CN109456152A - A kind of method that catalysis oxidation prepares P-methoxybenzal-dehyde to methoxy toluene - Google Patents
A kind of method that catalysis oxidation prepares P-methoxybenzal-dehyde to methoxy toluene Download PDFInfo
- Publication number
- CN109456152A CN109456152A CN201710794505.3A CN201710794505A CN109456152A CN 109456152 A CN109456152 A CN 109456152A CN 201710794505 A CN201710794505 A CN 201710794505A CN 109456152 A CN109456152 A CN 109456152A
- Authority
- CN
- China
- Prior art keywords
- manganese
- copper
- cobalt
- metal salt
- methoxybenzal
- 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.)
- Granted
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/27—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation
- C07C45/32—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen
- C07C45/33—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of CHx-moieties
- C07C45/34—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of CHx-moieties in unsaturated compounds
- C07C45/36—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of CHx-moieties in unsaturated compounds in compounds containing six-membered aromatic rings
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a kind of methods that catalysis oxidation prepares P-methoxybenzal-dehyde to methoxy toluene.This method is using transition metal salt and containing n-donor ligand as catalyst, and using acetonitrile as solvent, liquid-phase catalysis selective oxidation prepares P-methoxybenzal-dehyde to methoxy toluene.By selecting suitable containing n-donor ligand and coordinate transition metal salts to act on, reaction condition is mild, and step is simple, high catalytic efficiency.
Description
Technical field
The present invention relates to chemical field, specifically a kind of catalysis oxidation prepares to methoxyl group methoxy toluene
The method of benzaldehyde.
Background technique
P-methoxybenzal-dehyde is also known as anisic aldehyde, anisaldehyde, is colourless under room temperature to weak yellow liquid, it is lasting to have
The smell of similar hawthorn is the primary flavor for deploying hawthorn floral type, has the economic benefit of high value, while being also important
The intermediate of organic synthesis is widely used in the fields such as essence, medicine, pesticide, industry.P-methoxybenzal-dehyde is as acetal
Class fragrance has the characteristics that soft aroma and simple and elegant, lasting, can be used as high-grade fragrance, and its chemical property is stablized, fragrance
Diffusion is fast, is the important selection in flavors and fragrances industry, people is caused more and more to pay close attention to.In addition, it can in field of medicaments
Using the intermediate as preparation antihistamine drug, for preparing the drugs such as antibiotic oxyammonia benzylpenicillin.It can in terms of pesticide
Using as insecticide and desinsection agent addition agent, biological growth inhibitor.In industrial aspect, the additive of non-cyanogen galvanization can be used as
Excellent brightener, P-methoxybenzal-dehyde can obtain bright coating in wider current density, to be widely used in
Electroplating industry;In addition, P-methoxybenzal-dehyde can be also used for preparation functional polymer material, poly-ferrocene-is to methoxybenzene
Formaldehyde has good prospects in functional polymer material industrial application, it not only has special electrical property, and there are also good magnetic properties.
The synthetic method of P-methoxybenzal-dehyde is mainly the following method at present: (1) by methoxy methyl benzene oxidatoin
It is made;(2) it is alkylated to react under alkaline condition with dimethyl suflfate by parahydroxyben-zaldehyde and be made;(3) by propylene
The oxidation of base methyl phenyl ethers anisole is made;(4) it is aoxidized and is made by P-methoxybenzyl alcohol;(5) it is methylated by phenol through dimethyl suflfate,
Then it is made again through chloromethylation, hydrolysis;(6) it is methylated, is reoxidized obtained by p-methyl phenol.
These preparation methods at present, some raw materials such as P-methoxybenzyl alcohol is more expensive, though some raw materials are easy to get,
Synthesis process step is complicated too much, and reaction is not easy to control, and last handling process is more complicated, and gross production rate is lower.At present to first
Oxygroup toluene is many for the method that raw material prepares P-methoxybenzal-dehyde, but liquid-phase catalysis choice oxidation process is comparatively superior.
Summary of the invention
A kind of method that catalysis oxidation prepares P-methoxybenzal-dehyde to methoxy toluene.This method with transition metal salt with
Containing n-donor ligand is catalyst, and using acetonitrile as solvent, liquid-phase catalysis selective oxidation prepares to first methoxy toluene under temperate condition
Oxygroup benzaldehyde.By selecting suitable containing n-donor ligand and coordinate transition metal salts to act on, reaction condition is mild, and step is simple,
High catalytic efficiency.
