CN112048733A - Synthesis method of o-hydroxyanisole, m-hydroxyanisole and p-hydroxyanisole - Google Patents
Synthesis method of o-hydroxyanisole, m-hydroxyanisole and p-hydroxyanisole Download PDFInfo
- Publication number
- CN112048733A CN112048733A CN201910709641.7A CN201910709641A CN112048733A CN 112048733 A CN112048733 A CN 112048733A CN 201910709641 A CN201910709641 A CN 201910709641A CN 112048733 A CN112048733 A CN 112048733A
- Authority
- CN
- China
- Prior art keywords
- hydroxyanisole
- electrolyte
- electrolytic
- catalytic oxidation
- reaction
- 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
Abstract
The invention belongs to the technical field of organic synthesis, and particularly relates to a method for synthesizing o-hydroxyanisole, m-hydroxyanisole and p-hydroxyanisole, which comprises the steps of adding electrolyte into phenol and methanol which are used as raw materials, carrying out electrolytic catalytic oxidation under a certain current density, and then carrying out desolventizing, filtering and rectifying on the electrolyte to obtain corresponding products; the invention synthesizes o-hydroxyanisole, m-hydroxyanisole and p-hydroxyanisole for the first time by using an electrolytic catalytic oxidation method; compared with the conventional reaction, the reaction has the characteristics of low reaction temperature, rapid reaction, high yield, less three wastes and the like; different electrolytes can obtain products with different proportions, and the electrolytes can be selected according to requirements; compared with the conventional products obtained through nitration reaction, the method has the characteristic of high safety, and explosive intermediates do not exist; the raw materials of the invention have wide sources and low price.
Description
Technical Field
The invention belongs to the technical field of organic synthesis, and particularly relates to a synthesis method of o-hydroxyanisole, m-hydroxyanisole and p-hydroxyanisole.
Background
O-hydroxyanisole, also known as o-methoxyphenol, is commonly referred to as guaiacol. Colorless or yellowish crystals at normal temperature, or colorless to yellowish transparent oily liquid. Has an aromatic odor. Gradually turns into dark color in the open air or sunlight. The acidic components in the wood dry distillation oil contain 60-90% of creosote, wherein the creosote is mainly guaiacol. It is mainly used as organic synthetic preparation in medicine, pesticide, perfume and other industries, and also in cosmetics and chemical reagents. The compound can be used for synthesizing various anti-inflammatory and antibacterial drugs in medicines, such as potassium (calcium) guaiacol sulfonate, ibuprofen guaiacol ester, guaiacol glyceryl ether and the like; the plant growth regulator 5-nitroguaiacol sodium can be synthesized in the pesticide; can be directly used as perfume raw material in perfume industry, and can also be used for preparing vanillin and artificial Moschus; the antioxidant is used as an antioxidant in the cosmetic industry, belongs to a phenol antioxidant, has strong antioxidation, but is not suitable to be added too much, and is usually used in cooperation with a synergist, a metal ion chelating agent and the like; it is also used as other organic synthesis intermediates in chemical production, as gelatinizing agent, as antioxidant and analytical reagent in printing oil, etc. The synthesis method of o-hydroxyanisole is similar to that of p-hydroxyanisole, and the o-hydroxyanisole can be obtained by diazotizing and hydrolyzing o-anisidine; or o-nitrochlorobenzene can be used as a raw material to prepare o-nitroanisole, and the o-nitroanisole is further reduced to o-aminoanisole, and finally the product is prepared, wherein the yield of the method is about 60-70%; or extracting natural guaiacol from linza phenol, extracting, filtering, acid separating, and rectifying to obtain natural guaiacol.
M-hydroxyanisole, also known as m-methoxyphenol, is a colorless transparent liquid or a transparent pink red to red liquid with the smell of phenol. Can be used as an important intermediate of plastic antioxidant anti-aging agents, bactericides and photosensitive materials, and has great market demands at home and abroad. The partial methylation of resorcinol and dimethyl sulfate is commonly used in the industry to produce m-hydroxyanisole. The yield of the method is about 60 to 70 percent.
