CN118026832A - Method for preparing halogenated anthraquinone compounds in one step - Google Patents
Method for preparing halogenated anthraquinone compounds in one step Download PDFInfo
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- -1 anthraquinone compounds Chemical class 0.000 title claims abstract description 43
- 238000000034 method Methods 0.000 title claims abstract description 40
- 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 claims abstract description 29
- 238000006243 chemical reaction Methods 0.000 claims description 354
- 239000000243 solution Substances 0.000 claims description 117
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 93
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 89
- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Natural products C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 claims description 69
- 229940011182 cobalt acetate Drugs 0.000 claims description 31
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 claims description 31
- 229940071125 manganese acetate Drugs 0.000 claims description 31
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 claims description 31
- 238000001914 filtration Methods 0.000 claims description 29
- 238000002425 crystallisation Methods 0.000 claims description 28
- 230000008025 crystallization Effects 0.000 claims description 28
- 238000005406 washing Methods 0.000 claims description 27
- 238000003756 stirring Methods 0.000 claims description 26
- 238000009423 ventilation Methods 0.000 claims description 25
- CPELXLSAUQHCOX-UHFFFAOYSA-N Hydrogen bromide Chemical compound Br CPELXLSAUQHCOX-UHFFFAOYSA-N 0.000 claims description 24
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 24
- 239000001301 oxygen Substances 0.000 claims description 24
- 229910052760 oxygen Inorganic materials 0.000 claims description 24
- 230000002140 halogenating effect Effects 0.000 claims description 22
- 239000007789 gas Substances 0.000 claims description 20
- 239000002904 solvent Substances 0.000 claims description 20
- 239000003054 catalyst Substances 0.000 claims description 14
- 239000003795 chemical substances by application Substances 0.000 claims description 13
- 229910000042 hydrogen bromide Inorganic materials 0.000 claims description 12
- 239000003153 chemical reaction reagent Substances 0.000 claims description 11
- 125000000217 alkyl group Chemical group 0.000 claims description 10
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 6
- 230000035484 reaction time Effects 0.000 claims description 6
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims description 5
- 229910052739 hydrogen Inorganic materials 0.000 claims description 5
- 239000007795 chemical reaction product Substances 0.000 claims description 3
- 238000010790 dilution Methods 0.000 claims description 3
- 239000012895 dilution Substances 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- 239000011261 inert gas Substances 0.000 claims description 3
- 238000002360 preparation method Methods 0.000 claims description 3
- 238000007789 sealing Methods 0.000 claims description 3
- 238000003113 dilution method Methods 0.000 claims description 2
- 239000010413 mother solution Substances 0.000 claims description 2
- 238000003786 synthesis reaction Methods 0.000 abstract description 6
- 239000000047 product Substances 0.000 description 113
- NIQCNGHVCWTJSM-UHFFFAOYSA-N Dimethyl phthalate Chemical compound COC(=O)C1=CC=CC=C1C(=O)OC NIQCNGHVCWTJSM-UHFFFAOYSA-N 0.000 description 50
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical group Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 42
- BMYNFMYTOJXKLE-UHFFFAOYSA-N 3-azaniumyl-2-hydroxypropanoate Chemical compound NCC(O)C(O)=O BMYNFMYTOJXKLE-UHFFFAOYSA-N 0.000 description 25
- FBSAITBEAPNWJG-UHFFFAOYSA-N dimethyl phthalate Natural products CC(=O)OC1=CC=CC=C1OC(C)=O FBSAITBEAPNWJG-UHFFFAOYSA-N 0.000 description 25
- 229960001826 dimethylphthalate Drugs 0.000 description 25
- 238000004817 gas chromatography Methods 0.000 description 25
- 238000001816 cooling Methods 0.000 description 23
- 238000001035 drying Methods 0.000 description 23
- 230000001105 regulatory effect Effects 0.000 description 14
- 239000000758 substrate Substances 0.000 description 13
- 150000004056 anthraquinones Chemical class 0.000 description 9
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 8
- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical compound [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 description 8
- 230000008569 process Effects 0.000 description 7
- 239000012295 chemical reaction liquid Substances 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 5
- 238000005660 chlorination reaction Methods 0.000 description 5
- 239000000543 intermediate Substances 0.000 description 5
- 229910052748 manganese Inorganic materials 0.000 description 5
- 239000011572 manganese Substances 0.000 description 5
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 5
- 229910052753 mercury Inorganic materials 0.000 description 5
- 238000007254 oxidation reaction Methods 0.000 description 5
- BOCJQSFSGAZAPQ-UHFFFAOYSA-N 1-chloroanthracene-9,10-dione Chemical compound O=C1C2=CC=CC=C2C(=O)C2=C1C=CC=C2Cl BOCJQSFSGAZAPQ-UHFFFAOYSA-N 0.000 description 4
- GYMFBYTZOGMSQJ-UHFFFAOYSA-N 2-methylanthracene Chemical compound C1=CC=CC2=CC3=CC(C)=CC=C3C=C21 GYMFBYTZOGMSQJ-UHFFFAOYSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 238000005273 aeration Methods 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 4
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 239000001103 potassium chloride Substances 0.000 description 4
- 235000011164 potassium chloride Nutrition 0.000 description 4
- 238000000926 separation method Methods 0.000 description 4
- JHJLBTNAGRQEKS-UHFFFAOYSA-M sodium bromide Chemical compound [Na+].[Br-] JHJLBTNAGRQEKS-UHFFFAOYSA-M 0.000 description 4
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 4
- 229910017052 cobalt Inorganic materials 0.000 description 3
- 239000010941 cobalt Substances 0.000 description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000010907 mechanical stirring Methods 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000000746 purification Methods 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- BTLXPCBPYBNQNR-UHFFFAOYSA-N 1-hydroxyanthraquinone Chemical compound O=C1C2=CC=CC=C2C(=O)C2=C1C=CC=C2O BTLXPCBPYBNQNR-UHFFFAOYSA-N 0.000 description 2
- LUACOWBTSAPURU-UHFFFAOYSA-N 2-(2-methylbutan-2-yl)anthracene Chemical compound C1=CC=CC2=CC3=CC(C(C)(C)CC)=CC=C3C=C21 LUACOWBTSAPURU-UHFFFAOYSA-N 0.000 description 2
- ZXAGXLDEMUNQSH-UHFFFAOYSA-N 2-ethylanthracene Chemical compound C1=CC=CC2=CC3=CC(CC)=CC=C3C=C21 ZXAGXLDEMUNQSH-UHFFFAOYSA-N 0.000 description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 2
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 2
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 description 2
- ATUINOWSBQKFKB-UHFFFAOYSA-N anthracene phenol Chemical compound C1=CC=CC2=CC3=CC=CC=C3C=C12.C1(=CC=CC=C1)O ATUINOWSBQKFKB-UHFFFAOYSA-N 0.000 description 2
- 150000001454 anthracenes Chemical class 0.000 description 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 2
- 229910052794 bromium Inorganic materials 0.000 description 2
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 230000036541 health Effects 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 230000004807 localization Effects 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000007800 oxidant agent Substances 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 150000003254 radicals Chemical class 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- 235000010265 sodium sulphite Nutrition 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- CAHGWVAXFJXDNI-UHFFFAOYSA-N 1,4-dichloroanthracene-9,10-dione Chemical compound O=C1C2=CC=CC=C2C(=O)C2=C1C(Cl)=CC=C2Cl CAHGWVAXFJXDNI-UHFFFAOYSA-N 0.000 description 1
- KHUFHLFHOQVFGB-UHFFFAOYSA-N 1-aminoanthracene-9,10-dione Chemical compound O=C1C2=CC=CC=C2C(=O)C2=C1C=CC=C2N KHUFHLFHOQVFGB-UHFFFAOYSA-N 0.000 description 1
- 238000005863 Friedel-Crafts acylation reaction Methods 0.000 description 1
- 240000007817 Olea europaea Species 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000002246 antineoplastic agent Substances 0.000 description 1
- 229940041181 antineoplastic drug Drugs 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000007806 chemical reaction intermediate Substances 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000000502 dialysis Methods 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 238000010828 elution Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910001437 manganese ion Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000003541 multi-stage reaction Methods 0.000 description 1
- 238000005580 one pot reaction Methods 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000007342 radical addition reaction Methods 0.000 description 1
- 150000005839 radical cations Chemical class 0.000 description 1
- 238000007348 radical reaction Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 239000002699 waste material Substances 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
- Y02P20/584—Recycling of catalysts
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to the field of organic synthesis, and discloses a method for preparing halogenated anthraquinone compounds in one step.
