CN117945857A - Synthesis method for fusing sulfonated alkali into 4-hydroxy biphenyl by solvent method - Google Patents
Synthesis method for fusing sulfonated alkali into 4-hydroxy biphenyl by solvent method Download PDFInfo
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- biphenyl
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- alkali
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- sulfonic acid
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- YXVFYQXJAXKLAK-UHFFFAOYSA-N biphenyl-4-ol Chemical group C1=CC(O)=CC=C1C1=CC=CC=C1 YXVFYQXJAXKLAK-UHFFFAOYSA-N 0.000 title claims abstract description 90
- 239000003513 alkali Substances 0.000 title claims abstract description 59
- 238000000034 method Methods 0.000 title claims abstract description 34
- 239000002904 solvent Substances 0.000 title claims abstract description 30
- 238000001308 synthesis method Methods 0.000 title claims abstract description 6
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 claims abstract description 84
- 238000006243 chemical reaction Methods 0.000 claims abstract description 48
- 230000004927 fusion Effects 0.000 claims abstract description 43
- XDTYUYVIGLIFCW-UHFFFAOYSA-N 4-phenylbenzenesulfonic acid Chemical compound C1=CC(S(=O)(=O)O)=CC=C1C1=CC=CC=C1 XDTYUYVIGLIFCW-UHFFFAOYSA-N 0.000 claims abstract description 42
- 235000010290 biphenyl Nutrition 0.000 claims abstract description 42
- 239000004305 biphenyl Substances 0.000 claims abstract description 42
- 239000007787 solid Substances 0.000 claims abstract description 41
- 239000000706 filtrate Substances 0.000 claims abstract description 35
- 238000001914 filtration Methods 0.000 claims abstract description 35
- 239000007788 liquid Substances 0.000 claims abstract description 35
- 238000006277 sulfonation reaction Methods 0.000 claims abstract description 35
- 239000000203 mixture Substances 0.000 claims abstract description 29
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 24
- 238000010438 heat treatment Methods 0.000 claims abstract description 21
- 238000003756 stirring Methods 0.000 claims abstract description 20
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 66
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 45
- 239000012065 filter cake Substances 0.000 claims description 30
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 26
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 24
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 18
- 238000001035 drying Methods 0.000 claims description 17
- 238000005185 salting out Methods 0.000 claims description 13
- 239000011780 sodium chloride Substances 0.000 claims description 13
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 12
- 230000002194 synthesizing effect Effects 0.000 claims description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- 238000002844 melting Methods 0.000 claims description 10
- 239000002585 base Substances 0.000 claims description 6
- HIFJUMGIHIZEPX-UHFFFAOYSA-N sulfuric acid;sulfur trioxide Chemical compound O=S(=O)=O.OS(O)(=O)=O HIFJUMGIHIZEPX-UHFFFAOYSA-N 0.000 claims description 4
- RIOSJKSGNLGONI-UHFFFAOYSA-N 2-phenylbenzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC=C1C1=CC=CC=C1 RIOSJKSGNLGONI-UHFFFAOYSA-N 0.000 claims description 3
- 239000012046 mixed solvent Substances 0.000 claims description 3
- 230000001376 precipitating effect Effects 0.000 claims description 3
- CGEXUOTXYSGBLV-UHFFFAOYSA-N phenyl benzenesulfonate Chemical compound C=1C=CC=CC=1S(=O)(=O)OC1=CC=CC=C1 CGEXUOTXYSGBLV-UHFFFAOYSA-N 0.000 claims 1
- 239000002994 raw material Substances 0.000 abstract description 12
- 239000007864 aqueous solution Substances 0.000 abstract description 11
- NESLWCLHZZISNB-UHFFFAOYSA-M sodium phenolate Chemical compound [Na+].[O-]C1=CC=CC=C1 NESLWCLHZZISNB-UHFFFAOYSA-M 0.000 abstract description 11
- 239000006227 byproduct Substances 0.000 abstract description 10
- 238000005265 energy consumption Methods 0.000 abstract description 4
- 238000004939 coking Methods 0.000 abstract description 3
- 239000003960 organic solvent Substances 0.000 abstract 1
- 238000004811 liquid chromatography Methods 0.000 description 16
- 239000012265 solid product Substances 0.000 description 16
- 238000004458 analytical method Methods 0.000 description 15
- 238000001816 cooling Methods 0.000 description 9
- 239000000047 product Substances 0.000 description 8
- 238000005303 weighing Methods 0.000 description 7
- 239000002253 acid Substances 0.000 description 6
- 239000012086 standard solution Substances 0.000 description 6
- 230000008018 melting Effects 0.000 description 5
- 238000004821 distillation Methods 0.000 description 4
- 238000004128 high performance liquid chromatography Methods 0.000 description 4
