CN115477580A - Environment-friendly synthesis method and application of 3-hydroxy-2-methyl naphthoate - Google Patents
Environment-friendly synthesis method and application of 3-hydroxy-2-methyl naphthoate Download PDFInfo
- Publication number
- CN115477580A CN115477580A CN202111505329.XA CN202111505329A CN115477580A CN 115477580 A CN115477580 A CN 115477580A CN 202111505329 A CN202111505329 A CN 202111505329A CN 115477580 A CN115477580 A CN 115477580A
- Authority
- CN
- China
- Prior art keywords
- hydroxy
- reaction
- naphthoate
- methyl
- catalyst
- 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
- 238000001308 synthesis method Methods 0.000 title claims abstract description 14
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 103
- 238000006243 chemical reaction Methods 0.000 claims abstract description 62
- ALKYHXVLJMQRLQ-UHFFFAOYSA-N 3-Hydroxy-2-naphthoate Chemical compound C1=CC=C2C=C(O)C(C(=O)O)=CC2=C1 ALKYHXVLJMQRLQ-UHFFFAOYSA-N 0.000 claims abstract description 29
- 239000003054 catalyst Substances 0.000 claims abstract description 24
- 239000003456 ion exchange resin Substances 0.000 claims abstract description 23
- 229920003303 ion-exchange polymer Polymers 0.000 claims abstract description 23
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 claims abstract description 22
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 17
- 238000001816 cooling Methods 0.000 claims abstract description 11
- 238000001914 filtration Methods 0.000 claims abstract description 10
- 238000000034 method Methods 0.000 claims abstract description 8
- 238000010438 heat treatment Methods 0.000 claims abstract description 4
- 238000007599 discharging Methods 0.000 claims abstract description 3
- YVVBECLPRBAATK-UHFFFAOYSA-N methyl 3-hydroxynaphthalene-2-carboxylate Chemical compound C1=CC=C2C=C(O)C(C(=O)OC)=CC2=C1 YVVBECLPRBAATK-UHFFFAOYSA-N 0.000 claims description 27
- 239000011148 porous material Substances 0.000 claims description 15
- 230000015572 biosynthetic process Effects 0.000 claims 2
- 238000003786 synthesis reaction Methods 0.000 claims 2
- 230000035484 reaction time Effects 0.000 abstract description 8
- 238000010189 synthetic method Methods 0.000 abstract description 7
- 238000004519 manufacturing process Methods 0.000 abstract description 6
- 150000003839 salts Chemical class 0.000 abstract description 6
- 239000002440 industrial waste Substances 0.000 abstract description 5
- 239000002253 acid Substances 0.000 abstract description 3
- 238000009776 industrial production Methods 0.000 abstract description 2
- 239000011347 resin Substances 0.000 description 13
- 229920005989 resin Polymers 0.000 description 13
- 239000000047 product Substances 0.000 description 12
- 238000003756 stirring Methods 0.000 description 10
- 238000005886 esterification reaction Methods 0.000 description 9
- 239000012452 mother liquor Substances 0.000 description 6
- 238000002156 mixing Methods 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- 230000003197 catalytic effect Effects 0.000 description 4
- 239000000706 filtrate Substances 0.000 description 4
- 239000000178 monomer Substances 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 2
- 238000006482 condensation reaction Methods 0.000 description 2
- 230000018044 dehydration Effects 0.000 description 2
- 238000006297 dehydration reaction Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 239000002351 wastewater Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- RTBQQRFTCVDODF-UHFFFAOYSA-N 3-methoxynaphthalene-2-carboxylic acid Chemical compound C1=CC=C2C=C(C(O)=O)C(OC)=CC2=C1 RTBQQRFTCVDODF-UHFFFAOYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000007809 chemical reaction catalyst Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- UZUODNWWWUQRIR-UHFFFAOYSA-L disodium;3-aminonaphthalene-1,5-disulfonate Chemical compound [Na+].[Na+].C1=CC=C(S([O-])(=O)=O)C2=CC(N)=CC(S([O-])(=O)=O)=C21 UZUODNWWWUQRIR-UHFFFAOYSA-L 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- -1 ester compound Chemical class 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000002309 gasification Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 235000011121 sodium hydroxide Nutrition 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/08—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides with the hydroxy or O-metal group of organic compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/06—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing polymers
- B01J31/08—Ion-exchange resins