P-hydroxyanisole, white flaky or waxy crystals. Is an important intermediate of fine chemical products such as medicines, spices, pesticides and the like. It can also be used as polymer polymerization inhibitor, anti-aging agent, ultraviolet inhibitor, plasticizer, etc., and has wide application. The polymerization inhibitor is mainly used for producing vinyl monomers such as acrylonitrile, acrylic acid and esters thereof, methacrylic acid and esters thereof and the like. The most important advantage is that it can be directly used in polymerization without removing p-hydroxyanisole. It is also used as an anti-aging agent, a dye intermediate, an antioxidant BHA (3-tert-butyl-4-hydroxyanisole) for synthesizing edible oil and cosmetics, and the like. The conventional synthesis method comprises the steps of carrying out substitution reaction on p-nitrochlorobenzene to generate p-nitroanisole, and then carrying out Na reducing agent2And (3) reducing under the action of S to generate para-anisidine, and finally decomposing into a product of para-anisidine through diazotization reaction, wherein the yield of the method is about 60-70%.
From the current industrial production situation, the production of o-hydroxyanisole, m-hydroxyanisole and p-hydroxyanisole has the defects of more reaction steps, low yield and the like, and does not accord with the trend of green chemistry and sustainable development.
Disclosure of Invention
The invention solves the technical problems in the prior art and provides a method for synthesizing o-hydroxyanisole, m-hydroxyanisole and p-hydroxyanisole.
In order to solve the problems, the technical scheme of the invention is as follows:
a process for synthesizing o-hydroxyanisole, m-hydroxyanisole and p-hydroxyanisole includes such steps as adding electrolyte to phenol and methanol, electrolytic catalytic oxidizing.
The reaction formula is shown as formula I:
preferably, the electrolyte is organic sulfonic acid sodium salt or potassium salt or ammonium salt.
Preferably, the electrolyte is any one or more of sodium benzene sulfonate, potassium benzene sulfonate, ammonium benzene sulfonate, potassium p-toluene sulfonate, sodium p-toluene sulfonate, ammonium p-toluene sulfonate, sodium dodecyl sulfonate, potassium dodecyl sulfonate, ammonium dodecyl sulfonate, sulfuric acid, ammonium fluoroborate, sodium fluoroborate, tetraethylammonium p-toluene sulfonate, lithium bis (trifluoromethylsulfonyl) imide, methyl tributyl ammonium sulfate, sodium methoxide and potassium methoxide. Among them, sulfuric acid and lithium bis (trifluoromethylsulfonyl) imide are more preferable.
Preferably, the mass ratio of phenol to methanol to electrolyte is 50-900: 100-950: 50-400, preferably 50-500: 700-900: 100-400.
Preferably, the electrolysis temperature is 10-100 ℃, and more preferably 50-60 ℃.
Preferably, the anode material selected for the electrolytic catalytic oxidation reaction is graphite, a DSA anode, glassy carbon or a BDD electrode; with graphite being more preferred.
Preferably, the cathode material selected for the electrolytic catalytic oxidation reaction is graphite, titanium or stainless steel; among them, stainless steel is more preferable.
Preferably, the current density of the electrolytic catalytic oxidation reaction is kept between 100 and 3000A-m3Wherein, 400 to 1000A/m3Is more preferable.
Preferably, after the electrolytic catalytic oxidation reaction is completed, the electrolyte is desolventized, filtered and rectified to obtain a corresponding product.
More specifically, the method of the present invention is recommended to be performed according to the following steps: 100g of phenol was put into an electrolytic reaction flask, 900g of methanol was further put into the flask, and 100g of lithium bis (trifluoromethylsulfonyl) imide was further put into the flask as an electrolyte at 1000A/m3Carrying out electrolytic catalytic oxidation under the current density, wherein the anode material is glassy carbon, the cathode material is stainless steel, the electrolytic temperature is 50 ℃, and after 12h of electrolysis, the electrolyte is subjected to desolventizing, filtering and rectifying to obtain a corresponding product, the current efficiency is 85%, about 35g of incompletely reacted raw material phenol is left, about 6g of by-product, about 79g of total product, and the conversion rate is 90%. Wherein o-hydroxyanisole is about 30% of the product, m-hydroxyanisole is about 20% of the product, and p-hydroxyanisole is about 50% of the product.
Compared with the prior art, the invention has the advantages that,
1. the invention synthesizes o-hydroxyanisole, m-hydroxyanisole and p-hydroxyanisole for the first time by using an electrolytic catalytic oxidation method;
2. different electrolytes can obtain products with different proportions, and the electrolytes can be selected according to requirements.
3. Compared with the conventional reaction, the reaction has the characteristics of low reaction temperature, rapid reaction, high yield, less three wastes and the like;
4. compared with the conventional products obtained through nitration reaction, the method has the characteristic of high safety, and no explosive intermediate exists.