The technical solution of the present invention is as follows:
According to the present invention, this method using to methoxy toluene as substrate, using transition metal salt and containing n-donor ligand as catalyst,
Catalytic selective oxidation prepares P-methoxybenzal-dehyde under temperate condition.
Transition metal salt used is cobalt nitrate, cobalt acetate, cobalt chloride, cobaltous sulfate, acetylacetone cobalt, cobalt iso-octoate, oil
Sour cobalt, new cobalt decanoate, copper nitrate, copper acetate, copper chloride, copper sulphate, acetylacetone copper, isooctyl acid copper, copper oleate, neodecanoic acid
Copper, manganese nitrate, manganese acetate, manganese chloride, manganese sulfate, manganese acetylacetonate, manganese iso-octoate, manganese oleate, one of neodecanoic acid manganese or
Person is two or more.
The containing n-donor ligand is imidazoles, 2-methylimidazole, 2-ethyl-4-methylimidazole, benzimidazole, 1,10- phenanthrene hello
Quinoline, 2,2 '-bipyridyls, to tetramethoxy phenyl porphyrin, to one or more of tetracarboxylic phenyl porphyrin.
The concentration of transition metal salt is 10-2000ppm (with the metering of pure metal content), and preferably 200-600ppm is added
The quality of the containing n-donor ligand entered and the ratio of metal salt quality are 0.01-10, preferably 0.2-6.
Reaction dissolvent is acetonitrile, and substrate is 2.0mol/L to methoxy methyl benzene concentration, and reaction temperature is 40-140 DEG C, preferably
It is 60-110 DEG C, reaction time 1-12h, preferably 4-8h, reaction pressure 0.1-1.0MPa, preferably 0.2-0.6MPa.
For the present invention by selecting suitable containing n-donor ligand and coordinate transition metal salts to act on, reaction condition is mild, step letter
Single, catalysis is high to methoxy toluene oxidation efficiency.
Specific embodiment
Method provided by the invention is described in detail below with reference to embodiment, but the invention is not limited in any way.
Embodiment 1:
Contain to 60mL and 10mL is added in the autoclave of polytetrafluoro liner containing to methoxy toluene (2.0mol/L)
Cobalt nitrate acetonitrile solution, wherein the concentration of cobalt nitrate is 400ppm (with the calculating of Co content), is added to tetramethoxy phenyl porphyrin
80mg.Enclosed high pressure reaction kettle, stirring, is warming up to 80 DEG C, is filled with 0.4MPa oxygen, reacts 8h.After reaction, it is detected with GC
Reaction product is 38.1% to methoxy toluene conversion ratio, and the selectivity of P-methoxybenzal-dehyde is 42.3%.
Embodiment 2~5: repeating the reaction process of embodiment 1, the difference is that reaction condition and used transition metal salt
It is different.The specific reaction condition of each embodiment and the results are shown in Table 1.
Table 1, the specific reaction condition of embodiment 2~5
The result shows that metal manganese salt and containing n-donor ligand effect have preferable catalysis to methoxy toluene oxidation activity.
Embodiment 6:
Contain to 60mL and 10mL is added in the autoclave of polytetrafluoro liner containing to methoxy toluene (2.0mol/L)
Manganese iso-octoate acetonitrile solution, wherein the concentration of manganese iso-octoate is 200ppm (with the calculating of Mn content), and 1,10- ferrosin is added
100mg.Enclosed high pressure reaction kettle, stirring, is warming up to 100 DEG C, is filled with 0.6MPa oxygen, reacts 8h.After reaction, it is examined with GC
Reaction product is surveyed, is 48.3% to methoxy toluene conversion ratio, the selectivity of P-methoxybenzal-dehyde is 56.2%.
Embodiment 7~10: repeating the reaction process of embodiment 6, the difference is that reaction condition and used containing n-donor ligand
It is different.The specific substrate of each embodiment is listed in Table 2 below
Table 2, the specific reaction condition of embodiment 7~10
The result shows that porphyrin containing n-donor ligand and metal salt co-catalysis have preferable catalytic activity to methoxy toluene.
Claims (7)
1. a kind of method that catalysis oxidation prepares P-methoxybenzal-dehyde to methoxy toluene, it is characterised in that: this method is with mistake
Crossing metal salt and containing n-donor ligand is catalyst, and using acetonitrile as solvent, liquid-phase catalysis selective oxidation prepares to first methoxy toluene
Oxygroup benzaldehyde.