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/40—Substitution reactions at carbon centres, e.g. C-C or C-X, i.e. carbon-hetero atom, cross-coupling, C-H activation or ring-opening reactions
- B01J2231/49—Esterification or transesterification
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to the technical field of IPC of C07C67/08, in particular to an environment-friendly synthetic method of 3-hydroxy-2-methyl naphthoate and application thereof. The method comprises the following steps: adding 3-hydroxy-2-naphthoic acid and methanol into a reaction kettle, adding a catalyst, heating for reaction for 8-12 hours, cooling, filtering out the catalyst, recovering the reaction system to room temperature, cooling and discharging to obtain the product; wherein the reaction temperature is not lower than 100 ℃. The synthesis method provided by the invention does not adopt a large amount of concentrated sulfuric acid as a catalyst, the consumption of the concentrated sulfuric acid is at most 5% of the mass of the 3-hydroxy-2-naphthoic acid, a large amount of acid industrial waste salt is not generated, and the production mode is environment-friendly and safe. In addition, the invention adopts the ion exchange resin with a specific structure as the catalyst, and the ion exchange resin is matched with the catalyst for use to shorten the reaction time, so that the yield of about 95 percent is realized within the reaction time of about 12 hours, and the content of the 3-hydroxy-2-methyl naphthoate in the product is ensured to be not less than 98 percent, thereby being suitable for industrial production.
Description
Technical Field
The invention relates to the technical field of IPC of C07C67/08, in particular to an environment-friendly synthetic method of 3-hydroxy-2-methyl naphthoate and application thereof.
Background
The 3-hydroxy-2-methyl naphthoate is a key intermediate of a novel rubber functional auxiliary agent 3-hydroxy-2-naphthoylhydrazone (BMH), can be used for preparing the BMH, and is used for improving the heat build-up of tires and promoting the dispersibility of white carbon black. Methyl 3-hydroxy-2-naphthoate is an ester compound and can be prepared by conventional esterification reactions, for example, esterification of 3-hydroxy-2-naphthoic acid with methanol. For example, chinese patent CN106608821A discloses a process for producing methyl 3-hydroxy-2-naphthoate, wherein 3-methoxy-2-naphthoate is reacted with excess methanol under the catalysis of concentrated sulfuric acid to obtain the methyl 3-hydroxy-2-naphthoate. However, in these conventional processes, the esterification reaction often takes more than 24 hours, and the reaction is incomplete, a large amount of unreacted 3-hydroxy-2-naphthoic acid needs to be treated with alkaline water, the raw material loss is large, and a large amount of waste water and waste salt are generated. In actual production, in order to improve the reaction degree, a large amount of sulfuric acid is often used for catalysis, 0.51 ton of sulfuric acid is needed for producing one ton of products, and simultaneously, a large amount of liquid caustic soda is used for neutralization, so that a large amount of waste water and industrial waste salt are produced. Therefore, the traditional process has low production efficiency and is not environment-friendly, and further improvement is needed.
Disclosure of Invention
In view of the above technical problems, the first aspect of the present invention provides an environment-friendly synthesis method of methyl 3-hydroxy-2-naphthoate, which comprises the following steps: adding 3-hydroxy-2-naphthoic acid and methanol into a reaction kettle, adding a catalyst, heating for reaction for 8-12 hours, cooling, filtering out the catalyst, recovering the reaction system to room temperature, cooling, and discharging to obtain the product; wherein the reaction temperature is not lower than 100 ℃.
The methyl 3-hydroxy-2-naphthoate is prepared by dehydration condensation reaction of a reaction monomer 3-hydroxy-2-naphthoate (CAS: 92-70-6) and methanol under the action of a catalyst and under a high-temperature condition. Wherein 1 mol of 3-hydroxy-2-naphthoic acid is reacted with 1 mol of methanol to condense carboxyl in a 3-hydroxy-2-naphthoic acid structure with hydroxyl in a methanol structure, and one mol of water is removed to prepare the methyl 3-hydroxy-2-naphthoate. Wherein methanol is used in an excessive amount in order to sufficiently react the 3-hydroxy-2-naphthoic acid monomer.