- 230000020477 pH reduction Effects 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 3
- 239000002699 waste material Substances 0.000 description 3
- IAZDPXIOMUYVGZ-WFGJKAKNSA-N Dimethyl sulfoxide Chemical compound [2H]C([2H])([2H])S(=O)C([2H])([2H])[2H] IAZDPXIOMUYVGZ-WFGJKAKNSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 239000007810 chemical reaction solvent Substances 0.000 description 2
- 238000004587 chromatography analysis Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000013064 chemical raw material Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- ZYBWTEQKHIADDQ-UHFFFAOYSA-N ethanol;methanol Chemical compound OC.CCO ZYBWTEQKHIADDQ-UHFFFAOYSA-N 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 238000007499 fusion processing Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000004611 spectroscopical analysis Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 238000012795 verification Methods 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a synthesis method for fusing sulfonated alkali into 4-hydroxy biphenyl by a solvent method. Heating biphenyl to liquid state, adding sulfonating agent under stirring, heating to react, obtaining filtrate as biphenyl-4-sulfonic acid aqueous solution, and performing post-treatment on the filtrate to obtain biphenyl-4-sulfonic acid; and then adding the obtained biphenyl-4-sulfonic acid into a reaction kettle, adding alkali and alkali fusion solvent, lifting to react, taking out a solid-liquid mixture after the reaction is finished, distilling to recover the alkali fusion solvent, adding water into the rest solid to dissolve, filtering, and obtaining filtrate which is sodium phenolate aqueous solution, and carrying out post-treatment on the filtrate to obtain the 4-hydroxy biphenyl. According to the method, excessive biphenyl is used as a solvent for sulfonation, so that the problems of excessive disulfonation byproducts and low yield in the traditional biphenyl sulfonation process are solved, and the excessive biphenyl can be recovered; the organic solvent is used, so that the temperature required by the reaction is reduced, the coking loss of the raw materials due to uneven heating in the alkali fusion reaction process is reduced, the energy consumption is low, and the environment protection is facilitated.
Description
Field of the art
The invention belongs to the field of chemical raw material preparation, and particularly relates to a method for synthesizing 4-hydroxy biphenyl by a solvent method.
(II) background art
4-Hydroxy biphenyl (CAS number: 92-96-3), which is a common compound, has a white needle-shaped or sheet-shaped crystal on the appearance, and is widely applied to different fields of paint, pressure sensitive material, heat treatment, printing and dyeing auxiliary agent and the like, and has the structural formula:
The current industrial synthesis method for synthesizing 4-hydroxy biphenyl mainly uses the traditional sulfonation and alkali fusion process. In the traditional sulfonation, excessive concentrated sulfuric acid or fuming sulfuric acid is used as a sulfonating agent, so that a large amount of waste acid is generated, more disulfonated byproducts are generated, and a large amount of salt-containing wastewater is also generated. In the conventional alkali fusion technique, sodium hydroxide is usually used to heat the molten state to 300 ℃ or higher for alkali fusion. Or the mixture of sodium hydroxide and potassium hydroxide is adopted to carry out alkali fusion, so that the consumption of alkali can be greatly reduced, but the high temperature of 300-340 ℃ is still needed, the energy consumption is high, and the raw materials are easy to coke at high temperature to generate byproducts, so that the yield is reduced.
In summary, the process of sulfonation and alkali fusion of the transferred and melted biphenyl into 4-hydroxy biphenyl has the following defects: 1) The acid consumption in the sulfonation step is high, and a large amount of waste acid is generated; 2) The sulfonation step has more disulfonated byproducts and lower yield; 3) The reaction temperature of the alkali fusion step is too high, and the energy consumption is high; 4) The coking byproducts are more at the high temperature of the alkali fusion step.
(III) summary of the invention
The invention aims to provide a novel method for sulfonation of biphenyl solvent and alkali fusion into 4-hydroxy biphenyl aiming at the defects existing in the process of sulfonation of the conventional melted biphenyl and alkali fusion into 4-hydroxy biphenyl. The waste acid of the sulfonation step is avoided to be more, and the disulfonation byproducts are avoided to be more; the reaction temperature of the alkali melting step is too high, and high-temperature coking byproducts are more.
