CN117304139A - Synthesis method of tetrahydroanthraquinone epoxy compound - Google Patents
Synthesis method of tetrahydroanthraquinone epoxy compound Download PDFInfo
- Publication number
- CN117304139A CN117304139A CN202311121530.7A CN202311121530A CN117304139A CN 117304139 A CN117304139 A CN 117304139A CN 202311121530 A CN202311121530 A CN 202311121530A CN 117304139 A CN117304139 A CN 117304139A
- Authority
- CN
- China
- Prior art keywords
- tetrahydroanthraquinone
- hydrogen peroxide
- epoxy compound
- oxidant
- alkali metal
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- OTBHDFWQZHPNPU-UHFFFAOYSA-N 1,2,3,4-tetrahydroanthracene-9,10-dione Chemical compound O=C1C2=CC=CC=C2C(=O)C2=C1CCCC2 OTBHDFWQZHPNPU-UHFFFAOYSA-N 0.000 title claims abstract description 35
- 239000004593 Epoxy Substances 0.000 title claims abstract description 27
- 150000001875 compounds Chemical class 0.000 title claims abstract description 27
- 238000001308 synthesis method Methods 0.000 title claims description 7
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims abstract description 26
- 239000007800 oxidant agent Substances 0.000 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 22
- 230000003647 oxidation Effects 0.000 claims abstract description 21
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 21
- 230000001590 oxidative effect Effects 0.000 claims abstract description 21
- 239000000243 solution Substances 0.000 claims abstract description 17
- 229910000288 alkali metal carbonate Inorganic materials 0.000 claims abstract description 15
- 150000008041 alkali metal carbonates Chemical class 0.000 claims abstract description 15
- 229910000029 sodium carbonate Inorganic materials 0.000 claims abstract description 13
- 235000010265 sodium sulphite Nutrition 0.000 claims abstract description 11
- 239000002904 solvent Substances 0.000 claims abstract description 11
- 238000006243 chemical reaction Methods 0.000 claims abstract description 8
- 238000000034 method Methods 0.000 claims abstract description 8
- 238000001816 cooling Methods 0.000 claims abstract description 7
- 238000001035 drying Methods 0.000 claims abstract description 7
- 238000001914 filtration Methods 0.000 claims abstract description 7
- 238000010438 heat treatment Methods 0.000 claims abstract description 7
- 239000011259 mixed solution Substances 0.000 claims abstract description 7
- 238000005406 washing Methods 0.000 claims abstract description 7
- 238000010189 synthetic method Methods 0.000 claims abstract description 6
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 57
- 239000011790 ferrous sulphate Substances 0.000 claims description 11
- 235000003891 ferrous sulphate Nutrition 0.000 claims description 11
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims description 11
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims description 11
- PXLXSNXYTNRKFR-UHFFFAOYSA-N 6-ethyl-1,2,3,4-tetrahydroanthracene-9,10-dione Chemical group O=C1C2=CC(CC)=CC=C2C(=O)C2=C1CCCC2 PXLXSNXYTNRKFR-UHFFFAOYSA-N 0.000 claims description 10
- 239000007787 solid Substances 0.000 claims description 6
- MMCOUVMKNAHQOY-UHFFFAOYSA-N carbonoperoxoic acid Chemical group OOC(O)=O MMCOUVMKNAHQOY-UHFFFAOYSA-N 0.000 claims description 5
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 4
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 2
- -1 tetrahydroanthraquinone epoxide compound Chemical class 0.000 claims description 2
- AQLJVWUFPCUVLO-UHFFFAOYSA-N urea hydrogen peroxide Chemical group OO.NC(N)=O AQLJVWUFPCUVLO-UHFFFAOYSA-N 0.000 claims description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims 2
- 229910052751 metal Inorganic materials 0.000 claims 2
- 239000002184 metal Substances 0.000 claims 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims 1
- 229910052783 alkali metal Inorganic materials 0.000 claims 1
- 150000001340 alkali metals Chemical class 0.000 claims 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 claims 1
- 239000012266 salt solution Substances 0.000 claims 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims 1
- 235000017557 sodium bicarbonate Nutrition 0.000 claims 1
- 239000003153 chemical reaction reagent Substances 0.000 abstract description 2
- 239000000047 product Substances 0.000 description 19
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical group CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 8
- 230000000694 effects Effects 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- 238000003786 synthesis reaction Methods 0.000 description 6
- 239000012224 working solution Substances 0.000 description 6
- CCFHWXYYKVEZQD-UHFFFAOYSA-N 2-pentyl-1,2,3,4-tetrahydroanthracene-9,10-dione Chemical compound O=C1C2=CC=CC=C2C(=O)C2=C1CC(CCCCC)CC2 CCFHWXYYKVEZQD-UHFFFAOYSA-N 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 5
- 239000007810 chemical reaction solvent Substances 0.000 description 5
- 239000007857 degradation product Substances 0.000 description 5
- 238000004821 distillation Methods 0.000 description 5
- 229910021506 iron(II) hydroxide Inorganic materials 0.000 description 5
