Chemical compound [O-]Cl=O QBWCMBCROVPCKQ-UHFFFAOYSA-M 0.000 claims description 2
- 229940005993 chlorite ion Drugs 0.000 claims description 2
- 229910000402 monopotassium phosphate Inorganic materials 0.000 claims description 2
- 235000019796 monopotassium phosphate Nutrition 0.000 claims description 2
- LNOPIUAQISRISI-UHFFFAOYSA-N n'-hydroxy-2-propan-2-ylsulfonylethanimidamide Chemical compound CC(C)S(=O)(=O)CC(N)=NO LNOPIUAQISRISI-UHFFFAOYSA-N 0.000 claims description 2
- 239000006174 pH buffer Substances 0.000 claims description 2
- PJNZPQUBCPKICU-UHFFFAOYSA-N phosphoric acid;potassium Chemical compound [K].OP(O)(O)=O PJNZPQUBCPKICU-UHFFFAOYSA-N 0.000 claims description 2
- VISKNDGJUCDNMS-UHFFFAOYSA-M potassium;chlorite Chemical compound [K+].[O-]Cl=O VISKNDGJUCDNMS-UHFFFAOYSA-M 0.000 claims description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims 1
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 abstract description 27
- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Chemical compound C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 abstract description 17
- 239000007787 solid Substances 0.000 abstract description 16
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 abstract description 10
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 abstract description 5
- 238000001514 detection method Methods 0.000 abstract description 5
- 235000019253 formic acid Nutrition 0.000 abstract description 5
- 230000015572 biosynthetic process Effects 0.000 abstract description 4
- 238000003786 synthesis reaction Methods 0.000 abstract description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 3
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 3
- 239000001257 hydrogen Substances 0.000 abstract description 3
- 239000000463 material Substances 0.000 abstract description 3
- 239000005416 organic matter Substances 0.000 abstract description 3
- 239000000047 product Substances 0.000 abstract description 3
- 238000001228 spectrum Methods 0.000 abstract description 3
- FECNOIODIVNEKI-UHFFFAOYSA-N 2-[(2-aminobenzoyl)amino]benzoic acid Chemical class NC1=CC=CC=C1C(=O)NC1=CC=CC=C1C(O)=O FECNOIODIVNEKI-UHFFFAOYSA-N 0.000 abstract description 2
- 239000006227 byproduct Substances 0.000 abstract description 2
- 238000004811 liquid chromatography Methods 0.000 abstract description 2
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 27
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 10
- 238000003756 stirring Methods 0.000 description 10
- 239000007864 aqueous solution Substances 0.000 description 8
- 239000007788 liquid Substances 0.000 description 6
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 5
- 238000007792 addition Methods 0.000 description 5
- 239000003054 catalyst Substances 0.000 description 4
- 238000001704 evaporation Methods 0.000 description 4
- 239000012065 filter cake Substances 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- 238000000926 separation method Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- VHHDLIWHHXBLBK-UHFFFAOYSA-N anthracen-9-ylboronic acid Chemical compound C1=CC=C2C(B(O)O)=C(C=CC=C3)C3=CC2=C1 VHHDLIWHHXBLBK-UHFFFAOYSA-N 0.000 description 3
- 238000004821 distillation Methods 0.000 description 3
- 238000009776 industrial production Methods 0.000 description 3
- QPFMBZIOSGYJDE-UHFFFAOYSA-N 1,1,2,2-tetrachloroethane Chemical compound ClC(Cl)C(Cl)Cl QPFMBZIOSGYJDE-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 1
- BRUOAURMAFDGLP-UHFFFAOYSA-N 9,10-dibromoanthracene Chemical compound C1=CC=C2C(Br)=C(C=CC=C3)C3=C(Br)C2=C1 BRUOAURMAFDGLP-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- 235000011089 carbon dioxide Nutrition 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- XYIBRDXRRQCHLP-UHFFFAOYSA-N ethyl acetoacetate Chemical compound CCOC(=O)CC(C)=O XYIBRDXRRQCHLP-UHFFFAOYSA-N 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 229910003002 lithium salt Inorganic materials 0.000 description 1
- 159000000002 lithium salts Chemical class 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/16—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2603/00—Systems containing at least three condensed rings
- C07C2603/02—Ortho- or ortho- and peri-condensed systems
- C07C2603/04—Ortho- or ortho- and peri-condensed systems containing three rings
- C07C2603/22—Ortho- or ortho- and peri-condensed systems containing three rings containing only six-membered rings
- C07C2603/24—Anthracenes; Hydrogenated anthracenes
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1003—Carbocyclic compounds
- C09K2211/1011—Condensed systems
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to the technical field of synthesis of dye intermediates and electronic fluorescent materials, and provides a synthesis method of novel 9-anthracenecarboxylic acid, which comprises the following steps: the 9-anthracene formaldehyde is used as a raw material, the reaction is carried out under the action of an oxidant, an auxiliary agent and a pH buffering agent, after the reaction is finished, a solvent is evaporated, the pH value is adjusted to be 1-5, an organic matter is extracted, and then an organic phase is evaporated to obtain the 9-anthracene formic acid. The invention solves the problems of more by-products, low yield and the like of 9-anthracenecarboxylic acid synthesized by the prior art, the 9-anthracenecarboxylic acid is used as a raw material in the synthesis, the reaction is carried out under the action of an oxidant, an auxiliary agent and a pH buffering agent, and the prepared yellow solid is subjected to nuclear magnetic hydrogen spectrum identification and liquid chromatography detection, and the result shows that the prepared product has the structure of 9-anthracenecarboxylic acid and the purity can reach more than 99 percent.