Description
Technical Field
The invention relates to the field of organic synthesis, in particular to a method for preparing halogenated anthraquinone compounds in one step.
Background
The halogenated anthraquinone compound is a chemical intermediate with wide application, for example, 1-chloroanthraquinone can be further converted into dye molecules such as olive green R, 1-aminoanthraquinone and 1-hydroxyanthraquinone, and 1, 4-dichloroanthraquinone can be further converted into dye molecules such as vat brown BR and vat yellow FFRK, and can also be used as a precursor of anthraquinone antitumor drugs.
The conventional synthesis process of halogenated anthraquinone generally comprises multi-step reaction, taking synthesis of 1-chloroanthraquinone as an example, and comprises mercury localization method (sulfonation-chlorination), sodium sulfite method (nitrification-sulfonation-chlorination), direct chlorination method (nitrification-chlorination), phthalic anhydride method (nitrification-chloro-friedel-crafts acylation) and other methods.
Among them, mercury localization is the most industrially mature method, which has short reaction flow and high yield, however, mercury is a reagent that is extremely harmful to human health and environment, which puts high demands on product quality and emission of three wastes. Sodium sulfite is an alternative method for industrial mercury positioning, which avoids the use of mercury, but has the advantages of long reaction flow, more substituted isomers, lower reaction yield and no ideal production process. Finally, the direct chlorination process and phthalic anhydride process have the same problems, and the formation of polysubstituted products and monosubstituted isomers results in lower overall yields, and separation and purification of the products are also very challenging, so that industrial production has not been achieved so far.
In conclusion, it is easy to see that the development of a preparation method of a novel halogenated anthraquinone compound has important industrial significance, and the novel production process has the advantages of short reaction flow, high product yield, simple and convenient product separation and purification, environmental protection, low cost and the like.
Disclosure of Invention
In order to solve the technical problems, the invention provides a method for preparing halogenated anthraquinone compounds in one step. The method of the invention takes anthracene compound as substrate, oxygen-containing gas as oxidant, and the anthracene compound reacts with halogenating agent and catalyst together to realize one-step synthesis of halogenated anthraquinone compound.
The specific technical scheme of the invention is as follows: a method for preparing halogenated anthraquinone compounds in one step comprises the steps of uniformly mixing anthracene compounds, halogenating agents, catalysts and solvents, continuously introducing oxygen-containing gas for reaction, and separating after the reaction is finished to obtain halogenated anthraquinone compounds; the reaction formula is:
wherein R is H, C-C6 straight-chain alkyl or C1-C6 branched-chain alkyl.
The method of the invention takes anthracene compound as substrate, oxygen-containing gas as oxidant, and after mixing with halogenating agent and catalyst, can realize one-step synthesis of halogenated anthraquinone compound, and compared with the prior art, the method has the advantages of short reaction flow, high atom economy, convenient product separation and high yield.
Among them, it is emphasized that when R is an alkyl group, it is required to be strictly limited to a C1-C6 straight chain alkyl group or a C1-C6 branched alkyl group. The reason is that alkyl is a weak electron donating group, which can increase the electron cloud density of the reaction site to make the substrate more easily activated, but on the other hand, too large an alkyl substituent can cause larger steric hindrance to make the substrate difficult to access the catalytic center, so that it is necessary to define a suitable substituent for best reaction effect.
Preferably, the method specifically comprises the following steps: and (3) uniformly mixing a solvent and a catalyst, adding an anthracene compound and a halogenating reagent, sealing a reaction system, heating the reaction system to a reaction temperature, continuously introducing oxygen-containing gas, reacting under stirring to reach a reaction end point, adding water into a reaction mother solution for dilution, gradually separating out a reaction product in the dilution process, and filtering and washing to obtain the halogenated anthraquinone compound.
Preferably, the solvent is a mixture of acetic acid and water, and the mass ratio of acetic acid to water is 1:10-30, more preferably 1:15-20.
Preferably, the mass ratio of the anthracene compound to the solvent is 1:4 to 99, more preferably 1:10 to 20.
The amount of the solvent to be used is controlled within a certain range. In view of the reaction effect, if the solvent is used too little or the ratio of solvent to water is not suitable, the reaction by-product is increased, the consumption of the reactants is increased, and the subsequent purification process of the product is complicated. If the solvent is used in an excessive amount, the substrate concentration is too low, which results in an increase in separation energy consumption, from the viewpoint of reaction economy. Therefore, the solvent addition amount and ratio need to be controlled in an appropriate range.
Preferably, the halogenating reagent is selected from HCl, HBr, liCl, liBr, naCl, naBr, KCl and KBr.
Preferably, the molar ratio of the anthracene compound to the halogenating agent is 1:1 to 3, more preferably=1:1.2 to 1.5.