- NCNCGGDMXMBVIA-UHFFFAOYSA-L iron(ii) hydroxide Chemical compound [OH-].[OH-].[Fe+2] NCNCGGDMXMBVIA-UHFFFAOYSA-L 0.000 description 5
- 239000012295 chemical reaction liquid Substances 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 3
- 238000011084 recovery Methods 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- JBKVHLHDHHXQEQ-UHFFFAOYSA-N epsilon-caprolactam Chemical compound O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 description 2
- 239000012530 fluid Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 238000004659 sterilization and disinfection Methods 0.000 description 2
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 1
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000004061 bleaching Methods 0.000 description 1
- 239000012459 cleaning agent Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000009713 electroplating Methods 0.000 description 1
- 229960004887 ferric hydroxide Drugs 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- IEECXTSVVFWGSE-UHFFFAOYSA-M iron(3+);oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Fe+3] IEECXTSVVFWGSE-UHFFFAOYSA-M 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000003380 propellant Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000012756 surface treatment agent Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D301/00—Preparation of oxiranes
- C07D301/02—Synthesis of the oxirane ring
- C07D301/03—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds
- C07D301/12—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds with hydrogen peroxide or inorganic peroxides or peracids
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D303/00—Compounds containing three-membered rings having one oxygen atom as the only ring hetero atom
- C07D303/02—Compounds containing oxirane rings
- C07D303/12—Compounds containing oxirane rings with hydrocarbon radicals, substituted by singly or doubly bound oxygen atoms
- C07D303/32—Compounds containing oxirane rings with hydrocarbon radicals, substituted by singly or doubly bound oxygen atoms by aldehydo- or ketonic radicals
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a synthetic method of a tetrahydroanthraquinone epoxy compound, which comprises the following steps: (1) Adding tetrahydroanthraquinone and alkali metal carbonate into a reactor, adding a solvent, and slowly heating to 50-60 ℃; the mass ratio of the tetrahydroanthraquinone to the sodium carbonate is 10:0-1; (2) Adding an oxidant into the solution obtained in the step (1) to slowly oxidize the tetrahydroanthraquinone; (3) After the oxidation is completed, sodium sulfite and excessive oxidant are added for reaction until the content of the oxidant in the reaction solution is lower than 0.05wtThe%; (4) And (3) cooling and crystallizing the mixed solution obtained in the step (3), filtering, washing and drying to obtain the product tetrahydroanthraquinone epoxy compound. The method has the advantages of simple operation, low price and easy obtainment of the used reagent, high product purity and high yield, and has better popularization and application values.
Description
Technical Field
The invention relates to the technical field of hydrogen peroxide production, in particular to a synthesis method of degradation products in a working solution for producing hydrogen peroxide.
Background
The hydrogen peroxide is colorless transparent liquid, can be mixed with water in any proportion, and can be used for bleaching, three-waste treatment, organic and polymer synthesis, electroplating liquid purification, food industry disinfection, surface treatment agent in electronic industry, cleaning agent, disinfection in medical and pharmaceutical industries, rocket propellant and the like.
Along with the successful application of hydrogen peroxide in preparing caprolactam and epoxypropane, the application field of hydrogen peroxide in chemical synthesis is widened, and the production efficiency and the productivity of the device are improved greatly. In recent years, the annual acceleration of hydrogen peroxide productivity in China is about 10%, the annual production capacity of a single device reaches 10-80 ten thousand tons, and the total domestic production capacity breaks through 1500 ten thousand tons/year (which is equivalent to 27.5% of hydrogen peroxide).
The operation of the ultra-large hydrogen peroxide device has higher requirements on the performance of the working fluid, particularly the content of degradation products has important influence on the performance of the working fluid, and the content measurement of the degradation products needs standard substances for accurate quantitative measurement. The tetrahydroanthraquinone epoxy compound is used as one of degradation products in the working solution, and has great influence on the performance of the working solution, so that how to obtain the tetrahydroanthraquinone epoxy compound with high purity has great significance for quantitative determination of the content of the degradation products in the working solution and judgment of the physical properties of the working solution.