5. The raw materials are wide in source and low in cost.
Detailed Description
Example 1:
100g of phenol was put into an electrolytic reaction flask, 900g of methanol was further put into the flask, and 300g of methyltributylammonium methylsulfate was further added as an electrolyte at 800A/m3Electrolytic catalytic oxidation under current density, wherein the anode material is BDD electrode, and the cathode material is BThe electrolytic temperature of the steel is 20 ℃, the corresponding product can be obtained by desolventizing, filtering and rectifying the electrolyte after 12h of electrolysis, the current efficiency is 75%, about 45g of incompletely reacted raw material phenol is left, about 10g of by-product, about 51g of total product and 79% of conversion rate. Wherein o-hydroxyanisole is about 5% of the product, m-hydroxyanisole is about 10% of the product, and p-hydroxyanisole is about 85% of the product.
Example 2:
300g of phenol was put into an electrolytic reaction flask, and 700g of methanol and 200g of sulfuric acid were further put into the electrolytic reaction flask as an electrolyte at 3000A/m3Carrying out electrolytic catalytic oxidation under the current density, wherein the anode material is a DSA anode, the cathode material is titanium, the electrolytic temperature is 40 ℃, desolventizing, filtering and rectifying the electrolyte after the electrolysis is carried out for 12h to obtain a corresponding product, the current efficiency is 52%, the amount of incompletely reacted raw material phenol is 229g, the amount of byproducts is 10g, the total product is 80g, and the conversion rate is 85%. Wherein o-hydroxyanisole is about 20% of the product, m-hydroxyanisole is about 25% of the product, and p-hydroxyanisole is about 55% of the product.
Example 3:
500g of phenol was put into an electrolytic reaction flask, 500g of methanol was further put into the flask, and 150g of tetraethylammonium p-toluenesulfonate was further added as an electrolyte at 2000A/m3Carrying out electrolytic catalytic oxidation under the current density, wherein the anode material is graphite, the cathode material is titanium, the electrolytic temperature is 60 ℃, desolventizing, filtering and rectifying the electrolyte after the electrolysis is carried out for 12h to obtain a corresponding product, the current efficiency is 45%, the amount of incompletely reacted raw material phenol is about 434g, the amount of byproducts is about 12g, the total product is about 70g, and the conversion rate is 81%. Wherein o-hydroxyanisole is about 2% of the product, m-hydroxyanisole is about 2% of the product, and p-hydroxyanisole is about 96% of the product.
Example 4:
100g of phenol was put into an electrolytic reaction flask, 900g of methanol was further put into the flask, and 100g of lithium bis (trifluoromethylsulfonyl) imide was further put into the flask as an electrolyte at 1000A/m3Electrolytic catalytic oxidation is carried out under the current density, the anode material is glassy carbon, the cathode material is stainless steel,the electrolysis temperature is 50 ℃, the corresponding product can be obtained by desolventizing, filtering and rectifying the electrolyte after electrolysis for 12h, the current efficiency is 85%, about 35g of incompletely reacted raw material phenol is left, about 6g of by-product, about 79g of total product, and the conversion rate is 90%. Wherein o-hydroxyanisole is about 30% of the product, m-hydroxyanisole is about 20% of the product, and p-hydroxyanisole is about 50% of the product.
Example 5:
50g of phenol was put into an electrolytic reaction flask, 950 g of methanol was further put into the flask, and 400g of sodium p-toluenesulfonate was further added as an electrolyte at a rate of 400A/m3Carrying out electrolytic catalytic oxidation under the current density, wherein the anode material is a DSA anode, the cathode material is stainless steel, the electrolytic temperature is 10 ℃, desolventizing, filtering and rectifying the electrolyte after electrolysis for 12h to obtain a corresponding product, the current efficiency is 90%, the amount of incompletely reacted raw material phenol is about 22g, the amount of byproducts is about 2g, the total product is about 35g, and the conversion rate is 94%. Wherein o-hydroxyanisole is about 23% of the product, m-hydroxyanisole is about 17% of the product, and p-hydroxyanisole is about 60% of the product.
Example 6:
700g of phenol was put into an electrolytic reaction flask, 300g of methanol was further put into the flask, and 100g of sodium methoxide as an electrolyte was further added at 1000A/m3Carrying out electrolytic catalytic oxidation under the current density, wherein the anode material is a DSA anode, the cathode material is stainless steel, the electrolytic temperature is 80 ℃, desolventizing, filtering and rectifying the electrolyte after electrolysis for 12h to obtain a corresponding product, the current efficiency is 45%, about 655g of incompletely reacted raw material phenol remains, about 20g of byproducts, about 30g of total products, and the conversion rate is 52%. Wherein o-hydroxyanisole is about 10% of the product, m-hydroxyanisole is about 10% of the product, and p-hydroxyanisole is about 80% of the product.