The appropriate increase in the proportion of the halogenating agent can increase the conversion of the reaction substrate, while the halogenating agent is not excessively large in view of economy.
Preferably, the catalyst is a mixture of cobalt acetate, manganese acetate and hydrogen bromide.
Preferably, the molar ratio of the anthracene compound to the catalyst is anthracene compound to cobalt acetate to manganese acetate to hydrogen bromide=1:0.1-0.5:0.01-0.05:0.2-0.6, more preferably 1:0.2-0.3:0.02-0.03:0.3-0.4.
In the catalytic system of the invention, the addition of manganese and bromine can accelerate the oxidation reaction, reduce the production of CO 2 and CO which are excessive oxidation products, reduce the addition of cobalt and shorten or remove the induction period of the reaction. For the preparation of the halogenated anthraquinones according to the present invention, the possible reaction mechanism consists of two parts, represented by the following (in the case of anthracene):
The first reaction is an oxidation process from anthracene to anthraquinone, which mainly consists of oxidation-reduction cycle of manganese and cobalt, bromine is taken as a cocatalyst to abstract hydrogen atoms on a substrate to start a free radical reaction, cobalt can oxidize manganese ions, peroxide intermediates generated by Haber-Weiss cyclic decomposition reaction can be used, anthracene (R 1 =H) is firstly converted into anthracene phenol (R 1 =OH) under the action of the catalytic cycle, then the anthracene phenol is converted into hydrogen anthraquinone under the same catalytic cycle, and finally the oxidation process of converting the hydrogen anthraquinone into anthraquinone can be smoothly carried out under the condition of no catalysis (not shown in the reaction formula); the second reaction is the conversion process of anthraquinone to chloranthraquinone, the key intermediate of the reaction is anthraquinone radical cation, the intermediate is generated by single electron transfer process (SET) between anthraquinone and metal ion, and the radical cation and halogen in the reaction system generate radical addition and proton elimination reaction to generate final halogenated anthraquinone product.
Preferably, the pressure of the oxygen-containing gas is 0.5 to 3MPa, the aeration rate is 0.5 to 3L/min, more preferably, the pressure=1 to 2MPa, and the aeration rate=1.5 to 2L/min.
Preferably, the oxygen-containing gas is pure oxygen, air or a mixed gas of oxygen and an inert gas, and more preferably pure oxygen or air.
Preferably, the reaction temperature is 120 to 200 ℃, the reaction time is 1 to 6 hours, more preferably 160 to 180 ℃, and the reaction time is 2 to 4 hours.
The activation energy required for the oxidation reaction of different substrates is different and therefore needs to be carried out at different reaction temperatures. When the temperature is too low, the reaction substrate cannot be completely converted or stays in the reaction intermediate stage in a large amount, and when the temperature is too high, more active free radical intermediates appear in the reaction system at the same time, and byproducts with larger molecular weight appear, which is also unfavorable for ensuring the yield of the reaction.
Preferably, the halogenated anthraquinone compounds are separated by means of crystallization by means of elution and filtration.
Preferably, the mass ratio of the added water to the initial solvent is 1 to 3, more preferably 1.5 to 2.
Compared with the prior art, the invention has the following technical effects:
(1) The invention starts from anthracene compounds, can obtain halogenated anthraquinone products by only one-step reaction, has short reaction flow, high reaction yield, obviously reduced material consumption and energy consumption, and is more beneficial to cost control in industrial production.
(2) The reaction raw materials and the catalyst used in the method are cheap and easy to obtain, reagents harmful to human health or environment are not used, the method is more environment-friendly, and meanwhile, the safety of the reaction is greatly improved.
(3) The product obtained by the method is convenient to separate and purify, and the product with higher purity can be obtained only by filtering and washing.
Detailed Description
The invention is further described below with reference to examples.
General examples
A process for preparing halogenated anthraquinone compounds in one step includes such steps as mixing solvent with catalyst, adding anthracene compound and halogenating reagent, sealing reaction system, heating reaction system to reaction temp, continuously introducing oxygen-containing gas, stirring for reaction until reaction end, diluting mother liquid with water, gradually separating out reaction product, filtering and washing. The reaction formula is:
wherein R is H, C-C6 straight-chain alkyl or C1-C6 branched-chain alkyl.
Preferably, the solvent is a mixture of acetic acid and water, and the mass ratio of the acetic acid to the water is 1:10-30, more preferably 1:15-20; the halogenating reagent is selected from HCl, HBr, liCl, liBr, naCl, naBr, KCl and KBr; the catalyst is a mixture of cobalt acetate, manganese acetate and hydrogen bromide; the oxygen-containing gas is pure oxygen, air or a mixed gas of oxygen and an inert gas, and more preferably pure oxygen or air.
The mass ratio of the anthracene compound to the solvent is 1:4-99, more preferably 1:10-20; the molar ratio of anthracene compound to halogenating agent is 1:1-3, more preferably = 1:1.2-1.5; the molar ratio of the anthracene compound to the catalyst is anthracene compound to cobalt acetate to manganese acetate to hydrogen bromide=1:0.1-0.5:0.01-0.05:0.2-0.6, more preferably 1:0.2-0.3:0.02-0.03:0.3-0.4; the pressure of the oxygen-containing gas is 0.5-3 MPa, the aeration rate is 0.5-3L/min, more preferably the pressure=1-2 MPa, and the aeration rate=1.5-2L/min; the reaction temperature is 120-200 ℃, the reaction time is 1-6 h, more preferably 160-180 ℃, and the reaction time is 2-4 h; the mass ratio of the dilution water to the initial solvent is 1to 3, more preferably 1.5 to 2.
Example 1
5.34G (30 mmol) of anthracene, 3.55g (36 mmol) of hydrochloric acid (37 wt%) and 1.32g (7.5 mmol) of cobalt acetate, 0.13g (0.75 mmol) of manganese acetate, 1.77g (10.5 mmol) of hydrobromic acid (48 wt%) and 60g of acetic acid are added into a 100mL reaction kettle, the reaction kettle is closed, then is mechanically stirred and heated to 180 ℃, after the temperature is stabilized for 10min, standard air is introduced into the reaction kettle at a ventilation rate of 2L/min, a back pressure valve is adjusted to stabilize the pressure in the reaction kettle at 1.8MPa, and the reaction is started after 3h of reaction. After the reaction, transferring the reaction solution into a 250mL crystallization kettle, cooling the reaction solution to 10 ℃, dropwise adding 120mL of water into the reaction solution, continuously stirring the reaction solution, dropwise adding the water for about 2 hours, filtering the reaction solution by using a Buchner funnel to obtain a product, washing the product with water, drying the product in a 45 ℃ oven, analyzing the obtained product by using gas chromatography, and taking dimethyl phthalate as an internal standard, wherein the result is shown in Table 1.