In some embodiments, the mass ratio of the 3-hydroxy-2-naphthoic acid monomer to methanol may be 100: (250-400), which may be exemplified by a mass ratio of 100.
The 3-hydroxy-2-naphthoic acid and the methanol are subjected to esterification reaction at a high temperature, and the reaction temperature is not lower than 100 ℃. As a preferred technical scheme of the invention, the reaction temperature is 100-120 ℃. The heating contributes to an increase in the degree of reaction to some extent due to the endothermic reaction of the dehydration condensation reaction between 3-hydroxy-2-naphthoic acid and methanol.
However, since 3-hydroxy-2-naphthoic acid is a pale yellow crystal at normal temperature, methanol is a liquid, and if the reaction temperature is too high, it is higher than the boiling point of methanol, methanol is gasified, which affects the degree of reaction, and a safety accident may occur due to the increase of the reaction pressure caused by the gasification of methanol. The esterification reaction is carried out in a high-pressure reaction kettle, 3-hydroxy-2-naphthoic acid and methanol are mixed and dissolved, and then the temperature is increased to 100-120 ℃ for reaction, so that the reaction degree can be accelerated to a certain extent, the reaction time is shortened, the higher yield can be realized within 12 hours, and the yield after 12 hours of reaction can reach 95%.
In the invention, the esterification reaction of 3-hydroxy-2-naphthoic acid and methanol is carried out under high pressure, and in order to not ensure the full conversion of reaction monomers, the applicant finds that the pressure of a reaction kettle is further increased to be not lower than 0.3MPa while the reaction temperature is increased, so that the yield is more favorably improved in short reaction time. As a preferable technical scheme of the invention, the reaction pressure in the reaction process is not lower than 0.3MPa. Further preferably, the reaction pressure during the reaction is 0.3 to 0.5MPa.
After the esterification reaction of 3-hydroxy-2-naphthoic acid and methanol is completed under the conditions of high temperature and high pressure, the temperature of a reaction system is cooled to about 60 ℃, and the ion exchange resin is filtered and washed, dried and the like, so that the product can be repeatedly used. In addition, the redundant methanol in the system is distilled out by a mode of atmospheric distillation and the like, and can be further reused. And cooling the filtered mother liquor to room temperature, and drying to obtain a 3-hydroxy-2-methyl naphthoate product.
In the invention, the esterification reaction of 3-hydroxy-2-naphthoic acid and methanol is carried out under a proper amount of catalyst, and as a preferable technical scheme of the invention, the catalyst is concentrated sulfuric acid and/or ion exchange resin. The amount of the catalyst used in the present invention is not too high, and especially when concentrated sulfuric acid is used as the catalyst, the use of too high amount of the catalyst causes a large amount of industrial waste salt. If the amount is too small, the reaction rate is affected.
In the present invention, the catalyst is used in an amount of 3.5 to 7wt% based on the mass of the 3-hydroxy-2-naphthoic acid, and may be exemplified by 3.5wt%, 3.8wt%, 4.0wt%, 4.2wt%, 4.5wt%, 4.8wt%, 5.0wt%, 5.2wt%, 5.4wt%, 5.5wt%, 5.7wt%, 5.9wt%, 6.0wt%, 6.2wt%, 6.5wt%, 6.8wt%, 7.0wt%, etc. In the invention, when the catalyst is concentrated sulfuric acid, the catalyst refers to the concentrated sulfuric acid with the concentration of 98%.
In the present invention, ion exchange resins are preferably used as the reaction catalyst. In a preferred embodiment of the present invention, the average pore diameter of the ion exchange resin is
Further, the ion exchange resin has an average pore diameter of
Illustratively, the average pore diameter may be
And the like. The average pore diameter in the present invention is a physical quantity that characterizes the size of adsorption pores of the resin and can be determined according to the present inventionThe determination is made by testing in a manner conventional in the art.