The technical scheme adopted by the invention is as follows:
Heating biphenyl as a raw material, adding a sulfonating agent to sulfonate the biphenyl after the biphenyl is heated to a liquid state, wherein excessive biphenyl is used as a reaction solvent, slightly cooling after the reaction is finished, adding water to dissolve the biphenyl, filtering to obtain a filter cake, namely recovering the biphenyl, adding sodium chloride into the filtrate to carry out salting out, separating out solids, and filtering to obtain a filter cake to obtain a product biphenyl-4-sulfonic acid; adding the obtained biphenyl-4-sulfonic acid serving as a raw material for alkali fusion reaction, alkali and an alkali fusion solvent into an autoclave, heating to the reaction temperature for alkali fusion, cooling to room temperature after the reaction is finished, opening the autoclave, taking out a solid-liquid mixture, distilling to recover the alkali fusion solvent, filtering after dissolving the rest solid in water to obtain filtrate which is sodium phenolate aqueous solution, adding 15% hydrochloric acid into the filtrate for acidification, filtering after solid is separated out after the pH value is about 1-3 (more preferably 2), and drying a filter cake obtained after filtering to obtain the 4-hydroxybiphenyl. Compared with the traditional 4-hydroxydiphenyl production process, the invention provides a 4-hydroxydiphenyl synthesis method which is relatively low in cost and relatively friendly to environment, and the problems of more acid consumption, more byproducts and high energy consumption of the traditional process are avoided, and the specific scheme is as follows:
(1) Sulfonation step
Adding biphenyl into a reaction vessel, heating to 85 ℃ while stirring, dropwise adding a sulfonating agent while stirring, heating to 110-160 ℃ after dropwise adding, reacting for 1-6 h, adding water after the reaction is finished, dissolving, filtering, drying and recovering the filter cake which is water-insoluble reaction residual biphenyl, wherein the filtrate is biphenyl-4-sulfonic acid aqueous solution, adding sodium chloride into the filtrate for salting out, separating out biphenyl-4-sulfonic acid solid, filtering, and drying the filter cake to obtain biphenyl-4-sulfonic acid solid.
(2) Alkali fusion step
And (3) adding the biphenyl-4-sulfonic acid prepared in the step (1) and alkali melting solvent into an autoclave for reaction for 1-8 h at 210-260 ℃. And (3) distilling off and recovering the alkali fusion reaction solvent after the reaction is finished, adding a small amount of water into the residual solid to dissolve, filtering to remove insoluble substances, adding 15% hydrochloric acid into the filtrate to acidify until the pH value is about 2, separating out white flocculent solid, filtering, and drying the obtained filter cake to obtain the white solid 4-hydroxy biphenyl.
Preferably, in step (1), the raw biphenyl itself is used as a sulfonation solvent, and the biphenyl may be recovered after the reaction. The sulfonating agent is 98% concentrated sulfuric acid and fuming sulfuric acid; preferably 98% concentrated sulfuric acid.
Preferably, the molar ratio of biphenyl to sulfonating agent in the step (1) is 1-5; preferably 2 to 3.
Preferably, the reaction temperature after adding the sulfonating agent in the step (1) is 125-135 ℃.
Preferably, the reaction time in step (1) is 3 to 4 hours.
Preferably, the alkali in the step (2) is sodium hydroxide, potassium hydroxide or a mixed alkali of the sodium hydroxide and the potassium hydroxide in different proportions. ; sodium hydroxide is preferred.
Preferably, the reaction temperature in step (2) is 230 to 240 ℃.
Preferably, the reaction time in step (2) is 3 to 4 hours.
Preferably, in the step (2), the molar ratio of the alkali to the biphenyl sulfonic acid is 4-15: 1, a step of; preferably 8 to 10:1.
Preferably, the alkali-melting solvent in the step (2) is any one of methanol and ethanol and a mixed solvent of the methanol and the ethanol in different proportions; preferably, the alkali-melting solvent is methanol.
Preferably, in the step (2), the molar ratio of the alkali-melting solvent to the biphenyl sulfonic acid is 10-80: 1, a step of; preferably 25 to 35; :1.
The invention has the beneficial effects that: compared with the traditional process, the method has the advantages that the acid consumption is less in the sulfonation step, and the disulfonation byproducts are less; in the alkali fusion step, the temperature required by the reaction is reduced, and the generation of byproducts is reduced.