Example 2
10.68G (60 mmol) of anthracene, 7.1g (72 mmol) of hydrochloric acid (37 wt%) 2.64g (15 mmol) of cobalt acetate, 0.26g (1.5 mmol) of manganese acetate, 3.54g (21 mmol) of hydrobromic acid (48 wt%) and 70g of acetic acid are added into a 100mL reaction kettle, the reaction kettle is closed, then is mechanically stirred and heated to 180 ℃, standard air is introduced into the reaction kettle at a ventilation rate of 2L/min after the temperature is stabilized for 10min, a back pressure valve is adjusted to stabilize the pressure in the reaction kettle at 1.8MPa for reaction, and the reaction end is reached after 3h of reaction. After the reaction, transferring the reaction solution into a 250mL crystallization kettle, cooling the reaction solution to 10 ℃, dropwise adding 120mL of water into the reaction solution, continuously stirring the reaction solution, dropwise adding the water for about 2 hours, filtering the reaction solution by using a Buchner funnel to obtain a product, washing the product with water, drying the product in a 45 ℃ oven, analyzing the obtained product by using gas chromatography, and taking dimethyl phthalate as an internal standard, wherein the result is shown in Table 1.
Example 3
5.34G (30 mmol) of anthracene, 3.55g (36 mmol) of hydrochloric acid (37 wt%) and 1.32g (7.5 mmol) of cobalt acetate, 0.13g (0.75 mmol) of manganese acetate, 1.77g (10.5 mmol) of hydrobromic acid (48 wt%) and 60g of acetic acid are added into a 100mL reaction kettle, the reaction kettle is closed, then is mechanically stirred and heated to 150 ℃, after the temperature is stabilized for 10min, standard air is introduced into the reaction kettle at a ventilation rate of 2L/min, a back pressure valve is adjusted to stabilize the pressure in the reaction kettle at 1.8MPa, and the reaction is started after 3h of reaction. After the reaction, transferring the reaction solution into a 250mL crystallization kettle, cooling the reaction solution to 10 ℃, dropwise adding 120mL of water into the reaction solution, continuously stirring the reaction solution, dropwise adding the water for about 2 hours, filtering the reaction solution by using a Buchner funnel to obtain a product, washing the product with water, drying the product in a 45 ℃ oven, analyzing the obtained product by using gas chromatography, and taking dimethyl phthalate as an internal standard, wherein the result is shown in Table 1.
Example 4
5.34G (30 mmol) of anthracene, 3.55g (36 mmol) of hydrochloric acid (37 wt%) and 1.32g (7.5 mmol) of cobalt acetate, 0.13g (0.75 mmol) of manganese acetate, 1.77g (10.5 mmol) of hydrobromic acid (48 wt%) and 60g of acetic acid are added into a 100mL reaction kettle, the reaction kettle is closed, then is mechanically stirred and heated to 200 ℃, after the temperature is stabilized for 10min, standard air is introduced into the reaction kettle at a ventilation rate of 2L/min, a back pressure valve is adjusted to stabilize the pressure in the reaction kettle at 1.8MPa, and the reaction is started after 3h of reaction. After the reaction, transferring the reaction solution into a 250mL crystallization kettle, cooling the reaction solution to 10 ℃, dropwise adding 120mL of water into the reaction solution, continuously stirring the reaction solution, dropwise adding the water for about 2 hours, filtering the reaction solution by using a Buchner funnel to obtain a product, washing the product with water, drying the product in a 45 ℃ oven, analyzing the obtained product by using gas chromatography, and taking dimethyl phthalate as an internal standard, wherein the result is shown in Table 1.
Example 5
5.34G (30 mmol) of anthracene, 3.55g (36 mmol) of hydrochloric acid (37 wt%) and 1.32g (7.5 mmol) of cobalt acetate, 0.13g (0.75 mmol) of manganese acetate, 1.77g (10.5 mmol) of hydrobromic acid (48 wt%) and 60g of acetic acid are added into a 100mL reaction kettle, the reaction kettle is closed, then is mechanically stirred and heated to 180 ℃, after the temperature is stabilized for 10min, standard air is introduced into the reaction kettle at a ventilation rate of 2L/min, a back pressure valve is adjusted to stabilize the pressure in the reaction kettle at 1.5MPa, and the reaction is started after 3h of reaction. After the reaction, transferring the reaction solution into a 250mL crystallization kettle, cooling the reaction solution to 10 ℃, dropwise adding 120mL of water into the reaction solution, continuously stirring the reaction solution, dropwise adding the water for about 2 hours, filtering the reaction solution by using a Buchner funnel to obtain a product, washing the product with water, drying the product in a 45 ℃ oven, analyzing the obtained product by using gas chromatography, and taking dimethyl phthalate as an internal standard, wherein the result is shown in Table 1.
Example 6
5.34G (30 mmol) of anthracene, 3.55g (36 mmol) of hydrochloric acid (37 wt%) and 1.32g (7.5 mmol) of cobalt acetate, 0.13g (0.75 mmol) of manganese acetate, 1.77g (10.5 mmol) of hydrobromic acid (48 wt%) and 60g of acetic acid are added into a 100mL reaction kettle, the reaction kettle is closed, then is mechanically stirred and heated to 180 ℃, after the temperature is stabilized for 10min, standard air is introduced into the reaction kettle at a ventilation rate of 2L/min, a back pressure valve is regulated to stabilize the pressure in the reaction kettle at 2MPa for reaction, and the reaction end is reached after 3h of reaction. After the reaction, transferring the reaction solution into a 250mL crystallization kettle, cooling the reaction solution to 10 ℃, dropwise adding 120mL of water into the reaction solution, continuously stirring the reaction solution, dropwise adding the water for about 2 hours, filtering the reaction solution by using a Buchner funnel to obtain a product, washing the product with water, drying the product in a 45 ℃ oven, analyzing the obtained product by using gas chromatography, and taking dimethyl phthalate as an internal standard, wherein the result is shown in Table 1.