As a preferable technical scheme of the invention, the specific surface area of the ion exchange resin is not less than 40m 2 (ii) in terms of/g. More preferably, the ion exchange resin has a specific surface area of 50 to 60m 2 (ii)/g; illustratively, the specific surface area may be 50m 2 /g、50.5m 2 /g、51m 2 /g、51.5m 2 /g、52m 2 /g、52.5m 2 /g、53m 2 /g、53.5m 2 /g、54m 2 /g、54.5m 2 /g、55m 2 /g、55.5m 2 /g、56m 2 /g、56.5m 2 /g、57m 2 /g、57.5m 2 /g、58m 2 /g、58.5m 2 /g、59m 2 /g、59.5m 2 /g、60m 2 In terms of/g, etc. The specific surface area in the present invention is a physical quantity for characterizing the size of the particles, and can be obtained by performing a test in a conventional manner.
In a preferred embodiment of the present invention, the pore volume of the ion exchange resin is 0.2 to 0.5ml/g. Illustratively, the pore volume can be 0.2ml/g, 0.25ml/g, 0.28ml/g, 0.3ml/g, 0.32ml/g, 0.35ml/g, 0.38ml/g, 0.4ml/g, 0.42ml/g, 0.45ml/g, 0.48ml/g, 0.5ml/g, and the like.
The specific source of the ion exchange resin satisfying the above requirements is not particularly limited in the present invention, and various related ion exchange resin products known to those skilled in the art can be selected, including but not limited to, rohm and Haas A15 resin (15 WET catalyzed resin), etc.
In the process of completing the invention, the applicant finds that in the esterification reaction of 3-hydroxy-2-naphthoic acid and methanol, the reaction temperature is increased to be within the range of 100-120 ℃ under the condition of ensuring the reaction pressure of 0.3-0.5 MPa, and the yield of the reaction is favorably improved. Particularly, when an appropriate amount of the ion exchange resin having the specific pore diameter, specific surface area and specific pore volume is used as a catalyst, 95% yield can be achieved within about 12 hours of reaction, and the content (grade purity) of methyl 3-hydroxy-2-naphthoate in the product can be ensured to be higher than 98%. The applicant speculates that methanol is gasified and sufficiently adhered to the porous structure of the specific ion exchange resin at 100 to 120 ℃, and 3-hydroxy-2-naphthoic acid in the system can be more sufficiently contacted with methanol by utilizing the characteristics of the pore diameter, the specific surface area and the like, thereby contributing to improvement of the reaction degree and shortening of the reaction time. However, the larger the specific surface area, the smaller the pore size, and the higher the degree of reaction, and the applicants have found that when the pore size is too small, the specific surface area becomes too large, and the degree of reaction and yield are rather lowered. Probably because the pore size is too small, which prevents the 3-hydroxy-2-naphthoic acid in the system from contacting with methanol.
The second aspect of the invention provides the application of the methyl 3-hydroxy-2-naphthoate prepared by the environment-friendly synthesis method in the rubber field.
The technical scheme provided by the invention has the following beneficial effects：
According to the method for synthesizing the methyl 3-hydroxy-2-naphthoate, a large amount of concentrated sulfuric acid is not used as a catalyst, the using amount of the concentrated sulfuric acid is at most 5% of the mass of the 3-hydroxy-2-naphthoate, a large amount of acid industrial waste salt is not generated, and the production mode is environment-friendly and safe. In addition, the invention adopts the ion exchange resin with a specific structure as the catalyst, and the ion exchange resin is matched with the catalyst for use to shorten the reaction time, so that the yield of about 95 percent is realized within the reaction time of about 12 hours, and the content of the 3-hydroxyl-2-methyl naphthoate in the product is not lower than 98 percent, thereby being suitable for industrial production.