2. according to the method for claim 1, it is characterised in that: transition metal salt used is cobalt nitrate, cobalt acetate, chlorination
Cobalt, cobaltous sulfate, acetylacetone cobalt, cobalt iso-octoate, cobalt oleate, new cobalt decanoate, copper nitrate, copper acetate, copper chloride, copper sulphate, second
Acyl acetone copper, isooctyl acid copper, copper oleate, neodecanoic acid copper, manganese nitrate, manganese acetate, manganese chloride, manganese sulfate, manganese acetylacetonate are different pungent
Sour manganese, manganese oleate, one of neodecanoic acid manganese or two or more.
3. according to the method for claim 1, it is characterised in that: the containing n-donor ligand is imidazoles, 2-methylimidazole, 2- second
Base -4-methylimidazole, benzimidazole, 1,10- ferrosin, 2,2 '-bipyridyls, to tetramethoxy phenyl porphyrin, to tetracarboxylic benzene
One or more of base porphyrin.
4. according to the method for claim 1, it is characterised in that: the concentration of transition metal salt is 10-2000ppm in system
(with the metering of pure transition metal), preferably 200-600ppm, the quality for the containing n-donor ligand being added and the ratio of metal salt quality
For 0.01-10, preferably 0.2-6.
5. according to the method for claim 1, it is characterised in that: reaction dissolvent is acetonitrile, is to methoxy methyl benzene concentration
0.1-8.0mol/L, preferably 1.0-5.0mol/L reaction temperature be 40-140 DEG C, preferably 60-110 DEG C, reaction time 1-
12h, preferably 4-8h.
6. according to the method for claim 1, it is characterised in that: react the oxygen source used for oxygen.
7. according to method described in claim 1,5 or 6, it is characterised in that: reaction pressure 0.1-1.0MPa, preferably 0.2-
0.6MPa。
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201710794505.3A CN109456152B (en) | 2017-09-06 | 2017-09-06 | Method for preparing p-methoxybenzaldehyde by catalytic oxidation of p-methoxytoluene |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201710794505.3A CN109456152B (en) | 2017-09-06 | 2017-09-06 | Method for preparing p-methoxybenzaldehyde by catalytic oxidation of p-methoxytoluene |
Publications (2)
Publication Number | Publication Date |
---|---|
CN109456152A true CN109456152A (en) | 2019-03-12 |
CN109456152B CN109456152B (en) | 2021-10-29 |
Family
ID=65605893
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201710794505.3A Active CN109456152B (en) | 2017-09-06 | 2017-09-06 | Method for preparing p-methoxybenzaldehyde by catalytic oxidation of p-methoxytoluene |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN109456152B (en) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN112079707A (en) * | 2020-09-23 | 2020-12-15 | 中国科学院大连化学物理研究所 | Method for preparing carboxylic acid and co-producing alpha-olefin by catalytic oxidation of primary alcohol with cobalt salt |
CN112778106A (en) * | 2019-11-05 | 2021-05-11 | 中国科学院大连化学物理研究所 | Method for preparing anisaldehyde by catalytic liquid phase selective oxidation |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1695806A (en) * | 2004-05-13 | 2005-11-16 | 中国科学院大连化学物理研究所 | Catalysis system in use for oxidation reaction of toluene in liquid phase |
CN107011152A (en) * | 2016-01-27 | 2017-08-04 | 中国石化扬子石油化工有限公司 | The method that Selectivity for paraxylene catalysis oxidation prepares p-methylbenzoic acid |
CN107011151A (en) * | 2016-01-27 | 2017-08-04 | 中国石化扬子石油化工有限公司 | The method that benzaldehyde selectivity is improved during toluene liquid phase catalytic oxidation |
-
2017
- 2017-09-06 CN CN201710794505.3A patent/CN109456152B/en active Active
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1695806A (en) * | 2004-05-13 | 2005-11-16 | 中国科学院大连化学物理研究所 | Catalysis system in use for oxidation reaction of toluene in liquid phase |
CN107011152A (en) * | 2016-01-27 | 2017-08-04 | 中国石化扬子石油化工有限公司 | The method that Selectivity for paraxylene catalysis oxidation prepares p-methylbenzoic acid |
CN107011151A (en) * | 2016-01-27 | 2017-08-04 | 中国石化扬子石油化工有限公司 | The method that benzaldehyde selectivity is improved during toluene liquid phase catalytic oxidation |