Description
Technical Field
The invention relates to the technical field of synthesis of dye intermediates and electronic fluorescent materials, in particular to a synthesis method of 9-anthracenecarboxylic acid.
Background
The 9-anthracene formic acid is used as a dye intermediate and an electronic fluorescent material, and has the following structural formula:
the current method for synthesizing 9-anthracenecarboxylic acid is reported as follows:
GB2523811A reports that 9-anthracenecarboxylic acid is obtained by taking 9, 10-dibromoanthracene as a raw material, forming lithium salt by butyl lithium at the temperature of-78 ℃, and then treating with dry ice. The literature [ Tetrahedron Letters,2014, vol.55, #41, p.5671-5675] reports a process for the synthesis of 9-anthracenecarboxylic acid by reaction of 9-anthraceneboronic acid and ethyl acetoacetate in a yield of 87%. The 9-anthracene boric acid is not easy to obtain and has higher price. CN110577457 reports that the yield of 9-anthracenecarboxylic acid synthesized by using 9-anthraceneboronic acid and carbon dioxide as raw materials is 82%. However, the catalyst used and 9-anthraceneboronic acid are not readily available.
The document [ Transition Metal Chemistry,2019, vol.44, #2, p.167-173] reports that 9-anthracene formaldehyde is used as a raw material, the catalyst is catalyzed by a cobalt composite catalyst, LED lamp irradiates for 150 hours, the yield is 100%, and the catalyst is not easy to obtain in the process and is not suitable for industrial production.
The literature [ Chemistry Letters,2012, vol.41, #9, p.913-914,2] reports that 9-anthracenecarboxylic acid is synthesized with a yield of only 47% by using carbon dioxide and anthracene as raw materials.
Disclosure of Invention
Aiming at the problems of the prior art, the invention provides a novel synthesis method of 9-anthracenecarboxylic acid, which has the advantages of mild reaction conditions, simple operation and stable product quality and is suitable for industrial production.
The invention adopts the following technical scheme:
a synthesis method of 9-anthracene formic acid comprises the steps of taking 9-anthracene formaldehyde as a raw material, reacting under the action of an oxidant, an auxiliary agent and a pH buffering agent, evaporating to remove a solvent after the reaction is finished, adjusting the pH value to be 1-5, extracting an organic matter, and then evaporating to remove an organic phase to obtain the 9-anthracene formic acid.
Further, the oxidant is sodium chlorite, calcium chlorite or potassium chlorite.
Further, the molar ratio of the 9-anthracene formaldehyde to the chlorite ion is 1: 0.9-3.0.
Further, the auxiliary agent is 2-methyl-2-butene, 2-methyl-1-butene, resorcinol or sulfamic acid.
Further, the auxiliary agent is 2-methyl-2-butene, and the molar ratio of the 9-anthracene formaldehyde to the 2-methyl-2-butene is 1: 1.0-3.0.
In the technical scheme, the 2-methyl-2-butene is low in price and is easier to remove.
Further, the pH buffer is sodium dihydrogen phosphate or potassium dihydrogen phosphate.
Further, the molar ratio of the 9-anthracene formaldehyde to the pH buffering agent is 1: 1.0-3.0.
Further, the solvent used in the reaction is tert-butyl alcohol, isopropanol, acetone, tetrahydrofuran, acetonitrile, dioxane or N, N-dimethylformamide.
Furthermore, the solvent used in the reaction is isopropanol, and the mass ratio of the 9-anthracene formaldehyde to the isopropanol is 1: 10-20.