(IV) description of the drawings
FIG. 1 is a HPLC chart of biphenyl-4-sulfonic acid;
FIG. 2 is a HPLC chart of 4-hydroxybiphenyl;
FIG. 3 is a HPLC chart of a biphenyl-4-sulfonic acid and 4-hydroxybiphenyl mixture;
FIG. 4 is an HPLC chart of a base fusion product;
FIG. 5 is a graph of an external standard of biphenyl-4-sulfonic acid;
FIG. 6 is a graph of an external standard 4-hydroxybiphenyl;
FIG. 7 is a nuclear magnetic resonance spectrum of the product obtained by the reaction;
FIG. 8 shows the reaction mixture after the sulfonation of biphenyl;
FIG. 9 shows the biphenyl-4-sulfonic acid obtained by filtration after salting out with sodium chloride;
FIG. 10 shows the solid-liquid mixture taken out of the kettle after the biphenyl-4-sulfonic acid is alkali-melted with methanol solvent and sodium hydroxide;
FIG. 11 shows the precipitation of white flocculent 4-hydroxydiphenyl after acidification of the sodium phenolate solution obtained after alkali fusion with 15% dilute hydrochloric acid;
FIG. 12 shows that the target product 4-hydroxydiphenyl is obtained by filtering and drying the precipitated solid after acidification.
(Fifth) detailed description of the invention
The invention will be further described with reference to the following specific examples, but the scope of the invention is not limited thereto:
Example 1
(1) Sulfonation step
Adding 20g of biphenyl into a reactor, heating to 85 ℃ with stirring until the biphenyl is in a liquid state, dripping 6.5g of 98% concentrated sulfuric acid, heating to 135 ℃ for reaction for 4 hours after dripping, cooling slightly after finishing the reaction, adding 80ml of water, stirring for dissolving, filtering the obtained solid-liquid mixture, adding 28.8g of sodium chloride into the filtrate for salting out, filtering after separating out solids, drying the filter cake to obtain biphenyl-4-sulfonic acid solids, weighing 8.7g, carrying out liquid chromatography analysis on the solid product to detect the purity to be 91.0%, and obtaining the product with the yield of 52.1% in the sulfonation step.
(2) Alkali fusion step
8.7G (purity 91.0%) of biphenyl-4-sulfonic acid raw material obtained in the step (1) and 13.5g of sodium hydroxide are put into an autoclave to react for 4 hours at the temperature of 235 ℃ and then cooled to room temperature, a solid-liquid mixture is taken out after opening the autoclave, 37.5ml of methanol solvent is recovered by distillation, 50ml of water is added into the residual solid to dissolve and then is filtered, filtrate is sodium phenolate aqueous solution, the filtrate is acidified to pH value of 2 by 15% hydrochloric acid, white flocculent 4-hydroxy biphenyl is separated out and then is filtered, a filter cake is dried and then weighed for 3.9g, the purity of the solid product is 94.0% by liquid chromatography analysis and detection, and the yield of the alkali melting step is 64.3%.
Example 2
(1) Sulfonation step
Adding 20g of biphenyl into a reactor, heating to 85 ℃ with stirring until the biphenyl is in a liquid state, dripping 6.5g of 98% concentrated sulfuric acid, heating to 135 ℃ for reaction for 4 hours after dripping, cooling slightly after finishing the reaction, adding 80ml of water, stirring for dissolving, filtering the obtained solid-liquid mixture, adding 28.8g of sodium chloride into the filtrate for salting out, filtering after separating out solids, drying the filter cake to obtain biphenyl-4-sulfonic acid solids, weighing 8.7g, and carrying out liquid chromatography analysis on the solid product to detect that the purity is 91%, wherein the yield of the sulfonation step is 52.1%.
(2) Alkali fusion step
8.7G (purity 91.0%) of biphenyl-4-sulfonic acid raw material obtained in the step (1) and 19.0g of potassium hydroxide are put into an autoclave to react for 3-4 hours at the temperature of 230-240 ℃,40.1ml of methanol is cooled to room temperature, the autoclave is opened to take out a solid-liquid mixture, 37.5ml of methanol solvent is recovered by distillation, 50ml of water is added into the residual solid to dissolve and then is filtered, filtrate is sodium phenolate aqueous solution, the filtrate is acidified to pH value of 2 by 15% hydrochloric acid, white flocculent 4-hydroxy biphenyl is separated out and then is filtered, 3.5g of filter cake is weighed after drying, the purity of the solid product is detected to be 93.6% by liquid chromatography analysis, and the yield of the alkali fusion step is 57.6%.