Example 7
5.34G (30 mmol) of anthracene, 3.55g (36 mmol) of hydrochloric acid (37 wt%) and 1.32g (7.5 mmol) of cobalt acetate, 0.13g (0.75 mmol) of manganese acetate, 1.77g (10.5 mmol) of hydrobromic acid (48 wt%) and 60g of acetic acid are added into a 100mL reaction kettle, the reaction kettle is closed, then mechanical stirring is opened, the temperature is heated to 180 ℃, after the temperature is stabilized for 10min, standard air is introduced into the reaction kettle at a ventilation rate of 1.5L/min, a back pressure valve is regulated to stabilize the pressure in the reaction kettle at 1.8MPa, and the reaction is started after 3h of reaction, and the reaction end is reached. After the reaction, transferring the reaction solution into a 250mL crystallization kettle, cooling the reaction solution to 10 ℃, dropwise adding 120mL of water into the reaction solution, continuously stirring the reaction solution, dropwise adding the water for about 2 hours, filtering the reaction solution by using a Buchner funnel to obtain a product, washing the product with water, drying the product in a 45 ℃ oven, analyzing the obtained product by using gas chromatography, and taking dimethyl phthalate as an internal standard, wherein the result is shown in Table 1.
Example 8
5.34G (30 mmoL) of anthracene, 3.55g (36 mmoL) of hydrochloric acid (37 wt%) and 1.32g (7.5 mmol) of cobalt acetate, 0.13g (0.75 mmol) of manganese acetate, 1.77g (10.5 mmol) of hydrobromic acid (48 wt%) and 60g of acetic acid are added into a 100mL reaction kettle, the reaction kettle is closed, then is mechanically stirred and heated to 180 ℃, after the temperature is stabilized for 10min, standard air is introduced into the reaction kettle at a ventilation rate of 2L/min, a back pressure valve is adjusted to stabilize the pressure in the reaction kettle at 1.8MPa for reaction, and the reaction end is reached after 2h of reaction. After the reaction, transferring the reaction solution into a 250mL crystallization kettle, cooling the reaction solution to 10 ℃, dropwise adding 120mL of water into the reaction solution, continuously stirring the reaction solution, dropwise adding the water for about 2 hours, filtering the reaction solution by using a Buchner funnel to obtain a product, washing the product with water, drying the product in a 45 ℃ oven, analyzing the obtained product by using gas chromatography, and taking dimethyl phthalate as an internal standard, wherein the result is shown in Table 1.
Example 9
5.34G (30 mmol) of anthracene, 3.55g (36 mmol) of hydrochloric acid (37 wt%) and 0.66g (3.75 mmol) of cobalt acetate, 0.065g (0.375 mmol) of manganese acetate, 0.885g (5.25 mmol) of hydrobromic acid (48 wt%) and 60g of acetic acid are added into a 100mL reaction kettle, the reaction kettle is closed, then is mechanically stirred and heated to 180 ℃, after the temperature is stabilized for 10min, standard air is introduced into the reaction kettle at a ventilation rate of 2L/min, a back pressure valve is regulated to stabilize the pressure in the reaction kettle at 1.8MPa, and the reaction is started after 3h of reaction. After the reaction, transferring the reaction solution into a 250mL crystallization kettle, cooling the reaction solution to 10 ℃, dropwise adding 120mL of water into the reaction solution, continuously stirring the reaction solution, dropwise adding the water for about 2 hours, filtering the reaction solution by using a Buchner funnel to obtain a product, washing the product with water, drying the product in a 45 ℃ oven, analyzing the obtained product by using gas chromatography, and taking dimethyl phthalate as an internal standard, wherein the result is shown in Table 1.
Example 10
5.34G (30 mmol) of anthracene, 3.55g (36 mmol) of hydrochloric acid (37 wt%) and 1.32g (7.5 mmol) of cobalt acetate, 0.065g (0.375 mmol) of manganese acetate, 1.77g (10.5 mmol) of hydrobromic acid (48 wt%) and 60g of acetic acid are added into a 100mL reaction kettle, the reaction kettle is closed, then is mechanically stirred and heated to 180 ℃, after the temperature is stabilized for 10min, standard air is introduced into the reaction kettle at a ventilation rate of 2L/min, a back pressure valve is adjusted to stabilize the pressure in the reaction kettle at 1.8MPa, and the reaction is started after 3h of reaction. After the reaction, transferring the reaction solution into a 250mL crystallization kettle, cooling the reaction solution to 10 ℃, dropwise adding 120mL of water into the reaction solution, continuously stirring the reaction solution, dropwise adding the water for about 2 hours, filtering the reaction solution by using a Buchner funnel to obtain a product, washing the product with water, drying the product in a 45 ℃ oven, analyzing the obtained product by using gas chromatography, and taking dimethyl phthalate as an internal standard, wherein the result is shown in Table 1.
Example 11
5.34G (30 mmol) of anthracene, 3.55g (36 mmol) of hydrochloric acid (37 wt%) and 1.32g (7.5 mmol) of cobalt acetate, 0.26g (1.5 mmol) of manganese acetate, 1.77g (10.5 mmol) of hydrobromic acid (48 wt%) and 60g of acetic acid are added into a 100mL reaction kettle, the reaction kettle is closed, then is mechanically stirred and heated to 180 ℃, after the temperature is stabilized for 10min, standard air is introduced into the reaction kettle at a ventilation rate of 2L/min, a back pressure valve is adjusted to stabilize the pressure in the reaction kettle at 1.8MPa, and the reaction is started after 3h of reaction. After the reaction, transferring the reaction solution into a 250mL crystallization kettle, cooling the reaction solution to 10 ℃, dropwise adding 120mL of water into the reaction solution, continuously stirring the reaction solution, dropwise adding the water for about 2 hours, filtering the reaction solution by using a Buchner funnel to obtain a product, washing the product with water, drying the product in a 45 ℃ oven, analyzing the obtained product by using gas chromatography, and taking dimethyl phthalate as an internal standard, wherein the result is shown in Table 1.
Example 12
5.34G (30 mmol) of anthracene, 3.94g (40 mmol) of hydrochloric acid (37 wt%) and 1.32g (7.5 mmol) of cobalt acetate, 0.13g (0.75 mmol) of manganese acetate, 1.77g (10.5 mmol) of hydrobromic acid (48 wt%) and 61g of acetic acid are added into a 100mL reaction kettle, the reaction kettle is closed, then is mechanically stirred and heated to 180 ℃, standard air is introduced into the reaction kettle at an air-introducing rate of 2L/min after the temperature is stabilized for 10min, a back pressure valve is regulated to stabilize the pressure in the reaction kettle at 1.8MPa for reaction, and the reaction end is reached after 3h of reaction. After the reaction, transferring the reaction solution into a 250mL crystallization kettle, cooling the reaction solution to 10 ℃, dropwise adding 120mL of water into the reaction solution, continuously stirring the reaction solution, dropwise adding the water for about 2 hours, filtering the reaction solution by using a Buchner funnel to obtain a product, washing the product with water, drying the product in a 45 ℃ oven, analyzing the obtained product by using gas chromatography, and taking dimethyl phthalate as an internal standard, wherein the result is shown in Table 1.