In the technical scheme, the isopropanol is low in price and has good solubility to the substrate 9-anthracene formaldehyde.
Further, the reaction condition is controlled by 10-50 ℃.
Further, the reaction condition is that the temperature is controlled to be 20-30 ℃ and the reaction lasts for 2-3 hours.
Further, the solvent used for extraction is a water-immiscible solvent, including but not limited to ethyl acetate, dichloromethane, chloroform, dichloroethane, tetrachloroethane, toluene, xylene.
Further, the acid used for adjusting the pH is hydrochloric acid, sulfuric acid, nitric acid or acetic acid.
The invention has the beneficial effects that:
the synthesis method comprises the steps of taking 9-anthracene formaldehyde as a raw material, reacting under the action of an oxidant, an auxiliary agent and a pH buffering agent, evaporating a solvent after the reaction is finished, adjusting pH, extracting an organic matter, and evaporating an organic phase to obtain the 9-anthracene formic acid. The method has the advantages of fewer byproducts, easy purification, mild reaction conditions, simple operation and stable product quality, and is suitable for industrial production.
Drawings
FIG. 1 is a nuclear magnetic hydrogen spectrum identification map;
FIG. 2 is a liquid quality detection map;
FIG. 3 is a liquid phase detection profile.
Detailed Description
The present invention will be described in detail with reference to the following specific examples:
example 1
100g of 9-anthracenealdehyde, 1000g of isopropanol and 50g of 2-methyl-2-butene are added into a reaction bottle, 113.5g of sodium dihydrogen phosphate and 300g of aqueous solution are added into the reaction bottle while stirring, 68.6g of sodium chlorite and 300g of aqueous solution are added dropwise, and the temperature is controlled to be 20-30 ℃. After the dropwise addition, the reaction is stirred at room temperature for 2 hours. After the reaction was completed, the reaction solution was distilled off under reduced pressure, the solvent was distilled off, 50g of concentrated hydrochloric acid was used to adjust the pH to 2-3, a large amount of solid was precipitated, 1000g of ethyl acetate was added and stirred to dissolve the solid, filtration was performed, the filter cake was rinsed with 200g of ethyl acetate, liquid separation was performed, the organic phase was washed twice with 300g × 2 water, and the organic phase was distilled off to obtain 74.1g of yellow solid, yield: 69.32 percent.
The prepared yellow solid is subjected to nuclear magnetic hydrogen spectrum identification, and the result is shown in figure 1, and the structure of the yellow solid is 9-anthracenecarboxylic acid.
The yellow solid obtained by the preparation was subjected to liquid quality detection, as shown in FIG. 2, and it was found that the molecular weight thereof was 222.1, which was consistent with that of 9-anthracenecarboxylic acid.
And then, liquid chromatography detection is carried out, and the result is shown in figure 3, and the purity of the 9-anthracenecarboxylic acid prepared by the method can reach more than 99%.
Example 2
100g of 9-anthracenealdehyde, 1500g of isopropanol and 68g of 2-methyl-2-butene are added into a reaction bottle, 151g of sodium dihydrogen phosphate and 300g of aqueous solution are added into the reaction bottle while stirring, 87g of sodium chlorite and 300g of aqueous solution are added dropwise, and the temperature is controlled to be 20-30 ℃. After the dropwise addition, the reaction is carried out for 2 hours under room temperature stirring, reduced pressure distillation is carried out, the solvent is evaporated, 50g of concentrated hydrochloric acid is used for adjusting the pH value to be 2-3, a large amount of solid is separated out, 1000g of ethyl acetate is added, the solid is dissolved by stirring, filtration is carried out, a filter cake is rinsed by 200g of ethyl acetate, liquid separation is carried out, an organic phase is washed twice by 300g of multiplied by 2 water, and the organic phase is evaporated, so that 72g of yellow solid is obtained, and the yield: 67.29 percent.
Example 3
100g of 9-anthracenealdehyde, 1000g of isopropanol and 34.02g of 2-methyl-2-butene are added into a reaction bottle, 151g of sodium dihydrogen phosphate and 300g of aqueous solution are added into the reaction bottle while stirring, 39.47g of sodium chlorite and 300g of aqueous solution are added dropwise, and the temperature is controlled to be 20-30 ℃. After the dropwise addition, the reaction is carried out for 2 hours under room temperature stirring, reduced pressure distillation is carried out, the solvent is evaporated, 50g of concentrated hydrochloric acid is used for adjusting the pH value to be 2-3, a large amount of solid is separated out, 1000g of ethyl acetate is added, the solid is dissolved by stirring, the filtration is carried out, a filter cake is rinsed by 200g of ethyl acetate, liquid separation is carried out, an organic phase is washed twice by 300g of multiplied by 2 water, and the organic phase is evaporated, so that 75g of yellow solid is obtained, and the yield is: 69.65 percent.