Example 7:
900g of phenol was put into an electrolytic reaction flask, 100g of methanol was further put into the flask, and 50g of ammonium fluoroborate as an electrolyte was further added at a rate of 100A/m3Electrolytic catalytic oxidation under current density, wherein the anode material is BDD electrode, the cathode material is stainless steel, the electrolysis temperature is 100 ℃, and electrolysis is 1After 2h, desolventizing, filtering and rectifying the electrolyte to obtain a corresponding product, wherein the current efficiency is 55%, 892g of incompletely reacted raw material phenol remains, about 3g of byproducts remains, about 6g of total products remains, and the conversion rate is 60%. Wherein o-hydroxyanisole is about 13% of the product, m-hydroxyanisole is about 7% of the product, and p-hydroxyanisole is about 80% of the product.
It should be noted that the above-mentioned embodiments are only preferred embodiments of the present invention, and are not intended to limit the scope of the present invention, and all equivalent substitutions or substitutions made on the above-mentioned embodiments are included in the scope of the present invention.
Claims (10)
1. A process for synthesizing o-hydroxyanisole, m-hydroxyanisole and p-hydroxyanisole includes such steps as adding electrolyte to phenol and methanol, electrolytic catalytic oxidizing.
2. A synthesis process according to claim 1, characterised in that the electrolyte is an organic sulphonic acid sodium or potassium or ammonium salt.
3. The method of claim 1, wherein the electrolyte is any one or more of sodium benzenesulfonate, potassium benzenesulfonate, ammonium benzenesulfonate, potassium p-toluenesulfonate, sodium p-toluenesulfonate, ammonium p-toluenesulfonate, sodium dodecylsulfonate, potassium dodecylsulfonate, ammonium dodecylsulfonate, sulfuric acid, ammonium fluoroborate, sodium fluoroborate, tetraethylammonium p-toluenesulfonate, lithium bis (trifluoromethylsulfonyl) imide, methyl tributylammonium sulfate, sodium methoxide, and potassium methoxide.
4. The synthesis method according to claim 1, wherein the mass ratio of phenol to methanol to electrolyte is 50-900: 100-950: 50-400.
5. The synthesis method according to claim 1, wherein the electrolysis temperature is 10 to 100 ℃.
6. The synthesis method of claim 1, wherein the anode material selected for the electrolytic catalytic oxidation reaction is graphite, DSA anode, glassy carbon or BDD electrode.
7. The synthesis method of claim 1, wherein the cathode material selected for the electrolytic catalytic oxidation reaction is graphite, titanium or stainless steel.
8. The synthesis method according to claim 1, wherein the current density of the electrolytic catalytic oxidation reaction is maintained at 100 to 3000A/m3。
9. The synthesis method of claim 1, wherein after the electrolytic catalytic oxidation reaction is completed, the corresponding product is obtained by desolventizing, filtering and rectifying the electrolyte.