Detailed Description
Example 1
The embodiment discloses an environment-friendly synthetic method of 3-hydroxy-2-methyl naphthoate, which comprises the following steps: adding 100 g of 3-hydroxy-2-naphthoic acid, 300 g of methanol and 5 g of A15 resin (Rohm and Haas 15WET catalytic resin) into a 500ml autoclave, stirring and mixing for 25min, raising the temperature of the system to 110 ℃, adjusting the pressure of the autoclave to 0.4MPa, and stirring and reacting for 12 hours under the condition; then cooling to 60 ℃, filtering and filtering out the A15 resin (being reused in the next batch of reaction); distilling the filtrate in the system under normal pressure to distill out 150 g of methanol (which is repeatedly used in the next reaction); then the filtered mother liquor is cooled to room temperature and filtered, dried, washed and dried to obtain 102 g of light yellow solid methyl 3-hydroxy-2-naphthoate (yield is 95%), and the content of the methyl 3-hydroxy-2-naphthoate in the product is 98.2%.
Example 2
The embodiment discloses an environment-friendly synthetic method of 3-hydroxy-2-methyl naphthoate, which comprises the following steps: adding 100 g of 3-hydroxy-2-naphthoic acid, 300 g of methanol and 5 g of 98% sulfuric acid into a 500ml autoclave, stirring and mixing for 25min, raising the temperature of the system to 110 ℃, adjusting the pressure of the reaction kettle to 0.4MPa, and stirring and reacting for 12 hours under the condition; 150 g of methanol is distilled out from materials in the reaction system under normal pressure (reused in the next batch of reaction), then the filtered mother liquor is cooled to room temperature and filtered, and light yellow solid 3-hydroxy-2-methyl naphthoate 100 g (yield is 93%) is obtained after drying, and the content of 3-hydroxy-2-methyl naphthoate in the product is 97.2%.
Example 3
The embodiment discloses an environment-friendly synthesis method of 3-hydroxy-2-methyl naphthoate, which comprises the following steps: a500 ml autoclave was charged with 100 g of 3-hydroxy-2-naphthoic acid, 300 g of methanol and 5 g of ion exchange resin (A)
T-62MPDRY catalytic resin with the Mesh number of 16-40US Mesh), stirring and mixing for 25min, raising the temperature of the system to 110 ℃, adjusting the pressure of the reaction kettle to 0.4MPa, and stirring and reacting for 12 hours under the condition; then cooling to 60 ℃, and filtering out the ion exchange resin (which is repeatedly used in the next batch of reaction); distilling the filtrate in the system under normal pressure to distill out about 150 g of methanol (which is repeatedly used in the next reaction); then the filtered mother liquor is cooled to room temperature and filtered, dried, washed and dried to obtain 102 g of light yellow solid methyl 3-hydroxy-2-naphthoate (the yield is 91 percent), and the content of the methyl 3-hydroxy-2-naphthoate in the product is 97.8 percent.
Example 4
The embodiment discloses an environment-friendly synthetic method of 3-hydroxy-2-methyl naphthoate, which comprises the following steps: adding 100 g of 3-hydroxy-2-naphthoic acid, 300 g of methanol and 5 g of A15 resin (Rohm Haas 15WET catalytic resin) into a 500ml autoclave, stirring and mixing for 25min, raising the temperature of the system to 135 ℃, adjusting the pressure of the autoclave to 0.4MPa, and stirring and reacting for 12 hours under the condition; then cooling to 60 ℃, filtering and filtering out the A15 resin (being reused in the next batch of reaction); distilling the filtrate in the system under normal pressure to distill out 150 g of methanol (which is repeatedly used in the next reaction); then the filtered mother liquor is cooled to room temperature and filtered, dried, washed and dried to obtain 102 g (the yield is 93%) of light yellow solid methyl 3-hydroxy-2-naphthoate, and the content of the methyl 3-hydroxy-2-naphthoate in the product is 98.3%.