Disclosure of Invention
The invention aims to provide a synthetic method of a tetrahydroanthraquinone epoxy compound, which has the advantages of simple operation, low-cost and easily-obtained reagents, high product purity, high yield and good popularization and application values.
The invention adopts the following technical scheme to realize the purposes:
a synthetic method of a tetrahydroanthraquinone epoxy compound comprises the following steps:
(1) Adding tetrahydroanthraquinone and alkali metal carbonate into a reactor, adding a solvent, and slowly heating to 50-60 ℃; the mass ratio of the tetrahydroanthraquinone to the alkali metal carbonate is 10:0-1;
(2) Adding an oxidant into the solution obtained in the step (1) to slowly oxidize the tetrahydroanthraquinone;
(3) After the oxidation is completed, sodium sulfite is added, and the excessThe oxidant content in the reaction solution is lower than 0.05wt%；
(4) And (3) cooling and crystallizing the mixed solution obtained in the step (3), filtering, washing and drying to obtain the product tetrahydroanthraquinone epoxy compound, and distilling and recovering the reaction solvent for repeated use.
Further, in the step (1), the alkali metal carbonate may be sodium carbonate, potassium carbonate or sodium bicarbonate, and after the alkali metal carbonate is added, the pH value of the solution may be slowly adjusted before the oxidant is added, so as to enhance the oxidation effect and improve the oxidation yield.
Further, in the step (2), the oxidant is a percarbonate amide or hydrogen peroxide solution, and the oxidation time is 1-10 h. When the oxidant is percarbamide, the adding amount of the alkali metal carbonate in the step (1) is 0; when the oxidant is hydrogen peroxide solution, the mass ratio of the tetrahydroanthraquinone to the alkali metal carbonate in the step (1) is 10:0.5-1, preferably 10:0.75-1.
Further, in the step (2), the concentration of the hydrogen peroxide solution is 25-30wtThe pH value of the hydrogen peroxide solution is 3-7, preferably 5-7, and the pH value of the hydrogen peroxide solution is regulated by adding an alkali metal carbonate solution, so that the hydrogen peroxide is relatively stable when the pH value is lower, and is decomposed too quickly when the pH value is greater than 7, and more active oxygen is generated during the decomposition when the pH value is 5-7, and the hydrogen peroxide utilization rate is higher.
Further, in step (2), the oxidant is added by slowly adding hydrogen peroxide solution or percarbonic acid amide solid. The oxidizing agent cannot be added at one time, avoiding too fast a reaction or causing ineffective decomposition of hydrogen peroxide.
Further, in the step (2), the addition amount of the hydrogen peroxide solution is 1-100% of the mass of the tetrahydroanthraquinone or the addition amount of the percarbonic acid amide is 1-50% of the mass of the tetrahydroanthraquinone.
Further, in the step (3), the addition amount of sodium sulfite is 1-40% of the mass of the tetrahydroanthraquinone. By adding sodium sulfite, unreacted oxidant can be removed, so that the solvent recovery process is safer.
Further, in the step (1), the tetrahydroanthraquinone is tetrahydro2-ethyl anthraquinone shown in the formula 1 or tetrahydro2-amyl anthraquinone shown in the formula 2, and the solvent addition amount is 5-10 times of the mass of the tetrahydroanthraquinone. The solvent can be recycled by distillation, and the solvent is preferably ethanol.
。
Further, in the step (4), the tetrahydroanthraquinone epoxy compound is a tetrahydro2-ethylanthraquinone epoxy compound shown in the formula 3 or a tetrahydro2-pentylalraquinone epoxy compound shown in the formula 4.
。
Further, the purity of the tetrahydroanthraquinone epoxy compound is more than 99.5 percent. The product prepared by the invention has high purity and good uniformity, can be used as a standard sample, and is used for quantitatively determining the accurate content of the components in the working solution.