Non-Patent Citations (3)
Title |
---|
YU, JIATAO: "Copper(II)-promoted direct conversion of methylarenes into aromatic oximes", 《ORGANIC & BIOMOLECULAR CHEMISTRY》 * |
洪龙: "金属卟啉/金属盐复合催化氧化合成对甲氧基苯甲醛", 《广东化工》 * |
洪龙: "金属卟啉/金属盐复合催化氧化对甲氧基甲苯合成对甲氧基苯甲醛的研究", 《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑》 * |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN112778106A (en) * | 2019-11-05 | 2021-05-11 | 中国科学院大连化学物理研究所 | Method for preparing anisaldehyde by catalytic liquid phase selective oxidation |
CN112778106B (en) * | 2019-11-05 | 2022-06-03 | 中国科学院大连化学物理研究所 | Method for preparing anisaldehyde by catalytic liquid phase selective oxidation |
CN112079707A (en) * | 2020-09-23 | 2020-12-15 | 中国科学院大连化学物理研究所 | Method for preparing carboxylic acid and co-producing alpha-olefin by catalytic oxidation of primary alcohol with cobalt salt |
CN112079707B (en) * | 2020-09-23 | 2021-06-01 | 中国科学院大连化学物理研究所 | Method for preparing carboxylic acid and co-producing alpha-olefin by catalytic oxidation of primary alcohol with cobalt salt |
Also Published As
Publication number | Publication date |
---|---|
CN109456152B (en) | 2021-10-29 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
Dhakshinamoorthy et al. | Cascade reactions catalyzed by metal organic frameworks | |
Mahmudov et al. | New copper (II) dimer with 3-(2-hydroxy-4-nitrophenylhydrazo) pentane-2, 4-dione and its catalytic activity in cyclohexane and benzyl alcohol oxidations | |
CN109456152A (en) | A kind of method that catalysis oxidation prepares P-methoxybenzal-dehyde to methoxy toluene | |
US10099203B2 (en) | Method for the preparation of metal-organic compounds | |
Wang et al. | Nanospace engineering of metal‐organic frameworks for heterogeneous catalysis | |
Welther et al. | Iron (0) nanoparticle catalysts in organic synthesis | |
Chowdhury et al. | An iron catalyzed regioselective oxidation of terminal alkenes to aldehydes | |
CN103041826A (en) | Bimetal nanometer catalyst as well as preparation and application method thereof | |
Manoj et al. | The role of MOF based nanocomposites in the detection of phenolic compounds for environmental remediation-A review | |
Gangu et al. | A review on metal-organic frameworks as congenial heterogeneous catalysts for potential organic transformations | |
CN104119213B (en) | A kind of preparation method of vanillin food grade,1000.000000ine mesh | |
CN109734740A (en) | A kind of borate family metal organic framework compound and preparation method thereof | |
CN104923299A (en) | Ruthenium catalysts used for catalyzing acetophenone for producing alpha-phenylethanol, and preparation method thereof | |
CN109678708B (en) | Process for producing 3-hydroxypropionic acid ester | |
Shi et al. | Bi–Mn mixed metal organic oxide: A novel 3d-6p mixed metal coordination network | |
CN101391948B (en) | Method for preparing 3-methyl-2-butenoic acid | |
Abedi et al. | Self-assembled 3D heterometallic Zn (II)/K (I) metal–organic framework with the fluorite topology | |
EP1101768A1 (en) | Substituted Phosphanylphenolato[P,O]-metal-complexes for Polymerisation of Olefines | |
CN101310597B (en) | Agricultural antiseptic | |
CN104558061B (en) | Hypoboric acid benzene tricarboxylic acid cobalt-indium micro-porous crystal and preparation method thereof | |
CN108997386B (en) | Zinc metal organic complex constructed by double ligands and preparation method thereof | |
Turner et al. | A guest-templated (6, 3)-sheet constructed using asymmetric hydrogen-bonding anions | |
Bora et al. | Two-fold interpenetrating btc based cobaltous coordination polymer: A promising catalyst for solvent free oxidation of 1-hexene | |
CN103990469A (en) | Catalyst for synthesizing crotyl alcohol by carrying out selective hydrogenation on crotonaldehyde, and preparation method of catalyst | |
CN103896748B (en) | A kind of purposes of rhodium catalyst and adopt the method for this Catalyst Production aldehyde |
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 | ||
GR01 | Patent grant | ||
GR01 | Patent grant |