Example 5
The embodiment discloses an environment-friendly synthetic method of 3-hydroxy-2-methyl naphthoate, which comprises the following steps: adding 100 g of 3-hydroxy-2-naphthoic acid, 300 g of methanol and 5 g of A15 resin (Rohm Haas 15WET catalytic resin) into a 500ml autoclave, stirring and mixing for 25min, raising the temperature of the system to 75 ℃, adjusting the pressure of the autoclave to 0.4MPa, and stirring and reacting for 12 hours under the condition; then cooling to 60 ℃, filtering and filtering out the A15 resin (being reused in the next batch of reaction); distilling the filtrate in the system under normal pressure to distill out 150 g of methanol (which is repeatedly used in the next reaction); then the filtered mother liquor is cooled to room temperature and filtered, dried, washed and dried to obtain 102 g of light yellow solid methyl 3-hydroxy-2-naphthoate (yield is 88%), and the content of the methyl 3-hydroxy-2-naphthoate in the product is 93.4%.
From the experimental results, the production process in the synthetic method of the methyl 3-hydroxy-2-naphthoate is environment-friendly, and a large amount of concentrated sulfuric acid is not adopted, so that a large amount of acid industrial waste salt is not generated. In addition, by optimizing and modifying the conditions of the catalyst, the reaction temperature, the reaction pressure and the like, the reaction time is obviously shortened while high yield and purity are ensured, and the production efficiency is greatly improved.
Claims (10)
1. An environment-friendly synthesis method of 3-hydroxy-2-methyl naphthoate is characterized by comprising the following steps: adding 3-hydroxy-2-naphthoic acid and methanol into a reaction kettle, adding a catalyst, heating for reaction for 8-12 hours, cooling, filtering out the catalyst, recovering the reaction system to room temperature, cooling and discharging to obtain the product; wherein the reaction temperature is not lower than 100 ℃.
2. The environment-friendly synthesis method of methyl 3-hydroxy-2-naphthoate as claimed in claim 1, wherein the reaction temperature is 100-120 ℃.
3. The environment-friendly synthesis method of methyl 3-hydroxy-2-naphthoate as claimed in claim 1, wherein the reaction pressure in the reaction process is not lower than 0.3MPa.
4. The environment-friendly synthesis method of methyl 3-hydroxy-2-naphthoate as claimed in claim 3, wherein the reaction pressure in the reaction process is 0.3-0.5 MPa.
5. The environmentally friendly synthesis method of methyl 3-hydroxy-2-naphthoate according to any one of claims 1 to 4, wherein the catalyst is concentrated sulfuric acid and/or ion exchange resin.
6. The process for the environmentally friendly synthesis of methyl 3-hydroxy-2-naphthoate of claim 5, wherein the ion exchange resin has an average pore size of
7. The process for the environmentally friendly synthesis of methyl 3-hydroxy-2-naphthoate as claimed in claim 5, wherein the specific surface area of the ion exchange resin is not less than 40m 2 /g。
8. The environment-friendly synthesis method of methyl 3-hydroxy-2-naphthoate as claimed in claim 7, wherein the specific surface area of the ion exchange resin is 50-60 m 2 /g。
9. The environment-friendly synthesis method of methyl 3-hydroxy-2-naphthoate as claimed in claim 5, wherein the pore volume of the ion exchange resin is 0.2-0.5 ml/g.