Further, adding a solvent in the step (1), and then adding ferrous sulfate solids, wherein the addition amount of the ferrous sulfate solids is 5-10% of the mass of sodium carbonatewt %。
The invention has the following beneficial effects:
(1) After adding alkali metal carbonate in the step (1), the pH value of the solution can be slowly adjusted before adding the oxidant, so that the oxidation effect is enhanced, and the oxidation yield is improved;
(2) After the oxidation is finished, unreacted oxidant can be removed by adding sodium sulfite, so that the solvent recovery process is safer;
(3) The addition of the ferrous sulfate plays a certain role in catalysis, so that the generation of the tetrahydroanthraquinone epoxy compound is promoted, meanwhile, the ferrous sulfate can react with alkali metal carbonate to generate ferrous hydroxide, the ferrous hydroxide has a catalytic effect, in addition, the ferrous hydroxide is converted into ferric hydroxide in the presence of hydrogen peroxide, the synergistic catalytic effect is realized, the oxidation effect is improved, and the purity and the yield of the product are both improved.
Drawings
FIG. 1 is a liquid chromatogram of the product of example 1;
FIG. 2 is an enlarged view of the peak table in the liquid chromatogram of the product of example 1;
FIG. 3 is a liquid chromatogram of the product of example 2;
FIG. 4 is an enlarged view of the peak table in the liquid chromatogram of the product of example 2.
Detailed Description
The present invention is further described below with reference to examples, but the present invention is not limited to the examples, and it should be apparent to those skilled in the art that any modification of the present invention, equivalent substitution of raw materials for the product of the present invention, addition of auxiliary components, selection of specific modes, etc., fall within the scope of the present invention and the scope of disclosure.
Example 1
Synthesis of tetrahydro 2-ethylanthraquinone epoxy Compound:
(1) Adding 20g of tetrahydro 2-ethylanthraquinone into a reactor, adding 100g of ethanol, and slowly heating to 50-55 ℃;
(2) Slowly adding 4g of percarbonic acid amide solid into the solution obtained in the step (1), wherein the oxidation time is 10 hours;
(3) After the oxidation is completed, 3g of sodium sulfite is added;
(4) And (3) cooling and crystallizing the mixed solution obtained in the step (3), filtering, washing and drying to obtain 19.66g of the product tetrahydro 2-ethylanthraquinone epoxy compound, wherein the purity is 99.6%, the yield is 95.7%, and the reaction solvent can be recycled through distillation.
Example 2
Synthesis of tetrahydro 2-ethylanthraquinone epoxy Compound:
(1) Adding 20g of tetrahydro 2-ethylanthraquinone and 2g of sodium carbonate into a reactor, adding 200g of ethanol, and slowly heating to 55-60 ℃;
(2) Slowly adding 15ml of 25% hydrogen peroxide solution into the solution obtained in the step (1), wherein the oxidation time is 2 hours; the pH value of the hydrogen peroxide solution is 5-7, and the method for adjusting the pH value of the hydrogen peroxide solution is to add sodium carbonate solution for adjustment;
(3) After the oxidation is completed, adding 4g of sodium sulfite to react with an excessive amount of oxidant until the hydrogen peroxide content in the reaction liquid is lower than 0.05%;
(4) And (3) cooling and crystallizing the mixed solution obtained in the step (3), filtering, washing and drying to obtain 20.3g of the product tetrahydro 2-ethylanthraquinone epoxy compound, wherein the purity is 99.7%, the yield is 98.2%, and the reaction solvent can be recycled through distillation.
Example 3
Synthesis of tetrahydro 2-pentylalkanquinone epoxy Compound:
(1) Adding 20g of tetrahydro 2-amylanthraquinone and 1g of sodium carbonate into a reactor, adding 150g of ethanol, and slowly heating to 55-60 ℃;
(2) Slowly adding 10ml of 30% hydrogen peroxide solution into the solution obtained in the step (1), wherein the oxidation time is 4 hours; the pH value of the hydrogen peroxide solution is 3-4, and the method for adjusting the pH value of the hydrogen peroxide solution is to add sodium carbonate solution for adjustment;
(3) After the oxidation is completed, adding 2g of sodium sulfite to react with an excessive amount of oxidant until the hydrogen peroxide content in the reaction liquid is lower than 0.05%;
(4) And (3) cooling and crystallizing the mixed solution obtained in the step (3), filtering, washing and drying to obtain 19.31g of the product tetrahydro 2-amyl anthraquinone epoxy compound, wherein the purity is 99.59%, the yield is 95.2%, and the reaction solvent can be recycled through distillation.