Example 13
5.34G (30 mmol) of anthracene, 2.96g (30 mmol) of hydrochloric acid (37 wt%) 2.32 g (7.5 mmol) of cobalt acetate, 0.13g (0.75 mmol) of manganese acetate, 1.77g (10.5 mmol) of hydrobromic acid (48 wt%) 0.55g and 60g of acetic acid are added into a 100mL reaction kettle, the reaction kettle is closed, then is mechanically stirred and heated to 180 ℃, after the temperature is stabilized for 10min, standard air is introduced into the reaction kettle at a ventilation rate of 2L/min, a back pressure valve is adjusted to stabilize the pressure in the reaction kettle at 1.8MPa, and the reaction is started after 3h of reaction. After the reaction, transferring the reaction solution into a 250mL crystallization kettle, cooling the reaction solution to 10 ℃, dropwise adding 120mL of water into the reaction solution, continuously stirring the reaction solution, dropwise adding the water for about 2 hours, filtering the reaction solution by using a Buchner funnel to obtain a product, washing the product with water, drying the product in a 45 ℃ oven, analyzing the obtained product by using gas chromatography, and taking dimethyl phthalate as an internal standard, wherein the result is shown in Table 1.
Example 14
5.34G (30 mmol) of anthracene, 3.55g (36 mmol) of hydrochloric acid (37 wt%) and 1.32g (7.5 mmol) of cobalt acetate, 0.13g (0.75 mmol) of manganese acetate, 1.77g (10.5 mmol) of hydrobromic acid (48 wt%) and 60g of acetic acid are added into a 100mL reaction kettle, the reaction kettle is closed, mechanical stirring is opened and heated to 180 ℃, after the temperature is stabilized for 10min, a mixed gas of nitrogen and oxygen (with the oxygen content of 8 vol%) is introduced into the reaction kettle at the ventilation rate of 2L/min, the back pressure valve is regulated to stabilize the pressure in the reaction kettle at 1.8MPa, the reaction reaches the reaction end point after the reaction is finished, the reaction liquid is transferred into a 250mL crystallization kettle, 120mL of water is dropwise added into the reaction liquid after the reaction liquid is cooled to 10 ℃ and is continuously stirred, the dropwise addition of about 2h is completed, a product is obtained by using a Buchner funnel, the product is dried in an oven at 45 ℃ after the water is washed, the product is analyzed by using gas chromatography, and the obtained product is dimethyl phthalate as an internal standard, the result is shown in table 1.
Example 15
5.34G (30 mmol) of anthracene, 3.55g (36 mmol) of hydrochloric acid (37 wt%) and 1.32g (7.5 mmol) of cobalt acetate, 0.13g (0.75 mmol) of manganese acetate, 1.77g (10.5 mmol) of hydrobromic acid (48 wt%) and 60g of acetic acid are added into a 100mL reaction kettle, the reaction kettle is closed, mechanical stirring is opened and heated to 180 ℃, after the temperature is stabilized for 10min, a mixed gas of nitrogen and oxygen (with the oxygen content of 35 vol%) is introduced into the reaction kettle at the ventilation rate of 2L/min, the back pressure valve is regulated to stabilize the pressure in the reaction kettle at 1.8MPa, the reaction reaches the reaction end point after the reaction is finished, the reaction liquid is transferred into a 250mL crystallization kettle, 120mL of water is dropwise added into the reaction liquid after the reaction liquid is cooled to 10 ℃ and is continuously stirred, the dropwise addition of about 2h is completed, a product is obtained by using a Buchner funnel, the product is dried in an oven at 45 ℃ after the water is washed, the product is analyzed by using gas chromatography, and the obtained product is dimethyl phthalate as an internal standard, the result is shown in table 1.
Example 16
5.34G (30 mmoL) of anthracene, 3.55g (36 mmoL) of hydrochloric acid (37 wt%) and 1.32g (7.5 mmol) of cobalt acetate, 0.13g (0.75 mmol) of manganese acetate, 1.77g (10.5 mmol) of hydrobromic acid (48 wt%) and 60g of acetic acid are added into a 100mL reaction kettle, the reaction kettle is closed, then is mechanically stirred and heated to 180 ℃, after the temperature is stabilized for 10min, standard air is introduced into the reaction kettle at a ventilation rate of 2L/min, a back pressure valve is adjusted to stabilize the pressure in the reaction kettle at 1.8MPa for reaction, and the reaction end is reached after 3h of reaction. After the reaction, transferring the reaction solution into a 250mL crystallization kettle, cooling the reaction solution to 10 ℃, dropwise adding 120mL of water into the reaction solution, continuously stirring the reaction solution, dropwise adding the water for about 2 hours, filtering the reaction solution by using a Buchner funnel to obtain a product, washing the product with water, drying the product in a 45 ℃ oven, analyzing the obtained product by using gas chromatography, and taking dimethyl phthalate as an internal standard, wherein the result is shown in Table 1.
Example 17
5.34G (30 mmol) of anthracene, 3.55g (36 mmol) of hydrochloric acid (37 wt%) and 1.32g (7.5 mmol) of cobalt acetate, 0.13g (0.75 mmol) of manganese acetate, 1.77g (10.5 mmol) of hydrobromic acid (48 wt%) and 60g of acetic acid are added into a 100mL reaction kettle, the reaction kettle is closed, then is mechanically stirred and heated to 180 ℃, after the temperature is stabilized for 10min, standard air is introduced into the reaction kettle at a ventilation rate of 2L/min, a back pressure valve is adjusted to stabilize the pressure in the reaction kettle at 1.8MPa, and the reaction is started after 3h of reaction. After the reaction, transferring the reaction solution into a 250mL crystallization kettle, cooling the reaction solution to 10 ℃, dropwise adding 150mL of water into the reaction solution, continuously stirring the reaction solution, dropwise adding the water for about 2 hours, filtering the reaction solution by using a Buchner funnel to obtain a product, washing the product with water, drying the product in a 45 ℃ oven, analyzing the obtained product by using gas chromatography, and taking dimethyl phthalate as an internal standard, wherein the result is shown in Table 1.