10. The use of methyl 3-hydroxy-2-naphthoate prepared by the environmentally friendly synthesis method according to any one of claims 1 to 9 in the field of rubber.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111505329.XA CN115477580A (en) | 2021-12-10 | 2021-12-10 | Environment-friendly synthesis method and application of 3-hydroxy-2-methyl naphthoate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111505329.XA CN115477580A (en) | 2021-12-10 | 2021-12-10 | Environment-friendly synthesis method and application of 3-hydroxy-2-methyl naphthoate |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN115477580A true CN115477580A (en) | 2022-12-16 |
Family
ID=84420510
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202111505329.XA Pending CN115477580A (en) | 2021-12-10 | 2021-12-10 | Environment-friendly synthesis method and application of 3-hydroxy-2-methyl naphthoate |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115477580A (en) |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1067047A (en) * | 1992-05-08 | 1992-12-16 | 西南合成制药厂 | Aromatic ester or ether is the preparation method of 6-methoxynaphthalene methyl-formiate particularly |
| US5194665A (en) * | 1988-06-30 | 1993-03-16 | Hoechst Ag | Surfactants based on hydroxynaphthoic esters and preparation and use thereof |
| CN1772730A (en) * | 2004-11-08 | 2006-05-17 | 株式会社上野制药应用研究所 | Hydroxynaphthoic acid hydrazide compounds and method for preparing the same |
| CN111686798A (en) * | 2020-03-10 | 2020-09-22 | 秦婷 | BINOL axis chiral thiourea organic catalyst for preparing spiro tetrahydrothiophene |
-
2021
- 2021-12-10 CN CN202111505329.XA patent/CN115477580A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5194665A (en) * | 1988-06-30 | 1993-03-16 | Hoechst Ag | Surfactants based on hydroxynaphthoic esters and preparation and use thereof |
| CN1067047A (en) * | 1992-05-08 | 1992-12-16 | 西南合成制药厂 | Aromatic ester or ether is the preparation method of 6-methoxynaphthalene methyl-formiate particularly |
| CN1772730A (en) * | 2004-11-08 | 2006-05-17 | 株式会社上野制药应用研究所 | Hydroxynaphthoic acid hydrazide compounds and method for preparing the same |
| CN111686798A (en) * | 2020-03-10 | 2020-09-22 | 秦婷 | BINOL axis chiral thiourea organic catalyst for preparing spiro tetrahydrothiophene |
Non-Patent Citations (1)
| Title |
|---|
| 孙政: "3-羟基-2-萘甲酰腙的合成研究", 河南化工, vol. 37, no. 1, pages 26 - 28 * |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN111957346B (en) | Etherification catalyst for preparing methyl tertiary butyl ether from methanol-tertiary butyl alcohol and preparation method thereof | |
| CN102114432B (en) | Composite solid acid catalyst and preparation method and uses | |
| CN111484395B (en) | Method for recovering bisphenol A by catalyzing polycarbonate to carry out methanol alcoholysis by composite metal oxide | |
| CN115477580A (en) | Environment-friendly synthesis method and application of 3-hydroxy-2-methyl naphthoate | |
| CN110818573B (en) | Preparation method of 3,3 '-dichloro-4, 4' -diaminodiphenylmethane | |
| CN112011021A (en) | Preparation method of methylated melamine formaldehyde resin | |
| CN111995736A (en) | Preparation method of polycaprolactone polyol | |
| CN1684762A (en) | Catalyst, method for producing the same and method for the polymerisation of cyclic ethers on said catalyst | |
| CN1224621C (en) | Tetrahydrofuran refining process | |
| KR101153283B1 (en) | Method for Preparing Acetylated Lignin from Black Liquor in Alkaline Pulping | |
| CN108863770A (en) | A kind of technique of levulic acid preparation and its solvent and catalyst recycling | |
| CN112495360B (en) | Solid composite catalyst for continuously preparing 3-hydroxybutyraldehyde, and preparation method and application thereof | |
| CN111517962A (en) | Preparation method of amine anti-aging agent | |
| CN112679342A (en) | Preparation method of trans, trans-4, 4' -dicyclohexyl dicarboxylic acid | |
| CN101693646B (en) | Process for preparing dichloropropanol through glycerol chlorination method | |
| CN101245034B (en) | Technique for synthesizing ethyl cyanoacetate with interesterification method | |
| CN114768882B (en) | Heterogeneous catalyst for producing vulcanization accelerator TBBS by oxygen method and preparation method and application thereof | |
| CN109824478B (en) | New process for coproducing dimethyl hexyne diol and diacetone alcohol | |
| CN116371464B (en) | Polyionic liquid-hydrotalcite composite material, preparation method and catalytic application | |
| CN114656319B (en) | Preparation method of high-purity dicyclopentadiene | |
| CN115646543B (en) | Acid catalyst for synthesizing bisphenol F, and preparation method and application thereof | |
| CN115872841B (en) | Method for synthesizing 4,4' -dihydroxybiphenyl by disproportionation method | |
| WO1999016762A1 (en) | Process for purifying tetrahydrofurans used as starting material for polyether polyols | |
| CN112279783B (en) | Method for preparing 3-hydroxypropionitrile under supercritical condition | |
| TWI414358B (en) | A composite solid acid catalyst |
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 |