Example 3
(1) Sulfonation step
Adding 20.0g of biphenyl into a reactor, heating to 85 ℃ with stirring until the biphenyl is in a liquid state, dripping 7.0g of fuming sulfuric acid, heating to 135 ℃ for reaction for 4 hours after dripping, cooling slightly after finishing the reaction, adding 80ml of water, stirring for dissolution, filtering the obtained solid-liquid mixture, adding 28.8g of sodium chloride into the filtrate for salting out, filtering after separating out solids, drying the filter cake to obtain biphenyl-4-sulfonic acid solids, weighing 6.7g, and carrying out liquid chromatography analysis on the solid product to detect that the purity is 86.5%, wherein the yield of the sulfonation step is 38.4%.
(2) Alkali fusion step
6.7G (purity 86.5%) of biphenyl-4-sulfonic acid raw material obtained in the step (1) and 13.5g of sodium hydroxide are put into an autoclave to react for 4 hours at the temperature of 235 ℃ and then cooled to room temperature, a solid-liquid mixture is taken out after opening the autoclave, 26.4ml of methanol solvent is recovered by distillation, 50ml of water is added into the residual solid to dissolve and then is filtered, filtrate is sodium phenolate aqueous solution, the filtrate is acidified to pH value of 2 by 15% hydrochloric acid, white flocculent 4-hydroxy biphenyl is separated out and then is filtered, filter cake is dried and then weighed for 2.9g, the purity of the solid product is 92.5% by liquid chromatography analysis and detection, and the yield of the alkali melting step is 64.3%.
Example 4
(1) Sulfonation step
20G of biphenyl is put into a reactor, the temperature is raised to 85 ℃ under stirring, the biphenyl is in a liquid state, 6.5g of 98% concentrated sulfuric acid is added dropwise, and the temperature is raised to 135 ℃ after the dropwise addition is finished, and the reaction is carried out for 4 hours. After the reaction is finished, the mixture is cooled slightly, 80ml of water is added for stirring and dissolving, the obtained solid-liquid mixture is filtered, the filter cake is biphenyl and can be recovered, 28.8g of sodium chloride is added into the filtrate for salting out, the solid is filtered after precipitation, the filter cake is dried to obtain biphenyl-4-sulfonic acid solid, 8.7g of the solid is weighed, the purity of the solid product after filtration and drying is detected to be 91.0% by liquid chromatography analysis, and the yield of the sulfonation step is 52.1%.
(2) Alkali fusion step
8.7G (purity 91.0%) of biphenyl-4-sulfonic acid raw material obtained in the step (1) and 13.5g of sodium hydroxide are put into an autoclave, after the temperature is raised to 235 ℃ for 3-4 hours, the mixture is cooled to room temperature, the autoclave is opened, a solid-liquid mixture is taken out, 53.1ml of ethanol solvent is distilled and recovered, 50ml of water is added into the residual solid for dissolution, then filtration is carried out, filtrate is sodium phenolate aqueous solution, the filtrate is acidified to pH 2 by 15% hydrochloric acid, white flocculent 4-hydroxy biphenyl is separated out, filtration is carried out, a filter cake is dried, then 1.8g is weighed, the purity of the solid product is detected to be 93.8% by liquid chromatography analysis, and the yield of the alkali fusion step is 29.7%.
Example 5
(1) Sulfonation step
Adding 20.0g of biphenyl into a reactor, heating to 85 ℃ with stirring until the biphenyl is in a liquid state, dripping 6.5g of 98% concentrated sulfuric acid, heating to 135 ℃ for reaction for 4 hours after dripping, cooling slightly after finishing the reaction, adding 80ml of water, stirring for dissolving, filtering the obtained solid-liquid mixture to obtain a filter cake which is biphenyl, recycling, adding 28.8g of sodium chloride into the filtrate for salting out, filtering after separating out solids, drying the filter cake to obtain biphenyl-4-sulfonic acid solids, weighing 8.0g, and carrying out liquid chromatography analysis on the solid product to detect that the purity is 91.0%, wherein the yield of the sulfonation step is 52.1%.