TABLE 1
| Numbering device | Reaction conditions | 1-Chloroanthraquinone yield/% |
| Example 1 | Standard conditions | 91 |
| Example 2 | The substrate concentration was 11.3wt% | 89 |
| Example 3 | The reaction temperature is 150 DEG C | 15 |
| Example 4 | The reaction temperature is 200 DEG C | 79 |
| Example 5 | Air pressure 1.5MPa | 80 |
| Example 6 | Air pressure 2MPa | 91 |
| Example 7 | The air flow rate was 1.5L/min | 86 |
| Example 8 | Reaction time 2h | 84 |
| Example 9 | Co(OAc)212.5mol％,Mn(OAc)21.25mol％，HBr 17.5mol％ | 37 |
| Example 10 | Co(OAc)225mol％,Mn(OAc)21.25mol％，HBr 35mol％ | 45 |
| Example 11 | Co(OAc)225mol％,Mn(OAc)25mol％，HBr 35mol％ | 76 |
| Example 12 | 1.33Eq of halogenating reagent. | 92 |
| Example 13 | 1Eq of halogenating reagent. | 86 |
| Example 14 | The oxygen content in the oxygen-containing gas was 8vol% | 61 |
| Example 15 | The oxygen content in the oxygen-containing gas is 35vol% | 89 |
| Example 16 | The solvent composition was water: acetic acid=1:12 | 74 |
| Example 17 | Dialysis crystallization Water 150mL was added | 92 |
Example 18
5.76G (30 mmol) of 2-methylanthracene, 3.55g (36 mmol) of hydrochloric acid (37 wt%) and 1.32g (7.5 mmol) of cobalt acetate, 0.13g (0.75 mmol) of manganese acetate, 1.77g (10.5 mmol) of hydrobromic acid (48 wt%) and 60g of acetic acid are added into a 100mL reaction kettle, the reaction kettle is closed, then is mechanically stirred and heated to 180 ℃, after the temperature is stabilized for 10min, standard air is introduced into the reaction kettle at a ventilation rate of 2L/min, a back pressure valve is regulated to stabilize the pressure in the reaction kettle at 1.8MPa, and the reaction is started after 3h of reaction. After the reaction, transferring the reaction solution into a 250mL crystallization kettle, cooling the reaction solution to 10 ℃, dropwise adding 120mL of water into the reaction solution, continuously stirring the reaction solution, dropwise adding the water for about 2 hours, filtering the reaction solution by using a Buchner funnel to obtain a product, washing the product with water, drying the product in a 45 ℃ oven, analyzing the obtained product by using gas chromatography, and taking dimethyl phthalate as an internal standard, wherein the result is shown in Table 2.
Example 19
6.18G (30 mmol) of 2-ethylanthracene, 3.55g (36 mmol) of hydrochloric acid (37 wt%) and 1.32g (7.5 mmol) of cobalt acetate, 0.13g (0.75 mmol) of manganese acetate, 1.77g (10.5 mmol) of hydrobromic acid (48 wt%) and 60g of acetic acid are added into a 100mL reaction kettle, the reaction kettle is closed, then is mechanically stirred and heated to 180 ℃, after the temperature is stabilized for 10min, standard air is introduced into the reaction kettle at a ventilation rate of 2L/min, a back pressure valve is regulated to stabilize the pressure in the reaction kettle at 1.8MPa, and the reaction is started after 3h of reaction. After the reaction, transferring the reaction solution into a 250mL crystallization kettle, cooling the reaction solution to 10 ℃, dropwise adding 120mL of water into the reaction solution, continuously stirring the reaction solution, dropwise adding the water for about 2 hours, filtering the reaction solution by using a Buchner funnel to obtain a product, washing the product with water, drying the product in a 45 ℃ oven, analyzing the obtained product by using gas chromatography, and taking dimethyl phthalate as an internal standard, wherein the result is shown in Table 2.
Example 20
7.44G (30 mmol) of 2-tertiary amyl anthracene, 3.55g (36 mmol) of hydrochloric acid (37 wt%) and 1.32g (7.5 mmol) of cobalt acetate, 0.13g (0.75 mmol) of manganese acetate, 1.77g (10.5 mmol) of hydrobromic acid (48 wt%) and 0.18g of water are added into a 100mL reaction kettle, the reaction kettle is closed, then is mechanically stirred and heated to 180 ℃, after the temperature is stabilized for 10min, standard air is introduced into the reaction kettle at a ventilation rate of 2L/min, a back pressure valve is regulated to stabilize the pressure in the reaction kettle at 1.8MPa, and the reaction reaches the end point after 3h of reaction. After the reaction, transferring the reaction solution into a 250mL crystallization kettle, cooling the reaction solution to 10 ℃, dropwise adding 120mL of water into the reaction solution, continuously stirring the reaction solution, dropwise adding the water for about 2 hours, filtering the reaction solution by using a Buchner funnel to obtain a product, washing the product with water, drying the product in a 45 ℃ oven, analyzing the obtained product by using gas chromatography, and taking dimethyl phthalate as an internal standard, wherein the result is shown in Table 2.
Example 21
5.34G (30 mmol) of anthracene, 1.53g (36 mmol) of lithium chloride, 1.32g (7.5 mmol) of cobalt acetate, 0.13g (0.75 mmol) of manganese acetate, 1.77g (10.5 mmol) of hydrobromic acid (48 wt%) and 60g of acetic acid are added into a 100mL reaction kettle, the reaction kettle is closed, then is mechanically stirred and heated to 180 ℃, after the temperature is stabilized for 10min, standard air is introduced into the reaction kettle at a ventilation rate of 2L/min, a back pressure valve is regulated to stabilize the pressure in the reaction kettle at 1.8MPa, and the reaction is started after 3h of reaction. After the reaction, transferring the reaction solution into a 250mL crystallization kettle, cooling the reaction solution to 10 ℃, dropwise adding 120mL of water into the reaction solution, continuously stirring the reaction solution, dropwise adding the water for about 2 hours, filtering the reaction solution by using a Buchner funnel to obtain a product, washing the product with water, drying the product in a 45 ℃ oven, analyzing the obtained product by using gas chromatography, and taking dimethyl phthalate as an internal standard, wherein the result is shown in Table 2.
Example 22
5.34G (30 mmol) of anthracene, 2.1g (36 mmol) of sodium chloride, 1.32g (7.5 mmol) of cobalt acetate, 0.13g (0.75 mmol) of manganese acetate, 1.77g (10.5 mmol) of hydrobromic acid (48 wt%) and 60g of acetic acid are added into a 100mL reaction kettle, the reaction kettle is closed, then is mechanically stirred and heated to 180 ℃, after the temperature is stabilized for 10min, standard air is introduced into the reaction kettle at a ventilation rate of 2L/min, a back pressure valve is regulated to stabilize the pressure in the reaction kettle at 1.8MPa, and the reaction is started after 3h of reaction. After the reaction, transferring the reaction solution into a 250mL crystallization kettle, cooling the reaction solution to 10 ℃, dropwise adding 120mL of water into the reaction solution, continuously stirring the reaction solution, dropwise adding the water for about 2 hours, filtering the reaction solution by using a Buchner funnel to obtain a product, washing the product with water, drying the product in a 45 ℃ oven, analyzing the obtained product by using gas chromatography, and taking dimethyl phthalate as an internal standard, wherein the result is shown in Table 2.