Example 4
Synthesis of tetrahydro 2-pentylalkanquinone epoxy Compound:
(1) Adding 20g of tetrahydro 2-amylanthraquinone and 1.5g of sodium carbonate into a reactor, adding 120g of ethanol, and slowly heating to 55-60 ℃;
(2) Slowly adding 18ml of 27.5% hydrogen peroxide solution into the solution obtained in the step (1), wherein the oxidation time is 5h; the pH value of the hydrogen peroxide solution is 3-4, and the method for adjusting the pH value of the hydrogen peroxide solution is to add sodium carbonate solution for adjustment;
(3) After the oxidation is completed, adding 6g of sodium sulfite to react with an excessive amount of oxidant until the hydrogen peroxide content in the reaction liquid is lower than 0.05%;
(4) And (3) cooling and crystallizing the mixed solution obtained in the step (3), filtering, washing and drying to obtain 19.71g of the product tetrahydro 2-amyl anthraquinone epoxy compound, wherein the purity is 99.56%, the yield is 96.3%, and the reaction solvent can be recycled through distillation.
Example 5
The difference between the embodiment 5 and the embodiment 4 is that 0.15g of ferrous sulfate is added after the ethanol is added in the step (1), and the rest is the same as the embodiment 4, and the description is omitted; the purity of the product in the final step (4) is 99.92%, and the yield is 97.4%. The addition of ferrous sulfate plays a certain role in catalysis, and meanwhile, ferrous sulfate reacts with sodium carbonate to generate ferrous hydroxide, so that the ferrous hydroxide has a catalytic effect, the oxidation effect is improved, and the purity and the yield of the product are both improved.
Comparative example 1
The difference between comparative example 1 and example 4 is that sodium carbonate is not added in step (1), and the rest is the same as example 4, and is not repeated; the purity of the product in the final step (4) was 87.2% and the yield was 89.2%. Therefore, the addition of sodium carbonate can further adjust the pH value of the reaction solution to 8-10, so that the oxidation effect is improved.
Comparative example 2
The difference between comparative example 2 and example 4 is that the hydrogen peroxide solution in step (2) is commercial hydrogen peroxide (pH 1-2.9), the pH is not adjusted, and the rest is the same as example 4, and the description is omitted; the purity of the product in the final step (4) was 75.3%, and the yield was 84.2%. The pH value of the reaction liquid gradually decreases along with the addition of hydrogen peroxide, and the reaction effect is affected.
Comparative example 3
The difference between comparative example 3 and example 4 is that step (3) is omitted, and the rest is the same as example 4, and is not repeated; and in the final step (4), a large amount of bubbles are generated in the solvent recovery stage, so that the bubbles are easy to be detonated and have serious potential safety hazards.
Comparative example 4
The difference between comparative example 4 and example 5 is that in step (1), 0.5g of ferrous sulfate is added after ethanol is added, and the rest is the same as example 4, and no description is repeated; the purity of the product in the final step (4) was 82.3% and the yield was 91.2%. The addition of ferrous sulfate is excessive, fenton oxidation side reaction possibly occurs, the quality of the final product is reduced, and the product is blackened and has poor quality.
Claims (10)
1. A synthetic method of a tetrahydroanthraquinone epoxy compound comprises the following steps:
(1) Adding tetrahydroanthraquinone and alkali metal carbonate into a reactor, adding a solvent, and slowly heating to 50-60 ℃; the mass ratio of the tetrahydroanthraquinone to the alkali metal carbonate is 10:0-1;
(2) Adding an oxidant into the solution obtained in the step (1) to slowly oxidize the tetrahydroanthraquinone;
(3) After the oxidation is completed, sodium sulfite and excessive oxidant are added for reaction until the content of the oxidant in the reaction solution is lower than 0.05wt%；
(4) And (3) cooling and crystallizing the mixed solution obtained in the step (3), filtering, washing and drying to obtain the product tetrahydroanthraquinone epoxy compound.
2. The synthetic method according to claim 1, wherein in step (1), the alkali metal carbonate is selected from one or more of sodium carbonate, potassium carbonate, sodium bicarbonate.
3. The synthetic method of claim 1 wherein in step (2), the oxidizing agent is a percarbonic acid amide or hydrogen peroxide solution; when the oxidant is percarbamide, the adding amount of the alkali metal carbonate in the step (1) is 0; when the oxidant is hydrogen peroxide solution, the mass ratio of the tetrahydroanthraquinone to the alkali metal carbonate in the step (1) is 10:0.5-1, preferably 10:0.75-1.
4. The synthesis method according to claim 3, wherein the concentration of the hydrogen peroxide solution in the step (2) is 25 to 30wtThe pH value of the hydrogen peroxide solution is 3-7, preferably 5-7, and the method for adjusting the pH value of the hydrogen peroxide solution is to add alkali metal carbonic acidAnd (5) adjusting a salt solution.