(2) Alkali fusion step
8.7G (purity 91.0%) of biphenyl-4-sulfonic acid raw material obtained in the step (1) and 13.5g of sodium hydroxide are put into an autoclave, 29.2ml of ethanol and 20.1ml of methanol are put into the autoclave to react for 4 hours at the temperature of 235 ℃, then the mixture is cooled to room temperature, the solid-liquid mixture is taken out after the autoclave is opened, 44.5ml of methanol-ethanol mixed solvent is distilled and recovered, 50ml of water is added into the residual solid to dissolve and then is filtered, filtrate is sodium phenolate aqueous solution, the filtrate is acidified to pH of 2 by 15% hydrochloric acid, white flocculent 4-hydroxy biphenyl is separated out and filtered, a filter cake is weighed for 2.4g after being dried, the purity of the solid product is detected to be 96.3% by liquid chromatography, and the yield of the alkali fusion step is 39.6%.
Example 6
(1) Sulfonation step
10G of biphenyl is put into a reactor, the temperature is raised to 85 ℃ under stirring, the biphenyl is in a liquid state, 6.5g of 98% concentrated sulfuric acid is added dropwise, and the temperature is raised to 110 ℃ after the dropwise addition is finished, and the reaction is carried out for 1h. After the reaction is finished, the mixture is cooled slightly, 80ml of water is added for stirring and dissolving, the obtained solid-liquid mixture is filtered, the filter cake is biphenyl, the solid-liquid mixture can be recovered, 28.8g of sodium chloride is added into the filtrate for salting out, the solid is separated out and filtered, the filter cake is dried to obtain biphenyl-4-sulfonic acid solid, 4.3g of the solid is weighed, the purity of the solid product is 86.6% through liquid chromatography analysis, and the yield of the sulfonation step is 24.5%.
(2) Alkali fusion step
Adding 43g (purity 86.6%) of biphenyl-4-sulfonic acid raw material obtained in the step (1) and 25g of sodium hydroxide into an autoclave for reaction for 1h at the temperature of 210 ℃, cooling to room temperature, opening the autoclave, taking out a solid-liquid mixture, distilling to recover 56ml of methanol solvent, adding 100ml of water into the rest solid for dissolving, filtering, acidifying the filtrate to pH 2 with 15% hydrochloric acid to obtain white flocculent 4-hydroxy biphenyl, filtering, drying the filter cake, weighing 3.0g, and carrying out liquid chromatography analysis to detect that the purity of the solid product is 90.1%, wherein the yield of the alkali fusion step is 10.1%.
Example 7
(1) Sulfonation step
50G of biphenyl is put into a reactor, the temperature is raised to 85 ℃ under stirring, the biphenyl is in a liquid state, 6.5g of 98% concentrated sulfuric acid is added dropwise, and the temperature is raised to 160 ℃ after the dropwise addition is finished, and the reaction is carried out for 6 hours. After the completion of the reaction, the reaction mixture was cooled slightly, and 80ml of water was added thereto and dissolved with stirring. The obtained solid-liquid mixture is filtered, the filter cake is biphenyl and can be recovered, 28.8g of sodium chloride is added into the filtrate for salting out, the solid is separated out and filtered, the filter cake is dried to obtain biphenyl-4-sulfonic acid solid, 6.0g of the solid is weighed, the purity of the solid product is 94.7% by liquid chromatography analysis, and the yield of the sulfonation step is 36.7%.
(2) Alkali fusion step
Adding 6.0g (purity is 94.7%) of biphenyl-4-sulfonic acid raw material obtained in the step (1) and 14.6g of sodium hydroxide into an autoclave, heating to 260 ℃ for reaction for 8 hours, cooling to room temperature, opening the autoclave, taking out a solid-liquid mixture, distilling and recovering 70.8ml of methanol solvent, adding 50ml of water into the residual solid for dissolving, filtering, obtaining filtrate which is sodium phenolate aqueous solution, acidifying the filtrate with 15% hydrochloric acid to pH value of 2, filtering after precipitating white flocculent 4-hydroxy biphenyl, weighing 1.3g after drying filter cake, and carrying out liquid chromatography analysis on the solid product to detect purity to be 91.3%, wherein the yield of the alkali fusion step is 28.5%.
Example 8
(1) Sulfonation step
Adding 20g of biphenyl into a reactor, heating to 85 ℃ with stirring until the biphenyl is in a liquid state, dripping 6.5g of 98% concentrated sulfuric acid, heating to 135 ℃ for reaction for 4 hours after dripping, cooling slightly after finishing the reaction, adding 80ml of water, stirring for dissolving, filtering the obtained solid-liquid mixture, adding 28.8g of sodium chloride into the filtrate for salting out, filtering after separating out solids, drying the filter cake to obtain biphenyl-4-sulfonic acid solids, weighing 8.7g, carrying out liquid chromatography analysis on the solid product to detect the purity to be 91.0%, and obtaining the product with the yield of 52.1% in the sulfonation step.
(2) Alkali fusion step
8.7G (purity 91.0%) of biphenyl-4-sulfonic acid raw material obtained in the step (1) is put into an autoclave to react with 6.8g of sodium hydroxide, 9.5g of potassium hydroxide and 40.1ml of methanol, the temperature is raised to 235 ℃ and then the mixture is cooled to room temperature, the autoclave is opened to take out a solid-liquid mixture, 37.5ml of methanol solvent is recovered by distillation, 50ml of water is added into the residual solid to dissolve and then the solution is filtered, filtrate is sodium phenolate aqueous solution, the filtrate is acidified to pH value of 2 by 15% hydrochloric acid, white flocculent 4-hydroxy biphenyl is separated out and then filtered, 3.7g of filter cake is weighed after the filter cake is dried, the purity of the solid product is detected to be 93.5% by liquid chromatography analysis, and the yield of the alkali fusion step is 54.2%.
Example 9
(1) Preparation of biphenyl-4-sulfonic acid standard solution
0.05G of biphenyl-4-sulfonic acid standard sample is accurately weighed by an analytical balance and added into a 50mL volumetric flask, a small amount of chromatographic methanol is taken for dissolving, and then chromatographic methanol is added for constant volume to scale marks and shaking for standby. Taking 6 25mL volumetric flasks, respectively accurately sucking 6 biphenyl-4-sulfonic acid standard solutions with different volumes (1.25 mL, 2.50mL, 3.75mL, 5.00mL, 6.25mL and 7.50 mL) into the corresponding volumetric flasks by using a pipette, adding chromatographic methanol to fix the volume to a scale mark, and preparing a series of concentration samples (0.05 mg/mL, 0.10mg/mL, 0.15mg/mL, 0.20mg/mL, 0.25mg/mL and 0.30 mg/mL), shaking uniformly and then standing for later use;
(2) Drawing standard curve of biphenyl-4-sulfonic acid
Prepared six biphenyl-4-sulfonic acid samples with different concentrations (0.05 mg/mL, 0.10mg/mL, 0.15mg/mL, 0.20mg/mL, 0.25mg/mL, 0.30 mg/mL) were taken, each concentration was sampled accurately 3 times in equal volume, the average value was taken (Table 1), and a standard curve was drawn according to each concentration average value (FIG. 5).
Table 1: average peak area of biphenyl-4-sulfonic acid standard solution at different concentrations
Example 10
(1) Preparation of 4-hydroxy biphenyl standard solution
0.05G of the 4-hydroxybiphenyl standard sample is accurately weighed by an analytical balance and added into a 50mL volumetric flask, a small amount of chromatographic methanol is taken for dissolving, and then the chromatographic methanol is added for constant volume to a scale mark and is uniformly shaken for standby. Taking 6 25mL volumetric flasks, respectively accurately sucking 6 4-hydroxybiphenyl standard solutions with different volumes (1.25 mL, 2.50mL, 3.75mL, 5.00mL, 6.25mL and 7.50 mL) into the corresponding volumetric flasks by using a pipette, adding chromatographic methanol to fix the volume to a scale mark, and preparing a series of concentration samples (0.05 mg/mL, 0.10mg/mL, 0.15mg/mL, 0.20mg/mL, 0.25mg/mL and 0.30 mg/mL), shaking uniformly and then standing for later use;
(2) Drawing 4-hydroxy biphenyl standard curve
Six prepared 4-hydroxybiphenyl samples of different concentrations (0.05 mg/mL, 0.10mg/mL, 0.15mg/mL, 0.20mg/mL, 0.25mg/mL, 0.30 mg/mL) were taken, each concentration was sampled accurately 3 times in equal volumes and averaged (Table 2), and a standard curve was fitted to each concentration average (FIG. 6).
Table 2: average peak area of 4-hydroxy biphenyl standard solution under different concentrations
Example 11
Analyzing biphenyl-4-sulfonic acid and 4-hydroxy biphenyl products by using a liquid chromatographic analysis instrument, wherein the model of the liquid chromatographic analysis instrument is AGILENT HPLC-1260 Infinicity, the column temperature is 25 ℃, the flow rate is 1ml/min, the feeding amount is 0.02ml, and the proportion of mobile phases is as follows: v (methanol): v (aqueous phosphoric acid at pH 3) =55:45;
The final product 4-hydroxybiphenyl was dissolved with deuterated DMSO reagent and subjected to nuclear magnetic hydrogen spectrometry for structural verification (fig. 7), nuclear magnetic instrument model Varian Mercury Plus NMR.
Example 12
The reaction solution after the completion of the sulfonation of biphenyl is shown in FIG. 8. The biphenyl-4-sulfonic acid obtained by salting out with sodium chloride and filtering is shown in FIG. 9. The solid-liquid mixture is taken out of the kettle after the biphenyl-4-sulfonic acid is alkali-melted with methanol solvent and sodium hydroxide, and is shown in figure 10. The sodium phenolate solution obtained after alkali melting is acidified by 15% dilute hydrochloric acid to separate out white flocculent 4-hydroxy biphenyl as shown in figure 11. And (3) separating out solid after acidification, filtering and drying to obtain the target product 4-hydroxydiphenyl as shown in figure 12.
Claims (10)
1. A synthesis method for fusing sulfonated alkali into 4-hydroxy biphenyl by a solvent method is characterized in that: the method comprises the following steps:
1) Heating biphenyl to liquid state, adding sulfonating agent under stirring, heating to reaction temperature, dissolving in water after reaction, filtering to obtain filter cake, recovering to obtain biphenyl-4-sulfonic acid water solution, adding sodium chloride into the filtrate for salting out, precipitating white solid, filtering, and drying the filter cake to obtain biphenyl-4-sulfonic acid;
2) Adding the obtained biphenyl-4-sulfonic acid into a reaction kettle, adding alkali and alkali fusion solvent, raising the reaction temperature, starting the reaction, taking out a solid-liquid mixture after the reaction is finished, distilling to recover the alkali fusion solvent, adding water into the rest solid to dissolve, filtering, adding hydrochloric acid into the filtrate to acidify, precipitating white flocculent solid until the pH value is 1-3, filtering, and drying the obtained filter cake to obtain the 4-hydroxy biphenyl.
2. The method for synthesizing 4-hydroxybiphenyl by solvent-process sulfonation alkali fusion, according to claim 1, characterized in that: in the step 1), the mol ratio of biphenyl to sulfonating agent is 1-5:1.
3. The method for synthesizing 4-hydroxybiphenyl by solvent-process sulfonation alkali fusion according to claim 1, characterized in that in step 1), the sulfonating agent is selected from any one of sulfuric acid and fuming sulfuric acid.
4. The method for synthesizing 4-hydroxybiphenyl by solvent-process sulfonation alkali fusion according to claim 1, characterized in that in step 1), the reaction temperature is 110-160 ℃.
5. The method for synthesizing 4-hydroxybiphenyl by solvent-process sulfonation alkali fusion according to claim 4, characterized in that in step 1), the reaction temperature is 125-145 ℃.
6. The method for synthesizing 4-hydroxybiphenyl by fusing solvent-process sulfonated base according to claim 1, wherein in step 2), the base is selected from any one of sodium hydroxide and potassium hydroxide and mixed base of the two in different proportions.
7. The method for synthesizing 4-hydroxydiphenyl by fusing solvent-process sulfonated base as set forth in claim 1, wherein in step 2), the molar ratio of said base to diphenyl sulfonic acid is: 4-15: 1.
8. The method for synthesizing 4-hydroxybiphenyl by solvent-process sulfonated alkali fusion according to claim 1, characterized in that in step 2), the alkali-melting solvent is selected from any one of methanol and ethanol and mixed solvents of the two solvents in different proportions.
9. The method for synthesizing 4-hydroxybiphenyl by solvent-process sulfonated alkali fusion according to claim 1, characterized in that in step 2), the molar ratio of the alkali-melting solvent to the biphenylsulfonic acid is 10-80: 1.
10. The method for synthesizing 4-hydroxybiphenyl by solvent-process sulfonated alkali fusion according to claim 1, characterized in that in step 2), the reaction temperature is 210-260 ℃.
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