Example 23
5.34G (30 mmol) of anthracene, 2.68g (36 mmol) of potassium chloride, 1.32g (7.5 mmol) of cobalt acetate, 0.13g (0.75 mmol) of manganese acetate, 1.77g (10.5 mmol) of hydrobromic acid (48 wt%) and 60g of acetic acid are added into a 100mL reaction kettle, the reaction kettle is closed, then is mechanically stirred and heated to 180 ℃, after the temperature is stabilized for 10min, standard air is introduced into the reaction kettle at a ventilation rate of 2L/min, a back pressure valve is regulated to stabilize the pressure in the reaction kettle at 1.8MPa, and the reaction is started after 3h of reaction. After the reaction, transferring the reaction solution into a 250mL crystallization kettle, cooling the reaction solution to 10 ℃, dropwise adding 120mL of water into the reaction solution, continuously stirring the reaction solution, dropwise adding the water for about 2 hours, filtering the reaction solution by using a Buchner funnel to obtain a product, washing the product with water, drying the product in a 45 ℃ oven, analyzing the obtained product by using gas chromatography, and taking dimethyl phthalate as an internal standard, wherein the result is shown in Table 2.
Example 24
5.34G (30 mmol) of anthracene, 3.68g (36 mmol) of sodium bromide, 1.32g (7.5 mmol) of cobalt acetate, 0.13g (0.75 mmol) of manganese acetate, 1.77g (10.5 mmol) of hydrobromic acid (48 wt%) and 60g of acetic acid are added into a 100mL reaction kettle, the reaction kettle is closed, then is mechanically stirred and heated to 180 ℃, after the temperature is stabilized for 10min, standard air is introduced into the reaction kettle at a ventilation rate of 2L/min, a back pressure valve is regulated to stabilize the pressure in the reaction kettle at 1.8MPa, and the reaction is started after 3h of reaction. After the reaction, transferring the reaction solution into a 250mL crystallization kettle, cooling the reaction solution to 10 ℃, dropwise adding 120mL of water into the reaction solution, continuously stirring the reaction solution, dropwise adding the water for about 2 hours, filtering the reaction solution by using a Buchner funnel to obtain a product, washing the product with water, drying the product in a 45 ℃ oven, analyzing the obtained product by using gas chromatography, and taking dimethyl phthalate as an internal standard, wherein the result is shown in Table 2.
Example 25
5.34G (30 mmol) of anthracene, 4.28g (36 mmol) of potassium bromide, 1.32g (7.5 mmol) of cobalt acetate, 0.13g (0.75 mmol) of manganese acetate, 1.77g (10.5 mmol) of hydrobromic acid (48 wt%) and 60g of acetic acid are added into a 100mL reaction kettle, the reaction kettle is closed, then is mechanically stirred and heated to 180 ℃, after the temperature is stabilized for 10min, standard air is introduced into the reaction kettle at a ventilation rate of 2L/min, a back pressure valve is regulated to stabilize the pressure in the reaction kettle at 1.8MPa for reaction, and the reaction end point is reached after 3h of reaction. After the reaction, transferring the reaction solution into a 250mL crystallization kettle, cooling the reaction solution to 10 ℃, dropwise adding 120mL of water into the reaction solution, continuously stirring the reaction solution, dropwise adding the water for about 2 hours, filtering the reaction solution by using a Buchner funnel to obtain a product, washing the product with water, drying the product in a 45 ℃ oven, analyzing the obtained product by using gas chromatography, and taking dimethyl phthalate as an internal standard, wherein the result is shown in Table 2.
TABLE 2
| Numbering device | Reaction conditions | Product yield/% |
| Example 1 | Standard conditions | 91 |
| Example 18 | The substrate is 2-methylanthracene | 91 |
| Example 19 | The substrate is 2-ethylanthracene | 90 |
| Example 20 | The substrate is 2-tertiary amyl anthracene | 93 |
| Example 21 | The halogenating agent is lithium chloride | 88 |
| Example 22 | The halogenating agent is sodium chloride | 92 |
| Example 23 | The halogenating agent is potassium chloride | 92 |
| Example 24 | The halogenating agent is sodium bromide | 78 |
| Example 25 | The halogenating agent is potassium bromide | 77 |
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 (13)
1.A one-step preparation method of halogenated anthraquinone compounds is characterized in that: uniformly mixing an anthracene compound, a halogenating reagent, a catalyst and a solvent, continuously introducing oxygen-containing gas for reaction, and separating after the reaction is finished to obtain a halogenated anthraquinone compound; the reaction formula is:
wherein R is H, C-C6 straight-chain alkyl or C1-C6 branched-chain alkyl.
2. The method of claim 1, wherein: and (3) uniformly mixing a solvent and a catalyst, adding an anthracene compound and a halogenating reagent, sealing a reaction system, heating the reaction system to a reaction temperature, continuously introducing oxygen-containing gas, reacting under stirring to reach a reaction end point, adding water into a reaction mother solution for dilution, gradually separating out a reaction product in the dilution process, and filtering and washing to obtain the halogenated anthraquinone compound.
3. A method according to claim 1 or 2, characterized in that: the solvent is a mixture of acetic acid and water, and the mass ratio of the acetic acid to the water is 1:10-30.
4. A method as claimed in claim 3, wherein: the mass ratio of the anthracene compound to the solvent is 1:4-99.
5. A method according to claim 1 or 2, characterized in that: the halogenating reagent is selected from HCl, HBr, liCl, liBr, naCl, naBr, KCl and KBr.
6. A method according to claim 1 or 2, characterized in that: the molar ratio of the anthracene compound to the halogenating agent is 1:1-3.
7. A method according to claim 1 or 2, characterized in that: the catalyst is a mixture of cobalt acetate, manganese acetate and hydrogen bromide.
8. The method of claim 7, wherein: the molar ratio of the anthracene compound to the catalyst is anthracene compound to cobalt acetate to manganese acetate to hydrogen bromide=1:0.1-0.5:0.01-0.05:0.2-0.6.
9. A method according to claim 1 or 2, characterized in that: the pressure of the oxygen-containing gas is 0.5-3 MPa, and the ventilation rate is 0.5-3L/min.
10. A method according to claim 1 or 2, characterized in that: the oxygen-containing gas is pure oxygen, air or a mixed gas of oxygen and inert gas.
11. A method according to claim 1 or 2, characterized in that: the reaction temperature is 120-200 ℃ and the reaction time is 1-6 h.
12. The method of claim 2, wherein: the halogenated anthraquinone compounds are separated by means of solution crystallization and filtration.
13. The method of claim 2 or 12, wherein: the mass ratio of the added water to the initial solvent is 1-3.
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