10. The synthetic method of claim 1 wherein the synthetic method is performed according to the following steps: 100g of phenol was put into an electrolytic reaction flask, 900g of methanol was further put into the flask, and 100g of lithium bis (trifluoromethylsulfonyl) imide was further put into the flask as an electrolyte at 1000A/m3Carrying out electrolytic catalytic oxidation under the current density, wherein the anode material is glassy carbon, the cathode material is stainless steel, the electrolytic temperature is 50 ℃, and after 12h of electrolysis, the electrolyte is subjected to desolventizing, filtering and rectifying to obtain a corresponding product.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910494212 | 2019-06-05 | ||
| CN2019104942122 | 2019-06-05 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN112048733A true CN112048733A (en) | 2020-12-08 |
Family
ID=73609128
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910709641.7A Pending CN112048733A (en) | 2019-06-05 | 2019-08-01 | Synthesis method of o-hydroxyanisole, m-hydroxyanisole and p-hydroxyanisole |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN112048733A (en) |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1249362A (en) * | 1999-08-25 | 2000-04-05 | 福建师范大学 | Process for synthesizing o-, meta-, or p-methoxylbenzaldehyde by electrolysis |
| US20050252783A1 (en) * | 2004-05-11 | 2005-11-17 | Hana Hradil | Electroplating solution for gold-tin eutectic alloy |
| CN102505125A (en) * | 2011-10-27 | 2012-06-20 | 浙江理工大学 | Method for preparing 2,4-dimethylanisole |
| CN105217740A (en) * | 2015-10-26 | 2016-01-06 | 浙江工业大学 | A kind of Electrochemical hydriding treatment process containing lower concentration fluorinated aromatic hydrocarbon waste water |
| CN107805825A (en) * | 2017-11-28 | 2018-03-16 | 中国科学院新疆理化技术研究所 | The method of electrosynthesis glyoxal methyl phenyl ethers anisole |
-
2019
- 2019-08-01 CN CN201910709641.7A patent/CN112048733A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1249362A (en) * | 1999-08-25 | 2000-04-05 | 福建师范大学 | Process for synthesizing o-, meta-, or p-methoxylbenzaldehyde by electrolysis |
| US20050252783A1 (en) * | 2004-05-11 | 2005-11-17 | Hana Hradil | Electroplating solution for gold-tin eutectic alloy |
| CN102505125A (en) * | 2011-10-27 | 2012-06-20 | 浙江理工大学 | Method for preparing 2,4-dimethylanisole |
| CN105217740A (en) * | 2015-10-26 | 2016-01-06 | 浙江工业大学 | A kind of Electrochemical hydriding treatment process containing lower concentration fluorinated aromatic hydrocarbon waste water |
| CN107805825A (en) * | 2017-11-28 | 2018-03-16 | 中国科学院新疆理化技术研究所 | The method of electrosynthesis glyoxal methyl phenyl ethers anisole |
Non-Patent Citations (1)
| Title |
|---|
| ***等: "钼改性固体酸电解条件下催化合成甲氧基苯酚", 《第十一届全国青年催化会议论文集》 * |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CA1271772A (en) | Oxidation of organic compounds using ceric ions in aqueous methanesulfonic acid | |
| CN109825847B (en) | Process for preparing intermediates for alkoxylation of hindered amines | |
| Bunton et al. | Abnormally high nucleophilicity of micellar-bound azide ion | |
| CN107915644A (en) | A kind of method that p-aminophenyl ether is prepared using paranitrochlorobenzene as raw material | |
| CN112048733A (en) | Synthesis method of o-hydroxyanisole, m-hydroxyanisole and p-hydroxyanisole | |
| CN104607207A (en) | Titanium-salt-modified Raney nickel catalyst and method for synthesizing dihydroterpineol | |
| EP0217159B1 (en) | Aldehydes, acetals, alcohols and ethers with 3-methyl or 3,5-dimethylbenzyl groups, their preparation and their use as fragrance compounds | |
| CN110950745B (en) | Preparation method of phenylacetaldehyde | |
| CN109321939B (en) | Electrochemical synthesis method of thiazole compound | |
| MX2015000244A (en) | Method for producing vanillin. | |
| CN106220524A (en) | A kind of industrial raising N, the method for 2,3 trimethyl 2 butanamide production efficiencys | |
| CN104693338A (en) | Acrylic hyperdispersing agent and preparation method thereof | |
| CN114000169A (en) | Electrochemical preparation method of allicin compound | |
| DE2547383A1 (en) | (Para)-benzoquinone tetramethyl ketal prepn. - by anodic oxidn. of alkoxy-benzene derivs. in methanol contg. conductive salt | |
| CN106187725B (en) | The etherification method of parahydroxyben-zaldehyde and its derivative | |
| CN110204424A (en) | A kind of preparation method of biology base 2 phenylethyl alcohol | |
| CN114381749B (en) | Method for synthesizing menthyl formic acid | |
| DE2653646C2 (en) | Substituted propargylic alcohols | |
| DE10237196A1 (en) | Catalytic reduction of nitriles to aldehydes | |
| EP2289873B1 (en) | Process for the preparation of iodopropargyl compounds | |
| CN111996546B (en) | Preparation method of novel polymerization inhibitor based on tetramethyl piperidine nitroxide free radical phosphite triester | |
| DE4106661A1 (en) | 2-METHYLBENZALDEHYDDIALKYLACETALE | |
| CN102060737B (en) | Secondary alkyl sodium sulfonate posttreatment method | |
| CN113004135A (en) | Method for preparing thujopsis japonica ketonic acid by utilizing MTO catalysis | |
| CN103449993B (en) | Production method of 3-campholenyl-2-butanone |
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 | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20201208 |