Example 4
100g of 9-anthracenealdehyde, 2000g of isopropanol and 102.05g of 2-methyl-2-butene are added into a reaction flask, 151g of sodium dihydrogen phosphate and 300g of aqueous solution are added into the reaction flask under stirring, 131.59g of sodium chlorite and 300g of aqueous solution are added dropwise, and the temperature is controlled to be 20-30 ℃. After the dropwise addition, the reaction is carried out for 2 hours under room temperature stirring, reduced pressure distillation is carried out, the solvent is evaporated, 50g of concentrated hydrochloric acid is used for adjusting the pH value to be 2-3, a large amount of solid is separated out, 1000g of ethyl acetate is added, the solid is dissolved by stirring, filtration is carried out, a filter cake is rinsed by 200g of ethyl acetate, liquid separation is carried out, an organic phase is washed twice by 300g of multiplied by 2 water, and the organic phase is evaporated, so that 70.5g of yellow solid is obtained, and the yield is: 65.47 percent.
It is to be understood that the above description is not intended to limit the present invention, and the present invention is not limited to the above examples, and those skilled in the art may make modifications, alterations, additions or substitutions within the spirit and scope of the present invention.
Claims (10)
1. A synthesis method of 9-anthracenecarboxylic acid is characterized in that 9-anthraceneformaldehyde is used as a raw material, the reaction is carried out under the action of an oxidant, an auxiliary agent and a pH buffering agent, after the reaction is finished, a solvent is evaporated, the pH value is adjusted to 1-5, organic matters are extracted, and then an organic phase is evaporated, so that the 9-anthracenecarboxylic acid can be prepared.
2. The method for synthesizing 9-anthracenecarboxylic acid according to claim 1, wherein the oxidant is sodium chlorite, calcium chlorite or potassium chlorite.
3. The method for synthesizing 9-anthracenecarboxylic acid according to claim 2, wherein the molar ratio of 9-anthraceneformaldehyde to chlorite ion is 1: 0.9-3.0.
4. The method for synthesizing 9-anthracenecarboxylic acid according to claim 1, wherein the auxiliary agent is 2-methyl-2-butene, 2-methyl-1-butene, resorcinol or sulfamic acid.
5. The method for synthesizing 9-anthracenecarboxylic acid according to claim 4, wherein the auxiliary agent is 2-methyl-2-butene, and the molar ratio of 9-anthracenealdehyde to 2-methyl-2-butene is 1: 1.0-3.0.
6. The method for synthesizing 9-anthracenecarboxylic acid according to claim 1, wherein the pH buffer is sodium dihydrogen phosphate or potassium dihydrogen phosphate.
7. The method for synthesizing 9-anthracenecarboxylic acid according to claim 6, wherein the molar ratio of the 9-anthracenecarboxylic acid to the pH buffering agent is 1: 1.0-3.0.
8. The method for synthesizing 9-anthracenecarboxylic acid according to claim 1, wherein the solvent used in the reaction is tert-butanol, isopropanol, acetone, tetrahydrofuran, acetonitrile, dioxane or N, N-dimethylformamide.
9. The method for synthesizing 9-anthracenecarboxylic acid according to claim 8, wherein the solvent used in the reaction is isopropanol, and the mass ratio of 9-anthracenealdehyde to isopropanol is 1: 10-20.
10. The method for synthesizing 9-anthracenecarboxylic acid according to claim 1, wherein the reaction is carried out under the conditions of temperature control of 20-30 ℃ and reaction time of 2-3 hours.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110879538.4A CN113831237A (en) | 2021-08-02 | 2021-08-02 | Synthesis method of 9-anthracenecarboxylic acid |
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| CN114573452A (en) * | 2022-03-21 | 2022-06-03 | 哈尔滨理工大学 | Novel preparation method of 9-anthracenecarboxylic acid |
| WO2024105970A1 (en) * | 2022-11-14 | 2024-05-23 | 大阪新薬株式会社 | Method for producing anthracene-9-carboxylic acid, and reaction mixture |
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| CN114573452A (en) * | 2022-03-21 | 2022-06-03 | 哈尔滨理工大学 | Novel preparation method of 9-anthracenecarboxylic acid |
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