5. The synthesis method according to claim 3, wherein in the step (2), the amount of the hydrogen peroxide solution added is 1 to 100% by mass of the tetrahydroanthraquinone or the amount of the percarbonic acid amide added is 1 to 50% by mass of the tetrahydroanthraquinone.
6. The synthesis method according to claim 1, wherein in the step (3), the addition amount of sodium sulfite is 1-40% of the mass of the tetrahydroanthraquinone.
7. The method according to claim 1, wherein in the step (1), the tetrahydroanthraquinone is tetrahydro2-ethylanthraquinone represented by formula 1 or tetrahydro2-pentylalraquinone represented by formula 2
。
8. The method according to claim 1, wherein in the step (4), the tetrahydroanthraquinone epoxy compound is a tetrahydro2-ethylanthraquinone epoxy compound represented by formula 3 or a tetrahydro2-pentylalraquinone epoxy compound represented by formula 4
。
9. The method according to any one of claims 1 to 8, wherein in step (4), the purity of the tetrahydroanthraquinone epoxide compound is > 99.5%.
10. According to any one of claims 1-8The synthesis method of the metal carbonate is characterized in that in the step (1), a solvent is added, and then ferrous sulfate solid is added, wherein the addition amount of the ferrous sulfate solid is 5-10% of the mass of the metal carbonatewt %。
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311121530.7A CN117304139A (en) | 2023-09-01 | 2023-09-01 | Synthesis method of tetrahydroanthraquinone epoxy compound |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311121530.7A CN117304139A (en) | 2023-09-01 | 2023-09-01 | Synthesis method of tetrahydroanthraquinone epoxy compound |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN117304139A true CN117304139A (en) | 2023-12-29 |
Family
ID=89248894
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202311121530.7A Pending CN117304139A (en) | 2023-09-01 | 2023-09-01 | Synthesis method of tetrahydroanthraquinone epoxy compound |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN117304139A (en) |
-
2023
- 2023-09-01 CN CN202311121530.7A patent/CN117304139A/en active Pending
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US3957876A (en) | Process for the oxidation of cyclohexane | |
| JPS6256082B2 (en) | ||
| NO20030638L (en) | Process for producing hydrogen peroxide | |
| CN113979967B (en) | Method for catalytic synthesis of accelerator CBS by ionic liquid protective agent | |
| RU2013130867A (en) | METHOD FOR PRODUCING PROPYLENE OXIDE | |
| CN117304139A (en) | Synthesis method of tetrahydroanthraquinone epoxy compound | |
| FI60699C (en) | REFERENCE TO A CONTAINER WITHOUT CONTAINING SODIUM FORMATION | |
| GB1463050A (en) | Process for the manufacture of bromine | |
| US5401873A (en) | Preparation of methyl formate | |
| CN109896503B (en) | Solvent system and method for producing hydrogen peroxide by anthraquinone process | |
| US3959342A (en) | Process for the preparation of nitrilotriacetonitrile (NTN) | |
| CN116393120A (en) | Method and catalyst for preparing D, L-tartaric acid through microchannel reaction | |
| CN108530318B (en) | Method for synthesizing adiponitrile | |
| Campestrini et al. | Baeyer-Villiger oxidation of ketones by peroxomolybdenum complexes: a revisit | |
| US2955020A (en) | Method of preparing monopersulfates | |
| US3002813A (en) | Method of preparing monopersulfates | |
| US3058808A (en) | Production of chlorine dioxide | |
| CN115072764A (en) | Preparation method of metal nitrate | |
| Gogin et al. | One-pot production of substituted anthraquinones via the diene synthesis in the presence of Mo-VP heteropoly acid solutions | |
| CN114573452A (en) | Novel preparation method of 9-anthracenecarboxylic acid | |
| CN107628933A (en) | A kind of continuous production technology that the acetone of 1 methoxyl group 2 is synthesized by the propyl alcohol direct dehydrogenation of 1 methoxyl group 2 | |
| CN112321530A (en) | Preparation method of continuous synthetic rubber vulcanization accelerator CBS | |
| CN109293600B (en) | Method for removing residual hydrogen peroxide in epoxy chloropropane oil layer | |
| CN113845093A (en) | Method for continuously preparing peroxysulfuric acid by using microchannel reactor | |
| US3077383A (en) | Process for the production of hydrazine hydrate |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |