CN114149306A - Synthesis process of resorcinol - Google Patents
Synthesis process of resorcinol Download PDFInfo
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- CN114149306A CN114149306A CN202111494681.8A CN202111494681A CN114149306A CN 114149306 A CN114149306 A CN 114149306A CN 202111494681 A CN202111494681 A CN 202111494681A CN 114149306 A CN114149306 A CN 114149306A
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- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 title claims abstract description 89
- 238000000034 method Methods 0.000 title claims abstract description 26
- 238000003786 synthesis reaction Methods 0.000 title claims abstract description 10
- 230000015572 biosynthetic process Effects 0.000 title claims abstract description 9
- 230000002194 synthesizing effect Effects 0.000 claims abstract 8
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 37
- 238000010438 heat treatment Methods 0.000 claims description 22
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 claims description 21
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 20
- 238000006243 chemical reaction Methods 0.000 claims description 20
- FPQOEJPNPFCPNQ-UHFFFAOYSA-N cyclohex-4-ene-1,3-diol Chemical compound OC1CC=CC(O)C1 FPQOEJPNPFCPNQ-UHFFFAOYSA-N 0.000 claims description 20
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 18
- NMQQBXHZBNUXGJ-UHFFFAOYSA-N buta-1,3-dienyl acetate Chemical compound CC(=O)OC=CC=C NMQQBXHZBNUXGJ-UHFFFAOYSA-N 0.000 claims description 18
- 238000004321 preservation Methods 0.000 claims description 15
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 12
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 11
- 238000010992 reflux Methods 0.000 claims description 11
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 10
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 10
- 239000012298 atmosphere Substances 0.000 claims description 10
- 239000012295 chemical reaction liquid Substances 0.000 claims description 10
- 238000001816 cooling Methods 0.000 claims description 10
- 239000013078 crystal Substances 0.000 claims description 10
- 238000001914 filtration Methods 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 9
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 9
- 239000002253 acid Substances 0.000 claims description 8
- DKPFZGUDAPQIHT-UHFFFAOYSA-N butyl acetate Chemical compound CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 claims description 8
- 239000011261 inert gas Substances 0.000 claims description 5
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 4
- ZAFNJMIOTHYJRJ-UHFFFAOYSA-N Diisopropyl ether Chemical compound CC(C)OC(C)C ZAFNJMIOTHYJRJ-UHFFFAOYSA-N 0.000 claims description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 4
- 239000007789 gas Substances 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- NMQQBXHZBNUXGJ-SNAWJCMRSA-N [(1e)-buta-1,3-dienyl] acetate Chemical compound CC(=O)O\C=C\C=C NMQQBXHZBNUXGJ-SNAWJCMRSA-N 0.000 claims description 2
- 239000001569 carbon dioxide Substances 0.000 claims description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- 229920006395 saturated elastomer Polymers 0.000 claims 1
- 239000007787 solid Substances 0.000 claims 1
- 230000007613 environmental effect Effects 0.000 abstract description 4
- 230000003197 catalytic effect Effects 0.000 abstract description 3
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 abstract description 2
- 238000006356 dehydrogenation reaction Methods 0.000 abstract description 2
- 238000005265 energy consumption Methods 0.000 abstract 1
- 238000007363 ring formation reaction Methods 0.000 abstract 1
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 9
- 239000000047 product Substances 0.000 description 9
- 238000005303 weighing Methods 0.000 description 7
- 229910001873 dinitrogen Inorganic materials 0.000 description 5
- 235000011121 sodium hydroxide Nutrition 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- UNEATYXSUBPPKP-UHFFFAOYSA-N 1,3-Diisopropylbenzene Chemical compound CC(C)C1=CC=CC(C(C)C)=C1 UNEATYXSUBPPKP-UHFFFAOYSA-N 0.000 description 3
- 238000006277 sulfonation reaction Methods 0.000 description 3
- WDCYWAQPCXBPJA-UHFFFAOYSA-N 1,3-dinitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC([N+]([O-])=O)=C1 WDCYWAQPCXBPJA-UHFFFAOYSA-N 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- HIFJUMGIHIZEPX-UHFFFAOYSA-N sulfuric acid;sulfur trioxide Chemical compound O=S(=O)=O.OS(O)(=O)=O HIFJUMGIHIZEPX-UHFFFAOYSA-N 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- ZPQOPVIELGIULI-UHFFFAOYSA-N 1,3-dichlorobenzene Chemical compound ClC1=CC=CC(Cl)=C1 ZPQOPVIELGIULI-UHFFFAOYSA-N 0.000 description 1
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 239000005711 Benzoic acid Substances 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 230000029936 alkylation Effects 0.000 description 1
- 238000005804 alkylation reaction Methods 0.000 description 1
- KAVGXOKHWPNOAL-UHFFFAOYSA-N benzene-1,3-diol;sodium Chemical compound [Na].OC1=CC=CC(O)=C1 KAVGXOKHWPNOAL-UHFFFAOYSA-N 0.000 description 1
- 235000010233 benzoic acid Nutrition 0.000 description 1
- 229960003328 benzoyl peroxide Drugs 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000013064 chemical raw material Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 229940018564 m-phenylenediamine Drugs 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 238000007500 overflow downdraw method Methods 0.000 description 1
- 230000020477 pH reduction Effects 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- -1 salts sodium sulfite Chemical class 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulphite Substances [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 1
- 235000010265 sodium sulphite Nutrition 0.000 description 1
- 239000002910 solid waste Substances 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C37/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring
- C07C37/06—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by conversion of non-aromatic six-membered rings or of such rings formed in situ into aromatic six-membered rings, e.g. by dehydrogenation
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/09—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrolysis
- C07C29/095—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrolysis of esters of organic acids
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/02—Preparation of carboxylic acid esters by interreacting ester groups, i.e. transesterification
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a method for synthesizing resorcinol, belongs to the field of organic synthesis, and aims to solve the problems of high energy consumption, high environmental protection pressure and the like in the conventional resorcinol process. Cyclohexane having-OH or ═ O substituents at the 1 and 3 positions was synthesized by cyclization, and resorcinol was produced by catalytic dehydrogenation. The invention provides a safe, efficient, low-cost and environment-friendly resorcinol synthesis process.
Description
The technical field is as follows:
the invention relates to a synthesis process of resorcinol.
Background art:
resorcinol is an important fine organic chemical raw material and is widely used in the fields of medicines, pesticides, dyes, rubber, adhesives and the like. At present, the industrially mature and large-scale resorcinol production process mainly comprises a sulfonation alkali fusion method and a m-diisopropylbenzene oxidation method. The sulfonation method mainly uses benzene and fuming sulfuric acid as raw materials, and the resorcinol product is obtained through processes of sulfonation, neutralization, alkali fusion, acidification, extraction and the like, but the process needs a large amount of fuming sulfuric acid, hydrochloric acid and caustic soda, can generate a large amount of inorganic salts sodium sulfite and sodium sulfate, has high waste liquid treatment cost and low environmental friendliness; the m-diisopropylbenzene oxidation method takes benzene as a raw material, prepares m-diisopropylbenzene through alkylation, and obtains resorcinol and acetone as a byproduct through oxidation and hydrolysis, and has obvious advantages in the aspects of environmental protection, three wastes and economic aspects.
In addition, the literature reports that various resorcinol synthesis process routes are also reported: (1) benzene is nitrified to prepare m-dinitrobenzene, and then the m-dinitrobenzene is hydrogenated and reduced into m-phenylenediamine, and resorcinol is obtained through hydrolysis; (2) m-dichlorobenzene is used as a raw material, is hydrolyzed under an alkaline condition to obtain resorcinol sodium, and is acidified to obtain resorcinol; (3) the method comprises the following steps of (1) preparing resorcinol by taking benzoic acid as a raw material and performing catalytic oxidation at 50 ℃ under the action of a catalyst; (4) condensing acetone and acrylic acid to generate delta-keto acid, reacting with alcohol to obtain delta-keto ester, cyclizing the delta-keto ester in the presence of a catalyst, and finally dehydrogenating to obtain the resorcinol. However, the newly reported synthesis processes have not been industrialized for various reasons.
The invention content is as follows:
the invention aims to provide a safe, efficient, low-cost and environment-friendly resorcinol synthesis process aiming at the prior art.
The technical scheme adopted by the invention for achieving the aim is to provide resorcinol prepared by a catalytic dehydrogenation method from cyclohexane with-OH or ═ O substituent groups at the 1 and 3 positions, wherein the reaction principle is as follows:
a synthesis process of resorcinol comprises the following specific steps:
(a) respectively dissolving vinyl acetate and 1-acetoxyl-1, 3-butadiene in a solvent to prepare a solution, dropwise adding the 1-acetoxyl-1, 3-butadiene solution into the vinyl acetate solution under an inert gas atmosphere, and keeping the temperature to continue reacting for 1-3h after dropwise adding;
(b) adding sodium hydroxide in batches, heating to 40-60 ℃ after adding the sodium hydroxide, and reacting for 1-3 hours in a heat preservation manner;
(c) dropwise adding acid to adjust the pH value to 5-6, filtering the reaction liquid, cooling and crystallizing to obtain 4-cyclohexene-1, 3-diol crystals;
(d) adding 4-cyclohexene-1, 3-diol into water, slowly dropwise adding a hydrogen peroxide solution with the mass fraction of 20%, carrying out heat preservation reaction after dropwise adding, then adding acid, heating up, carrying out reflux reaction for 1-2h, and extracting and concentrating by using an extracting agent to obtain a resorcinol product.
The feeding molar ratio of the vinyl acetate to the 1-acetoxy-1, 3-butadiene in the step (a) is 1:0.5-1.5, and the reaction temperature is 10-30 ℃.
The solvent in the step (a) is one or more of methanol, ethanol and isopropanol.
The inert gas in the step (b) is one or more of nitrogen, carbon dioxide and rare gas.
The acid in the step (c) and the step (d) is one or more of hydrochloric acid and sulfuric acid.
In the step (d), the temperature of the heat preservation reaction is 40-60 ℃, and the temperature of the heating reflux is 100-150 ℃.
In the step (d), the extracting agent is one or more of n-butyl alcohol, n-butyl acetate, isopropyl ether and ethyl acetate.
The invention is realized by adopting the following technical scheme: under the inert gas atmosphere, 1-acetoxyl group-1, 3-butadiene solution is dripped into vinyl acetate solution, the feeding molar ratio is 1:0.5-1.5, and the reaction temperature is 10-30 ℃. After the dropwise addition is finished, keeping the temperature and continuously reacting for 1-3 h; adding sodium hydroxide in batches, heating to 40-60 ℃ after adding the sodium hydroxide, and reacting for 1-3 hours in a heat preservation manner; dropwise adding acid to adjust the pH value to 5-6, filtering the reaction liquid, cooling and crystallizing to obtain 4-cyclohexene-1, 3-diol crystals; adding 4-cyclohexene-1, 3-diol into water, slowly dropwise adding 20% hydrogen peroxide solution, carrying out heat preservation reaction at 40-60 ℃ after dropwise adding, then adding acid, heating to 100-.
The invention has the following advantages:
the reaction is mild, and the reaction temperature is low; the requirement on equipment is low, a lot of solid waste is not generated, the cost is saved, and the environmental protection pressure is low; the yield of resorcinol is high, about 95-98%.
The specific implementation mode is as follows:
example 1
Weighing 8.61g of vinyl acetate and 10.09g of 1-acetoxyl-1, 3-butadiene, respectively dissolving in 50mL of methanol, dropwise adding a 1-acetoxyl-1, 3-butadiene solution into the vinyl acetate solution under the atmosphere of nitrogen gas, reacting at the temperature of 10 ℃, and keeping the temperature to continue reacting for 1 hour after dropwise adding; adding 25g of saturated sodium hydroxide solution in batches, heating to 40 ℃ after adding, and reacting for 2 hours under the condition of heat preservation; dropwise adding hydrochloric acid to adjust the pH value to 5-6, filtering the reaction liquid, cooling and crystallizing to obtain 4-cyclohexene-1, 3-diol crystals; adding 4-cyclohexene-1, 3-diol into water, slowly dropwise adding 20% hydrogen peroxide solution, reacting at 50 ℃ for 2h after dropwise adding, then adding sulfuric acid, heating to 110 ℃, performing reflux reaction for 2h, and extracting and concentrating through n-butyl acetate to obtain the resorcinol product.
The resorcinol yield was determined to be 95.12%.
Example 2
Weighing 7.75g of vinyl acetate and 11.21g of 1-acetoxyl-1, 3-butadiene, respectively dissolving in 50mL of ethanol, dropwise adding a 1-acetoxyl-1, 3-butadiene solution into the vinyl acetate solution under the atmosphere of argon gas, reacting at the temperature of 20 ℃, and keeping the temperature to continue reacting for 2 hours after dropwise adding; adding 25g of saturated sodium hydroxide solution in batches, heating to 40 ℃ after adding, and reacting for 3 hours under the condition of heat preservation; dropwise adding hydrochloric acid to adjust the pH value to 5-6, filtering the reaction liquid, cooling and crystallizing to obtain 4-cyclohexene-1, 3-diol crystals; adding 4-cyclohexene-1, 3-diol into water, slowly dropwise adding 20% hydrogen peroxide solution, reacting at 50 ℃ for 2 hours after dropwise adding, then adding sulfuric acid, heating to 120 ℃, performing reflux reaction for 1.5 hours, and extracting and concentrating by n-butyl alcohol to obtain the resorcinol product.
The resorcinol yield was determined to be 96.45%.
Example 3
Weighing 8.61g of vinyl acetate and 11.21g of 1-acetoxyl-1, 3-butadiene, respectively dissolving in 50mL of isopropanol, dropwise adding a 1-acetoxyl-1, 3-butadiene solution into the vinyl acetate solution under the atmosphere of nitrogen gas, reacting at the temperature of 25 ℃, and keeping the temperature to continue reacting for 2 hours after dropwise adding; adding 25g of saturated sodium hydroxide solution in batches, heating to 50 ℃ after adding, and reacting for 3 hours under the condition of heat preservation; dropwise adding sulfuric acid to adjust the pH value to 5-6, filtering the reaction liquid, cooling and crystallizing to obtain 4-cyclohexene-1, 3-diol crystals; adding 4-cyclohexene-1, 3-diol into water, slowly dropwise adding 20% hydrogen peroxide solution, keeping the temperature at 50 ℃ after dropwise adding, reacting for 3 hours, then adding hydrochloric acid, heating to 130 ℃, performing reflux reaction for 1.5 hours, and extracting and concentrating by isopropyl ether to obtain the resorcinol product.
The resorcinol yield was determined to be 97.14%.
Example 4
Weighing 8.61g of vinyl acetate and 11.21g of 1-acetoxyl-1, 3-butadiene, respectively dissolving in 50mL of isopropanol, dropwise adding a 1-acetoxyl-1, 3-butadiene solution into the vinyl acetate solution under the atmosphere of nitrogen gas, reacting at the temperature of 30 ℃, and keeping the temperature to continue reacting for 2 hours after dropwise adding; adding 25g of saturated sodium hydroxide solution in batches, heating to 60 ℃ after adding, and reacting for 3 hours under the condition of heat preservation; dropwise adding hydrochloric acid to adjust the pH value to 5-6, filtering the reaction liquid, cooling and crystallizing to obtain 4-cyclohexene-1, 3-diol crystals; adding 4-cyclohexene-1, 3-diol into water, slowly dropwise adding 20% hydrogen peroxide solution, keeping the temperature at 60 ℃ after dropwise adding, reacting for 3 hours, then adding sulfuric acid, heating to 140 ℃, performing reflux reaction for 2 hours, and extracting and concentrating by ethyl acetate to obtain the resorcinol product.
The resorcinol yield was determined to be 97.68%.
Example 5
Weighing 86.1g of vinyl acetate and 112.1g of 1-acetoxyl-1, 3-butadiene, respectively dissolving in 500mL of methanol, dropwise adding a 1-acetoxyl-1, 3-butadiene solution into the vinyl acetate solution under an argon gas atmosphere, reacting at the temperature of 25 ℃, and keeping the temperature to continue reacting for 2 hours after dropwise adding; adding 250g of saturated sodium hydroxide solution in batches, heating to 50 ℃ after adding, and reacting for 3 hours under the condition of heat preservation; dropwise adding sulfuric acid to adjust the pH value to 5-6, filtering the reaction liquid, cooling and crystallizing to obtain 4-cyclohexene-1, 3-diol crystals; adding 4-cyclohexene-1, 3-diol into water, slowly dropwise adding 20% hydrogen peroxide solution, keeping the temperature at 60 ℃ after dropwise adding, reacting for 2h, then adding sulfuric acid, heating to 140 ℃, performing reflux reaction for 2h, and extracting and concentrating through n-butyl acetate to obtain a resorcinol product.
The resorcinol yield was determined to be 96.31%.
Example 6
Weighing 86.09g of vinyl acetate and 112.13g of 1-acetoxyl-1, 3-butadiene, respectively dissolving in 500mL of ethanol, dropwise adding a 1-acetoxyl-1, 3-butadiene solution into the vinyl acetate solution under the atmosphere of nitrogen gas, reacting at the temperature of 30 ℃, and keeping the temperature to continue reacting for 2 hours after dropwise adding; adding 250g of saturated sodium hydroxide solution in batches, heating to 55 ℃ after adding, and reacting for 3 hours under the condition of heat preservation; dropwise adding hydrochloric acid to adjust the pH value to 5-6, filtering the reaction liquid, cooling and crystallizing to obtain 4-cyclohexene-1, 3-diol crystals; adding 4-cyclohexene-1, 3-diol into water, slowly dropwise adding 20% hydrogen peroxide solution, reacting at 60 ℃ for 2h after dropwise adding, then adding sulfuric acid, heating to 150 ℃, performing reflux reaction for 2h, and extracting and concentrating by isopropyl ether to obtain the resorcinol product.
The resorcinol yield was determined to be 97.21%.
Example 7
Weighing 86.09g of vinyl acetate and 112.13g of 1-acetoxyl-1, 3-butadiene, respectively dissolving in 500mL of isopropanol, dropwise adding a 1-acetoxyl-1, 3-butadiene solution into the vinyl acetate solution under the atmosphere of nitrogen gas, reacting at the temperature of 30 ℃, and keeping the temperature to continue reacting for 2 hours after dropwise adding; adding 250g of saturated sodium hydroxide solution in batches, heating to 60 ℃ after adding, and reacting for 3 hours in a heat preservation manner; dropwise adding hydrochloric acid to adjust the pH value to 5-6, filtering the reaction liquid, cooling and crystallizing to obtain 4-cyclohexene-1, 3-diol crystals; adding 4-cyclohexene-1, 3-diol into water, slowly dropwise adding 20% hydrogen peroxide solution, keeping the temperature at 60 ℃ after dropwise adding, reacting for 2 hours, then adding sulfuric acid, heating to 150 ℃, performing reflux reaction for 2 hours, and extracting and concentrating by ethyl acetate to obtain the resorcinol product.
The resorcinol yield was determined to be 98.26%.
Claims (8)
1. A synthesis process of resorcinol is characterized in that: the method comprises the following specific steps:
(a) respectively dissolving vinyl acetate and 1-acetoxyl-1, 3-butadiene in a solvent to prepare a solution, dropwise adding the 1-acetoxyl-1, 3-butadiene solution into the vinyl acetate solution under an inert gas atmosphere, and keeping the temperature to continue reacting for 1-3h after dropwise adding;
(b) adding sodium hydroxide in batches, heating to 40-60 ℃ after adding the sodium hydroxide, and reacting for 1-3 hours in a heat preservation manner;
(c) dropwise adding acid to adjust the pH value to 5-6, filtering the reaction liquid, cooling and crystallizing to obtain 4-cyclohexene-1, 3-diol crystals;
(d) adding 4-cyclohexene-1, 3-diol into water, slowly dropwise adding a hydrogen peroxide solution with the mass fraction of 20%, carrying out heat preservation reaction after dropwise adding, then adding acid, heating up, carrying out reflux reaction for 1-2h, and extracting and concentrating by using an extracting agent to obtain a resorcinol product.
2. The process of synthesizing resorcinol according to claim 1, wherein: the feeding molar ratio of the vinyl acetate to the 1-acetoxy-1, 3-butadiene in the step (a) is 1:0.5-1.5, and the reaction temperature is 10-30 ℃.
3. The process of synthesizing resorcinol according to claim 1, wherein: the solvent in the step (a) is one or more of methanol, ethanol and isopropanol.
4. The process of synthesizing resorcinol according to claim 1, wherein: the inert gas in the step (a) is one or more of nitrogen, carbon dioxide and rare gas.
5. The process of synthesizing resorcinol according to claim 1, wherein: the sodium hydroxide in the step (b) is liquid sodium hydroxide solution or solid sodium hydroxide in a 1-saturated state by mass time sharing.
6. The process of synthesizing resorcinol according to claim 1, wherein: the acid in the step (c) and the step (d) is one or more of hydrochloric acid and sulfuric acid.
7. The process of synthesizing resorcinol according to claim 1, wherein: in the step (d), the temperature of the heat preservation reaction is 40-60 ℃, and the temperature of the heating reflux is 100-150 ℃.
8. The process of synthesizing resorcinol according to claim 1, wherein: in the step (d), the extracting agent is one or more of n-butyl alcohol, n-butyl acetate, isopropyl ether and ethyl acetate.
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Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
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